In Honor of Nobel Laureate Prof. M Stanley Whittingham
| SESSION: GlassTueAM-R10 | Durán International Symposium on Sustainable Glass Processing and Applications |
| Tue. 28 Nov. 2023 / Room: Boardroom | |
| Session Chairs: Erik Muijsenberg; John Parker; Session Monitor: TBA | |
In May 2021, the news that glass communities everywhere had been waiting for winged its way round the world; the United Nations had endorsed 2022 as the International Year of Glass. The application had taken the previous 18 months to prepare and included a 30-minute video, an electronic brochure and printed documents explaining the vital role glassy materials play in helping the world achieve the humanitarian goals encompassed in the UN 2030 declarations. The submission of the application rested largely on the International Commission on Glass, along with the Community of Glass Associations and the International Committee for Museums and Collections of Glass (ICOM-Glass). Nineteen countries co-sponsored the Resolution A/75/L.84, approving the International Year of Glass. More than 2500 institutions, companies, artists and individuals from 95 countries all over the world have written to support this common dream and messages continue coming. The book Welcome to the Glass Age, focusing on the various UN 2030 goals was published and a great and successful Opening Ceremony was held in the Room of Human Rights in the Palace of nations in Geneva, on 10-11 February 2022. More than 4800 online attendants on 11th February joined the 150 in person participants, constituting the biggest event in the history of glass field but also the most wider in the history of United nations. In July, the ICG Congress in Berlin celebrating the DGG’s centenary gathered more than 850 participants and Tokyo celebrated a brilliant closing ceremony on 8-9th December. Several Trade Fairs displayed parallel events promoting IYOG2022 and the role of Glass in Society, in particular VITRUM 2021, GLASSMAN, in Monterrey, 11-12th May; Mir-Stekla in Moscow, 6-9th June; and Glasstech in Düsseldorf, 20-23th September, 2022. Glasspex/Glasspro in Mumbai and the China International Glass Industrial Technical Exhibition were moved to 2023.Other worldwide activities included: a) a US Glass Day, Washington DC, April, b) an ‘Iberoamerican International Congress Women in Glass. Artists and Scientists’, Madrid, Spain in May, d) an International Festival of Art, Stourbridge, UK, August, e) a place within the Venice Biennale in September and f) dedicated issues of several glass Journals.Events were organised locally with up to 10 000 activities, including ideas and materials such as posters, display boards, articles, comics and U tube clips. People from every corner of the planet contributed to the arts, the imaginative use of glass in architecture, its recyclability, and its role in ensuring our well-being. A key issue in the approval of IYOG2022 was the power of glass as a tool to build a more sustainable and a fairer planet. Glass containers represent the best example of circular economy, where one bottle is produced from other bottle, closing the circle of non-waste process. But glass in every application (glazings, vehicles windscreens, TV plasma glass, solar panels or turbine eolic blades) has also infinite lives. Flat glass industry is using more than 50% of recycled glazing, saving energy and much reducing CO2 emissions. We have a long route to run to ensure the infinite lives of glass, using and reusing this magical material that is reborn each time with new lives and applications.
12:00: [GlassTueAM02] OSThis dramatic 17 minute video recreates the atmosphere of last December’s Debriefing Session in New York at the UN Headquarters; it showcases many ‘International Year of Glass’ events, particularly ones that supported the UN 2030 Education and Equality Goals. A voiceover links amazing images and provides a context which makes the jigsaw whole. Along the video a summary of the most relevant events of IYOG2022 are presented with the aim of providing a roadmap to travel the Age of GlassThe video is designed and produced by the Executive committee of IYOG2022It is produced by Marco Demichelis.
12:25: [GlassTueAM03] OS PlenaryHow can we reduce our carbon emissions with new furnace concepts and ideas. New ideas only can be safely developed and tested by using validated Computational Fluid Dynamics (CFD) such as GS Glass Furnace Model (GS GFM). It is quite logical that no glass producer will build a new furnace concept melting 100+ tons per day without thorough analysis, calculations and extensive CFD modeling. Lately most glass producers are asking how to reduce carbon emissions with either increasing the amount of electric melting or hydrogen. We have seen in the past such intensive use of CFD modeling when the Oxy-fuel applications emerged. Now with the next generation of large Hybrid (with more than 50% electric boosting) or all Electric melters we can see an increase in demand once again. “La Maison Française du Verre » (LMFV) is producing borosilicate glass for cookware in its factory of Châteauroux (France). Its hybrid furnace is melting around 160 tons per day and its design is improved during each rebuilt, every 5 years, focusing on glass quality and energy efficiency. Currently, the combustion space using oxygen and natural gas, combined with electric boosting within the bath of glass. This configuration has been successful in increasing the electrical energy to a high degree, resulting in significantly reduced CO2 emissions.To address the rebuilt needed in 2022, to face the realities of global warming and to tackle once gain CO2 emissions, “La Maison Française du Verre”, Glass Service a.s and F.I.C worked together during three years to determine what could be the next step for this furnace and its forehearths.The presentation will be divided into three parts:First, we will present an overview of the initial data analysis and all the benefits obtained for the understanding of the furnace and its potential evolutions. Secondly, we will describe a synthesis of the modeling and design work, for the furnace and one of its forehearth, to obtain a final recommendation. There was a redesign discussed in implementing new design features and to convert the entire design into a FIC-HVP-system that potentially can go all Electric with 80% Energy savings.To conclude, we will show final results after the rebuilt led during summer 2022 The final furnace emits only 157 kg of CO2 per ton molten glass.
12:50: [GlassTueAM04] OSHow can we reduce our carbon emissions with new furnace concepts and ideas. New ideas only can be safely developed and tested by using validated Computational Fluid Dynamics (CFD) such as GS Glass Furnace Model (GS GFM). It is quite logical that no glass producer will build a new furnace concept melting 100+ tons per day without thorough analysis, calculations and extensive CFD modeling. Lately most glass producers are asking how to reduce carbon emissions with either increasing the amount of electric melting or hydrogen. We have seen in the past such intensive use of CFD modeling when the Oxy-fuel applications emerged. Now with the next generation of large Hybrid (with more than 50% electric boosting) or all Electric melters we can see an increase in demand once again.“La Maison Française du Verre » (LMFV) is producing borosilicate glass for cookware in its factory of Châteauroux (France). Its hybrid furnace is melting around 160 tons per day and its design is improved during each rebuilt, every 5 years, focusing on glass quality and energy efficiency. Currently, the combustion space using oxygen and natural gas, combined with electric boosting within the bath of glass. This configuration has been successful in increasing the electrical energy to a high degree, resulting in significantly reduced CO2 emissions.To address the rebuilt needed in 2022, to face the realities of global warming and to tackle once gain CO2 emissions, “La Maison Française du Verre”, Glass Service a.s and F.I.C worked together during three years to determine what could be the next step for this furnace and its forehearths.The presentation will be divided into three parts:First, we will present an overview of the initial data analysis and all the benefits obtained for the understanding of the furnace and its potential evolutions. Secondly, we will describe a synthesis of the modeling and design work, for the furnace and one of its forehearth, to obtain a final recommendation. There was a redesign discussed in implementing new design features and to convert the entire design into a FIC-HVP-system that potentially can go all Electric with 80% Energy savings.To conclude, we will show final results after the rebuilt led during summer 2022 The final furnace emits only 157 kg of CO2 per ton molten glass.
| SESSION: GlassTuePM1-R10 | Durán International Symposium on Sustainable Glass Processing and Applications |
| Tue. 28 Nov. 2023 / Room: Boardroom | |
| Session Chairs: John Parker; Bertrand Cazes; Session Monitor: TBA | |
Sustainability in any area of human endeavour requires the involvement of the wider population through education that actively engages people’s interest and ensures that goals are both clearly understood and achievable. In turn this requires partnerships between government, industry, educational establishments from schools to academia, but critically with the communications media, whose messages are often transmitted ‘under the radar’. A second aspect is how to fully understand and ensure the preservation of technologies, to allow reconstruction, repair, innovation… This requires an in-depth understanding of how things work, accurate and comprehensive recording, and the forward transmission across the generations of practical skills. In reality, as industries come and go, so critical knowledge can be lost or may have to be relearned. This is where the museum community and libraries play such an important role – their activities should target many operational levels. Information storage too needs to be in many different forms from the written word to dynamic, 3D images via the skills of master craftsmen that we label as experience or even muscle memory. This talk will highlight what organisations like the International Commission on Glass and ICOM with their broad international perspective are able to offer, the role they have in shaping the future of glass in Society and some specific outcomes of the 2022 International Year of Glass.
14:30: [GlassTuePM106] OSIn early 2020, Glass for Europe released the 2050 vision 'Flat glass in a climate neutral Europe'. Three years later, the industry is already on the move, busy pursuing all different avenues to maximize its contributions to the climate neutral economy. The presentation will summarize the main elements of this 2050 vision from manufacturing, processing, product development and end-of-life management and look into progress already achieved by flat glass manufacturers.
A special focus will be placed on the added-value of advanced flat glass products, manufacturing decarbonisation and recycling.
References:
Glass for Europe - 2050 I Flat glass in a climate neutral economy - 2020.
Expectations have changed, and customers increasingly value the contribution to society and to the planet that companies pledge and make choices based on how companies respond. Today, businesses are facing increasing expectations from stakeholders to create sustainable and long-term value. According to the research, 87% of people across society agree that stakeholders are most important to long term company success, correspondingly customers increasingly value the contribution to society and to the planet that companies pledge and make choices based on how companies respond. Sustainability trends now require more integrated and cross functional approaches of companies, and the global developments rapidly accelerated the attention on ESG issues. In addition to the climate crisis, issues such as the EU Green Deal and the Energy Crisis brought energy transition, sustainable manufacturing, and shift to recyclable products to the top of the agenda. Running a “sustainable” business isn't about "gate to gate" actions, it's about putting sustainability at the centre of your shareholder value proposition and acting collectively to respond to today's requirements. No approach has not been harmonized with the needs of the planet and society cannot be sustainable. As a global company that operates 45 production facilities located in 14 countries around the world, Şişecam needs to manage our large and widespread organization holistically. This structure and scope necessitate a strategy that is inclusive and compatible with global trends. From this point of view, Şişecam has created its new term sustainability strategy “CareforNext”, with a holistic and inclusive perspective to covers the entire ecosystem with the philosophy of “people first”. Under this strategic approach, the company is committed to taking responsibility boldly, without leaving anyone behind, for all our stakeholders in the entire value chain. Şişecam’s aim is to achieve strong global transformation goals that align with UN Sustainable Development Goals (SDGs). In line with the priority targets set under the standard methodology, we track our progress every year, report it transparently, and take steps as needed accordingly.
15:20: [GlassTuePM108] OSThe presentation will look at the options for the glass industry to decarbonise by investigating all fuel options in melting and forming. The presentation will give examples on what has been achieved so far and what more can be done. It will discuss large scale electric furnace melting and especially show how a recent installation on a glass forehearth has cut energy use by nearly 90% and eliminated carbon dioxide from the process if the electricity is green.
| SESSION: GlassTuePM2-R10 | Durán International Symposium on Sustainable Glass Processing and Applications |
| Tue. 28 Nov. 2023 / Room: Boardroom | |
| Session Chairs: Stephen Whettingsteel; Urmilla Jokhu-Sowell; Session Monitor: TBA | |
The formation and accumulation of pharmaceutical waste is a global problem. In excess of 30 billion vials are disposed of annually, and yet no recycling targets have been set for pharmaceutical glass. That is 351,000 tonnes of lost CO2, €26,325,000 lost Carbon Credit, and a cost of €655,000,000 for the disposal of the glass. Pharmaceutical glass is generalised as being parenteral pharmaceutical containers of a sterile medication for parenteral administration (injection or infusion) and encompassing ampules, vials, syringes, and lab bottles. Borosilicate glass is used in the pharmaceutical industry due to its high chemical stability. However, sue to its higher melting temperature it is unsuitable for the traditional container glass or window glass markets. The additional medicinal residues in the empty vials make them even more of a challenge to recycle. Historically the medical industry has been cautious over the handling of spent parenteral packaging from hospitals to domestic sites, focusing on yellow bag or bin collection and destruction through incineration, a practice designed to minimise risk to the patient, practitioners, or the public, but rarely been considerate of the environment. Producer responsibility and decarbonising has become centre stage with national health services and consumers demanding change. Regulators such as the EU are evaluating regulations to include the pharmaceutical industry within the packaging regulations. The components of parenteral packaging have historically challenged their re-use as well as the proportionally high CO2 cost of their collection, sterilisation, deconstruction, and re-assembly. A more considerate approach is required, one where the packaging is recorded, processed, and recovered on site. This presentation will look at these challenges, including the physical properties of borosilicate, contamination, and financial constraints. Then examine the solutions already available, open-loop recycling and the associated CO2 benefits of its processing and recovery, as well as new marketable products and cullet production. As well as highlighting the definite need for policies and regulations in this particular area of glass recycling. As a result, the suggested strategy for the recycling of pharmaceutical waste glass involves the development of a compact parenteral packaging deconstruction machine which is fully auditable, can sterilise all materials during deconstruction, processing and recycling. The recovery of each element significantly decreases the CO2 footprint of the pharmaceutical industry and offers full accountability in accordance with producer responsibility and current and future packaging regulations.
16:25: [GlassTuePM210] OSIn recent years, there have been more natural disasters, storms and significant temperature extremes in both colder climates and hotter climates due to climate change. Meanwhile our aging building stock is not equipped to sufficiently handle these disturbances to maintain indoor environments to protect occupants. This paper and presentation will focus on how the architectural glass and glazing community can help with building resiliency. High-performance architectural glass products are available in both new construction and retrofit/remodel options to extend the habitability of buildings during extreme weather conditions. Windows and doors can be designed to help maintain the structural integrity of buildings during windstorms, fire and other disasters, as well as helping to insulate the building envelope during extreme summer heat and winter cold. In the event of extended power disruption, high-performance windows enhance building resiliency and maintain habitable interior temperatures for longer periods of time. Recent studies by the United States Department of Energy and the National Laboratories show that improving passive efficiency, such as, by installing high-performance window and doors that meet or exceed current energy code, saves lives during periods of extreme heat and cold. For example, “installing passive measures in existing single-family buildings to meet code requirements extends habitability by as much as 120% during extreme cold and by up to 140% during extreme heat." Another study demonstrated “over a 7-day cold spell following a winter blackout when the temperature outdoors drops to 10°F, the house or office with high-performance windows cools from 70°F to about 55°F whereas the buildings with conventional windows can drop below freezing (25°F-35°F).” Federal initiatives aimed at encouraging U.S. states to adopt the most recent energy codes can contribute to more widespread access to passive efficiency measures such as high-performance windows and doors.
References:
[1] • Franconi, E, E Hotchkiss, T Hong, M Reiner et al. 2023. Enhancing Resilience in Buildings through Energy Efficiency. Richland, WA: Pacific Northwest National Laboratory. PNNL-32737, Rev 1. • https://www.glassmagazine.com/news/white-house-announces-national-initiative-advance-building-codes-based-international-codes • https://www.glassmagazine.com/news/fema-issues-building-code-strategy-improved-resilience • Environmental and Energy Study Institute- Built Infrastructure Description: https://www.eesi.org/topics/built-infrastructure/description • https://eurocladsystems.com/heres-how-much-energy-youll-save-with-new-windows-and-doors/ • https://www.cardinalcorp.com/technology/case-studies/ • https://www.glass.org/triple-glazing-and-embodied-energy-yes-juice-worth-squeeze • Atelier 10 study for Urban Green "Baby its cold inside" • Zero Energy Windows, Arasteh, D; Selkowitz, S; Apte, J; LaFrance, M, Proceedings of the 2006 ACEEE Summer Study on Energy Efficiency in Buildings, August 13-18, 2006, Pacific Grove, CA.
Vitrification is a widely used technology for treating high-level radioactive wastes (HLW) [1]. Borosilicate glasses are the matrix internationally selected for the immobilization of HLW. However, the use of this glass is linked to melting at high temperatures or sintering the glass powders loaded with wastes, which poses a risk of evaporation of volatile radioactive elements [2]. An attractive technology that implies the use of boro-aluminosilicate glasses (BASG) to produce materials with interesting properties for the stabilization of contaminants is the alkali activation [3]. Alkali-activated materials (AAMs) are widely recognized as eco-friendly alternatives to conventional high-CO2 binders. Alkali-activation technology also plays an important role in advancing the circular economy by effectively transforming inorganic waste streams into valuable products [4]. One of the promising areas for AAMs is the wastewater treatment. Various works addressed this topic. However, the use of these materials for immobilizing nuclear waste has been investigated less frequently, probably due to the intrinsic complexity of radioactive materials, that include a long half-life, high activity, solubility in water, and high volatility. One of the highly problematic radionuclides is cesium [5]. This work presents a new method of cesium immobilization, using alkali activation of BASG. This sustainable approach involves reused powdered glass from discarded pharmaceutical vials that are treated with a 2.5 M CsOH aqueous solution. The glass powders are suspended in the solution and consolidated at 40°C for 7 days, resulting in condensation reactions at hydrated surface layers. The products from partial glass dissolution combine with Cs+ ions to form a boro-pollucite (CsBSi2O6) solid solution. The immobilization process involves the formation of a stable gel that binds both the residual glass powder and the newly formed crystal phase. The main novelty lies in the use of a very low temperature to incorporate cesium into a framework mineral structure, which is recognized as one of the most promising options for storing radioactive cesium. Additionally, boro-pollucite represents the first example of an insoluble crystalline phase formed through the combination of activation by an alkaline compound (CsOH) and glass dissolution products. Cesium remains immobilized in blocks that can withstand immersion in boiling water. Further stabilization was achieved through the formation of glass matrix viscous flow sintered at temperatures as low as 700°C. The content of cesium remained almost constant before and after sintering. The effectiveness of the immobilization is confirmed by leaching test using the MCC-1 standard.
References:
[1] Jantzen, C. (2011). Development of glass matrices for high level radioactive wastes. In Handbook of advanced radioactive waste conditioning technologies (pp. 230-292). Woodhead Publishing.
[2] Lago, D. (2022). Cesium immobilization in porous silica and 137Cs self-heating simulations. Journal of Nuclear Materials, 565, 153697.
[3] Davidovits, J. (2011). Geopolymer Chemistry and Applications, 3rd Edition. Geopolymer Institute.
[4] Mazzi, A., Sciarrone, M., & Bernardo, E. (2023). Environmental performance of glass foam as insulation material from waste glass with the alkali activation process. Heliyon, 9(8).
[5] Caurant, D. (2007). Glasses, glass-ceramics and ceramics for immobilization of highly radioactive nuclear wastes. Nova Science.
For the sustainability, chemical treatments such as sol-gel coatings offer a means of increasing the strength of glasses, leading to lighter and more durable products and functionality such as antireflective coating on Photovoltaic panels. The sol-gel coating process involves chemical reactions during the formation of coatings on surfaces. Sol-gel coatings can enhance the strength of glasses and other brittle materials by filling in surface micro-flaws and providing a self-healing effect. And, with chemical engineering durable antireflective coatings on photovoltaic panels can be attained [1,2,3,4].
In this study, our primary focus will be on research and development studies related to strength improvement with sol-gel coating for bottles and durable anti reflective for PV glass. By changing the mold design, glassware can be made lighter. Sol-gel coatings offered a way to improve the strength of glassware by up to 20% without altering the design. Photovoltaic modules are deployed in many different environmental conditions and it is important that the panels have durable anti-reflective coatings
As a result, chemical treatments have the potential to provide significant increases in the strength and durability of glass, making glass more sustainable in a variety of applications such as glass container and solar panels.
References:
[1] I. H. C. Karbay, R. Budakoglu, E. O. Zayim, App. Surf. Sci. (2015) 1890-1894.
[2] G.A. Sobacı, O.B. Okan, K. Kazmanlı, R. Budakoğlu, J. Sol-Gel Sci. (2022) 102, 493–503
[3] U. iringer, A. Duran, Y. Castro, I. Milosev, J. Electrochem. Soc. (2018) 165 (5) C213-C225.
[4] C. Li, Z. Zhou, W Cao, Y. Zheng, Q. Wang, Y Huang, S. Shen, Appl. Glass Sci. (2019) 329-339.
| SESSION: GlassTuePM3-R10 | Durán International Symposium on Sustainable Glass Processing and Applications |
| Tue. 28 Nov. 2023 / Room: Boardroom | |
| Session Chairs: Andreas Diegeler; Session Monitor: TBA | |
Glass development works traditionally iteratively by melting series of samples, investigating their properties, and then melting more samples with modified composition. The whole process might be pretty long and can take several months, up to one year in special cases. Fraunhofer ISC has developed a rapid-screening systems during the last years, which is currently being optimized in collaboration with the BAM in Berlin.The robotic glass melting systems currently running in Berlin allows the melting of 20 samples during 24 hours and is backed up with high throughput RFA, LIBS and DSC devices for chemical composition, glass transition and crystallization characterization. As an additional option, the system can be extended with a robotic in-line characterization module for fundamental glass properties like viscosity, thermal expansion and crystallization behavior. Therefore, the method TOM - Thermo-Optical-Measurement method" was developed at Fraunhofer ISC to characterize physical and chemical parameter of glass.Recent advances include the preparation of larger samples with masses of up to 200 g, an optimized cooling process and a better batch as well as glass melt homogenization system.Further advancements of the system towards the development of glass-ceramics as well as enamel systems are discussed.
References:
[1] Scholze, H. Glass: Nature, Structure, and Properties. Springer. Göttingen 1991, p. 30
[2] Fluegel, A., Earl, D.A., Varshneya, A.K., Oksoy, D.: Statistical analysis of viscosity, electrical resistivity, and further glass melt properties. In: High temperature glass melt property database for process modeling. Editors: Seward III, TP, Vascott, T. The American Ceramic Society, Westerville, Ohio, 2005, p. 187-256
[3] Yang, Y., Han, J., Zhai, H., 2022. Prediction and screening of glass properties based on high-throughput molecular dynamics simulations and machine learning. In: Journal of Non-Crystalline Solids 597(1-3):121927
[4] Bødker, ML, Bauchy, M., Du, T., Mauro, JC, Smedskjaer, MM.. 2022. Predicting glass structure by physics-informed machine learning. In: npj Computational Materials, Volume 192, p. 1-9
[5] Raether, F., Meinhardt, J., Schulze-Horn, P. 2007. TOM - A versatile thermooptical measuring system for the optimization of heat treatments. In: Ceramic Forum International 84(4), p. E18-E21
The implementation of the circular economy is a challenge nowadays. The recent consumption model brought inappropriate use of natural resources, bringing great consequences to the world. Industrial production contributes to CO2 emissions and the glass industry has a great challenge in this context. Glass is a 100% recyclable, noble material and, if reinserted as a secondary raw material back into the chain, it makes a great contribution to reducing emissions.The biggest challenge is building the reverse logistics chain for this material, as most glass industries are receptive to this raw material. Only countries participating in the European Union have an organized and funded collection system to ensure that recycling is possible. The challenge in Brazil is huge, it is a country of continental dimensions, with recent legislation and where the chain is structured to generate income for collectors.Glass is a material with low added value, which limits its collection through, however, high recyclability and possible applications in different segments, such as the glass industry, paints, ceramics, abrasives and filters.
References:
[1] Guia da Reciclagem de Vidros, Abividro
[2] Panorama, Abrelpe
[3] Ciclosoft 6, Lixo Municipal
| SESSION: GlassWedAM-R10 | Durán International Symposium on Sustainable Glass Processing and Applications |
| Wed. 29 Nov. 2023 / Room: Boardroom | |
| Session Chairs: Ali Efe Caglayan; Refika Budakoglu; Session Monitor: TBA | |
Bioactive glasses were the first synthetic materials to bond to bone, and for several decades they have been used clinically to regenerate bone [1]. They can degrade in physiological solutions at a rate matching that of bone formation, and through a combination of apatite crystallization on their surface layer and ion release they stimulate cell proliferation [2]. Bioactive glasses thus actively promote healing of tissue, such as bones or skin lesions [3]. They can also kill bacteria where antibiotics have failed [4]. These properties make bioactive glasses unique materials which have changed how we think about biomaterials. This talk discusses how glass structure controls bioactive glass properties and how these materials are currently used in the clinic.
References:
[1] JR Jones, DS Brauer, L Hupa, DC Greenspan, Bioglass and bioactive glasses and their impact on healthcare. Int J Appl Glass Sci 7 (2016) 423-434.
[2] DS Brauer, Bioactive glasses—structure and properties. Angew Chemie Int Ed 54 (2015) 4160-4181.
[3] JR Jones, Review of bioactive glass: From Hench to hybrids. Acta Biomater 9 (2014) 4457-4486.
[4] NC Lindfors et al., Bioactive glass S53P4 as bone graft substitute in treatment of osteomyelitis. Bone 47 (2010) 212-218.
Advocacy includes educating the public; providing information and resources to individuals. For Glass it is vital to support or denounce policies such as healthcare, education, and environmental regulations.
It has to be ensured that all people in society are able to have their voice heard on issues that are important to them. Protect and promote their rights. Have their views and wishes genuinely considered when decisions are being made about their lives. It is a deliberate process of influencing those who make decisions about the change you want to see. Successful advocates are able to articulate issues so that they inspire others and motivate them to take action.Right kind of Advocacy helps to explore options and rights (without pressuring), provide information to help make informed decisions, help to contact relevant people, or contact them on Industry’s behalf. After the success of IYoG, it is imperative that baton for Glass promotion remains high and that too collectively by the industry associations on some of the common issues with the help of UNICEF, WHO, UN, WWF, FEVE, GPI, ICG, Glass Worldwide, Glass International and other media/magazines etc. i.e., on Health/Environmental/Forest/Marine/Energy topics. The AIGMF especially since 2018 has been pro-active by involving college and school students via its annual Youth outreach programs and the results have been extra-ordinary, who generally think out of the box. Together, we were able to deliver some interesting projects for the benefit of society at large, some of the effective campaign/s from India were: (winners work will be shown over the PPT) Green Energy via Solar Glass (2023)Glass in our Lives (2022)Glass Protects (2021)Green as Glass (2020)Adopt a Glass Bottle I and II (2018 & 2019)Numerous worldwide activities on Glass under the aegis of ICG/IYoG as well as FEVE’s successful campaign on ‘Glass is Life’ are good examples of such effective programs. It will be appropriate to run a regular global/annual campaign on a common theme to make Glass more visible in our daily lives; as a voluntary service to society, thereby bringing increased awareness of Glass for all segments i.e. float, container, pharma, solar, specialty glasses etc.
In the small country of the Netherlands a number of sheet glass manufacturers launched an initiative, back in 2000, to set up a voluntary recycling scheme in order to meet their responsibilities as producers of sheet glass. Three organizations participated in the initiative: the Manufacturers of Double Glazing in the Netherlands (FIGIN), wholesalers and importers of sheet glass, who were collectively represented by the Glass Branch Organization (GBO) and the Dutch Glass Federation (NGF). To that end they conducted an experiment in the northern provinces of the Netherlands. On the basis of the favorable results of that experiment, the Ministry of Housing, Spatial Planning and Environment gave its approval to the system and the method used for financing it. In 2002, the foundation Vlakglas Recycling Nederland, VRN for short, was founded.This organization now coordinates at country-level all activities associated with recycling and collecting waste glass in an efficient, environmentally friendly manner and at the lowest possible cost. It supports and coordinates the participating companies and agencies; it also oversees the collection of the recycling fee and acts as an information point for all those involved. Furthermore, the foundation promotes awareness of and enthusiasm for recycling glass. The government of the Netherlands has also demonstrated its commitment to this process by legislating for the sheet glass recycling levy on all traded and imported double and triple insulating glazing.The paper will explain the VRN system, its business model, its 20-years + functioning, its lessons learned and its view on closing the flat glass recycling loop for a decarbonized economy.- The current situation with flat glass recycling, the limitations for flat glass furnaces, the quality demands from the glass industry, the EPR system VRN as implemented in the Netherlands explained,Recycling cycle lessons learned,Current developments and challenges, and future views on circularity and decarbonisation
12:50: [GlassWedAM04] OSWeathering phenomena occurring during storage of tableware glasses with the different chemical composition have been examined using Scanning Electron Microscopy (SEM) and Electron Diffraction X-Ray Analysis (EDX). The tumblers of different chemical composition of tableware glass, crystalline type, have been prepared in a pot furnace. They have been packed in paper boxes and placed in the storehouse. Samples were withdrawn after 4 months, one and half year and 4 years. The SEM and EDX analysis have been done from the inner surface of the samples as well as concentration profiles of the glass wall have been measured by EDX. Relevant differences in surface layer chemical composition were observed. The comparison of the Na2O and SiO2 change is discussed in connection with the glass weathering resistance of different glass composition.
| SESSION: ElectrochemistryWedPM1-R10 | 4th Intl. Symp. on Electrochemistry for Sustainable Development |
| Wed. 29 Nov. 2023 / Room: Boardroom | |
| Session Chairs: Alexander Oleinick; Ali Seifitokaldani; Session Monitor: TBA | |
Electrochemical calibration curves recorded at enzyme-modified micro- or nanoelectrodes are often quantitatively analysed using graphical approaches directly inspired from the practice widely used in enzymatic analysis when enzymes as well as their substrate and cofactors are homogeneously distributed in the electrolytic solution [1-3]. We will introduce a concise and simple but highly representative model [4] that demonstrates that this practice yields incorrect interpretation of the experimental results even for simple Michaelis-Menten mechanisms. The present modelling makes it possible to establish the correct relationships linking calibration currents and bulk substrate concentrations by a simple method allowing to take into account the biases due to diffusional constraints when steady or quasi-steady state conditions are achieved as occurs experimentally during calibrations of micro- and nanoelectrochemical sensors.These correct relationships provide kinetic data characterizing a given sensor that ought to be considered whenever a calibrated enzymatic electrochemical sensor is aimed to be used under non-steady state condition, e.g., as for monitoring transient concentration releases of target analytes under in vivo or pseudo in vivo conditions.The authors would like to acknowledge support from joint sino-french CNRS IRP NanoBioCatEchem. CA thanks Xiamen University for his Distinguished Visiting Professor position.
References:
[1] Y. Wang, D. Mishra, J. Bergman, J.D. Keighron, K.P. Skibicka, A.-S. Cans. Ultra-fast glutamate biosensor recordings in brain slices reveal complex single exocytosis transients. ACS Chem.Neurosci. 10 (2019) 1744-1752
[2] X.K. Yang, F.L Zhang, W.T. Wu, Y. Tang, J. Yan, Y.L. Liu, C. Amatore, W.H. Huang. Quantitative Nano-Amperometric Measurement of Intravesicular Glutamate Content and of its Sub-Quantal Release by Living Neurons. Angew. Chem. Int. Ed. 60 (2021) 15803-15808.
[3] M.Yuan, S. Sahin, R. Cai, S. Abdellaoui, D.P. Hickey, S.D. Minteer, R.D. Milton. Creating a Low-Potential Redox Polymer for Efficient Electroenzymatic CO2 Reduction. Angew.Chem. Int. Ed. 57 (2018) 6582-6586.
[4] R. Dannaoui, X.-K. Yang, W.-H. Huang, I. Svir, C. Amatore, A. Oleinick, 2023, submitted.
The increasing levels of carbon dioxide (CO2) emissions and their detrimental effects on the environment have spurred a growing interest in developing sustainable strategies for carbon utilization. Electrocatalytic CO2 conversion has emerged as a promising approach, offering a viable pathway to mitigate CO2 emissions and produce value-added products simultaneously [1,2]. The utilization of electrocatalysts is pivotal in the electrochemical conversion of CO2 as they enable efficient and selective reactions, leading to the valuable transformation of CO2. Consequently, the development of highly efficient and selective electrocatalysts becomes a fundamental aspect in enhancing the energy efficiency of this emerging technology in the era of energy transition from fossil fuel to renewable resources. Understanding the reaction mechanism is crucial as it provides insights into the underlying processes and enables the design of more effective electrocatalysts tailored towards producing the desired products. By unraveling the reaction mechanism, researchers can identify key factors influencing catalytic performance and make informed choices in electrocatalyst design, leading to improved efficiency and selectivity in CO2 reduction reaction (CO2RR). Metals have been widely investigated for the CO2RR, with extensive research conducted both experimentally and computationally. Among them, copper has gained significant attention as a unique electrocatalyst for the production of hydrocarbon fuels and chemicals such as methane, ethylene, and ethanol. However, achieving high selectivity at industrially relevant high current densities, typically greater than 1 A/cm2, remains a significant challenge [3,4]. The reaction mechanism for CO2 electroreduction on copper-based electrocatalysts is primarily elucidated by integrating density functional theory (DFT) calculations on large surface slab models and in-situ spectro-electrochemistry techniques using single crystals or large polycrystalline particles. However, the reaction mechanism on extremely small nanoparticles, approximately 1 nm in size, may differ from observations on larger particles due to their lower coordination number and higher reactivity. To date, there is a lack of systematic studies in the literature specifically examining the changes in the reaction mechanism over extremely small nanoparticles. The focus of research has predominantly been on larger particles, and there is limited understanding of how the behavior and reaction pathways may differ for nanoparticles on the order of 1 nm. In this study, we conducted experimental electrocatalysis combined with DFT computations to systematically analyze the changes in the reaction mechanism as the particle size becomes extremely small. Our investigation focused on two case studies involving copper and tin electrocatalysts. The results demonstrate that utilizing small nanoparticles with sizes of 1 nm or smaller leads to a shift in the reaction pathway, enabling the production of products that were challenging to achieve with conventional catalysts. Moreover, we observed a substantial increase in the electrocatalytic activity, and we successfully achieved partial current densities greater than 1 A/cm2. These findings underscore the importance of nanoparticle size in manipulating the reaction mechanism and unlocking improved performance in electrocatalysis. This advancement brings us closer to the realization of sustainable chemical and fuels production, ultimately contributing to the development of net-zero emission technologies. By leveraging the potential of small nanoparticles, we can pave the way for a more efficient and environmentally friendly approach to address the global challenges of carbon emissions and promote a greener future.
References:
[1] Md. Kibria, J.P. Edwards, C.M. Gabardo, C.T. Dinh, A. Seifitokaldani, D. Sinton, E.H. Sargent, Electrochemical CO2 Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design, Advanced Materials, 31 (2019) 1807166
[2] R. Lin, J. Guo, X. Li, P. Patel, A. Seifitokaldani, Electrochemical Reactors for CO2 Conversion, Catalysts, 10 (2020) 5, 472
[3] C.T. Dinh, T. Burdyny, Md. Kibria, A. Seifitokaldani, C.M. Gabardo, F.P. G. Arquer, A. Kiani, J.P. Edwards, P.D. Luna, O.S. Bushuyev, C. Zou, R. Quintero-Bermudez, Y. Pang, D. Sinton, E.H. Sargent, CO2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface, Science, 360 (2018) 6390, 783-787
[4] F.P.G. Arquer, C.T. Dinh, A. Ozden, J. Wicks, C. McCallum, A.R. Kirmani, D.H. Nam, C. Gabardo, A. Seifitokaldani, X. Wang, Y.C. Li, F. Li, J. Edwards, L.J. Richter, S.J. Thorpe, D. Sinton, E.H. Sargent, CO2 electrolysis to multicarbon products at activities greater than 1 A cm−2, Science 367 (2020) 6478, 661-666
The anode material is one of the critical component of a Solid Oxide Fuel Cell (SOFC) which is helpful to provide a triple-phase boundary for hydrogen and oxide ion reactions to take place at high operating temperatures. We, therefore, prepared Ti-substituted SDC20 as anode material and systematically investigated the phase study which showed cubic phase formation of the system and complete solid solubility of the system. Density functional theory (DFT) results showed enhanced oxygen vacancy formation in the prepared sample. The local density of state (LDOS) results showed that bandwidth center energy of Ti doed SDC20 between O-2p and Ti-3d overlapped compared with parent SDC20. Moreover, Ti substitution enhanced the mesoporosity in the sample which helped the electrochemical reaction in the anode side of SOFC. The polarization resistance of Ti-doped SDC20 was compatible with NiO and the composite electrode was stable for long hours. The preliminary results show that Ti-doped SDC20 oxide is a promising cathode material for SOFCs.
References:
[1] Dong Guo, Aoye Li, Chunling Lu, Dongchao Qiu, Bingbing Niu, Biao Wang, High activity and stability of cobalt-free SmBa0.5Sr0.5Fe2O5+δ perovskite oxide as cathode material for solid oxide fuel cells, Ceramics International, 2023, doi.org/10.1016/j.ceramint.2023.08.145
| SESSION: CorrosionWedPM2-R10 | 2nd Intl Symp. on Corrosion for Sustainable Development |
| Wed. 29 Nov. 2023 / Room: Boardroom | |
| Session Chairs: Raman Singh; Session Monitor: TBA | |
Graphene has triggered unprecedented research excitement for its exceptional characteristics. The most relevant properties of graphene as corrosion resistance barrier are its remarkable chemical inertness and impermeability and toughness, i.e., the requirements of an ideal surface barrier coating for corrosion resistance, thus, an interest in graphene coating as a disruptive approach to corrosion mitigation. However, the extent of corrosion resistance due to chemical vapour deposition (CVD) graphene coatings has been found to vary considerably in different studies. The author’s group demonstrated the ultra-thin graphene coatings developed on copper and nickel by CVD to improve corrosion resistance of the metals by two orders of magnitude in aggressive aqueous chloride environments. In contrast, other reports suggest the graphene coating to actually enhance corrosion rate of copper, particularly during extended exposures. Author’s group has investigated the reasons for such contrast in corrosion resistance due to graphene coating as reported by different researchers, and on the basis of the findings, they have succeeded in developing multilayer graphene coatings that conferred durable corrosion resistance to copper and nickel in the aggressive chloride environment. Corrosion and its mitigation costs dearly (any developed economy loses 3-4% of GDP due to corrosion, which translates to ~$250b to annual loss USA). In spite of traditional approaches of corrosion mitigation (e.g., use of corrosion resistance alloys such as stainless steels and polymeric coatings), loss of infrastructure due to corrosion continues to be a vexing problem. Therefore, it is technologically as well as commercially attractive to explore graphene coating as a disruptive approach to durable corrosion mitigation. However, developing graphene coating on the most common engineering alloy, mild steel by CVD is a non-trivial challenge. The presentation will discuss the challenges, and their successful circumvention that enabled graphene coatings on mild steel, and presents results demonstrating durable and remarkable corrosion resistance of graphene-coated mild steel.
16:25: [CorrosionWedPM210] OLThe theories for localized corrosion, such s pitting corrosion, stress corrosion cracking, corrosion fatigue, flow-assisted corrosion, and galvanic corrosion, among other mechanisms and general corrosion have tended to develop independently, many on an ad hoc basis. In this paper a unified theory is resented in which all known forms of localized and general corrosion are accommodated under s singly mathematical framework. The physicoelectrochemical factors that lead to the development of one form of attack over anther are identified and are illustrated by reference to specific examples. Knowing these factors allows us to predict the form of attacks (2) that might be expected for any given metal/alloy under any given set of environmental conditions.
16:50: [CorrosionWedPM211] OLGreat advances have been made in recent years in developing viable theories for stress corrosion cracking (SCC) and corrosion fatigue (CF), particularly with the advent of the Coupled Environment Fracture Model (CEFM) and the Coupled Environment Corrosion Fatigue Model (CECFM), respectfully. Both models are highly deterministic in that the model predictions are constrained by the natural laws, specially by the conservation of charge and mass, Faraday’s law of the equivalence of mass/charge, and by the traditional laws of chemistry. The outcome is that the models can predict the crack growth rate (CGR) under constant loading and under fatigue conditions as accurately as can be measured. The illustration of the application of the models to predicted SCC and CF damage in water-cooled nuclear power rector coolant systems is presented.
17:15: [CorrosionWedPM212] OSAluminum alloys find widespread use in industries such as aerospace, automotive, marine, and oil and gas, owing to their exceptional properties. However, their susceptibility to localized corrosion can lead to catastrophic failures in-service. Mechanical surface treatment emerges as a promising approach to enhance the mechanical and corrosion properties of aluminum alloys. Numerous recent studies have investigated the impact of mechanical surface treatment on the corrosion behavior of aluminum in various forms, including cast, wrought, powder metallurgy, and additive manufacturing. This review focuses on the corrosion response of aluminum alloys subjected to different mechanical surface processing techniques. A wide range of processes, such as peening, rolling, extrusion, laser shock peening, and equal channel angular pressing (ECAP), are systematically reviewed. These methods have the potential to significantly alter the microstructure, mechanical properties, and electrochemical response of the aluminum surface. The outcomes of such surface treatments include but are not limited to introduction of a residual stress field, increased dislocation density, grain refinement, enhanced surface roughness, and formation of surface damage or discontinuities. This review discusses the general corrosion behavior, susceptibility to localized corrosion, stress corrosion cracking (SCC), corrosion fatigue, intergranular corrosion, and cavitation, along with the influence of processing parameters on microstructure and corrosion properties. Additionally, a comprehensive comparison of corrosion testing results is provided where applicable.
| SESSION: CorrosionWedPM3-R10 | 2nd Intl Symp. on Corrosion for Sustainable Development |
| Wed. 29 Nov. 2023 / Room: Boardroom | |
| Session Chairs: Raman Singh; Session Monitor: TBA | |
The design and fabrication of stimuli-responsive smart anti-corrosive coatings with merits of eco-friendliness, multifunctionality and long-acting is a major demand in corrosion protective field, which can be fulfilled by adding smart microcapsules (MCs) into coatings [1,2] Nevertheless, owning to the unclear release controlling mechanism of MCs, the design of high-performance MCs on-demand fails to be achieved. In addition, the existing MCs are mostly fabricated by synthetic materials with undesirable eco-friendliness. On the other hands, although the addition of MCs can significantly improve the corrosion protective performance, this single function fails to fulfill multifunctional integration needs of protective coatings [3,4]. To tackle above issues, a MC is assembled by choosing 2-mercaptobenzimidazole (2-MBI) as inhibitor, HNTs as inhibitor carrier, and ε-PLL, SA as well as CTS as encapsulating polyelectrolytes. The release controlling mechanism was analyzed by UV-vis technique and the key factors regulating inhibitor release rate are also confirmed. In 3.5 wt.% NaCl solutions the inhibitor can be timely released in response to the invasion of water. In addition, the releasing speed was enhanced with the increments of pH values of release mediums. Furthermore, the whole release process can lasts for 216 hours. The release behavior fulfills the requirements of sensitivity, selectivity and sustainability raised by long-term smart anticorrosive coatings. Both the solubility of inhibitor and the porosity of SA layer regulate the release rate of inhibitor. The outermost CTS layer offers MCs superior antimicrobic performance, while the complex encapsulation with ε-PLL and SA significantly prolongs the release process. As comparing with the reference coating, the proposed water-based epoxy coating with 1 wt.% MCs embedded can provide an excellent corrosion protective. In addition, the tensile strength of proposed coating is increased by 20% and the wet adhesion (72 hours) is also increased by 20%. arine environment.
References:
[1] Q. Wang, W. Wang, X. Ji, X. Hao, C. Ma, W. Hao, X. Li, S. Chen, ACS Appl Mater Interfaces, 13 (2021) 3139-3152
[2] D. Li, B. Gong, Y. Liu, Z. Dang, Chemical Engineering Journal, 415 (2021)
[3] Z. Wu, D. Huang, W. Wei, W. Wang, X. Wang, Q. Wei, M. Niu, M. Lin, J. Rao, Y. Xie, Journal of Cleaner Production, 209 (2019) 273-282
[4] R. Zhang, Y. Li, Y. He, D. Qin, Journal of Materials Research and Technology, 9 (2020) 10148-10156
Fly ash (FA) is a fine powder collected as residue in the exhaust gases from combustion chambers of pulverized coal fired boilers at thermal power plant stations. It is usually solid, irregularly spherical in shape; at times, it is a cenosphere with a hollow spherical shape. The size, chemical composition and the colour of fly ash vary depending on the coal type used in coal power stations.Generally, fly ash particles are light to dark-grey in colour with sizes range up to several hundred microns. Fly ash normally consists of predominantly aluminium silicates with a range of other metal oxide being present. It has been used in several areas, such as cement and concrete applications, bricks, highway pavement, road bases, and backfills. In most countries, fly ash is usually under-utilized.In this study, as received fly ash from Cement Australia owned coal-power furnaces and subsequently modified into near whitened fly ash (with 96 % whiteness of calcium carbonate) – a UNSW developed technology - were utilized as reinforcement in virgin white polymer polyethylene, using up to 50 weight wt. % of fly ash.Results indicate that near whitened fly ash produces filled polypropylene composites visibly almost as white as the neat PP polymer. Also, tensile modulus and notched Charpy impact properties of the fly ash filled composites are substantially enhanced by the fly ash addition.Scanning electron microscopy of notched impact fracture surfaces show smaller size fly ash particles are embedded in the interlamellar textural matrix of the polymer, thereby absorbing / transferring significant mechanical energy under impact.
References:
[1] A Zaeni, Sri Bandyopadhyay, C Sorrell, A Yu, J Rider, S Dain, C White, D Blackburn: Colour control in fly ash as combined function of particle size and chemical composition, Fuel, 89, 2, 2010, 399-404
[2] Sri Bandyopadhyay, Akhmad Zaeni, Dilip Nath, Aibing Yu, Qinghua Zeng, Darryl Blackburn & Chris White : Advanced utilization of as received and near whitened fly ash in polypropylene polymer to improve mechanical, notched impact and whiteness colour properties International Journal of Plastics Technology volume 14, pages 51–56 (2010)
| SESSION: EnergyTueAM-R11 | 8th Intl. Symp. on Sustainable Energy Production: Fossil; Renewables; Nuclear; Waste handling , processing, & storage for all energy production technologies; Energy conservation |
| Tue. 28 Nov. 2023 / Room: DiscoRoom | |
| Session Chairs: Manfred Mauntz; Harold Dodds; Session Monitor: TBA | |
Transformers, being among the most expensive equipment in networks, necessitate proper utilization, including regular maintenance and the implementation of life-extension techniques when feasible. The aging process of the transformer oil and cellulose paper insulation system produces by-products such as moisture, acids, and sludge, which contribute to the accelerated degradation of transformer insulation. Consequently, removing these by-products through oil regeneration has the potential to significantly extend the lifespan of transformers. Typically, the oil regeneration process involves the percolation of oil through an adsorbent system, followed by filtration and degasification. Various types of sorbents, such as fuller’s earth, alumina, molecular sieves, and silica-kaolin-sand mixtures, are utilized in the regeneration process. Combining the continuous oil regeneration directly at the transformer with the implementation of an online oil condition monitoring system offers numerous benefits and advantages: the combined solution analyses parameters to detect faults early, enabling proactive maintenance and minimizing transformer failure risks. Accurate oil condition data optimizes maintenance planning, reduces downtime, and enhances operational efficiency. Timely detection of oil degradation and faults avoids costly repairs, extends transformer lifespan, and reduces unplanned outages. The continuous filtration, dehydration, and deacidification of the insulation oil keep the transformer in a peak condition. [1]
References:
[1] Matharage S, Liu S, Liu Q, Wang Z: Investigation on the acid removal performance of oil regeneration sorbent materials. Lect Notes Elect Eng., Proceedings of the 21st International Symposium on High Voltage Engineering, August 26-30, 2019, Budapest, Hungary
Oil field discovery is a special profession that uses specific maps on the potential and existing oil fields. These maps help the study to know the existing oils fields and draw conclusions on possible new exploitable oil fields. Historically these oil fields have been described on paper maps and later in multiple tape records. The tape records have become numerous in such a degree that they can take several floors of a buildings to held and keep them safe. In this paper a new technology has been developed to digitalize all the tape records and save them in compatible databases that makes much easier and efficient their use.
12:25: [EnergyTueAM03] OS KeynoteProvided that hydrogen can be safely stored and transported at high densities, hydrogen fuel cells would offer highly efficient and completely environmentally friendly solutions for vehicle propulsion. However, neither compressed gas nor liquid hydrogen seems safe enough for everyday use in mobile applications given the risk of accidents and their possible consequences in urban environments related to the high flammability of hydrogen. Therefore, approaches consisting in adsorbing hydrogen atoms (i.e., H rather than H2) appear to offer an excellent solution for its storage in order to propel light and heavy vehicles in urban environments and evidently in between cities. Moreover, compared to solutions based on electric batteries, the ecological and environmental advantage would be obvious.Among the possible materials for storing hydrogen, graphene (Gr) has been suggested to be one of the most promising materials provided that a significant H/Gr weight ratio (ww%) is achieved. Specifically, the US Department of Energy (DOE) has set a target of 5.5 ww% to be achieved by 2025 as a condition for becoming operational. This goal is however extremely far from what can be achieved presently by direct storage of hydrogen molecules (H2) even using single graphene monolayers (SLGr) by physical adsorption because this requires extreme temperatures and pressures given the too weak attractive van der Waals forces and the stability of H2 with respect to its two dissociated atoms (H) and the intrinsic stability of the graphene sp2-carbon resonant network.In this respect, if possible, a stable chemical adsorption of atomic hydrogen on SLGr appears as the Holy Grail with a theoretical maximum storage capacity of 7.7 ww% for Gr-H atomic adducts and optimal safety conditions and performance. However, generating compact Gr-H adducts from H2 again requires extreme temperatures and pressures.On the contrary, hydrogen atoms can easily be produced under mild conditions by electrochemical reduction of common aqueous acidic solutions at the surface of a platinum nanoelectrode placed in straight contact with a SLGr (see adjacent figure) and spread spontaneously on the graphene sheet by reversible adsorption and site to site hopping diffusion at room temperature and atmospheric pressure and without significantly distorting the graphene geometry suggesting a physisorption rather than a covalent bonding [1]. The amount of platinum needed is minimal because it only serves as a catalyst as we were able to demonstrate using dynamic electrochemistry and SERS isotopic Raman spectroscopy. In addition, the process significantly rapid kinetics and its storage capacity (6.6 ww%, viz., more than 85% of the theoretical maximum, being already higher than the target set by DOE [2]) are associated with a substantial stability of the Gr-H layers at room temperature and atmospheric pressure. Furthermore, one would not need to proceed through the intermediacy of hydrogen gas for Gr-H reservoir loading, nor for its unloading to feed fuel cells anodes, removing then two important steps. The authors would like to acknowledge support from joint sino-french CNRS IRP NanoBioCatEchem. CA thanks Xiamen University for his Distinguished Visiting Professor position.
References:
[1] Q. He, L. Zeng, L. Han, M.M. Sartin, J. Peng, J.F. Li, A. Oleinick, I. Svir, C. Amatore, Z.Q. Tian, D. Zhan. Electrochemical Storage of Atomic Hydrogen on Single Layer Graphene J. Am. Chem. Soc., 143, 2021, 18419–18425.
[2] Hydrogen and Fuel Cell Technologies Office. Target Explanation Document: Onboard Hydrogen Storage for Light-Duty Fuel Cell Vehicles. https://www.energy.gov/eere/fuelcells/downloads/target-explanation-document-onboard-hydrogen-storagelight-duty-fuel-cell.
With the world's population increasing from eight billion currently to approximately nine billion by the year 2040, achieving a healthy lifestyle for all people on earth will depend, in part, on the availability of affordable energy, especially electricity. This presentation considers the various choices, or options, for producing electricity and the consequences associated with each option. The options are fossil, renewable, and nuclear. The consequences associated with these three options are addressed in five different areas: public health and safety, environmental effects, economics, sustainability, and politics. All options are needed, but some options are better than others when compared in the five areas. This presentation is a brief summary of a short course entitled “Energy Choices and Consequences”, which was initially created by the author several years ago and is continuously updated. The presentation will provide updated information through October of 2023.
References:
"Energy Choices and Consequences," an invited Keynote presentation given at the Istanbul Nuclear Power Plant Summit, Istanbul, Turkey (May 30, 2014)
"Update on Energy Choices and Consequences," an invited Keynote presentation given at the New Energy Forum in Qingdao, China (September 21, 2014)
"Update on Energy Choices and Consequences," an invited presentation given at the City University of Hong Kong in Hong Kong, China (September 25, 2014)
“Electricity Production Choices and Consequences - 2019 Update,” an invited presentation given at the SIPS2019 International Symposium on Sustainable Energy Production, Paphos, Cyprus (October 24, 2019)
| SESSION: EnergyTuePM1-R11 | 8th Intl. Symp. on Sustainable Energy Production: Fossil; Renewables; Nuclear; Waste handling , processing, & storage for all energy production technologies; Energy conservation |
| Tue. 28 Nov. 2023 / Room: DiscoRoom | |
| Session Chairs: Manfred Mauntz; Harold Dodds; Session Monitor: TBA | |
Deep GHG emission reduction is needed within 3 decades to avoid the worst effects of climate change. At the same time, a more circular economy is to be realized as well. Industry is responsible for a large share of the global GHG emissions and energy and raw material demand is diverse, caused by a wide range of fundamentally different production processes and technologies.Achieving a net zero or even negative GHG emission industry within 3 decades is therefore a daunting challenge. At the same time, energy efficiency improvement, fundamentally new processes such as biobased chemical industry vs. petrochemical industry, or electrified processes, the use of low carbon energy carriers as green electricity, green hydrogen and biomass, Carbon Capture Utilization and Storage (CCUS) and, last but not least, a change to circular value chains with strongly reduced demand for primary materials offer ample opportunities. However, what are optimal combinations for each sector over time is a question of daunting complexity, with many interdependencies between the decarbonizing energy system (and energy infrastructure) and industry itself. Speed of innovation and cost decline versus the lifetime of the capital stock in industry is another fundamental set of factors determining optimal pathways. The presentation addresses the opportunities for achieving cost effective pathways and what Research, Development, Demonstration and Deployment (RDDD) agenda emerges from these insights, including options to achieve negative emissions (e.g. by BECCS options). The outlook for many core industries (such as steel, chemicals and plastics) is that zero or even negative GHG emissions can be achieved with a mix of mentioned options combined with competitive cost levels when compared to future fossil fuel prices. At the same time, a circular economy is realized, while all these future processes are much cleaner compared to their conventional counterparts. International collaboration is highly desired to realize such pathways because the R&D and upscaling efforts needed for all key sectors and industry regions are too large for any country alone. Overall however, the transition to a (more than) GHG neutral and circular industry especially offers first of all a set of interlinked major opportunities.This contribution is based on extensive advanced system analysis modelling work on regional, national and international level, combined with rigorous analysis of process analysis and insights in technological learning of a wide range of mitigation options.
14:30: [EnergyTuePM106] OSThe basic characteristics of different feedstock materials to be used as fuel in a gasification process vary with the chemical and physical properties, bulk density, amount of fiber, moisture content etc. Hence the gasification potential of different biomass fuels need to be investigated in terms their suitability, performance and required preparation before gasification. This paper presents results of a preliminary study on the gasification behavior, potential, operational challenges (in terms of stability of operation, bridging, steam accumulation, and clinker formation) and their remedies for gasification of Oil Palm Fronds (OPF) feedstock. A simpler method of determining moisture content of OPF with a direct measurement content of OPF with a direct measurement of the density of a sample was developed. In addition, the equilibrium moisture content of OPF biomass was determined. The axial temperature profile of the downdraft gasifier run on OPF feedstock was found to be in good agreement with literature values and investigation of stability of operation in terms of the dynamic temperature profile of the gasifier with operating time was found to be in the range of ±60 oC/min which was found to be satisfactory compared to literature. The study of variation of syngas heating value with operation time showed that the lower heating value (LHV) of syngas was found to above 4 MJ/Nm3 (4.7 to 5.26 MJ/Nm3) throughout the stable operation time, which indicates satisfactory output comparable with woody biomass.
References:
Demirbas, A., (2008). "Green Energy and Technology, Trabzon: Springer International Publishing".
Pereira, E.G., Sliva, J.N., Oliveira, J.L. & Machado, C.S. (2012). "Sustainable Energy : A Review of Gasification Technologies". Renewable and Sustainable Energy Reviews, 16, pp.4753–4762.
Sarker, S., (2016). "Thermochemical Gasification of Local Lignocellulosic Biomass via Fixed-Bed and Fluidized-Bed Reactors". University of Agder.
J. B. e. a. Milligan, (1993) "Results from a transparent open-core downdraft gasifier," Advances in Thermochemical biomass conversion, Ed. A.V. Bridgwater, UK.
T. B. Reed, B. Levie, M. S. Graboski, and M. L. Markson, (1983) "Mathematical model for stratified downdraft gasifiers," in Preprints of Papers Presented at August 25, 1983 Meeting ACS. vol. Preprint Volume 28, No. 5., D. o. F. C. American chemical society, Ed. Washington, DC.: ACS Fuel Division, pp. 410-420.
R. K. Manurung and A. A. C. M. Beenackers, (1993) "Modeling and simulation of an open core down-draft moving bed rice husk gasifier", Ed. A. V. Bridgwater, UK ed. vol. Ed. A. V. Bridgwater, UK: Advances in Thermochemical biomass conversion, Ed. A. V. Bridgwater, UK.
F. Lettner, H. Timmerer, and P. Haselbacher, (2007) "Biomass gasification - State of the art description,".
M. N. Z. Moni and S. A. Sulaiman, (2009) "Development of a Biomass Downdraft Gasifier for Oil Palm Fronds," in National Postgraduates Conference on Engineering, Science and Technology, Tronoh, Perak, Malaysia.
M. Dogru, C. R. Howarth, G. Akay, B. Keskinler, and A. A. Malik, (2002) "Gasification of hazelnut shells in a downdraft gasifier," Energy, vol. 27, pp. 415-427.
G. Gautam, (2010) "Parametric Study of a Commercial-Scale Biomass Downdraft Gasifier: Experiments and Equilibrium Modeling." vol. Master of science: Auburn University, p. 168.
M. Barrio, (2002) "Experimental investigation of small-scale gasification of woody biomass," in Faculty of Enginnering Science and Technology. vol. PhD 7491 Trondheim, Norway: The Norwegian university of Science and Technology, p. 222.
Atnaw, S. M., Sulaiman, S. A., and Moni, M. N. Z. (2013a) "Experimental study on temperature profile of fixed-bed gasification of oil-palm fronds." AIP Conference Proceedings, 233.
Atnaw, S. M., Sulaiman, S. A., and Yusup, S. (2011). "A simulation study of downdraft gasification of oil-palm fronds using ASPEN PLUS." J. Applied Sci., 11(11), 1913-1920.
Atnaw, S. M., Sulaiman, S. A., and Yusup, S. (2013b). "Syngas production from downdraft gasification of oil palm fronds." Energy, 61, 491-501.
Atnaw, Samson Mekbib, Shaharin Anwar Sulaiman, Lakhveer Singh, Zularisam A. Wahid, Che Ku Mohammad Faizal Bin Che, and Ku Yahya. (2017) "Modeling and Parametric Study for Maximizing Heating Value of Gasification Syngas." BioResources 12, no. 2: 2548-2564.
If we produce from gas condensate reservoir while its pressure is under dew point pressure, there will be a liquid accumulation area adja cent to the well. These formed condensates cause many problems, including a negative impact on production and productivity. In fact, this destructive effect of condensate is due to the tendency of the reservoir rock to be wet with liquids, which causes the porous media to be blocked by this phase. This negative effect is so destructive that, along with other damage to the reservoir, such as skin factor, its value should be taken into account in the calculations. The research done on this issue has shown that methods can be used to open the path for the passage of gas. The best method to achieve this goal is to reduce capillary pressure, which two methods are suggested for this purpose: reducing the tendency for wetting by liquid and gas miscible injecting to reduce the interfacial tension between gas and condensate, which both of these mechanisms lead to capillary pressure reduction. Such studies need to know and evaluate the behavior of gas and condensate and the petrophysical properties of the reservoir in order to be able to chose the best chemical composition of injected gas into the reservoir. In this paper, condensate blocking problem and its solution for a gas condensate reservoir will be discussed.
References:
1. D.R Mc Cord & Assoc., "Reservoir Engineering and Geological Study and Analysis for Fracture Operation", vol. 2, 1974.
2. D.R.Mc Cord & Assoc., "Fracture Study of Asmari Reservoir", 1975.
3. "Log Interpretation Charts", Schlumberger Well Services, 1989.
4. "Schlumberger Log Interpretation Principles", Schlumberger Educational ervices, 1989.
5. Tiratsoo, E.N., "Oil Field of the World", Gulf Publishing Company, 1986.
6. Sylvain j. pirson, "WELL LOG ANALYSIS", Prentice-Hall, 1989.
7. Thompson & Wright, "OIL PROPERTY EVALUATION", Colorado School of Mines, 1985.
8. James R. Jorden & Frankl. Campbell,"Well Logging", Society of Petroleum Engineers, 1994.
At the beginning of the production of an oil field, the energy may be high enough to be able of continuing the production only with natural motive force, so at this stage, there is no need for artificial lift. After several years of oil production, the oil reservoir pressure will be depleted, so in this stage, an artificial driving force is needed to continue production. Gas lifting is one of the most effective and cheapest methods of artificial lift techniques that are used to reduce the oil density by mixing the oil with the gas which is injected at the lower part of the production string. This artificial gas lift method uses an external source of high-pressure gas to supplement the formation gas to lift the wellbore fluids. In the gas lift operation, the injection and production wells will be unique, which means that in a single well, the gas will be injected into the oil zone through the tubing, while the oil will be produced through the annulus. This article discusses the gas lift method and its effects on oil production from an oil well.
| SESSION: EnergyTuePM2-R11 | 8th Intl. Symp. on Sustainable Energy Production: Fossil; Renewables; Nuclear; Waste handling , processing, & storage for all energy production technologies; Energy conservation |
| Tue. 28 Nov. 2023 / Room: DiscoRoom | |
| Session Chairs: Manfred Mauntz; Harold Dodds; Session Monitor: TBA | |
Well testing operation of gas condensate reservoirs is one of the complex issues in reservoir engineering. Performing this operation requires precision sampling and laboratory analysis and if these things are not followed, the obtained results will be uninterpretable. The reason for the complexity of well testing for gas condensate reservoirs can be related to phase changes, condensate remaining in finer pores, the two-phase flow of gas and liquid, phase redistribution in and around the well, and finally, re-evaporation of condensate into the gas phase. In such conditions, it has been observed that the graph of the derivative of pressure in terms of time in the gas condensate reservoirs after transition from the dew point looks like scattered and cannot be interpreted. Now, considering these conditions, the exact reason for this phenomenon should be understood and the suitable corrections should be found for the application of these data or, if necessary, a suitable technique for performing well testing operations on gas condensate reservoirs should be designed. Methods which can normally be taken for this purpose is using of mathematical relations that provide the appropriate virtual pressure for the purposed gas condensate, considering the geological and petrophysical properties of the formation and PVT properties and equations of state for reservoir fluid. In this paper, Well Test and its application for a gas condensate reservoir will be discussed.
References:
1. D.R Mc Cord & Assoc., "Reservoir Engineering and Geological Study and Analysis for Fracture Operation", vol. 2, 1974.
2. D.R.Mc Cord & Assoc., "Fracture Study of Asmari Reservoir", 1975.
3. "Log Interpretation Charts", Schlumberger Well Services, 1989.
4. "Schlumberger Log Interpretation Principles", Schlumberger Educational ervices, 1989.
5. Tiratsoo, E.N., "Oil Field of the World", Gulf Publishing Company, 1986.
6. Sylvain j. pirson, "WELL LOG ANALYSIS", Prentice-Hall, 1989.
7. Thompson & Wright, "OIL PROPERTY EVALUATION", Colorado School of Mines, 1985.
8. James R. Jorden & Frankl. Campbell,"Well Logging", Society of Petroleum Engineers, 1994.
Gas injection in oil reservoirs causes the oil to be directed towards production wells and the amount of oil recovery in the reservoir increases by changing the thermodynamic properties of the reservoir fluid. In this paper, the effect of natural gas injection in a normal oil reservoir has been studied and the changes obtained on the fluid properties of the reservoir due to this injection have been investigated. For this purpose, first, the properties of primary reservoir fluid have been studied. Then, properties of current reservoir fluid which were achieved by PVT tests have been studied. Phase behavior of current reservoir fluid was compared with phase behavior of primary reservoir fluid. It was found that phase behavior of reservoir fluid has been changed due to gas injection into this reservoir.
References:
1- A.A.Zick, ARCO Oil & Gas Co,” A Combined Condensing /Vaporizing Mechanism in the Displacement of oil by Enriched Gases” SPE 15493, (1986)
2- Wong, G.K., Fors, R.R., Casassa, J.S., and Hite, R.H., “Design, Execution, and Evaluation of Fracture and Pack (F&P) Treatments in Unconsolidated Sand Formations in the Gulf of Mexico”, SPE 26563, 68th Annual Technical Conference and Exhibition, Houston, TX, 3 - 6 October, 1993.
3- Z. Novosad, “Composition and Phase Changes in Testing and Producing Retrograde Gas Wells”, SPE Reservoir Engineering, vol. 11, 1996, pp. 231-235.
Clay minerals have different effects such as reducing effective porosity and permeability on the petrophysical properties of hydrocarbon reservoirs. Also, the presence of clay in parts of the well causes instability of the well wall. For this reason, the study and understanding of clay is very important in petroleum studies. Clay minerals have many industrial uses due to their special characteristics. The role of this mineral in the engineering behavior of building materials and rock mechanics cannot be ignored. The type and abundance of this mineral is very important in the petroleum industry and causes many problems in this industry. Although water based drilling has been widely accepted in recent years due to its cheapness, ease and no damage to the environment, the effect of water on the swelling of clay minerals (clay hydration) causes many problems in drilling operations. Also, the migration of fine clay particles is another destructive effect of these minerals in the petroleum industry. Although this mineral has many problems in the petroleum industry, its presence plays a role in the processes of oil formation, its preservation, hydrocarbon composition, and it can be useful as a catalyst in various stages of oil refining. In this paper, importance of clay minerals in the petroleum industry has been discussed.
17:15: [EnergyTuePM212] OLWhat gives meaning and life to the project is the project management. The basis of project management is the systematic control of time, cost, quantity and quality variables in all phases of the project and achieving an optimal combination of the mentioned components. The project manager, with the help of prominent experts who work on a project in the form of a system, must explore the various relationships between the different activities of the project phases and take into account all the limitations and requirements (technical, economic, human, political, etc.), organize a comprehensive plan for the implementation of the project. If we take a look at the project situation in oil and gas companies, we will see that every year many projects are defined in these companies and a lot of money is allocated to them. Every year, some companies suffers from the prolongation of projects. The non-fulfillment of the goals of the projects imposes a lot of economic and social losses on the oil and gas companies. If we add opportunity costs to these losses, the losses will be much more than these. If these cases are precisely rooted, one of the factors of such a situation is neglecting project management knowledge and not using the tools of this knowledge in these projects. In this paper, Importance of project management and its role in oil and gas industries will be discussed.
| SESSION: EnergyTuePM3-R11 | 8th Intl. Symp. on Sustainable Energy Production: Fossil; Renewables; Nuclear; Waste handling , processing, & storage for all energy production technologies; Energy conservation |
| Tue. 28 Nov. 2023 / Room: DiscoRoom | |
| Session Chairs: Harold Dodds; Session Monitor: TBA | |
Addressing the emerging global challenge of Climate Change, the global energy transition to renewable energy sources is imperative. It brings forth the genesis of the energy transition driven by renewable energy sources. It has been clearly understood that energy transition over the years has taken place in a variety of forms. Some are considered under the framework of time-line, long-term or short-term energy transition, while others focus on the shift of market fuel, and fuel source, some are driven by end-use devices or prime movers, technology change, and other socio-technical factors. Certain specific factors influence and finally determine the process of the energy transition. All countries worldwide demand energy for economic growth, and therefore energy security is critical for all nations. The objectives of the paper are firstly to examine various types of energy transition. Secondly, to investigate the role of renewables in the global energy transition, examining the parameters such as a share in the primary energy demand, installed capacity, etc. Thirdly, identify the factors that affect determine the deployment of renewable energy such as energy imports, R&D funds, energy prices etc. [1]. Fourthly, to examine the role of renewables in contributing to energy security by computing a Renewable Energy Security Index (RESI) by deploying the methodology of the Principal Component Analysis (PCA) method [2]. The renewable energy security index has been improving over the period 2000-2018 and is significantly correlated with all four aspects of energy security availability, accessibility, acceptability, and affordability [3]. Consequently, the economies across all nations should adopt appropriate pathways of the energy transition towards renewable energy sources not only to achieve energy security but also energy efficiency.
References:
[1] Hache, E. (2018). Do renewable energies improve energy security in the long run? International economics, 156, 127-135.
[2] Hotelling, H. (1933). Analysis of a complex of statistical variables into principal components. Journal of Educational Psychology, 24, 417–441, and 498–520.
[3] Jung, Y. (2005). APERC-energy outlook up to 2030.
To initiate oil production from an oil well, a connecting channel is required between the reservoir formations and the wellbore. In cased hole completions, this connecting channel is provided by perforation, and in uncased hole completions, this connecting channel is provided by an open hole through which oil can flow from the oil reservoir formations to the oil well bore. If these formations are permeable with high permeability, oil can flow easily through the sand into production wells. These produced fluids may carry entrained therein sand, particularly when the subsurface formation is unconsolidated. Nevertheless, produced sand is undesirable for many reasons; when it reaches the surface, sand can damage equipment such as valves, pipelines, pumps and separators and for that must be removed from the produced fluids at the surface. Further, the produced sand may partially or completely clog the well, substantially lead to poor performance in wells and, ultimately, inhibiting production, thereby making necessary an expensive work-over. In addition, the sand flowing from the subsurface formation may leave therein a cavity which may result in caving of the formation and collapse of the casing.
One of the challenges faced by oil and gas companies in the wells workover and production operations is the produced sand associated with oil produced. The ability to predict the production of sand for oil wells of a reservoir with the aim of deciding to use different methods of its control is considered a fundamental issue. Therefore, analyzing and examining sand production conditions and choosing the optimal drilling route before drilling a well are very relevant aspects that are not receiving enough attention. Also, in conditions where sand production is unavoidable, it is imperative to choose the right sand control method and wellbore design. For instance, a reliable and adequate prediction of whether the well is sanded or not and the decision whether or not to install packers inside the wellbore is highly important. If the phenomenon of sand production occurs and packers are not installed to prevent sand production, problems will increase along with sand production. In general, the aim of this paper is to review different methods of predicting sand production such as laboratory, field, theoretical and experimental methods that have been used in different parts of the world.
References:
1- Abass H.H., A.H. Habber, A. Shebatalhamd, "Sand control during drilling, perforation, completion and production", SPE 81492, (2003)
2- Goodman R. E. (1989) "Introduction to Rock Mechanics", 2nd edn. John Wiley,Chichester
3- Hall, C.D., Harrisberger,W.H. "Stability of sand arches: A key to sand control". J. Petr. Tech.22, 821– 829. (1970)
4- Haugen, K., Kvernvold, O., Ronold, A., Sandberg, R. (1995). "Sand erosion of wear resistant materials: Erosion in choke valves". Wear 186–187, 179–188.
5- Van den Hoek, P.J., Hertogh, G.M.M., Kooijman, A.P., de Bree, Ph., Kenter, C.J., Papamichos, E. (2000a). "A new concept of sand production prediction: theory andlaboratory experiments". SPE Drilling & Completion 15, 261–273.
6- Morita, N. (1994), "Field and laboratory verification of sand-production prediction models", SPE Drilling & Completion 9, 227–235.
7- Morita, N., Whitfill, D.L., Massie, I., Knudsen, T.W. (1989a). “Realistic sand production prediction: Numerical approach”. SPE Production Eng. 4, 15–24.
8- Risnes, R., Bratli, R.K., Horsrud, P. (1982). “Sand stresses around a wellbore”. Soc.Petr. Eng. J. 22, 883–898.
9- Skjærstein, A., Tronvoll, J., Santarelli, F.J., Jøranson, H. (1997). “Effect of water breakthrough on sand production: experimental and field evidence”. SPE38806. In: SPE ATCE, San Antonio, TX, October 5–8.
10- Han, G., Dusseault, M.B. (2002). “Quantitative analysis of mechanisms for water related sand production”. SPE73737. In: SPE International Symposium on Formation Damage Control, Lafayette, LA, February 20–21.
11- Tronvoll, J., Dusseault, M.B., Sanfilippo, F., Santarelli, F.J. (2001), “The tools of sand management”, SPE71673. In: SPE ATCE, New Orleans, LA, September 30–October 3.
12- Tronvoll, J., Fjær, E. (1994), “Experimental study of sand production from perforation cavities”, Int. J. Rock Mech. Min. Sci. Geomech. Abstr. 31, 393–410.
13- Bouhroum, A., & Civan, F., "A Critical Review of Existing Gravel-Pack Design Criteria," Journal of Canadian Petroleum Technology, Vol. 34, No. 1, 1995, pp. 35-40.
14- Geilikman, M. B., Dusseault, M. B., & Dullien, F. A. L., "Sand Production as a Viscoplastic Granular Flow," SPE 27343 paper, SPE International Symposium onFormation Damage Control, February 9- 10, 1994, Lafayette, Louisiana, pp. 41-50.
15- Hayatdavoudi, A., "Formation Sand Liquefaction: A New Mechanism for Explaining Fines Migration and Well Sanding," SPE 52137 paper, SPE Mid-Continent Operations Symposium, March 28-31, 1999, Oklahoma City, Oklahoma, pp. 177-180.
16- Saucier, R. J., "Successful Sand Control Design for High Rate Oil and Water Wells, "J. of Petroleum Technology, Vol. 21, 1969, p. 1193.
17- Saucier, R. J., "Considerations in Gravel-Pack Design," J. of Petroleum Technology, Vol. 26, 1974, p. 205.
18- Skjaerstein, A., & Tronvoll, J., "Gravel Packing: A Method of Wellbore Re-enforcement or Sand Filtering?," SPE 37506 paper, SPE Production Operations Symposium, March 9-11, 1997, Oklahoma City, Oklahoma, pp. 871-879.
19- Tiffin, D. L., King, G. E., Larese, G. E., & Britt, R. E., "New Criteria for Gravel and Screen Selection for Sand Control," SPE 39437 paper, SPE Formation Damage Control Conference, February 18-19, 1998, Lafayette, Louisiana, pp. 201-214.
20- Penberthy, W.L. and Shaughnessy, C.M., "Sand Control", SPE Series on Special Topics, Volume 1, 1992.
21- Suman, G.O. Jr., Ellis, R.C., and Snyder, R.E., "Sand Control Handbook", Second Edition, Gulf Publishing Company, Houston, Texas, 1991.
22- Sparlin, D.D., “Sand and Gravel - A Study of Their Permeabilities”, SPE Paper 4772, SPE Symposium on Formation Damage Control, New Orleans, Louisiana, February 7-8,1974.
23- Ledlow, L.B., "High-Pressure Packing With Water: An Alternative Approach to Conventional Gravel Packing", SPE Paper 26543, SPE 68th Annual Technical Conference and Exhibition, Houston, Texas, October 3-6,1993.
24- Wong, G.K., Fors, R.R., Casassa, J.S., and Hite, R.H., “Design, Execution, and Evaluation of Fracture and Pack (F&P) Treatments in Unconsolidated Sand Formations in the Gulf of Mexico”, SPE 26563, 68th Annual Technical Conference and Exhibition, Houston, TX, 3 - 6 October, 1993.
| SESSION: covid19WedAM-R11 | Guerrant International Symposium (2nd Intl Symp. on COVID-19/Infectious Diseases & their implications on Sustainable Development) |
| Wed. 29 Nov. 2023 / Room: DiscoRoom | |
| Session Chairs: William Petri Jr; Scott Heysell; Session Monitor: TBA | |
My career in science separates into two distinct halves: The first half was focused on basic mechanisms by which bacterial toxins cause diarrhea and whether those mechanisms could be used in better diagnosis and treatment. Realizing that simple salt, sugar and water ORT would be hard to beat, the second half became focused on the potentially life-long developmental and cognitive consequences of enteric infections (EE) that were not solved by simple ORT. [This was for 2 reasons: it was not caused by just acute dehydration and it was associated with gut barrier disruption and inflammation that occurred even more frequently without overt diarrhea but with widespread, previously unrecognized ‘silent’ infections with multiple pathogens (predominantly bacterial and parasitic).]I shall review first the basic science lessons I have learned from Mother Nature and second, the profound importance of understanding the threats to us all of not understanding the human ravages of disparity and inequity. These are linked in lessons for the survival of our Homo sapiens species as we know it. [They also reflect how my research career evolved from its first to its second half]Cholera & Turista re cAMP/cGMP taught Nobel laureates Gilman and Murad very different lessons; and also a potential explanation for why we have the dreaded Alzheimer’s Disease ApoE4 risk allele. Vicious cycles of poverty include three ‘new’ diseases: stunted growth, impaired cognitive development and later life metabolic diseases (HAZdrop, COGhit and METsyn).The second half moved from understanding the molecular mechanisms of cholera and E. coli toxins’ opposite effects on adenylate and guanylate cyclase respectively to both surprisingly cause severe secretory diarrhea (as with epidemic cholera and ‘Turista’), hoping to improve on ORT, to realizing the greater, lasting importance of the “environmental enteropathy” (EE) that many enteric pathogens cause with potential long-term impairment of children’s growth and even cognitive development. I will note the impact, biomarkers, mechanisms and remediation of EE.This work led to my writing about the “Evolution of Evolution: The Survival Value of Caring,” in which we can learn that evolution itself may be changing the fastest, traits that were once advantageous evolve to become disadvantageous and even threaten our survival. The imperative of bridging our science with our humanity requires nothing less than a broadening of our concept of “self,” and a “Declaration of Interdependence.” How the poorest on our planet fare is what will determine the fate of us all.Thankfully, we have experts who can address sustainability lessons from COVID-19, TB and other pandemics (with Drs. Petri and Sinha) as well as threats to us all from troubling global disparities (with Drs. Scharf and Heysell) here with us today.
12:00: [covid19WedAM02] OLIntroduction: We discovered that IL-13 is elevated in patients with COVID-19, promoted disease in a mouse model, and in a RCT showed that IL-13/IL-4 blockade with dupilumab (anti-IL4Ra mAb) reduced mortality in patients with COVID-19. IL-13 induces the deposition of the polysaccharide hyaluronan (HA) in the lungs, and inhibition of the HA receptor CD44 protects from SARS-CoV-2 disease. We are determining the mechanisms by which alarmins such as IL-33 initiate a type 2 immune response, how IL-13 is induced, and its impact on HA matrices and CD44-mediated inflammation and disease.Hypothesis: We hypothesize that IL-13 produced by ILC2s in the lung during COVID-19 induces a hyaluronan (HA) matrix that via HA receptors (including CD44+) recruits inflammatory cells, resulting in respiratory failure.Significance: Uncovering the mechanisms of IL-13-induced hyaluronan matrices and signaling in driving COVID-19 severity has the promise of novel therapeutic approaches directed at the IL-13 - hyaluronan pathway, as well as being of importance for other pulmonary diseases where hyaluronan is known to contribute.
References:
[1] 1. Sasson J, Donlan AN, Ma JZ, Haughey HM, Coleman R, Nayak U, Mathers AJ, Laverdure S, Dewar R, Jackson PEH, Heysell SK, Sturek JM, Petri WA Jr. Safety and Efficacy of Dupilumab for the Treatment of Hospitalized Patients With Moderate to Severe Coronavirus Disease 2019: A Phase 2a Trial. Open Forum Infect Dis. 2022 Jul 27;9(8):ofac343. doi: 10.1093/ofid/ofac343. PMID: 35959207; PMCID: PMC9361171.
[2] 2. Donlan AN, Sutherland TE, Marie C, Preissner S, Bradley BT, Carpenter RM, Sturek JM, Ma JZ, Moreau GB, Donowitz JR, Buck GA, Serrano MG, Burgess SL, Abhyankar MM, Mura C, Bourne PE, Preissner R, Young MK, Lyons GR, Loomba JJ, Ratcliffe SJ, Poulter MD, Mathers AJ, Day A, Mann BJ, Allen JE, Petri WA Jr. IL-13 is a driver of COVID-19 severity. JCI Insight. 2021 Jun 29; PMID: 33688686
Objectives: Unlike most of the world’s nations, the Russian Federation has a growing incidence of people living with human immunodeficiency virus (HIV). Tuberculosis (TB) is the leading killer of people with HIV, and certain regions in Russia and countries of the former Soviet Union suffer endemic TB compounded by multidrug-resistant strains. In partnership with an academic university in the U.S. and regional academic and public health institutions in Irkutsk, Siberia in the Russian Federation, and supported by joint Russian Foundation for Basic Research and U.S. National Institutes of Health grants, we sought to understand the HIV/TB co-epidemic in Irkutsk, define the intersection of microbe, host and social factors that drive transmission and outcomes, and develop a person-centered mobile health-based programme to enhance integration of HIV and TB care in the region.Results: We initially determined phenotypic and genotypic relationships within antibiotic resistance determining regions of regionally diverse circulating Mycobacterium tuberculosis strains including the identification of novel strains with enhanced intracellular survival. We then enrolled a prospective cohort of people with drug-resistant TB, the majority with HIV co-infection, and found distinct patterns of individual pharmacodynamic variability of key anti-TB drugs that determined treatment outcome when controlling for other co-variates. As injection drug use was treated with forms of incarceration and removal from larger society without access to opioid replacement therapy, injection drug use and other stigmatized behaviors were found to contribute to the social drivers of disease acquisition and treatment outcome. Thus, we next evaluated outcomes for a cohort of people with HIV, TB, and substance use in Irkutsk after participation in a multi-feature mHealth intervention called MOCT. Sixty patients were enrolled during hospitalization for TB. The majority linked to HIV care by 6 months (83%). Self-scoring of confidence in ability to communicate with HIV providers improved from baseline (median score 8, scale 1-10) to 6 months (10, p = 0.004). A higher proportion of the MOCT subset refilled antiretroviral therapy for HIV (69% vs. 43% in pre-intervention cohort, p = 0.01), with fewer deaths in the MOCT subset at 6 months (1 death vs. 10 deaths in pre-intervention cohort, p = 0.02) and a decreased likelihood of developing the composite outcome of death/failure to achieve viral suppression at 6 months (adjusted odds ratio = 0.33, p = 0.029). At the height of programmatic integration prior to Russia’s invasion of Ukraine, 4,640 people had attended mobile screening events for HIV testing in the Irkutsk region, 338 (7.5%) were HIV infected and linked to care; of those in care throughout the region, 2,005 were using the MOCT app. Conclusions: Our experience demonstrated that microbe, host and importantly sociobehavioral drivers of a considerable TB and HIV co-epidemic can served by using multimodal mobile health-based program to overcome stigma and social isolation, and enhance communication and streamline workflow between providers across multiple collaborating institutions. Social marginalization, such as policies of incarceration for addiction or exclusion of minority populations of sexual orientation or gender identity, were commonalities consistently shared in the HIV epidemic in Siberia/Russian Federation and the U.S. Gains toward inclusion and beneficial health outcomes that were observed prior to the abrupt end of the partnership following Russia’s invasion of Ukraine, are notably tenuous, and expected to erode as the war persists.
12:50: [covid19WedAM04] OS InvitedCOVID-19 pandemic cause several impacts worldwide. All countries are affected and there are millions of death during the crisis. The lesson learnt from the crisis can be useful knowledge for our future. It is no doubt that the collaboration among mankind is the core concept for fighting for any global castastrophie. Although the problem is already not serious, it still requires further research and development toward the problem and other new problem emering problems. At present, post COVID-19 pandemic stage, several problems still remain and there are possibilities of new emerging problems. To achieve a sustainable development in the post-COVID-19 world, the multidisciplinary and interdisciplianry collaboration is proven useful and effective approach. In this talk, the importance of consillence of science, art and humanistic in corresponding to global criss is highlighted. The implication for future sutainable development is concluded.
| SESSION: covid19WedPM1-R11 | Guerrant International Symposium (2nd Intl Symp. on COVID-19/Infectious Diseases & their implications on Sustainable Development) |
| Wed. 29 Nov. 2023 / Room: DiscoRoom | |
| Session Chairs: Rebecca Scharf; Pranay Sinha; Session Monitor: TBA | |
The first one thousand days in a person’s life set the stage for the rest of development, learning, and participation in community. The brain is developing at a very rapid rate, and neurons undergo proliferation, growth, migration, differentiation, synapse formation, and myelination in this critical time period. Many life influences contribute to early neurodevelopment, including caregiver stimulation, security and attachment, nutrition, safety and health. Infants who experience higher burdens of poverty, illness or malnutrition are more likely to experience challenges in growth and development. Enteric infections are common in children growing up in low- and middle-income countries. Enteric infections may cause diarrheal illness, and may also contribute to environmental enteropathy, malnutrition, challenges with linear growth, and school days lost due to poor health. Children growing in families who experience high rates of illness may not be able to participate in play, learning experiences and exploration as often as healthier peers. Enteric disease may lead to malnutrition and lack of nutrients needed for healthy brain growth and child development. In seeking to reduce educational disparities, interventions that target early life influences may help provide children with the best opportunities for health and thriving. In this session, we will explore the available data on early life infections and academic outcomes, as well as discuss opportunities for intervention.
14:30: [covid19WedPM106] OLTB is set to regain its position as the leading infectious killer worldwide. The World Health Organization’s (WHO’s) End-TB Strategy aims to end the global TB pandemic by 2035. Since its launch in 2015, the strategy has marshalled unprecedented political will, international collaboration, and funding to develop better diagnostic tests, new drugs, and a new vaccine. However, we have not even reached the halfway mark in our TB elimination goals. In this presentation, I shall argue that the reason for this disappointing progress might be underinvestment in a therapy we already have: food.Undernutrition blunts the function of the immune system and increases the risk for TB so much so that it is likened to HIV/AIDS and called “nutritionally acquired immunodeficiency syndrome” or N-AIDS. Undernourished patients with TB get sicker, have more extensive lung damage, and are more likely to die from TB. It would be unimaginable to leave HIV/AIDS untreated so why do we tolerate neglect of N-AIDS?Based on modeling studies, feeding an undernourished individual and increasing their body mass index (BMI) from 16 to 20 would decrease their risk for TB disease by about 50 percent. This would be as beneficial as the new TB vaccine, which is generating great enthusiasm. Of course, feeding people has benefits beyond mitigating TB risk: prevention of complications from vitamin and mineral deficiencies, protection against other infectious diseases, increased economic productivity, and decreased human suffering due to hunger. Thus, reducing undernutrition on a population-level may represent a sustainable approach to eliminating TB and preserving human capital which draws on lessons Dr. Guerrant has taught us all. To meet the goals of the End-TB Strategy, we must take immediate and radical action. Continued investment in diagnostics, drugs, and vaccines is critical, but we must also invest in meals as we do in medicines. The only way to make rapid progress toward TB elimination is extend our work upstream and focus on prevention by addressing socioeconomic factors such as undernutrition.
14:55: [covid19WedPM107] OS PlenaryThe post-COVID transformation of healthcare education is required to be aligned with the societal needs and with the evolving healthcare delivery systems. In the past few years, the world experienced unprecedented devastation, disruption, and death due to the COVID-19 global Pandemic. At the same time, the Pandemic acts as a transformation catalyst that accelerated the implementation and adoption of long overdue changes in healthcare education and practice, including telehealth and virtual learning. Interprofessional collaboration during the pandemic was able to foster healthcare transformation in several ways at the policy and legislative level, such as the fast-tracking of internationally trained professions. The role and use of digital technologies, specifically with the emergence of artificial intelligence (AI) and metaverse, in healthcare education and practice are being extended and solidified by the pandemic. Macro-level policies acknowledging the importance of population health are key for future interprofessional collaboration of stakeholders to address inequalities. Similarly, interprofessional collaboration is key to addressing the proliferation of misinformation. Interprofessional education and collaborative practice (IPECP) can be effectively utilized to combat misinformation by increasing health literacy amongst health professions and the communities they serve. Going forward, the integration and sustainability of digital technologies, AI, metaverse and IPECP in healthcare education and practice are crucial and the experience of utilizing these new approaches within the context of the COVID-19 pandemic should be reflected on, researched, and evaluated to inform future global healthcare systems and the workforce to provide and achieve the Quintuple Aim (better health, better care, better value, better work experience, and better health equity). As we are emerging out of the Pandemic, we have a unique opportunity to leverage on the lessons learned from the pandemic in fostering the healthcare transformation through innovation, digital technologies, and collaboration.
References:
[1] Khalili, H., Park, V., Daulton, B., Langlois, S., Wetzlmair, L. C., MacMillan, K. M., El-Awaisi, A., Green, C., Ballard, J., Pandey, J. Konrad, S. C., Frost, J., Başer Kolcu, M. I.., Kolcu, G., McCartan, C., Baugh, G., Gaboury, I., Breitbach, A., Brown, R., Pfeifle, A. (2022). Interprofessional Education and Collaborative Practice (IPECP) in Post-COVID Healthcare Education and Practice Transformation Era – Discussion Paper. Joint Publication by InterprofessionalResearch.Global, American Interprofessional Health Collaborative & Canadian Interprofessional Health Collaborative, ISBN: 978-1-7366963-3-0. Available at www.interprofessionalresearch.global
The post-COVID transformation of healthcare education is required to be aligned with the societal needs and with the evolving healthcare delivery systems. In the past few years, the world experienced unprecedented devastation, disruption, and death due to the COVID-19 global Pandemic. At the same time, the Pandemic acts as a transformation catalyst that accelerated the implementation and adoption of long overdue changes in healthcare education and practice, including telehealth and virtual learning. Interprofessional collaboration during the pandemic was able to foster healthcare transformation in several ways at the policy and legislative level, such as the fast-tracking of internationally trained professions. The role and use of digital technologies, specifically with the emergence of artificial intelligence (AI) and metaverse, in healthcare education and practice are being extended and solidified by the pandemic. Macro-level policies acknowledging the importance of population health are key for future interprofessional collaboration of stakeholders to address inequalities. Similarly, interprofessional collaboration is key to addressing the proliferation of misinformation. Interprofessional education and collaborative practice (IPECP) can be effectively utilized to combat misinformation by increasing health literacy amongst health professions and the communities they serve. Going forward, the integration and sustainability of digital technologies, AI, metaverse and IPECP in healthcare education and practice are crucial and the experience of utilizing these new approaches within the context of the COVID-19 pandemic should be reflected on, researched, and evaluated to inform future global healthcare systems and the workforce to provide and achieve the Quintuple Aim (better health, better care, better value, better work experience, and better health equity). As we are emerging out of the Pandemic, we have a unique opportunity to leverage on the lessons learned from the pandemic in fostering the healthcare transformation through innovation, digital technologies, and collaboration.
References:
[1] Khalili, H., Park, V., Daulton, B., Langlois, S., Wetzlmair, L. C., MacMillan, K. M., El-Awaisi, A., Green, C., Ballard, J., Pandey, J. Konrad, S. C., Frost, J., Başer Kolcu, M. I.., Kolcu, G., McCartan, C., Baugh, G., Gaboury, I., Breitbach, A., Brown, R., Pfeifle, A. (2022). Interprofessional Education and Collaborative Practice (IPECP) in Post-COVID Healthcare Education and Practice Transformation Era – Discussion Paper. Joint Publication by InterprofessionalResearch.Global, American Interprofessional Health Collaborative & Canadian Interprofessional Health Collaborative, ISBN: 978-1-7366963-3-0. Available at www.interprofessionalresearch.global
| SESSION: covid19WedPM2-R11 | Guerrant International Symposium (2nd Intl Symp. on COVID-19/Infectious Diseases & their implications on Sustainable Development) |
| Wed. 29 Nov. 2023 / Room: DiscoRoom | |
| Session Chairs: Hossein Khalili; Ranjan Ramasamy; Session Monitor: TBA | |
Society has hugely benefitted from recent advances in biological sciences through numerous applications in medicine, agriculture and industry. Current trends in society, governance structures and communications are however beginning to constrain potential benefits in some ways. Limitations are illustrated with examples selected from our own findings on the impacts of global climate change on mosquito borne diseases [1] involving the adaptation of fresh water mosquito vectors to salinity in coastal areas [1,2], the decrease in dengue transmission during COVID-19 lockdown [3], the recent spread of the malaria vector Anopheles stephensi in South Asia and Africa [4], as well as the use of molecular diagnostic techniques for differentiating tick-borne Lyme Disease and Relapsing Fever Borreliosis [5]. The contribution made by the recently developed vaccines in saving lives and preventing severe illness due to the COVID-19 throughout the world is widely recognised. However, some avoidable hindrances in the global implementation of the COVID-19 vaccination program that could have further reduced morbidity and mortality from COVID-19, are highlighted as another example.
References:
[1] Ramasamy R, Surendran SN. Front Physiol. 2012, 3:198. doi: 10.3389/fphys.2012.0198.
[2] Ramasamy R, Surendran SN, Jude PJ, Dharshini S, Vinobaba M. PLoS Negl Trop Dis. 2011, 5:11. e1369. doi: 10.1371/journal.pntd.0001369.
[3] Surendran SN, Nagulan R, Tharsan A, Sivabalakrishnan K, Ramasamy R. Trop Med Infect Dis. 2022, 7(10):287. doi: 10.3390/tropicalmed7100287.
[4] Surendran SN, Sivabalakrishnan K, Sivasingham A, Jayadas TTP, Karvannan K, Santhirasegaram S, Gajapathy K, Senthilnanthanan M, Karunaratne SP, Ramasamy R. Front Public Health. 2019, 7:53. doi: 10.3389/fpubh.2019.00053.
[5] Shah JS, Liu S, Du Cruz I, Poruri A, Maynard R, Shkilna M, Korda M, Klishch I, Zaporozhan S, Shtokailo K, Andreychyn M, Stricker RB, Ramasamy R. Healthcare (Basel). 2019, 7(4):121. doi: 10.3390/healthcare7040121.
HVAC systems and air purifiers in classrooms, offices, and most other indoor spaces have an inherent design flaw when tackling the challenge of capturing airborne pathogens, such as COVID, Influenza, RSV, common cold and others, that can spread airborne-transmitted diseases [1,2]. Both technologies pull the air from one location to another within the indoor space: depending on whether it is an HVAC system or an air purifier, the air is pulled to either an HVAC air return or that of an air intake of an air purifier, thus potentially infecting others [3]. This study presents a proprietary, multiple patent-protected Air-Clenz™ technology platform that efficiently and quickly captures and purifies the exhaled air from each indoor occupant (in the form of a breath, cough, sneeze), before it disperses in the room atmosphere, and releases the purified air back into the venue, all within 5 seconds. Air-Clenz™ technology can be either built into a computer monitor or laptop, or can be attached as a retrofit, aftermarket peripheral, to existing monitors and laptops. Moreover, Air-Clenz™ system for classroom desks has been developed, which permits seated students to easily see and correspond with their teachers, while the system quickly captures and cleans air exhaled by the students and the surrounding general room air and releases it back as clean air as 99%+ free of pathogens, dust, smoke and other pollutants. The Clean Air Changes per Hour (ACH) is increased over 300 % depending on the number of Air-Clenz™ units utilized in the indoor venue. For a classroom of 20 students and a teacher, for instance, the ACH increases from 3 (assumed this is provided with the existing classroom HVAC) to ACH ~ 10, which is well-above than the recommended ideal ACH ~ 6 by Harvard T.H. Chan Public School of Health. A Computational Fluid Dynamics (CFD) model study proved that more than 95% of aerosols and droplets exhaled by the indoor occupants are being captured by the Air-Clenz™-enabled computer monitors, laptops or desks while the room noise level is below 35 dB. Air-Clenz™ technology is a versatile cost-effective platform that can lead to a significant reduction of the cross-infection risk in the current COVID-19 pandemic, but also a solution for minimizing any future airborne-transmitted diseases in confined multi-occupant indoor venues. Moreover, the exhaled-air-capturing-and-purification system enables better indoor air quality, which will result in better cognitive functions, performance, productivity, and happiness of the indoor occupants [4].
References:
[1] Wang C.C., Pratner K.A., Sznitman J., Jimenez J.L., Lakdawala S.S., Tufekci Z. and Marr L.C. 2021. Airborne transmission of respiratory viruses, Science 373, eabd9149.
[2] Allen J.G., and Ibrahim A.M. 2021. Indoor Air Changes and Potential Implications for SARS-CoV-2 Transmission, JAMA, 325(20): 2112-2113.
[3] Walkinshaw DS and Horstman RH (2023), Covid 19 and beyond: a procedure for HVAC systems to address infectious aerosol illness transmission. Front. Built Environ. 9:999126.
[4] Allen J. G., MacNaughton P., Satish U., Santanam S., Vallarino J., and Spengler J.D. 2015. Associations of Cognitive Function Scores with Carbon Dioxide, Ventilation, and Volatile Organic Compound Exposures in Office Workers: A Controlled Exposure Study of Green and Conventional Office Environments, Environmental Health Perspectives, volume 124, number 6, 805.
| SESSION: OxidativeTueAM-R1 | Ozawa International Symposium (3rd Intl. Symp. on Oxidative Stress for Sustainable Development of Human Beings) |
| Tue. 28 Nov. 2023 / Room: Dreams 1 | |
| Session Chairs: Haruhiko Inufusa; Koji Fukui; Session Monitor: TBA | |
Many different types of dementia exist, with Alzheimer's disease (AD) accounting for the majority of cases.
The greatest risk factor for AD is aging, which is the result of oxidative stress that has accumulated over the years. In addition, amyloid-β accumulated in the AD brain generates free radicals that cause inflammation in the surrounding neurons, leading to mitochondrial dysfunction and eventual neurodegeneration. In other words, the development of AD is the result of a vicious cycle of oxidative stress, inflammation, and mitochondrial dysfunction established over a long period of time, and the progression of AD is no exception.
The pathogenesis of AD is said to occur 20 years before clinical symptoms appear. Therefore, starting treatment after the onset of symptoms could be too late to be effective.
Twendee X (TwX, Oxicut®︎) is an antioxidant formula shown to have a preventive effect for human mild cognitive impairment (MCI) in a multicenter, randomized, double-blind, placebo-controlled, prospective intervention trial. Previous studies have shown that in diabetes, which hastens cognitive decline, TwX intake not only lowers blood glucose levels but also suppresses autophagy dysfunction. TwX has also been shown to positively affect neurogenesis in the hippocampal dentate gyrus, telomere elongation, and mitochondrial function. This suggests that TwX may prevent or halt the progression of dementia from all angles.
This study suggests that TwX may not only prevent dementia, but may also aid in its treatment.
References:
1. Tadokoro K, Morihara R, Abe K, et al. Clinical Benefits of Antioxidative Supplement Twendee X for Mild Cognitive Impairment: A Multicenter, Randomized, Double-Blind, and Placebo-Controlled Prospective Interventional Study. J Alzheimers Dis. 2019; 71(3): 1063-1069.
2. Inufusa H. Characterization of cell protection effects of Twendee X by oxidative stress. J World Mitochondria Soc. 2016; 2: 42.
3. Haruhiko I. Composition for protection against cytotoxic effects. Tima Foundation. Patent No. 5777821. 2015-9-9.
4. Feng T, Yamashita T, Abe K, et al. In Vitro Free Radical Scavenging Activities of Dietary Supplements by Electron Spin Resonance. Brain Supplements. 2020; 2: 1-12.
A collection of numerous casses and stories worldwide will be described on the effect of Twendee X and MTControl on the people’s life. They range from improving the quality of life of normal healthy people at various stages of their life and more importantly on people that suffer from various diseases before, during or after treatments. This collection help develop scientific placebo based studies on the effect of Twendee. The success stories are numerous and impressive.
12:25: [OxidativeTueAM03] OSHangovers after drinking, acne on face, constipation, lack of sleep and lethargy, worries and anxiety, and lifestyle-related diseases all have a significant impact on the quality of daily life. Quality of life is based on the individual's physical and mental health. For example, hangover reduces the quality of normal life. Improving the quality of daily routines is important for healthy longevity and a fulfilling life.
Twendee X (TwX, Oxicut®︎) and Twendee S (TwS, SUPALIV®︎) are composition of antioxidant supplements containing a total of eight vitamins, amino acids and CoQ10.TwX and TwS contain the same ingredients but in different mixture ratio and amount.
Twendee Mtcontrol (TwM, Mtcontrol®︎) is based on TwX with seven additional ingredients. In this study, consumption was monitored after 1-2 months of of TwS, TwX, and TwM.
TwS taken to prevent hangover after drinking, the unpleasant smell by themselves of the next morning disappeared at the same time. TwX taken to improve acne on the face, the patient slept well at the same time. TwM taken to improve fatigue, the patient had an improved bowel movement at the same time. As shown above, a wide range of improvements in daily life have been reported.
These results suggest that TwS, TwX, and TwM may regulate the rhythm of daily life.
References:
1) Novel compositions and uses thereof WO 2008071790 A3.
2) Antioxidant composition and its use in diabetes EP 1932542 A1.
3) Hirano S, Inufusa H, Yoshikawa T, et al. Anti-oxidant Twendee X, for maintenance of Singing voice. Brain Supplement. 2023; 5; 1-7.
4) Fukui K, You F, Inufusa H, et al. Twendee X, a mixed antioxidant supplement, improves congnitive function, coordination, and neurotrophic factor expression in long-term vitamin E-deficient mice. J clin Biochem Nutr. 2023 Mar;72(2):93-100.
Vitamin E deficiency accelerates in vivo oxidation and is closely related to aging. Accumulation of oxidative products increases risk of developing serious disorders such as dementia and cardiovascular events [1]. Normally, our bodies maintain a balance between oxidation and reduction, but the redox balance gradually collapses as we age. To prevent oxidation, we should take supplements. The supplement market is growing year by year all over the world. One combination supplement is Twendee X, which contains 8 substances [2]. However, the detailed scientific evidence for Twendee X has not yet been elucidated. In this study, long-term vitamin E-deficient mice were fed Twendee X and measured cognitive and motor functions using the Morris water maze and rota-rod tests [3]. Vitamin E-deficient mice had significantly impaired cognitive and motor functions, learning rate was comparable to normal aged mice. Treatment with Twendee X significantly improved both dysfunctions. However, serum indices did not differ with or without Twendee X. These results indicate that Twendee X has a potential as a powerful antioxidant supplement through protection against in vitro oxidation.
References:
[1] Yoshida, N, Kato, Y, Takatsu, H, et al., Biomedicines 10 (2022) 28.
[2] Tadokoro, K, Morihara, R, Ohta, Y, et al., J Alzheimer’s Dis, 71 (2019) 1063-1069.
[3] Fukui, K, Onodera, K, Shinkai, T, et al., Ann NY Acad Sci, 928 (2001) 169-176.
| SESSION: OxidativeTuePM1-R1 | Ozawa International Symposium (3rd Intl. Symp. on Oxidative Stress for Sustainable Development of Human Beings) |
| Tue. 28 Nov. 2023 / Room: Dreams 1 | |
| Session Chairs: Christian Andre Amatore; Koji Fukui; Session Monitor: TBA | |
Reactive oxygen species (ROS) and nicotinamide adenine dinucleotide (NADH) are important intracellular redox-active molecules involved in various pathological processes including inflammation, neurodegenerative diseases, cancer, etc. However, their fast dynamic changes and mutual regulatory kinetic relationship during these biological processes were hard to simultaneously investigate intracellularly at single cells level. A dual-channel nanowire electrode integrating two conductive nanowires [1], one functionalized with platinum nanoparticles [2], and the other with conductive polymer [3], was nanofabricated to allow the selective and simultaneous real-time monitoring of intracellular ROS and NADH releases by mitochondria in single living MCF-7 tumoral cells stimulated by resveratrol. The release of ROS was observed to occur a few tenths of a second before that of NADH. Beyond the importance of such an information impossible to acquire by other means, this work established the feasibility of simultaneously monitoring two intracellular species and their kinetics relationships over sub-second time scales. It is expected that this concept will benefit to a deeper understanding of mutual regulatory relationship between crucial intracellular molecular markers during physiological and pathological processes as well as for evaluating medical treatments.The authors would like to acknowledge support from joint sino-french CNRS IRP NanoBioCatEchem. CA thanks Xiamen University for his Distinguished Visiting Professor position.
References:
[1] Y.T. Jiao, H. Jiang, W.T. Wu, Y.T. Qi, M.Y. Wen, X.K. Yang, Y.R. Kang, X.W. Zhang, C. Amatore, W.H. Huang. Biosensors and Bioelectronics, 2023, 222, 114928.
[2] H. Jiang, X.W. Zhang, Q.L. Liao, W.T. Wu, Y.L. Liu, W.H. Huang. Small, 2019, 15, 1901787.
[3] H. Jiang, Y.T. Qi, W.T. Wu, M.Y. Wen, Y.L. Liu, W.H. Huang. Chem. Sci., 2020, 11, 8771.
Systemic sclerosis (SSc) is a disease of hardening of the skin and internal organs which is presumed to be caused by a complex combination of autoimmunity, fibrosis, and vascular lesions, yet the detailed mechanism is unknown. There is no established treatment, and women are at higher risk of developing the disease than men.
The involvement of reactive oxygen species (ROS) in Raynaud's phenomenon and anti-PDGFR (Platelet-Derived Growth Factor Receptor)-stimulating autoantibodies in SSc has been suggested. In fact, dermal fibroblasts of SSc patients produce large amounts of ROS themselves, which induce collagen synthesis. Therefore, SSc is considered to be closely associated with elevated levels of oxidative stress.
Twendee X (TwX, Oxicut®︎) is an antioxidant compound with mitochondrial protection properties that contains eight different ingredients, and studies have shown that TwX can potentially improve intestinal microbiota, chronic fatigue syndrome, sleep apnea, and more.
We tested whether TwX has an ameliorative effect on SSc using a hypochlorous acid (HOCl)-induced SSc mouse model. Mouse SSc induced by oxidants such as HOCl is said to exhibit clinical and biological manifestations very similar to those observed in human SSc, including skin and visceral fibrosis, vascular damage, and autoimmunity.
One month prior to the 6-week HOCl administration, mice were given drinking water (Control) or TwX-containing water ad libitum, and were dissected 2 days after the last HOCl administration to compare their skin lesions, immune status, and major protein expression with the Control group. The study showed that TwX had a favorable effect on clinical, immune, and physiological parameters in HOCl-induced SSc mice.
These results suggest that TwX may aid in the treatment and prevention of SSc.
References:
1) Batteux F, Kavian N, Servettaz A. New insights on chemically induced animal models of systemic sclerosis. Current opinion in rheumatology. 2011
2) Ogawa F, Shimizu K, Takehara K, et al. Serum levels of 8-isoprostane, a marker of oxidative stress, are elevated in patients with systemic sclerosis. Rheumatology (Oxford). 2006;45(7):815-8.
3) Sambo P, Baroni SS, Orlandini G, et al. Oxidative stress in scleroderma: maintenance of scleroderma fibroblast phenotype by the constitutive up-regulation of reactive oxygen species generation through the NADPH oxidase complex pathway. Arthritis and rheumatism. 2001 Nov;44(11):2653-64.
4) Novel compositions and uses thereof WO 2008071790 A3.
5) Antioxidant composition and its use in diabetes EP 1932542 A1.
Aging is a universal degenerative disease. Aging is classified into physiological and pathological. The progression rate of pathological aging varies among individuals, and reactive oxygen species is deeply involved in pathological aging. One of the most serious phenomena during aging is dementia. To prevent age-related neurodegenerative disorders, treatment with antioxidants is effective. Twendee Mt Control which is a supplement contains 15 substances and anyone can buy it. However, the detailed scientific evidence is not enough. In the present study, we treated combination supplement to aged mice, and measured their cognitive and motor functions. We purchased aged mice and treated them with Twendee Mt Control for one month. Cognitive and motor functions were measured by the Morris Water maze and rota-rod test [1]. Normal aged mice had significantly reduced learning ability. Treatment with Twendee Mt Control improved significantly. Twendee Mt Control significantly improved time-to-fall scores on the rota-rod test. Finally, treatment with Twendee Mt Control showed a high training effect in the treadmill test. These results indicated that treatment with Twendee Mt Control has a potential as a powerful antioxidant supplement through protection against age-related neuronal and motor dysfunctions.
References:
[1] [1] Fukui, K, Onodera, K, Shinkai, T, et al., Ann NY Acad Sci, 928 (2001) 169-176.
Why does baby smell good while the elderly has a distinctive odor? According to a publication by Shiseido Research Center in 2001(1), 2-nonenal is an unsaturated aldehyde with unpleasant odor caused by oxidative degradation reactions of ω-7 unsaturated fatty acids such as palmitoleic acid and bacenic acid found on the skin surface. This means that age-related oxidative stress is a cause of 2-nonenal. In other words, an increase in oxidative stress due to aging is the cause of age-related odor. We measured the change in age-related odor by reducing oxidative stress. Antioxidant composition Twendee X (TwX) was given who has age related odor for 4 weeks. The portable odor sensor KUNKUN BODY (Konica Minolta) was used for 10 participants to measure aging odor. Seventy-four participants were also monitored questionnaires.
Several participants whose odor KUNKUN BODY scores were 80-100, which dropped scores to zero after 3 weeks. Seventy-two of the 74 cases showed a decrease in age-related odor.
Oxidative stress increases with age and is a cause of many diseases. The development of age-related odors suggests increased oxidative stress. Reduction of age-related odors with the antioxidant composition TwX is suggested not only to reduce bad odors but also to maintain health.
References:
1.Inufusa H. Characterization of cell protection effects of Twendee X by oxidative stress. J World Mitochondria Soc. 2016; 2: 42.
2. Haruhiko I. Composition for protection against cytotoxic effects. Tima Foundation. Patent No. 5777821. 2015-9-9.
3. Haze S, Gozu Y, Nakamura S, Kohno Y, Sawano K, Ohta H, Yamazaki K. 2-Nonenal newly found in human body odor tends to increase with aging. J Invest Dermatol. 2001 Apr;116(4):520-4.
| SESSION: OxidativeTuePM2-R1 | Ozawa International Symposium (3rd Intl. Symp. on Oxidative Stress for Sustainable Development of Human Beings) |
| Tue. 28 Nov. 2023 / Room: Dreams 1 | |
| Session Chairs: Fuhua Yang; Christian Andre Amatore; Session Monitor: TBA | |
Glutamate (Glu) is one of the most important excitatory transmitter in the nervous system. Impairment of its vesicular release due to β-amyloid (Aβ) oligomers liberation in the brain is thought to participate in pathological processes leading to Alzheimer’s disease. However, before this work [1] it was unclear whether soluble Aβ42 oligomers affect intravesicular amounts of Glu or its release in the brain, or both.
Nanoelectrochemical measurements which will be presented used amperometric nanowire Glu biosensors to test single Glu-generating neuronal varicosities. This revealed that soluble Aβ42 oligomers first caused a dramatic increase in vesicular Glu storage and stimulation-induced release, accompanied by a high level of parallel spontaneous exocytosis. This was shown to ultimately result in the depletion of intravesicular Glu content enforcing greatly reduced Glu release.
Molecular biology tools and mouse models of Aβ amyloidosis have further established that the transient hyperexcitation observed during the primary pathological stage was mediated by an altered behavior of VGLUT1 responsible for transporting Glu into synaptic vesicles. Thereafter, an overexpression of Vps10p-tail-interactor-1a, a protein that maintains spontaneous release of neurotransmitters by selective interaction with t-SNAREs, resulted in a depletion of intravesicular Glu content, triggering advanced-stage neuronal malfunction. These findings are expected to open perspectives for remediating Aβ42-induced neuronal hyperactivity and neuronal degeneration in the context of initiation of Alzheimer disease.
The authors would like to acknowledge support from joint sino-french CNRS IRP NanoBioCatEchem. CA thanks Xiamen University for his Distinguished Visiting Professor position.
References:
1. Xiao-Ke Yang, Fu-Li Zhang, Xue-Ke Jin, Yu-Ting Jiao, Xin-Wei Zhang, Yan-Ling Liu, Christian Amatore, Wei-Hua Huang. Nanoelectrochemistry reveals how soluble Aβ42 oligomers alter vesicular storage and release of glutamate. Proc. Nat. Acad. Sci. USA 120 (2023) e2219994120.
The vocal fold is a vibratory mucosa essential for creating voice, but it is fragile after injury, and once it is scarred, voice becomes hoarse and harsh, which is difficult to recover. Regeneration of the mucosa after injury is important to avoid such dysphonia. Our previous research indicated that oxidative stress is one of the leading issues that causes scarring of the vocal fold, and anti-oxidant can preserve the tissue. The current clinical trial examined the effects of the strong anti-oxidant, Twendee X (TWX), on regeneration of the vocal fold after surgery. Materials and Methods: Ten patients received surgery for vocal fold pathologies including polyp, leukoplakia, CIS, etc. They were randomly assigned to TWX group which were treated with TWX perioperatively and control group without TWX treatment. The vocal fold function after the surgery was assessed at 1 to 3 months using stroboscopy and acoustic parameters. TWX group indicated significantly better vibratory parameters on stroboscopy at 1 month through 3 months as compared to the control group. TWX group also showed better GRBAS scale and loudness of the voice. TWX was shown to be effective for better recovery of the vocal fold after surgery with less scarring.
16:50: [OxidativeTuePM211] OLThere are various allergic diseases existing. In Japan, about 1 in 2 of the population suffers from some sort of allergic disease, making it a national disease. Familiar examples include asthma, rhinitis, atopic dermatitis, and hay fever. These symptoms are largely related to oxidative stress, which increases due to inflammation caused by allergens such as pollen and dust invading the body. As the number of patients increases and the burden of medical costs rises, a treatment without side effects is needed.
Twendee X (TwX) is a safety-tested, mixed antioxidant supplement composed of vitamins and amino acids. To evaluate whether TwX improves these symptoms, a questionnaire survey was conducted on the symptoms of several allergic diseases. The results showed that about 80% of the participants showed improvement in most diseases after taking TwX compared to before.
The results suggest TwX can contribute to the future treatment of allergies as well as to the reduction of health care costs.
References:
1) Inufusa H, Greiffenclau M, Novel compositions and uses thereof. Patent Cooperation Treaty (PCT) 2,008,071,790. priority date 2006-12-15.
2) Inufusa, H. Characterization of cell protection effects of Twendee X by oxidative stress. J World Mitochondria Soc. 2016, 2, 42.
3) Inufusa, H. Composition for protection against cytotoxic effects. TIMA Foundation. Patent No. 5777821, 2015-9-9.
Background: The vocal fold is a vibratory mucosa essential for creating voice, but it is fragile after injury, and once it is scarred, voice becomes hoarse and harsh, which is difficult to recover. Our previous research indicated that oxidative stress can cause scarring of injured vocal folds, and anti-oxidant can avoid the scarring. Basic fibroblast growth factor (FGF) has been proved to have anti-oxidant effects in vascular sclerosis. The current study examined the effects of FGF for preservation of the vocal fold after injury. Materials and Methods: Sprague Dawley rats were used as the model of vocal fold injury. Unilateral vocal fold was resected and immediately treated with FGF or saline injection (sham control). Scarring of the vocal folds were assessed at 2 months after the injury. Results: FGF group showed better wound healing with less scarring as compared to the sham. Hyaluronic acid was significantly better preserved. Gene expression analyses indicated significantly higher expression of HAS and HGF in FGF group. Conclusion: FGF was revealed to prevent vocal fold scarring through anti-fibrotic and possibly anti-oxidant effects.
| SESSION: OxidativeTuePM3-R1 | Ozawa International Symposium (3rd Intl. Symp. on Oxidative Stress for Sustainable Development of Human Beings) |
| Tue. 28 Nov. 2023 / Room: Dreams 1 | |
| Session Chairs: Haruhiko Inufusa; Session Monitor: TBA | |
Ulcerative colitis (UC) is defined as a diffuse, nonspecific inflammation of unknown origin that continuously damages the colonic mucosa from the rectal side, often leading to erosions and ulcers. It is associated with frequent abdominal pain and sometimes diarrhea with bloody stools. There are more than 160,000 cases of the disease in Japan, but no cure has yet been established.
Although the exact cause of the disease has not yet been clarified, oxidative stress has long been implicated, as it has been observed that reactive oxygen species (ROS) increase in inflamed tissues. Reduction of ROS and improvement of oxidative stress may improve UC.
Twendee X (TwX, Oxicut®︎) is an antioxidant supplement containing eight active ingredients consisting of vitamins and amino acids; Twendee Mtcontrol (TwM, Mtcontrol®︎) is a supplement with seven active ingredients added to TwX to increase its antioxidant capacity. The therapeutic effects of antioxidants were tested in a mouse model of UC with dextran sodium sulfate (DSS), a commonly used treatment in UC research. TwX and TwM were found to ameliorate the negative physical effects of UC in the DSS model.
The results suggest that antioxidant treatment may be effective for UC.
References:
1. Japan Intractable Diseases Information Center. 2023. https://www.nanbyou.or.jp/. Accessed 15 Jun 2023.
2. Lih-Brody L, Powell SR, Collier KP, Reddy GM, Cerchia R, Kahn E, Weissman GS, Katz S, Floyd RA, McKinley MJ, Fisher SE, Mullin GE. Increased oxidative stress and decreased antioxidant defenses in mucosa of inflammatory bowel disease. Dig Dis Sci. 1996 Oct;41(10):2078-86.
3. Nakase H, Uchino M, Shinzaki S, Matsuura M, Matsuoka K, Kobayashi T, Saruta M, Hirai F, Hata K, Hiraoka S, Esaki M, Sugimoto K, Fuji T, Watanabe K, Nakamura S, Inoue N, Itoh T, Naganuma M, Hisamatsu T, Watanabe M, Miwa H, Enomoto N, Shimosegawa T, Koike K. Evidence-based clinical practice guidelines for inflammatory bowel disease 2020. J Gastroenterol. 2021 Jun;56(6):489-526.
4. Kim JJ, Shajib MS, Manocha MM, Khan WI. Investigating intestinal inflammation in DSS-induced model of IBD. J Vis Exp. 2012 Feb 1;(60):3678.
Nanopore electrochemistry refers to the promising measurement science based on elaborate pore structures, which offers a well-defined geometric confined space to adopt and characterize single entities by electrochemical technology.1-3 The electrochemical confined effect within the nanopore displays the incredible ability to achieve single entity discrimination by focusing energy (e.g. electrochemical, light energies and et al.) into small areas, converting the intrinsic properties of single entities into visible electrochemical read-outs with ultra-high temporal-spatial resolution. Furthermore, the excellent resolution of confined nanopore technology also permits the possibility to resolve the transient signals for further revealing the information of single biomolecules dynamics. The chemical controlled confinement inside nanopore provides the advanced electrochemically confined effects to convert the transient single molecule difference into the enhancing signal with high temporal-spatial resolution. In our group, the nanopore electrochemistry has been further applied into disease diagnostics by identifying rare sub-populations, DNA/protein sensing by reading the sequential differences and uncovering the fundamental chemical reactions pathways by revealing the hidden intermediates.
References:
[1] Ying, Y. L.; Long, Y. T., J. Am. Chem. Soc. 2019, 141 (40), 15720-15729.
[2] Jiang, J.; Li, M. Y.; Wu, X. Y.; Ying, Y. L.; Han, H. X.; Long, Y. T. Nat. Chem., 2023, 15(4), 578-586.
[3] Li, X.-Y.; Y.-L. Ying, X.-X. Fu, Y.-J. Wan, Y.-T. Long, Angew. Chem. Int. Ed., 2021, 14862.
[4] Z.-L. Hu, M.-Z. Huo, Y.-L. Ying, Y.-T. Long, Angew. Chem. Int. Ed. 2021, 14738.
| SESSION: OxidativeWedAM-R1 | Ozawa International Symposium (3rd Intl. Symp. on Oxidative Stress for Sustainable Development of Human Beings) |
| Wed. 29 Nov. 2023 / Room: Dreams 1 | |
| Session Chairs: Fuhua Yang; Eugenia Trushina; Session Monitor: TBA | |
A decreased ability to maintain consistent energy production and a low level of oxidative stress in brain cells have been identified among the underlying factors for the development of various neurodegenerative conditions, such as Alzheimer's disease (AD). Mitochondria play a central role in maintaining energy homeostasis and generating reactive oxygen species in cells. Mitochondrial dysfunction is well documented in AD patients. However, recent evidence has revealed the important roles of mitochondria signaling in adapting to energy stress, promoting survival and function, and restoring energy levels. Mitochondria signaling coordinates several crucial cellular mechanisms, including maintaining energy balance, metabolic functions, autophagy, epigenetic modifications, regulating inflammation, providing antioxidant protection, and regulating cell death. Thus, harnessing mitochondrial signaling could represent a novel therapeutic strategy to improve and maintain multiple essential mechanisms of cell survival. We have developed small molecules that target mitochondria and mildly reduce the activity of mitochondrial complex I, resulting in the induction of mild energetic stress. This approach has proven effective in delaying the onset of AD in multiple transgenic mouse models and promoting healthy aging in wild-type mice [1-6]. The mechanism of action involves activating various neuroprotective mechanisms involved in adaptive stress response, which ultimately results in promoting health and longevity, and restoring mitochondria function and energy balance in the brain.
References:
[1] Zhang L, Zhang S, Maezawa I, Trushin S, Minhas P, Pinto M, Jin LW, Prasain K, Nguyen TD, Yamazaki Y et al: Modulation of mitochondrial complex I activity averts cognitive decline in multiple animal models of familial Alzheimer's Disease. EBioMedicine 2015, 2(4):294-305.
[2] Cunnane SC, Trushina E, Morland C, Prigione A, Casadesus G, Andrews ZB, Beal MF, Bergersen LH, Brinton RD, de la Monte S et al: Brain energy rescue: an emerging therapeutic concept for neurodegenerative disorders of ageing. Nat Rev Drug Discov 2020, 19(9):609-633
[3] Stojakovic A, Trushin S, Sheu A, Khalili L, Chang SY, Li X, Christensen T, Salisbury JL, Geroux RE, Gateno B et al: Partial inhibition of mitochondrial complex I ameliorates Alzheimer's disease pathology and cognition in APP/PS1 female mice. Commun Biol 2021, 4(1):61.
[4] Trushina E, Trushin S, Hasan MF: Mitochondrial complex I as a therapeutic target for Alzheimer's disease. Acta Pharm Sin B 2022, 12(2):483-495
[5] Stojakovic A, Chang SY, Nesbitt J, Pichurin NP, Ostroot MA, Aikawa T, Kanekiyo T, Trushina E: Partial Inhibition of Mitochondrial Complex I Reduces Tau Pathology and Improves Energy Homeostasis and Synaptic Function in 3xTg-AD Mice. J Alzheimers Dis 2021, 79(1):335-353.
[6] Panes J, Nguyen tKO, Gao H, Christensen TA, Stojakovic A, Trushin S, Salisbury JL, Fuentealba J, Trushina E: Partial Inhibition of Complex I Restores Mitochondrial Morphology and Mitochondria-ER Communication in Hippocampus of APP/PS1 Mice. Cells 2023, 12.
Uropathogenic Escherichia coli (UPEC) causes urinary tract infections, e.g., cystitis, which are treated by gentamicin. The protein ss, encoded by the rpoS gene, controls E. coli general resistance. We discovered that rpoS deletion renders UPEC more sensitive to Gm and other bactericidal antibiotics, and proteomic analysis suggested a weakened antioxidant defense as the reason. Reactive oxygen species (ROS) detectors (psfiA gene reporter and appropriate chemicals) indicated greater ROS generation by Gm in the mutant. Gm treatment along with an antioxidant, or under anaerobic conditions (that prevent ROS formation), decreased drug lethality. Treating UPEC infection of mice bladder corroborated these findings in vivo. Thus, oxidative stress produced by insufficient quenching of metabolic ROS accounted for greater sensitivity of the mutant. E. coli strains missing antioxidant proteins also generated greater ROS and were also more sensitive to Gm. These lacked the ROS quencher proteins, (e.g., SodA/SodB; KatE/SodA), or the pentose phosphate pathway proteins, which provide NADPH (e.g., Zwf/Gnd; TalA) required by the quenchers. We have recently made similar findings with norfloxacin. Use of a microfluidic device indicated that the results applied to a single cell level. Gm is known to kill bacteria by inhibiting protein synthesis, but UPEC has developed resistance to this mode of killing. Therefore, these findings provide a timely means of restoring Gm effectiveness by curbing antioxidant proteins. Using bioinformatic approaches, we have identified several small molecules that inhibit these proteins and can enhance Gm effectiveness. In space flights, astronauts often suffer from cystitis. Bacterial gene regulation can differ in normal vs. microgravity (MG) experienced during space flights. However, the “EcAMSat” Stanford/NASA mission showed that ss-controls Gm resistance also in MG. EcAMSat employed a free- flying “nanosatellite” equipped with a technically sophisticated microfluidic system for autonomous determination of UPEC sensitivity to Gm and its telemetric transmission in real time during space flight to Earth. Bacterial multidrug resistance (MDR), such as the one regulated by the emrRAB operon and the EmrR protein is a major public health problem. Its activation is due to alteration in the EmrR protein conformation, which too can be prevented by small molecules and bioinformatic approaches that we have pursued. Another such pump along with penetration barriers contribute to bacterial biofilm antibiotic resistance. Several collaborators contributed to this work; they will be identified in the presentation.
12:25: [OxidativeWedAM03] OLAgeing is driven by the inexorable and stochastic accumulation of damage in biomolecules vital for proper cellular function. Although this process is fundamentally haphazard and uncontrollable, senescent decline and ageing is broadly influenced by genetic and extrinsic factors. Numerous gene mutations and treatments have been shown to extend the lifespan of diverse organisms ranging from the unicellular yeast Saccharomyces cerevisiae to primates. It is becoming increasingly apparent that most such interventions ultimately interface with cellular stress response mechanisms, suggesting that longevity is intimately related to the ability of the organism to effectively cope with both intrinsic and extrinsic stress. Key determinants of this capacity are the molecular mechanisms that link ageing to main stress response pathways. How each pathway contributes to modulate the ageing process is not fully elucidated. Mitochondrial impairment is a major hallmark of several age-related neurodegenerative pathologies, including Alzheimer’s and Parkinson’s diseases. Accumulation of damaged mitochondria has been observed in post-mortem brains of Alzheimer’s disease patients. Mitophagy is a selective type of autophagy mediating elimination of damaged mitochondria, and the major degradation pathway, by which cells regulate mitochondrial number in response to their metabolic state. Little is known about the role of mitophagy in the pathogenesis of Alzheimer’s disease. We find that neuronal mitophagy is impaired in animal models of Alzheimer’s disease. Indeed, mitophagy stimulation restores learning and memory capacity, in these animals. Moreover, age-dependent decline of mitophagy both inhibits removal of dysfunctional or superfluous mitochondria and impairs mitochondrial biogenesis resulting in progressive mitochondrial accretion and, consequently, deterioration of cell function. Our observations indicate that defective removal of damaged mitochondria is a pivotal event in neurodegeneration. These findings highlight mitophagy as a potential target for the development of innovative, effective therapeutic interventions towards battling human neurodegenerative disorders.
12:50: [OxidativeWedAM04] OSOxidative stress has long been considered to contribute to brain aging and age-related neurodegenerative disorders including Parkinson’s and Alzheimer’s disease1. Data over the last few years suggests that one important mechanism driving neuropathology associated with these disorders is a process known as cellular senescence. In response to stressors including agents which elicit oxidative or proteotoxic stress, cells may undergo conversion to a resting state where they are not capable of replicating and forming tumors. However, maintenance of these cells over long periods of time in the aging organism can result in increased inflammatory events known as the senescent associated secretory phenotype or SASP which is damaging to neighboring tissues, including within the brain. Here, I will present data suggesting that not only does cellular senescence occur in conjunction with age-related neurodegenerative diseases, but that elimination of senescent cells may constitute a therapeutic avenue for these disorders2-4. This is dependent however on selectivity of senescent cell removal which avoids off-target effects on other cell types.
References:
[1] Walton and Andersen (2019). Unknown fates of (brain) oxidation: close encounter with neuronal senescence. FRBM 134: 695-701.
[2] Chinta, Woods, et al. (2018). Cellular senescence is induced by the environmental neurotoxin paraquat and contributes to neuropathology linked to Parkinson’s disease. Cell Rep. 22:930-940.
| SESSION: MedicineWedPM1-R1 | 2nd Intl. Symp. on Technological Innovations in Medicine for Sustainable Development |
| Wed. 29 Nov. 2023 / Room: Dreams 1 | |
| Session Chairs: Hans Leuenberger; Gregory Knipp; Session Monitor: TBA | |
In 1869 Friedrich Miescher, Basel, first identified "nuclein" inside the nuclei of human white blood cells. This term was later changed to “deoxyribonucleic acid” (DNA) [1]. Erwin Schrödinger published in 1944 “What is Life?” by predicting the role of DNA [1] as genetic code [2]. Based on the work of Nobel Laureate Ilya Prigogine, Hans Leuenberger wrote “What is Life? A new Human Model of Life, Disease and Death – A Challenge for Artificial Intelligence and Bioelectric Medicine Specialists” [3] for the 40th anniversary of SWISS PHARMA. Later he presented “Virtual Patient & in-silico Design of Solid Dosage Forms”[4]. The current model of a Virtual Patient is described by 4 pillars of the Center of Pharmacometrics & Systems Pharmacology, CPSP, at the University of Florida [5] consisting of Population Pharmacokinetic and Pharmacodynamic Modeling, Real World Outcomes, Artificial Intelligence and Mechanistic Modeling. The goal of CPSP is to create a rigorous and integrative academic translational science program in quantitative clinical pharmacology with a focus on bio-simulation. The common denominator is modeling. The first two pillars are linked to many patients. Artificial Intelligence tries to mimic a human being in 4 steps, Machine Learning, Deep Learning, Theory of Mind, and Self Awareness. Mechanistic Modeling is inspired by Physiologically‐Based Pharmacokinetic Modeling and Simulations that need to be complemented by cardio-vascular and nervous wiring system etc. In other words, the holistic VIRTUAL PATIENT can be described as an organic supercomputer able to replicate, consisting of approximately 40 1012 cells as microprocessors [3, 4]. This healthy being corresponds to stage 4 of Artificial Intelligence. The computer operating system of the VIRTUAL PATIENT is, as we know, sensitive to single drugs, to a combination of drugs (HIV treatment), to the combination of Syrosigopine, and Metformin as an anti-cancer agent [6]. Thus, the combination of low dose generic drugs opens a new research avenue in drug discovery [7] avoiding preclinical trials. Since Paracelsus, University of Basel, we know that the toxicity of a substance depends on the dose. Unfortunately, the early dose of a discovered drug is usually high for showing a significant effect. Our system is sensivitive to food, such as grapefruit, which is interacting with drugs, to parasites such as worms, to bugs and to viruses, etc. If our body (computer hardware) is severely damaged by a car accident can it be rebooted as a supercomputer, respectively reanimated as human being in an emergency room? As conclusions, it is proposed 1) to systematically evaluate combinations of n drugs, with n = 2, 3...m low dose generic drugs. In an optimal case new safe therapies of n drugs showing less side effects can be registered. 2) The pharmaceutical industry should adopt the workflow of the automotive industry by first evaluating in-silico the tablet formulations before manufacturing the drug delivery systems [8]. Thus, time to market can be reduced. 3) The sensitivity of the VIRTUAL PATIENT = DIGITAL TWIN can be explored on the basis of Clinical Phase I – III studies using a combination of n low dose generic drugs [7].
References:
[1] Pray, L. (2008) Discovery of DNA structure and function: Watson and Crick. Nature Education 1(1):100
[2] Erwin Schrödinger, WHAT IS LIFE? First published 1944 Reprinted 1945, 1948, 1951, 1955, 1962, Canto edition with Autobiographical Sketches and © Cambridge University Press 1992 Foreword to What is Life? by Roger Penrose, 14th printing 2013.
[3] Hans Leuenberger, “What is Life? A new Human Model of Life, Disease and Death, SWISS PHARMA, 41 (2019) Nr. 1, 20 – 36; & PHARM TECH JAPAN, 35, 14 (2019) 55(2765)-61(2771) in Japanese.
[4] H. Leuenberger, invited lecture, Virtual Patient & In-Silico Design of Solid Dosage Forms at the 12th PBP World Meeting on Pharmaceutics, Biopharmaceutics and Pharmaceutical Technology (11.05 - 14.05.2021).
[5] Stephan Schmidt et al, Requirements, expectations, challenges and opportunities associated with training the next generation of pharmacometricians, open access, May 2, 2023, https://doi.org/10.1002/psp4.12970.
[6] Benjamin et al, Syrosingopine sensitizes cancer cells to killing by metformin. Sci. Adv. 2, e1601756 (2016).
[7] H. Leuenberger, invited Keynote Lecture, Gala Technology 2013, May 8, Artificial Intelligence, Digital Revolution & New Research Avenues, Shinagawa Prince Hotel, Tokyo.
[8] D. Maneerojpakdee et al. An attempt to adopt the workflow of the automotive and aircraft industry for the design of drug delivery vehicles , Pharm. Tech. Japan, 33,11 (2017) 145-156.
The term “Therapeutic Orphans” was first used by Dr. Harry Shirkey in 1962 to describe pediatric populations. Over fifty years later, pediatric drug development is still largely an unmet area of therapeutic need based on the various physiological, clinical, and formulation challenges associated with age-based population dosing. Moreover, access to pediatric dosage forms is limited throughout the world as highlighted by the World Health Organization’s Global Accelerator for Paediatric Formulations business plan. Access to pediatric formulations is most limited in remote areas where resources are limited, and there is a greater utility of off label use of compounded adult formulations where the dose control is not ensured. Here we will highlight our efforts to address the global need for sustainable, verified strategies to develop reproducible, extemporaneous formulations that can easily be transferred to remote areas where resources are limited. Towards this aim, easily generated pediatric formulation strategies developed at Purdue with the intent to transfer the approaches to collaborators in Africa will be discussed. One of the primary causes for this lack of pediatric drug development is the inability to accurately predict clinical safety and efficacy at different pediatric developmental stages early in translation. This lecture will also highlight some of the challenges that currently face preclinical development of pediatric medicines and the potential utility of the juvenile porcine model as a preclinical model for pharmacokinetic testing during formulation development. Our aim is to develop reproducible pediatric formulation approaches that require minimal technological advances, which can be produced at different doses in remote clinics. We will also highlight our efforts to verify performance by ensuring reproducible exposure in preclinical testing utilizing the juvenile swine model to ensure that safety and efficacy can be met. An illustration of a simple formulation strategy that has been transferred from Purdue to Tanzania
References:
1. R. Kulkarni, N. Yumibe, Z. Wang, X. Zhang, C.C. Tang, K. Ruterbories, A. Cox, R. McCain, G.T. Knipp. J. Pharm. Sci. 101 (2012) 4327-4336. PubMed PMID: 22899546.
2. S.M. Abdel-Rahman, G.L. Amidon, A. Kaul, V. Lukacova, A.A. Vinks, G.T. Knipp; Members of the BCS Task Force. Clin. Ther. 34 (2012) S11-24.
3. W.J. Roth, C.B. Kissinger, R.R. McCain, B.R. Cooper, J.N. Marchant-Forde, R.C. Vreeman, S. Hannou, G.T. Knipp. Assessment of juvenile pigs to serve as human pediatric surrogates for preclinical formulation pharmacokinetic testing. AAPS J. 15 (2013) 763-774.
4. K. Brouwer, L.M. Aleksunes, B. Brandys, G.P. Giacoia, G. Knipp, V. Lukacova, B. Meibohm, S.K. Nigam, M. Rieder, S.N. de Wildt. Clin. Pharmacol Ther. 98 (2015) 266-87.
5. M. Lavan, X. Wang, R. McCain, A. Jannasch, B. Cooper, S. Hostetler, S. Byrn, G. Knipp AAPS PharmSciTech 22 (2021) 40.
MAPKs signaling proteins that regulate essentially all stimulated cellular processes. Dysregulation of these kinases is involved in many diseases such as cancer and inflammation. A hallmark of the MAPKs’ activity is their nuclear translocation, where they activate many targets including transcription factors and chromatin modifiers. The MAPKs do not use the canonical nuclear shuttling machinery, importin (Imp-α∙β/NLS). Rather, we elucidated the mechanism of stimulated nuclear translocation of ERK1/2 (ERK) that upon stimulation is phosphorylated on its nuclear translocation signal (NTS) that allow interaction with Imp7, that transfers ERK to the nucleus [1]. P38/JNK interact mainly with Imp9 (and to a lesser extent Imp7) that further binds Imp3 to escort these MAPKs to the nucleus [2]. These mechanisms are very specific to the distinct MAPKs and serve as an unexplored level of transcriptional regulation, crucial for proliferation and differentiation. We identified the Imp7/kinase interaction and prepared peptides based on these sequences. These peptides (EPE for ERK and PERY for p38/JNK) competes out the binding, preventes nuclear translocation, as well as their nuclear and pathological effects [3,4]. The prevention of nuclear translocation in cancer and inflammation models, was more effective with less side effects than the MAPK inhibitors that are currently in clinical use or trials. We are now developing the aforementioned drugs into clinical use for melanoma, as well as pancreatic, colon and breast cancers.
References:
[1] Chuderland, D.; Konson, A.; Seger, R. Identification and characterization of a general nuclear translocation signal in signaling proteins. Mol. Cell 2008, 31, 850-861.
[2] Zehorai, E.; Seger, R. Beta-Like Importins Mediate the Nuclear Translocation of MAPKs. Cell. Physiol. Biochem. 2019, 52, 802-821, doi:10.33594/000000056.
[3] Plotnikov, A.; Flores, K.; Maik-Rachline, G.; Zehorai, E.; Kapri-Pardes, E.; Berti, D.A.; Hanoch, T.; Besser, M.J.; Seger, R. The nuclear translocation of ERK1/2 as an anticancer target. Nat Commun 2015, 6, 6685, doi:10.1038/ncomms7685.
[4] Maik-Rachline, G.; Zehorai, E.; Hanoch, T.; Blenis, J.; Seger, R. The nuclear translocation of the kinases p38 and JNK promotes inflammation-induced cancer. Sci Signal 2018, 11, doi:10.1126/scisignal.aao3428.
When the state of Israel was established in 1948, a severe conflict raised immediately concerning the consumption of wild plants. On the one hand, the decision makers of the new state, mostly Ashkenazi Jews, or with Western-European mentality. This society made very little use of wild plants, both as food and for medicinal purposes. This society demanded total halt of the use of wild plants, and legislations were made to assure that this prohibition was enforced. On the contrary, the local Arab (Palestinian) society made extensive use of many wild plants, mainly for nutrition purposes, but very extensive use for medicinal treatments.This situation resulted in great tension between the two societies. The Arab society risked the collection of these plants, and when got caught by the Israeli authorities, Arabs had to suffer different punishments and fines.But the situation can not be summarized as we described above. The prohibition of wild plants use gave its positive results in the next few decades. In some areas, the overuse of wild plants resulted almost extinction, for example, Gundelia tournifortii (عكّوب, עכובית הגלגל), a very nutritious and tasty plant (when cooked), was completely extinct in the Wadi Ara area. The plant survived complete extinction in the entire country since the Arab society in the Northern Negev region, did not eat it, because it is thorny, so “its camel food, not for humans”. But when people of the North realized that the started mass collection, mainly for export purposes, to Jordan, and from Jordan to the Gulf region.So, the conflict reached a critical point, then the nature preservation authorities realized that some compromise must be made. With great efforts and almost endless discussions, we managed to find this compromise.Use of wild plants is not only pure science. It is before and after all, human societies and traditions, and these must be respected to an extent of nature preservation and meeting traditional societies needs.
| SESSION: MedicineWedPM2-R1 | 2nd Intl. Symp. on Technological Innovations in Medicine for Sustainable Development |
| Wed. 29 Nov. 2023 / Room: Dreams 1 | |
| Session Chairs: Hans Leuenberger; Gregory Knipp; Session Monitor: TBA | |
A 197Au solution with bi-distilled water was prepared using a single gold electrode, connected to a special oscillator with a sinewave voltage of 50 Hz at 160 V. It was known that it was not possible to detect gold in such a solution by chemical analysis at room temperature. Thus, neutron activation analysis (NAA) by creating 198Au seemed to be the method of choice for detecting the missing gold. 198Au is a b emitter that decays to an exited state of 198Hg nucleus, subsequently emitting a g photon of 411.8 keV, that can easily be detected. For this purpose, three solutions were prepared: Sample 0: 100 ml of water as zero-reference in case of impurities. For samples I and II, 200 ml of the same water were treated by a single electrode for 16 hours. Immediately after the treatment, the 200 ml were split into two samples perfectly mixed: sample II, i. e. 100 ml of the treated water was heated above 60°C, sample 0, had been heated before, and sample I, i. e. 100 ml of the treated but not heated water. All 3 samples together were exposed to a flux of thermal neutrons. Result: only the treated and warmed sample II showed the typical peak of g photons with the energy 411.8 keV. Samples 0 and I did not show any trace of gold. Sample I, as well as the other samples, were kept at room temperature for 11 days. The other samples behaved as expected. After a delay of 11 days, sample I was heated above 60°C. Interestingly, no g - photon was detected at 411.8 keV and after a second NAA (on the same, i. e. 11th day) no trace of Au was present anymore. A tentative theoretical explanation of this phenomenon is given by assuming that water can be considered as a semiconductor. Thus, also a photonic band gap can be expected. In other words, and in this context, the 411.8 keV g - rays were localized, if the temperature of the solution is kept below 60°C. This hypothesis is validated by the experimental results, since after heating up sample I above 60°C a mirrorless lasing happened. The fact that no trace of gold was visible is the proof of concept, that the remaining 197Au nuclei show a photonuclear reaction 197Au (g, n) 196Au decaying rapidly into 196Hg. However, in a first step the 198Au (g, n) 197Au reaction occurred leading to a reversal of the 197Au (n, g) 198Au reaction. In other words, the photonuclear reaction excited the collective movements of the neutrons and protons of the 197Au nucleus leading to giant g resonances, and to the ejection of a neutron. In a second experiment the gold electrode was activated by exposure to thermal neutrons. Very similar results were obtained with the exception that between 15% to 20% of the unheated sample showed the 411.8 keV transition.
16:25: [MedicineWedPM210] OLAugmented reality (AR) involves the overlay of computer-generated images onto the user’s real-world visual field to modify or enhance the user’s visual experience. With respect to neurosurgery, AR integrates preoperative and intraoperative imaging data to create an enriched surgical experience that has been shown to improve surgical planning, refine neuronavigation, and reduce operation time. In addition, AR has the potential to serve as a valuable training tool for neurosurgeons in a way that minimizes patient risk while facilitating comprehensive training opportunities. The increased use of AR in neurosurgery over the past decade has led to innovative research endeavors aiming to develop novel, more efficient AR systems while also improving and refining present ones. In this review, we provide a concise overview of AR, detail current and emerging uses of AR in neurosurgery and neurosurgical training, discuss the limitations of AR, and provide future research directions. Following the guidelines of the Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA), 386 articles were initially identified. Two independent reviewers (GH and AC) assessed article eligibility for inclusion, and 31 articles are included in this review. The literature search included original (retrospective and prospective) articles and case reports published in English between 2013 and 2023. AR assistance has shown promise within neuro-oncology, spinal neurosurgery, neurovascular surgery, skull-base surgery, and pediatric neurosurgery. Intraoperative use of AR was found to primarily assist with surgical planning and neuronavigation. Similarly, AR assistance for neurosurgical training focused primarily on surgical planning and neuronavigation. However, studies included in this review utilize small sample sizes and remain largely in the preliminary phase. Thus, future research must be conducted to further refine AR systems before widespread intraoperative and educational use.
16:50: [MedicineWedPM211] OL KeynoteCancer remains a complex and devastating disease, posing significant challenges to global healthcare. To address this pressing issue, pioneering research and innovative therapeutic approaches are essential. A novel frontier in cancer research lies in the investigation of microgravity (µg) conditions, such as those experienced during space travel, as a potential catalyst for advancing cancer research and personalized medicine. We will explore the promising intersection of cancer, microgravity (µg) conditions experienced during space travel, and personalized medicine as a novel frontier in cancer research highlighting the collective potential to revolutionize cancer treatment and therapy development.Importantly, the limitations of the standard one-size-fits-all cancer treatment have led to a growing emphasis on personalized medicine. Tailoring treatments to individual patients based on their unique genetic makeup, environment, and lifestyle has been shown to enhance treatment efficacy while minimizing adverse effects. In this context, microgravity emerges as an intriguing avenue for exploration, offering new insights into cancer biology and therapeutic interventions.We will focus on the profound impact of microgravity on cellular behaviour and molecular processes in cancer cells. Investigating real (r-) and simulated (s-) µg environments provides a research platform to identify novel pathways and potential targets for cancer treatment. Additionally, µg environments facilitate the formation of three-dimensional (3D) tumour models, such as multicellular spheroids and organoids, which accurately mimic the in vivo tumour microenvironment. These 3D models offer invaluable tools for preclinical drug screening and personalized cancer therapy development.The confluence of cancer, microgravity, and personalized medicine presents a transformative opportunity to accelerate cancer research and therapeutic development. By harnessing the unique conditions of µg to deepen our understanding of cancer biology and tailoring treatments to individual patients, this novel approach has the potential to pave the way for a new era in cancer care. The integration of personalized medicine with µg-based cancer research holds promise for optimized treatment outcomes and advancing cancer therapy, ultimately bringing us closer to overcoming this formidable disease.
References:
[1] Hanahan D, Weinberg RA. Hallmarks of cancer: the next generation. Cell. 2011 Mar 4;144(5):646-74. doi: 10.1016/j.cell.2011.02.013
[2] Ries LAG, Young JL, Keel GE, et al. SEER Survival Monograph: Cancer Survival Among Adults: US SEER Program, 1988-2001, Patient and Tumor Characteristics. Bethesda, MD: National Cancer Institute, SEER Program; 2007.
[3] Saxena S, Thompson JP, Colgate EC, et al. Cancer and spaceflight: molecular mechanisms and future therapeutic targets. Semin Cancer Biol. 2021 Apr;70:272-281. doi: 10.1016/j.semcancer.2021.02.005.
[4] Takahashi A, Kaji K, Sasaki Y, et al. Simulated microgravity facilitates cell migration and inhibits cell proliferation via suppressing FAK activity regulated by ERK signaling pathway. Sci Rep. 2017 Aug 1;7(1):6802. doi: 10.1038/s41598-017-07232-1
[5] Wang R, Xu H, Peng Z, et al. 3D cell culture under microgravity condition maintains malignant properties of cancer cells with respect to gene expression and drug resistance. Cell Prolif. 2019 Jan;52(1):e12512. doi: 10.1111/cpr.12512
[6] Xiao H, Sun J, Li Z, et al. Microgravity potentiates stem cell proliferation while sustaining the capability of differentiation. Stem Cells Dev. 2015 Oct 15;24(20):2405-15. doi: 10.1089/scd.2014.0512.
[7] Zhang W, Pan Y, Li F, et al. Novel insights into therapy of cancer: implication of 3D cell culture. Front Pharmacol. 2020 Feb 25;10:1666. doi: 10.3389/fphar.2019.01666
[8] Zhu M, Liang C, Duan X, et al. The Effect of Real Microgravity on Cancer Biology: A Systematic Review. Front Oncol. 2020 Sep 4;10:1343. doi: 10.3389/fonc.2020.01343.
[9] Zong C, Zhang J, Huang Y, et al. Zero gravity promotes the invasion of thyroid cancer cells by increasing exosome secretion. Cell Biol Int. 2019 Mar;43(3):316-325. doi: 10.1002/cbin.11092.
Magnetic gold nanoparticles (mGNP) have become a great interest of research for nanomaterial scientists because of their significant magnetic and plasmonic properties applicable in biomedical applications. Various synthetic approaches and surface modification techniques have been used for mGNP including the most common being the coprecipitation, thermal decomposition, and microemulsion methods in addition to the Brust Schiffrin technique, which involves the reduction of metal precursors in a two-phase system (water and toluene) in the presence of alkanethiol. The hybrid magnetic–plasmonic nanoparticles based on iron core and gold shell are being considered as potential theragnostic agents. Herein, in addition to future works, we will discuss recent developments for synthesis and surface modification of mGNP with their applications in modern biomedical science such as drug and gene delivery, bioimaging, biosensing, and neuro-regenerative disorders. I shall also discuss the techniques based on my research related to the biological applications of mGNP.
| SESSION: OxidativeWedPM3-R1 | Ozawa International Symposium (3rd Intl. Symp. on Oxidative Stress for Sustainable Development of Human Beings) |
| Wed. 29 Nov. 2023 / Room: Dreams 1 | |
| Session Chairs: TBA Session Monitor: TBA | |
In multicellular organisms, cells typically communicate by sending and receiving chemical signals. Chemical messengers involved in the exocytosis of neuroendocrine cells or neurons are generally assumed to only originate from the fusing of intracellular large dense core vesicles (LDCVs) or synaptic vesicles with the cellular membrane following stimulation. Accumulated evidence suggests that exosomes - one of the main extracellular vesicles (EVs) - carrying cell-dependent DNA, mRNA and proteins etc. play an essential role in cellular communication. Due to experimental limitations, it has been difficult to monitor the real-time release of individual exosomes, which impedes a comprehensive understanding of the basic molecular mechanisms and the functions of exosomes. We introduce amperometry with microelectrodes to capture the dynamic release of single exosomes from a single living cell, distinguish them from other EVs and identify between the molecules inside exosomes and those secreted from LDCVs. We show that similar to many LDCVs and synaptic vesicles, exosomes released by neuroendocrine cells also contain catecholamine transmitters. This finding reveals long-range chemical communication via exosome-encapsulated chemical messengers and a potential interconnection between the two release pathways, changing the canonical view of exocytosis of neuroendocrine cells and possibly neurons. This defines a new mechanism for chemical communication at the fundamental level and opens new avenues in the research of the molecular biology of exosomes in the neuroendocrine and central nervous systems. In addition, electrochemically renewable surface-enhanced Raman spectroscopy (SERS) microprobes enable real-time dynamic measurement of ROS released from single cells, which lays the foundation for the development of the integrated technology of electrochemistry and Raman.
References:
[1]K. Hu, K. L. V. Long, F. Wang, X. Zhang, C. Gu, N. Fang, N. T. N. Phan and A. G. Ewing, J. Am. Chem. Soc. 2023, 21, 11499.
Stroke is a major disease burden worldwide and over 85% incidences are ischemic stroke. Tissue plasminogen activator (t-PA) is the only FDA approved drug for acute ischemic stroke, but its use is limited with the restrictive time window within 4.5 hours and the complications of the blood brain barrier (BBB) disruption and hemorrhagic transformation (HT). Exploring molecular targets to reducing the BBB permeability and HT incidence is timely important to develop novel therapeutic approaches for reducing the complications and increasing outcome in ischemic stroke.Oxidative/nitrosative stress and neuroinflammation are two crucial pathological processes in ischemic stroke. Reactive nitrogen species (RNS) and high mobility group box 1 protein (HMGB1) are important cytotoxic factors contributing to cerebral ischemia-reperfusion injury. Peroxynitrite (ONOO-) is a representative RNS but its roles in mediating inflammation signaling in the blood-brain barrier (BBB) damage and hemorrhagic transformation (HT) in ischemic brain injury remain unclear. In basic study, our group has tested the hypothesis that ONOO- could directly mediate HMGB1 signaling in ischemic brains with delayed t-PA treatment [1,2]. In clinical studies, we found that plasma nitrotyrosine (NT, a surrogate marker of ONOO-) was positively correlated with HMGB1 level in acute ischemic stroke patients. Plasma levels of nitrotyrosine and HMGB1 were increased in t-PA-treated ischemic stroke patients with hemorrhagic transformation [2]. Furthermore, animal experiments revealed that FeTmPyP, a representative ONOO- decomposition catalyst (PDC), significantly inhibited the activations of HMGB1/TLR2/MMP-9 signaling cascades, preserved collagen IV and tight junction claudin-5 in ischemic rat brains with delayed t-PA treatment. ONOO- donor SIN-1 directly induced HMGB1/TLR2/MMP-9 signaling cascades in naive rat brains in vivo and brain microvascular endothelial b.End3 cells in vitro. Those results suggest that ONOO- could activate HMGB1/TLR2/MMP-9 signaling, contributing to the BBB disruption and HT in ischemic brain injury [1-2]. We also demonstrate that ONOO- mediated MMPs and NLRP3 inflammasome could aggravate the BBB damage and HT and induce poor outcome in ischemic stroke with hyperglycemia [3]. Thus, the interactions of ONOO- and inflammation factors play crucial roles in the BBB disruption and HT. For drug discovery, we found that medicinal plant compounds, such as baicalin and glycyrrhizin, and a classic Chinese medicinal formula named Angong Niuhuang Pill regulated the RNS/Cav-1/MMP signaling cascades, decreased the mortality rate, attenuated the BBB disruption, HT, brain swelling, and improved neurological outcomes in the ischemic stroke rat model with delayed t-PA treatment [1-4]. In conclusion, targeting peroxynitrite-mediated inflammation signaling cascades could be a potential adjuvant therapy to prevent hemorrhagic transformation and improve outcome in ischemic stroke with delayed t-PA treatment, potentially extending the therapeutic window for thrombolysis.
References:
[1] Chen HS, Guan BH, Chen X, Chen XM, Li CM, Qiu JH, Yang D, Liu KJ, Q SH, Shen JG. Baicalin attenuates blood-brain barrier disruption and hemorrhagic transformation and improves neurological outcome in ischemic stroke rats with delayed t-PA treatment: Involvement of ONOO--MMP-9 pathway. Translational Stroke Research 2019; 9(5): 515-529.
[2] Chen H, Guan B, Wang B, Pu H, Bai X, Chen X, Liu J, Li C, Qiu J, Yang D, Liu K, Wang Q, Qi S, Shen J. Glycyrrhizin prevents hemorrhagic transformation and improves neurological outcome in ischemic stroke with delayed thrombolysis through targeting peroxynitrite-mediated HMGB1 signaling. Translational Stroke Research 2020;11(5):967-982
[3] Chen H, Guan B, Chen S, Yang D, Shen J. Peroxynitrite activates NLRP3 inflammasome and contributes to hemorrhagic transformation and poor outcome in ischemic stroke with hyperglycemia. Free Radical Biology and Medicine 2021; 165, 171-183
[4] Chen H, Luo Y, Tsoi B, Qi S, Shen J. Angong Niuhuang Wan reduces hemorrhagic transformation and mortality in ischemic stroke rats with delayed thrombolysis: involvement of peroxynitrite-mediated MMP-9 activation. Chinese Medicine 2022; 17(1):51
| SESSION: OxidativeThuAM-R1 | Ozawa International Symposium (3rd Intl. Symp. on Oxidative Stress for Sustainable Development of Human Beings) |
| Thu. 30 Nov. 2023 / Room: Dreams 1 | |
| Session Chairs: Russel Reiter; Session Monitor: TBA | |
Melatonin (N-acetyl-5-methoxytryptamine) was discovered as a secretory product of the mammalian pineal gland in 1958. At the time, melatonin was thought to be exclusively synthesized and released from the pineal gland at night with the duration of the nocturnal melatonin elevation being related to the length of the daily dark period. Since the duration of the night length varies seasonally, melatonin rhythm was originally believed to regulate only circadian (sleep/wake cycle) and circannual (annual reproductive fluctuations in seasonally breeding species) rhythms, i.e., to function as both a physiological clock and as a calendar. Subsequently, melatonin was also identified in non-mammalian vertebrates, all of which have a pineal gland, and soon thereafter in invertebrates including unicells and in plants, none of which have a pineal gland [1]; thus, melatonin synthesis is obviously not exclusively of pineal origin. Within the last three decades, melatonin or its synthesizing enzymes have been found in prokaryotes including true bacteria and archaebacteria (archaeans). Thus, melatonin presumably evolved in prokaryotes about 3.0-2.5 billion years ago. During eukaryogenesis, which occurred an estimated 2.5 – 2.0 billion years ago, prokaryotes were engulfed by early eukaryotes for food and energy; the prokaryotes eventually established a symbiotic relationship with the eukaryotes that had phagocytized them, and they eventually evolved into mitochondria. The origin of mitochondria from prokaryotes is a widely accepted theory. The melatonin-synthesizing activity of the prokaryotes was retained in all eukaryotic mitochondria [2]. As a result, the mitochondria of many cells of present-day eukaryotes may also produce melatonin; thus, vertebrates have two sources of melatonin. The pineal gland of vertebrates discharges melatonin into the blood and cerebrospinal fluid (the releasable pool) for circadian and circannual rhythm regulation. Additionally, all plant and animal species synthesize melatonin in their mitochondria, which is used as an antioxidant in the cell of origin (the non-releasable pool).Numerous publications have shown melatonin to be a multifaceted and highly efficient direct free radical scavenger and an indirect antioxidant. Melatonin quenches highly destructive reactive oxygen (ROS) and reactive nitrogen species as does many of its metabolites in what is referred to as the antioxidant cascade. Additionally, melatonin promotes the activities of numerous antioxidant enzymes while inhibiting pro-oxidant enzyme activities. Since mitochondria are a major source of ROS generation when electrons leak from complexes I and II of the electron transport chain and chemically reduce nearby ground-state oxygen to the superoxide anion radical, melatonin synthesis in mitochondria is ideally situated to reduce free radical damage [3]. Supplemental melatonin limits elevated oxidative stress in many pathologies, such as in models of ischemia/reperfusion including stroke and heart attack, exposure of animals to heavy metals, environmental particulate matter, microplastics, hyperglycemia and atherosclerosis, excessive alcohol, conventional medications including chemotherapies, illegal drugs, ionizing radiation, neurodegenerative diseases, and those caused by dysfunctional mitochondria. These studies have been extended to humans where melatonin has similar protective actions. Some of the functions of melatonin involve transmembrane receptors which are widely distributed while other actions are receptor-independent [4].
References:
[1] D. Zhou, Y, Yu, J. Zhang, R. Zhang, Z, Mou, X. Zhang, Z. Li, X. Feng, S. Chen, R.J. Reiter. Front. Endocrinol. 10 2019) 19249.
[2] D.X. Tan, L.C. Manchester, Z. Liu, S.A. Rosales-Corral, D. Acuna-Castroviejo, R.J. Reiter. J. Pineal Res., 54 (2013) 127-138.
[3] R.J. Reiter, S.A. Rosales-Corral, D.X. Tan, M.J. Jou, A. Galano, B. Xu. Cell. Mol. Life Sci. 74 (2017) 3863-3881.
[4] R.J. Reiter, Q. Ma, R. Sharma. Physiology (Bethesda) 35 (2020) 86-95
Melatonin (N-acetyl-5-methoxytryptamine) was discovered as a secretory product of the mammalian pineal gland in 1958. At the time, melatonin was thought to be exclusively synthesized and released from the pineal gland at night with the duration of the nocturnal melatonin elevation being related to the length of the daily dark period. Since the duration of the night length varies seasonally, melatonin rhythm was originally believed to regulate only circadian (sleep/wake cycle) and circannual (annual reproductive fluctuations in seasonally breeding species) rhythms, i.e., to function as both a physiological clock and as a calendar. Subsequently, melatonin was also identified in non-mammalian vertebrates, all of which have a pineal gland, and soon thereafter in invertebrates including unicells and in plants, none of which have a pineal gland [1]; thus, melatonin synthesis is obviously not exclusively of pineal origin. Within the last three decades, melatonin or its synthesizing enzymes have been found in prokaryotes including true bacteria and archaebacteria (archaeans). Thus, melatonin presumably evolved in prokaryotes about 3.0-2.5 billion years ago. During eukaryogenesis, which occurred an estimated 2.5 – 2.0 billion years ago, prokaryotes were engulfed by early eukaryotes for food and energy; the prokaryotes eventually established a symbiotic relationship with the eukaryotes that had phagocytized them, and they eventually evolved into mitochondria. The origin of mitochondria from prokaryotes is a widely accepted theory. The melatonin-synthesizing activity of the prokaryotes was retained in all eukaryotic mitochondria [2]. As a result, the mitochondria of many cells of present-day eukaryotes may also produce melatonin; thus, vertebrates have two sources of melatonin. The pineal gland of vertebrates discharges melatonin into the blood and cerebrospinal fluid (the releasable pool) for circadian and circannual rhythm regulation. Additionally, all plant and animal species synthesize melatonin in their mitochondria, which is used as an antioxidant in the cell of origin (the non-releasable pool).Numerous publications have shown melatonin to be a multifaceted and highly efficient direct free radical scavenger and an indirect antioxidant. Melatonin quenches highly destructive reactive oxygen (ROS) and reactive nitrogen species as does many of its metabolites in what is referred to as the antioxidant cascade. Additionally, melatonin promotes the activities of numerous antioxidant enzymes while inhibiting pro-oxidant enzyme activities. Since mitochondria are a major source of ROS generation when electrons leak from complexes I and II of the electron transport chain and chemically reduce nearby ground-state oxygen to the superoxide anion radical, melatonin synthesis in mitochondria is ideally situated to reduce free radical damage [3]. Supplemental melatonin limits elevated oxidative stress in many pathologies, such as in models of ischemia/reperfusion including stroke and heart attack, exposure of animals to heavy metals, environmental particulate matter, microplastics, hyperglycemia and atherosclerosis, excessive alcohol, conventional medications including chemotherapies, illegal drugs, ionizing radiation, neurodegenerative diseases, and those caused by dysfunctional mitochondria. These studies have been extended to humans where melatonin has similar protective actions. Some of the functions of melatonin involve transmembrane receptors which are widely distributed while other actions are receptor-independent [4].
References:
[1] D. Zhou, Y, Yu, J. Zhang, R. Zhang, Z, Mou, X. Zhang, Z. Li, X. Feng, S. Chen, R.J. Reiter. Front. Endocrinol. 10 2019) 19249.
[2] D.X. Tan, L.C. Manchester, Z. Liu, S.A. Rosales-Corral, D. Acuna-Castroviejo, R.J. Reiter. J. Pineal Res., 54 (2013) 127-138.
[3] R.J. Reiter, S.A. Rosales-Corral, D.X. Tan, M.J. Jou, A. Galano, B. Xu. Cell. Mol. Life Sci. 74 (2017) 3863-3881.
[4] R.J. Reiter, Q. Ma, R. Sharma. Physiology (Bethesda) 35 (2020) 86-95.
Carbon quantum dots (CQDs), depending on their surface functionalization, have found utility across a number of biological applications [1-4].
Here, we demonstrate that individual CQDs can serve multifunctional roles, which is a key requisite for the development of drugs for neurodegenerative disorders such as Parkinson’s disease (PD) [5].
Na-citrate-, phenylboronic acid-, and 4-aminophenylboronic acid-derived CQDs were evaluated for their ability to intervene in amyloid-forming trajectories and restore intracellular homeostasis under oxidative stress.
While all three CQDs were able to prevent the soluble-monomer to mature-fibril conversion of hen-egg white lysozyme, Na-citrate- and 4-aminophenylboronic acid-derived CQDs in particular were also able to scavenge reactive oxygen species when exposed to a broad spectrum of free radical generators. Furthermore, Na-citrate and 4-aminophenylboronic acid CQDs preincubated in a neuroblastoma-derived SHSY-5Y cell line were able to rescue it from rotenone (neurotoxicant)-induced cell death while demonstrating no difference in cytotoxicity up to 120 μg/mL (compared to untreated controls). The CQDs were also able to restitute cells from rotenone-elicited apoptosis and oxidative stress. Together, these results suggest that CQDs can serve as a one-pot solution for multifactorial diseases such as PD by serving as a neuroprotectant. Importantly, the use of CQDs as multifactorial interventional agents represents a sustainable mechanism by which to advance biomedicine.
References:
[1] Savelieff, M. G.; Nam, G.; Kang, J.; Lee, H. J.; Lee, M.; Lim, M. H. Development of multifunctional molecules as potential therapeutic candidates for Alzheimer’s disease, Parkinson’s disease, and amyotrophic lateral sclerosis in the last decade. Chem. Rev. 2019, 119 (2), 1221– 1322, DOI: 10.1021/acs.chemrev.8b00138
[2] De, B.; Karak, N. A green and facile approach for the synthesis of water soluble fluorescent carbon dots from banana juice. RSC Adv. 2013, 3 (22), 8286– 8290, DOI: 10.1039/c3ra00088e
[3] Sachdev, A.; Gopinath, P. Green synthesis of multifunctional carbon dots from coriander leaves and their potential application as antioxidants, sensors and bioimaging agents. Analyst 2015, 140 (12), 4260– 4269, DOI: 10.1039/C5AN00454C
[4] Molaei, M. Carbon quantum dots and their biomedical and therapeutic applications: a review. RSC Adv. 2019, 9 (12), 6460– 6481, DOI: 10.1039/C8RA08088G
Alla I. Potapovich a, Tatyana V. Kostyuk a, Tatsiana G. Shutova b, Vladimir A. Kostyuka*a Byelorussian state university, Niezaližnasci Avenue, 4, 220030, Minsk, BelarusbInstitute of Chemistry of New Materials, National Academy of Sciences of Belarus, Skaryny Street, Minsk 220141, Belarus The antiradical activity of flavonoids in simple biochemical systems was discovered more than 30 years ago [1]. Subsequently, the antioxidant and anti-inflammatory effects of flavonoids were demonstrated in human cells upon exposure to various inflammatory stimuli [2, 3]. However, despite their numerous biological activities, the clinical use of flavonoids is limited mainly due to their low water solubility, which results in poor cellular uptake and poor permeability of flavonoids through the skin. To overcome these limitations, potential drug molecules can be incorporated into liposomes or polymer nanoparticles, which have great potential as drug carriers [4]. In this work, we evaluated the cellular effects of native and microstructured flavonoids. Microcrystals of quercetin and resveratrol coated with (polyallylamine hydrochloride/sodium polystyrenesulfonate)4 or (chitosan/dextran sulfate)4 shells were prepared by layer-by-layer assembly. Cultured human HaCaT keratinocytes were exposed to UV-C, after which the cells were incubated with native and microstructured flavonoids. Phosphorylation of histones H2AX, DNA damage, cell viability and integrity were assessed. The data obtained indicate that native and microstructured flavonoids added immediately after exposure to UV-C increased cell viability in a dose-dependent manner, however, the effectiveness of microstructured quercetin was more pronounced than that of the native compound. It has been shown that flavonoids can activate the process of repairing genetic damage, while the coated quercetin (chitosan/dextran sulfate)4 was more effective than the native compound in reducing the amount of DNA damage in the nuclei of keratinocytes exposed to UV-C radiation.
References:
[1] I.B. Afanas'ev, A.I. Dcrozhko, A.V. Brodskii, V.A. Kostyuk, A.I. Potapovitch, Biochem pharmacol (1989) 38 (11), 1763-176.
[2] V.A. Kostyuk, A.I. Potapovich, T.O. Suhan, C. de Luca, L.G. Korkina, Eur j pharmacol (2011) 658 (2-3), 248-256
[3] A.I. Potapovich, V.A. Kostyuk, T.V. Kostyuk, C. de Luca, L.G. Korkina, Inflamm Res (2013) 6:773–780.
[4] T. Sahu, Y.K. Ratre, S. Chauhan, L. Bhaskar, M.P. Nair, H.K. Verma, J Drug Deliv Sci Technol (2021) 63:102487
| SESSION: MedicineFriAM1-R1 | 2nd Intl. Symp. on Technological Innovations in Medicine for Sustainable Development |
| Fri. 1 Dec. 2023 / Room: Dreams 1 | |
| Session Chairs: Hans Leuenberger; Session Monitor: TBA | |
Despite the discovery of new drugs and therapeutics for the treatment of diseases, confirmation of their effectiveness and safety of use requires additional long-term studies. A safe and fast method for this that does not require research on living organisms is computer molecular modeling. The application of artificial intelligence (AI) methods is also an important step today [1,2]. The most well-known and used molecular modeling methods are molecular dynamics and docking methods, and so on [3,4]. However, despite having several advantages, these methods also have disadvantages that can be of critical importance when conducting experiments.We propose an effective approach to the modeling and study of biological systems and biochemical processes, particularly processes in cells under various scenarios of interaction: an algebraic approach that has been proven effective in many other scientific areas. In the modeling process, we combine an algebraic approach with AI methods.The algebraic approach is based on the theory of agents and environments initiated by Letychevskyi and Gilbert [5]. This approach is implemented in our software tools for the modeling of biological models.We have developed a formal model of the cell apoptosis process, which various scenarios of interactions between cell elements and different agents (enzymes, viruses, nanoparticles, etc.) can cause. When running a given model, we can analyze the changes in the environment under certain conditions and explore the properties or states of the environment that can be achieved in the modeling process.In the developed models, we consider the following properties: (1) reachability of the cell degradation phase or apoptosis process inhibition under given influencing factors and their parameters (quantitative ratio between metalloproteinases/glutaminases and their inhibitors, the influence of nanoparticles and/or irradiation, etc.); and (2) determination of the initial state of the environment (indicators of the temperatures, concentrations, and structures of substances; acidity, characteristics of the studied cell, etc.) needed to reach the desired behavior scenario.A feature of algebraic modeling, in contrast to simulation modeling and probabilistic methods, is its ability to abstract from specific values and consider multiple scenarios of system behavior rather than one specific scenario. This makes it possible to conduct an effective search for the environment or substances that have the necessary effect on cellular processes and that can be used to destroy diseased cells in the corresponding treatment process, particularly in oncological diseases.We can consider modeling at different levels of abstraction depending on the chosen experiment: at the level of the atomic structure of substances and quantum–mechanical interaction, at the level of the molecular structure of substances, and at the level of interaction of biological objects. To effectively search models and narrow the search space for them due to the high complexity of models, neural networks are used, which are trained on known scenarios of cellular processes.At this research stage, a method of applying algebraic modeling was developed to study the effect of enzymes such as multidomain zinc metalloproteinase, glutamine, and transglutaminase 2 on the activation and inhibition of the cell apoptosis process.
References:
[1] Liu, Ke, Xiangyan Sun, Lei Jia, Jun Ma, Haoming Xing, Junqiu Wu, Hua Gao, Yax Sun, Florian Boulnois, and Jie Fan. “Chemi-Net: A Molecular Graph Convolutional Network for Accurate Drug Property Prediction.” International Journal of Molecular Sciences 20, no. 14 (2019): 3389. https://doi.org/10.3390/ijms20143389.
[2] Ramsundar, Bharath, Bowen Liu, Zhenqin Wu, Andreas Verras, Matthew Tudor, Robert P. Sheridan, and Vijay Pande. “Is Multitask Deep Learning Practical for Pharma?” Journal of Chemical Information and Modeling 57, no. 8 (2017): 2068–76. https://doi.org/10.1021/acs.jcim.7b00146.
[3] Lauria, A., M. Tutone, M. Ippolito, L. Pantano, and A. Almerico. “Molecular Modeling Approaches in the Discovery of New Drugs for Anti-Cancer Therapy: The Investigation of P53-MDM2 Interaction and Its Inhibition by Small Molecules.” Current Medicinal Chemistry 17, no. 28 (2010): 3142–54. https://doi.org/10.2174/092986710792232021.
[4] Hou, De-Xing, and Takuma Kumamoto. “Flavonoids as Protein Kinase Inhibitors for Cancer Chemoprevention: Direct Binding and Molecular Modeling.” Antioxidants & Redox Signaling 13, no. 5 (2010): 691–719. https://doi.org/10.1089/ars.2009.2816.
[5] Letichevsky, Alexander, and David Gilbert. “A Model for Interaction of Agents and Environments.” Recent Trends in Algebraic Development Techniques, 2000, 311–28. https://doi.org/10.1007/978-3-540-44616-3_18.
Hepatitis B (HBV) and C (HCV) are two among other forms of infections for which co-infection in HIV has been associated with alteration of the immune response, increased risk of progression to liver diseases and increased risk of hepatotoxicity associated to antiretroviral therapy. This study was aim to establish the prevalence of hepatitis B surface antigen (HBsAg) and hepatitis C antibody (HCVAb) among HIV patients, treatment outcomes and possible risk factors in Kumba Health, in the South West Region of Cameroon. We performed a systematic screening using Rapid Diagnostic Test, for HBsAg and HCVAb among 299 HIV patients enrolled at the treatment centers in Kumba Health District with all positives for HBV or HCV confirmed by the ELISA and results analyzed using SPSS version 20. Out of the 299 participants, 36 (12.0%) were positive for HBV and 12 (4%) for HCV by both RDT and ELISA, out of which 52 HIV patients, 36 HIV/HBV and 12 HIV/HCV patients were involved in the prospective cohort study for 24 months which permitted monitored the immune response (CD4 counts and viral load test), as well as variation of biochemical parameters (ALAT/ASAT, albumin, bilirubine, creatinine) and weights of the studied participants. There were positive variations in all the biomarkers and immune response measurement which differed among the different groups and so this result could be used for health decisions regarding co-infecteds.
09:05: [MedicineFriAM103] OLChemotherapy as an adjuvant therapy that has largely failed to significantly improve outcomes for aggressive brain tumors; some reasons include a weak blood brain barrier penetration and tumor heterogeneity. Recently, there has been interest in designing effective ways to deliver chemotherapy to the tumor. In this review, we discuss the mechanisms of focused chemotherapies that are currently under investigation. Nanoparticle delivery demonstrates both a superior permeability and retention. However, thus far, it has not demonstrated a therapeutic efficacy for brain tumors. Convection-enhanced delivery is an invasive, yet versatile method, which appears to have the greatest potential. Other vehicles, such as angiopep-2 decorated gold nanoparticles, polyamidoamine dendrimers, and lipid nanostructures have demonstrated efficacy through sustained release of focused chemotherapy and have either improved cell death or survival in humans or animal models. Finally, focused ultrasound is a safe and effective way to disrupt the blood brain barrier and augment other delivery methods. Clinical trials are currently underway to study the safety and efficacy of these methods in combination with standard of care.
09:30: [MedicineFriAM104] OLThe contact angle (CA: deg) method [1] has been used for the determination of the wettability of solids and semisolid substrates such as cosmetics and formulations for cutaneous applications [2]. As regards biomaterials, this method can evaluate the hydration state of skin [2] and demonstrate its usefulness in the beauty sector field [3]. On this basis, our work aimed to evaluate the basal moisturizing level of in-vivo skins of a workers group (subjects test) employed in a commercial holding company sited in Treviso (Italy). The skin wettability of each subject test (ST) was evaluated using a portable MobilDrop DSA2 mobile tensiometer (tenskinmeter®)[2] and a single drop of microfiltered water (Ares Solida srls, Treviso, Italia). The water CAs measurements were performed before and after the skin application of a liposome dispersion (Skindecoder®) and a commercial hydration cream (shc). The test was repeated after seven days during which each subject test kept its systemic hydration level administrating two liters of water per day. Our work demonstrated a decrease of water CAs measured after the application of Skindecoder® (ST RU=-58%, ST ROS=-51%, ST GIU=-51.98, ST MATT=-56.80%, ST ROB=-65.54%, ST GRE=-55.16%, ST ILA=-81.28%) and chc (ST RU=-68.77%, ST ROS=-26.30%, ST GIU=-32.23, ST MATT=-45.48%, ST ROB=-41.30%, ST GRE=-48.98%, ST ILA=-45.65%) at t0. That demonstrated the increase of hydration state due to the two formulations' application. The basal water CAs measured after seven days decreased for ST RU (-13.22%), ST ROS (-51.15%), ST GIU (-3.09%), ST MATT (-10.63%), ST ROB (-21.73%), ST GRE (-12.00%), and ILA (-8.02%). These data show that the regular administration of 2Lt of water per day causes a decrease in the water CAs of STs with a measurable increase in skin hydration that depends on the biological properties of each worker tested. Our pilot study opened with the perspective of considering the moisturizing of the human epidermis as a possible biological parameter to control in a rapid and non-invasive way the employee's health about their water intake during job activities in public and private institutions.
References:
[1] [1] F.M. Etzler, Mittal (Ed.) Advances in Contact Angle Wettability&Adhesion, Scrivener Publishing LLC, 13 (2018) 229-329.
[2] [2] D. Rossi, A. Bettero, Mittal (Ed.) Advances in Contact Angle Wettability&Adhesion, Scrivener Publishing LLC, 4 (2020) 115-144.
[3] [3] D. Rossi, N. Realdon, Mittal and H.S. Bui (Eds.) Surface Science and Adhesion in Cosmetics (2021).
| SESSION: IronTueAM-R2 | Assis International Symposium (9th Intl. Symp. on Advanced Sustainable Iron & Steel Making) |
| Tue. 28 Nov. 2023 / Room: Dreams 2 | |
| Session Chairs: Tateo Usui; Marcos De Campos; Session Monitor: TBA | |
Following a brief description of the background, a life timeline of industrial and scientific activity during 48 years will be presented. It will cover first the work done for more than 2 industrial companies including Acesita and Mannesmann and the successes achieved during that time such as the development of the first fluid system to inject charcoal in the blast furnace and it’s successful industrial implementation as the first Powder Charcoal System implemented with success worldwide.The scientific activity at UFOP will follow along with the successes achieved such as participation in the Excellence Program of CSN (Companhia Siderúrgiac Nacional) as a visiting professor.The establishment during thirty years as professor, researcher and Scientist of many collaborations with the best universities and professors in the world and especially in Asia will be described.The successes achieved as the first researcher worldwide working with biomass (waste from the Agriculture) and biogas in the blast furnace will also be described. Life learned lessons will also be described.
12:00: [IronTueAM02] OS KeynoteGas carburizing of solid steel is carried out by using a large amount of hydrocarbon in order to keep the furnace atmosphere as long as constant, because carbon from hydrocarbon is consumed for carburization of the steel surface and hydrogen remains in the furnace. In the present study, selective removal methods of H2 were surveyed and fundamental experiment was done by using Proton Conductor SrZr1-xYxO3-a , which was prepared by spark plasma sintering method; hydrogen gas was separated from wet simulated coke oven gas atmosphere at high temperature successfully. At the same time, reported method to selectively remove H2 was also applied to bench scale furnace for gas carburizing of solid steel by using gas filter module made of poli-imido fiber tube. The control of the furnace atmosphere was very important to keep it constant, which was also studied numerically as well as experimentally. Finally, selective removal of H2 from the furnace was verified experimentally and the flow rate of so-called “carrier gas” (hydrocarbons) could be reduced more than 75 % under the condition of the same quality of steel surface by the carburization treatment. As a result, exhaust gas volume could also be reduced and the burnt exhaust gas, namely, CO2 emission was minimized.
References:
[1] Yujiro Yokoyama, Tomoyuki Mizukoshi, Itsuo Ishigami and Tateo Usui: Numerical Analysis and Control of Gas Carburizing under Changes in Gas Compositions, Materials Science Forum, 522-523(2006), pp.589 - 594.
[2] Hirokazu KONISHI, Hiroshi NISHIMURA, Tateo USUI and Iwao KATAYAMA: Preparation of Proton Conductor SrZr1-xYxO3-a for Pure Hydrogen Separation in High Temperature Range (in Japanese), Journal of High Temperature Society, 34(2008)3, pp.123 - 129.
[3] Tomoyuki Mizukoshi, Yujiro Yokoyama, Hideaki Hoshino, Itsuo Ishigami and Tateo Usui: New Gas Carburizing Method for Minimizing CO2 Emission by Saving Resources and Selective Removal of H2 in Furnace (in Japanese), Journal of High Temperature Society, 35(2009)1, pp.50 - 54.
[4] Tomoyuki Mizukoshi, Hideaki Hoshino, Yujiro Yokoyama, Itsuo Ishigami and Tateo Usui: Numerical Analysis on Carbon Concentration Profiles of Gas Carburized Low Alloy Steel under Fluctuating Atmosphere, NETSU SHORI (Journal of the Japan Society for Heat Treatment), 49(2009), Special Issue, pp.319 - 322.
[5] Yujiro Yokoyama, Tomoyuki Mizukoshi, Itsuo Ishigami and Tateo Usui: Relationship between Vacuum Carburizing Conditions and Surface Carbon Concentration of SNCM815, NETSU SHORI, 49(2009), Special Issue, pp. 323 - 326.
[6] Hirokazu KONISHI, Takuya MATSUMOTO, Tateo USUI and Tomoyuki MIZUKOSHI: Characteristic of Proton Conductor Prepared by Spark Plasma Sintering in the Simulated Coke Oven Gas, Tetsu-to-Hagané (in Japanese), 96 (2010)10, pp.629 - 635.
[7] Yujiro Yokoyama, Tomoyuki Mizukoshi, Itsuo Ishigami and Tateo Usui: Development and Verification of Vacuum Carburizing Model Considering Graphite Deposition on Low Alloy Steel (in Japanese), Report of Technology Research Institute of Osaka Prefecture, No.23 (2009), pp.65 - 71.
[8] Tomoyuki Mizukoshi, Yujiro Yokoyama, Hideaki Hoshino, Itsuo Ishigami, Hirokazu Konishi and Tateo Usui: Influence of Alloying Elements on Carburizing Reaction Rate Constant of Low Alloy Steel in CO-CO2-N2 Atmosphere, Proceedings of The International Symposium on Ironmaking for Sustainable Development 2010 (ISISD 2010), (January, 2010, Osaka, Japan), pp.165 - 168, ISIJ (The Iron and Steel Institute of Japan).
[9] Hideaki Hoshino, Tomoyuki Mizukoshi, Yujiro Yokoyama, Itsuo Ishigami and Tateo Usui: Carburizing Rates of Vacuum Carburization by Acetylene Gas at 1.33 kPa, Proceedings of The International Symposium on Ironmaking for Sustainable Development 2010 (ISISD 2010), (January, 2010, Osaka, Japan), pp.169 - 172, ISIJ.
[10] Yujiro Yokoyama, Hideaki Hoshino, Tomoyuki Mizukoshi and Tateo Usui: Relationship between Vacuum Carburizing Conditions and Surface Carbon Concentration of SCM415, Proceedings of The International Symposium on Ironmaking for Sustainable Development 2010 (ISISD 2010), (January, 2010, Osaka, Japan), pp.173 - 176, ISIJ.
[11] Yujiro Yokoyama, Tomoyuki Mizukoshi, Itsuo Ishigami and Tateo Usui: Numerical Analysis and Control of Gas Carburizing under Changes in Gas Compositions, Abstracts of International Symposium on High-Temperature Oxidation and Corrosion, (November, 2005, Nara, Japan), Poster P39, ISIJ.
[12] Tomoyuki Mizukoshi, Hideaki Hoshino, Yujiro Yokoyama, Itsuo Ishigami and Tateo Usui: Numerical Analysis on Carbon Concentration Profiles of Gas Carburized Low Alloy Steel under Fluctuating Atmosphere, 17th International Federation for Heat Treatment and Surface Engineering Congress 2008 (October, 2008, Kobe, Japan), Poster P10, p.226, Japan Society for Heat Treatment.
[13] Yujiro Yokoyama, Tomoyuki Mizukoshi, Itsuo Ishigami and Tateo Usui: Relationship between Vacuum Carburizing Conditions and Surface Carbon Concentration of SNCM815, 17th International Federation for Heat Treatment and Surface Engineering Congress 2008 (October, 2008, Kobe, Japan), Poster P12, p.228, The Japan Society for Heat Treatment. [The Poster Award for 17th IFHTSE Congress 2008 (October 29, 2008)]
[14] Tomoyuki Mizukoshi, Itsuo Ishigami, Yujiro Yokoyama and Tateo Usui: For Development of Eco-friendly Carburizing Treatment Method (Part 1) - Construction and Application of Kinetics Model for Vacuum Carburizing - (in Japanese), NETSU SHORI, 50 (2010)6, pp.589 - 600.
[15] Yujiro Yokoyama, Tomoyuki Mizukoshi, Itsuo Ishigami and Tateo Usui: For Development of Eco-friendly Carburizing Treatment Method (Part 2) - Effect of Surface Graphite Deposition on Carbon Profile of Vacuum Carburized Steel - (in Japanese), NETSU SHORI, 52(2012)5, pp.257 - 262.
[16] Tomoyuki Mizukoshi, Itsuo Ishigami, Yujiro Yokoyama and Tateo Usui: For Development of Eco-friendly Carburizing Treatment Method (Part 3) - Proposal for Controlling Gas Carburizing based on Surface Reaction Rate and Diffusion of Carbon - (in Japanese), NETSU SHORI, 53(2013)6, pp.302 - 309.
[17] Tomoyuki Mizukoshi, Itsuo Ishigami, Yujiro Yokoyama and Tateo Usui: For Development of Eco-friendly Carburizing Treatment Method (Part 4) - Saving Energy and Resources in Gas Carburizing Process by Selective Removal of H2 in Furnace - (in Japanese), NETSU SHORI, 54(2014)4, pp.205 - 211.
One way for energy storage is hydrogen production of the excess of electric energy. However Hydrogen storage is quite complicated because hydrogen is only liquid at 20 Kelvin. Also, as easily explained by the Carnot cycle, there are losses along the several steps of liquid hydrogen production, as for example, hydrolysis efficiency, compression and liquefaction efficiency, and so on. However, excess electric energy can be transformed into hydrogen and immediately used for metal reduction. Here it is discussed the technical and economic feasibility of using hydrogen for iron reduction. Oil importer countries may turn to hydrogen usage in industry, thus avoiding oil price fluctuation, or also coal price fluctuation. Even with higher prices, the use of hydrogen in metallurgical processes gives alternatives to non-renewable commodities. This detail is relevant for strategic planning of governments.
12:50: [IronTueAM04] OS KeynoteThis work consists of a study of the application of different types of biomass in the steelmaking process, these are the biomasses: Macaúba, soy, corn, elephant grass, sugarcane bagasse and coffee husks, considering that Steelmaking is responsible for 5% of emissions of greenhouse gases (CH4 and CO2). There is an attempt to replace part of the coal in the steelmaking process with biomass, but it is not possible to eliminate it completely because carbon is important in the reduction stage of Blast Furnaces, in addition, biomass needs to undergo processes and treatments that give it the desired characteristics. Biomass is all organic matter used to produce energy, which can be added to coke or injected into blast furnaces. Brazil's biodiversity needs to be used by ours through the incorporation of agribusiness residues into the steel sector. But to improve the calorific potential and decrease the reactivity of the biomass, additives can be added, as well as tar, which act by reducing the porosity of the biomass. In addition, demineralization can be performed to remove the inorganic part of the biomass in order to decrease its reactivity. The pyrolysis of biomass consists of heating the organic material without the presence of oxygen, direct thermal decomposition occurring (500 to 900°C) because when the temperature increases, the volatiles are eliminated, leaving carbon. Torrefaction is carried out at lower temperatures than pyrolysis (around 300°C) and is a technique that reduces the costs of cogeneration power plant because the biomass in this process becomes friable and easy to handle, but the torrefaction problem is that it does not concentrate the fixed carbon content.
| SESSION: IronTuePM1-R2 | Assis International Symposium (9th Intl. Symp. on Advanced Sustainable Iron & Steel Making) |
| Tue. 28 Nov. 2023 / Room: Dreams 2 | |
| Session Chairs: Tateo Usui; Giulio Antunes De Medeiros; Session Monitor: TBA | |
Industries have been directing their efforts towards improving their production processes, looking for new levels of environmental excellence. After the Paris Agreement set a framework for worldwide developments aimed at mitigating emissions and achieving a positive balance between anthropogenic emission sources, decarbonization has become a global objective. In this context, the use of by-products from other production processes has become essential for industries aiming to implement circular economy principles and contribute to the achievement of ESG goals.In the search for sustainable and innovative ways to generate value for the production of iron ore pellets and for the society hosting its industrial complex, Samarco has identified opportunities to study raw materials obtained from residue generated in the mining of ornamental stones. Samarco’s pelletizing plants are located in a region with the highest production of iron ore pellets in the West and the fifth largest production of ornamental stones in the world. Because of that, its location is ideal for the implementation of circular economy practices by developing sustainable pelletizing raw materials from the high volume of waste generated in the extraction of granite and marble.Samarco is the global pioneer in the use of marble mining residue as an input for pellet production due to the chemical and grindability similarity between marble and the calcitic limestone in the region. After laboratory and industrial-scale tests with excellent physical, chemical, and metallurgical results, results showed that the marble waste from the region has high CaO content, reducing the specific consumption by 16% in comparison to calcitic limestone, to meet the required physicochemical conditions for iron ore fired pellets. This results in a CO2eq- reduction of 6.84 kg per ton of pellets, contributing to decarbonization in pelletizing, in addition to increasing the iron content of the fired pellets by 0.5%. Approximately 800 tons of marble mining waste removed daily from the environment are used as a fluxing agent and basicity corrector in iron ore pellets destined for blast furnaces and direct reduction reactors around the world.Another sustainable raw material for use in iron ore pellets intended for direct reduction reactors is obtained from the cutting of granite stones. This input works as a coating agent, acting as a physical barrier capable of mitigating the tendency of pellets to stick together during reduction at high temperatures (between 950 and 1050 °C). The residue from granite cutting has ideal chemical characteristics and particle size to serve as a coating on pellets, remaining adhered to the surface of the agglomerates even during handling and until their use in the steel industry.In addition to raw materials produced from residue in the mining of ornamental stones, Samarco has been innovatively seeking to diversify the energy matrix of its industrial complex through the increased use of renewable energies, specifically carbonized biomass, as an alternative to fossil fuels such as coal and coke.The carbonization, handling, and fragmentation of charcoal for the supply of independent and integrated pig iron and ferroalloy production plants generate fine carbonaceous residues (charcoal fines), which do not achieve the granulometric specifications for reuse in other metallurgical processes. This material is discarded into the environment without prior treatment, which can have environmental, economic, and social impacts. In this context, studies have shown an opportunity for the recovery and reuse of these fines due to their considerable energy potential.The use of these materials in processes such as pelletizing is considered carbon-neutral since the capture of CO2 occurs during the growth and development of the trees planted to produce the charcoal through the process of photosynthesis. This amount of CO2 is sufficient to compensate what is released during the production (carbonization) and combustion of the charcoal. Substituting the solid fuel matrix for the pelletizing plant in 50% of charcoal can reduce up to 22 kgCO2eq- per ton of pellets. This represents nearly 190.000 tons per year of CO2 removed from the atmosphere.The higher friability of charcoal is advantageous for processes like pelletizing. Being a friable material facilitates grinding the fuel, making it easier to achieve the required particle size for sintering and pelletizing. Samarco conducted laboratory tests incorporating charcoal fines into pellet production to increase the diversification of its energy matrix with new renewable fuels. Both charcoal and charcoal fines were successfully tested on an industrial scale in 2023.This article aims to explore technical aspects related to improving the quality of iron ore pellets and its decarbonization through the use of sustainable by-products in their production.
References:
[1] CASTRO, N. F. et al. Impacto do APL de rochas ornamentais do Espírito Santo nas comunidades. In: Recursos minerais & sustentabilidade territorial. Arranjos Produtivos Locais. Rio de Janeiro: CETEM/MCTI, 2011. v.2. p.139-176.
[2] BRAGA DS, CRISCUOLO LG, CARVALHO JL, Carvão vegetal como alternativa energética para pelotização. 47º Seminário de Redução de Minério de Ferro, 5º Simpósio Brasileiro de Aglomeração de Minério de Ferro, 02 a 06 outubro, São Paulo, SP, Brasil. 2017
[3] FERREIRA OC. Emissões de Gases de Efeito Estufa na Produção e no Uso do Carvão Vegetal. Economia e Energia, n° 20. 2000.
[4] BAILON, A. M. G., SIMÕES, H. O., BUENO, P. G., PEREIRA, J. G., DOELLINGER, T. M., BIANCHI, M. R. R. Determinação de metodologia para avaliação das causas de colagem em reatores de redução direta. In: Seminário de Redução de Minério de Ferro e Matérias-Primas, 41, 2011, Vitória. Simpósio Brasileiro de Minério de Ferro, 12, 2011, Vitória. BAILON et al. (2011).
[5] BOECHAT, F. O; CARVALHO, R. M. de ; TAVARES, L. M. . Avaliação de interações entre quebradores e clusters em forno de redução direta usando o método dos elementos discretos. Tecnologia em metalurgia, materiais e mineração, v. 14, p. 349-356, 2017.
[6] CATTABRIGA, L. Utilização de resíduos de rochas ornamentais na composição de pastas de cimento para completação de poços petrolíferos. 2010. 62 f. Monografia (Conclusão de Curso) – Engenharia de Petróleo e Gás. Faculdade de Espírito Santo, Cachoeiro de Itapemirim, ES, 2010.
[7] BAILON, A.M.G., Simões, H.O., Fonseca, M.C. - Avaliação de fases microestruturais e resistência a compressão de pelotas de minério de ferro com diferentes níveis de sinterização. In: 45º Ironmaking / 16º Iron Ore / 3º Agglomeration - vol. 45, num.45 (2015)
[8] SILVA, I. G. - Uso de resíduos provenientes do processo de corte de mármores como um substituto dos fundentes na produção de pelotas de minério de ferro. Dissertação de Mestrado, IFES, Espírito Santo.2014
FLOGEN Technologies Inc. has developed an integrated Design/Decision-Making/Control/Optimization/Automation System combines several needs on supply side, on production side, on metal sales side and on financial side. It supports cost prediction and cost follow up on the energy and consumables side and is integrated with databases that manages numerous types of essays. This has been at various blast furnaces of pig iron. The system instantaneously makes a complete optimization of all raw materials, including limestone, silica, air and oxygen volumes, in order to achieve specific targets according to the needs of the company. The main achievements of the implementation of the FLOGEN CONTOP system were the increase of the pig iron production by about 14% and the decrease of total consumption of charcoal (breeze and fines) by about 4%. Additionally, fines injected through the tuyeres were decreased, temperature and composition of slag and pig iron (including Si and P) were better controlled and silica addition as a flux was minimized. An overall instantaneous mass and energy balance helped fix various mechanical and procedural problems in the plant. CONTOP system was also successfully used to determine the annual procurement strategies by predicting various raw material cost-based scenarios related to productivity and fuel consumption in short- and long-term future. CONTOP increased productivity and reduced cost up to the highest designed limit of the technology. CONTOP also changed the way of operating from a reactive wait-the-lab-results-approach to a proactive forecast-and-act approach.
14:55: [IronTuePM107] OS KeynoteClimate change and environmental impacts reflect the externalities of a global model of unsustainable production and consumption. However, even in the face of a chaotic environmental scenario, the exploitation of resources and consequently Greenhouse Gas (GHG) emissions continue to increase, thus causing an increase in temperature and possible irreversible impacts on the planet. The Circular Economy presents itself as a tool for mitigating extraction and cooperation for efficient resource management, avoiding waste [1] . Currently, the transport sector is the main responsible for Greenhouse Gas (GHG) emissions, making the transformation of this sector's value chain urgent[2] . In a national context, motor vehicles are the main means of transport used, in the year 2022 there were approximately 115 million vehicles registered in Brazil. Revealing the expressive growth rate compared to 2010 data, with approximately 65 million vehicles circulating in the national territory[3] . A study carried out in 2018 shows that the transport sector was responsible for 23% of the total amount of CO2 emissions worldwide in 2017. In addition to being one of the world's largest consumers of oil[4] . The 100% electric vehicle therefore appears as a promising solution to this scenario of mitigating air pollution, especially in urban centers where its concentration occurs. This article proposes to develop a method for collecting and analyzing the characteristics observed by consumers when choosing their own vehicle. It seeks to identify stages of awareness and the transition movement between internal combustion vehicles and 100% electric vehicles. To this end, the research developed a form via Google Forms aimed at evaluating the parameters used by consumers when considering the possibility of migrating to 100% electric models. This form was applied to seventy-six (76) citizens living in the State of Rio de Janeiro, invited to participate in the research. The findings suggest evidence of different stages of awareness and acceptance regarding the transition to 100% electric vehicles. Thus, one of the solutions proposed by this work is the transition from internal combustion vehicles to electric vehicles fueled with ethanol, which, in addition to contributing significantly to reducing dependence on fossil fuels, encourage the search for renewable energy sources such as those coming from of biomass. In order to positively impact the scenario of GHG emissions caused by the sector.
References:
[1] ANACLETO, Nathália Balzana. (2022). Circularidade na construção civil: análise e avaliação aplicadas a oito casos no estado do Rio de Janeiro (Dissertação de Mestrado). Programa de Pós-Graduação em Arquitetura e Urbanismo da Universidade Federal Fluminense, Niterói.
[2] MINISTÉRIO DO MEIO AMBIENTE. Inventário nacional de emissões atmosféricas por veículos automotores rodoviários. Brasil, 2013.
[3] IBGE. Frota de Veículos. 2023. Disponível em:
[4] CORDEIRO, Ana Carolina; LOSEKANN, Luciano. 2018. Os desafios do processo de difusão do carro elétrico no Brasil. Disponível em: <04c844642997f2143aab25578215f3257293.pdf (semanticscholar.org)>. Acesso em: junho de 2023
The exhaustion of natural resources (quantity and quality) and CO2 emission controls are becoming increasingly important in steel industry. A lot of steel engineers studied various means to decrease reducing agent at blast furnace for reduction of CO2 emissions. For example, injection of waste plastics and carbon neutral materials such as biomass into blast furnace is better alternative. Especially, biomass has novel advantage, namely, no CO2 emissions, because of carbon neutral. Production of carbon composite iron ore agglomerates having good reducibility and strength is becoming one of the most important subjects. Carbon composite iron oxide pellets using semi-char or semi-charcoal were proposed in order to enhance the reduction rate of iron oxide. The carbonization was done under a rising temperature condition until arriving at a maximum carbonization temperature Tc,max to release some part of the volatile matter included (V.M.). Starting point of reduction of carbon composite pellet using semi-charcoal produced at Tc,max = 823 K under the rising reduction-temperature condition was observed at the reduction temperature TR = 833 K, only a little higher than Tc,max (823 K), which was the aimed phenomena. As Tc,max increases, the emitted carbonization gas volume increases, while the residual V.M. decreases, and, as a whole, the total heat value of the carbonization gas emitted tends to increase monotonically.
References:
[1] Tateo Usui, Hirokazu Konishi, Kazuhira Ichikawa, Hideki Ono, Hirotoshi Kawabata, Francisco B. Pena, Matheus H. Souza, Alexandre A. Xavier and Paulo S. Assis, “Evaluation of Carbonisation Gas from Coal and Woody Biomass and Reduction Rate of Carbon Composite Pellets”, Advances in Materials Science and Engineering, Vol.2018, Article ID 3807609, 2018, pp.1-14
[2] . Konishi, T. Usui and K. Azuma, “The Preparation and Reduction Behavior of Carbon Composite Iron Oxide Pellets Using Semi-coal- char”, Tetsu-to-Hagané, 92, 2006, pp.802-808.
[3] H. Konishi, A. Yamashita and T. Usui, “Effect of Residual Volatile Matter on Reduction of Iron Oxide in Carbon Composite Pellets”, Journal of JSEM (Japanese Society for Experimental Mechanics), 8, 2008, Special Issue, pp.142-146.
[4] H. Konishi, T. Usui and A. Yamashita, “Effect of Residual Volatile Matter on Reduction Reaction between Semi-coal-char and Iron Oxide”, Tetsu-to-Hagané, 95, 2009, pp.467-472.
[5] H. Konishi, K. Ichikawa and T. Usui, “Effect of Residual Volatile Matter on Reduction of Iron Oxide in Semi-charcoal Composite Pellets”, ISIJ International, 50, 2010, pp.386-389.
[6] H. Konishi, T. Usui and T. Harada, “The Preparation and Reduction Behavior of Charcoal Composite Iron Oxide Pellets”, Journal of High Temperature Society, 34, 2008, pp.14-19.
[7] H. Konishi, S. Fujimori and T. Usui, “Reduction Behavior of Iron Oxide in Semi-charcoal Composite Pellets”, Journal of High Temperature Society, 35, 2009, pp.33-39.
[8] T. Ariyama and M. Sato, “Optimization of Ironmaking Process for Reducing CO2 Emissions in the Integrated Steel Works”, ISIJ International, 46, 2006, pp.1736-1744.
[9] M. Asanuma et al., “Development of Waste Plastics Injection Process in Blast Furnace”, ISIJ International, 40, 2000, pp.244-251.
[10] T. Ariyama, R. Murai, J. Ishii and M. Sato, “Reduction of CO2 Emissions from Integrated Steel Works and Its Subject for a Future Study”, ISIJ International, 45, 2005, pp.1371-1378.
[11] T. Matsumura, M. Ichida, T. Nagasaka and K. Kato, “Carbonization Behaviour of Woody Biomass and Resulting Metallurgical Coke”, ISIJ International, 48, 2008, pp.572-577.
[12] M. Nakano, M. Naito, K. Higuchi and K. Morimoto, “Non-spherical Carbon Composite Agglomerates: Lab-scale Manufacture and Quality Assessment”, ISIJ International, 44, 2004, pp.2079-2085.
| SESSION: IronTuePM2-R2 | Assis International Symposium (9th Intl. Symp. on Advanced Sustainable Iron & Steel Making) |
| Tue. 28 Nov. 2023 / Room: Dreams 2 | |
| Session Chairs: Giovanni Felice Salierno; Session Monitor: TBA | |
Iron ore sintering is a high temperature, high volume process for producing raw material for blast furnace, and the quality requirements for sinter is high strength and Tumbler index, good reducibility and reduction degradation index (RDI). The process involves high temperature gas-solid reaction, drying and condensation, and melting and solidification phenomena. Simulation of the iron ore sintering process reveals considerable variation in thermal and melting profile in the sinter bed [1,2]. Melting is very low in the top critical zone just below the ignition hood, giving rise to low sinter strength and high return fines, where as in the bottom layers melting is much higher, producing glassy phase with low reducibility. Suction pressure applied in the wind boxes for gas velocity in the sinter bed is one of the important process parameter for the sintering process, which is optimized here in three locations, top, middle and lower zones by optimization technique such as Genetic Algorithm (GA), for better melting and sinter quality in the three zones representing the total sinter strand [3].Sinter quality which is combination of high strength and good reducibility, can be attributed to partial melting of about 30%, in the sinter bed. However due to non-uniform combustion zone in the sinter bed, melting is very low in the top critical zone, whereas melting is much higher in the lower regions. Therefore, to overcome this non-uniform melting along the sinter bed height, two-layer sintering process is envisaged with higher coke rate in the top layer, and lower coke rate in the bottom layer. The two-layer sintering process have been optimized by using Multi-Objective Genetic Algorithm, with different coke rates in the top and bottom layers. The thickness of the top and bottom layers are also varied for optimization. The two objectives for optimization are uniform 30% melting throughout the sinter bed, along with minimum overall coke rate, giving rise to two conflicting objectives for Pareto optimization [4]. The lower coke rate in the bottom layer up to the Burn through point (BTP), gives additional benefit of reducing pollution and greenhouse gases [2,5] like CO, CO2, SOx, and toxic gases such as NOx, dioxin and furan.
References:
[1] N. K. Nath, A. J. D. Silva and N. Chakraborti: Dynamic Process Modeling of Iron Ore Sintering: Steel Research: (1997); Vol. 68, No. 7, 285-292.
[2] J.A.D. Castro, N.K. Nath, A.B. Franca, V.S. Guilherme and Y. Sasaki. Analysis of iron ore sintering process based on alternative gaseous fuels from steelworks by multiphase multicomponent model; Ironmaking and Steelmaking, (2012), Vol. 39, No. 8, pp 605-613
[3] N. K. Nath and Kishalay Mitra. Optimization of Suction Pressure for Iron Ore Sintering by Genetic Algorithm. Ironmaking and Steelmaking, 2004, Vol. 31, No 3, pp 199-206.
[4] N. K. Nath and K. Mitra. Mathematical modeling and optimization of two-layer sintering process for sinter quality and fuel efficiency by genetic algorithm; Materials and Manufacturing Processes, (2005), Vol. 20, No. 3, pp 335-349.
[5] C.F.C.D. Assis, J.A.S. Tenorio, P.S. Assis and N.K. Nath. Experimental Simulation and Analysis of Agricultural Waste Injection as an Alternative Fuel for Blast Furnace; Energy & Fuels, ACS Pub. 2014, Vol. 28, pp7268-7273.
In the development of the sintering of Ni-Ti alloys, it was noted the importance of carrying out an analysis regarding the influence of compaction load factors, temperatures and sintering times on their properties, given that these alloys are raw materials for biomedical products, such as implants and prostheses that need to have a high quality standard. The present study exposes the reasons why some samples showed more porosity than others, especially it is important to highlight that such samples with more porosity had a considerable decrease in hardness and mechanical resistance. The sintering temperature adopted was 1118°C, for periods of 12h and 24h, using analytical argon 2.0, taking into account the necessary care due to the high reactivity of titanium with other chemical elements. However, it was investigated why the samples that stayed in the oven for 24 hours had more pores compared to those that lasted 12 hours. Furthermore, it was observed that the greater the load applied, the greater the compaction of the alloy and the lower the porosity after sintering. The compression loads used were 21t and 30t, showing considerable differences in the final result of the specimens.
16:50: [IronTuePM211] OSSamarco has been using advanced process control with proven benefits, recognizing that the use of these technologies is a constant necessity. In the main stages of the production process, the "Advanced Process Control System" (SCAP) is employed, which consists of a multivariable control based on conventional control tools and fuzzy logic, simulating human thinking in decision-making.SCAPs are computer programs that incorporate specific tools and knowledge to solve operational tasks, controlling the processes autonomously and intelligently. The practices and expertise of specialists are incorporated into the systems through the control strategy, usually aiming to stabilize and optimize the production processes. The strategy is composed of models and rules, constituting the intelligence of the system for decision-making.The expert system maximizes the profitability of the operation of the most important equipment involved, from the iron ore beneficiation to the fired pellet. These systems automatically receive information from the controllers and use various advanced techniques to generate new appropriate set-points for the process at a very high frequency. These set-points are established to continuously pursue the objectives of Samarco's control strategy in different stages of the production process.In the flotation stage, where the ore is separated from contaminants such as silica, the control method that best reflects the strategy and produces the best results is fuzzy logic, which consists of a set of rules that reproduce the best operational practices. Accompanying the expert system is the foam image analysis system, which measures the drag velocity, crucial for control. Another established and patented technology used by Samarco is the online silica analyzer, which provides information about the silica trend in the concentrate, as well as X-ray analyzers, which provide the iron trend in the tailings. These tools have contributed to maximizing the metallurgical recovery in conventional flotation and reducing the variability of silica content in the final concentrate. The main objective was to maximize the metallurgical recovery in conventional flotation and reduce the variability of silica content in the final concentrate. Combined with the foam image analysis system and the online silica analyzer, the tool has proven capable of achieving the expected objectives, bringing stability to the process, standardizing operations, and reducing input consumption by approximately 17.78%.In the filtration stage, vacuum pressure and the number of pumps are adjusted to achieve the appropriate moisture level for the pelletizing stage. SCAPs play a decisive role in adjusting vacuum pressure and automating filter rotation cycles to optimize moisture and process productivity. In addition to reducing variability, there has been a reduction in moisture of approximately 2.26%. In the iron ore green pellet formation, it is a dynamic process with complex control requirements. In manual control, the local operator is responsible for process adjustments, and the timing and proportion of their actions depend on individual perception. With the implementation of the pelletizing SCAP, were achieved automated, standardized, and optimized control of the green pellet growth rate on the pelletizing discs. After implementation, there was a reduction in pellets out of size specification, a reduction in input raw material’s consumption, improvement in the quality of the final product and high productivity. The variability was reduced by 37.4%, the size range of 8 to 16 mm was increased by approximately 1.15% and productivity increased by approximately 6.1%.For controlling the variables in the pelletizing plant’s furnace, the SCAP's actions determine the optimal configuration of the fans based on the temperatures and pressures of the wind boxes. The controller also optimizes the ideal burning profile based on the grate feeding rate. The result is a reduction in variability with an improvement in the physical quality of the burnt pellets. Variability was reduced by 49.8%, specific gas consumption decreased by approximately 19.58%, and thermal consumption decreased by approximately 10.54%.Optimized decision-making improves process control by reducing variability and shifting averages towards operational limits. The observed benefits include capacity/production optimization, yield optimization, loss reduction, cost reduction, improvement in the quality of the final product, environmental compliance, and others.This article aims to describe how SCAP processes input information through conventional calculations and statistical calculations combined with "crisp" and "fuzzy" rules in order to reduce variability in the main stages of the production process.
References:
[1] Luis Alberto Sfalsin Passos; João Luis Moreira; Adilson Jorge; Marcos Vinicios Silva Cavalcante. MELHORIA NO DESEMPENHO DO PROCESSO DE PRODUÇÃO DE PELOTAS DE MINÉRIO DE FERRO EM DISCOS DE PELOTIZAÇÃO PELA UTILIZAÇÃO DE SISTEMAS OTIMIZANTES COM LÓGICA NEBULOSA , p. 4872-4883. In: 44º Seminário de Redução de Minério de Ferro e Matérias-primas, 15º Simpósio Brasileiro de Minério de Ferro e 2º Simpósio Brasileiro de Aglomeração de Minério de Ferro, Belo Horizonte - Brasil, 2014.
[2] Nogueira, André; Pires, Fernando Andrade; Silva, Flávio Thimótio da; Gontijo, Marcelo Montalvão. APLICAÇÃO DE SISTEMA ESPECIALISTA PARA CONTROLE DA FLOTAÇÃO CONVENCIONAL DO CONCENTRADOR 2 DA SAMARCO , p. 737-742. In: 45º Ironmaking / 16º Iron Ore / 3º Agglomeration, Rio de Janeiro, 2015.
The increase in the added value of the product from the steel making process, in the production of steel and different rolled products for the various industrial sectors, together with actions to reduce CO2 emissions. The demand forecast for 2050 is considers and must be ensured by a 100% renewable system [1]. The transition to a 1.5-2°C world will fundamentally change exiting the resource flows of both metals and fóssil fuels [2]. It has been shown to be an option for the viability of environmental protection projects, such as way to improve the profitability of the activity. Within this scenario, biomass has been presented as a source of energy of great utility, when it comes to renewable sources like the sugar and alcohol mil cogeneration systems and industrial and service sector [3]. The circular economy and low carbon or by the reduction of natural gas itself with CO2 sequestration in the process. It can only ever be one of a range of sustainability orientated initiatives that manifests in the here and now [4].
Demark utilizes the greatest proportion of agricultural wastes for power generation at 16.8%, followed by Finland (15.6%), Brazil (8.4%) [5]. The conversion of biomass energy into heat, using steam-generating boilers, presents adequate yields, when used together with gases produced internally by the process, since it provides energy in a form that is easily usable by the steel making process, either in the form of steam. for use in industrial processes or for sending air to blast furnaces or for generating electricity.
Biomass has 45% carbon, 42% oxygen, 5% hydrogen and 8% other minerals in its composition. The feasibility of using biomass in Brazil as fuel in steam generating boilers requires a comprehensive and conclusive study, in relation to the real influence on the agricultural process, the carbon market and other sources such as biogas.
Faced with the scenario of viability of consumption of this source in steam boilers, the context of Brazil and a vision of the current scenario of consumption of biomass. It will be like a discussion to the theme.
References:
REFERENCES:
[1] Luz, Thiago José Da, et al. “Complementarity Between Renewable Energy Sources and Regions - Brazilian Case”. Brazilian Archives of Biology and Technology, vol. 66, 2023, p. e23220442. DOI.org (Crossref), https://doi.org/10.1590/1678-4324-2023220442.
[2] Watari, Takuma, et al. “Sustainable Energy Transitions Require Enhanced Resource Governance”. Journal of Cleaner Production, vol. 312, agosto de 2021, p. 127698. DOI.org (Crossref), https://doi.org/10.1016/j.jclepro.2021.127698.
[3] La Picirelli De Souza, Lidiane, et al. “Life Cycle Assessment of Prospective Scenarios Maximizing Renewable Resources in the Brazilian Electricity Matrix”. Renewable Energy Focus, vol. 44, março de 2023, p. 1–18. DOI.org (Crossref), https://doi.org/10.1016/j.ref.2022.11.002.
[4] Figge, Frank, et al. “Definitions of the Circular Economy: Circularity Matters”. Ecological Economics, vol. 208, junho de 2023, p. 107823. DOI.org (Crossref), https://doi.org/10.1016/j.ecolecon.2023.107823.
[5] Zheng, Yingying, et al. “Carbon Footprint Analysis for Biomass-Fueled Combined Heat and Power Station: A Case Study”. Agriculture, vol. 12, no 8, agosto de 2022, p. 1146. DOI.org (Crossref), https://doi.org/10.3390/agriculture12081146.
| SESSION: IronTuePM3-R2 | Assis International Symposium (9th Intl. Symp. on Advanced Sustainable Iron & Steel Making) |
| Tue. 28 Nov. 2023 / Room: Dreams 2 | |
| Session Chairs: José Hamilton Tavares; Session Monitor: TBA | |
The mining industry seeks innovative and sustainable solutions for its production processes in the face of the international macroeconomic scenario. The Brazilian iron mining industry is among the largest in the world, with iron ore being one of its main export products. The majority of Brazilian iron ore is found in the Alegria Complex, located in the state of Minas Gerais, Brazil. The geological context of this region includes the presence of friable itabirite formations. At greater depths, where weathering processes are typically less active, iron ore bodies tend to have lower iron content and higher hardness/compactness. The use of iron ores with lower iron content and higher compactness, responsible for generating more waste during beneficiation, is occurring at a time when mining must develop technologies to reduce its environmental impact. As an alternative to depositing waste in dams, the sandy material can be filtered and stacked. However, the ultrafine portion (slimes) of the waste, which is rich in iron and not efficiently filtered through vacuum processes, possesses challenges and opportunities. This study evaluated the effectiveness of adding different percentages of ultrafine iron ore (slimes) in the pelletization process as an alternative to its disposal as waste. The ultrafines are obtained during the ore beneficiation process, and their reuse was aimed primarily at metallurgical recovery during beneficiation, as they can contain up to 48% iron in their composition. The results of this alternative use is reduction in its potential as an environmental liability and the reutilization of this waste, promoting a more sustainable mining production by significantly contributing to the management of non-renewable resources. Additionally, this initiative makes the segment more competitive by utilizing low-cost raw materials. The results of this study evaluates iron ore pellets produced from pellet feed incorporating high-specific-surface material, the ultrafine portion. Samarco’s pilot pelletizing plant conducted tests to assess the chemical, physical, metallurgical quality, and microstructural phase formation in pellets produced from different levels of specific surface area in the pellet feed. Degradation during handling tests of the pellets were also performed, considering resistance to surface and volumetric fragmentation due to impact. The results show the ideal process constraints for specific surface, loss on ignition, incorporation content of ultrafines, and chemical quality for pellet production within the highest standards of excellence historically practiced by Samarco, with significant gains in impact resistance and decrease of degradation during handling of the pellets.
References:
[1] 1. TAVARES, L.M., CARVALHO, R.M., 2011, Modeling ore degradation during handling using continuum damage mechanics, International Journal of Mineral Processing, v. 101, p. 21-27. 2. FONSECA, M.C. - Influência da distribuição granulométrica do pellet feed no processo de aglomeração e na qualidade da pelota de minério de ferro para redução direta – 142 páginas. Dissertação de Mestrado, REDEMAT – Ouro Preto, 2004.
Titanium nitride films were deposited onto SUS304 substrates under various film thickness, deposition temperatures, and substrate bias voltages. Their protective quality was evaluated by electrochemical testing in accordance with the critical passivation current density (CPCD) method. Two types of tests were employed to evaluate corrosive behavior of coated substrates: a high-temperature and high-pressure corrosion test; and a measurement of the change in anodic current density with immersion time. A scanning electron microscope was used to examine surface morphology and fractured cross-sections of the films. Residual stress in the films was determined by the sin2 method. An increase in film thickness engendered high protective quality. That protective quality was improved with increasing deposition temperature; micrometerorder pores were observed on all parts of films deposited at lower deposition temperatures, whereas few pores existed on films deposited at higher temperatures. This result indicates that these pores are one factor influencing overall protective quality. A film deposited with no substrate bias voltage displayed morphology with a typical columnar-structure; it also demonstrated complete protective quality. As the bias voltage increased, protective quality deteriorated, whereas an excess increase in the bias voltage gave rise to a slightly higher protective quality. Films with lower compressive stress had only a few pores and possessed higher protective quality, suggesting that pore formation originates in compressive stress. Corrosion tests indicated that the coated substrates corroded more rapidly as compressive stress in the film increased. The effect of compressive stress on maintenance of corrosion-protective quality was treated quantitatively. The rate of increase in the exposed area of the substrate was estimated from variation of an anodic current density with immersion time. This evaluation indicates that a decrease in compressive stress contributes greatly to maintenance of protective quality.
References:
[1] Ken'ichi Miura, Itsuo Ishigami, Masato Kuno and Hiroyuki Kaneda: Grain Size Dependence of Hardness of TiN Films Deposited by Reactive HCD Ion Plating (in Japanese), Journal of Japan Institute of Metals, 59(1995), pp.303 - 311.
[2] Ken'ichi Miura, Itsuo Ishigami and Tomoyuki Mizukoshi: Effects of Preparation Conditions on Chemical Composition and Hardness of Titanium Nitride Films Prepared by Reactive HCD Ion Plating (in Japanese), Journal of Japan Institute of Metals, 63(1999), pp.949 - 958.
[3] Ken'ichi Miura, Itsuo Ishigami and Tomoyuki Mizukoshi: Mixing of Oxygen in Titanium Nitride Films Formed by Reactive HCD Ion Plating (in Japanese), Journal of Japan Institute of Metals, 64 (2000), pp.508 - 517.
[4] Ken'ichi Miura and Itsuo Ishigami: Effect of Residual Stress on Lattice Parameter and Hardness of Titanium Nitride Films Deposited by Reactive HCD Ion Plating (in Japanese), Journal of Japan Institute of Metals, 65 (2001), pp.972 - 980.
| SESSION: IronWedAM-R2 | Assis International Symposium (9th Intl. Symp. on Advanced Sustainable Iron & Steel Making) |
| Wed. 29 Nov. 2023 / Room: Dreams 2 | |
| Session Chairs: Alexandro Uliana; Mauricio Cota Fonseca; Session Monitor: TBA | |
The drying process of iron ore pellets in the travelling grate pelletizing furnace is carried out through the transfer of heat from the hot gas by convection, with gaseous flows that initially occur upwards and then downwards, through the bed of pellets. The furnaces are designed according to the characteristics of the iron ores. However, over time, changes occur in the iron ore mineralogical characteristics that strongly affected the process kinetics, making the process inefficient. At Samarco, after the exhaustion of the Germano mine, the hydrated iron ore were incorporated into the process, mainly with the mineral goethite, demanding a greater input of thermal energy. In addition to removing the free moisture in the pellets, it was also necessary promote the thermal decomposition of goethite. With the aim of improving the drying process of iron ore pellets, especially in older furnaces, studies were carried out evaluating the effects of microwave irradiation in the drying process. Initially, laboratory experiments were carried out with homemade equipment (frequency of 2450 MHz and power of 1,000 W) for small samples of pellets, and then in a semi-industrial equipment (frequency of 915 MHz and power of 18 kW) for a greater mass of pellets. The study investigates the use of microwaves in the iron ore drying process and the effect on the green pellets quality.
12:00: [IronWedAM02] OSSamarco’s iron ore concentration process consists, basically, of the following steps: crushing, screening, grinding, desliming, coarse flotation, fine flotation, regrinding and columns flotation. After the mill, an ultrafine material rich in iron is generated and, after the desliming step, this material is discarded in actually disposed in a pit. The main idea of this study is to develop a new co-product to be used as a raw material in steelmaking processes. The challenges were the low levels of iron and high levels of silica and alumina, incompatible with the products offered on the market, and the granulometry of the ultrafine material (70% of mass passing through 10 micrometers). To make the product more attractive to the market, it was necessary to develop a magnetic concentration process for the ultrafine ore, increasing its iron content with adequate mass recovery. The iron content in the concentration product is inversely proportional to the mass recovery and the amount of material to be disposed of in suitable structures. After the concentration stage, the ultrafine material passes through a dewatering stage in thickener and press filter route, resulting in an ultrafine pellet feed with ideal humidity for agglomeration in discs, intensive mixers or extruders. The agglomerates can be heat-treated in a travelling grate furnace or be produced with a cold bonded binder, to acquire physical strength for handling and transport to customers. There will be an increase in the overall metallic yield of the process and a significant reduction in the area required for waste disposal, increasing sustainability and reducing business risks.
12:25: [IronWedAM03] OSThe revolution of industries provided the increase and speed of productions, mainly the production of steel [1]. In the specific context of shipbuilding, the use of steel plays a fundamental role in the design of vessels. Despite being a 100% recyclable material [2], there are few incentives for this practice in the sector. This is due to the predominant linear production model, where waste is still seen as a worthless by-product that cannot be reused. In this sense, the use of steel from scrap recycling, inserting it in the construction phase of vessels, emerges as one of the ways to promote the circular economy and guide the adoption of good construction practices for this sector. This paper intends to identify Transpetro's fleet of oil tankers and estimate the total steel demand for the construction of Suezmax class oil tankers. Based on the data collected, an analysis was made of the possible impacts caused if this fleet were built exclusively with recycled steel[3]. The article discusses if Transpetro [4] has any decommissioning fund and/or sustainable decommissioning planning, aiming to guarantee the reinsertion of the steel from these vessels in a new production cycle. It also discusses fiscal policies [5] that encourage the reinsertion of steel in the shipbuilding chain and how legislation has cooperated or delayed circularity actions in the sector. We will see that by incorporating circularity practices in this industry it will be possible to dissociate the construction process from the practice of extraction of new natural resources, resulting in the reduction of operational costs, promotion of the ship steel recycling market, and the environmentally correct disposal of this waste. Contributing significantly to the preservation of the environment and the reduction of Greenhouse Gas (GHG) emissions.
References:
[1] PIRES, Marco Cordeiro. O Brasil, o Mundo e a Quarta Revolução Industrial: reflexões sobre os impactos econômicos e sociais. Revista de Economia Política e História Econômica. Número 40 – julho de 2018.
[2] Instituto Nacional dos Distribuidores de Aço - INDA. (2021). AÇO: UMA ESCOLHA SUSTENTÁVEL. Recuperado em 13 de maio de 2023, de Por dentro do Aço – INDA.
[3] Sanchez, Euler & Pereira, Newton & Ribeiro, Natalia. (2017). Reciclagem de Navios e Embarcações: um mal necessário. October 2017. Conference: XXV Congresso Panamericano de Engenharia Naval. At: Panamá.
[4] JESUS, C. G. Contribuições para análise da tecnologia e do trabalho na indústria de construção naval brasileira. Revista Ciências do Trabalho, n. 9, p. 1997-2007, 2017.
[5] Assembleia Legislativa do Estado do Rio de Janeiro - ALERJ. (2023). ESTADO DO RIO PODE CONCEDER BENEFÍCIOS FISCAIS PARA ESTIMULAR ATIVIDADES DE RECICLAGEM DE EMBARCAÇÕES. Recuperado em 21 de maio de 2023, de https://www.alerj.rj.gov.br/Visualizar/Noticia/55709?AspxAutoDetectCookieSupport=1
Reheating of steel ingots in batch furnace such as soaking pit and box furnace, and Concast steel products like bar, billets and slabs in continuous furnace such as walking beam, and pusher type furnace is an important step for further thermo-mechanical processing like forging and rolling operations. Concast Steel and ingots are heated up to 1100 – 1250 C, and since this is a high temperature and energy intensive process, excess heating time will cause productivity and energy loss, as well as oxidation or scale loss. On the other hand, if it is heated very fast causing high thermal variation between the surface and core temperature, will lead to thermal stress, distortion and crack formation. Furthermore, rapid heating without thermal homogenization can cause problems during hot rolling or forging operations, which may lead to, roll stuck, cracking and forging problems. Therefore, the aim of the heating process is to avoid any excessive thermal stress, particularly in the vulnerable ferrite to austenite phase transformation range, and also to achieve thermal homogenization with optimum time and energy efficiency. To numerically simulate the process, a detailed two dimensional finite difference model is developed by using generalized axisymmetric equation, and Crank-Nicholson technique. To accurately simulate the process. The model also has to consider all the complexities of the process like anomalous behaviour of thermal conductivity of steel and latent heat of phase transformation. The model has been validated with limited number of Lab-experiments in a muffle furnace. Model based Process Control system have been developed for both batch and continuous reheating process, with Graphical User Interface (GUI) for plant application.
References:
[1] N.K Nath, Arunava Chowdhury and Paulo S. Assis. ‘Numerical simulation of ingot and concast steel reheating in batch and continuous type furnace to optimize energy efficiency, quality and productivity’, STIS (2013), Jamshedpur, Dec. 16-18, P75.
[2] N.K. Nath and Sachin L. Borse. Process Model based Software System for Steel Reheating Furnace for Energy Efficiency, Quality and Productivity; Advances in Computational Science and Technology, Vol. 5, No. 2, (2012), pp 819-824.
[3] Priyamvada Praharaj and N.K. Nath. Numerical simulation and experimental study of ingot heating process for time and energy efficiency for quality and productivity of the process, 3rd STIS conf., (2017), IIT Kanpur, pp 435-438.
[4] Arunava Chowdhury and N.K. Nath. Mathematical model based software system for optimization of steel slab and ingot reheating in walking beam furnace; ISOR Journal of Mechanical and Civil Engineering (IOSR-JMCE), (2015), pp 12-20.
| SESSION: IronWedPM1-R2 | Assis International Symposium (9th Intl. Symp. on Advanced Sustainable Iron & Steel Making) |
| Wed. 29 Nov. 2023 / Room: Dreams 2 | |
| Session Chairs: Marcos De Campos; Paulo Assis; Session Monitor: TBA | |
One of the biggest contaminants of soil, groundwater and surface water - leachate - also called percolated liquid, is the result of the enzymatic action of microorganisms and products resulting from the degradation of waste and water infiltration in landfills. This can prejudice the health of the population nearby the area. This study aimed to evaluate the implementation of a leachate treatment method (liquid from the decomposition of waste landfilled in the municipality of Conselheiro Lafaiete, Minas Gerais) with a focus on cost reduction and environmental improvement. The study was carried out during two years in Ouro Preto. We had studied a huge number of bibliographical references that portrayed about microwaves, alternative treatment of slurry and various subjects about it. Then, a composite sample was collected from the stabilization pond (inlet) and a composite sample from the output pond. The collection was carried out at three different points of the exit and entrance lagoon of the Sanitary Landfill in Conselheiro Lafaiete. Experiments were carried out with microwaves, organic coagulants and vertiver grass after treatment of manure in microwaves. The following parameters were analyzed: pH, BOD5, COD, Nitrate, Total Solids, Total Nitrogen, Phosphorus and Dissolved Oxygen, Total Aluminum, Total Lead, Total Copper, Total Chromium, Total Nickel, Total Zinc, Total Iron and Manganese, before and after the alternative slurry treatment. Among the results presented in this work, vetiver grass (Vetiveria zizanioides), when cultivated in a hydroponic system, is a plant with possible potential for phytoremediation of leachate leachate.
References:
EHRIG, H. J. Quality and Quantity of Sanitary Landfill Leachate. Waste Management & Research I, p. 53-68. 1989.
M. Strous, J.G. Kuenen, M.S. Jetten, Key physiology of anaerobic ammonium oxidation, Appl. Environ. Microbiol. 65 (1999) 3248–3250 (accessed October 25, 2017), http://www.ncbi.nlm.nih.gov/pubmed/10388731
M. Strous, J.G. Kuenen, M.S. Jetten, Key physiology of anaerobic ammonium oxidation, Appl. Environ. Microbiol. 65 (1999) 3248–3250 (accessed October 25, 2017), http://www.ncbi.nlm.nih.gov/pubmed/10388731.
M. Umar, H.A. Aziz, M.S. Yusoff, Trends in the use of Fenton, electro-Fenton and photo-Fenton for the treatment of landfill leachate, Waste Manage. 30 (2010) 2113–2121, http://dx.doi.org/10.1016/j.wasman.2010.07.003.
K.A. Third, A.O. Sliekers, J.G. Kuenen, M.S. Jetten, The CANON system (Completely Autotrophic Nitrogen-removal Over Nitrite) under ammonium limitation: interaction and competition between three groups of bacteria, Syst. Appl. Microbiol. 24 (2001) 588–596, http://dx.doi.org/10.1078/0723-2020-00077.
The current economic development model in global society has been progressively contributing to environmental degradation. It was intensified after the Industrial Revolution and is based on the linearity of extraction, production and waste generation[1]. This problem is particularly felt in the construction industry, responsible for a significant percentage of waste. Responses to this process include the proposition of a circular production economic model, according to which products should be designed to be reused, remanufactured, refurbished, and recycled, serving as input for a new production process[2]. This paper explores circular economy [3] approaches focused on the construction process. It proposes to develop a method for analyzing circularity practices and processes for the sector. It seeks to identify stages of construction practices considering the possibility of transition from linear to circular systems. To this end, the research developed a system of indicators [4] [5] to evaluate practices in relation to circularity parameters explored in the literature. This indicator system was applied to eight cases of construction companies operating in the state of Rio de Janeiro, which were invited to participate in the research. The findings suggest indications of different stages in the industry's transition to circular production.
References:
[1] Associação Brasileira de Empresas de Limpeza Pública e Resíduos Especiais - ABRELPE. (2021). Panorama dos Resíduos Sólidos no Brasil 2021. Recuperado em 07 de janeiro de 2022, de Download Panorama 2021 – Abrelpe.
[2] GONÇALVES, Daniel Bertoli. Desenvolvimento sustentável: o desafio da presente geração. Revista Espaço Acadêmico, ano V, n.51, agosto, 2005.
[3] WEETMAN, Catherine. Economia Circular: Conceitos e estratégias para fazer negócios de forma mais inteligente, sustentável e lucrativa. Autêntica Business - 2019.
[4] SILVA, Vanessa Gomes da. SILVA, Maristela Gomes da. AGOPYAN, Vahan. Avaliação de edifícios no Brasil: da avaliação ambiental para avaliação de sustentabilidade. Ambiente Construído, Porto Alegre, v. 3, n. 3, p. 7-18, jul./set. 2003
[5] SILVA, Vanessa Gomes da. Tecnologias para construção habitacional mais sustentável. Habitação mais Sustentável - Documento Metodologias de avaliação de desempenho ambiental de edifícios: estado atual e discussão metodológica. Projeto Finep 2386/04. São Paulo, 2007
The big trend nowadays is the replacement of coal plants by wind and solar. This may affect the price of electric energy, enabling processes where the electric energy is relevant, as for example secondary metallurgy where arc furnaces have large applications. Here we will discuss the impact of the new methods of energy generation on the cost of steel production in the next decades. It is forecasted that the price of electric energy will continue high in the next 5-10 years, while the coal energy plants were not completely replaced by wind or solar. Also, energy storage is expensive , and this precludes price energy reduction. The high price of energy storage is a significant bottleneck concerning price reduction of energy. Energy can be exported as a reduced metal, and countries with surplus of electric energy can become exporters of metals for countries with energy deficit. Brazil has one of the best conditions in the world for wind energy production in states near the equator line as Rio Grande do Norte and Ceará. These states are also promising places for production of other reduced metal, as for example aluminum.
15:20: [IronWedPM108] OSThis paper shows many types of taxes and incentives for export and import from Brazil.
These issues are shown in the paper and proves that by using the right of these taxes all of buyer and seller can have good benefits for their products and company.
References:
1. Constituição Federal /88- https://www.planalto.gov.br/ccivil_03/constituicao/constituicao.htm
2. Emenda Constitucional nº 42/2003 - https://www.planalto.gov.br/ccivil_03/constituicao/emendas/emc/emc42.htm
3. Lei Complementar nº 87/96 - https://www.planalto.gov.br/ccivil_03/leis/lcp/lcp87.htm
4. Lei Complementar n° 116/2003 - https://www.planalto.gov.br/ccivil_03/leis/lcp/lcp116.htm
5. Lei nº 9.363/96 - http://www.planalto.gov.br/ccivil_03/leis/l9363.htm
| SESSION: IronWedPM2-R2 | Assis International Symposium (9th Intl. Symp. on Advanced Sustainable Iron & Steel Making) |
| Wed. 29 Nov. 2023 / Room: Dreams 2 | |
| Session Chairs: Paulo Assis; Session Monitor: TBA | |
It is a well-known fact that steel is an important material used in many engineering applications, such as in the automotive industry, construction and machinery industries. In addition, desulfurization is a crucial process in steelmaking, since sulfur is an undesirable chemical element in steel’s composition. Although it results in better quality steel, it leads to a non-green slag that if not handled correctly may harm the environment. This study has the goal of discussing the process of desulfurization of hot metal in torpedo cars using CaC2 (calcium carbide) based desulfurizer and presenting the introduction and the possibility of reusing the slag in other green applications. Desulfurization is a pre-treatment that removes the sulfur located in hot metal throughout the chemical reaction of the desulfurizer injected in molten metal inside of the torpedo car.Therefore, after collecting the desulfurization slag from a local industrial process, the analysis of its properties starts, which was conducted using proper tools such as Scanning Electron Microscopy and also using X-Ray Diffraction and Fluorescence Analysis. In such manner, there will be a complete description of the slag's characteristics, which will lead to discussions about making the desulfurization’s slag disposal a greener alternative, such as implementing other uses like agriculture.
16:25: [IronWedPM210] OSA numerical simulation procedure is proposed for analyzing the partial replacement of pulverized coal injection by hydrogen, oxygen, and blast furnace gas (BFG) injections mixed with pulverized coal (PCI) within the tuyeres of large blast furnaces. The massive use of hydrogen-rich gas is highly attractive to the steelmaking blast furnace in the context of carbon net-zero hot metal production. Likewise, this new approach allows for increasing productivity and decreasing the specific emissions of carbon dioxide toward a net-zero carbon ironmaking technology. Nevertheless, pulverized coal injection gas mixture is a complex technology, in addition to the impact on chemical reactions and energy exchange, the internal temperature and gas flow pattern can also change drastically. With a view to assessing the state of the furnace in this complex operation, a comprehensive mathematical model using the multiphase theory was developed. The model simultaneously handles bulk solids (sinter, small coke, pellets, granular coke, and iron ore), gas, liquid metal and slag, and coal powder phases. The associated conservation equations are formulated for momentum, mass, chemical species, and energy while being discretized and solved using finite volume techniques. The numerical model was validated against the reference operating conditions using 220 kilograms per ton of pig iron (kg/tHM) of pulverized coal. Therefore, the combined injection of different concentrations of fuel hydrogen, blast furnace gas, and oxygen was simulated for replacing 40, 60 and 80 kg/tHM of coal injection. Theoretical analysis showed that the best scenario with stable operation conditions could be achieved with a productivity increase of 20% corresponding to a CO2 reduction of 15% and 60 kg/tHM of PCI replacement
References:
[1] Castro, J.A.; Takano, C.; Yagi, J. A theoretical study using the multiphase numerical simulation technique for effective use of H2 as blast furnaces fuel. J. Mater Res Technol., 2017, 6, 258-270.
[2] Adilson de Castro, J.; Medeiros, G.A.d.; Oliveira, E.M.d.; de Campos, M.F.; Nogami, H. The Mini Blast Furnace Process: An Efficient Reactor for Green Pig Iron Production Using Charcoal and Hydrogen-Rich Gas: A Study of Cases. Metals 2020, 10, 1501. https://doi.org/10.3390/met10111501
[3] Castro, J.A. A Multi-Dimensional Transient Mathematical Model of Blast Furnace Based on Multi-Fluid Model. Doctor Thesis, Ph.D.-Tohoku University, Sendai, Japan, 2001.
[4] Castro, J.A.; Araujo G.M.; Mota I.O.; Sasaki Y.; Yagi J. Analysis of the combined injection of pulverized coal and charcoal into large blast furnaces. J Mater Res Technol., 2013, 2, 308-314.
Steelmaking is impossible without ferroalloys; up to 95% of ferroalloys is used in steelmaking, and growth of production of ferroalloys is driven by growth of steelmaking, which is expected to reach 2,500 Mt by 2050. Currently, more than 50 projects are in progress to decrease carbon emission in steelmaking. In comparison with ironmaking, which has more than a dozen different technologies, ferroallomaking is very conservative; it is based on the carbothermal reduction of oxides in submerged electric arc furnaces at high temperatures. The paper considers reduction of manganese oxides by hydrogen to MnO and carbothermal reduction of manganese, chromium and titanium oxides in hydrogen. MnO can be processed further to metallic manganese in the electrolytic process. Direct reduction of stable metal oxides (manganese, chromium, titanium, silicon and other oxides) to the metallic state requires very high H2 to H2O ratio, which can be achieved by the carbothermal reduction in hydrogen. Carbothermal reduction in hydrogen can be implemented at lower temperatures in the solid state with potential advantages over conventional reduction of oxides from molten slags.
17:15: [IronWedPM212] OSThe rupture of Brazil's Fundão Dam in November 2015, known as the largest environmental disaster in the country's history, resulted in the immediate release of approximately 40 million cubic meters of iron ore tailings into the environment. This catastrophe had widespread and devastating effects, contaminating water bodies, disrupting ecosystems, displacing communities, and raising long-term health and environmental concerns. It underscores the necessity of stringent safety measures and responsible environmental management in the mining industry and the ongoing need for remediation and restoration efforts.The present study sought to evaluate the relationship between sediment characteristics and land use within the Water Resources Planning and Management Unit (UPGRH) of the “Piranga River”, Minas Gerais. This river represents one of the most crucial sub-basins of the “Doce River” in Brazil. The Piranga River was the first basin affected by the Iron Dam Break. Sediments in this context are complex geochemical entities that yield information essential for understanding the interactions of various processes occurring in fluvial environments. They originate from both natural soil weathering processes and anthropogenic activities, making them integral components of the watershed.Bottom sediments serve as indicators of the environmental impacts resulting from the improper disposal of domestic and industrial effluents in ecosystems. This study entailed two campaigns conducted in June 2019 and March 2020, during which a total of 14 samples were collected from pre-defined locations within the UPGRH of the Piranga River. This area had been significantly affected by a dam disaster involving the mining company Samarco in the municipality of Mariana, Minas Gerais. Subsequently, the collected samples were subjected to drying, homogenization, sieving, and digestion processes. The grain size analysis results, obtained for both dry and rainy seasons, revealed that sediments from the region affected by the Samarco disaster exhibited finer grain sizes compared to those from unaffected rivers that were also assessed. This grain size analysis corresponded with the specific land use in these areas, as exemplified by the sampling point in the Casca River, which featured a coarser sand-related grain size and was known for such activity.In summary, this research aimed to elucidate the extent to which human activities within a watershed can impact water quality and, consequently, sediment quality.
| SESSION: IronWedPM3-R2 | Assis International Symposium (9th Intl. Symp. on Advanced Sustainable Iron & Steel Making) |
| Wed. 29 Nov. 2023 / Room: Dreams 2 | |
| Session Chairs: Tateo Usui; Session Monitor: TBA | |
The depletion of reserves of high-quality primary ore raw materials (quartzite, bauxite), the upward trend in the cost of coke, etc., presupposes an integrated approach to the use of mineral raw materials and coal mining products. Involving coal mining waste in the metallurgical process is one of the promising directions for organizing the production of complex silicon and silicon-aluminum alloys based on the electrothermal properties of high-ash carbonaceous rocks. The content of basic oxides in the ash of carbonaceous rocks, as well as the price, allows us to consider it as a cheap source of the corresponding elements in the composition of complex ferroalloys. The purpose of this work is to develop a rational resource-saving technology for the smelting of ferrosilicoaluminum using carbonaceous rocks. The technology for smelting ferrosilicoaluminum involves the use of high-ash coal waste with minor additions of quartzite without the use of coke. The process of reduction of silicon and aluminum is provided by carbonaceous rock. Waste carbonaceous rocks with an ash content of
50-65% are a unique material and are a natural mixture of oxides of silicon, aluminum and carbon. The mineral component of the rocks is 92-96% composed of silicon, aluminum and iron oxides, and the sum of silicon and aluminum oxides is at least 89-90%. The content of SiO2 and Al2O3 in the ash part is in the range of 55-60% and 30-35%, respectively. Coal mass in rocks, depending on ash content. is 20-34% with a content of up to 15-18% volatile compounds. This composition of carbonaceous rocks guarantees the production of a silicon-aluminum alloy with a silicon content of 50-65%, aluminum 10-30% and the rest iron [1-3]. The alloy is smelted in ore-thermal electric furnaces with a constant loading of charge materials and periodic release of smelting products - alloy and slag, and the amount of slag does not exceed 3-5% of the weight of the alloy.
References:
[1] Baisanov S.O., Tolymbekov M.Zh., Takenov T.D. etc. Mastering the technology of electrothermal smelting of ferrosilicon aluminum from coal waste at Ispat-Karmet OJSC. Steel, 2000. No. 7. P. 28-30.
[2] Baisanov S.O., Tolymbekov M.Zh., Karemkov A.A. Chekimbaev A.F. Terlikbaeva A.K. New types of carbonaceous rocks for smelting ferrosilicon aluminum // Steel. 2008. No. 8. – P. 59-61.
[3] Tsymbal V.P., Bogomekov V.I., Tolymbekov M.Zh. and others. Efficiency of using ferrosilicoaluminum for steel deoxidation // Steel, 2000, No. 6. – P. 24
Following anode overpotential measurements and the derivation of the theoretical interrelationship between dissolved alumina concentration and cell voltage (constant current density) in the mid-1960’s, aluminium smelting technology cell designs shifted to central channel multi-point alumina feeding with two rows of prebaked anodes. While this enabled a dramatic reduction in perfluorocarbons (PFC) coevolution at the anodes. Since then cell sizes have necessarily increased from ~80 kA to near 600 kA. With two liquid layers a necessary design feature, spatial variations in process conditions have re-emerged due to the kinetics of alumina dissolution, and the limited electrolyte volume. This has re-introduced limited PFC co-evolution under some operating conditions. Simultaneously, because of other cell design features, zones of high sodium co-deposition in the aluminium have resulted. The higher sodium levels lower the faradaic efficiency from previous achievable levels, as well as dramatically reducing the cathode life. From “autopsies” of cells that been prematurely cut out or undergone “early failure” it becomes evident that a redesign of the cell, coupled with better choice of structural materials, is necessary if the modern technology is to again achieve low energy consumption and maximum environmental responsibility. Illustrative examples will be used.
| SESSION: IronThuAM-R2 | Assis International Symposium (9th Intl. Symp. on Advanced Sustainable Iron & Steel Making) |
| Thu. 30 Nov. 2023 / Room: Dreams 2 | |
| Session Chairs: Wilson Ferreira Santos Jr.; Session Monitor: TBA | |
The major thrust of global efforts to decarbonize global steel production aims at the transition from blast furnace/BOF steel production to electric furnace (EAF) steel production with the EAF fed by various combinations of DRI (direct reduced iron), HBI (hot briquetted iron), “green” pig iron and scrap. The challenges start with the observation that circa 60 % of global stee; production is in the Asia-Pacific area where most of the BF/BOF facilities are less than 15 years old; thus, too early for retirement (financially) and extend to the dominant Australia iron ore base that is not suitable for DRI/HBI shaft furnace use. For the rest of the world, the challenges include the CAPEX/OPEX requirements for high grade ore beneficiation, pellet plants, DRI/HBI plants and EAF facilities as well as the associated raw material challenges: iron ore quality, pellet availability, biomass consistency, scrap quality, and the cost of “green” reducing gas: H2 produced from renewable energy. The potential solutions to the above challenges will be outlined.
12:00: [IronThuAM02] OSA numerical simulation procedure is proposed for analyzing hydrogen, oxygen, and blast furnace gas (BFG) injections mixed with pulverized coal within the tuyeres of large blast furnaces. The massive use of hydrogen-rich gas is highly attractive to the steelmaking blast furnace in the context of carbon net-zero hot metal production. Likewise, this new approach allows for increasing productivity and decreasing the specific emissions of carbon dioxide toward a net-zero carbon ironmaking technology. Nevertheless, mixed gas with pulverized coal injections is a complex technology with drastic changes in the inner temperature and gas flow patterns, beyond their effects on the chemical reactions and energy exchanges. Focusing on the evaluation of inner furnace status under such complex operation a comprehensive mathematical model has been developed using the multi-interactions of phases theory. The model treats simultaneously the lump solids (sinter, small coke, pellets, granular coke, and iron ores), gas, liquids metal and slag, and pulverized coal phases. The governing conservation equations are formulated for momentum, mass, chemical species, and energy simultaneously discretized and solved using the finite volume technique. The numerical model is verified against a reference operational condition using pulverized coal of 195 kilograms per ton of hot metal (kg/thm). Thus, combined injections of varying fuel hydrogen, BFG, and oxygen concentrations are simulated for 180 and 220 kg/thm of coal injection. Theoretical analysis showed that stable operations conditions could be achieved with a productivity increase of 53%. Finally, we demonstrated that the net carbon utilization per hot metal ton decreased to 15%.
References:
[1] Castro JA, Takano C, Yagi J. A theoretical study using the multiphase numerical simulation technique for effective use of H2 as blast furnaces fuel. J. Mater Res Technol 2017; 6:258-270.
[2] de Castro JA, de Medeiros GA, de Oliveira EM. A Comprehensive Modeling as a Tool for Developing New Mini Blast Furnace Technologies Based on Biomass and Hydrogen Operation. J. Sustain. Metall. 2020; 6:281-293.
[3] de Castro JA, de Medeiros GA, de Oliveira EM, de Campos MF, Nogami H. The Mini Blast Furnace Process: An Efficient Reactor for Green Pig Iron Production Using Charcoal and Hydrogen-Rich Gas: A Study of Cases. Metals. 2020; 10(11): 1501-1522.
There is currently in the mining industry, as well as in other industries, a movement seeking to increase investments in decarbonization processes to help combat global warming. Among some initiatives taken is replacing diesel-powered mobile equipment in the mines with electricity-powered equipment, such as electric off-highway trucks or even belt conveyors in the mining operation. Samarco is a Brazilian mining company that, since its conception, has used a conveyor belt mining system in its mining operation, using only a small number of trucks to complement the mining process. This mining process that combines conveyor belts and trucks has brought environmental gains for the company, since the environmental impact of conventional truck-only mining is greater than that of the combined system. To measure these gains, a medium-term mining plan was developed in which two fleet scenarios were detailed. One scenario contemplated a high level of detail of belt mining seeking its maximization, while the other considered the operation performed 100% by trucks, eliminating the use of conveyor belts. Through the comparison of these two scenarios, it was possible to make an inventory of atmospheric emissions and greenhouse gases for each one of them, considering data such as types of equipment, diesel consumption, total distance travelled, and energy consumption. The results showed that the fleet scenario with conveyor belts results in periods with up to 15% less greenhouse gas emissions and 37% fewer total particulates compared to the truck-only scenario. Therefore, the results confirm the environmental benefits of the method and the need to look for ways to even expand it in future operations through a study to identify the potential areas in the long-term mining plan.
12:50: [IronThuAM04] OSThe shaft furnace known Midrex is used for the production of direct reduced iron with the use of reformed gas. Another process based on shaft reactors is the Tecnored process, which exhibits the great advantage of using self-reducing agglomerates. Therefore, it was proposed a combination of the shaft furnace for direct reduction with self-reducing pellet burden. In addition, with the aim of improving the furnace efficiency and reducing the need for reformed gas, the injection of natural gas and oxygen into the bustle region is proposed. Thus, it is possible to exploit the advantages of direct reduction involving high amounts of hydrogen and faster reactions of the self-reducing process to decrease the CO2 emission, compared to that of blast furnace. The energy profile, productivity, and carbon emission of the traditional shaft furnace were compared with the simulated results after partial replacement of the burden with self-reducing pellets containing fines of elephant grass charcoal. The simulation results for a combination of 15% of self-reducing pellets in the burden with 3.5% oxygen and natural gas injections were the best among the scenarios simulated, with the productivity being 2.9 ton/m3/day and the decrease in the amount of reformed gas being 18%.
References:
[1] Castro JA, Rocha EP, Oliveira EM, Campos MF, Francisco
AS. Mathematical modeling of the shaft furnace process
for producing DRI based on the multiphase theory. REM -
International Engineering Journal. 2018;71(1):81-87
| SESSION: IronFriAM1-R2 | Assis International Symposium (9th Intl. Symp. on Advanced Sustainable Iron & Steel Making) |
| Fri. 1 Dec. 2023 / Room: Dreams 2 | |
| Session Chairs: Marcos De Campos; Session Monitor: TBA | |
The large scale industrial processes involved in Iron and Steelmaking are very complex in nature and very much challenging to understand. A lot of modeling and simulation efforts have been made by numerous workers in the past to have an insight of the process and predict the behavior of the process due to changes in operating parameters and raw material conditions. The iron and steelmaking processes involve dynamic interaction between various phases namely slag, metal, gas and solid, existing altogether at very high temperatures, along with other coupled phenomena like dissolution of solid charge/scrap and fluxes. The overall modeling of such complex reactor involves chemical reaction thermodynamics calculations at interface as well as mass transport rates considering the nature and behavior of fluid flow and diffusion processes.Such complex process could be modeled very effectively by coupling of slag/metal, metal/gas and gas/solid reactions using multicomponent mixed transport-control theory [1]. In the overall sense, the thermodynamics and mass transport based kinetic limitations inside the reactor are integrated together in an intelligent manner depending upon the mixing behavior and mass transport characteristics across various regions inside the reactor. A multireactor-based approach and multicomponent mixed control method as explained above was used to model BOF Steelmaking process as well as MIDREX Process. The macro programming capability of FactSage [2] was used to program such models in an innovative manner which was also validated by using the data from Steel Plant (JSW Steel Ltd.). In BOF Steelmaking Process, This approach was used to study the decarburization rates and their contributions coming from the jet impact (hot-spot) zone, slag–metal–gas emulsion, and bath boiling for different levels of mixing in the metal bath by variation of other operating parameters [3,4]. In MIDREX Process the model was developed by considering the process as a counter current reactor consisting of multiple conceptual reactors. The fraction of gas being utilized in each reactor zone is estimated using the kinetic considerations of the process. The overall kinetic effect involving the effect of mass transfer control in the gas, and solid product, along with chemical reactions at the interface of the unreacted solid surface were considered. The model was used to predict the carbon content, production rate and metallization for the given set of input variables [5].This approach of modeling the large scale reactor process is very much effective tool as explained by the examples of BOF and MIDREX processes. The effect on CO2 emissions and energy consumption due to various possible changes in the process operating strategies, parameters and raw materials could be studied very effectively with the help of such innovative models where they may act as an efficient guiding tool.
References:
[1] Robertson, D.G.C.; Deo, B.; Ohguchi, S. Multicomponent Mixed-Transport-Control Theory for Kinetics of Coupled Slag/Metal and Slag/Metal/Gas Reactions: Application to Desulphurization of Molten Iron. Ironmak. Steelmak. 1984, 11, 41–56.
[2] FactSage. Center for Research in Chemical Thermodynamics, Polytechnique de Montreal, Canada. Available online: www.factsage.com
[3] Prasenjit Singha and Ajay Kumar Shukla, "Contribution of Hot-Spot Zone in Decarburization of BOF Steel-Making: Fundamental Analysis Based upon the FactSage-Macro Program", Metals, 2022, vol. 12(4),p. 638. https://www.mdpi.com/2075-4701/12/4/638/htm
[4] Prasenjit Singha and Ajay Kumar Shukla, "Dynamic Basic Oxygen Steelmaking Process and Its Industry Validation", JOM-Journal of Metallurgy, 2023, vol. 75, p. 3890–3899. https://link.springer.com/article/10.1007/s11837-023-06003-1
[5] Sunil Yadav, Srishilan C, and Ajay Kumar Shukla “Thermodynamic Model of MIDREX Ironmaking Process using FactSageTM and Macro Facility", Metallurgical and Materials Transactions B, 2023. (Accepted on September 20). https://link.springer.com/article/10.1007/s11663-023-02928-9
The dynamic process models reported so far in literature have ignored the fact that there are critical points of change over to chaotic dynamics during the progress of blow in a BOF. These critical points usually change the path of the blow profile and lead to either dry slag formation or slopping. The end point values of phosphorus, carbon and temperature may be severely affected by the occurrence or critical points. Hence it is of great practical importance to track these points online. A discrete dynamic analysis of the blow, while being tracked by a discrete surrogate model, helps to reveal the possibility of occurrence of the critical point in advance so that a proactive action can be taken in time to avoid the critical point altogether or better manage the situation with time. The “slopping” indicators based on sound measurement do help but are too late to act upon. Chaos control is necessary during the blow for control of phosphorus, carbon, and temperature at tap.
References:
[1] Fundamentals of Steelmaking Metallurgy, Brahma Deo and Rob Boom, Prentice Hall, London, 1993.
[2] Multicomponent mixed transport control theory for the kinetics of coupled slag-metal and slag-metal-gas reactions, D.G.C.Robertson, Brahma Deo and S.Ohguchi, Ironmaking and Steelmaking, 11 (1984), P 41-56.
[3] Mathematical model for computer simulation and control of steelmaking, Brahma Deo, P. Ranjan and A. Kumar, Steel Research, 58 (1987), P 427-431
[4] Characterization of slag-metal-droplet-gas emulsion in oxygen, steelmaking converters, Brahma Deo, A. Karamchetty, A. Paul, P.K.Singh and R.P.Chhabra, ISIJ Int. 36(1996), P 658-666.
[5] Control of slag formation, foaming, slopping, and chaos in BOF, Brahma Deo, Aart Overbosch, Bert Snoeijer, Debasis Das, Karumanchi Srinivas, Technical paper 2712, Trans IIM, 2013, 66(5-6)543-554
[6] Optimal operation of BOF under chaotic conditions, Brahma Deo,ASIA STEEL International Conference on February 6-9, 2018 at Bhubaneswar, Odisha, India
The steel industry provides large quantities of raw material for the society at the cost of large emissions of CO2, however, and thus contributing to the global warming. Therefore, it is imperative for the steel industry to undergo a transition to low-CO2 ironmaking technologies within the next 5-10 years. In order to reach sustainable ironmaking, recycled hydrogen as a reducing agent is the most promising path to follow [1], although the traditional blast furnace (BF) and its H2-intensive variant next to Midrex and Energiron will still play an important role during the transition process. However, independent of the applied technology, it is common understanding that a thorough knowledge of the governing process parameters is critical to the design, control and optimization. Experimental investigations are very limited due to harsh operating conditions and involved costs so that innovative simulation technologies are more than welcomed to gain a deeper insight into the underlying physics of these processes, for which the extended discrete element method (XDEM) has crystallised as the most promising road to follow [2]. It treats the iron bearing material and coke as a discrete phase with its descend in the reactor and thermodynamic state i.e. drying, reduction through carbon monoxide and hydrogen and melting of ore particles and coke oxidation while a coupling to traditional computational fluid dynamics (CFD) describes the fluid and thermodynamics in the void space between the particles including an exchange of momentum, heat and mass between the gas and particles. This versatile and unique technology allows applying XDEM to a large variety of ironmaking reactors to even represent them as digital twins and to support the transition to “green” steel. A thorough analysis of predicted uncovers the hidden complexity and contributes significantly to a deeper understanding and thus, promotes strongly a shift from current empirical-based practice to a truly advanced multi-physics simulation technology. Hence, information from digital twins is already available at an early stage of design avoids costly re-designs. Problems are identified before they even occur and down-times are reduced. These findings support decision-makers and help them to make informed decisions. Consequently, a faster time-to-discovery and time-to-solution is obtained.
References:
[1] Ma K, Deng J, Wang G, Zhou Q, Xu J. Utilization and impacts of hydrogen in the ironmaking processes: A review from lab-scale basics to industrial practices. International Journal of Hydrogen Energy. 2021;46:26646-64.
[2] B. Peters, M. Baniasadi, M. Baniasadi, The eXtented Discrete Element Method (XDEM): An Advanced Approach to Model Blast Furnace, ISBN 978-953-51-5824-0.
Sekisui Chemical has been developing technologies to efficiently convert CO2 to CO with Reverse Water Gas Shift (RWGS) reaction by Chemical Looping(CL).
Among the various CO2 utilization approaches, the RWGS reaction plays a pivotal role, since it produces synthesis gas (syngas or CO + H2), the building block of numerous conversion processes. Average CO generation yields are 40~60%1 with conventional RWGS. Introduction of metal oxide as an Oxygen Storage Material (OSM) would bring the RWGS reaction further by splitting the reaction itself into a reduction and oxidation reaction, referred to as a RWGS-CL, an intensified version of the conventional RWGS. By switching the gas flow between at least two reactors after the OSM is reduced or oxidised, respectively, a quasi-continuous process can be achieved, which is more efficient compared to the classical RWGS as it yields partially separated gas streams, simplifying the downstream gas separation. The CL technology developed by Sekisui has validated >90% CO yield and 80% H2 conversion at demonstration with blast furnace gas in Spain2, due to the non-equilibrium nature of the looping process, which can be employed to achieve high yield. This achievement is a result of NEDO's international joint research and development project (JPNP20005) in the field of clean energy.
In Japan, Sekisui Chemical has started a demonstration project to produce high-performance chemicals by combining this CO2 to CO technology with the downstream bio-process from waste incineration plants, and plans to start a sales business of these high-performance chemicals produced from CO2 derived from wastes in 20303. In addition, Sekisui has started collaboration with Tokai Carbon in Japan for the purpose of manufacturing CO2-derived carbon products using this CO2 to CO technology4.
By applying the CO2 to CO technology to CO2-containing waste gas in steelmaking process, Sekisui hopes to contribute to CCU and decarbonization in steel plants.
References:
[1] “The reverse water gas shift reaction: a process systems engineering perspective” M. González-Castaño, B. Dorneanu and H. Arellano-García. Reaction Chemistry and Engineering. Royal Society of Chemistry. March 2021.
[2] https://www.sekisuichemical.com/news/2023/1389171_40406.html
[3] https://green-innovation.nedo.go.jp/en/project/bio-manufacturing-technology/
[4] https://www.sekisuichemical.com/news/2023/1386378_40406.html
| SESSION: IronFriAM2-R2 | Assis International Symposium (9th Intl. Symp. on Advanced Sustainable Iron & Steel Making) |
| Fri. 1 Dec. 2023 / Room: Dreams 2 | |
| Session Chairs: Tateo Usui; Session Monitor: TBA | |
Phylum Mollusca is one of the richest phyla in living species [1]. Within this classification is the gastropod Melanoides tuberculata (O. F. Müller, 1774), with an operculum, which protects it from environmental weather [2]. One of the limiting factors for organisms is light, altering behavior, reproductive period and distribution [3].This study aimed to observe the effect caused to Melanoides tuberculata by different types of lamps.Samples of Melanoides tuberculata were sampled in Rio Grande, in Água Comprida/MG. In the laboratory, samples of five animals were separated in each aquarium with an approximate volume of 800 ml. The aquariums were aerated and the physical-chemical parameters of the water. Each of the six aquariums was subjected to a different type of light, one of which was designated as a control. The other treatments were UV lamp C; Ultraviolet lamp A; Incandescent lamp; Cool white compact fluorescent lamp and Warm white compact fluorescent lamp.The physical-chemical parameters showed variations between treatments, but these were not significant. The Incandescent Lamp seems to have favored primary production. Animal survival varied significantly between treatments. When using the parametric test for analysis of variance, comparing the means of treatments; a “p” value equal to 0.000 was obtained, indicating a probability of less than one millionth that the differences were due to chance. Treatment with the UVC lamp determined the death of all animals. On the other hand, the treatment with the highest survival rate was the treatment with a warm white compact fluorescent lamp.
References:
[1] A. Pelli, F. M. SANTOS, S. A. Abrão, P. R. S. Camargo, N. P. U. Barbosa, P. S. Assis. Efeitos de lâmpadas, com diferentes comprimentos de onda, sobre o molusco gastrópode Physa acuta. Research, Society and Development, 11 (2022), e53311932126
[2] H. A. Pinto, A. L. Melo. Distribuição temporal de Melanoides tuberculata (Mollusca: Thiaridae) naturalmente infectados por Centrocestus formosanus (Trematoda: Heterophyidae) no Brasil. Lundiana 11 (2013) 79-82
[3] P. S. Assis, A. Pelli, G. A. Gois, A. C. Carvalho, G. S. Araújo. Ultrasonic waves for the control of Limnoperna fortunei – the golden mussel. Concilium, 23 (2023) 364–382
The growing world population, climate change, and geopolitical disruptions are major and global challenges of today. Consequently, governments and the private sector increasingly work towards responsible and sustainable development strategies to address climate change. These initiatives commonly recognize the importance of metals in the green transition, industry decarbonization, resource conservation. Steel is the most abundant construction material that plays a crucial role in the energy transition, infrastructure, mobility, and living standards in all regions. However, the annual cost of corrosion, estimated at US $2.2 trillion by the World Bank, is over 3% of the world’s GDP. Via galvanizing, zinc provides the most cost-effective protection for steel, decreasing overall lifetime maintenance costs and resource needs (raw material and energy) by multiplying the durability of steel constructions. As a result, steel and zinc are closely interwoven at product level and in their recycling loops. When galvanized steel is recycled, both materials become available via mature recycling routes.Innovations in galvanized steel production and use require flexibility and innovations. This relates to products as well as to production and recycling: Through joint projects such as the International Zinc Association’s Galvanized Autobody Partnership, both industries ensure that galvanizing technology advances hand in hand with innovations in steel production. Similarly, the durability of galvanized rebar used in concrete reinforcement provides increased safety for transportation and construction in corrosive environments (e.g., roadway deicing, offshore/coastal windfarms). The steel and the zinc sector both have developed decarbonization roadmaps. Impactful changes are under way that will result in technological changes in steel production. The zinc industry will work with the steel industry on identifying opportunities for increased recycling while decarbonizing both sectors. The paper will provide an overview of sustainable production, use and recycling practice for zinc in its use as corrosion protection for steel. This includes decarbonization, mitigating effects of climate change, circularity, and responsible sourcing. Examples from sustainable production at Hindustan Zinc Ltd. round off the paper.
References:
[1] S. Grund, E. van Genderen, M. van Leeuwen: „Decarbonizing the zinc industry while maximizing zinc circularity”, proceedings of EMC 2023
[2] S. Grund, E. van Genderen: “Life Cycle Assessment and Carbon Footprint for SHG Zinc Production”, submitted for publication in proceedings of PbZn 2023
[3] L. Rostek, E. Pirard, A. Loibl: “The long-term availability of zinc: Potential contributions from recycling and necessary ones from mining”, Resources, Conservation & Recycling Advances 19 (2023) 200166
[4] L. Rostek, L.A. Tercero Espinoza, D. Goldmann, A. Loibl: “A dynamic material flow analysis of the global anthropogenic zinc cycle: Providing a quantitative basis for circularity discussions”, Resources, Conservation & Recycling 180 (2022) 106154
The role of mathematical models in improving the technology of blast furnace melting is shown [1]. Examples of new developments of the Institute of Metallurgy of the Ural Branch of the Russian Academy of Sciences in the field of digital models of blast furnace production are given, in particular, two-dimensional and three-dimensional mathematical models of the thermal state of various zones of the blast furnace [2, 3]. New developments in the field of analysis and control of various thermophysical and physico-chemical phenomena occurring in various zones of the blast furnace allow us to raise the technology and methods of conducting blast furnace melting to a fundamentally new level, allowing us to save fuel and energy resources. The possibility of using a digital model at a pace with the process when using sensor readings through the database management system of the blast furnace shop of the enterprise is shown.
References:
[1] A.N. Dmitriev. Mathematical modeling of the blast furnace process. Cambridge: Cambridge Scholars Publishing Ltd, 2019. – 330 p.
[2] A.N. Dmitriev, Zolotykh M.О., G.Yu. Vitkina Perfection of sinter, coke and blast furnace production by application of digital technologies within the frame of “Industry 4.0” concept. Ferrous Metallurgy. Bulletin of Scientific, Technical and Economic Information. 2020; 76(4):339-343.
[3] A.N. Dmitriev, Ya.M. Gordon, M.O. Zolotykh, G.Yu. Vitkina Mathematical Modeling and Practical Tasks Solution of Blast Furnace Smelting / AISTech 2016 Proceedings. © 2016 by AIST. P. 3141-3146.
This paper considers the possibility of using and improving the mathematical model of heat exchange of the blast furnace process, taking into account the injection of synthesis gas (with different amounts of hydrogen in it) [1-3]. The analysis of existing models of heat exchange of a blast furnace is carried out and arguments are given justifying the need to take into account the characteristics of synthesis gas in the model. In a blast furnace, additional hydrogen in synthesis gas can be used as a partial replacement for coke, which will reduce the amount of carbon dioxide emissions into the atmosphere and increase the energy efficiency of the process. The use of synthesis gas in a blast furnace has a number of advantages and disadvantages. However, when analyzing the current environmental situation, it should be noted that the technology of using synthesis gas has great prospects. Calculations based on the improved model showed a more accurate assessment of the heat transfer characteristics in the blast furnace process when using synthesis gas. The results of the study can be used to effectively optimize the parameters of technological processes in blast furnace production.
References:
[1] A.N. Dmitriev. Mathematical modeling of the blast furnace process. Cambridge, UK, Cambridge Scholars Publishing Ltd. 209 p. ISBN 1-5275-4053-7, ISBN 978-1-5275-4053-8.
[2] A.N. Dmitriev, M.O. Zolotykh, G.Y. Vitkina, R.V. Alektorov, Yu.E. Burova. State Registration Certificate № 2022665099 IMMDP (Institute of Metallurgy Model of Domna Process). Applicant and patent holder: Institute of Metallurgy of the Ural Branch of the Russian Academy of Sciences (IMET UB RAS) (RU); № 2022663874; declaration: 22.07.2022; publ.: 09.08.2022.
[3] M.S. Yalunin, G.Y. Vitkina, A.N. Dmitriev, M.O. Zolotykh, R.V. Alektorov. Estimation of influence of gas-reducer with high hydrogen fraction on efficiency of blast furnace melting. Proceedings of X All-Russian Scientific-Practical Conference of Students, Postgraduate Students and Young Scientists "Thermal Engineering and Informatics in Education, Science and Production" with international participation, 19-20 May, 2022. Russia, Ekaterinburg, 2022. P. 185-190.
| SESSION: IronFriPM1-R2 | Assis International Symposium (9th Intl. Symp. on Advanced Sustainable Iron & Steel Making) |
| Fri. 1 Dec. 2023 / Room: Dreams 2 | |
| Session Chairs: Vladimir Tsepelev; Session Monitor: TBA | |
Nanocrystalline magnetically soft materials were discovered by Yoshizawa, Yamauchi and Oguma in 1986 [1, 2]. This was preceded by numerous research and development of amorphous magnetically soft materials, beginning in 1960. In order to obtain an amorphous structure, ultrafast quenching of a metallic melt with a cooling rate of about 106 K/s is used. Under industrial conditions, amorphous tape with a thickness of about 20 μm is produced using the flat jet method [3]. In scientific research, the amorphous Fe-B alloy is widely used in which boron acts as an element that promotes amorphization. For industrial purposes the Fe-Si-B alloy [4] is more suitable, in which silicon is additionally introduced to increase the crystallization temperature and reduce the coercive force.
The study of multicomponent melts shows that the structures of liquid and solid states are interrelated. The most homogeneous structure has the melt heated above the critical temperature, which corresponds to the temperature of structural transformations. Amorphous precursor obtained from homogeneous melt has greater ductility and hardness, higher enthalpy of crystallization. After nanocrystallization of the amorphous precursor obtained from the superheated melt, a material with higher permeability was obtained, which can be attributed to the increased proportion of small nanocrystals of about 2 nm.
Production of magnetic systems from nanocrystalline materials can be divided into several technological operations [5]. The initial operation is the melting of an alloy of a given chemical composition. This is followed by superfast quenching of the melt to form an amorphous precursor in the form of a ribbon with a thickness of about 20 nm. Thermal processing of the amorphous precursor should ensure the formation of a nanocrystalline structure with a guaranteed level of magnetic properties. As a rule, a magnetic curcuit or core is made from the amorphous precursor beforehand. In this paper the physical properties of nanocrystalline alloys in the liquid state, the influence of chemical composition on the nanocrystallization process, magnetic properties, in particular magnetic losses, and the application of magnetically soft nanocrystalline alloys, mainly for power electronics, are discussed.
References:
[1] Yoshizawa, Y.; Yamauchi, K.; Oguma, S. Fe-base soft magnetic alloy and method of producing same. US Patent 4881989 1989, Nov. 21, Priority Japan 61-297838 1986, Dec. 15.
[2] Yoshizawa, Y.; Oguma, S.; Yamauchi, K. New Fe-based soft magnetic alloys composed of ultrafine grain structure. J. Appl. Phys. 1988, 64, 6044–6046, doi:10.1063/1.342149.
[3] Narasimhan, M.C. Continuous casting method for metallic strips. US Patent 4142571 1979, Mar. 6, Priority 1977, Aug. 2.
[4] Luborsky, F.E.; Becker, J.J.; Walter, J.L.; Liebermann H.H. Formation and magnetic properties of Fe-B-Si amorphous alloys. IEEE Trans. Magn. 1979, 15, 1146–1149, doi:10.1109/TMAG.1979.114870.
[5] Starodubtsev, Yu.N. Physical properties and application of soft magnetic materials, Hotline–Telecom, Moscow, 2020; pp. 244–249.
Sinter Plant is a major contributor towards Emission of Suspended Particulate Matter(SPM) in an Integrated Steel Plant[1]. Over the past decade, Sinter Plants at Tata Steel Jamshedpur (TSJ) have pioneered innovation starting from Raw Material handling, ESP (Electrostatic Precipitator) maintenance and health monitoring, leading to achieving benchmark level stack reductions[2]. Our journey from 425 kg/hr in FY’12 to < 100 kg/hr in FY’23 involved operational excellence, strategic maintenance practices and digital innovations including pioneering efforts in AI-ML. This paper elucidates the expedition of TSJ Sinter Plants in lowering dust concentration from stack from >75 mg/Nm3 levels to below 30 mg/Nm3. This was achieved by establishing process innovations, control in raw material consumption and quality, enhancing maintenance monitoring of ESPs, and the use of HFTR (High Frequency Transformer Rectifier) units in sinter making. The strategy employed in TSJ plant revolves around three main pillars – People, Process & Technology. In the people front, level of awareness, alertness and responsible behaviour was inculcated by special training, incentive schemes and building a sense of belongingness to the problem. In the Process part, extensive use of research, understanding the cause of higher stack emission was done at the beginning. Big data analytics was applied on long term data showed that ESP inlet temperature, Temperature at Wind Box#10, ESP inlet suction etc played a big role. Accordingly process control loops were designed and implemented through algorithms based on statistical models and thermodynamic models. This unique feature of integrating the above models gave prediction of stack emission to the tune of >95% accuracy. Finally, this predictive models led to installation of some technological advances, such as HFTR, MFTR transformers. TSJ plant also developed a novel use of ESP dust, which was eliminated from its recycling to the sinter making process. As a result of the above three pronged strategy, the stack emission concentration could be reduced to a level of below 15 mg/Nm3, which is perhaps comparable to the World Benchmark for plants employing ESP only as waste gas dedusting method. TSJ has embarked on some more innovative technology, which will reduce the stack dust concentration below 10 mg/Nm3 with ESP alone. The paper will elucidate the complete journey and a success story of more than a decade, which will be worth sharing with the world.
References:
[1] Applied Electrostatic Precipitation, Edited by Ken Parker
[2] Investigation of the Contents of the Stack Emissions of Iron, VB Angalakuditi
Brazil is one of the largest steel producers in the world, occupying the ninth position in the world ranking, with 1.8% of all world production (WORLD STEEL ASSOCIATION, 2022). The Brazilian production of crude steel in the year 2022 consumed around 34.1 million tons, 23.75% of which was produced using the electric melt shop method (INSTITUTO AÇO BRASIL, 2022). The increasing production of steel results in an increase in waste generation, since slag and PAE have fundamental functions in the steel manufacturing process, in order to guarantee good quality to the final product. These two by-products were considered of little or no value to the industry, and with the increase in production and the need for possible alternatives, adding value to these residues became necessary for the development of new markets. Electric melt shop dust (EAP) is generated during electric arc furnace (EAF) operation as a by-product of steel making. The high temperature used in the process for melting and refining the raw material (~1600°C) causes volatile elements, such as zinc, to volatilize and subsequently oxidize inside the furnace, producing metallic oxides in the form of particulate matter. Non-volatile elements, slag and additives, can be ejected from the liquid/gas interface by exploding carbon monoxide bubbles. Then, these can be oxidized and dragged by the gases generated in the process, being collected as dust in the dedusting system, normally through bag filters. Under such conditions, the various metal oxides can combine to form different compounds. As a result of these factors, the EAP undergoes a series of physical and chemical phenomena by which substances that give rise to the EAF powder are considered (PICKLES; MARZOUGHI, 2018; HOSSEINI et al., 2016).
References:
[1] Guézennec AG, Huber JC, Patisson F, Sessiecq P, Birat JP & Ablitzer D (2005) Dust 79 formatnio in electric arc furnace: Birth of the particles. Powder Technology 157: 2 – 11.
[2] S. Hosseini, S.M. Soltani, P.S. Fennell, S.Y. Thomas, M.K. Aroua. Production and applications of electric-arc-furnace slag as solid waste in environmental technologies : a review. Environ. Technol. Rev., 5 (2016), pp. 1-14.
[3] Pickles, C.A., Marzoughi, O., 2018. Thermodynamic investigation of the sulphation roasting of electric arc furnace dust. Minerals 9, 18. https://doi.org/10.3390/ min90100.
| SESSION: NanomaterialsTueAM-R3 | Echegoyen International Symposium (8th Intl. Symp. on Synthesis & Properties of Nanomaterials for Future Energy Demands) |
| Tue. 28 Nov. 2023 / Room: Dreams 3 | |
| Session Chairs: Dirk Michael Guldi; Fred Wudl; Session Monitor: TBA | |
Following a brief introduction about the background and some personal details, a scientific history of the research work during the years will be presented along the method used to approach new and emergent areas. A scientific timeline will be presented starting from early academic career to the most recent activity and covering many research fields from supramolecular chemistry to fullerene electrochemistry and endohedral fullerene structures. Life learned lessons will also be described.
12:00: [NanomaterialsTueAM02] OS Plenary“Plastics are a large group of synthetic organic materials whose common quality is that they can be molded into desired shapes—and they are now everywhere.”….“But plastics are now most indispensable in health care in general and in hospitals in particular. Life now begins (in maternity wards) and ends (in intensive care units) surrounded by plastic items made above all from different kinds of PVC: flexible tubes (for feeding patients, delivering oxygen, and monitoring blood pressure), catheters, intravenous containers, blood bags, sterile packaging, trays and basins, bedpans and bed rails, thermal blankets.” [1]
At the beginning of the XX century, with the exception of diamond, materials science was absolutely dominated by inorganic solids. This was the case, even though Bakelite had been patented in 1907. By mid-century organic engineering materials were rapidly finding applications as phone housings and radio housings, pens, mechanical pencils, circuit boards, etc. A whole art deco field in the arts, crafts and architecture was fueled by plastics from the 1920’s on. [2] Toward the end of the XX century, implements that relied solely on cement and metals, such as airplanes, automobiles and vehicle bridges were being made out of plastics (thermosets) and even recycled plastics. [3].
The subtler area of materials science, electronics, was governed by silicon and, to a lesser extent, germanium. Organic electrical conductors were slowly being developed towards the end of the century, receiving a strong impetus with the appearance of organic metals, superconductors and semiconductors, as well as the preparation of polyacetylene and other semiconductor polymer films and the discovery that they could be coaxed to increase their conductivity upon oxidation or reduction (doping). [4]
In this presentation the emphasis will be on the electrical conductivity of organic materials and their technological applications such as light emitting diodes, photovoltaics, thermoelectrics and batteries.
References:
[1] How the World Really Works by Smil, Vaclav Viking, an imprint of Penguin Publishing Group, a division of Penguin Random House, LLC
[2] Art deco https://www.decolish.com/bakelite.html
[3a] http://www.axionsi.com/wp-content/uploads/2016/05/Worlds-First-Thermoplastic-Bridges-KIM-CHANDRA-metric.pdf. [b] HDHMWPE https://www.orencocomposites.com/prefab-bridges?gclid=CjwKCAjw3ueiBhBmEiwA4BhspHA1IlBMxnBm5_VlNoQlDGJdAatYUrQm4gusPgya7QGzHzN6_Rvz3RoC-R0QAvD_BwE
[4] Klauk, Hagen (Ed.) Organic electronics. More materials and applications 2010, Wiley-VCH, Weinheim. ISBN 9783527640218 electronic bk.
“Plastics are a large group of synthetic organic materials whose common quality is that they can be molded into desired shapes—and they are now everywhere.”….“But plastics are now most indispensable in health care in general and in hospitals in particular. Life now begins (in maternity wards) and ends (in intensive care units) surrounded by plastic items made above all from different kinds of PVC: flexible tubes (for feeding patients, delivering oxygen, and monitoring blood pressure), catheters, intravenous containers, blood bags, sterile packaging, trays and basins, bedpans and bed rails, thermal blankets.” [1]
At the beginning of the XX century, with the exception of diamond, materials science was absolutely dominated by inorganic solids. This was the case, even though Bakelite had been patented in 1907. By mid-century organic engineering materials were rapidly finding applications as phone housings and radio housings, pens, mechanical pencils, circuit boards, etc. A whole art deco field in the arts, crafts and architecture was fueled by plastics from the 1920’s on. [2] Toward the end of the XX century, implements that relied solely on cement and metals, such as airplanes, automobiles and vehicle bridges were being made out of plastics (thermosets) and even recycled plastics. [3].
The subtler area of materials science, electronics, was governed by silicon and, to a lesser extent, germanium. Organic electrical conductors were slowly being developed towards the end of the century, receiving a strong impetus with the appearance of organic metals, superconductors and semiconductors, as well as the preparation of polyacetylene and other semiconductor polymer films and the discovery that they could be coaxed to increase their conductivity upon oxidation or reduction (doping). [4]
In this presentation the emphasis will be on the electrical conductivity of organic materials and their technological applications such as light emitting diodes, photovoltaics, thermoelectrics and batteries.
References:
[1] How the World Really Works by Smil, Vaclav Viking, an imprint of Penguin Publishing Group, a division of Penguin Random House, LLC
[2] Art deco https://www.decolish.com/bakelite.html
[3] (a)http://www.axionsi.com/wp-content/uploads/2016/05/Worlds-First-Thermoplastic-Bridges-KIM-CHANDRA-metric.pdf. [b] HDHMWPE https://www.orencocomposites.com/prefab-bridges?gclid=CjwKCAjw3ueiBhBmEiwA4BhspHA1IlBMxnBm5_VlNoQlDGJdAatYUrQm4gusPgya7QGzHzN6_Rvz3RoC-R0QAvD_BwE
[4] Klauk, Hagen (Ed.) Organic electronics. More materials and applications 2010, Wiley-VCH, Weinheim. ISBN 9783527640218 electronic bk.
Conventionally, noble metal nanoparticles, such as gold are synthesized using a reducing agent like sodium borohydride (NaBH4) or sodium citrate at elevated temperatures and alkaline pH, with stabilizers added to control the size and dispersion of the nanoparticles [1]. While sodium citrate is sometimes used as a single reducing and stabilizing agent, it is limited in the range of gold nanoparticle sizes that can be obtained [2]. Fullerenes and polyhydroxy fullerenes have been coated on gold nanoparticles as they can impart excellent electronic properties in addition to providing stability [3, 4].
We have discovered that polyhydroxy fullerenes (PHF) can act as a single reducing and stabilizing agent by simple mixing of the gold chloride with PHF at room temperature [5]. The gold nanoparticles obtained are monodisperse as characterized by dynamic light scattering and high resolution-transmission electron microscopy. The size of gold nanoparticles is controllable by changing to ratio of reactants and range from 1 nm gold nanoclusters to 100 nm nanoparticles. We studied the mechanism of nanoparticle formation with PHF and proposed a three step process. In the first step, electrostatic attraction between negatively charged PHF and gold cations lead to formation of agglomerate. In the second step, PHF reduces gold cations and formation of Au-O-PHF bonds were detected by electron energy loss spectroscopy and x-ray photoelectron spectroscopy. In the third step, agglomerates containing gold nanoparticles disperse to yield monodisperse colloid. The gold nanoparticles obtained with method is stable for at least 2 years.
The novel PHF-mediated synthesis method can also be applied to other noble metals. The surface PHF coating on noble metal nanoparticles integrates the properties of both metal and carbon nanoparticles, resulting in superior functional applications. Our findings open up new opportunities for metallic nanoparticle preparation methods, properties, and applications.
References:
1. De Souza, C.D., B.R. Nogueira, and M.E.C.M. Rostelato, Review of the methodologies used in the synthesis gold nanoparticles by chemical reduction. Journal of Alloys and Compounds, 2019. 798: p. 714-740.
2. Al-Johani, H., et al., The structure and binding mode of citrate in the stabilization of gold nanoparticles. Nature Chemistry, 2017. 9(9): p. 890-895.
3. Bończak, B., et al., Gold Nanoparticles Functionalized with Fully Conjugated Fullerene C60 Derivatives as a Material with Exceptional Capability of Absorbing Electrons. The Journal of Physical Chemistry C, 2019. 123(10): p. 6229-6240.
4. Kokubo, K., et al., Gold Nanoparticles Stabilized by Molecular Fullerenols. ChemNanoMat, 2020. 6(4): p. 524-528.
5. Krishna, V., Functionalized fullerene metal nanocomposites. USPTO, 2022. US11267708
| SESSION: NanomaterialsTuePM1-R3 | Echegoyen International Symposium (8th Intl. Symp. on Synthesis & Properties of Nanomaterials for Future Energy Demands) |
| Tue. 28 Nov. 2023 / Room: Dreams 3 | |
| Session Chairs: Marta Plonska Brzezinska; Yuhuang Wang; Session Monitor: TBA | |
The goal of our studies is to apply carbon nanostructures, referred to as multi-layered fullerenes or carbon nanoonions (CNOs), for the controlled organization of resins [1], polymeric chains [2],[3] or triazines [4],[5], which, as a consequence, are a significant force for the ordered organization of pores within the synthesized materials. The critical role of using CNOs to design nanocomposites is in achieving high-quality modification of the 3D architecture and organization of the porous structure in such a way that the obtained materials possess an orderly distribution of pores and a homogenous pore size distribution (micro, meso and macro). The presence of micropores in porous materials results from the surface properties of the carbon nanoparticles. Bigger pores, such as meso and macropores, arise mainly from crosslinking of the oligomeric/polymeric chains or triazines. Incorporating functionalized CNOs leads to organized polymerization or formation of triazine skeleton in a three-dimensional manner. Therefore, the suitable choice of substrate structure enables further control of the meso and macroporosity of the porous nanocomposites. These parameters can be consciously controlled by selecting appropriate components and their percentage composition in the final mixture. A synergistic effect of both components may be observed, creating a material with new and unusual porosity superior to using one type of pore.
The best electrochemical performances were obtained when using the nitrile-functionalized pyrrolo[3,2-b]pyrrole unit to form triazine rings. The synthesis relies on forming a triazine ring as a covalent bond between organic building blocks to achieve covalent triazine-based frameworks (CTFs) with specific diameters forming a porous framework. CTFs constitute an emerging class of high-performance materials due to their porosity and the possibility of structural control at the molecular or atomic level. However, using CTFs as electrodes in supercapacitors is hampered by their low electrical conductivity and a strong stacking effect between adjacent CTF sheets. Therefore, we covalently immobilized triazine-based structures on CNOs to organize pores three-dimensionally.
Combining CNOs with the triazine framework produced a material with unique physicochemical properties, exhibiting the highest specific capacitance value of 638 F/g in aqueous acidic solutions. It should be emphasized that the specific capacitance value for hybrids was 1.5-2 times higher than that for the CTF reference. We examined the factors responsible for such a significant increase in electrochemical efficiency. This phenomenon is attributed to many factors. The material exhibits a large surface area, a high micropore content, a high graphitic N, and N-sites with basicity and semi-crystalline character. Thanks to the high structural organization and reproducibility and remarkably high specific capacitance, these systems are promising materials for use in electrochemistry. For the first time, hybrid systems containing triazine-based frameworks and CNOs were used as electrodes for supercapacitors.
The studies were performed under the financial support of the National Science Centre, Poland, grants #2017/25/B/ST5/01414 and #2019/35/B/ST5/00572 to M.E.P-B.
References:
[1] G. Siemiaszko, J. Breczko, A. Hryniewicka, A. Ilnicka, K. H. Markiewicz, A. P. Terzyk, M. E. Plonska-Brzezinska, Sci Rep 2023, 13, 6606.
[2] G. Siemiaszko, A. Hryniewicka, J. Breczko, O. F. Delgado, K. H. Markiewicz, L. Echegoyen, M. E. Plonska-Brzezinska, ACS Appl. Polym. Mater. 2022, 4, 2442–2458.
[3] G. Siemiaszko, A. Hryniewicka, J. Breczko, K. Brzezinski, M. E. Plonska-Brzezinska, Chem. Commun. 2022, 58, 6829–6832.
[4] A. Hryniewicka, J. Breczko, G. Siemiaszko, A. Papathanassiou, K. Góra-Marek, K. Tarach, K. Brzezinski, A. Ilnicka, A. Terzyk, K. Markiewicz, L. Echegoyen, M. Plonska-Brzezinska, Pyrrolo[3,2-b]Pyrrole-Based Covalent Triazine Framework: Three-Dimensional Organization of Pores Using Nanostructural Spherical Carbon, Chemistry, 2022.
[5] A. Hryniewicka, J. Breczko, G. Siemiaszko, K. Brzezinski, A. Ilnicka, A. Terzyk, M. Plonska-Brzezinska, Hierarchical Porosity of Hybrid Carbon Nanomaterials Based on a Covalent Triazine Framework for High-Performance Capacitive Energy Storage, Chemistry, 2022.
Carbon materials have played an essential role in the development of lithium-ion batteries enabling transformative technologies including portable electronics, remote sensors, flying cars and electric vehicles. To meet the growing demand of the energy storage market, next generation batteries must provide dramatically increased capacity and cycling life, operate reliably, fast and safe, at reduced size and weight. Carbon nanomaterials hold great potential in offering a viable solution to these challenges. This talk will discuss current trends in the design of graphene and carbon nanotubes for batteries with high energy and power densities with extended cycling stability. Engineering porous graphene structures with low tortuosity for fast ion transport and chemical modification of the graphene surfaces for increased lithiophilicity are industrially scalable strategies to increase capacity, improve cycle life while simultaneously enhance rate capability and eliminate dendrite formation in batteries.
14:55: [NanomaterialsTuePM107] OS InvitedMetal single atoms in nitrogen doped carbon materials (M-NC) have attracted plenty of attention during the last decades in the field of electrocatalysis for oxygen reduction and carbon dioxide conversion amongst others. In the cathode of proton exchange membrane fuel cells Fe-NC are the most promising solution to scarce and expensive Platinum-group-metal catalysts,[1] and in the cathode of CO2 conversion electrolysers, Fe and Ni-NC are predicted to be as active as Au or Ag.[2] However, their controlled synthesis and stability for practical applications remains challenging. Approaches to enhancing their catalytic performance include increasing the loading of Fe single atoms, for example by decoupling high temperature pyrolysis and Fe coordination atoms, or enhancing the intrinsic activity of the FeNx sites, for example by engineering of coordination environment or creation of dual atom catalysts.[3–5] However, the metal utilization within these materials remains very low owing to the lack of scaffolds that combine adequate micro- and mesoporosity.
In this work we employ inexpensive 2,4,6-Triaminopyrimidine (TAP) with MgCl2.6H2O as porogen to prepare a highly porous N-doped carbon material.[6] The hydrogen bonding between nitrogen moieties of TAP and the water molecules of the Mg salt allows an optimal interaction during pyrolysis that leads to remarkable porosity in the nitrogen-doped material (~3300 m2 g-1) and very available N sites for Fe or Ni coordination. The subsequent low temperature metal coordination (Figure 1) results in a highly active O2 reduction to electrocatalyst with a mass activity 4.0 A g-1 at 0.8 VRHE in acid electrolyte, and one the highest turnover frequency for CO2 reduction reported to date for M-NC materials.[7] Additionally in-situ nitrite stripping reveals a high active site density of >2×1019 sites g-1; and a electrochemical active site utilisation of 52% and 76% for Fe and Ni-NC, respectively, up to our knowledge the highest reported to date. Aberration corrected high-angle annular dark field scanning transmission electron microscopy, time-of-flight secondary ion mass spectrometry, X-ray absorption extended fine structure and density functional theory calculations were employed to assess the electrochemical stability and the intrinsic activity of the active sites.
References:
[1] F. Jaouen, D. Jones, N. Coutard, V. Artero, P. Strasser, A. Kucernak, Johnson Matthey Technol. Rev. 2018, 62, 231.
[2] A. S. Varela, N. Ranjbar Sahraie, J. Steinberg, W. Ju, H.-S. Oh, P. Strasser, Angew. Chemie Int. Ed. 2015, 54, 10758.
[3] A. Pedersen, J. Barrio, A. Li, R. Jervis, D. J. L. Brett, M. M. Titirici, I. E. L. Stephens, Adv. Energy Mater. 2022, 12, 2102715.
[4] A. Mehmood, M. Gong, F. Jaouen, A. Roy, A. Zitolo, A. Khan, M. Sougrati, M. Primbs, A. M. Bonastre, D. Fongalland, G. Drazic, P. Strasser, A. Kucernak, Nat. Catal. 2022, 5, 311.
[5] J. Barrio, A. Pedersen, J. Feng, S. C. Sarma, M. Wang, A. Y. Li, H. Yadegari, H. Luo, M. P. Ryan, M.-M. Titirici, I. E. L. Stephens, J. Mater. Chem. A 2022, 10, 6023.
[6] J. Barrio, A. Pedersen, S. C. Sarma, A. Bagger, M. Gong, S. Favero, C.-X. Zhao, R. Garcia‐Serres, A. Y. Li, Q. Zhang, F. Jaouen, F. Maillard, A. Kucernak, I. E. L. Stephens, M.-M. Titirici, Adv. Mater. 2023, 35, 2211022.
[7] S. C. Sarma, J. Barrio, A. Bagger, A. Pedersen, M. Gong, H. Luo, M. Wang, S. Favero, C.-X. Zhao, Q. Zhang, A. Kucernak, M.-M. Titirici, I. E. L. Stephens, ChemRxiv 2023.
Defects in solids, including semiconducting single-walled carbon nanotubes, have recently gained significant interest as atomic traps for electrons, excitons, and their quantum coupling. The covalent bonding of organic functional groups to the sp2 carbon lattice creates molecularly tunable sp3 quantum defects with unique properties and potential applications in various fields. Unlike native defects, which usually quench exciton photoluminescence, synthetic defects in single-walled carbon nanotubes fluoresce brightly in the shortwave infrared, producing single photons at room temperature. Known as "organic color centers," these quantum defects have opened up exciting opportunities for researchers in chemistry, physics, materials science, and biomedical engineering. In this talk, I will discuss recent progress in this emerging field of synthetic quantum defects, focusing on the unique properties and potential applications of organic color centers in semiconducting single-walled carbon nanotubes. The talk will highlight the exciting opportunities these quantum defects offer and will provide insight into the rapidly expanding research and applications of these fascinating quantum systems.
References:
1. Brozena, A.; Kim, M.J.; Powell, L. R.; Wang, Y. H.. Nature Reviews Chemistry 2019, 3, 375–392.
2. Wang, Y. H. Science 2022, 377, 473-474.
3. Qu, H.; Wu, X.; Fortner, J.; Kim, M.; Wang, P.; Wang, Y.H. ACS Nano 2022, 16, 2, 2077–2087.
4. Wang, P.; Fortner, J.; Luo, H.; Kłos, J.; Wu, X.; Qu, H.; Chen, F.; Li, Y.; Wang, Y.H. J. Am. Chem. Soc. 2022, 144, 29, 13234-13241.
5. Wu, X.J.; Kim, M.J.; Qu, H.; Wang, Y.H. Nature Communications 2019, 10: 2672.
6. Kwon, H.; Furmanchuk, A.; Kim, M.; Meany, B.; Guo, Y.; Schatz, G. C.; Wang, Y.H. J. Am. Chem. Soc. 2016, 138, 6878-6885
7. Piao, Y. M.; Meany, B.; Powell, L. R.; Valley, N.; Kwon, H.; Schatz, G. C.; Wang, Y. Nature Chemistry 2013, 5, 840-845.
| SESSION: NanomaterialsTuePM2-R3 | Echegoyen International Symposium (8th Intl. Symp. on Synthesis & Properties of Nanomaterials for Future Energy Demands) |
| Tue. 28 Nov. 2023 / Room: Dreams 3 | |
| Session Chairs: Dirk Michael Guldi; Steven De Feyter; Session Monitor: TBA | |
Carbon is the key to many technological applications that have become indispensable in our daily life. Altering the periodic binding motifs in networks of sp3-, sp2-, and sp-hybridized C-atoms is the conceptual starting point for a broad palette of carbon allotropes. The past two decades have served as a test-bed for measuring the physico-chemical properties of low-dimensional carbon with the advent of fullerenes (0D), followed in chronological order by carbon nanotubes (1D), carbon nanohorns, and, most recently, by graphene (2D). These species are now poised for use in wide-ranging applications. Expanding global needs for energy have led to a significant effort to develop alternatives to fossil fuels. While alternative sources for energy are already in use, they comprise a small percentage of the energy demands needed to carry us through the 21st century. No single source will solve the global needs, but the development of photovoltaics has vast potential as a point-of-use power source. Recent work has shown that hybrid photoelectrochemical efforts with a percolation network of photon absorbers coupled to an electron/hole transporter in combination with advanced photon management are the ideal design for realizing breakthroughs in high photon conversion efficiencies suitable for the catalysis of water. I will report on our efforts regarding a unifying strategy to use the unprecedented charge transfer chemistry of 0D fullerenes, the ballistic conductance of 1D carbon nanotubes, and the high mobility of charge carriers in 2D graphene, together in a groundbreaking approach to solving a far-reaching challenge, that is, the efficient use of the abundant light energy around us. For example, hybrid photoelectrochemical efforts with a percolation network of photon absorbers coupled to an electron/hole transporter in combination with advanced photon management are the ideal design for realizing breakthroughs in high photon conversion efficiencies suitable for the catalysis of water.
16:25: [NanomaterialsTuePM210] OSProton Electrolyte Membrane Fuel Cells (PEMFCs) hold great potential as energy conversion solutions for stationary and transportation purposes. However, in order to compete with internal combustion engines, it is crucial to enhance their durability (1). This study delves into the advancements in membrane electrode assemblies (MEAs) for High-Temperature Polymer Electrolyte Membrane Fuel Cells (HT-PEMFCs). The HT-PEMFCs under investigation were operated within the temperature range of 160-170 °C, utilizing either pure humidified hydrogen or humidified reformate with varying compositions (2).
The elevated operating temperature of high-temperature PEM fuel cells (HT-PEMFCs) opens up new horizons, enabling the utilization of methanol or methanol-water mixtures as viable fuels for commercial fuel cell systems. Remarkably, HT-PEM cells exhibit outstanding tolerance to CO impurities, surpassing 3 vol-% without experiencing substantial performance degradation. Additionally, their heightened resistance to H2S and SO2 poisoning significantly bolsters their operational efficiency, paving the way for improved energy conversion. Our research has unveiled the remarkable durability of HT-PEMFCs incorporating a thermally cross-linked m-PBI membrane. Over an extended period of 9,200 hours, these cells exhibited an impressively low decay rate of only 0.5 μV/h at 0.2 A/cm². The single cell performance has shown an exceptional stability over a span of 10,000 hours, with 9.3 μV/h degradation rate at a current density of 0.4 A/cm². These findings signify a significant stride towards attaining long-lasting and reliable HT-PEMFC systems.
Additionally, we have demonstrated that increasing the pressure of the incoming gases to 1.5 bar (abs) - as anticipated - leads to performance improvements. Preliminary results have showcased a power density of 0.5 W/cm² at 0.8 A/cm², highlighting the promising potential of this technology.
Our study involved rigorous continuous operation and over 1400 start-stop cycles to comprehensively analyze the degradation effects in HT-PEMFCs. The start-stop cycles revealed a degradation rate of 60 µV per cycle, as observed during current density cycling ranging from 0 to 400 mA/cm². These findings shed light on the impact of repeated start-stop events on the performance and longevity of HT-PEMFCs, providing valuable insights for further optimization and durability enhancement.
We continue improving our products (HT-PEMFCs), looking for innovative solutions to current limitations on HT-PEMFC durability.
References:
1) J. O. Jensen, D. Aili, H. A. Hjuler, Q. Li, High Temperature Polymer Electrolyte Membrane Fuel Cells - Approaches, Status and Perspective, ISBN 978-3-319-17081-7; DOI 10.1007/978-3-319-17082-4, Springer International Publishing, New York, 2015.
2) M. Tonny, D. Jakobsen, L. N. Cleemann, H. Becker, D. Aili, T. Steenberg, H. A. Hjuler, L. Seerup, Q. Li, J.O. Jensen, J. Power Sources, 342 (2017) 570-578.
Two-dimensional materials have interesting properties. Taking full advantage of their characteristics, surface functionalization may be required;
In this presentation, I will mainly focus on the functionalization of graphite, graphene, and transition metal dichalcogenides using molecules, though the concepts can also be applied to other 2D materials.
Nanostructuring is at the heart of all functionalization protocols that we develop because it opens new possibilities for control and functionality. A variety of scanning probe microscopy methods are used for visualization, characterization, and manipulation.
The first approach is based on molecular self-assembly at the interface between a liquid or air, and graphite or 2D materials [1].
A second approach is based on the covalent attachment of molecules on 2D materials via covalent chemistry. It will be demonstrated how top-down scanning probe microscopy and optical lithography can be used to structure such covalently modified surfaces in addition to bottom-up strategies that provide control on the density and layer thickness, as well as submicron to nanoscale nanostructure [2,3,4]. Covalently modified surfaces can for instance be implemented for sensing purposes [5].
A third approach does not focus on the functionalization of the surface, but uses the surface as a support for the in-plane covalent stitching of molecules, leading to the formation of on-surface 2D dynamic covalent polymers [6,7].
A variety of molecule-based functionalization strategies, and combinations thereof, lead to unique substrate architectures, as revealed by local scanning probe microscopies.
References:
[1] A. Cucinotta, C. Kahlfuss, A. Minoia, S. Eyley, K. Zwaenepoel, G. Velpula, W. Thielemans, R. Lazzaroni, V. Bulach, M. Wais Hosseini, K. S. Mali, and S De Feyter, J. Am. Chem. Soc., 145, 2, 1194–1205 (2023)
[2] L. Verstraete, S. De Feyter, Chem. Soc. Rev., 50, 5884 (2021)
[3] K. Tahara, Y. Kubo, S. Hashimoto, T. Ishikawa, H. Kaneko, A. Brown, B. E. Hirsch, S. De Feyter, Y. Tobe, J. Am. Chem. Soc. 16, 7699 (2020)
[4] M. C. Rodríguez González, A. Leonhardt, H. Stadler, S. Eyley, W.Thielemans, S. De Gendt, K. S. Mali, S. De Feyter, ACS Nano, 6, 10618 (2021)
[5] S. Freddi, M. C. Rodriguez Gonzalez, P. Carro, L. Sangaletti, S. De Feyter, Angew. Chem. Int. Ed., 61, e202200115 (2022)
[6] G. Zhan, Z.-F. Cai, M. Martínez-Abadía, A. Mateo-Alonso, S. De Feyter, J. Am. Chem. Soc., 13, 5964 (2020)
[7] G. Zhan, Z. F. Cai, K. Strutyński, L. Yu, N. Herrmann, M. Martinez-Abadia, M. Melle-Franco, A. Mateo-Alonso, S. De Feyter, Nature, 603, 835 (2022)
Perylenediimides (PDIs) are highly stable and versatile dyes, which have been widely used as electron-acceptor moieties in the construction of systems for artificial photosynthesis or for optoelectronic applications, including solar cells [1].
On the other hand, azobenzenes are very well-known molecules, characterized by its photoinduced trans-cis isomerization process, which is reversible either by light (with a different wavelength from that of the initial reaction) or thermally in the dark. This property, together with their photostability, turns them into ideal entities for various molecular devices, specifically as light triggered switches [2].
Recently, we have initiated the photophysical study of PDI-azobenzene ensembles obtaining exciting results [3]. Herein, we will present the extension of these studies to include phthalocyanines into the equation, as they are robust materials with excellent electron donor characteristics [4].
References:
[1] F. Würthner, C. R. Saha-Möller, B. Fimmel, S. Ogi, P. Leowanawat, D. Schmidt, Chem. Rev. 2016, 116, 962.
[2] (a) H. D. Bandara, S. C. Burdette, Chem. Soc. Rev. 2012, 41, 1809; (b) J. L. Rodríguez-Redondo, Á. Sastre-Santos, F. Fernández-Lázaro, D. Soares, G. C. Azzellini, B. Elliott, L. Echegoyen, Chem. Commun. 2006, 1265.
[3] N. Zink-Lorre, S. Seetharaman, D. Gutiérrez-Moreno, F. Fernández-Lázaro, P. A. Karr, F. D’Souza, Chem. Eur. J. 2021, 27, 14996.
[4] (a) G. de La Torre, C. G. Claessens, T. Torres, Chem. Commun. 2007, 2000; (b) Phthalocyanine Materials: Synthesis, Structure and Function (Ed.: N. B. McKeown), Cambridge University Press, Cambridge,1998.
| SESSION: NanomaterialsTuePM3-R3 | Echegoyen International Symposium (8th Intl. Symp. on Synthesis & Properties of Nanomaterials for Future Energy Demands) |
| Tue. 28 Nov. 2023 / Room: Dreams 3 | |
| Session Chairs: Jianyuan Zhang; Session Monitor: TBA | |
The ability to easily and cheaply transport CO2 from point-sources, such as power plants, to multiple, potentially distant, utilization sites of widely varying scales will enable wider utilization of carbon capture (CC) from flue gas. In the case of algal biomass cultivation, the use of carbonate sorbents for CC, transport, and delivery to algae has the potential to 1) eliminate the requirement for co-location of algal production facilities with power plants or costly, low-volume pipelines, 2) develop a means of inorganic carbon transport, storage, and delivery tuned directly to seasonal and daily algal productivity levels, and 3) reduce CC costs. Directly delivering CO2 from the sorbent to algae avoids the need for a desorber and compressor in the CO2 capture system, thus eliminating up to 90% of the energy use and ~60% of the capital cost of a typical capture system.Lawrence Livermore National Laboratory has developed advanced manufactured composite sorbent materials that captures CO2 as sodium bicarbonate, encapsulated within a CO2-permeable polymer to increase the surface area and improve carbon capture rates by an order-of-magnitude compared with carbonate solution. In collaboration with Sandia National Laboratories, we have demonstrated the biocompatibility and ability of these composite sorbents to deliver CO2 and control the media pH in algal cultures up to 100L. In collaboration with University of Arizona and Southwest Technologies LLC, we are now scaling up the composite sorbent material synthesis and integrating our CC system with a natural gas flue gas stream, coupled with a delivery system to 1000 L algal pond to perform 30-day continuous tests (Figure 1).This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. (LLNL-ABS-854252)
18:20: [NanomaterialsTuePM314] OS InvitedIn the past two decades, various cycloaddition reactions to modify fullerenes have been developed as highly robust, modular, and functional-group-tolerant methods, including the Diels-Alder cycloaddition, Bingel-Hirsch cyclopropanation, Prato 1,3-dipolar addition, diazoaddition, benzyne addition, etc. To a large extent, the reactions on endohedral metallofullerenes (EMFs) mirrored these reactions. Fullerenes and EMFs are typically electron acceptors in these nucleophilic additions. The reactivity and regioselectivity are highly similar, which brings consistency but also limitations. First, certain fullerenes (e.g., C60) are reactive in many reactions, but relatively electron-rich species, such as EMFs, often require harsh conditions, more equivalents of small-molecule reactants, and even so may still have low yields, and sometimes, no reaction. Moreover, in the small-molecule reactants, if there are electron withdrawing groups (EWG) affecting the reaction site, the reaction is difficult. Meanwhile, from a regioselectivity point of view, when other factors are comparable the electron-deficient bonds tend to react which limits the feasibility to regioselectively functionalize an electron-rich bond. Here we report a new inverse electron demand Diels-Alder (IEDDA) reaction in which the fullerene and EMFs are electron donors, and the diimines, analogue of dienes, are the electron acceptors. In the IEDDA reactions, diimines were generated in-situ with an oxidizing agent, such as PbO2. Contrary to the trend in most fullerene additions, the diimines with electron withdrawing groups show higher reactivity. On C70, the unusual cc-[5,6] adduct was the major product. Metallofullerenes Sc3N@C80 and Lu3N@C80 show higher reactivity than empty fullerenes C60 and C70. The adducts were characterized by single crystal structures and were found to be [5,6] adducts. Moreover, the reaction on EMFs were reversible, providing a new approach for chemical separation of EMFs.
| SESSION: NanomaterialsWedAM-R3 | Echegoyen International Symposium (8th Intl. Symp. on Synthesis & Properties of Nanomaterials for Future Energy Demands) |
| Wed. 29 Nov. 2023 / Room: Dreams 3 | |
| Session Chairs: Tomas Torres; Josep Maria Poblet; Session Monitor: TBA | |
Since the isolation of the first endohedral metallofullerene (EMF) La@C82,1 intensive research has been devoted to this family of compounds that encapsulate metal atoms or clusters in their inner void space.2 Exohedral functionalization of EMFs is a key step to obtain new materials for multiple applications. For instance, water-soluble gadofullerenes are used as powerful contrast agents in medicine.3 Derivatization has also become an essential tool to purify and separate fullerene mixtures.4 Cycloadditions as Bingel-Hirsch reaction, Prato reaction, Diels-Alder reaction, or carbene and benzyne additions were among the most used reactions, although multicomponent reactions have been also considered recently.5 Computational chemistry has helped so far not only to understand the regioselectivity of a wide variety of chemical functionalization on EMFs, but also to disclose in many cases their reaction mechanisms.6 We here will present an overview of our computational studies on the reactivity of EMFs and will focus on recent results on actinidofullerenes, a family recently isolated and characterized by the groups of Ning Chen in Soochow and Echegoyen at UTEP.7 In mono-actinidofullerenes, the actinide tends to have oxidation state +4, which involves an important metal-cage interaction with significant covalent contributions. This feature makes them different from lanthanofullerenes, where the metal is usually with oxidation state +3. Consequently, the electronic structure, properties as well as reactivity of actinidofullerenes are expected to be different compared to their lanthanide counterparts.
References:
1. Chai, Y.; Cuo, T.; Jin, C.; Haufler, R. E.; Felipe Chibante, L. P.; Fure, J.; Wang, L.; Alford, J. M.; Smalley, R. E. J. Phys. Chem. 1991, 95, 7564-7568.
2. Popov, A. A.; Yang, S.; Dunsch, L. Chem. Rev. 2013, 113, 5989-6113.
3. a) Shu, C.; Corwin, F. D.; Zhang, J.; Chen, Z.; Reid, J. E.; Sun, M.; Xu, W.; Sim, J. H.; Wang, C.; Fatouros, P. P.; Esker, A. R.; Gibson, H. W.; Dorn, H. C. Bioconjugate Chem. 2009, 20, 1186-1193; b) Wang, T.; Wang, C. Small 2019, 15, 1901522.
4. a) Chen, N.; Zhang, E.-Y.; Tan, K.; Wang, C.-R.; Lu, X. Org. Lett. 2007, 9, 2011-2013; b) Koenig, R. M.; Tian, H.-R.; Seeler, T. L.; Tepper, K. R.; Franklin, H. M.; Chen, Z.-C.; Xie, S.-Y.; Stevenson, S. J. Am. Chem. Soc. 2020, 142, 15614-15623.
5. Li, Y.; Emge, T. J.; Moreno-Vicente, A.; Kopcha, W. P.; Sun, Y.; Mansoor, I. F.; Lipke, M. C.; Hall, G. S.; Poblet, J. M.; Rodriguez-Fortea, A.; Zhang, J. Angew. Chem. Int. Ed. 2021, 60, 25269-25273.
6. a) Rodríguez-Fortea, A.; Campanera, J. M.; Cardona, C. M.; Echegoyen, L.; Poblet, J. M. Angew. Chem. Int. Ed. 2006, 45, 8176-8180; b) Alegret, N.; Rodriguez-Fortea, A.; Poblet, J. M. Chem. Eur. J. 2013, 19, 5061-5069; c) Osuna, S. Swart, M.; Solà, M. Phys. Chem. Chem. Phys. 2011, 13, 3585-3603.
7. a) Wang, Y.; Morales-Martínez, R.; Zhang, X.; Yang, W.; Wang, Y.; Rodriguez-Fortea, A.; Poblet, J. M.; Feng, L.; Wang, S.; Chen, N. J. Am. Chem. Soc. 2017, 139, 5110-5116; b) Cai, W.; Abella, L.; Zhuang, J.; Zhang, X.; Feng, L.; Wang, Y.; Morales-Martínez, R.; Esper, R.; Boero, M.; Metta-Magaña, A.; Rodriguez-Fortea, A.; Poblet, J. M.; Echegoyen, L.; Chen, N. J. Am. Chem. Soc. 2018, 140, 18039-18050; c) Yao, Y.-R.; Roselló, Y.; Ma, L.; Puente Santiago, A. R.; Metta-Magaña, A.; Chen, N.; Rodriguez-Fortea, A.; Poblet, J. M.; Echegoyen, L. J. Am. Chem. Soc. 2021, 143, 15309-15318.
For almost two decades, intensive work from experimental and theoretical groups has made it possible to advance in the understanding of structural and electronic properties of endohedral metallofullerenes and cluster metal fullerenes. Hence, several groups have proposed diverse rules related with the relative stability of fullerene cages.[1] All of them considered the potential energy when they predict the stability of IPR and non-IPR isomers based on the ionic model, in which the guest transfers usually between three and six electrons to the hosting carbon cage. Those guidelines have explained why the highly symmetric C80(Ih) cage is the preferred fullerene when there is a transfer of six electrons, like in the well-known Sc3N@C80,[2] or in many other examples, such as Lu3N@C80, La2@C80, Y3@C80, etc.[3] In endohedral fullerenes with four or less electron transfer between host and guest, there is not a prevalent structure, like C80(Ih), and the diversity of captured carbon cages is larger, the theoretical prediction of the most abundant species to be formed in a K-H reactor being much more difficult. In addition to the relative potential energy, it is also necessary to consider the enthalpic and entropic contributions to the stability of the endohedral fullerenes. A systematic theoretical analysis for a series of A@C2n fullerenes with A = Th and U, in combination with accurate experimental characterization, have allowed us to show that the structures of A4+@C2n4- species are different from those of cluster fullerenes, such as Sc2O4+@C2n4-, Sc2S4+@C2n4-or Sc2C24+@C2n4-.[4] Here, we will present some of the most recent studies carried out in collaboration with Prof. Luis Echegoyen concerning to stabilization of non-IPR, formation of strong covalent actinide-actinide bons and electrochemical reactions in endofullerenes.[5]
References:
[1] Campanera, J. M.; Bo, C.; Poblet, J. M., Angew. Chem., Int. Ed. 2005, 44, 7230-7233; Rodríguez-Fortea, A.; Alegret, N.; Balch, A. L.; Poblet, J. M., Nature Chem. 2010, 2, 955; Garcia-Borràs M., Osuna S., Swart M., Luis J.M., Solà M. Angew. Chem. Int.. Ed. 2013, 52, 9275-9278; Wang, Y.; Díaz-Tendero, S.; Martín, F. and Alcamí, M. J. Am. Chem. Soc., 2016, 138, 1551–1560
[2] Stevenson, S.; Rice, G.; Glass, T.; Harich, K.; Cromer, F.; Jordan, M. R.; Craft, J.; Hadju, E.; Bible, R.; Olmstead, M. M.; Maitra, K.; Fisher, A. J.; Balch, A. L.; Dorn, H. C., Nature 1999, 401, 55.
[3] Popov, A. A.; Yang, S.; Dunsch, L., Chem. Rev. 2013, 113, 5989-6113.
[4] W. Cai, L. Abella, J. Zhuang, X. Zhang, L. Feng, Y. Wang, R. Morales-Martínez, R. Esper, M. Boero, A. Metta-Magaña, A. Rodríguez-Fortea, J. M Poblet, L. Echegoyen, N. Chen J. Am. Chem. Soc. 2018, 140, 18039-18050.
[5] X. Zhang, Y. Wang, R. Morales-Martínez, J. Zhong, C. de Graaf, A. Rodríguez-Fortea, J. M Poblet, L. Echegoyen, L. Feng, N. Chen J. Am. Chem. Soc. 2018, 140, 3907-3915; A. Moreno-Vicente, Y. Roselló, N. Chen, L. Echegoyen, P.W. Dunk, A. Rodríguez-Fortea, C. de Graaf, J. M Poblet, J. Am. Chem. Soc. 2023, 145, 6710-6718.
Subphthalocyanines (SubPcs) are well-known cone-shaped chromophores consisting of three 1,3-diiminoisoindole units assembled around a boron atom [1,2,3]. As a result of their 14 pi-electron aromatic core and their tetrahedral geometry, SubPcs exhibit outstanding physical and optoelectronic properties (e.g., strong dipole moment, excellent light absorption in the 550-650 nm, rich redox features, and excellent charge transport capabilities), that have been skillfully used in variety of applied fields, such as molecular photovoltaics, among others. SubPcs were used by us as non-fullerene acceptors in bulk heterojunctions (BHJ) solar cells. On the other hand as part of our systematic investigation in the preparation and study of novel SubPc-based D–A systems, we have used 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) as partner for SubPcs. Moreover, in the case of unsymmetrically substituted SubPcs (i.e., prepared by cyclotrimerization of a phthalonitrile with no C2v symmetry), they present inherent chirality and the corresponding couple of enantiomers can be isolated. Columnar aggregates based on chiral SubPcs have been also prepared, giving rise to ferroelectric self-assembled molecular materials showing both rectifying and switchable conductivity. These chromophores have been incorporated in multicomponent systems showing a panchromatic response and allowing the tuning and controlling intramolecular FÖRSTER Resonance Energy Transfer for Singlet Fission
References:
[1] G. Lavarda, J. Labella, M. V. Martinez-Diaz, M. S. Rodriguez Morgade, A. Osuka, T.
Torres, Chem. Soc. Rev. 2022, 51, 9482-9619.
[2] J. Labella, G. Lavarda, L. Hernández-López, F.Aguilar-Galindo, S.Díaz-Tendero, J. Lobo-Checa, T. Torres, J. Am. Chem. Soc. 2022, 144, 16579-16587
[3] J. Labella, T. Torres, Trends in Chemistry, 2023, https://doi.org/10.1016/j.trechm.2023.02.003
There has been significant interest in incorporating chromophoric compounds into optoelectronic applications based on metal-organic frameworks (MOFs). This approach has provided materials that can be easily integrated into devices, including photovoltaics, light-emitting diodes, and transistor-related applications.[1]
Phthalocyanines are a family of synthetic analogues of porphyrin compounds chemically and thermally stable, which makes them useful in applications that require robust materials. They are excellent electron donors, making them useful in optoelectronic devices.[2] Additionally, phthalocyanines can be easily modified by attaching different chemical groups to their periphery or to the axial position, which allows for fine-tuning of their properties. In this context, silicon phthalocyanines (SiPc), equipped with axial coupling groups, represent a good candidate to combine with metallic atoms, to afford MOF-based chromophoric assemblies, where the inter-linker and metal ion distances, as well as the overall geometry, are crucial parameters to tune the electronic coupling between MOF building blocks. Recently, we have shown that MOF thin films can be successfully assembled using SiPc as linkers, resulting in a porous material that can be used as an optical resonator.[3]
In this communication, we will present our recent advances on SiPc compounds, axially functionalized with carboxylic acid appends and peripherally substituted with different groups and the evaluation of their capability to generate, in combination with Zn atoms, optically active SiPc-based MOF thin films which show systematically tuned J-type electronic coupling.[4]
References:
[1] D.-H. Chen, H. Gliemann and C. Wöll, Chem. Phys. Rev. 2023, 4, 011305.
[2] (a) G. de La Torre, C. G. Claessens,T. Torres, Chem.Commun. 2007,2000–2015; (b) Phthalocyanine Materials: Synthesis, Structure and Function (Ed.:N. B. McKeown), Cambridge University Press, Cambridge,1998.
[3] R. Haldar, Z. Fu, R. Joseph, D. Herrero, L. Martín-Gomis, B.S. Richards, I. A. Howard, A. Sastre-Santos, C. Wöll, C. Chem. Sci. 2020, 11(30), 7972–7978.
[4] a) V. Sobrino-Bastán, L. Martín-Gomis, Á. Sastre-Santos, J. Porphyrins Phthalocyanines, 2023, 10.1142/S1088424622500961. b) H. Chen, L. Martín-Gomis, J. C Fischer, I. A Howard, D. Herrero, V. Sobrino-Bastán, Á. Sastre-Santos, R. Haldar, C. Wöll 2023, submitted.
| SESSION: NanomaterialsWedPM1-R3 | Echegoyen International Symposium (8th Intl. Symp. on Synthesis & Properties of Nanomaterials for Future Energy Demands) |
| Wed. 29 Nov. 2023 / Room: Dreams 3 | |
| Session Chairs: Fernand Marquis; David Gonzalez Rodriguez; Session Monitor: TBA | |
In this communication, we would like to show two recent examples in our group in which we exploit the confined nanospaces purposedly created in two very different self-assembled structures to selectively host specific molecules.
The first case comprises tubular nanostructures with custom-tailored pores, which are assembled by coupling two cooperative supramolecular processes of different hierarchy and acting in orthogonal directions. Chiral cyclic tetramers are first formed from 4 monomeric π-conjugated subunits by H-bonding interactions between nucleobase directors. A proper monomer preorganization affords high chelate cooperativities in solution[1] and onto surfaces.[2] When these cyclic species are subjected to a supramolecular polymerization process, helical self-assembled nanotubes are formed via nucleation-growth cooperative mechanisms in organic solvents[3] and in water.[4] Interestingly, the inner pore of these nanotubes can be coated with functional groups of opposite solvophilicity to the external medium, so as to host molecules that show an affinity for this environment.
The second case consists of a novel kind of Zn(II)bis-porphyrin nanocages constructed by imine condensation under thermodynamic control. These cages have two main conformations, depending on the arrangement of the imine bonds, and can host a wide diversity of ditopic nitrogen ligands that fit into its relatively rigid nanocavity. Remarkably, the cage is also an excellent host for fullerene.
References:
1] a) C. Montoro-García, M. J. Mayoral, R. Chamorro, D. González-Rodríguez, Angew. Chem. Int. Ed. 2017, 56, 15649-15653; b) D. Serrano-Molina, C. Montoro-García, M. J. Mayoral, A. de Juan, D. González-Rodríguez, J. Am. Chem. Soc. 2022, 144, 5450–5460.
[2] N. Bilbao, I. Destoop, S. De Feyter, D. González-Rodríguez, Angew. Chem. Int. Ed. 2016, 55, 659–663.
[3] a) V. Vázquez-González, M. J. Mayoral, R. Chamorro, M. M. R. M. Hendrix, I. K. Voets, D. González-Rodríguez, J. Am. Chem. Soc. 2019, 41, 16432-16438; b) V. Vázquez-González, M. J. Mayoral, F. Aparicio, P. Martínez-Arjona, D. González-Rodríguez, ChemPlusChem 2021, 86, 1087–1096.
[4] a) F. Aparicio, P. Chamorro, R. Chamorro, S. Casado, D. Gonzalez-Rodriguez, Angew. Chem. Int. Ed. 2020, 59, 17091-17096; b) P. B. Chamorro, F. Aparicio, R. Chamorro, N. Bilbao, S. Casado, D. González-Rodríguez, Org. Chem. Front. 2021, 8, 686-696.
The importance of charge transfer (CT) and charge transport (CTr) for supporting life on Earth and for making our modern ways of living possible cannot be overstated.1 Concurrently, electric dipoles are everywhere and understanding how they affect CT and CTr is of principal importance for addressing medical challenges and controlling the functionality of a wide range of materials and devices.2,3 Discussions of the idea about dipole effects on CT date back to the mid 20th century.4 Reported experimental evidence from the 1990s and 2000s demonstrated the importance of dipole effects on CT.5-7 The dipole-generated localized electric fields modulate the electronic properties of the CT moieties. The notion for such effects focusses on dipole-induced changes in the reduction potentials of the acceptor and the oxidized donor, affecting the CT driving forces and thus, the Franck-Condon (FC) contributions to the CT kinetics. We recently demonstrated that to harness such effects, which are inherently enormous, (1) the dipoles should be placed as closed as possible to the electron donor and acceptor, and (2) the media polarity should be lowered.8,9 Polar media, indeed, stabilize charged states and in general, enhances the rates of CT. Polar media, however, screen the field permeation and damps the dipole effect on the electron donor and acceptor. Using hydrocarbons as a medium, results in electron transfer rates along the dipole that are six times larger than the rates for the same system when in polar solvents, such as acetonitrile.8 The same localized field effects in non-polar medium completely shut down the electron transfer against the dipole. As important as the dependence of CT kinetics and thermodynamics on medium polarity is, the interfacial nature of electrode processes presents challenges for characterizing this dependence.10,11 While the polarity that solvated species experience in the bulk of a electrolyte solution is readily attainable, it is still challenging to determine the polarity of the microenvironment at the electrode surfaces where the redox processes occur.12 An increase in electrolyte concertation in organic solvents increases their polarity, which is opposite for aqueous solutions.11,12 At the electrode surfaces, however, the increase rigidity of the double layer, especially under applied voltage, decreases the oreitnational polarization, which principally contributed to the dielectric constant of solvents with large dipoles.12 That is, the polarity that CT species experience at electrode surfaces is smaller than that in the bulk of the solution. Global-fit analysis on the dependence of measured reduction potentials on the polarity of the solvent and the electrolyte concentrations offers a means for estimating the effective polarity that redox species experience at electrode surfaces.12 Such electrochemical analysis improves not only the characterization of CT thermodynamics, but also the quantification of the dipole effects on CT, which has key implications for electronics, photonics and energy science and engineering.
References:
1. Derr, J. B.; Tamayo, J.; Clark, J. A.; Morales, M.; Mayther, M. F.; Espinoza, E. M.; Rybicka-Jasińska, K.; Vullev, V. I. “Multifaceted aspects of charge transfer” Phys. Chem. Chem. Phys. 2020, 22, 21583-21629.
2. Derr, J.; Tamayo, J.; Espinoza, E. M.; Clark, J.; Vullev, V. I. “Dipole-Induced Effects on Charge Transfer and Charge Transport. Why Molecular Electrets Matter?” Can. J. Chem. 2018, 96, 843-858.
3. Rybicka-Jasińska, K.; Vullev, V. I. “Molecular electrets–Why do dipoles matter for charge transfer and excited-state dynamics?” J. Photochem. Photobiol. A 2020, 401, 112779.
4. Yomosa, S. "Charge-Transfer Molecular Compounds in Biological Systems" Prog. Theor. Phys. Suppl. 1967, 40, 249-263.
5. Steffen, M. A.; Lao, K. Q.; Boxer, S. G. "Dielectric Asymmetry in the Photosynthetic Reaction Center" Science, 1994, 264, 810-816.
6. Galoppini, E.; Fox, M. A. "Effect of the Electric Field Generated by the Helix Dipole on Photoinduced Intramolecular Electron Transfer in Dichromophoric α-Helical Peptides" J. Am. Chem. Soc. 1996, 118, 2299–2300.
7. Yasutomi, S.; Morita, T.; Imanishi, Y.; Kimura, S. "A Molecular Photodiode System That Can Switch Photocurrent Direction" Science 2004, 304, 1944-1947.
8. Krzeszewski, M.; Espinoza, E. M.; Červinka, C.; Derr, J. B.; Clark, J. A.; Borchardt, D.; Beran, G. J. O.; Gryko, D. T.; Vullev, V. I. “Dipole Effects on Electron Transfer are Enormous” Angew. Chem. Int. Ed. 2018, 57, 12365-12369.
9. Bao, D.; Upadhyayula, S.; Larsen, J. M.; Xia, B.; Georgieva, B.; Nuñez, V.; Espinoza, E. M.; Hartman, J. D.; Wurch, M.; Chang, A.; Lin, C.-K.; Larkin, J.; Vasquez, K.; Beran, G. J. O.; Vullev, V. I. “Dipole-Mediated Rectification of Intramolecular Photoinduced Charge Separation and Charge Recombination,” J. Am. Chem. Soc. 2014, 136, 12966-12973.
10. O’Mari, O.; Vullev, V. I. “Electrochemical analysis in charge-transfer science: The devil in the details.” Curr. Opin. Electrochem. 2022, 31, 100862.
11. Espinoza, E. M.; Clark, J. A.; Soliman, J.; Derr, J. B.; Morales, M.; Vullev, V. I. “Practical Aspects of Cyclic Voltammetry: How to Estimate Reduction Potentials When Irreversibility Prevails” J. Electrochem. Soc. 2019, 166, H3175-H3187.
12. Mayther, M. F; O’Mari, O.; Flacke, P.; Bhatt, D.; Andrews, S.; Vullev, V. I. "How Do Liquid-Junction Potentials and Medium Polarity at Electrode Surfaces Affect Electrochemical Analyses for Charge-Transfer Systems?" J. Phys. Chem. B 2023, 127, 1443-1458.
Carbon nanotubes and graphene are almost perfect molecules with truly amazing combinations of thermal, electrical, and structural properties. However, to harvest their full potential they need to be fully integrated as hybrid materials in all sorts of matrices. Full integration requires their development beyond conventional composites so that the level of the non-nano material is designed to integrate fully with the molecules of carbon nanotubes and graphene. Here the nano materials are part of the matrix rather than a differing component, as in the case of conventional composites. To advance the development of multifunctional materials integrating nanotubes and graphene, this research is focused on the simultaneous control of the nano architecture, structural properties, the thermal and the electrical conductivity of fully integrated nano hybrid materials systems. These hybrid materials systems are designed to surpass the limits of rule of mixtures in conventional composite design. The goals are to implement multifunctional designs to fully mimic the properties of carbon nanotubes and graphene on larger scales, from the nano, to the meso, to the micro and to the macro scales, and to enhance the thermal and electrical the management, in addition to the control of other properties such as mechanical strength and fracture toughness. These new approaches involve exfoliation, functionalization, dispersion, stabilization, alignment, polymerization, reaction bonding and coating, designed to achieve full integration. Typical examples of structural applications of polymeric and ceramic matrices and applications in energy systems such as capacitors and batteries as well as other material systems are presented and discussed.
References:
[1] Marquis, F.D.S. “Carbon Nanotube Nanostructured Hybrid Materials Systems for Renewable Energy Applications” JOM, Vol 63, 1 (2011) 48 2. Marquis, F.D.S. and L.P.F. Chibante “Improving the Heat Transfer of Nanofluids and Nanolubricants with Carbon Nanotubes” JOM, 12 (2005) 32-44. 3. Functional Composites of Carbon Nanotubes & Applications”, Lee, K-P, Gopalan, A.I. and Marquis, F.D.S. Marquis, Research Signpost (2009), ISBN 978-81-7895-413-4. 4. Marquis, F.D.S. “The Nanotechnology of Carbon Nanotube Nanofluids” in “Functional Composites of Carbon Nanotubes and Applications”, Lee, K-P, Gopalan, A.I. and Marquis, F.D.S. Marquis, ISBN 978-81-7895-413-4, (2009).
The 19th century is often referred to as the age of iron, the 20th century as the age of silicon, and the 21st century as the age of carbon. In this century, from the perspective of environmental conservation and economic security, research on harnessing natural energy is becoming increasingly important. In this presentation, we will introduce a new organic solar cell that actively employs nanocarbon materials, which are anticipated to be a groundbreaking next-generation solar cell.
Electron transport layers employing vacuum-deposited fullerene derivatives, properties of carbon nanotube thin films created through wet and dry processes and their applications to bottom and top contact electrodes respectively, and hole transport materials using carbon nanotubes are discussed. This paper presents organic thin-film solar cells and perovskite solar cells that utilize these functionalized nanocarbon materials.
References:
Angew. Chem. Int. Ed. 2022, 61, e202203949; Appl. Phys. Express 2022, 15, 046505; Comm. Chem. 2021, 4, 74; Bull. Chem. Soc. Jpn. 2021, 94, 1080 (Review Article); J. Am. Chem. Soc. 2019, 141, 16553; Chem. Mater. 2019, 31, 8432; Chem. Commun. 2019, 55, 11837; Adv. Energy Mater. 2019, 9, 1901204; J. Mater. Chem. A 2019, 7, 4072; Chem. Commun. 2018, 54, 11244 (Review Article); J. Mater. Chem. A 2018, 6, 14553; J. Mater. Chem. A 2018, 6, 5746; Angew. Chem. Int. Ed. 2018, 57, 4607; J. Mater. Chem. A 2018, 6, 1382; J. Phys. Chem. C 2017, 121, 25743; J. Phys. Chem. Lett. 2017, 8, 5395; Nano Lett. 2015, 15, 6665; J. Am. Chem. Soc. 2015, 137, 7982.
| SESSION: NanomaterialsWedPM2-R3 | Echegoyen International Symposium (8th Intl. Symp. on Synthesis & Properties of Nanomaterials for Future Energy Demands) |
| Wed. 29 Nov. 2023 / Room: Dreams 3 | |
| Session Chairs: Francis D'Souza; Emilio Palomares; Session Monitor: TBA | |
Electron donor-acceptor hybrids comprised of single-wall carbon nanotubes (SWCNT) are promising functional structures having direct applications in energy conversion schemes and molecular optoelectronics.1-3 For building such hybrids and exfoliation of SWCNTs, the pi-stacking ability of large aromatic compounds such as pyrene is one of the commonly employed approaches. Often, the desired donor or acceptor entities are functionalized to carry one or more pyrene entities and allowed to interact with CNTs. As a suitable electron donor, BODIPYs stand out owing to their ease of structural modifications and rich spectral and redox properties. Consequently, several donor-acceptor conjugates comprised of BF2-chelated dipyrromethene, BODIPY, and the well-known electron acceptor, C60 have been developed. In the present study, we have newly synthesized a nano tweezer comprised of covalently linked BODIPY-C60 carrying two pyrenylstyryl arms. Compound 1 is further allowed to interact with SWCNT(6,5) and SWCNT(7,6) to form the supramolecular C60-BODIPY-SWCNT triads. Upon spectral, electrochemical, and computational characterization, pump-probe spectroscopic studies covering a wide femto-to-millisecond time scale have been performed to establish the occurrence of photoinduced charge separation.4 The presence of CNT prolonged the lifetime of the charge-separated states revealing the success of the present molecular design strategy for energy harvesting applications.
References:
1. D’Souza, F.; Sandanayaka, A. S. D.; Ito, O. ‘SWNT-Based Supramolecular Nanoarchitectures with Photosensitizing Donor and Acceptor Molecules’ J. Phys. Chem. Letts. 2010, 1. 2586-2593.
2. C. B. KC, G. N. Lim, and F. D’Souza, ‘Accelerated Charge Separation in Graphene Decorated Multi-Modular Tripyrene-Subphthalocyanine-Fullerene Donor-Acceptor Hybrids,’ Angew. Chem. Int. Ed. 2015, 54, 5088-5092.
3. M. Barrejon, L. M. Arellano, F. D’Souza, F. Langa, ‘Bidirectional charge transfer in carbon-based hybrid nanomaterials’ Nanoscale, 2019, 11, 14978-14992.
4. S. Kazemi, Y. Jang, A. Liyanage, P. A. Karr, and F. D’Souza, A Carbon Nanotube Binding Bis(pyrenylstyryl)BODIPY-C60 Nano Tweezer: Charge Stabilization through Sequential Electron Transfer, Angew. Chem. Int. Ed. 2022, 61, e202212474 (1-7),
During my lecture, I will present our latest results (1,2) on characterising different types of solar cells from DSSC and OPV to MAPI using advanced photo-induced time-resolved techniques. Using PICE (Photo-induced charge extraction), PIT-PV (Photo-induced Transient PhotoVoltage) and other techniques, we have been able to distinguish between capacitive electronic charge, and a larger amount of charge due to the intrinsic properties of the perovskite material. Moreover, the results allow us to compare different materials, used as hole transport materials (HTM), and the relationship between their HOMO and LUMO energy levels, the solar cell efficiency and the charge losses due to interfacial charge recombination processes occurring at the device under illumination. These techniques and the measurements carried out are key to understanding the device function and improving further the efficiency and stability of perovskite MAPI-based solar cells. Last, the advances in self-assembled molecules, as selective contacts, for perovskite solar cells will be shown. SAMs have been paramount to achieving high solar-to-energy conversion values and increasing the stability of perovskite solar cells.
References:
[1] J. Jímenez-López, BDM Pusher, Dirk M. Guldi, E. Palomares. J. Am. Chem. Soc. 2020, 142 (3) 1236.
[2] E. Yalcin, M. can, C. Rodríguz-Seco, E. Aktas, R. Pudi, W. Cambararu, S. Demiç, E. Palomares. Energ. Environ. Sci., 2019, 12, 1 230.
Polymer mechanochemistry studies the interaction between mechanical force and polymer materials, in both fluid- and solid-state systems, through the development of so-called mechanophores.[1][2] The latter are chemical motifs that generate physicochemical signals in response to the cleavage of weak bonds, which may be covalent or supramolecular.[2] Some mechanophores exhibit the particularly attractive feature of being mechanochromic, meaning that they change their optical properties (absorption or emission of light) as a consequence of the force-triggered bond cleavage event.[3][4] This has paved the way for their use as force sensors to predict/anticipate the end-of-life or mechanical failure of polymer materials.[5]
This contribution will address covalent, heterolytic mechanophores, i.e., motifs that dissociate into ion pairs upon mechanical stimulation. This force-triggered bond cleavage mechanism has primarily been reported in solutions but is not often encountered in solid-state systems. Our group has recently provided the first example of a heterolytic mechanophore that can be mechanically activated in solid-state materials leveraging appropriately designed triarylmethane scaffolds (Tr). By performing uniaxial deformation experiments in conjunction with optical techniques in a home-built setup, we will show that the initially colorless Tr species dissociate into brightly colored, resonance-stabilized triarylcarbenium ions (Tr+)and anionic counterparts.[6] Additionally, the strong mechanochromic response can be easily tuned via simple structural modifications. The fundamental and applicative implications of our findings will be further discussed.
References:
[1] J. Li, C. Nagamani, J. S. Moore, Acc. Chem. Res. 2015, 48, 2181–2190.
[2] Y. Chen, G. Mellot, D. Van Luijk, C. Creton, R. P. Sijbesma, Chem. Soc. Rev. 2021, 50, 4100–4140.
[3] M. M. Caruso, D. A. Davis, Q. Shen, S. A. Odom, N. R. Sottos, S. R. White, J. S. Moore, Chem. Rev. 2009, 109, 5755–5798.
[4] C. Calvino, L. Neumann, C. Weder, S. Schrettl, J. Polym. Sci. Part A Polym. Chem. 2017, 55, 640–652.
[5] M. Abi Ghanem, A. Basu, R. Behrou, N. Boechler, A. J. Boydston, S. L. Craig, Y. Lin, B. E. Lynde, A. Nelson, H. Shen, et al., Nat. Rev. Mater. 2021, 6, 84–98.
[6] J. R. Hemmer, C. Rader, B. D. Wilts, C. Weder, J. A. Berrocal, J. Am. Chem. Soc 2021, 143, 18859–18863.
While recent advances in functional materials increasingly involve the inclusion of metal-oxide domains [1], reproducibility problems inherent to their incorporation remain an often success-limiting challenge. In this context, molecular science could play a transformative role by using the tractability and versatile solution-state chemistries of well-defined molecular complexes to simplify device fabrication. This is demonstrated by using coordination complexes of structurally and electronically recognizable fragments of bulk metal oxides as versatile molecular "modules" for replacing the parent materials. For example, soluble hexaniobate complexed molecular fragments of cubic-spinel and monoclinic Co3O4 are highly active analogs of bulk cobalt oxide, with the HOMO and LUMO energies of the complexes, 1, closely matching those of the valence- and conduction-bands of the parent bulk oxides. Use of 1 as a tractable analog of cobalt-oxide nanocrystals is demonstrated by its deployment as a co-catalyst for the direct Z-scheme reduction of CO2 by solar light and water [2]. Alternatively, complexed semiconductor cores can activate molecular polyoxoniobate cluster-anion ligands themselves as nucleophilic sites for CO2 reduction. Although pure and functionalized solid-state polyniobates such as layered perovskites and niobate nanosheets are photocatalysts for renewable-energy processes [3], analogous reactions by molecular polyoxoniobates are nearly absent from the literature. Under simulated solar-light, however, hexaniobate cluster-anion encapsulated 30-NiII-ion "fragments" of surface-protonated cubic-phase-like NiO cores activate the hexaniobate ligands themselves. Photoexcitation of the NiO cores promotes charge-transfer reduction of NbV to NbIV, increasing electron density at bridging oxo atoms of Nb–&#m181;-O–Nb linkages that bind and convert CO2 to CO. Photogenerated NiO “holes” simultaneously oxidize water to dioxygen. In related work, hexaniobate ligands are used to arrest the growth of metal-oxide NCs and stabilize them as water-soluble complexes. This is exemplified by hexaniobate-complexed 2.4-nm monoclinic-phase CuO NCs, whose ca. 350 Cu-atom cores feature quantum-confinement effects [4] that impart an unprecedented ability to catalyze visible-light water oxidation with no added photosensitizers or applied potentials, and at rates exceeding those of hematite NCs [5]. Together, the above findings point to polyoxoniobate-ligand entrapment as a potentially general method for harnessing the catalytic activities of semiconductor fragments as the cores of versatile, entirely-inorganic complexes.
References:
(1) Li, X.; Yu, J.; Jaroniec, M.; Chen, X. Cocatalysts for Selective Photoreduction of CO2 into Solar Fuels. Chem. Rev. 2019, 119, 3962-4179.
(2) Zhang, W.; Mohamed, A. R.; Ong, W.-J. Angew. Chem. Int. Ed. 2020, 59, 22894-22915.
(3) Nishioka, S.; Hojo, K.; Xiao, L.; Gao, T.; Miseki, Y.; Yasuda, S.; Yokoi, T.; Sayama, K.; Mallouk, T. E.; Maeda, K., Science Advances, 2022, 8, eadc9115.
(4) M. A. Holmes, T. K. Townsend, F. E. Osterloh, Chem. Commun. 2012, 48, 371-373.
(5) S. Corby, R. R. Rao, L. Steier, J. R. Durrant, Nat. Rev. Mater. 2021, 6, 1136-1155.
| SESSION: NanomaterialsWedPM3-R3 | Echegoyen International Symposium (8th Intl. Symp. on Synthesis & Properties of Nanomaterials for Future Energy Demands) |
| Wed. 29 Nov. 2023 / Room: Dreams 3 | |
| Session Chairs: Noe Alvarez; Session Monitor: TBA | |
This talk will report fundamental calculations and experimental studies for chemical bond formation of open-ended vertically oriented carbon nanotubes (CNTs) to copper metal surfaces.1 Chemical bonds, preferentially covalent, between metal atoms and functional groups (linkers) at the open ends of CNTs is highly desired in order to create a robust connection and anchoring the CNTs to macroscopic metal surfaces.2-3 In addition, a chemical connection between metals and CNTs is critical for wiring two metals through a single CNT.4-5 Unlike traditional methods that rely on synthesis, where good quality CNTs are grown directly on metal substrates at temperatures above 600 °C this method reports covalent bond formation at temperatures as low as 120 °C. The reported theoretical calculations demonstrate that C atoms on aminophenyl can form a bridge like covalent bonds with two adjacent Cu atoms on (100), (110), and linear bond on (111) Cu crystal lattice substrates. The aminophenyl of bonded carbon atom was employed as linker molecule to simulate intramolecular electron transport between chemically connected carbon nanotubes and copper metals in this carbon/metal hybrid materials. The strength of the bonding was experimentally evaluated by placing the hybrid (CNT/Cu) material in solution and exposing to bath sonication. To our surprise, the CNTs remained attached to the substrate even after 30 min sonication. In addition, adhesive tape was applied to remove the bonded CNT array from the metal surface. The area from where CNT arrays were removed revealed that some CNTs still remained attached to the copper surface, supporting the strong bonding to the metal. XPS, FT-IR, Raman analysis and scanning electron microscopy images support the formation of direct connections between the vertically aligned CNTs and the metal substrates. The reported covalent bond formation is expected to facilitate the application of CNTs in multiple fields such as biomaterials, electrocatalysis, sensor development and electronics.
References:
1. Nawarathne, C. P.; Hoque, A.; Ruhunage, C. K.; Rahm, C. E.; Alvarez, N. T., Applied Sciences-Basel 2021, 11 (20).
2. Kaur, S.; Raravikar, N.; Helms, B. A.; Prasher, R.; Ogletree, D. F., Nature Comm. 2014, 5, 3082, 1-8.
3. Daneshvar, F.; Chen, H.; Noh, K.; Sue, H.-J., Nanoscale Advances 2021, 3 (4), 942-962.
4. Fediai, A.; Ryndyk, D. A.; Cuniberti, G., Physical Review B 2015, 91 (16).
5. Gao, F.; Qu, J.; Yao, M., Journal of Electronic Packaging 2011, 133, 020908 (2), 1-4.
The electrocatalytic properties of some fullerenes, particularly for hydrogen evolution reactions (HER), were recently studied and predicted by computational studies. The catalytic performance of the most common fullerenes is deficient compared to other carbon-based nanocatalysts. Here, for the first time, we provide insights into how functionalization can alert the electron density on the carbon cages of the fullerenes and influence the highly purified C60 compounds to achieve better hydrogen oxidation reaction (HOR) activity using a combination of experimental and theoretical approaches. The bis-pyrrolidine hexa-adducts of the C60 compound exhibited remarkable HOR catalytic activity of metal-free catalyst with a current density of 4.1 µA/cm2 and mass activity of 27 A· mg-1 at 0.4 V at room temperature. These results further demonstrate the relevance of such novel molecular catalysts for developing new HOR catalysts for fuel cell applications.
| SESSION: NanomaterialsThuAM-R3 | Echegoyen International Symposium (8th Intl. Symp. on Synthesis & Properties of Nanomaterials for Future Energy Demands) |
| Thu. 30 Nov. 2023 / Room: Dreams 3 | |
| Session Chairs: Miguel A. Alario Franco; Mark Hersam; Session Monitor: TBA | |
Knowing that solids are formed by atoms, and that atoms have, indeed, a size, it is no wonder that the size of atoms does influence the Chemistry of Solids. However, the way the atoms size makes its influence can be rather elaborate, even surprising¡. In the present lecture, after a brief introduction of atoms and ions sizes, we will present two examples of the marked influence of Rare Earth (RE) ions sizes in two very interesting cuprate families:
* The High Pressure/High Temperature Solid State Synthesis of Materials of the so-called rutheno-cuprate family: RuSr2RECu2O8 (The unexpected influence of the f-electrons)
* The presence, or absence, of superconducting properties in the family of partly substituted copper in YSrCuO: i.e. Mo0.3Cu0.7Sr2RECuO7+d. (Anion & cation order/disorder)
* The third example shows the correlation of P & T in the ordering in the A & B positions of a quadruple perovskite “Sr2RECu2IrO9-”.[3]
References:
1.-M.Á. Alario-Franco*, Rocío Ruiz- Bustos & A.J. Dos Santos-García Inorg. Chem. (2008) 47,146475-6481.
2.-Xabier Martínez de Irujo-Labalde, Esteban Urones-Garrote, Susana García-Martín & Miguel Ángel Alario-Franco*: Inorg. Che .(2018) 57, 19, 12038-12049.
3.- M.Á. Alario-Franco et al, Turning points in Solid State Materials. RSC Publishing (2008)151-164
Layered two-dimensional (2D) materials interact primarily via van der Waals bonding, which has created new opportunities for heterostructures that are not constrained by epitaxial lattice matching requirements [1]. However, since any passivated, dangling bond-free surface interacts with another via non-covalent forces, van der Waals heterostructures are not limited to 2D materials alone. In particular, 2D materials can be integrated with a diverse range of other materials, including those of different dimensionality, to form mixed-dimensional van der Waals heterostructures [2]. Furthermore, chemical functionalization provides additional opportunities for tailoring the properties of 2D materials [3] and the degree of coupling across heterointerfaces [4]. In this manner, a variety of optoelectronic and energy applications can be enhanced including photodetectors, optical emitters, supercapacitors, and batteries [5-7]. Due to their unique physics, mixed-dimensional heterostructures also enable unprecedented electronic and quantum functionality to be realized including gate-tunable Gaussian heterojunctions, neuromorphic memtransistors, and high-purity single-photon emitters [8-10]. In addition to technological implications for electronic and energy technologies, this talk will explore several fundamental issues including band alignment, doping, trap states, and charge/energy transfer across van der Waals heterointerfaces.
References:
[1] D. Lam, et al., ACS Nano, 16, 7144 (2022).
[2] D. Jariwala, et al., Nature Materials, 16, 170 (2017).
[3] S. H. Amsterdam, et al., Journal of Physical Chemistry Letters, 12, 4543 (2021).
[4] S. Padgaonkar, et al., Accounts of Chemical Research, 53, 763 (2020).
[5] D. Lam, et al., ACS Nano, 16, 11315 (2022).
[6] K.-Y. Park, et al., Advanced Materials, 34, 2106402 (2022).
[7] N. S. Luu, et al., Accounts of Materials Research, 3, 511 (2022).
[8] V. K. Sangwan and M. C. Hersam, Nature Nanotechnology, 15, 517 (2020).
[9] X. Yan, et al., Advanced Materials, 34, 2108025 (2022).
[10] M. I. B. Utama, et al., Nature Communications, 14, 2193 (2023).
Nanostructures of graphene demonstrate a wide range of optical, electronic, and magnetic properties depending on their size and chemical structures, which renders them promising as next-generation carbon-based nanomaterials, e.g., for nanoelectronics, spintronics, photonics, and solar energy conversion. Large polycyclic aromatic hydrocarbons (PAHs) possess the nanoscale graphene structures and have demonstrated the unique optoelectronic and magnetic properties predicted theory, thus attracting renewed attentions as atomically precise nanographenes [1]. We have recently developed the synthesis of dibenzo[hi,st]ovalene (DBOV) as a nanographene with a combination of zigzag and armchair edges, which demonstrated high stability, strong red emission, and optical gain properties [2]. The post-synthetic edge-functionalization of DBOV could be achieved through regioselective bromination, enabling the introduction of various substituents for modulating the optoelectronic and photophysical properties. For example, functionalization of DBOV with two fluoranthene imide (FAI) groups induced red-shift of the absorption and emission bands, increase of the Stokes shift, and enhancement of the stimulated emission (SE) signals with significantly reduced excited state absorption, allowing the efficient lasing at 720 nm [3]. On the other hand, we have more recently synthesized other unprecedented nanographenes with armchair, zigzag, and fjord edges, such as dibenzo[a,m]dinaphtho[3,2,1-ef:1',2',3'-hi]coronene (DBDNC), showing nonplanar structures by the single-crystal X-ray [4,5]. Notably, DBDNC displayed a SE signal at 710 nm with a longer lifetime than that of DBOV, presumably due to the suppression of intermolecular interactions. These results provide a further insight into the relationship between the PAH structures and their photophysical properties, paving the way toward their photonic applications.
References:
[1] G. M. Paternò, Goudappagouda, Q. Chen, G. Lanzani, F. Scotognella, A. Narita, Adv. Optical Mater. 9 (2021) 2100508.
[2] G. M. Paternò, Q. Chen, X.-Y. Wang, J. Liu, S. G. Motti, A. Petrozza, X. Feng, G. Lanzani, K. Müllen, A. Narita, F. Scotognella, Angew. Chem. Int. Ed. 56 (2017) 6753–6757.
[3] G. M. Paternò, Q. Chen, R. Muñoz-Mármol, M. Guizzardi, V. Bonal, R. Kabe, A. J. Barker, P. G. Boj, S. Chatterjee, Y. Ie, J. M. Villalvilla, J. A. Quintana, F. Scotognella, K. Müllen, M. A. Díaz-García, A. Narita, G. Lanzani, Mater. Horiz. 9 (2022) 393–402.
[4] X. Xu, G. Serra, A. Villa, R. Muñoz-Mármol, S. Vasylevskyi, M. Gadea, A. Lucotti, Z. Lin, P. G. Boj, R. Kabe, M. Tommasini, M. Á. Díaz-García, F. Scotognella, G. M. Paternò, A. Narita, Chem. Sci. 13 (2022) 13040–13045.
[5] X. Xu, R. Muñoz-Mármol, S. Vasylevskyi, A. Villa, G. Folpini, F. Scotognella, G. Maria Paternò, A. Narita, Angew. Chem. Int. Ed. 62 (2023) e202218350.
The design of supramolecular capsules with large cavities is attractive because they feature potential advantages as platforms to selectively bind large guests, such as fullerenes and Endohedral Metallofullerenes (EMFs).1 Generally, the practical applications of EMFs are hampered by their limited availability. Furthermore, their chromatographic purification (HLPC) is very challenging and in some cases it is not successful. Our group reported a porphyrin-based supramolecular tetragonal prismatic nanocapsule (1),2 which features an internal cavity with size complementary and electrostatic relationship specific for a brand new family of Uranium-based EMFs.3 Nanocapsule 1 is able to sequentially and specifically recognize U2@Ih-C80 and Sc2UC@Ih-C80 among all those compounds present in the crude, simply by soaking crystals in a solution of the reaction crude. The stepwise and selective encapsulation of U-based EMFs allowed their separation and further purification by solvent-washing, obtaining highly pure fractions of the desired compounds in one step. Follow-up studies with U-based C78 soots indicate that not only the internal clusterelectronics but also the shape of the carbon cages strongly influences the selectivity of the nanocapsule.Taking advantage of the tight binding of fullerenes in our porphyrin-based supramolecular tetragonal prismatic nanocapsules, these are used as supramolecular shadow masks to tame the over-reactivity of Bingel-Hirsch-type cyclopropanation reactions and, more importantly, to have full control on the equatorial regioselectivity and on the number of additions.4 Thus, exclusively equatorial bis-, tris- and tetrakis-C60 adducts using ethyl-bromomalonate are stepwise obtained and fully characterized (NMR, UV-vis and XRD). Furthermore, the regioselectivity control is finely tuned using a three-shell Matryoshka-like assembly towards the synthesis of a single trans-3 bis-Bingel-C60 for the first time.5 These results, fully attributed to the confinement control imposed by the capsule’s cavity, represent a novel and unique strategy to infer regio-control to the synthesis of fullerene multi-adducts. We envision that the described protocol will produce a plethora of derivatives for applications such as solar cells.
References:
[1] C. Fuertes-Espinosa, M. Pujals and X. Ribas, Chem, 2020, 6, 3219-3262.
[2] C. García-Simón, M. Garcia-Borràs, L. Gómez, T. Parella, S. Osuna, J. Juanhuix, I. Imaz, D. Maspoch, M. Costas and X. Ribas, Nat. Commun., 2014, 5, 5557
[3] C. Fuertes-Espinosa, A. Gómez-Torres, R. Morales-Martínez, A. Rodríguez-Fortea, C. García-Simón, F. Gándara, I. Imaz, J. Juanhuix, D. Maspoch, J. M. Poblet, L. Echegoyen and X. Ribas, Angew. Chem. Int. Ed., 2018, 57, 11294-11299
[4] C. Fuertes-Espinosa, C. García-Simón, M. Pujals, M. Garcia-Borràs, L. Gómez, T. Parella, J. Juanhuix, I. Imaz, D. Maspoch, M. Costas and X. Ribas, Chem, 2020, 6, 169-186
[5] E. Ubasart, O. Borodin, C. Fuertes-Espinosa, Y. Xu, C. García-Simón, L. Gómez, J. Juanhuix, F. Gándara, I. Imaz, D. Maspoch, M. von Delius and X. Ribas, Nat. Chem., 2021, 13, 420-427
| SESSION: NanomaterialsFriAM1-R3 | Echegoyen International Symposium (8th Intl. Symp. on Synthesis & Properties of Nanomaterials for Future Energy Demands) |
| Fri. 1 Dec. 2023 / Room: Dreams 3 | |
| Session Chairs: Ovidiu Crisan; Session Monitor: TBA | |
The formation of hybrid nanostructures in spintronic devices has been investigated as a response to specific needs especially in nanoelectronics or adjacent fields where combined optical and magnetic response to various excitations is required for various types of sensing. With the advent of high accuracy and high resolution fabrication technologies such as lithography, coupling phenomena at the nanoscale may become accessible. The integration of the magnetic and semi-conductor components adds new capabilities to the electronic devices. While spin phenomena have long been investigated within the context of conventional ferromagnetic materials, the study of spin generation, relaxation, and spin-orbit coupling in non-magnetic materials took off only recently with the advent of hybrid spintronics and it is here many novel materials and architectures can find their greatest potentials in both science and technology. Here we present initial approach to nanostructuring of hybrid patterned structures based on magnetic FePt-based bilayers, as well as their response to the optical excitation of magnetization, in view of potential applications as THz spintronic emitters. Indeed, spintronic THz emitters made of L10 phase ferromagnetic/non-magnetic bilayers, can exhibit spin-to-charge current transition, resulting in controlled and tunable THz pulse emission. This work is funded through National Recovery and Resilience Plan, research component I8 grant PNRR contract 47 / 2023, from Romanian Ministry of Research, Innovation and Digitalization.
08:40: [NanomaterialsFriAM102] OS InvitedPorphyrins are versatile macrocycles that fulfill vital functions in living systems; the property richness of porphyrins allows their exploitation in different application fields, and in my group we have been particularly interested in sensing applications [1]. Although it is true that monomeric porphyrins possess valuable properties, their self-assembly in sophisticated, size and shape-controlled suprastructures, conjugated with their integration with inorganic species to obtain hybrid materials, can significantly boost their potentialities, leading to advanced functional materials with improved properties. The deposition of layers of porphyrin-based materials onto the surface of different transducers [2], such as for example quartz crystal microbalances (QMB), has led to the preparation of sensor arrays successfully exploited in different application fields, such as environmental control, or medical diagnosis [3]. Furthermore, the implementation of elements of chirality on such systems widens their applicability to chiral discrimination, a challenging task for chemical sensors. Chiral porphyrin-based architectures can be obtained from either chiral or achiral platforms. The latest progress in the development of these hybrid systems will be presented and discussed.
References:
[1] R. Paolesse, S. Nardis, D. Monti, M. Stefanelli, C. Di Natale, Chem. Rev. 117 (2017), 2517-2583.
[2] G. Magna, S. Nardis, D. Monti, M. Stefanelli, C. Di Natale, R. Paolesse, Dalton Trans. 50 (2021) 5724-5731.
[3] C. Di Natale, R. Paolesse, E. Martinelli, R. Capuano, Anal. Chim. Acta 824 (2014), 1-17.
Inorganic fluorine-based compounds are found today as nano-components in many applications, including energy storage and conversion, photonics, electronics, medicinal chemistry, and more [1]. The strategic importance of nano-fluorinated materials can be illustrated by several examples drawn from various scientific fields. In the field of energy storage, fluorinated carbon nanoparticles (F-CNPs) are tested as active materials in primary lithium batteries, while 3d-transition metal fluorides and oxyfluorides, mainly iron-, cobalt- and titanium- based have been proposed as electrodes in secondary batterie(reversible) s. In all-solid-state batteries, materials derived from fluorite- (CaF2) or tysonite- (LaF3) structural types can be used as solid electrolytes, provided the F- anions are highly mobile. Nanocrystalline rare-earth fluorides are currently used for their photoluminescent properties at the micro- or nanoscale.
Functionalized nanoparticles and nanostructured compounds based on solid-state inorganic fluorides are used in many other advanced fields, including fluorinated graphene quantum dots (FGQDs), solar cells (DSSC, QDSSC), transparent conducting films (TCF), solid state lasers, nonlinear optics (NLO), UV absorbers, etc.
Their role is also decisive in medicine and biotechnologies [2], where doped rare-earth fluoride nanocrystals serve as luminescent biomarkers thanks to their up- and down-conversion properties, allow fluorine labeling of nanoparticles and in-vivo 19F NMR. Relevant nanotherapeutics include photodynamic therapy (PDT), luminescent thermometry, radiotracers for positron emission tomography (PET), theranostic nano-agents that incorporate both imaging probes and therapeutic media, and are therefore capable of carrying out both diagnosis and therapy within the same nano-object.
References
References:
[1] “Progress in Fluorine Science”, A. Tressaud Series Editor, Elsevier, Vol. 1, “Photonic & Electronic Properties of Fluoride Materials”, A.Tressaud & K. Poeppelmeier Eds. (2016). // Vol. 2 “New Forms of Fluorinated Carbons”, O. Boltalina & T. Nakajima, Eds. (2016). // Vol. 3 “Modern Synthesis Processes and Reactivity of Fluorinated Compounds”, H. Groult, F. Leroux & A. Tressaud, Eds. (2017). // Vol. 4 “Fluorine & Health: Pharmaceuticals, Medicinal Diagnostics, and Agrochemicals”, G. Haufe, & F. Leroux Eds. ( 2018).
[2] Fluoride Nanoparticles for Biomedical Applications, M.S.Pudovkin, R.M.Rakhmatullin, in: “Nanoparticles in Medicine”, Shukla, A. (ed), Springer (2020). https://doi.org/10.1007/978-981-13-8954-2_5
Our research group is interested in the application of supramolecular chemistry to understand and manipulate biology.[1,2] Our work philosophy is based in the importance of weak and non-covalent forces to control the shape and the topology of biomolecules, which are governed by the principles described by supramolecular chemistry. These supramolecular lessons can then be applied to control the properties and function of biomolecules. We believe that by modulating the shape we can mimic, control and improve functional behaviour. With focus in supramolecular interactions for artificial membranes and tubular composites, we investigate the construction of synthetic systems for controlling and emulating biology and life-like soft systems.[3-5]
References:
[1] General review: A. Fuertes, J. Marisa, J. R. Granja, J. Montenegro, Chem. Commun. 2017, 53, 7861–7871.
[2] Delivery review: I. Lostalé-Seijo, J. Montenegro, Nat. Rev. Chem. 2018, 2, 258–277.
[3] Membrane transport and delivery applications: a) I. Lostalé-Seijo, I. Louzao, M. Juanes, J. Montenegro, Chem. Sci. 2017, 8, 7923–7931. b) 1.Barba-Bon, A. et al. Nature, 2022, 603, 637–642.
[4] Synthetic supramolecular biocomposites: a) I. Insua, J. Montenegro, J. Am. Chem. Soc. 2020, 142, 1, 300-307, b) Méndez-Ardoy, A. et al. Angew. Chem. Int. Ed. 2020, 59, 6902–6908. d) 1.Booth, R., Insua, I., Ahmed, S., Rioboo, A. & Montenegro, J. Nat Commun. 2021, 12, 6421.
| SESSION: NanomaterialsFriAM2-R3 | Echegoyen International Symposium (8th Intl. Symp. on Synthesis & Properties of Nanomaterials for Future Energy Demands) |
| Fri. 1 Dec. 2023 / Room: Dreams 3 | |
| Session Chairs: Yutaka Matsuo; Session Monitor: TBA | |
Rare-earth permanent magnets have a broad range of applications, in motors of electric and hybrid cars, in wind turbines, and in any machine where efficiency is important [1]. Many countries are establishing rigorous standards for electric motors efficiency, as IE4 and IE5 [1,2].A rotating machine as an electric motor has two main components: a rotor and a stator. In essence, by using a permanent magnet in the rotor, the efficiency of the machine can be increased. This save an energy that would be used to magnetize the rotor. This also makes possible that the motor can be of the brushless type, thus avoiding friction.In the electrical motors, the magnets need to present high resistance against reversal of magnetization. The motor heats during the motor operation. As consequence, the magnets embedded in the stator also heats. There is much research on increasing motor efficiency [3], especially in the case of electric cars, where automony is an important issue, and where batteries are very expensive.Nanocrystalline magnets display better resistance against reversal of magnetization. Here this subject is discussed by considering magnetostatic and exchange energy terms. The mechanisms of reversal of magnetization in nanocrystalline permanent magnets are reviewed. Nanocrystalline Rare-earth magnets can be used in motors, or also in thin films [4]. Crystallographic texture effects on the coercivity are also discussed [5].
References:
[1] https://commission.europa.eu/news/new-eu-rules-boost-energy-efficiency-electric-motors-2021-06-30_en
[2] https://eandt.theiet.org/content/articles/2023/03/motoring-into-the-ie5-era-for-energy-efficiency/
[3] https://fox5sandiego.com/automotive/internet-brands/how-lucid-leaps-past-tesla-with-smaller-motors/amp/
[4] https://link.springer.com/article/10.1007/s13204-023-02931-1
[5] https://www.sciencedirect.com/science/article/abs/pii/S0304885322010046
The possible utilization of biological nano-logic circuits in the integration and regulation of DNA repair, and their potential use by cells in rapid sub-second decision making and calculations are discussed. Given advantages of logic type control, one would expect that if it hadn't arisen the during the initial abiotic phase of evolution, then it would have arisen to control at least some biological processes over the next approximately 3 billion years of evolution, where single celled life was likely the only form of life on Earth. Several of the required components have been identified in cells, such as biological concentration oscillations, which behave as an analogue of the square wave time base in electronic sequential digital circuits, and at least one phosphologic gate. Globular protein logic gates would be ~10% of the size, in terms of their linear dimensions (1/1000th of the volume), of their smallest current electronic counterparts. The study of the control of cellular data processing pathways will reveal the relative importance of analog versus digital control. These future studies will likely give rise to the tools necessary to therapeutically exploit this information.
11:10: [NanomaterialsFriAM207] OSπ-Organic diradicals are molecules with two unpaired electrons which emerge from the total or partial rupture of a chemical bond, typically a π-double bond.1 Such unpaired electrons are stabilized by delocalization over the π-system and, to some extent, remain chemically inert. This allows the possibility to exploit these new chemical species with broken bonds in organic electronic applications.2 In this contribution, we will describe the electronic structure of such organic diradical molecules and will address the key points that allow their implementation in organic field effect transistors devices,3 in photonics, in thermoelectric or thermopower applications.4
References:
1. J. Casado, Topic in Current Chemistry, 2017, 375, 73.
2. Stephen Forrest, Organic electronics: Foundations and Applications, Oxford University press, 2020.
3. S. Mori, S. Moles Quintero, N. Tabaka, R. KishI, R. González Núñez, A. Harbuzaru, R. Ponce Ortiz, J. Marín-Beloqui, S. Suzuki, C. Kitamura, C. J. Gómez-García, Y. Dai, F. Negri, M. Nakano, S. Kato, J. Casado, Angew. Chem. Int. Ed. 2022, 61, e202206680.
4. D. Yuan, D. Huang, S. Medina Rivero, A. Carreras, C. Zhang, Y. Zou, X. Jiao, C. R. McNeill, X. Zhu, C. Di, D. Zhu, D. Casanova, J. Casado, CHEM, 2019, 5, 964-976.
In recent years, carbon materials are widely investigated because of their extraordinary chemical, electrical and physical properties. But most of the researchers utilizes graphite, graphene, reduced graphene oxide (rGO), carbon nanotubes (CNT), etc., as carbon material due to their excellent aforsaid properties. Keeping this in mind, we have syntheized the candle carbon soot using candle flame at room temperture conditions. We have observed that a simple flame of candle is used to synthesize the layers of carbon soot on desired substrate. This synthesis method has become an alternative rote for the preparation of carbon nanomaterials because of its advantages of low cost and mass production. Also, we have investigated , the acid treatment of candle soot is drastically improved their structural and electrical properties as compared to as-synthesized soot. The effect of acid functionalization on the candle soot structure were investigated by X-ray diffraction (XRD) and Raman spectroscopy. This material has potential application in battery, photovoltaic cell, electronics and sensor.
References:
[1] 1. Rajkumar et al, Candle soot carbon nanoparticles as high-performance universal anode for M-ion (M = Li+, Na+ and K+) batteries, Journal of Power Sources, 458, (2020) 228064.
[2] 2. Swapana Phara et al, A noble metal-free candle soot derived carbon electrocatalyst for simultaneous H2 generation and wastewater treatment, Journal of Physics and Chemistry of Solids, 173, (2023), 11110.
[3] 3. Shivani Dhall et al, Room temperature hydrogen gas sensor using candle carbon soot” International Journal of Hydrogen Energy 45 (2020) 14997
| SESSION: NanomaterialsFriPM1-R3 | Echegoyen International Symposium (8th Intl. Symp. on Synthesis & Properties of Nanomaterials for Future Energy Demands) |
| Fri. 1 Dec. 2023 / Room: Dreams 3 | |
| Session Chairs: Akimitsu Narita; Session Monitor: TBA | |
In the present communication we will focus on the use of organic charge transporting materials that have synthesized in our lab and used to prepare Perovskite-based Solar Cells.1,2
In our research group we have dedicated a great effort on the preparation and study of novel organic compounds for their incorporation in perovskite solar devices, either as hole or electron-transporting layers. Thus, we have reported the use of fullerenes3,4 and NDIs5 as electron transporting layers in PSCs, to prepare efficient and stable devices. On the other hand we have prepared a great variety of hole transporting materials, including polymers,6 and Oligotryarylamine (OTA) functionalized with different cores such as HexaArylBenzene (HAB),7fullerene,8 or pillarene9 among others, to prepare highly efficient and stable in PSCs.
References:
1) Pascual, J.; Delgado, J. L.; Tena-Zaera, R. J. Phys. Chem. Lett. 2018, 9, 28933; 2) S. F. Volker, S. Collavini, J. L. Delgado, ChemSusChem 2015, 8, 3012. 3) Collavini, S.; Kosta, I.; Völker, S. F.; Cabanero, G.; Grande, H. J.; Tena-Zaera, R.; Delgado, J. L. ChemSusChem 2016, 9, 1263; 4) Pascual, J.; Kosta, I.; Ngo, T. T.; Chuvilin, A.; Cabanero, G.; Grande, H. J.; Barea, E. M.; Mora-Seró, I.; Delgado, J. L.; Tena-Zaera, R. ChemSusChem VIP 2016, 9, 2679; 5) S. Valero, A. Cabrera-Espinoza, S. Collavini, J. Pascual, N. Marinova, I. Kosta, J. L. Delgado, Eur. J. Org. Chem. 2020, 5329; 6) S. Valero, S. Collavini, S. F. Völker, M. Saliba, W. R. Tress, S. M. Zakeeruddin, M. Grätzel, and J. L. Delgado, Macromolecules, 2019, 52, 2243; 7) M. Shasti, S. F. Völker, S. Collavini, S. Valero, F. Ruipérez, A. Mortezaali, S. M. Zakeeruddin, M. Grätzel, A. Hagfeldt, J. L. Delgado, Org. Lett,. 2019 21, 3261; 8) S. F. Völker, M. Vallés-Pelarda, J. Pascual, S. Collavini, F. Ruiperez, E. Zuccatti, L. E. Hueso, R. Tena-Zaera, I. Mora-Seró and J. L. Delgado, Chem.–Eur. J., 2018, 24, 8524; 9) O.Bettucci, J. Pascual, S.-H. Turren-Cruz, A. Cabrera-Espinoza, W. Matsuda, S. F. Völker, H. Köbler, I. Nierengarten, G. Reginato, S. Collavini, S. Seki, J.-F. Nierengarten, A. Abate, J. L. Delgado, unpublished results.
The activation of small molecules play an important role to towards more sustainable chemical processes. Renewable solar and wind resources can provide the energetic driving for such reactions, leading to electrocatalytic transformations. Here, I will present our research on the cathodic, reductive activation of O2, N2 and CO2 using trimetal substituted polyoxometalates as active site functional mimics of redox metalloenymes. Second, I will present the use of metal guest-Keplerate host supramolecules as inorganic analogs of redox metalloenyme assemblies.Cathodic activation of O2: Paradoxically, nature’s monooxygenase enzymes activate O2 typically via a two-electron reductive pathway. Both Fe and Cu-based catalysis using reducing agents under protic conditions is known, but surprisingly, cathodic electrocatalysis using H2O as a proton and electron source is almost unreported. Recently, we found that iron Keplerates, {Fe30W72} can be used as electrocatalysts for the oxidation of light alkanes and alkenes in water.[1] Mechanistic studies have revealed that reaction intermediates have reactivity profiles similar to those observed for Compound I of cytochrome P-450.[2] More recently, we have also found that tetra-Cu Weakley polyoxometalates also are also very efficient electrocatalysts for the cathodic activation of O2 and show reactivity profiles similar to those of the iron Keplerates.Reduction of CO2 to CO: The removal of CO2 from the atmosphere through is capture or sequestration is a feasible technology, however, is not sustainable due to the high cost of the process and the low value of captured CO2requiring the transformation of CO2 to a higher valued products. Therefore, we have prepared a series of trimetallo substituted polyoxometalates that on the one hand can catalyze the reversible reduction of CO2 and oxidation of CO,and on the other hand can be tuned to reduce CO2 with very low overpotentials.[3]Reduction of N2 to NH3: The electrification of ammonia synthesis is a key target for its decentralization and toward lowering the impact of chemical processes on atmospheric carbon dioxide concentrations. Using catalyst a tri-iron substituted polyoxotungstate, {SiFe3W9} in the presence of either Li+ or Na+ cations as promotors through their binding to {SiFe3W9} we show that in an undivided cell electrolyzer, rates of NH3 formation was at up to 1.15 nmol sec–1 cm–2 with moderate faradaic efficiencies of ~25%. Based on an assumption of arbitrary 10% catalyst coverage on a Cu foil cathode, a TOF of 64 sec–1 was calculated. Iron-nickel guest-{Mo60W72} host supramolecules as an inorganic functional mimic of a hydrogenase enzyme: Can soluble inorganic metal oxides and the related guest-host complexes with encapsulated transition metals incorporated through assembly reactions, act as functional analogues of redox metalloenzymes that carry out multielectron transformations of small molecules? Here we show, that Fe-Ni assemblies bound to mercaptopropionate lignads within {Mo60W72} acts as a hydrogenase enzyme complex electro- and photoelectrochemically (PEC) forming hydrogen from protons and electrons. Reactions rate comparable to those found in the wild type enzyme are observed with very high faradaic efficiency under PEC conditions.
References:
[1] M. Bugnola, R. Carmieli, R. Neumann, ACS Catalysis, 2018, 8, 3232-3236.
[2] M. Bugnola, K. Shen, E. Haviv, Ronny Neumann, ACS Catalysis, 2020, 10, 4227-4237.
[3] D. Azaiza-Dabbah, C. Vogt, F. Wang, A. Masip-Sánchez, C. de Graaf, J.M. Poblet, E. Haviv, R. Neumann, Angewandte Chemie International Edition, 2022, 61, e202112915.
Finding novel solutions to combat climate change is one of the most challenging and pressing issues the humankind is currently facing.[1] While the production of solar fuels is still at a low technology readiness level, solutions need to be shown now to authorities and general public so that quick adaptation to renewable energies is achieved. With some European countries forcing fossil fuels out of their economies, hydrogen is seen as a very promising solution to deliver zero emission transportation.[2]
In this presentation, I will give an overview of project SEAFUEL.[3] SEAFUEL aims to use the renewable resources across the Atlantic Area to power the local transport fleet and support the shift towards a low-carbon economy. This demonstration project is the first example of integrating the use of solar energy and seawater to produce green hydrogen. In addition, the green hydrogen will be used to power a fleet of vans and some fuel cell buses, used locally by our partner in Tenerife ITER, as well as regional bus operator TITSA.
In parallel to the technology developments, academic partners in Liverpool and Galway have worked on the development on new electrode materials to fabricate electrolysers capable to operate under low-grade water. The latest developments in the field are discussed to guide research into new selective and efficient water splitting catalysts [4].
References:
[1] https://www.un.org/sustainabledevelopment/sustainable-development-goals/
[2] http://hydrogencouncil.com/
[3] http://www.seafuel.eu
[4] Tong et al. Nature Energy 2020, 5, 367-377.
| SESSION: NanomaterialsFriPM2-R3 | Echegoyen International Symposium (8th Intl. Symp. on Synthesis & Properties of Nanomaterials for Future Energy Demands) |
| Fri. 1 Dec. 2023 / Room: Dreams 3 | |
| Session Chairs: Ira Weinstock; Session Monitor: TBA | |
In recent years, considerable research has been carried out exploring the potential of oxide glasses as cathode materials for solid-state batteries [1-3]. Among these materials, alkali-transition metal oxide (TMO)-phosphate-based glasses garnered significant interest due to their, stable frameworks, minimal volume changes, thermodynamic stability, and excellent alkali storage capacity. Furthermore, as consist of both alkali and TM ions, which can exist in various oxidation states, these systems can exhibit the mixed ionic-polaronic conduction mechanism. Such feature has proven to be highly effective in facilitating the intercalation and deintercalation of alkali ions. It is also crucial that cathode materials have high thermal stability, which can be improved by incorporating metal oxides, for instance Nb2O5, into their composition [4].This talk will focus on the electrical properties of glasses from Na2O-V2O5-Nb2O5-P2O5 system. By varying the concentration of V2O5 (10 and 25 mol%) in two series, we aim to examine how its content influences the electrical transport mechanism, permitting us to evaluate its possible polaronic contribution by utilizing Solid-state impedance spectroscopy (SS-IS). Obtained conductivity spectra are studied in detail using two model-free scaling procedures, namely Summerfield and Sidebottom scaling. The results reveal that glasses with lower V2O5 content (10 mol%) exhibit a purely ionic conduction mechanism, indicating that V2O5 does not contribute to electrical conductivity via a polaronic mechanism. On the other hand, for glasses with higher V2O5 (25 mol%) and low Nb2O5 (0 and 5 mol%) content, a mixed ionic-polaronic conductivity is observed with dominant polaronic contribution. Interestingly, with further increase in Nb2O5 above 10 mol%, there is a switch in conduction mechanism and ionic one prevails. These findings provide valuable insights into the mixed-conductive glass system and shed light on the roles of V2O5 and/or Nb2O5, showcasing the ability to fine-tune the mechanism of electrical conductivity by adjusting the content of oxide glass and its ratio. Lastly, obtained results will be compared with our recent studies of conductivity mechanism in glasses with various TMO and alkali ions [5] and pure polaronic glasses [6].
References:
[1] C. Wang et al. J. Mater. Sci. Technol. 66 (2021) 121–127.
[2] C. Wang, & J. Hong, Electrochem. Solid-State Lett. 10, (2007) A65.
[3] A. Lannerd et al. Green Sustainable Process for Chemical and Environmental Engineering and Science, Elsevier (2023) 223-262.
[4] B. Getachew, K.P. Ramesh, G.V. Honnavar, Mater. Res. Express 7 (2020) 095202.
[5] A. Šantić et al. Acta Materialia 175 (2019) 46-54.
[6] A. Bafti et al. Nanomaterials 12 (2022) 639.
In the last few years, the mechanical bond has been added to the chemistry toolbox for SWNT modification.[1] In this presentation, I will first discuss the characteristics of the mechanical bond that make it appealing for SWNTs. I will then describe the potential advantages of making mechanically-interlocked derivatives of SWNTs (MINTs), as compared to covalent or classic supramolecular derivatives of SWNTs, and go on to explain our approach for the synthesis of MINTs.[2,3] Finally, I will illustrate with examples how the making of MINTs can contribute to modifying the surface properties of SWNTs,[4] modulating their electronic properties,[5] and linking them to functional molecular fragments.[6,7]In the 2D materials field, I will describe the covalent grafting of 2H-MoS2 flakes on graphene monolayers embedded in field-effect transistors.[8] A bifunctional molecule was used that features a maleimide and a diazonium functional group, known to connect to sulfide- and carbon-based materials, respectively. MoS2 flakes were first exfoliated, functionalized by reaction with the maleimide moieties, then anchored to graphene through the diazonium groups. This approach enabled the simultaneous functionalization of several devices. The electronic properties of the resulting heterostructure are shown to be dominated by the MoS2–graphene molecular interface.I will also discuss the journey that has led to these results, including the development of a “click” chemistry reaction for transition metal-dichalcogenides,[9-11] and insights into the covalent patterning of graphene.[12-14]
References:
[1] A. López-Moreno, J. Villalva, E. M. Pérez, “Mechanically interlocked derivatives of carbon nanotubes: synthesis and potential applications” Chem. Soc. Rev. 2022, 51, 9433-9444.
[2] A. de Juan, Y. Pouillon, L. Ruiz-González, A. Torres-Pardo, S. Casado, N. Martín, A. Rubio, E. M. Pérez, Angew. Chem., Int. Ed. 2014, 53, 5394-5400.
[3] E. M. Pérez, Chem. Eur. J. 2017, 23, 12681-12689.
[4] A. López-Moreno, B. Nieto-Ortega, M. Moffa, A. de Juan, M. M. Bernal, J. P. Fernández-Blázquez, J. J. Vilatela, D. Pisignano, E. M. Pérez, ACS Nano 2016, 10, 8012-8018.
[5] M. Blanco, B. Nieto-Ortega, A. de Juan, M. Vera-Hidalgo, A. López-Moreno, S. Casado, L. R. González, H. Sawada, J. M. González-Calbet, and E. M. Pérez, Nat. Commun. 2018, 9, 2671.
[6] S. Moreno-Da Silva, J. I. Martínez, A. Develioglu, B. Nieto-Ortega, L. de Juan-Fernández, L. Ruiz-Gonzalez, A. Picón, S. Oberli, P. J. Alonso, D. Moonshiram, E. M. Pérez, E. Burzurí, J. Am. Chem. Soc. 2021, 143, 21286-21293.
[7] W. Zhang, M. Guillén-Soler, S. Moreno-Da Silva, A. López-Moreno, M. L. Ruiz-González, M. Giménez, E. M. Pérez Chem. Sci., 2022, 13, 9706-9712.
[8] M. Vázquez Sulleiro, A. Develioglu, R. Quirós-Ovies, L. Martín-Pérez, N. Martín Sabanés, M. L. Gonzalez-Juarez, I. J. Gómez, M. Vera-Hidalgo, V. Sebastián, J. Santamaría, E. Burzurí, E. M. Pérez, Nat. Chem. 2022, 14, 695-700.
[9] M. Vera-Hidalgo, E. Giovanelli, C. Navio, E. M. Pérez, J. Am. Chem. Soc. 2019, 141, 3767-3771.
[10] R. Quirós-Ovies, M. Vázquez Sulleiro, M. Vera-Hidalgo, J. Prieto, I. J. Gómez, V. Sebastián, J. Santamaría, E. M. Pérez, Chem. Eur. J. 2020, 26, 6629-6634.
[11] M. Vázquez Sulleiro, R. Quirós-Ovies, M. Vera-Hidalgo, I. J. Gómez, V. Sebastián, J. Santamaría, E. M. Pérez, Chem. Eur. J. 2021, 27, 2993.
[12] J J Navarro, S Leret, F Calleja, D Stradi, A Black, R Bernardo-Gavito, M Garnica, D Granados, A L Vazquez de Parga, E M Pérez, and R Miranda, Nano Lett. 2016, 16, 355-361.
[13] J. J. Navarro, F. Calleja, R. Miranda, E. M. Pérez, A. L. Vázquez de Parga, Chem. Commun. 2017, 53, 10418-10421.
[14] A. Naranjo, N. Martín Sabanés, M. Vázquez Sulleiro, E. M. Pérez Chem. Commun. 2022, 58, 7813-7816.
Understanding of chemical behaviour of actinide elements is essential for the effective management and use of actinide materials. However, actinide structural chemistry is challenging from the perspectives of both experiments and theories. To date, some of the important actinide bonding motifs, such as actinide-actinide metal-metal bond and actinide multiple bond, can only be obtained in the unstable clusters in gas phase. The hollow internal cavity of fullerene buckyballs has been known to be able to encapsulate novel metallic units, especially those otherwise very reactive or virtually impossible to prepare clusters. In this talk, we will present our recent studies of novel actinide endohedral fullerenes, focusing on their unique bonding behaviors. We found that unprecedented actinide metal-metal bond and actinide-lanthanide metal-metal bond can be formed and stabilized inside a series of dimetallic metallofullerenes, such as U2@Ih(7)-C80 , Th2@Ih(7)-C80 and ThLn( Ln= Y, Dy)@Ih(7)-C2n. In addition, we obtained a series of stable molecule compounds which contains unique actinide bonds such as axial U=C bond and U≡C triple bond, enabling the experimental characterizations of these actinide bonds for the first time. These research results provide new perspective to the study of actinide bonds and endohedral fullerenes.
17:20: [NanomaterialsFriPM317] OSAmmonium ion (NH4+) based aqueous hybrid supercapacitors (AHSCs) are attracting attention due to their environmental friendliness and excellent electrochemical performance [1-2]. Two-dimensional (2D) transition metal nitrides, carbides, and/or carbonitrides (MXenes) are the best choice for AHSCs cathode materials due to excellent performance, but the self-stacking effect of two-dimensional materials limits their wide application [3]. To solve this problem, we propose to grow 2H-MoS2 nanosheets on the surface of Ti3C2Tx MXene, constructing heterostructures at the interface (HS-2H-MS@MXene). On the one hand, 2H-MoS2 nanosheets are evenly distributed and oriented perpendicularly to the MXene surface. This arrangement enhances the material's specific surface area, creating additional sites for NH4+ to reach to the MXene bone. On the other hand, the interface between the two materials forms a heterostructure that effectively prevents the recombination of charge carriers and facilitates fast redox reactions. The results show that the HS-2H-MS@MXene single electrode has a batter capacitance of 722.13 F/g at 1A/g, surprising rate capability (61.6% at 20 A/g) and excellent cycle stability of 90.1 % (after 5,000 cycles at 10 A/g), outperforming 2H-MoS2 and the pristine MXene. Using activated carbon (AC) as the anode to assemble AHSC (HS-2H-MS@MXene//AC), it provides aspecific energy of 51.1 Wh/kg at 750.6 W/kg. It maintains an ultra-high capacitance of 95.6% after 10,000 charge/discharge cycles. In addition, density function theory (DFT) results show that the HS-2H-MS@MXene (Tx=O) electrode possesses higher conductivities. The calculated band energies, adsorption energies (Eads), and diffusion barriers proved the enhanced conductivities of the HS-2H-MS@MXene electrode. This study could potentially introduce a novel concept for the advancement of high-performance cathode materials in the context of AHSCs.
References:
[1] Javed, Muhammad Sufyan, Xiaofeng Zhang, Salamat Ali, Syed Shoaib Ahmad Shah, Awais Ahmad, Iftikhar Hussain, Shahid Hussain et al. "Boosting the energy storage performance of aqueous NH4+ symmetric supercapacitor based on the nanostructured molybdenum disulfide nanosheets." Chemical Engineering Journal 471 (2023): 144486.
[2] Pan, Y., Yuan, L., Liu, L., Fang, W., Hou, Y., Fu, L. and Wu, Y., 2023. Critical Advances of Aqueous Rechargeable Ammonium Ion Batteries. Small Structures, p.2300201.
[3] Yang, Li, Wei Zheng, Joseph Halim, Johanna Rosen, ZhengMing Sun, and Michel W. Barsoum. "A Highly Reversible Aqueous Ammonium‐Ion Battery based on α‐MoO3/Ti3C2Tz Anodes and (NH4) xMnO2/CNTs Cathodes." Batteries & Supercaps 6, no. 3 (2023): e202200432.
The aqueous hybrid supercapacitor (AHSC) based on ammonium ion (NH4+) is an interesting energy storage device with excellent properties. However, the scarcity of appropriate and effective cathode materials limited its practicality. Two-dimensional (2D) transition metal nitrides, carbides, and/or carbonitrides (MXenes) show potential as cathode materials, but their low capacitance also limits their applicability. Here, we synthesized N-functionalized 2D MXene (Ti3C2Tx) with Ti2N interface engineering (Ti2N/Ti3C2Tx), which displayed not only superior capacitance and rate capability but also a cycling stability then pristine Ti3C2Tx. Ex-situ XRD and XPS were used to study the fast transport of electrons/ions and its charge storage mechanism at the interface of Ti2N/Ti3C2Tx. Furthermore, density functional theory (DFT) calculations were employed to validate the superior conductivity at the interface of the Ti2N/Ti3C2Tx(Tx = OH) electrode. Moreover, AHSC was assembled with the Ti2N/Ti3C2Tx as cathode and activated carbon as anode possesses outstanding energy storage performance. This study not only elucidates the charge storage process of Ti2N/Ti3C2Tx but also provide new insights for designing novel cathode materials for energy storage devices.
| SESSION: SolidStateChemistryTueAM-R4 | Poeppelmeier International Symposium(3rd Intl Symp on Solid State Chemistry for Applications & Sustainable Development) |
| Tue. 28 Nov. 2023 / Room: Dreams 4 | |
| Session Chairs: Shiv Halasyamani; Session Monitor: TBA | |
Paraphrasing Nobel Laureate Arno Penzias who famously titled one of his many lectures “Logical Machines for Rational People”, this talk will show that while most racemates crystalize in centrosymmetric structures, some do not, and these form an important and often overlooked class of Chiral and/or Polar Matter with broken inversion symmetry. This talk is based in part on a paper that we published several years ago with the title “Machine-learning-assisted Synthesis of Polar Racemates,” the authors were M. L. Nisbet, I. M. Pendleton, G. M. Nolis, K. J. Griffith, J. Schrier, J. Cabana, A. J. Norquist, and K. R. Poeppelmeier, J. Am. Chem. Soc., 142(16), 7555–7566 (2020) that describes our efforts to synthesize other new members of a peculiar class of noncentrosymmetric (NCS) materials first reported in “From Racemic Units to Polar Materials,” R. Gautier, A. Norquist, and K. R. Poeppelmeier, Cryst. Growth Des., 12, 6267–6271 (2012). These interesting NCS phases contain equal numbers of oppositely handed chiral species forming an important, often overlooked class of materials with useful properties. We prepared a series of NCS racemic compounds with the formula [Cu(bpy)2(H2O)]2[MF6]2•3H2O (M = Ti4+, Zr4+, Hf4+; bpy = 2,2’bipyridine), denoted as CBM-0D. The polarity of the anion leads to inversion symmetry breaking, By following a machine learning-augmented composition space approach, we were able to synthesize the two missing members of the CBM-0D family (M = Ti4+, Zr4+) and learned that each polar CBM-0D phase forms in competition with a unique nonpolar coordination polymer (denoted as CBM-1D) based on [Cu(bpy)(H2O)2]2+ and [MF6]2- units. Phase stability of the CBM-0D compounds depends strongly on the choice of M, with the 1D structure predominating when M = Ti while the 0D structure is favored for M = Zr, Hf. To understand these differences in structure-directing properties between [TiF6]2- and [ZrF6]2-/[HfF6]2-, we performed x-ray absorption spectroscopy measurements and density functional theory calculations to probe local differences in electronic structure and describe them in terms of the second-order, or pseudo-, Jahn-Teller effects present in each [MF6]2- anion.
12:00: [SolidStateChemistryTueAM02] OSNonlinear optical (NLO) materials are critical in generating coherent light through frequency conversion, e.g., second harmonic generation (SHG). From the ultraviolet (UV) to the infrared (IR), NLO materials have expanded the range of the electromagnetic spectrum accessible by solid-state lasers. Wavelengths where NLO materials are still needed include the UV (~200 - 400nm) and deep UV (< 200nm). Coherent deep-ultraviolet (DUV) light has a variety of technologically important uses including photolithography, atto-second pulse generation, and in advanced instrument development. Design strategies will be discussed, as well as synthetic methodologies. In addition, the crystal growth, characterization, and structure-property relationships in new UV and DUV NLO materials discovered in our laboratory will be presented. Finally, our crystal growth capabilities and recent crystal growth of functional materials will be described.
12:25: [SolidStateChemistryTueAM03] OLPbCrO3 perovskite was first synthesized by Roth and deVries in the late 1960s [1]. Chamberland and Moeller [2] also synthesized PbCrO3 and their structural results were in agreement with the previous ones but, in addition, reported an unusual broadening of the diffraction peaks even using monochromatic CuKa1 radiation. These broad lines in the X-ray powder patterns were also observed for the same compound by Goodenough et al. [3]. However, in these works neither atomic concentration nor microstructural studies were considered and/or analyzed. A rather puzzling situation concerning the 3d-metal, (4+) lead-based perovskites, resides in the fact that while PbTiO3 is tetragonal with c/a 1⁄4 1.064 and ferroelectric with Tc763 K [4], and PbVO3 is also tetragonal with a higher tetragonality factor, c/a 1⁄4 1.229 [3,4], PbCrO3 has been described as cubic. This is unexpected as in terms of ionic size the following trend is observed: VIr4+Cr< VIr4+V< VIr4+Ti, (0.55, 0.58, and 0.605 A, respectively [4]). Thus, one could expect that PbCrO3 should be even more tetragonal since the Cr(IV)–O bond would be more covalent. We have performed a structural and microstructural study using XRD, selected area electron diffraction (SAED) and high-resolution transmission electron microscopy (HRTEM) to elucidate the origin of the abnormal broadening of the XRD maxima and to clarify the origin of the cubic structure of PbCrO3. In this way, it is shown that the lead-perovskite compound ‘‘PbCrO3’’ has a Pb deficiency, resulting in a modulated structure within a complex microdomain texture.
References:
[1] W.L. Roth, R.C. DeVries, J. Appl. Phys. 38 (1967) 951.
[2] B.L. Chamberland, C.W. Moeller, J. Solid State Chem. 5 (1972) 39.
[3] R.V. Sphanchenko, V.V. Chernaya, A.A. Tsirlin, P.V. Chizhov,, D.E. Sklovsky, E.V. Antipov, Chem. Mater. 16 (2004) 3267.
[4] A.A. Belik, M. Azuma, T. Saito, Y. Shimakawa, M. Takano, Chem. Mater. 17 (2005) 269.
From 1950 to 2015, more than 4.9 billion metric tons of new plastic materials were put into landfills or the environment. Unfortunately, this number will continue to increase due to the yearly production of over 350 million metric tons of plastic, of which 79% is quickly discarded. This plastic waste is not only a significant environmental issue but also a concern for human health. However, these wastes contain valuable amounts of energy and carbon that could be used as feedstock in the chemical industry. To combat the plastic waste crisis, there are ongoing efforts to transform these wastes into high-value chemicals through chemical upcycling. Our research has shown that earth-abundant zirconia nanoparticles can cleave the C-C bond in polyethylene to create a narrow distribution of small hydrocarbon molecules catalytically.[1] This material consists of nanoparticles of zirconia embedded in the walls of mesoporous silica, named as L-ZrO2@mSiO2. The mSiO2 coating on zirconia nanoparticles helps to stabilize the coordinatively unsaturated surface sites needed for catalysis. Our DFT calculations show that these oxides can mediate C-C bond hydrogenolysis with activity comparable to Pt/C. This is due to L-ZrO2@mSiO2 containing a combination of small crystalline ZrO2 with mSiO2, which we hypothesize to contain a large number of ZrOx defect sites that exhibit catalytic activity. A new bifunctional (hydroxy)organozirconium oxide species has been suggested for catalytic chemistry. The hydrogenolysis with L-ZrO2@mSiO2 is a previously unrecognized heterogeneous analog of the SOMC-catalyzed C-C cleavage processes.[2-4]
References:
[1] S. Chen, A. Tennakoon, K.-E. You, A. L. Paterson, R. Yappert, S. Alayoglu, L. Fang, X. Wu, T. Y. Zhao, M. P. Lapak, M. Saravanan, R. A. Hackler, Y.-Y. Wang, L. Qi, M. Delferro, T. Li, B. Lee, B. Peters, K. R. Poeppelmeier, S. C. Ammal, C. R. Bowers, F. A. Perras, A. Heyden, A. D. Sadow and W. Huang, Nat. Catal. 6 (2023) 161-173.
[2] S. Norsic, C. Larabi, M. Delgado, A. Garron, A. de Mallmann, C. Santini, K. C. Szeto, J.-M. Basset and M. Taoufik, Catal. Sci. Technol. 2 (2012) 215-219.
[3] V. Dufaud and J. M. Basset, Angewandte Chemie - International Edition 37 (1998) 806-810.
[4] F. Quignard, C. Le´cuyer, A. s. Choplin, D. l. Olivier and J.-M. Basset, J. Mol. Catal. 74 (1992) 353-363.
| SESSION: SolidStateChemistryTuePM1-R4 | Poeppelmeier International Symposium(3rd Intl Symp on Solid State Chemistry for Applications & Sustainable Development) |
| Tue. 28 Nov. 2023 / Room: Dreams 4 | |
| Session Chairs: Romain Gautier; Session Monitor: TBA | |
Nonlinear optical (NLO) materials, known for their strong second harmonic generation (SHG), have garnered significant interest attributed to their wide-ranging applications [1-2]. While the conventional approach to enhance SHG involves the design of NLO-active molecular units, recent studies have explored an innovative approach by incorporating vacancies and local structural distortions in solid-state materials, further improving the NLO effect.This presentation aims to highlight recent advancements in the design and synthesis of tungsten bronze (TB) oxides with enhanced NLO properties. It investigates the influence of vacancies-induced local structural distortions on the SHG response and presents a molecular design strategy for the development of novel NLO materials [3]. The talk covers the synthesis, structures, and characterizations of a series of novel TB oxides, along with the introduction of transition metal-doped tungsten bronze oxides that exhibit unique structures and exceptionally large SHG responses [4].Additionally, a polar tetragonal TB oxide with a reversible phase transition and an extraordinary SHG intensity is presented [5]. The incorporation of vacancies in TB oxide structures results in local structural distortions that strengthen the dipole moments of neighboring octahedra, significantly enhancing the SHG response. The observed colossal SHG intensity and phase-matchable behavior in the TB oxides underscore the effectiveness of the proposed molecular design strategy. Furthermore, the vacancies-induced structural distortions hold promise for the development of NLO materials with superior performance.
References:
[1] P.A. Franken, A.E. Hill, C.W. Peters, G. Weinreich, Phys. Rev. Lett. 7 (1961) 118-119.
[2] P.S. Halasyamani, K.R. Poeppelmeier, Chem. Mater. 10 (1998) 2753-2769.
[3] K. Lin, P. Gong, S. Chu, Q. Li, Z. Lin, H. Wu, Q. Wang, J. Wang, M. J. Kim, K. Kato, C.-W. Wang, X. Liu, Q. Huang, J. Chen, H. Zhu, J. Deng, X. Xing, J. Am. Chem. Soc. 142 (2020) 7480-7486.
[4] Y. Pi, Y. Kuk, K.M. Ok, Adv. Funct. Mater. 33 (2023) 2214985.
[5] Y. Kuk, S.B. Bae, S.M. Yang, K.M. Ok, Adv. Sci., 10 (2023) 2301374.
Our research primarily focuses on the exploratory syntheses of inorganic solid functional compounds, aiming to unravel the intricate relationships between crystallographic structures and their corresponding macroscopic properties, notably nonlinear optical (NLO) phenomena, second-harmonic generations [1-5] and thermoelectric properties [6-10]. For example, we have developed the first monofluorophosphates exhibiting excellent second-harmonic generation capabilities,[1, 2] along with pioneering advancements in inorganic solid state NLO switch materials with a linearly tunable Tc. [3]Additionally, we have proposed a novel design theory based on π conjugation confinement structures for achieving deep ultraviolet second-harmonic generation compounds [4]. Furthermore, our investigations into chalcogenides have uncovered the intriguing band structure engineer bucket effect that severs as a guideline for exploratory synthesis of novel chalcogenide with a desired band gap. [5] We have explored various thermoelectric compounds, such as CsCu5Se3, KCu5Se3, Ag9GaSe6, among others. Our findings have shed light on the profound influence of complex structures featuring soft- and rigid-sublattices, multiple coordination spheres, and mixed valence states, ultimately leading to reduced lattice thermal conductivity. For instance, the interlayer π-bond interactions in Bi8Se7 have demonstrated a substantial increase in carrier mobility along the direction of structure stacking. [6-10]
References:
[1] [1] Lu, J.; Yue, J. N.; Xiong, L.; Zhang, W. K.; Chen, L.; Wu, L. M. Uniform Alignment of Non-π-Conjugated Species Enhances Deep Ultraviolet Optical Nonlinearity. J. Am. Chem. Soc. 2019, 141, 8093−8097.
[2] Pan, C. Y.; Yang, X. R.; Xiong, L.; Lu, Z. W.; Zhen, B. Y.; Sui, X.; Deng, X. B.; Wu, L. M.; Chen, L. Solid-State Nonlinear Optical Switch with the Widest Switching Temperature Range Owing to Its Continuously Tunable Tc. J. Am. Chem. Soc. 2020, 142, 6423−6431.
[3] Yang, Y. C.; Liu, X.; Zhu, C. F.; Zhu, L.; Wu, L. M.; Chen, L. Inorganic Solid-State Nonlinear Optical Switch with a Linearly Tunable Tc Spanning a Wide Temperature Range. Angew. Chem. Int. Ed. 2023, 62, e202301404.
[4] Xiong, L.; Wu, L. M.; Chen, L. A General Principle for DUV NLO Materials: π-Conjugated Confinement Enlarges Band Gap. Angew. Chem. Int. Ed. 2021, 60, 25063–25067.
[5] Liu, Q. Q.; Liu X.; Wu, L. M.; Chen, L. SrZnGeS4: A Dual-Waveband Nonlinear Optical Material with A Transparency Spanning UV–Vis and Far-IR Spectral Regions. Angew. Chem. Int. Ed. 2022, 61, e202205587.
[6] Jia, F.; Liu, Y. Y.; Zhang, Y. F.; Shu, X.; Chen, L.; Wu, L. M. Bi8Se7: Delocalized Interlayer π Bond Interactions Enhancing Carrier Mobility and Thermoelectric Performance Near Room Temperature. J. Am. Chem. Soc. 2020, 142, 12536−12543.
[7] Ma, N.; Li, Y. Y.; Chen, L.; Wu, L. M. α‑CsCu5Se3: Discovery of a Low-Cost Bulk Selenide with High Thermoelectric Performance. J. Am. Chem. Soc. 2020, 142, 11, 5293-5303.
[8] Ma, N.; Li, F.; Li, J. G.; Liu, X.; Zhang, D. B.; Li, Y. Y.; Chen, L.; Wu, L. M. Mixed-Valence CsCu4Se3: Large Phonon Anharmonicity Driven by the Hierarchy of the Rigid [(Cu+)4(Se2−)2](Se−) Double Anti-CaF2 Layer and the Soft Cs+ Sublattice. J. Am. Chem. Soc. 2021, 143, 18490−18501.
[9] Li, F.; Liu, X.; Ma, N.; Yang, Y. C.; Yin, J. P.; Chen, L.; Wu, L. M. Overdamped Phonon Diffusion and Nontrivial Electronic Structure Leading to a High Thermoelectric Figure of Merit in KCu5Se3. J. Am. Chem. Soc. 2023, 145, 14981−14993.
[10] Liu, J. Y.; Chen. L.; Wu, L. M. Ag9GaSe6: High-Pressure-Induced Ag Migration Causes Thermoelectric Performance Irreproducibility and Elimination of Such Instability. Nat. Commun. 2022, 13, 2966.
| SESSION: SolidStateChemistryTuePM2-R4 | Poeppelmeier International Symposium(3rd Intl Symp on Solid State Chemistry for Applications & Sustainable Development) |
| Tue. 28 Nov. 2023 / Room: Dreams 4 | |
| Session Chairs: Alexander Norquist; Session Monitor: TBA | |
The current drive to ‘de-carbonise’ energy production and transport has led to an increasing demand for high-density, high-power, energy storage systems. Lithium-ion batteries can fulfill many of these energy storage requirements, but in many cases increases in storage capacity and cell longevity are required, especially for transport applications. A further issue is materials availability – most lithium-ion battery cathodes utilize rare and expensive metals (Co, Ni, Mn) which hamper the large scale adoption of these technologies.We have been working to address these challenges by focusing on the development of lithium-ion cathode materials which utilize earth abundant elements, with a particular focus on iron – an element which is challenging to incorporate within high-voltage cathode materials. In addition, we have been investigating the role of oxygen redox processes in high energy-density systems. Recent work on some novel Fe-based cathode materials will be presented along with work looking at oxygen redox processes in model cathode systems.
16:25: [SolidStateChemistryTuePM210] OSMixed-anion compounds are attracting attention because of novel functions that are not found in oxides [1]. In this presentation, I show several examples where strain can alter structures and properties of mixed-anion compounds. The first example is anion-vacancy ordered perovskite SrV(O,N)3-x thin film, in which the period and orientation of anion-deficient layers can be altered by biaxial strain from a substrate [2]. In EuVO2H films, substrate strain induces electron transfer from Eu2+ to V3+, resulting in a 4-fold enhancement of the ferromagnetic transition temperature and perpendicular magnetic anisotropy [3]. In addition, in a series of layered oxychalcogenides synthesized at high pressure, the giant tensile strain provided during decompression process from the chalcogen layer can add new functions to the oxide layer [4-5].
References:
[1] H. Kageyama et al., Nat. Commun. 9, 772 (2018).
[2] T. Yamamoto et al., Nat. Commun. 11, 5923 (2020).
[3] M. Namba et al., submitted.
[4] Y. Matsumoto et al., Angew. Chem. Int. Ed. 57, 756 (2019).
[5] Y. Yang et al., Inorg. Chem. 61, 7026 (2022).
Bismuth and lead are main group elements, but these have charge degree of freedom stemming from 6s2 (Bi3+ and Pb2+) and 6s0 (Bi5+ and Pb4+) electronic configurations. Stereochemical 6s2 lone pairs of Bi3+ and Pb2+ induce polar distortions as typically observed in PbTiO3 and BiFeO3. These are coupled with charge variation and magnetism of transition metals resulting in various functionalities. From left to right in the periodic table, BiCrO3 to BiCoO3 are all Bi3+M3+O3. However, BiNiO3 has an unusual Bi3+0.5Bi5+0.5Ni2+O3 charge distribution. An intermetallic charge transfer between Bi5+ and Ni2+ takes place under pressure leading to the Bi3+Ni3+O3 high-pressure phase. BiNiO3 decomposes on heating at 500 K, but La substitution for Bi or Fe substitution for Ni destabilizes the Bi charge disproportionation and (Bi,La)3+(Ni,Fe)3+O3 appears on heating at an ambient pressure. Because of the contraction of Ni-O bond owing to the oxidation of Ni2+ to Ni3+, negative thermal expansion, shrinkage of volume on heating, is observed.Similar charge distribution changes are observed three times in PbMO3. PbVO3 is Pb2+V4+O3 like Pb2+Ti4+O3, but PbCrO3, PbMnO3 and PbFeO3 were found to be Pb2+0.5Pb4+0.5M3+O3. PbCoO3 has turned out to be Pb2+Pb4+3Co2+2Co3+2O12. PbNiO3 has a valence distribution of Pb4+Ni2+O3. Namely, PbMO3 changes from Pb2+M4+O3 to Pb2+0.5Pb4+0.5Cr3+O3 (average valence state of Pb3+M3+O3) to Pb2+0.25Pb4+0.75Co2+0.5Co3+0.5O3 (Pb3.5+Co2.5+O3) and to Pb4+M4+O3 according to the order in the periodic table and the depth of d level.Among these compounds, BiCoO3 and PbVO3 have PbTiO3-type polar structures with enhanced c/a ratios exceeding 1.2 because of the stereochemical activities of 6s2 one pairs of Bi3+ and Pb2+ and dxy orbital ordering of Co3+ and V4+. Giant negative thermal expansions in PbVO3 derivatives will also be discussed.
References:
[1] M. Azuma et al., Annu. Rev. Mater. Res., 51, 329 (2021).
Deep-UV (DUV) coherent lights are of great importance to high-tech applications including photolithography photoemission spectroscopy, and attosecond pulse generation. An effective method for obtaining DUV laser is through cascading second-harmonic generation (SHG) of the nonlinear optical (NLO) crystals with large SHG responses, wide transparent window down to DUV region, and sufficient birefringence. Currently, except KBe2BO3F2 (KBBF), no NLO crystal is available for the direct SHG in DUV, but KBBF suffers from the two serious drawbacks, i.e. layering tendency and using carcinogenic BeO in its synthesis, which make the largest thickness of KBBF is only 3.7 mm, far from satisfying commercial requirements. Here we report a new DUV NLO crystal, Cs3B11P2O23 (CBPO), which shares all of the favorable NLO properties of KBBF, including large SHG response (3 × KDP), wide transparent region (165-3503 nm) and suitable birefringence (0.075@532 nm), but does not require BeO in the synthesis and can be easily grown as large (so far up to 20 × 17 × 8 mm3) crystal. With these crystals, we determined type-I phase-matching SHG and third harmonic generation limit of 199 and 188 nm, respectively, and successfully obtained 199 nm DUV coherent radiation based on a direct SHG of CBPO using 398 nm of fundamental laser. These indicate CBPO will be promising as the next generation of DUV NLO crystal.
References:
[1] Liu, H. A.; Wu, H. P.; Hu, Z. G.; Wang, J. Y.; Wu, Y. C.; Yu, H. W., Cs3(BOP)2(B3O7)3: A Deep-Ultraviolet Nonlinear Optical Crystal Designed by Optimizing Matching of Cation and Anion Groups. J. Am. Chem. Soc. 2023, 145, 12691-12700.
| SESSION: SolidStateChemistryTuePM3-R4 | Poeppelmeier International Symposium(3rd Intl Symp on Solid State Chemistry for Applications & Sustainable Development) |
| Tue. 28 Nov. 2023 / Room: Dreams 4 | |
| Session Chairs: Hongcheng Lu; Session Monitor: TBA | |
Due to the chemical and physical properties interesting for applications, a better understanding of the composition and bonding in crystal structures of intermetallic compounds is necessary and – at the same time – is a challenge [1]. Composed of elements that are located in the periodic table around the Zintl border and on its left side, intermetallic compounds show valence-electron demand in comparison with the normal valent materials, which may be expressed as the number of electrons in the last shell per atom (ELSA). This hinders the application of bonding concepts based on the 8–N rule [2] to understand the organization of these substances in a simple way. In consequence, these materials do not follow the usual valence rules and require special concepts for the understanding of their chemical composition and crystal structure [3]. This was the driving force to extend the 8−N concept by considering the participation of d electrons (penultimate shell) in bonding events (18−N rule). On a natural way, the further resolving of this situation should involve the analysis of multi-atomic bonding as a mechanism of satisfying the local electron demands in a chemical system.An application of new quantum-chemical tools opens the way to systematic real-space definition of the basic categories for chemical bonding description. The analysis of chemical bonding in position space has developed in the last decades into an important quantum–chemical tool for study the stoichiometric and structural organization of intermetallic compounds. Using this approach – also under ELSA deficiency conditions - opens the way to systematic real-space definition of the basic categories for chemical bonding description. It allows evaluation of the atomic charges and charge transfer between the atoms, detection and visualization of the interaction between two and more atoms, evaluation of its polarity, quantization of the bond type and bond order, and - finally – calculation of the energetic characteristics of atomic interactions [4].
References:
[1] L. Pauling, Chem. Eng. News 1947, 25, 2970.
[2] W. B. Pearson, Acta Crystallogr. 1964, 17, 1.
[3] Yu. Grin. In: J. Reedijk, K. Poeppelmeier, eds. Comprehensive Inorganic Chemistry II, vol. 2. Oxford, Elsevier, 2013, 359.
[4] F. R. Wagner, Yu. Grin. In: J. Reedijk, K. Poeppelmeier, eds. Comprehensive Inorganic Chemistry III, Oxford Elsevier, Oxford, 2022; https://doi.org/10.1016/B978-0-12-823144-9.00189-8.
Ubiquitous carbonic acid, H2CO3, a key molecule in biochemistry, geochemistry, and also extraterrestrial chemistry, is synthetically known [1], also from spectroscopic studies [2], but it is often considered, even up to the present day, a somewhat mysterious “non-existing” molecule. In fact, the molecule has never been directly seen because high pressure is needed to stabilize it, as easily shown by electronic-structure theory. After an eight-years research study, the crystal structure of carbonic acid has been determined from neutron-diffraction data [3] on a deuterated sample in a specially built hybrid clamped cell [4] made from “Russian alloy”. At 1.85 GPa, D2CO3 crystallizes in the monoclinic space group P21/c with a = 5.392(2), b = 6.661(4), c = 5.690(1) Å, β = 92.66(3)°, Z = 4, with one symmetry-inequivalent anti-anti shaped D2CO3 molecule forming dimers [5], as qualitatively predicted before. Quantum chemistry from plane waves using local orbitals evidences π bonding within the CO3 molecular core, very strong hydrogen bonding between the molecules, and a massive influence of the Madelung field; phonon calculations emphasize the locality of the vibrations, being rather insensitive to the extended structure. Now that carbonic acid has been firmly established, this may be useful for other fields, for example CO2 “sequestration” and its consequences. Likewise, carbonic acid probably plays a role in our solar system, say, on outer gas planets such as Uranus or Neptune and, also, on the Jupiter moon Europa. Finally, many chemistry textbooks must be rewritten because the simplest molecule consisting of water and carbon dioxide actually exists and can be observed.
References:
[1] G. Gattow, U. Gerwarth, Angew. Chem. Int. Ed. Engl. 4 (1965) 149.
[2] T. Loerting, C. Tautermann, R. T. Kroemer, I. Kohl, A. Hallbrucker, E. Mayer, K. R. Liedl, Angew. Chem. Int. Ed. 39 (2000) 891–894.
[3] M. Hofmann, R. Schneider, G. A. Seidl, J. Rebelo-Kornmeier, U. Garbe, R. Schneider, R. C. Wimpory, U. Wasmuth, U. Noster, Phys. B 385–386 (2006) 1035–1037.
[4] S. Benz, A. Möller, T. Marioneck, M. Hofmann, J. Brenk, R. Dronskowski, Rev. Sci. Instrum. 90 (2019) 026103.
[5] S. Benz, D. Chen, A. Möller, M. Hofmann, D. Schnieders, R. Dronskowski, Inorganics 10 (2022) 132.
| SESSION: SolidStateChemistryWedAM-R4 | Poeppelmeier International Symposium(3rd Intl Symp on Solid State Chemistry for Applications & Sustainable Development) |
| Wed. 29 Nov. 2023 / Room: Dreams 4 | |
| Session Chairs: Kent Griffith; Session Monitor: TBA | |
Metal halide perovskites are a promising class of materials for next-generation photovoltaic and optoelectronic devices. The discovery and full characterization of new perovskite-derived materials are limited by the difficulty of growing high quality crystals needed for single-crystal X-ray diffraction studies. Additionally, the toxicity and chemical instability of lead containing perovskites affects their commercial viability. As such, non-lead containing systems have been the focus on considerable interest in recent years. We present an automated, high-throughput approach for copper halide perovskitoid single crystal discovery, based on an antisolvent vapor diffusion crystallization route. The high-throughput experimental route, and associated results, are presented as a means to rapidly identify and optimize synthesis conditions for the formation of high-quality single crystals. A series of new compounds were discovered, including both copper halide perovsketoids and alternative hybrid materials. Analysis of the crystallization fields for each compound enabled the elucidation of formation principles that govern their formation, including reactant concentrations and the formation of hydrogen-bonding networks.
12:00: [SolidStateChemistryWedAM02] OSHybrid halide perovskite semiconductors have proven to be prominent candidates for many optoelectronics applications, spanning from solar cells and LEDs to photodetection and lasing. [1-2] They exhibit a unique combination of fine-tunable traits that cannot be met by any other class of semiconductors, deriving directly from their hybrid nature. Finding a way to generate porosity in this class of materials would allow them to be utilized in currently unexplored applications such as sensing, photonic crystals, integrated waveguides, and solid-state batteries. We recently developed a general strategy for generating porosity to hybrid metal halide materials using molecular cages serving as structure-directing agents and counter-cations. [3] The reaction of the [2.2.2] cryptand (DHS) linker with Pb(II) in acidic media gave rise to the first porous 2D metal halide semiconductor with formula (DHS)2Pb5Br14. The corresponding material is stable in water for over a year, while gas and vapor sorption studies revealed that it can selectively and reversibly adsorb H2O and D2O at room temperature (RT). Solid-state NMR measurements and DFT calculations verified the incorporation of H2O and D2O in the organic linker cavities, and shed light on their molecular configuration. In addition to porosity, the material exhibits broad light emission centered at 617 nm with a full width at half-maximum (FWHM) of 284 nm (0.96 eV). The recorded water stability is unparalleled for hybrid metal halide and perovskite materials, while the generation of porosity opens up new pathways toward unexplored applications (e.g. solid-state batteries) for this class of hybrid semiconductors. This work sets the foundation for a new family of versatile hybrid semiconductors, namely porous metal halide semiconductors (PMHS), solving current stability material deficiencies, whereby means of molecular and crystal engineering, the path towards commercialization is open.
References:
[1] Ke, W.; Spanopoulos, I.; Stoumpos, C. C.; Kanatzidis, M. G., “Myths and reality of HPbI3 in halide perovskite solar cells”, Nat. Commun. 2018, 9, 4785.
[2] Spanopoulos, I.; Hadar, I.; Ke, W.; Guo, P.; Sidhik, S.; Kepenekian, M.; Even, J.; Mohite, A. D.; Schaller, R. D.; Kanatzidis, M. G., “Water-Stable 1D Hybrid Tin(II) Iodide Emits Broad Light with 36% Photoluminescence Quantum Efficiency”, J. Am. Chem. Soc. 2020, 142, 9028.
[3] Azmy, A.; Li, S.; Angeli, G. K.; Welton, C.; Raval, P.; Li, M.; Zibouche, N.; Wojtas, L.; Reddy, G. N. M.; Guo, P.; Trikalitis, P. N.; Spanopoulos, I., “Porous and Water Stable 2D Hybrid Metal Halide with Broad Light Emission and Selective H2O Vapor Sorption”, Angew. Chem. Int. Ed., 2023, 135, e202218429, 1.
Hybrid lead halides of perovskite type have recently shown a great potential in optoelectronic applications. For this reason, many research groups are currently exploring this chemical system to discover new low dimensional hybrid perovskites. However, discovering such materials is challenging as the necessary structure determination by X-ray crystallography is time consuming and non-perovskite compounds are very often synthesized instead of perovskites. In this context, we developed a deep learning approach, which automatically and accurately assign the structure type from the X-ray diffraction patterns of new hybrid lead halides [1]. The models could automatically identify new hybrid perovskites with an accuracy of 92%. Interestingly, we were able to identify and explain the key features in the diffraction patterns, which allow the machine learning algorithms to discriminate between perovskites and non perovskites. From this information, the scientists’ ability in discriminating the different structure types is augmented and such algorithms could be included in autonomous materials discovery cycles in the future.
References:
[1] F. Massuyeau, T. Broux, F. Coulet, A. Demessence, A. Mesbah, R. Gautier, Advanced Materials 2022, 31(41), 2203879.
Hydrogen transport in solids has received attention owing to its potential for electrochemical devices, including fuel/electrolysis cells and gas separation membranes. Materials conducting hydrogen in the form of protons (H+), that is, proton conductors have been investigated steadily. However, fast hydrogen transport at intermediate temperatures of 200–400°C or without humidification, remains a challenge.The hydride ion (H–) possesses low charge density, in contrast to the extremely high charge density of protons, and consequently has high polarizability. Such a basic characteristic is favorable for fast ion conduction in general. Discoveries of two H– conducting solids around 2015, that are metal hydride BaH2 [1] and hydride-oxide (oxyhydride) La2–x–ySrx+yLiH1–x+yO3–y [2], have triggered active materials exploration in recent years. Achieving a superior H– conducting solid electrolyte is now an important milestone in the development of electrochemical devices that utilize its strong reducing ability, such as batteries with high energy density and fuel/electrolysis cells with high efficiency.We found a layered perovskite (K2NiF4-type) Ba–Li oxyhydride (BLHO) with an appreciable amount of hydrogen vacancies that presents long-range order at room temperature [3]. Increasing the temperature results in the disappearance of the ordering in structure, inducing a high and temperature-independent H– conductivity of more than 0.01 S/cm above 315ºC. Stabilizing the high-temperature phases of BLHO by appropriate elemental substitution would be a principal strategy for the electrochemical use of H– in the intermediate temperature range [4].Development of materials working in the much lower temperature range is also underway [submitted]. Very recently, it is reported that LaH3–d-based compounds exhibit high H– conductivity around room temperature [5,6]. We prepared Sr-substituted LaH3–d with slight O2–incorporation, represented as chemical formula La1–xSrxH3–x–2yOy (0.1 ≤ x ≤ 0.6, y < 0.2; LSHO), which exhibited H– conductivities of 10–4 S/cm at room temperature. The galvanostatic discharge reaction using an all-solid-state cell composed of Ti|LSHO|LaH3–d showed that the Ti electrode was completely hydrogenated to TiH2 for x ≥ 0.2, whereas a short circuit occurred for x = 0.1. These experimental observations, together with calculation studies on the density of states and the defect formation energy, provide clear evidence that electropositive cation, such as Sr, doping critically suppresses the electron conduction in LaH3–d.
References:
[1] M. C. Verbraeken et al. Nat. Mater. 14, 95 (2015).
[2] G. Kobayashi, et al. Science 351, 1314 (2016).
[3] F. Takeiri, et al. Nat. Mater. 21, 325 (2022).
[4] K. Okamoto, et al. Adv. Sci, 10, 2203541 (2023).
[5] K. Fukui, et al. J. Am. Chem. Soc. 144, 1523 (2022).
[6] W. Zhang, Nature 616, 73 (2023).
| SESSION: SolidStateChemistryWedPM1-R4 | Poeppelmeier International Symposium(3rd Intl Symp on Solid State Chemistry for Applications & Sustainable Development) |
| Wed. 29 Nov. 2023 / Room: Dreams 4 | |
| Session Chairs: Paul Salvador; Session Monitor: TBA | |
In transition metal fluorides, the fairly strong ionic character of the M-F bonding between fluoride and metal allows a better understanding of most of their electronic properties such as conductivity, transport properties, optical behavior, multiferroism. For example the varied observed magnetic bahiviors: ferro-, antiferro-, ferri-, low-dimensional- magnetisms, can be interpreted easily following the Goodenough superexchange rules[1, 2]. The physicochemical properties of transition metal fluorides can generally be inferred from the types of bonds occurring in the structural networks and connected with the magnetic structures [3].
Inorganic fluorinated materials are found as components in many applications, including energy storage and conversion, photonics, electronics, medicinal chemistry, etc [4]. The strategic importance of these materials will be illustrated by several examples taken from various scientific domains: Fluoride materials used as electrodes in Li-ion batteries and in catalysis / Nanocrystalline fluorides derived from fluorite- (CaF2) or tysonite- (LaF3) types used as solid electrolytes in All-solid-state batteries utilizing the high mobility of F- anions / Rare-earth based fluorides used as up- and down-conversion luminophores, at the micro- or nanoscale / Multiferroic d-transition metal fluorides derived from the perovskite, i.e. layered BaMF4 or TTB-K3Fe5F15, in which magnetism and ferroelectricity coexist / Fluorine-based superconductors obtained by F-doping in cuprate systems La2CuO4 and Sr2CuO3 or in F-doped oxypnictide LnFePnO1-xFx [5].
Finally, solid-state inorganic nanofluorides are used in many other advanced domains such as dye-sensitized solar cell, transparent conducting films, solid state lasers, nonlinear optics, UV absorbers, frequency doubling. Their role is also decisive in medicine and biotechnologies, where nano-crystals of doped rare-earth fluorides can be used as theranostic nano-agents integrating both imaging probes and therapeutic media, and are therefore able to perform diagnostic and therapy within a single nano-object.
References:
[1] Magnetism and the Chemical Bond, J. B. Goodenough, Interscience Publ. (1963)
[2] Crystal chemistry and magnetic properties of CrIIBIIIF5 compounds, A. Tressaud, J.M. Dance, J. Ravez, J. Portier, P. Hagenmuller, J.B. Goodenough, Mat. Res. Bull., 8, 1467, (1973).
[3] Crystal Chemistry and Selected Physical Properties of Inorganic Fluorides and Oxide-Fluorides, M. Leblanc, V. Maisonneuve, A. Tressaud, Chem. Rev. 115, 1191(2015).
[4] Photonic & Electronic Properties of Fluoride Materials, A.Tressaud & K. Poeppelmeier Eds., Vol. 1 “Progress in Fluorine Science”, A. Tressaud Series Editor, Elsevier, (2016).
[5] Fluorine, a Paradoxical Element, A. Tressaud, Elsevier (2019).
Bi and Pb have a unique 6s0 and 6s2 electron configuration that creates charge degrees of freedom. Due to the lack of this 6s1 electron configuration, a property called valence skipper, Bi takes 3+ and 5+ and Pb takes 2+ and 4+. In particular, for perovskite compounds containing Bi or Pb at the A site, the valence state changes according to the depth of the d-orbitals of the transition metal ions corresponding to the order in the periodic table of the elements due to the close relationship between the 6s level of Pb or Bi and the 3d level of the 3d transition metal ions. For BiMO3, M= Cr, Mn, Fe, Co, the state is Bi3+M3+O3, while BiNiO3 has a specific valence state of Bi3+0.5Bi5+0.5Ni2+O3. PbMO3 has Pb2+0.5Pb4+0.5MO3 for M= Ti and V, Pb2+0.5Pb4+0.5M3+O3 for M= Cr and Fe, PbCoO3 has Pb2+0.25Pb4+0.75Co2+0.5Co3+0.5O3, PbNiO3 has Pb4+Ni2+O3. In BiNiO3 and PbMO3 (M = Cr, Fe and Co), Bi and Pb become charge disproportionated in the 6s0 and 6s2 states, and temperature- and pressure-induced elimination of charge disproportionation and charge transfer phase transitions occur. These charge transfer phase transition causes leads to unique physical properties such as negative thermal expansion.
14:55: [SolidStateChemistryWedPM107] OSLow dimensional quantum magnets have been extensively investigated recently because of their novel intriguing quantum phenomena such as spin liquid and spin-charge separation, and their relation to high temperature superconductivity.[1] However, experimental realization of such low dimensional quantum magnets is still difficult, in particular experimentally realizing the specific magnetic lattices and models such as one dimensional (1D) chain lattice and two dimensional (2D) triangular lattice and Kagomé lattice, which have been theoretically predicted and investigated. Thus, discovery of experimental magnetic lattices is crucial to test theoretical predictions or to explore novel exotic phenomena. In this talk, experimental realization and magnetic properties of several new low dimensional quantum antiferromagnets with specific magnetic lattices will be introduced, including the nearly-ideal 1D spin chain systems (2,2’-bipyridyl)FeF3·2H2O with S = 5/2 and MF2(bibp)2 (bibp = 4,4’-bis(1-imidazolyl)biphenyl) (M = Co, S = 3/2, Ni, S = 1), 1D zig-zag chain systems MIO3F (M = Ni, Co) with spin-flop transition,[2] 1D mixed-spin chain systems MVF6(pyrazine)2·4H2O with constrast magnetic behaviors, 2D triangular systems KMB4O6F3 (M = Co, Ni, Fe) and Ni(HPO3)(4,4’-bipyridyl)H2O, 2D Kagomé systems M3(PO3)(4,4’-bipyridyl)3(H2O)6·4H2O.
References:
[1] L. Balents, Nature 2010, 464, 199-208.
[2] D. Wang, L. Kong, P. Fan, H. Chen, S. Zhu, W. Liu, L. Cao, Y. Sun, S. Du, J. Schneeloch, R. Zhong, G. Gu, L. Fu, H. Ding, H. Gao, Science 2018, 362, 333-335.
Perovskite oxides ABO3 continue to be a major subject in materials science because of its chemical and structural diversity1. Of particular interest is the interplay between A and B cations with finite d/f electrons, which, for example, causes inter-site charge transfer (ICT), leading to novel phenomane such as negative thermal expansion and metal-to-insulator transitions. The ICT properties are controlled by cationic substitution, but the mechanism is complicated by three-dimensional (3D) structures. Mixed-anion compounds began to draw attention as game-changing inorganic materials. Since, compared with conventional inorganic compounds such as oxides, mixed-anion compounds may exhibit unique coordination and resultant extended structures, from which fundamentally different chemical and physical property may emerge. In my talk, a new oxyhydride EuVO2H, prepared via anion-exchange reactions of EuVO3perovskite oxide, will be presented [1]. EuVO2H with alternating layers of EuH and VO2 exhibit ICT between the heteroanion layers. While bulk EuVO2H is a ferromagnetic insulator with TC = 10 K, application of external pressure or biaxial strain from a substrate to a EuVO2H film causes ICT to occur from the EuIIH layer to the VIIIO2 layer. The strained film exhibits a 4-fold increase in TC and, despite the absence of orbital angular momentum, Eu2+ exhibits giant magnetic anisotropy with its easy axis perpendicular to the film, which is favorable for devices such as high-density memory. The present results provide new possibilities for the acquisition of novel functions by alternating layered structures of heteroanions. If time allows, other examples of strain engineering of perovskite structures and properties including SrV(O,N)3-x [2]will be presented.
References:
[1] Nambe et al., submitted.
[2] Yamamoto et al., Nat. Commun 11, 5923 (2020)
| SESSION: SolidStateChemistryWedPM2-R4 | Poeppelmeier International Symposium(3rd Intl Symp on Solid State Chemistry for Applications & Sustainable Development) |
| Wed. 29 Nov. 2023 / Room: Dreams 4 | |
| Session Chairs: Julia-Maria Hubner; Session Monitor: TBA | |
In this work, we focus on multinuclear solid-state NMR, X-ray, and neutron characterization to explore the relationship between composition, crystal structure, and defect chemistry in a series of complex sodium and lithium niobium oxides. The role of defects on electrochemical transport properties in these new high-rate electrode or solid electrolyte materials will be discussed. Starting with average structure models from X-ray and neutron diffraction, we then turn to a local structure perspective from NMR that is more sensitive to defects and disorder. One- and two-dimensional 6,7Li and 23Na NMR spectra provide insights on mobile cation positions and dynamics as well as alkali sublattice vacancies. (Ir)reversible changes upon cycling are identified. DFT calculations and numerical simulations support the spectral assignments in these complex oxides.A central focus of this work are the compounds NaNb7O18 and NaNb13O33, which we report as battery materials and study by NMR for the first time. Both structures are derivatives of the Wadsley–Roth structure that can rapidly intercalate lithium. However, the role of sodium in the structure raises interesting questions. Sodium nominally sits in a single crystallographic site with a square planar coordination environment, which is rather unusual for sodium and gives rise to a large and characteristic quadrupolar lineshape in 23Na NMR. What we find is that even the pristine NaNb13O33 phase, i.e., before lithium is intercalated, is more complicated than the static picture previously reported by X-ray diffraction. Moreover, only half the sodium in NaNb7O18 has been accounted for in the structure reported from diffraction data. We show that, in both structures, sodium sits not only in the square planar site but occupies perovskite-like sites within tunnels in the Wadsley–Roth structure. This conclusion is supported by DFT and phase boundary mapping. Comparisons are made to related sodium niobium oxide compounds.
16:25: [SolidStateChemistryWedPM210] OSCubic alkaline-earth manganite perovskites have been the focus of many computational and physical studies because of their potential multiferroic properties, in which the ferromagnetic and ferroelectric order originate from the electrons on the Mn4+ ions and their bonding with oxygen, resulting in a potentially strong magnetoelectric coupling. Depending on the composition, especially the size of the alkaline earth cation and oxygen content, the ground state structure can adopt various polytypic perovskite structures [1-4], which differ in the amount of cubic or hexagonal stacking of the eutactic (nearly close-packed) planes, which also controls the amount of corner-sharing and face-sharing Mn-O octahedra. BaMnO3 has a ground state structure called 2H, which has all hexagonal stacking and all face shared octahedra, while SrMnO3 adopts the 4H structure, which has half hexagonal / half cubic stacking and half corner-shared / half face-shared octahedra. The 3C (or cubic) versions of these materials have all cubic stacking and all corner-shared octahedra, and are known or predicted to be strongly coupled multiferroics. In the Sr1-xBaxMnO3 system, the highest known Ba-content to form in the 3C structure is x = 0.5.In this work we revisit the Sr1-xBaxMnO3 system with the goal of understanding the fundamental challenges to the epitaxial synthesis of cubic polytypes. While controlling thermodynamic parameters, e.g. temperature, pressure, component activity, etc., during bulk synthesis has proven invaluable in accessing some specific metastable polytypes, it is clear that stabilizing a 3C BSMO compound will be increasingly difficult with higher Ba concentrations (x > 0.5), and that additional parameters are needed. Epitaxial stabilization is one method that offers an additional structure-directing thermodynamic parameter: the interface with the substrate. Furthermore, kinetic processes during epitaxial growth also can impact nucleation outcomes, and in some cases improve the possibilities of accessing new metastable materials. Nevertheless, the largest known value of x found for thin films is 0.5 [5], identical to bulk material, for very thin (< 10 nm) on particular substrate (DyScO3) [5]. We will review a high-throughput deposition method we call combinatorial substrate epitaxy (CSE), where films are deposited upon epi-polished polycrystalline substrates, and describe its utility for understanding thermodynamic influences on 3C and 4H growth for (Ca,Sr,Ba)MnO3. We demonstrate that all film-substrate perovskite polytype pairs align their eutactic planes and directions, regardless of substrate type or orientation. Finally, we show that certain orientations lead to improved metastable film formation than others. Focusing on pushing the stability boundary of Sr1-xBaxMnO3 beyond x=0.5, we focus on films of x = 0.5 and 0.6. We will demonstrate that kinetic aspects control polymorph formation as well, with 4H seeming to have a kinetic advantage over 3C. Interval pulsed laser depostion (iPLD), where growth is interrupted after deposition of approximately a monolayer [6] to allow for kinetic relaxation processes to occur, was combined with CSE to demonstrate that Sr0.4Ba0.6MnO3-y can be stabilized as a 3C polytype when controlling both thermodynamic and kinetic factors. Both film flatness and, more importantly, volume of the 3C polymorph improved with iPLD, resulting in 40 nm single-phase Sr0.4Ba0.6MnO3-y films on single-crystal DyScO3 and polycrystalline GdScO3. The results imply that iPLD improves persistent nucleation of highly metastable phases and offers a new approach to epitaxial stabilization of novel materials, including more Ba-rich BSMO compositions in the 3C structure.
References:
[1] T. Negas and R. S. Roth, J. Solid State Chem. 1 (1970) 409-418.
[2] T. Negas and R. S. Roth, J. Solid State Chem. 3 (1971) 323-339.
[3] T. Negas, J. Solid State Chem. 6 (1973) 126-150.
[4] B. Dabrowski, O. Chmaissem, J. Mais, S. Kolesnik, J. D. Jorgensen, J. Solid State Chem. 170 (2003) 154–164
[5] E. Langenberg, R. Guzman, L. Maurel, L. Martinez de Banos, L. Morellon, M. R. Ibarra, J. Herrero-Martin, J. Blasco, C. Magen, P. A. Algarabel, J. A. Pardo, ACS Appl. Mater. Interfaces 7 (2015) 23967–23977.
[6] G. Koster, G. J. Rijnders, D. H. Blank, H. Rogalla, Appl. Phys. Lett. 74 (1999) 3729-3731.
Recently, supply chain pressures tied to the geopolitics and scarcity of Li, Co, and other metals have led to the first increase in Li-ion cell price ever, with the cost of essential precursors skyrocketing to new highs. This kind of volatility makes deploying Li-ion batteries at grid scales challenging, despite their many advantages in terms of large operating potentials and slow self-discharge rates. While a tremendous amount of work has explored replacing Li with more abundant cations like Na or Mg the possibility of harnessing negatively charged anions like fluoride, has largely been overlooked because trying to move anions around through closely packed lattices is tantamount to playing a game of atomic Jenga®. This talk will present our group’s recent work that reports the first example of a reversible battery based on the electrochemical (de)insertion of F-ions at room temperature. We demonstrate that after three cycles, one full equivalent of F-ions can be reversibly cycled in CsMnFeF6. Electrochemical impedance spectroscopy and Mössbauer spectroscopy suggests the formation of fluoride vacancies in early cycles generates mixed-valent Fe that enhances the electrical conductivity of the electrode. Furthermore, ex situ powder diffraction reveals a subtle expansion and contraction of the cubic lattice during oxidation (insertion) and reduction (removal) respectively, that eventually leads to the evolution of new reflections corresponding to a closely related orthorhombic polytype in later cycles. This topotactic transformation suggests that structural derivatives of the fluorite structure offer a promising class of materials for creating high-performance F-ion insertion electrodes.
17:15: [SolidStateChemistryWedPM212] OLThe ever-growing application of deep-ultraviolet (deep-UV, λ < 200 nm) nonlinear optical (NLO) materials in various fields requires searching for candidates to generate the deep-UV lasers through direct second-harmonic generation (SHG) method. Among them, fluorooxoborates, benefiting from the large optical band gap, high anisotropy and ever-greater possibility to form non-centrosymmetric structures activated by the large polarization of the functionalized [BOxF4-x](x+1)- (x =1, 2 and 3) building blocks, have been considered as the new fertile fields for searching the deep-UV NLO materials. Two series of fluorooxoborates AB4O6F (A = NH4, Na, Rb, Cs, K/Cs and Rb/Cs) and MB5O7F3 (M = Ca, Sr, Mg) were rationally designed and synthesized, which not only inherit the favorable structural characteristics of KBBF, but also possess superior optical properties. Property characterizations reveal that these two series possess the optical properties (deep-UV cutoff edges, large SHG responses, improved growth habit and also large birefringence to ensure the phase matching behavior in the deep-UV spectral region, etc.) required for the deep-UV NLO applications, which make them potential candidates to produce the deep-UV coherent light by the direct SHG process.
References:
[1]. Mutailipu, M and Pan, S. L.* etc. Chem. Rev. 2021, 121, 1130-1202.
[2]. Mutailipu, M and Pan, S. L.* etc. Acc. Chem. Res. 2019, 52, 791.
[3]. Zhang, B. B and Pan, S. L.* etc. Angew. Chem. Int. Ed. 2017, 56, 3916.
[4]. Shi, G. Q.; Pan, S. L* and Poeppelmeier, K. R.* etc. J. Am. Chem. Soc. 2017, 139, 10645.
[5]. Wang, X. F and Pan, S. L.* etc. CsB4O6F: Angew. Chem. Int. Ed. 2017, 56, 14119.
[6]. Wang, Y and Pan, S. L.* etc. Angew. Chem. Int. Ed. 2018, 57, 2150.
[7]. Zhang, Z. Z and Pan, S. L.* etc. Angew. Chem. Int. Ed. 2018, 57, 6577.
[8]. Mutailipu, M and Pan, S. L.* etc. Angew. Chem. Int. Ed. 2018, 57, 6095.
[9]. Xia, M.; Mutailipu, M* and Pan, S. L.* etc. Angew. Chem. Int. Ed. 2021, 60, 14650.
| SESSION: SolidStateChemistryWedPM3-R4 | Poeppelmeier International Symposium(3rd Intl Symp on Solid State Chemistry for Applications & Sustainable Development) |
| Wed. 29 Nov. 2023 / Room: Dreams 4 | |
| Session Chairs: Shilie Pan; Session Monitor: TBA | |
To design materials for energy, electronic and ionic mobility are key features. The chemical bonding involving transition metal or rare-earth ions with more electronegative elements is the common thread. Imagining novel compounds and networks by associating at least two anions with different electronegativity in order to create competitive bonds around metallic ions allow us tuning physical and chemical properties and generating new one’s. It represents also a growing challenge in the field of inorganic synthesis routes, the knowledge of motley structures and finally the transport (electronic+ ionic) properties.In this journey, we will explore the interest to mix fluorine with less electronegative anions in order to create unusual transport properties 1. Original synthesis routes involving fluorine and at least one additional anion will be presented and discussed with its diversity. Crystal structures will be analyzed and solved considering anionic order and disorder2. Finally the physical and chemical properties will be correlated to the composition and structural features, illustrating the fantastic playground offered by mixing anions in inorganic compounds containing fluorine 1,2.
References:
[1] J.B. Vaney, B. Vignolle, A. Demourgues, E. Gaudin, E. Durand, C. Labrugère, F. Bernardini, A. Cano and S. Tencé, Topotactic fluorination of intermetallics : a novel route towards quantum materials. Nature Comm, 13, 1462 (2022).
[2] J. Gamon, J.B. Bassat, A. Villesuzanne, M. Duttine, M. Batuk, D. Vandemeulebroucke, J. Hadermann, F. Alassani, F. Weill, E. Durand and A. Demourgues. Impact of anionic ordering on the iron site distribution and valence states in oxyfluorideSr2FeO3+xF1-x (x=0.08, 0.2) with a layered perovskite network. Inorg. Chem. 62, 27, 10822-10832, (2023).
Since several thousands of years, metallic elements and especially their alloys and intermetallic compounds constitute one of the material foundations responsible for the development of humankind. The large variety of known intermetallic compounds comprise beneficial properties, including ductility, and hardness, and feature structural patterns ranging from simple close-packed structures to complex quasicrystals. Especially complex structures often feature unique atomic arrangements with both localized and delocalized bonding interactions, making their characterization and the understanding of structure-bonding-property relations and formation conditions a fascinating quest in the search for overarching schemes in the class of intermetallics. In the following contribution, two examples of structural complexity in intermetallic compounds, with an emphasis on atomic arrangements and formation conditions, will be discussed.Au4Si. Gold and silicon do not form stable binary phases. The binary system is of scientific and technological interest because the eutectic mixture Au80Si20 shows a remarkably low melting point of 363(3)°C. The application of fast cooling techniques led to a metastable binary phase 'Au4Si' close to the eutectic composition, but due to the structural complexity, and sensitivity of the compound, the characterization has remained a challenge. By testing different preparation methods with variable cooling rates, good-quality single crystals of Au4Si were obtained recently [1]. Au4Si crystallizes in a complex √18×√2×1 superstructure of the PtHg4 type, based on the distortion of vertex-sharing Si@Au8 cubes into bisdisphenoids. Au4Si decomposes upon heating and at room temperature even in high vacuum, highlighting its metastability. Electronic structure analysis reveals a pseudogap at the Fermi energy, which is enhanced by the superstructure through the relief of Au-Au antibonding interactions. The pseudogap is associated with a Zintl-type bonding scheme, which can be extended to the locally ordered liquid. Nd-Ru. Despite the interesting magnetic and superconducting properties of the phases in the binary systems RE-Ru (RE = La, Pr, Nd), the compounds at about 35-38 at.% Ru have remained uncharacterized due to their complex crystal structure [2,3]. High-resolution diffraction experiments (beamline Cristal, synchrotron Soleil, France) on single crystals of the Nd compound revealed a composite structure comprising observable satellites up to the 29th order. The partial overlap required manual indexing and processing of the satellite reflections which will be explained in detail in this contribution. The resulting 3D+1 structure was solved in space group X4/nbm(00g)00ss with a = 15.6130(8) Å, c = 6.3258(4) Å, q ≈ 2/23. In [001] direction, Nd atoms form chimneys, hosting linear Ru-Ru chains. This structural arrangement is closely related to that of Y44Ru25 [4] and in turn to that of Nd51r3 (Pu5Rh3-type, [5]).
References:
[1] J.-M. Hübner, B.C. Bierman, R. Wallenberg, D. Fredrickson, J. Am. Chem Soc., 144 (2022) 21016−21021.
[2] A. Palenzona, F. Canepa, J. Less-Common Met., 157 (1990) 307 – 313.
[3] A. Palenzona, F. Canepa, J. Less-Common Met., 162 (1990) 267-272.
[4] M. L. Fornasini, A. Mugnoli, A. Palenzona, J. Less-Common Met., 154 (1989) 149 – 156.
[5] D. Paccard, J. Le Roy and J. M. Moreau, Acta Crystallogr. Sect. B, 35 (1979) 1315.
| SESSION: SolidStateChemistryThuAM-R4 | Poeppelmeier International Symposium(3rd Intl Symp on Solid State Chemistry for Applications & Sustainable Development) |
| Thu. 30 Nov. 2023 / Room: Dreams 4 | |
| Session Chairs: Steven De Feyter; Session Monitor: TBA | |
Chemical patterning of graphene is relevant in several different domains of science and technology with exciting possibilities in electronics, catalysis, sensing, and photonics. Despite intense efforts, spatially controlled, (multifunctional) covalent chemical patterning of graphene is not straightforward to achieve. The lack of control primarily originates from the inherently poor reactivity of the basal plane of graphene which necessitates the use of harsh chemistries. In my talk, I will present two examples of covalent chemical patterning of graphene and graphite using diazonium chemistry. In the first case, spatially resolved multicomponent covalent chemical patterning of single layer graphene was achieved using a facile and efficient method. Three different functional groups could be covalently attached to the basal plane in dense, well-defined micrometer wide patterns using a combination of lithography and a self-limiting variant of diazonium chemistry requiring no need for graphene activation. The layer thickness of the covalent films could be controlled down to 1 nm. In the second case, i will present sub-10 nm chemical patterning of graphite achieved using the electrochemical diazonium chemistry. Here, an elegant combination of covalent and non-covalent chemistry was used to achieve 5-6 nm wide linear chemical patterns with excellent pattern transfer fidelity. Throughout the discussion, i will highlight the critical role of scanning probe microscopy, namely STM, AFM and AFM-IR in providing critical spatial and spatiochemical information at the nanometer scale where conventional analytical techniques fail to provide accurate information.
References:
[1] ACS Nano 2021, 15, 10618−10627
[2] Nanoscale, 2023, 15, 10295–10305
Intermetallics constitute the largest group of inorganic compounds [1], often displaying intriguing and unprecedented structural features and physical properties. Among them, those containing rare-earth metals (RE) enabled relevant breakthroughs and are set to play a key role in future technologies, required to successfully face emerging challenges. The rational design of such materials is still hampered by the lack of understanding of the structure–bonding relationships, as classical valence rules cannot be effectively applied [2]. Thus, relevant achievements may only stem from systematic experimental and theoretical investigations. In this work, the preparation and structural characterization of several RE–M–Tt (M = s, p or transition metals; Tt = Si, Ge, Sn) with more than 50at% of Tt are presented. Interatomic distances were in all cases compatible with the formation of covalent Tt interactions, building up polyanionic dumbbells, chains, layers, and frameworks resulting in a Tt homo-connectivity ranging from 1 to 3; for some representative, as RE2MgGe6 and RE2Pd3Ge5, the Zintl rules were still formally fulfilled. Aiming at overcoming the approximation that the interactions between the Tt-polyanions and the surrounding metals are of the ionic type, in-depth chemical bonding analyses were performed, mainly applying quantum chemical techniques in position space [2]. Particular attention was devoted to the nature of interactions between the RE and the M metals, often neglected in the literature. For these purposes new tools and techniques were introduced or extended, namely the Penultimate Shell Correction (PSC0), the Electron Localizability Indicator (ELI-D) fine structure, and the 8–Neff rule [3,4]. Independently on the intermetallic stoichiometry, the following trends were described: RE metals turned out to be always involved in multi-atomic covalent bonds with the polyanions through the Tt “lone pairs”; RE are involved in polar covalent interactions with late transition metals, particularly those of the 4th and 5th period. These outcomes clearly suggest that the chemical role of the RE as large cations lying in the biggest cavities must be definitely abandoned. Recent results on some intermetallics only formed by elements to the left of the p-block, like LaAuMg2 and RENi5, surprisingly revealed RE–Au/Ni bonds analogous to those described for the tetrelides. Thus, the chemical behavior of LaNi5 and CeNi5 was investigated testing them as Sabatier’s catalysts in the reduction of CO2 to CH4. The knowledge of the chemical bonding in the bulk phases enabled the understanding of surface phenomena taking place during the catalytic experiments, particularly on the adsorption and dissociation of H2 molecules.
References:
[1] R. Nesper, Angew. Chemie, 30 (1991), 789-817
[2] F.R. Wagner, Yu. Grin, "Chemical bonding analysis in position space" pp. 222-237, in Comprehensive Inorganic Chemistry III, 3rd ed. (2023), edited by J. Reedijk and K. R. Poeppelmeier
[3] R. Freccero, P. Solokha, S. De Negri, A. Saccone, Yu. Grin, F.R. Wagner, Chem. Eur. J., 25 (2019), 6600-6612
[4] R. Freccero, Yu. Grin, F.R. Wagner, Dalton Trans., 52 (2023), 8222-8236
Because the strength, toughness and other key engineering properties of heterogeneous materials are strong dependent on their grain size and density, the quest to achieve simultaneously dense and fine, ultrafine, nano, and nanostructured grain size materials has been one of the most important and difficult challenges in materials science and engineering. In this research we explore novel approaches for producing dense and fine, ultrafine, nano, and nanostructured heterogeneous materials. Typical approaches consist of reaction synthesis, sonochemistry, combustion synthesis, and shock wave synthesis followed by dynamic and static consolidation and densification pre and post reaction synthesis. Typical heterogeneous materials covered in this research consist of tungsten heavy alloys, coated graphite powders, metal silicides, aluminides and multiphase, multi microstructural constituent ceramic armor materials. The synthesized and densified materials are fully characterized by OM. SEM, TEM, STEM, EDX analysis, quantitative image analysis, X-Ray diffraction and mechanical testing. This paper focuses and discusses the mechanisms of reaction synthesis in binary metallic systems and the effect of reaction and processing parameters on the microstructure and densification of typical materials under intense shock loading.
12:50: [SolidStateChemistryThuAM04] OS InvitedAs is known, quantum mechanics is inextricably linked with classical mechanics. Its justification is connected with the need to consider the interaction of a microparticle with a macroscopic classical measuring device [1]. The basic dynamical equation, the Schrödinger equation, was postulated by Schrödinger but actually derived from the Hamilton-Jacobi equation for action in classical mechanics by introducing the wave function in some form, which is now called the semiclassical approximation. The width of the levels, "inside which" the energy spectrum is continuous, is a sign of the partially classical nature of the dynamics in quantum systems. Quantum-classical mechanics is not a "mixture" of quantum mechanics and classical mechanics, but is a substantially modified quantum mechanics, in which the initial and final states are quantum in the adiabatic approximation, and the chaotic transient state due to chaos is classical. The Franck-Condon principle in molecular physics avoids the consideration of transient state dynamics, which is unreasonably assumed to be unimportant. Classicality, which is immanently inherent in quantum mechanics itself, in molecular physics, is supplemented by classicism, which is associated with the Franck-Condon principle. It is assumed that the fast quantum transition of an electron from the ground to the excited electronic state of the molecule occurs between the turning points of classically moving nuclei, where the nuclei are at rest. In fact, the classical nature of motion in molecular physics is not associated with the Franck-Condon principle, but with the chaotic dynamics of the motion of an electron and nuclei in a transient state. As is known, the theory of quantum transitions in quantum mechanics is based on the convergence of a series of time-dependent perturbation theory. This series converges in atomic and nuclear physics, as well as in molecular physics, provided that the Born-Oppenheimer adiabatic approximation and the Franck-Condon principle are strictly observed. If this condition is not met, the series of time-dependent perturbation theory diverges. Obviously, in real molecules, the adiabatic approximation is not strictly observed, which makes the application of Franck-Condon principle unfounded in theory, and with it the whole physical picture of molecular transitions based on it. The only physical way to eliminate the singularity of the series of time-dependent perturbation theory in molecular physics is the postulate of the presence of dynamics in the transient electron-nuclear(-vibrational) state, which the Franck-Condon principle ignores, and that this dynamics is chaotic. In this case, in the case of strong chaos, as in the case of the Franck-Condon picture of molecular transitions, the transition rates do not depend on the specific dynamics of the transient state, but depend only on the initial and final states, taken in the adiabatic approximation. In the case of weak chaos, against the background of chaos, the regular nature of the dynamics of the transient state manifests itself. Chaos, which is weak in the case of large molecules, may be strong in the case of small molecules. Therefore, the Franck-Condon picture of transitions often gives good agreement with experimental data on optical spectra in conventional molecular spectroscopy of small molecules. In photochemistry, where, as a rule, we deal with large molecules, where chaos is not strong, but weak, elements of dynamic self-organization often appear in the chaotic dynamics of the transient state. A striking example of this is the well-known narrow and intense J-band of J-aggregates of polymethine dyes [2]. Thus, in the case of small molecules, the Franck-Condon principle gives the correct result, although an erroneous theory and an erroneous physical picture are used. In the case of large molecules, this erroneous theory and the erroneous physical picture no longer lead to the correct result. The analogue of this situation is the collision between two pictures of the world, namely, geocentric and heliocentric. As is well known, the correct picture is the heliocentric picture of the world, in which the Earth rotates around its own axis. However, being on the surface of the Earth, this rotation is perceived by the observer as the movement of the Sun across the sky, which is well simulated by an erroneous geocentric picture. The exit from the surface of the Earth to a sufficiently large distance into space directly shows the fallacy of the geocentric picture of the world. This is analogous to the transition from the transient state dynamics in standard optical spectroscopy, which is strongly chaotic in small molecules and therefore insignificant, to the transient state dynamics in photochemistry, where elements of regular motion appear for large molecules against the background of transient chaos (dozy chaos [3]).
References:
[1] Landau, L.D.; Lifshitz, E.M. Quantum Mechanics, Non-Relativistic Theory, 3rd ed.; Elsevier: Amsterdam, The Netherlands, 1977.
[2] Egorov, V.V. The J-Band of J-Aggregates as the Egorov Nano-Resonance. Comput. Sci. Math. Forum 2023, 7, 31.
[3] Egorov, V.V. Quantum–classical mechanics: Nano-resonance in polymethine dyes. Mathematics 2022, 10(9), 1443.
| SESSION: SolidStateChemistryFriAM1-R4 | Poeppelmeier International Symposium(3rd Intl Symp on Solid State Chemistry for Applications & Sustainable Development) |
| Fri. 1 Dec. 2023 / Room: Dreams 4 | |
| Session Chairs: Richard Dronskowski; Session Monitor: TBA | |
We report our recent advances in the science and technology of materials fabrication in magnetic fields via magneto-synthesis [1,2]. The capabilities and feasibility of the magneto-synthesis are strongly supported by evidence gleaned over the last six decades [3] and our own studies in recent years. However, the uniqueness and importance of magnetic energy for quantum material synthesis have not been widely recognized until very recently. Nevertheless, it is clear that magnetic fields can not only improve crystal homogeneity via Lorentz forces, but also can modify phase boundaries by taking advantage of the dependence of the Gibbs free energy on the applied magnetic field. Magneto-synthesis works particularly well for quantum materials with strong spin-orbit interactions and near-degeneracies [2], that can offer exquisite control of structural and physical properties unattainable by other means. This Lecture presents our most recent results of single-crystal quantum materials via magneto-synthesis with comparison drawn with those of the counterpart materials synthesized without magnetic field. The overall
significance of the magneto-synthesis could be comparable to that of the floating-zone technology first developed in the 1950s, which made ultrapure semiconductors possible and was a critical enabling factor for the eventual development of semiconductor devices.
References:
[1] Gang Cao, Hengdi Zhao, Bing Hu, Nicholas Pellatz, Dmitry Reznik, Pedro Schlottmann and Itamar Kimchi, npj Quantum Materials 5, 83 (2020)
[2] Gang Cao and Lance E. De Long, Chapter 6, Physics of Spin-Orbit-Coupled Oxides, Oxford University Press; Oxford, 2021
[3] O. Guillon, C. Elsässer, O. Gutfleisch, J. Janek, S. Korte-Kerzel, D. Raabe and C. A. Volkert, Materials Today 21, 527 (2018)
The well-known optical absorption J-band arises as a result of the formation of J-aggregates of polymethine dyes in their aqueous solutions. Compared to dye monomers, this band is narrow and high intensity, and redshifted. The narrowness and high intensity of the J-band are used in many applications, in particular, in the development of modern dye lasers. The J-band was discovered experimentally by Jelley and independently by Scheibe in 1936 [1,2]. In 1938, Franck and Teller [3] gave a theoretical explanation of the J-band based on the Frenkel exciton model. In 1984, based on the same exciton model, Knapp explained the shape of the J-band [4]. Subsequently, within the framework of the Frenkel exciton model, the shape of the J-band was studied by a large number of theorists, including the author of this abstract [5]. The author's reviews [6,7] provide a detailed critique of the explanation of the nature of the J-band based on the Frenkel exciton model. In particular, a significant drawback of this model is its inability to explain in principle the nature and shape of the optical bands of polymethine dye monomers from which J-aggregates are formed [6–8]. The author gives an alternative explanation of the nature of the J-band in the framework of a new fundamental physical theory, namely, in the framework of quantum-classical mechanics of elementary electron transfers in condensed media, which includes an explanation of the nature and shape of the bands of polymethine monomers that form J-aggregates [8] . Quantum-classical mechanics is a significantly modified quantum mechanics, in which the initial and final states of the "electron + nuclear environment" system for its "quantum" transitions are quantum in the adiabatic approximation, and the transient chaotic electron-nuclear(-vibrational) state due to chaos is classical [8]. This chaos is called dozy chaos. The new explanation of the nature and shape of the J-band is based on the so-called Egorov nano-resonance discovered in quantum-classical mechanics [8]. Egorov nano-resonance is a resonance between the electron motion and the motion of the reorganization of the nuclei of the environment during quantum-classical transitions in the optical chromophore under the condition of weak dozy chaos in the electron-nuclear(-vibrational) transient state [9].
References:
[1] Jelley, E.E. Spectral absorption and fluorescence of dyes in the molecular state. Nature 1936, 138, 1009–1010.
[2] Scheibe, G. Variability of the absorption spectra of some sensitizing dyes and its cause. Angew. Chem. 1936, 49, 563.
[3] Franck, J.; Teller, E. Migration and photochemical action of excitation energy in crystals. J. Chem. Phys. 1938, 6, 861–872.
[4] Knapp, E.W. Lineshapes of molecular aggregates, exchange narrowing and intersite correlation. Chem. Phys. 1984, 85, 73–82.
[5] Makhov, D.V.; Egorov, V.V.; Bagatur’yants, A.A.; Alfimov, M.V. Efficient approach to the numerical calculation of optical line shapes for molecular aggregates. J. Chem. Phys. 1999, 110, 3196–3199.
[6] Egorov, V.V.; Alfimov, M.V. Theory of the J-band: From the Frenkel exciton to charge transfer. Phys. Uspekhi 2007, 50, 985–1029.
[7] Egorov, V.V. Theory of the J-band: From the Frenkel exciton to charge transfer. Phys. Procedia 2009, 2, 223–326.
[8] Egorov, V.V. Quantum–classical mechanics: Nano-resonance in polymethine dyes. Mathematics 2022, 10(9), 1443-1–1443-25.
[9] Egorov, V.V. The J-Band of J-Aggregates as the Egorov Nano-Resonance. Comput. Sci. Math. Forum 2023, 7, 31.
The current sustainable development trends tightly connected with the meeting of climate agenda, growth in the electronics industry, and digital transformation have forced the global research and industrial community to focus on newer technologies based on application of rare metals and other related critical materials. The rare metals include five subgroups, namely light RMs (Be, Li, Rb, Cs), refractory metals (V, Zr, Hf, Nb, Mo, Ru, Rh, Hf, Ta, W, and Re), scattered metals (Ga, In, Tl, Ge, Se, and Te), significant group of rare earth metals (Sc, Y, and lanthanides), and radioactive metals (out of our consideration). Among RMs, the most significant rise of consumption over the last two decades was observed for rare earths and lithium, while consumption of refractory and scattered metals demonstrated more moderate increase. RMs are characterised by relatively low abundance in the earth’s crust but are of crucial role in a wide range of modern industrial applications such as mobile devices, wind turbines, robotics, electric vehicles, aerospace, hydrogen energy, catalysts, medical imaging, electronics, optics, photonics, energy efficient lighting, etc. The newer technologies based on the application of RMs should promote future well-being of society by driving the development of more sustainable, green, and clean energy sources, formation of healthier environment, and higher life standards. We all currently witness the growing consumption of RMs that triggers the development of more comprehensive and productive mining, beneficiating, metallurgical, chemical and materials processing technologies. At this point it is worth noting that mining and further processing of RM mineral resources requires intense consumption of traditional energy sources such as coal, oil, natural gas, pet coke, hydroelectric power, etc. Moreover, it is followed by environmental degradation (surface and ground waters, air, and soil), creating dust containing rare and radioactive metals (U, Th), other toxic metals and chemicals, greenhouse and some toxic gases emissions, etc. Serious concerns are also related to active and all-time growing usage of RM containing instruments, magnets, batteries, electronic parts, equipment, etc. amid lack of recycling (currently below 1%). As a result, mountains of e-waste rich of RMs are growing across the globe and have already led to environmental and health impacts in many countries including India, Russia, China, Australia, US, Brazil, and EU countries. In view of the above, the nowadays research activities should be focused on the development of truly environment-friendly technologies capable to secure RM supply by equally relaying on both primary (deposits, ocean bed sediments, etc.) and secondary resources (electronic and industrial waste). The latter may cover a substantial part of the demand for RMs. In this talk, we will outline a number of advanced technologies elaborated at our institute including chemical processing of RM minerals, obtaining of high-purity materials for electronics and photonics, high value-added products for energy conversion, and technologies for recycling of different types of industrial waste (e-waste, rare earth based magnets, Li-Ion batteries, etc.).
| SESSION: AdvancedMaterialsTueAM-R5 | 7th Intl Symposium on New & Advanced Materials and Technologies for Energy, Environment, Health and Sustainable Development |
| Tue. 28 Nov. 2023 / Room: Heliconia | |
| Session Chairs: Fernand Marquis; Daniel Kanzler; Session Monitor: TBA | |
Sustainable development is a comprehensive and complex system of systems requiring multidisciplinary and interdisciplinary science and technology inputs with economic, environmental, and social objectives. In broad terms, sustainable development is achieved when the present needs and challenges are met without placing in jeopardy the ability of future generations to meet their own needs and challenges. The trade space is very wide, and the multitude of trade-offs generate considerable challenges and make it often difficult to achieve an effective balance, most beneficial to all concerned. During the last sixty years the planet’s population has grown exponentially, from 2 to almost 8 billion people, and the technological progress achieved in certain global locations has been tremendous, especially in the industrialized countries. These trends are expected to continue, even at faster rates, and to extend to other global locations. However, all these associated technological activities in the pursuit of better living standards have created a considerable depletion of resources and pollution of land, water, air, and natural resources. Thus, it is imperative that we achieve more with less, implementing considerable energy efficiencies and activating the transition to alternative and renewable energy sources. To reach these goals considerable achievements have been obtained in the development of new and advanced materials such as light weight metallic alloys, metal matrix composites, intermetallic and carbon fiber composites, and hybrid materials systems. Nano, nano-structured and nano-hybrid carbon-based materials systems and nanotechnologies have also been deployed with considerable and transformative impact on energy, environment, and health. This presentation focuses on global perspectives of the impact of certain new and advanced materials and technologies on sustainable development with examples from several of its domains.
12:00: [AdvancedMaterialsTueAM02] OS KeynoteA large part of infrastructure in different high-tech countries e.g. in the USA, Germany was built in the 60’s and 70’s. Not only bridges and tunnels, but also nuclear power plants were built in these years. Our modern state is based on this infrastructure. Currently, the focus of everybody is on the infrastructure, following the first catastrophic failures. The load on the infrastructure is higher than ever planned and their reliability reached its limits. Even with the plan to renew the infrastructure in the upcoming years, the particular task would be impossible. With the current trend to sustainability it appears obvious, that there is a need for a change. The solution might be found in aerospace and aviation. In the late 80’s, the safety critical sector of aviation was faced with a similar situation: The need for airplanes was rising, however the predicted safe-lifetime of the planes was reached. The solution was to accept defects in the components. “Have Cracks Will Travel” a project of the US Airforce was called, which describes the change of the lifetime assessment towards the damage-tolerant concept, supported by a non-destructive testing program. This program made the lifetime extension possible and saved billions of dollars, at the same time increasing the reliability of aircrafts. Based on this example, we developed a useable framework for various safety critical industries and it has been introduced worldwide in different industries. For the presentation, we prepared examples from Finland and their approach on the final deposit of spent nuclear fuel, the German Automotive market and the Swiss Railway safety plan as well as a solution for the civil engineering issue of aged bridges in Germany. We also give an outlook what is possible using the tools of an environment called Industry 4.0, regarding the sustainability. We are convinced that the topics non-destructive inspections and monitoring are an essential part of our future. And sustainability is not a choice, it is a necessity all over the world! Where the presented procedure will be a helpful tool to establish safety, social endurance and economical resilience .
12:25: [AdvancedMaterialsTueAM03] OSHigh-entropy alloys have been in development for about two decades [1,2]. The ever-increasing interest of researchers in these materials is due to the broad possibilities of obtaining unique mechanical and functional properties [3]. The selection of alloying elements and heat treatments allows properties to be shaped for a wide variety of applications. In the AlCoCrFeNi alloy, the greatest effects are observed when the aluminum content is changed, which is due to the difference in atomic radii of the constituent elements [4]. One of the most important topics is to clarify the mechanisms of strengthening of these materials.The authors of this paper analyzed the deformation and fracture processes of AlxCoCrFeNi-based alloys (x=0¸1.0). They studied the effect of aluminum content and titanium addition on changes in microstructure and mechanical properties. Materials were produced by arc melting of pure metals in an argon atmosphere. Crystal structures of the samples were analyzed by means of X-ray diffraction (XRD) using an Empyrean Panalytical powder diffractometer (Malvern Panalytical). Microstructure studies were carried out on a SEM-FIB DualBeam Scios 2 scanning electron microscope equipped with an EDS chemical composition analyzer. Keyence optical microscope was used to analyze the fractures. Tensile tests were carried out during a tensile test of microsamples on an Instron machine using an Aramis vision system for strain assessment. Hardness was measured by the Vickers method under a load of 98 N using an INNOVATEST hardness tester.XRD studies showed that the crystal structure of the alloys is dependent on the aluminum content. At x=0 there is a homogeneous structure of a solid solution, crystallizing in the fcc system, increasing the content of Al causes the appearance of a bcc phase, the proportion of which increases with increasing Al content, while the addition of titanium caused the appearance of numerous intermetallic phases. Similar changes were observed in the microstructure of the materials. The x=0 alloy is characterized by a homogeneous structure with no separations. In contrast, at x=0.5, the microstructure shows a large proportion of dendrites of the solid solution of the alloying elements. A mixture of phases is visible in the interdendritic spaces, with the structural elements of this mixture having dimensions of less than 1 mm. Segregation of alloying elements within the phases is observed. As the aluminum content increases, the proportion of the phase mixture increases. At x=1.0, the microstructure consists of regular grains inside which a substructure at the nanometer level is visible. In the case of an alloy with the addition of titanium, numerous separations of intermetallic phases additionally appear. Mechanical properties also change decisively with the aluminum content in the alloy. An increase in Al content resulted in an increase in Rm (Rm=560¸1200 MPa for x=0¸0.7 respectively) and hardness, and a decrease in ductility. With up to x=0.7 content, the samples showed high ductility within e=15¸30%. At x=1 and for the alloy with the addition of titanium, brittle fracture of the alloy took place. Analysis of the obtained results allows us to conclude that the mechanical properties are influenced by both the mechanism of solution strengthening and the microstructure of the alloys.
References:
[1] J.W. Yeh, Y.L. Chen, S.J. Lin, S.K. Chen, Mater. Sci. Forum 560 (2007) 1–9.
[2] [2] Y. Zhang, T.T. Zuo, Z. Tang, M.C. Gao, K.A. Dahmen, P.K.Liaw, Z.P. Lu, Progress in Materials Science 61 (2014) 1–93.
[3] M. Tokarewicz, M. Grądzka-Dahlke, K. Rećko, M.Łępicka, K. Czajkowska, Materials 15 (2022) 1-15.
[4] T.-T. Shun, W.-J. Hung, Adv. Mater. Sci. Eng. 2018 (2018) 5826467.
Nanodispersed iron oxides obtained using the electroerosion dispersion (EED) technology [1-3] were developed by M. Monastyrov, and used to produce dietary supplement LisoferrinTM and feed additive Nano-Fe+TM. The supplement and additive were certified in Ukraine and Poland.The effects of composition of polyvalent nanodisperse iron oxide, quercetin and vitamin C - LisoferrinTM was studied on 60 women with metabolic syndrome (MS) who were divided equally into the main and control groups. Patients of the main group received dietary supplement LizoferrinTM, patients of the control group received a placebo. Anthropometric indicators, blood plasma glucose fasting and 2h after oral glucose tolerance test (OGTT), fasting blood serum lipids, microvascular endothelium function were determined before and 1 month after use of LizoferrinTM or placebo. The use of LizoferrinTM led to a decrease fasting plasma glucose and glucose level 2h after OGTT in patients with prediabetic disorders. Serum concentration of total cholesterol and low-density lipoproteins cholesterol were decreased in individuals with atherogenic dyslipidemia. Along with this, there was an improvement in the functional state of the endothelium of microvessels, which is evidenced by an increase in the maximum volume velocity of skin blood flow as tested with reactive hyperemia. The beneficial effects of polyvalent nanodisperse iron oxide, quercetin and vitamin C on cardiovascular risk factors were demonstrated by the authors for the first time in patients with metabolic syndrome [4] .The efficiency of nanodispersed iron oxide powder solved in glycerin - nano-Fe+TM was studied during agricultural animal growing. The dosage of nano-Fe+TM feed additive was carried out at the rate of 0.1 mg of powder per 1 kg of live weight of animals per day. According to the results of research, the effectiveness of the nano-Fe+TM during the cultivation of various species and technological groups of agricultural animals (suckling piglets, young pigs in the growing period and young sheep in the growing period) has been established. The use of the nano-Fe+TM contributes to an increase in productivity - increases in the live weight of piglets by 11.4%, young pigs by 7.7%, young sheep by 7.3%. The effectiveness of the nano-Fe+TM is confirmed by the data obtained during the research on the average daily increase in the live weight of animals, the difference between young pigs and sheep during the growing period of the experimental and control groups according to this indicator was statistically significant in favor of the animals of the experimental groups (Р < 0.05). For example, the difference in average daily live weight gains between young pigs of the experimental (403 ± 36 g) and control (343 ± 39 g) groups is 60 g (17.5%).The preservation of the animal population of the experimental groups is at the same level as the control group and is 100%. Nano-dispersed iron oxide powder (nano-Fe+TM) is characterized by its effectiveness during the cultivation of young farm animals and was recommended for use on livestock farms in Ukraine by L. Pogorilyy UkrNDIPVT.
References:
[1] B. Halbedel, T. Prikhna, P. Quiroz, T. Kups, M. Monastyrov, Current Applied Physics, 18(11) (2018) 1410–1414.
[2] M.K. Monastyrov, T.A. Prikhna, A.G. Mamalis, W. Gawalek, P.M. Talanchuk, R.V. Shekera Nanotechnology Perceptions, 4 (2008) 179–187.
[3] M. Monastyrov, T. Prikhna, B. Halbedel, A.G. Mamalis, O. Prysiazhna, Nanotechnology Perceptions. 15(1) (2019) 48–57. N24MO18A
[4] V. Shatilo, I. Antonyuk-Shcheglova, S. Naskalova, O. Bondarenko, M. Monastyrov, T. Prikhna Positive effects of quercetin, iron oxide nanoparticles and ascorbic acid composition in the treatment of women with metabolic syndrome // Ageing and Longevity. 4(1) (2023) 8-15. Retrieved from http://aging-longevity.org.ua/index.php/journal-description/article/view/89
| SESSION: AdvancedMaterialsTuePM1-R5 | 7th Intl Symposium on New & Advanced Materials and Technologies for Energy, Environment, Health and Sustainable Development |
| Tue. 28 Nov. 2023 / Room: Heliconia | |
| Session Chairs: Andreas Diegeler; Janusz Lipkowski; Session Monitor: TBA | |
Molecular inclusion has been in chemical practice for over two centuries but it happened in the 1950th when the physicochemical nature of the systems became clear to science. The subset named ‘clathrates’ was the first to be characterized on structural (1948) and thermodynamic (1959) background. Presently a very large class of compounds are considered as clathrates. These are either genuine clathrates, with no bonding interactions between host and guest components, and several structurally analogous compounds with stronger interactions, namely ionic, inorganic and other ‘clathrates’.Water is extremely important host material, able to form a variety of clathrate or clathrate-like ‘compounds’. This behaviour was first discovered by Davy in 1809 who crystallized chlorine in the form of pentahydrate (as determined a couple of years later by Faraday). Characteristic feature of these compounds is non-stoichiometry, hence the ‘penta’-hydrate was the approximate value. Very many clathrate hydrates are known recently and some are of special technological importance. Of special value is methane clathrate. Huge amounts of this material have been found in permafrost regions and even much more is present under the sea, at depths approximately equal 500 m or more. Since 2013 these deposits are being exploited, however experimentally, by Japan and somewhat later by China. Some details will be discussed, including the idea of methane desorption combined with CO2 sequestration. Ecological problems associated with the processes will be signalled.Another class of inclusion compounds known sine the end of 19th century are cyclodextrins, obtained by a special fermentation of starch. Also in this very case the technology-oriented studies started in mid XX century. Cyclodextrins, native and chemically modified, are presently a huge industry worldwide providing enormously large variety of products, from pharmaceutical, food additives, environment friendly additives in technological processes, It will be briefly illustrated with the use of cyclodextrin derived anti-COVID preparations.Of historical value are technological attempts to apply the high selectivity of molecular inclusion expressed by some coordination complexes towards petrochemical mixtures[KM1] , like C8 (xylenes and ethylbenzene). Labofina has arrived up to semicommercial scale but the process appeared non-competitive due to a trivial problem of filtering fine powders of the clathrates. It is nevertheless important to point out extremely important and controllable selectivities in these systems enabling even efficient separations of mixtures of isotopomers. On analytical scale these compounds are used in thee, so-called, clathrate chromatography.Other examples will be shown and illustrated, including the family of calixarene hosts, cucurbiturils and cavitands. Some dynamic properties of the solids will be demonstrated on selected examples.
14:30: [AdvancedMaterialsTuePM106] OSAs global temperatures rise, the need for thermal comfort increases, and household incomes rise around the world, the energy consumption for heating, ventilation and air conditioning systems increases [1], [2]. Monthly electricity consumption increases by 3.2% for each additional day with a mean temperature exceeding 90 °F (32.2 oC) relative to a 65–70 °F (18.3-21.1 oC) day[2]. During summer days the highest electricity demand is during the peak hours (from 12 pm to 6 pm). Power companies are seeking methods to shift some of the load to off-peak hours because they have difficulty in keeping up with the demand during peak hours [3]. Significant economic benefit could be achieved when some of the electric load is shifted to off-peak due to differential pricing system for peak and off-peak periods of energy use [4]. One of the solutions investigated in this study is the integration of phase change materials (PCM) in the ceilings and walls of a building enclosure [3]. The PCMs are latent heat energy storage materials with high heat of fusion. These materials absorb or release the latent heat during the phase change. Different kinds of PCMs are available for use in a latent heat storage system such as salts hydrates, paraffin, and fatty acids [5]. The integration of PCMs will enhance energy storage in building envelop, maintain a room temperature closer to the desired temperature for a longer time, delay air temperature maximum to an off-peak demand period, and increase human comfort by decreasing the frequency of internal air temperature swings [4]. Energy storage improves energy utilization and conversation and decreases carbon emissions. Presently, in buildings thermal energy is primarily stored as sensible heat in the envelop and interior. Latent heat storage systems have certain benefits in comparison to sensible heat storage systems in that phase change materials store a relatively large amount of heat per unit volume.
In this study, an energy storing oriented strand board (OSB) wood-based panel has been developed. OSB is widely used in the northern hemisphere for the outer building envelope as it has good mechanical properties to bear loads. Thermal energy storing capability has been achieved by integrating wax, a phase change material (PCM), in wood board. Shape stabilized phase change material (SSPCM) based on high density polyethylene is the host for the PCM in the oriented strand board (OSB). Different additives were added to increase the percentage of PCM that can be used in SSPCM preparation without leakage during the phase change, serve as flame retardant since organic PCM is flammable, or to enhance the bonding between the SSPCM and wood strands which will lead to better mechanical properties. The heat flux and the temperature through the thickness of the board were recorded. To evaluate the heat storage properties of SSPCM, differential scanning calorimetry (DSC) was used. While a Cone Calorimeter was used to test the flammability properties of OSB-SSPCM boards. The results suggest that the integration of SSPCM in oriented strand board lowers the heat flux as compared to OSB without SSPCM and could be a viable material for use in buildings to reduce energy consumption and that the addition of nano magnesium hydroxide enhances the desired flammability properties of OSB-SSPCM, which can be potentially used in civil construction.
References:
[1] D. Zhou, C. Y. Zhao, and Y. Tian, “Review on thermal energy storage with phase change materials (PCMs) in building applications,” Appl. Energy, vol. 92, pp. 593–605, 2012, doi: 10.1016/J.APENERGY.2011.08.025.
[2] L. W. Davis and P. J. Gertler, “Contribution of air conditioning adoption to future energy use under global warming,” Proc. Natl. Acad. Sci. U. S. A., vol. 112, no. 19, 2015, doi: 10.1073/pnas.1423558112.
[3] C. K. Halford and R. F. Boehm, “Modeling of phase change material peak load shifting,” Energy Build., vol. 39, no. 3, pp. 298–305, Mar. 2007, doi: 10.1016/J.ENBUILD.2006.07.005.
[4] M. Farid, A. M. Khudhair, S. A. K. Razack, and S. Al-Hallaj, “A Review on Phase Change Energy Storage : Materials and Applications,” Therm. Energy Storage with Phase Chang. Mater., pp. 4–23, Jul. 2021, doi: 10.1201/9780367567699-2.
[5] L. Sánchez, P. Sánchez, A. de Lucas, M. Carmona, and J. F. Rodríguez, “Microencapsulation of PCMs with a polystyrene shell,” Colloid Polym. Sci. 2007 28512, vol. 285, no. 12, pp. 1377–1385, Jul. 2007, doi: 10.1007/S00396-007-1696-7.
Coumarins are natural compounds with wide application in organic synthesis as acceptors in different organic reactions with nucleophilic reagents and dienophiles in Diels-Alder reactions as well in reactions of [2+2] or [2+3] cycloaddition and as intermediates in the synthesis of products of practical interest. On the other hand, especially important are their antimicrobial, antiviral, anticancer, enzyme inhibition, anti-HIV, and antioxidant activities as well as their influence over central nervous system [1]. A third large area of application of coumarin derivatives are modern technologies. They can be applied as excellent luminophores and laser dyes. Coumarin derivatives may be used as ligands for metal complexes and for modification of organic and inorganic supports.The investigations on the chemical behavior of the 3-substituted 2-oxo-2H-1-benzopyranes (coumarins) toward nucleophilic reagents represented them as good acceptor in the 1,4-addition reactions. Acknowledgements: The support by the project EXTREME, funded by the Bulgarian Ministry of Education and Science, D01-76/30.03.2021 through the program “European Scientific Networks” is gratefully acknowledged.Reactions of the 3-substituted coumarins with organomagnesium, and organozinc reagents as well as with Ivanov’s reagent were carried out and the corresponding 2-oxochromanes were isolated with good yields. The reactions with their analougs 1,2-benzoxaphosphorine as substrate had the same synthetic progress but in these cases were isolated only two of possible diastereoisomers. The reactions were carried out under ultrasound irradiation and the yields of the target products were higher and the results were accurate and precise. Interestingly nucleophilic addition of halogen subsituted anhydride in the presence of Zn lead to formation of biscoumarins. Conditions suggested by us represent a new method for the synthesis of this type of compounds under simple and eco-friendly experimental set up.
References:
[1] Borges, F.; Roleira, F.; Milhazes, N.; Santana, L.; Uriarte, E. Curr. Med. Chem. 2005, 12, 887-916.
[2] Riveiro, M. E.; De Kimpe, N.; Moglioni, A.; Vázquez, R.; Monczor, F.; Shayo, C.; Davio, C. Curr. Med. Chem. 2010, 17, 1325-1338.
[3] Al-Majedy, Y.; Kadhum, A. A.; Ibraheem, H.; Al-Amiery, A.; Moneim, A. A.; Mohamad, A. B. A Sys. Rev. Pharm. 2018, 9, 49-54.
The climate change that we are driving with our hunger for energy, mobility, consumption and global networking will primarily harm ourselves and our future generations. Economic prosperity and global resource consumption have so far gone hand in hand - our planet is already no longer sufficient for our needs, we are living "on credit". How can we make the leap forward to a resource-conserving circular economy? On the one hand, globalization and worldwide networking create prosperity and jobs; on the other, they create enormous competitive pressure in production and social standards. To survive in this competition, we need to drive key technologies forward. As parent institute to quite a number of different entities, the Fraunhofer ISC is privileged to combine first-rate expertise in materials science with long-standing experience in materials processing, application and analysis. The Institute focuses on affordable health care and regenerative therapies, on resource and energy efficiency, and on sustainability, emphasizing the use of regrowing and economically friendly raw materials, the avoidance of critical materials as well as on smart and sustainable processing techniques. The ISC is one of the leading European R&D centers for material-based research and development in the fields of energy, environment and health with innovative material solutions and technologies for sustainable products and essential contributions to solving the major global issues and challenges of the future. Our talk will go through several approaches of Fraunhofer ISC to go forward saving our blue planet.
| SESSION: AdvancedMaterialsTuePM2-R5 | 7th Intl Symposium on New & Advanced Materials and Technologies for Energy, Environment, Health and Sustainable Development |
| Tue. 28 Nov. 2023 / Room: Heliconia | |
| Session Chairs: Zhen Chen; Wael Zatar; Session Monitor: TBA | |
Twenty six percent of reinforced and prestressed concrete highway bridges in the United States need repair or replacement. Proper use of available and promising sustainable technologies plays a critical role in the nation’s economy and the safety of the traveling public. Employing fiber-reinforced polymer (FRP) advanced materials has recently been accepted as a rational and sustainable rehabilitation option for structurally deteriorated infrastructure. Despite the advancement in FRP techniques, inspection of its installation presents a significant challenge to its widespread use. To ensure durability and capacity of externally bonded FRP structures, it is critical to evaluate the potential for debonding failure and surface defects. In this study, experimental and theoretical investigations on employing ground-penetrating radar (GPR) and infrared tomography (IRT) methods were carried out to evaluate reinforced concrete bridge deck slabs externally bonded with glass FRP (GFRP), carbon FRP (CFRP), and a combination thereof. Eight externally bonded FRP concrete deck slab specimens were prepared: three with CFRP, four with GFRP, and one with hybrid CFRP/GFRP. Cracks, voids, and debonding were artificially made on the surface of the concrete deck slabs. Test variables include location and size of surface voids, and rebar diameters and debonding. Improved 2-D and 3-D image reconstruction was established. The results showed that the developed software, using the enhanced image reconstruction technique, provide clear images of the FRP-strengthened deck slabs. Test data revealed that the GPR technique could accurately determine rebar diameters, as well as size and location of voids. The GRP, however, could not well predict debonding and cracks. Results obtained from the IRT indicated that it can detect and locate near-surface defects with a good accuracy. The study suggests that the combination of the GPR and IRT techniques can be effectively employed to image internal defects of FRP-strengthened concrete bridges.
References:
[1] ACI PRC-228.3-23: What an Owner Should Know about Nondestructive Testing – Technote, American Concrete Institute (ACI), ACI Committee 228 (2023).
[2] W.A. Zatar, H.D. Nguyen, H.M. Nghiem, American Concrete Institute Special Publication 346 (2021) 11-30.
[3] W.A. Zatar, H.D. Nguyen, H.M. Nghiem, Journal of Infrastructure Preservation and Resilience, 1(1) (2020) 1-13.
[4] W.A. Zatar, H.D. Nguyen, Proceedings of 5th International Conference on Sustainable Construction Materials and Technologies (SCMT5), United Kingdom (2019).
It is given a brief overview of high efficiency motors [1-3] and the materials used in these machines.This subject has attracted big interest because the applications in electric vehiclesInternal Permanent Magnet Synchronous Reluctance Motors have attracted a significante attention because its high efficiency.It is discussed motor designs with or without permanent magnets.Axial flux machines are also discussed, as well as in-wheel motors.It is also discussed the possibility of using Halbach arrays of magnets.It is shown that, for embedded magnets, the Halbach arrangement is not advantageous.Halbach arrangements usually are surface mounted.It is also discussed the types of magnets used in electric cars. A better design avoids the heating of system, thus allowing the use of magnets with small amount of dysprosium in the phase (NdPrDy)2Fe14BA simple way of improving motor efficiency is by decreasing the thickness of the steel sheets used as soft magnetic core.Segmentation is a possibility for using high permeability materials as for example GO (Grain Oriented) steels
References:
[1] TEIXEIRA, J. C.; CHILLET, C. ; YONNET, J. . Structure Comparison of buried PMSM for flux weakening operation. In: 6 th Inter, conf. on Electrical Machines and Drives, 1993, Manchester. Proceedings of EMD 93, 1993. p. 365-370.
[2] https://www.powerelectronictips.com/gallery-power-electronics-on-display-at-the-ieee-ecce-energy-conversion-congress/
[3] https://hal.science/hal-03304650/document
Vegetable fiber cement is a new compound made from a mixture of cement, inorganic waste (slag) and plant fibers (banana, sisal, coconut, eucalyptus or other plants). Vegetal fiber cement has several advantages over common fiber cement. This material stands out mainly for not offering health risks related to inorganic dust, as occurs with mineral fibers. In addition, reinforcing the cementitious matrix with plant fibers improves the mechanical performance and durability of these materials. Another advantage is related to water absorption. The vegetable fiber cement samples have a relevant waterproofing capacity.The purpose of this work is the development and characterization of a concrete material reinforced with natural fibers. The use of plant fibers in civil construction is sustainable and environmentally friendly. The inorganic residue used was red clay. Vegetal fibers of Sansevieria trifasciata (popularly known as Espada de São Jorge in Brazil) were tested as reinforcement of the cementitious matrix. Sansevieria trifasciata fibers can increase the mechanical strength of the cementitious matrix. The fibers were subjected to an alkaline treatment in order to increase their surface area. In addition, the fiber size was also tested. The fiber size has a direct influence on its dispersion in the matrix. The material was subjected to compression and structural physical tests (absorption index, voids index, specific mass), treatment and characterization of the vegetable fiber, and also the granulometry of the cement mixture. The results indicate that the fiber size and the chemical treatment previously carried out significantly influence the physical properties and ability to withstand compressive load.
17:15: [AdvancedMaterialsTuePM212] OS KeynoteTo better dissipate energy under transient loading with less solid fraction, shocked metallic foam responses have been investigated with different spatial discretization methods at different scales. Molecular dynamics (MD) and the finite element method (FEM) are representative discrete particle and continuous methods, respectively. The Material Point Method (MPM) is a continuum-based particle method that is formulated based on the weak form of the governing equations in a way like the FEM. Based on the recent research results [Saffarini et al., 2023; Su and Chen, 2023], we are performing a comparative study of shocked metallic foam responses with both MD and MPM to understand the porous interfacial effect on failure evolution in shocked metallic foam assembly. Essential features of the responses at the same spatial scale as obtained with both discretization procedures will be presented in the conference for a representative composite system. It appears from the preliminary study that the MD and MPM solutions are consistent at the same scale. Thus, it might be feasible to compare the MD and MPM solutions for verification in multiscale simulation of extreme events. In addition, the porous interfacial effect might produce the failure evolution similar to the failure wave phenomenon as observed in shocked brittle solids [Kanel et al., 2005]. Further research is required to quantify the failure evolution in metallic solids shocked at different levels.
References:
[1] Kanel, G.I., Razorenov, S.V., Savinykh, A.S., A. Rajendran, and Chen, Z., “A Study of the Failure Wave Phenomenon in Glasses Compressed at Different Levels,” Journal of Applied Physics, Vol. 98, pp. 113523-113530, 2005.
[2] Saffarini, M., Sewell, T., Su, Y., and Chen, Z., “Atomistic Study of the Impact Response of Bicontinuous Nanoporous Gold as a Protection Medium: Effect of Porous-Nonporous Interface on Failure Evolution,” Computational Materials Science, Vol. 228, No. 112363, 2023.
[3] Su, Y., and Chen, Z., “Study of the Shear-band Evolution across the Interface between Different Spatial Scales,” accepted for publication in Computational Particle Mechanics, 2023.
| SESSION: AdvancedMaterialsTuePM3-R5 | 7th Intl Symposium on New & Advanced Materials and Technologies for Energy, Environment, Health and Sustainable Development |
| Tue. 28 Nov. 2023 / Room: Heliconia | |
| Session Chairs: Marcos De Campos; Session Monitor: TBA | |
Water bodies have systematically suffered from pollution caused by urban and industrial activities. Heavy metals are in a category of contaminants of lakes, rivers and seas that are of great concern. The development of environmentally correct alternatives is necessary to neutralize the action of heavy metals. It is worth noting that numerous solutions have already been adopted in order to remove heavy metals from seas and lakes. However, the production of some products to remove contaminants causes environmental pollution. Therefore, it is extremely important to develop an environmentally friendly synthesis route, so that the production process is consistent with the purpose of the final product. The objective of this work is the development of an environmentally friendly route for the synthesis of bifunctional zero valency iron using agro-industry residues with low added value. They have a metallic phase (zero valency iron) to degrade the harmful metals and an organic phase (grape peel biomass) suitable for adsorption pollutants. The particles were produced by a green route using Mentha spicata extract as an iron-reducing agente of Fe3+. The results indicated the presence of ferrous material in the samples. Furthermore, the functionality of the composite was analyzed by spectrophotometry, with a reduction of up to 53% of heavy metal ions (Cr6 +) in contaminated water. Therefore, the biocomposite is functional and has the ability to remove heavy metals.
18:20: [AdvancedMaterialsTuePM314] OSThis work aims to provide theoretical guidance about fabricating high-efficiency electroluminescent materials by means of smart molecular design. Density functional theory is utilized to investigate the geometric structures of the two heterocyclic thiophene and silicon pentadiene dithienosiloles (DTS) derivatives. It is shown that different substituents in the side chain have minor influences on the geometric properties of rigid molecules, whereas the electronic structure and charge transport performance can be tuned effectively. 5-flurophenyl DTS can be regarded as a promising bipolar charge transport material with equilibrated hole and charge transfer performance.
| SESSION: AdvancedMaterialsWedAM-R5 | 7th Intl Symposium on New & Advanced Materials and Technologies for Energy, Environment, Health and Sustainable Development |
| Wed. 29 Nov. 2023 / Room: Heliconia | |
| Session Chairs: Pierre Collignon; Kasturi Vasudevan; Session Monitor: TBA | |
The "green industrialization" of heat and surface treatments involves the search for new technologies and processes. Hybrid technologies open new perspectives for protection and durability for heavily stressed mechanisms requiring multifunctional properties, while being energy efficient.We studied two hybrid technologies and the properties obtained in relation to the applications. For each of these Duplex processes, we also evaluated the benefits from an energy and environmental point of view.[1].[2]The first hybrid process carried out either in a plasma nitriding system either in a "coating system" is a combination of a plasma nitriding treatment and a DLC tribological coating intended for heavily stressed mechanical components . While obtaining remarkable multifunctional properties, this process is particularly well suited for the energy and ecological transition. We present an example of the potential for "green industrialization" through a hybrid duplex DLC treatment, gearboxes for electric cars compared to the current process.In addition, the very energetic plasma sources available in a coating equipment allow the nitriding of AISI 316L and 304 stainless steels and to obtain strong S phase growth kinetics [3]. Thus, by associating the characteristics of the substrate with the nitriding properties (S phase) of wear and compression resistance and the tribological properties of a DLC coating, this hybrid process opens up great industrial perspectives.The second hybrid process studied consists of the association of PVD coating by arc evaporation and magnetron sputtering. The research was conducted in two directions:To improve tribological or corrosion resistance properties by associating hard layers with layers or self-lubricating particles.To improve biocompatibility and inhibition of bacterial proliferation by associating TiN, ZrN, TiAlN coatings with the addition of copper or silver by co-deposition or multilayers [4]Hybrid processes, by implementing several technologies in a single piece of equipment, allow for the realization of multifunctional processes. These offer a very strong potential for industrialization not only thanks to the multiple properties obtained, but also thanks to the reductions in CO2 emissions that they allow.
References:
[1] Duplex treatment of active screen plasma nitriding and amorphous hydrogenated carbon coating Author links open overlay panelAkio Nishimoto a, Rei Amano b, Takazumi Tamiya b Volume 6, 1 December 2021, 100129
[2] Hybrid Technology for multifunctional coatings properties Pierre Collignon ICMTF 2018
[3] A Novel DC Plasma Nitriding at low gas pressure 304 austenitic stainless steel , by Shukai Wang, Wei Cai, Jingcai Li, Wei Wei, Jing Hu
[4] Silver Doped diamond-like carbon antibacterial and corrosion resistance coating on titanium by, Anca Mazare, Alexandre Anghel, Cristina Surdu-Bob, Georgeta Totea, Iona Demetrescu, Daniela Ionita
Facing today’s demands on components in general industry, aerospace, automotive or medical industry, lightweight and a tailored surface might be the right answer to reduce waste in terms of wear or frictional energy losses. PEO, plasma-electrolytical oxidation, remains as an unknown or at least niche surface technology, giving lightweight metals a hard and robust protection shell. Expiring an increasing interest in the research society in the last decade, it is supposed to be a promising candidate for increasing lightweight potential but being not ready for wide industrial applications by being too expensive or applicable only on small parts or series [1]. The Ultraceramics® PEO surfaces are on the market for over 20 years, applied under different harsh conditions. The Ultraceramic® -surfaces can withstand high loading by vibrations giving lightweight alloys like Aluminum or Magnesium a very high corrosion and wear protection [2]. Combining the high wear resistance of the PEO surfaces with polymers like doped PEEK, we can achieve low friction and wear in tribological applications without additional lubricants, leading to sustainable systems. Further improvement can be done using laser radiation for patterning and selective laser sintering of the polymer top coating [4]. Most recently, we found that especially in the case of Aluminum casting alloys an adopted PEO process leads to positive tribological behavior in combination with novel low-viscosity oils. The utilization of Direct interference laser structuring and hybridizing with a solid lubricating polymer manifold the positive effect. A 1000-h tribological test just being finished before this submission proves a very promising solution with low friction and almost no wear after a long period [3]. In this talk we will report on our tribological and corrosion test results within our laboratory accompanied by SEM and EDS findings for different CERANOD surface solutions. These findings we will compare and correlate with some different application cases of our clients, who utilize our solutions on their end products to enable the usage of lightweight metals under harsh tribological, vibrating and /or corrosive environments, and, thus, saving a lot of energy and resources.
References:
[1] L. Pezzato, L. Lorenzetti, L. Tonelli, G. Bragaggia, M. Dabalà, C. Martini, K. Brunelli, Effect of SiC and borosilicate glass particles on the corrosion and tribological behavior of AZ91D magnesium alloy after PEO process, Surface and Coatings Technology 428 (2021) 127901. https://doi.org/10.1016/j.surfcoat.2021.127901.
[2] A. Buling, J. Zerrer, Increasing the application fields of magnesium by ultraceramic®: Corrosion and wear protection by plasma electrolytical oxidation (PEO) of Mg alloys, Surface and Coatings Technology 369 (2019) 142–155. https://doi.org/10.1016/j.surfcoat.2019.04.025.
[3] A. Buling, J. Zerrer, Unknown tribological possibilities - Wear resistance for light metals by PEO, hybrid, and laser functionalized surface solutions, Wear 523 (2023) 204825. https://doi.org/10.1016/j.wear.2023.204825.
[4] A. Buling, J. Zerrer, Lifting Lightweight Metals to a New Level—Tribological Improvement by Hybrid Surface Solutions on Aluminium and Magnesium, Lubricants 8 (2020) 65. https://doi.org/10.3390/lubricants8060065.
Green composites are an alternative to conventional non biodegradable composites in many applications. In the reported work, the mechanical and physical properties of vulcanised natural rubber (NR) reinforced with wool fibre were investigated. A comparative study of vulcanised rubber with vulcanised rubber-wool composite was conducted with emphasis on diffusion characteristics, moisture absorption, thermal and UV degradation, biodegradation, acoustic properties, cure characteristics etc. The developed NR-wool composite contained 50% vulcanised rubber and 50% wool fibre. Various analytical techniques such as XRD, SEM, FTIR, etc. were adopted to characterize both vulcanised rubber and the composites. The thermal and UV degradation of the composites were also investigated by keeping the composites for ageing under standard conditions. The results showed that, in comparison with the vulcanized rubber sample, the tensile strength of the NR-wool composites was reduced whereas, the hardness increased by 84.26%. During diffusion studies, it is observed that the mol % uptake of toluene into the matrix of the composites was considerably less in comparison to that of vulcanised rubber. The cure time data shows that the maximum torque in the cure curve which is an indication of the extent of crosslinking increased to almost 500% in the NR-wool composites in comparison with vulcanized rubber. After incorporating 50% wool in NR, the curing time was reduced to almost half in comparison with vulcanized rubber. The cross-sectional SEM images depict fibre pullout and voids, which indicates less interfacial adhesion of the wool fibre with the rubber matrix. The FTIR studies indicate no specific chemical interaction between the wool and NR inside the composites. The moisture uptake of the NR-wool composite was found to be higher than the vulcanized rubber due to the presence of hydrophilic wool fibre.
12:50: [AdvancedMaterialsWedAM04] OSThe electrodynamic properties of new composite materials based on AlN and made by the free sintering method, with the addition of diamond powders in the amount of 1-5 wt.% were investigated, in the frequency range of 1-10 GHz. As a result of the studies of the structure and phase composition, it was established by X-ray phase analysis that during the sintering process, the graphitization of diamond powder takes place, and after refining the results obtained by the Rietveld method, show that the content of the graphite phase was 0.8, 1.7, and 3.8 wt.% for the materials in which added diamond powder before sintering in amounts of 1, 3, and 5 wt.%, respectively. The study of electrodynamic characteristics showed an increase in the imaginary and real values of the dielectric constant with an increase in the graphite content. Dielectric losses at 10 GHz increase from 0.05 to 0.08 for composites as the amount of graphite phase increases from 0.8 to 3.8 wt. %. It is shown that at frequencies from 1 to 10 GHz, the real part of the dielectric constant for composite materials of each composition practically does not change, while the imaginary part increases slightly. At the same time, an increase in dielectric losses with increasing content of the graphite phase was noted in the entire measured frequency range.
| SESSION: AdvancedMaterialsWedPM1-R5 | 7th Intl Symposium on New & Advanced Materials and Technologies for Energy, Environment, Health and Sustainable Development |
| Wed. 29 Nov. 2023 / Room: Heliconia | |
| Session Chairs: Fernand Marquis; Marcos De Campos; Session Monitor: TBA | |
The efficient removal of atmospheric pollutants such as oxides of carbon and nitrogen is of great concern for society since it those oxides are directly related to the human health as well as climate changes. Cerium dioxide is a reducible oxide, which often is crucial component in various adsorption or catalytic systems for removal of nitrogen oxide, the so-called deNOx processes, as well as for adsorption or conversion of carbon monoxide. By this reason, understanding of atomistic details of the interaction of CO or NOx with ceria-based systems is important for developing of new air purification technologies and improving the existing ones. This is the goal of the present work, which was done with the support by the project EXTREME, funded by the Bulgarian Ministry of Education and Science, D01-76/30.03.2021.The main feature of cerium dioxide is the oxygen storage capacity, allowing release and accommodation of oxygen depending on the reaction conditions [1]. In order to clarify the specific sorption and catalytic properties of cerium dioxide based systems we performed series of periodic quantum chemical calculations. The calculations were performed with DFT+U approach using periodic code VASP with the gradient corrected PW91 exchange-correlation functional. In relation to deNOx processes we modeled the interaction of NO and NO2 with cerium dioxide surface and nanoparticles and studied the formation of various surface species for which we estimated the reaction energies and vibrational frequencies to be compared with experimental data. On reduced ceria we considered two new surface species, nitric oxide dianion and surface azides [2]. In addition, we clarified the vibrational frequencies of specific types of hyponitrites, nitrites and nitrites [3].For CO adsorption on cerium dioxide we studied also several surface intermediates – different types of carbonates, hydrogen carbonates, and formates [4]. For carbon monoxide we also clarified the reaction paths for catalytic oxidation on platinum, supported on cerium dioxide as we considered both isolated ionic platinum species and small platinum clusters as active sites for the process [5].
References:
[1] G.N. Vayssilov, Y. Lykhach, A. Migani, T. Staudt, G.P. Petrova, N. Tsud, T. Skála, A. Bruix, F. Illas, K.C. Prince, V. Matolín, K.M. Neyman, J. Libuda, Nature Mater, 10, 310-315 (2011).
[2] M.Y. Mihaylov, E.Z. Ivanova, H.A. Aleksandrov, P.St. Petkov, G.N. Vayssilov, K.I. Hadjiivanov, Appl. Catal. B: Environ., 2015, 176–177, 107–119.
[3] M.Y. Mihaylov, V.R. Zdravkova, E.Z. Ivanova, H.A. Aleksandrov, P.St. Petkov, G.N. Vayssilov, K.I. Hadjiivanov, J. Catal., 2021, 394, 245-258.
[4] G.N. Vayssilov, M. Mihaylov, P.St. Petkov, K.I. Hadjiivanov, К.M. Neyman, J. Phys. Chem. C, 115, 23435–23454 (2011).
[5] I.Z. Koleva, H.A. Aleksandrov, G.N. Vayssilov, ACS Catal. 13, 5358–5374 (2023).
There is a great worldwide effort in research for the creation of technologies that allow the generation of energy through the use of new renewable biofuels that replace the traditional fuels derived from petroleum. We propose the synthesis of renewable biodiesel that was synthesized via chemical reaction of homogeneous alkaline transesterification and with ethyl route, from mixtures with different organic sources of fatty acids, proportions of composition between residual vegetable oil from frying and commercial linseed vegetable oils. The reaction was carried out in basic medium. The catalyst used (potassium hydroxide) was finely dispersed in infinite dilution condition, in order to ensure an effective nanotechnological condition for optimizing the degree of conversion of the mixture. The objective of these study is to understand the influence on the quality of the biodiesel produced, based on the most up-to-date specifications informed by the ANP. The evaluated parameters were measurement of specific mass; reaction yield of esters by mass; acid index and kinematic viscosity measurement at 40 0C. In addition, the results showed that regardless of the sample composition, the results of the kinematic viscosity measurement at 40 0C are in accordance with the current national biodiesel specifications. In conclusion, the results showed that the rheological classification for all samples consisted of the Newtonian fluid model, or the Power Law model when the power index is equal to unity (n=1).
14:55: [AdvancedMaterialsWedPM107] OL KeynoteBioactive compounds in edible plants and foods are vital for human and planetary health, yet their significance and potential remain underappreciated. These natural bioactives, as part of whole diets, ingredients, or supplements, can modulate multiple aspects of human health, wellness, and performance [1]. Recent advancements in omics, computational biology, and artificial intelligence, combined with the development of personalised [2] and precision nutrition [3], have catalysed the convergence of nutrition and medicine, and facilitated more efficient and affordable healthcare solutions that leverage the power of food for prevention and therapy. Innovation in this field is crucial to feed a growing global population sustainably and healthily. This requires significant changes in our food system, spanning agriculture, production, distribution, and consumption [4]. As we are facing pressing population and planetary health challenges, investing in bioactive-based solutions is an opportunity to improve and sustain our health care systems, protect biodiversity and the health of our soils, waters, and atmosphere, while creating value for consumers, patients, communities, and stakeholders [5]. Translational research and innovation in the field of natural bioactives are currently being developed at two levels, using a systems-oriented approach: first, at biological level, the interplay between these compounds and the human host and microbiome is being elucidated through omics research [6], computational biology [7], and artificial intelligence [8], to accelerate both discovery and validation; second, at ecosystem level, efforts are focused on producing diverse, nutrient-rich, flavourful, and resilient, yet high-yield agricultural crops, and educating consumers to make informed choices that benefit both their health and the planet [4]. Adopting such systems perspective helps: unravel the relationships between bioactives, nutrition, and sustainability outcomes, harnessing the power of nature to promote human health and wellbeing; foster sustainable agriculture and protect the ecosystem [5]. Therefore, interdisciplinary and international collaboration is needed for a new era of science, research, and development of practical food-based solutions for some of the most pressing challenges of humanity in the Anthropocene [9].
References:
[1] Kussmann M; Bioactive Comp. Health Disease 2022, 5(10) 222-234: “Nature has the answers: discovering and validating natural bioactives for human health”.
[2] Kaput J, Pontes Monteiro J, Morine M, Kussmann M: „Personalised Nutrition“ in Elsevier’s Reference Collection in Biomedical Sciences 2022: “Comprehensive Precision Medicine”. Eds: Ramos K, Slikker W.
[3] Berciano Benitez S, Figueiredo J, Brisbois T, Alford S, Koecher K, Eckhouse S, Ciati R, Kussmann M, Ordovas JM, Stebbins K, Blumberg JB. Frontiers Nutrition 2022 (9) 979665: “Precision Nutrition: Maintaining Scientific Integrity and Realizing Market Potential”.
[4] Kaput J, Kussmann M, Mendoza Y, Le Coutre R, Cooper K, Roulin A; Genes & Nutrition 2015 (10) 12: “Enabling nutrient security and sustainability through systems research”.
[5] Kussmann M, Abe Cunha DH, Berciano Benitez S; Frontiers Nutrition 2023 (10) 1193848: “Bioactive compounds for human and planetary health”.
[6] Andraos S, Wake M, Saffrey R, Burgner D, Kussmann M, O’Sullivan JM. Adv. Nutr. 2019 10(6) 944-952: “Perspective: Advancing Understanding of Population Nutrient–Health Relations via Metabolomics and Precision Phenotypes”.
[7] Michelini S, Balakrishnan B, Parolo S, Matone A, Mullaney J, Young W, Gasser O, Priami C, Lombardo R, Kussmann M. BMC Microbiol. 2018 (6) 171: ”A reverse metabolic approach to weaning: In silico identification of immune-beneficial infant gut bacteria, mining their metabolism for prebiotic feeds and sourcing these feeds in the natural product space”.
[8] Doherty A, Wall A, Khaldi N, Kussmann M. Frontiers Genetics 2021 (12) 768979: “Artificial Intelligence in functional food ingredient discovery and characterisation with a focus on bioactive plant and food peptides”.
[9] Kussmann M, Hayek M, Berciano Benitez S; Frontiers Nutrition 2023 Research Topic: “Nutrition for humanity in the Anthropocene – for healthier people on a healthier planet” FrontiersNutrition2023 NutritionHumanityAnthropocene
Shape memory alloys take place in a class of adaptive structural materials called intelligent or smart materials by giving stimulus response to changes in the external conditions. These alloys exhibit dual characteristics, from viewpoint of shape reversibility, shape memory effect and superelasticity with the recoverability of two shapes at different conditions. These alloys are functional materials with these properties and used as shape memory elements in many interdisciplinary fields. Shape memory effect is initiated with thermomechanical treatments on cooling and deformation and performed thermally on heating and cooling, with which shape of the materials cycles between original and deformed shapes in reversible way. Therefore, this behavior can be called Thermoelasticity. Deformation in low temperature condition is plastic deformation, with which strain energy is stored in the materials and releases on heating by recovering the original shape. This phenomenon is governed by the thermomechanical and thermoresponsive transformations, thermal and stress induced martensitic transformations. Thermal induced martensitic transformations occur on cooling with cooperative movement of atoms in -type directions on {110} - type plane of austenite matrix along with the lattice twinning reaction and ordered parent phase structures turn into the twinned martensite structures. Twinned structures turn into detwinned martensite structures by means of stress induced martensitic transformations with deformation. On heating after these treatments, detwinned martensite structures turn into the ordered parent phase structures, by means reverse austenitic transformation. Superelasticity is performed in only mechanical manner by stressing and releasing the material in elasticity limit at a constant temperature in the parent austenite phase region, and shape recovery occurs instantly upon releasing, by exhibiting the elastic material behavior. Therefore, this behavior can be called mechanical memory. Superelasticity is performed in non-linear way, unlike normal elastic materials behavior, loading and releasing paths are different in stress-strain diagram, and cycling loop refers to the energy dissipation. Superelasticity is also result of stress induced martensitic transformation, and the ordered parent phase structures turn into the detwinned martensite structures by stressing the materials. It is important that lattice twinning and detwinning reactions play important role in martensitic transformations.Copper based alloys exhibit this property in metastable beta-phase region. Lattice twinning and lattice invariant shear is not uniform in these alloys and cause the formation of complex layered structures. The layered structures can be described by different unit cells as 3R, 9R or 18R depending on the stacking sequences on the close-packed planes of the ordered lattice. The unit cell and periodicity are completed through 18 layers in direction z, in case of 18R martensite in ternary copper-based alloys, and unit cells are not periodic in short range in direction z.In the present contribution, x-ray diffraction and transmission electron microscopy (TEM) studies were carried out on copper based CuAlMn and CuZnAl alloys. X-ray diffraction profiles and electron diffraction patterns exhibit super lattice reflections. X-ray diffractograms taken in a long-time interval show that diffraction angles and intensities of diffraction peaks change with the aging duration at room temperature. This result refers to the rearrangement of atoms in diffusive manner.
| SESSION: AdvancedMaterialsWedPM2-R5 | 7th Intl Symposium on New & Advanced Materials and Technologies for Energy, Environment, Health and Sustainable Development |
| Wed. 29 Nov. 2023 / Room: Heliconia | |
| Session Chairs: Sanjeev Khanna; Malgorzata Gradzka-Dahlke; Session Monitor: TBA | |
Condition monitoring means troubleshooting and maintenance of machines without interruption in their operation and is performed based on accurate information obtained from the equipment status [1]. The basis for condition monitoring is troubleshooting and the prediction of the fault occurring without causing the machine to stop working [2]. There are four general strategies for fault prediction, namely experience-based methods, statistical modeling, artificial intelligence methods, and physical modeling [3].In this paper, the estimation of the remaining useful life (RUL) of angular contact ball bearing using time-domain signal processing method is discussed. An experimental setup based on acoustic emission (AE) signal is used to extract and collect the desired data. The residual life test is performed on the SKF 7202 BEP angular contact ball bearing. Sixty-time domain features have been introduced and used for fault detection. Improved Distance Evaluation (IDE) method has been used for feature dimensionality reduction and the best 10 features have been selected. K-Nearest Neighbors (KNN) algorithm has been used to investigate the classification accuracy of IDE based on selected features for classifying healthy and faulty bearings. The results show that the IDE method enables natural fault detection in bearings with high precision. To validate the performance of the KNN classifier, performance indices such as accuracy, precision, and specificity are applied. The results show that kurtosis, FM4, k factor, energy, and peak are the best features and kurtosis has the highest KNN rank with accuracy, precision, and specificity of 97%, 93%, and 94%, respectively.
References:
[1] Jardine, A. K., Lin, D., & Banjevic, D. (2006). A review on machinery diagnostics and prognostics implementing condition-based maintenance. Mechanical Systems and Signal Processing, 20(7), 1483–1510.
[2] Sikorska, J. Z., Hodkiewicz, M., & Ma, L. (2011). Prognostic modelling options for remaining useful life estimation by industry. Mechanical Systems and Signal Processing, 25(5), 1803–1836.
[3] Vachtsevanos, G., Lewis, F., Roemer, M., Hess, A., & wu, B. (2006). Intelligent fault diagnosis and prognosis for engineering systems. New Jersey: John Wiley & Sons.
Predicting and interpreting experimental results in the field of materials science poses many challenges and also represents a promising path. As a result, the directions for improvement or extension related to materials engineering procedures are multiple and constantly expanding. In view of assisting synthesis and characterization of functional compounds, a consequent contribution is nowadays provided by computational modelling. This latter offers the opportunity to both complement the experimental works towards mechanism comprehension or structural characterization during the process of concrete evaluation of materials capabilities and to predict certain features prior to experiments. Quantum mechanical modelling is notably reaching growing use, in many ways and for various areas including notably the case of materials for energy (see e.g. [1,2]). Beyond the possibility to access properties of electrochemical/spectroscopic/structural or defects nature as well as indications concerning ion transport, electron conduction, etc. of these compounds or those belonging to other research fields – for instance by calling to density functional theory calculations [3-11] –, particular attention can additionally be focused on accurate electronic structure scrutinization. In many situations, this further step is of crucial help when searching for structure-property relationships. The route towards innovation and breakthrough can surely be accelerated thanks to the combination of quantum chemical modelling and methodologies belonging in particular to topological analysis of the electron density. While doping, oxygen/lithium or other metal (de-)insertion, effects of polymorphism, polyanion modulation, etc in inorganic matrices for M-ion batteries or Solid Oxide Fuel Cells traditionally constitutes one of the most prevalent playgrounds for computational studies, the more nascent field – in terms of development and applications – of batteries relying on organic electrode materials brings new perspectives and shifts the search in new directions. In this last context, the quest for most performant compounds is linked e.g. to new backbones identification, functionalization, isomerism/heteroatom substitution, redox centre change, etc. may benefits from the possibility to employ molecular modelling, prior to experiment, as a first estimation of their capabilities. By focusing on selective examples, the interest of combined use of quantum chemical modelling and topological analysis of the electronic structure of various compounds belonging either to organic or inorganic species will be illustrated in the purpose of driving the engineering search towards rationalization of phenomena and an educated guess of novel, innovating or optimized materials
References:
[1] A. A. Franco, A. Rucci, D. Brandell, C. Frayret, M. Gaberscek, P. Jankowski, P. Johansson, Chemical Reviews 119 (2019) 4569-4627.
[2] A. A. Franco, C. Frayret, Chapter, “Modeling the design of batteries for medium- and large-scale energy storage“, in the Book: “Advances in batteries for medium and large-scale energy storage”, Elsevier, Boston, MA, (2015).
[3] C. Frayret, A. Villesuzanne, M. Pouchard, F. Mauvy, J.-M. Bassat, J.-C. Grenier, Journal of Physical Chemistry C 114 (2010) 19062–19076.
[4] C. Frayret, A. Villesuzanne, M. Pouchard, F. Mauvy, J.-M. Bassat, J.-C. Grenier, Defect and Diffusion Forum 323-325 (2012) 233-238.
[5] C. Frayret, A.Villesuzanne, M. Pouchard, S. Matar, International Journal of Quantum Chemistry 101 (2005) 826-839.
[6] C. Frayret, A. Villesuzanne, M. Pouchard, Chemistry of Materials 17 (2005) 6538-6544.
[7] C. Frayret, A. Villesuzanne, N. Spaldin, E. Bousquet, J.-N. Chotard, N. Recham, J.-M. Tarascon, Physical Chemistry Chemical Physics 12 (2010) 15512–15522.
[8] C. Frayret, C. Masquelier, A. Villesuzanne, M. Morcrette, J.-M. Tarascon, Chemistry of Materials 21 (2009) 1861-1874.
[9] I. Andron, C. Frayret, M. Gaudon, A. Fargues, M. Duttine, O. Toulemonde, V. Jubera, Materials Research Bulletin 142 (2021) 111384(1-10).
[10] G. Bonnard, A.-L. Barrès, Y. Danten, D. G. Allis, O. Mentré, D. Tomerini, C. Gatti, E.I. Izgorodina, P. Poizot, C. Frayret, RSC Advances 3 (2013) 19081-19096.
[11] G. Bonnard, A.-L. Barrès, O. Mentré, D. G. Allis, C. Gatti, P. Poizot, C. Frayret, CrystEngComm 15 (2013) 2809-2821.
[12] C. Frayret, D. Tomerini, C. Gatti, Y. Danten, M. Bécuwe, F. Dolhem, P. Poizot, in: CIMTEC 2014 13th International Conference on Modern Materials and Technologies – 6th Forum on New Materials, Techna-Group Series Advances in Science and Technology, June 16 – 19, 2014, Montecatini Terme, Italy, 146-151.
[13] D. Tomerini, C. Gatti, C. Frayret, Physical Chemistry Chemical Physics 17 (2015) 8604-8608.
[14] D. Tomerini, O. Politano, C. Gatti, C. Frayret, Physical Chemistry Chemical Physics 18 (2016) 26651-26660.
[15] D. Tomerini, C. Gatti, C. Frayret, Physical Chemistry Chemical Physics 18 (2016) 2442-2448.
[16] A.E. Lakraychi, F. Dolhem, F. Djedaïni-Pilard, A. Thiam, C. Frayret, M. Becuwe, Journal of Power Sources 359 (2017) 198-204.
[17] F. Lambert, Y. Danten, C. Gatti, C. Frayret, Physical Chemistry Chemical Physics 22 (2020) 20212-20226.
[18] F. Lambert, Y. Danten, C. Gatti, B. Bocquet, A.A. Franco, C. Frayret, Journal of Physical Chemistry A 127 (2023) 5104–5119.
Ti2InN is the first nitride in the MAX-phase family (into Cr2AlC prototype) for which superconductivity was reported A.D. Bortolozo et al. [1]. It was proposed that the substitution of carbon in Ti2InC for nitrogen increases the superconducting transition temperature from 3.1 K to about 7.3 K due to an increase of the electronic density of states at the Fermi level (EF) from 3.67 for 4.02 states/(eV cell) [1]. The structure of Ti2InN in [1] was characterized only by X-ray. X ray pattern showed peaks of in Ti2InN and the presence of small amount of In. Unfortunately, SEM EDX or TEM studies of the synthesized material were not reported in literature. The Ti2InN samples of the study by Bortolozo et al. [1] In the present study, we prepared samples by different methods. The first two stages of synthesis followed exactly the route described in [1]. The third stage (pressure treatment) was modified. Route1: We repeated the method described in [1] but with 130 bar of nitrogen instead of argon. Route 2: Sintering in Ar in a sealed quartz ampoule. Routes 3, 7 and 8: Spark plasma sintering (SPS) at 38-50 MPa in contact with hBN. Route 4: High pressure-high temperature (HP-HT) sintering under 4 GPa in contact with hBN. Route 5: Repetition of Route 1 after removing air from the furnace more carefully. Using HP-HT, SPS methods and sintering in sealed quartz ampoule in Ar in the third stage (Routes 2, 3, 4, 7 and 8), we succeeded to synthesize Ti2InN samples containing 85.3-94 wt.% of Ti2InN (with lattice parameters a=0.3073(7)-0.3078(8) nm, c=1.4012(4)-1.4030(8) nm, unit cell volume V=114.667´10-3 - 115.114 ´10-3 nm3 ) which demonstrated superconducting behavior with Tc (onset) near 5 K. The samples prepared by SPS and HP-HT methods were highly dense. However, all samples showed a very broad magnetic transition (as susceptibility) not saturating down to 2 K. No macroscopic Meissner phase was established. The magnetization was far too weak to evidence bulk superconductivity of the entire sample (would require around 30 A/m) and hence of Ti2InN. The signal stems either from a minority phase, or from surface superconductivity. According to SEM EDX study, the stoichiometry of the Ti2InN phase of these samples were very close to 211, but in many cases a small excess of nitrogen or the presence of oxygen and even carbon (in one case) were found. We should not exclude that superconductivity in Ti2InN may be very sensitive towards non-stoichiometry (like in the case of oxygen content in YBa2Cu3O7-d , when reduction of oxygen below 6.6-6.5 atoms per one unite cell leads to disappearance of superconductivity) or toward impurities. A pressure of 130 bar of nitrogen was not enough to suppress the decomposition of Ti2InN at 900 oC (Routes 1 and 5). The material decomposed because of In sublimation and aggregation into drops on the top of the samples (a maximum of 54 wt.% Ti2InN was observed in the materials after 10 h heating). The sample prepared by Route 1 demonstrated the best SC behavior, but the amount of Ti2InN was only 6.5 wt.%. Instead, 9 wt. % TiN, 14.5 wt. % In, 61 wt. % TiO2 and 9 wt. % In2O3 were found. The large amount of oxygen containing phases can be explained by the fact that not all air was removed from the furnace before the high nitrogen pressure was created. In the case of Route 5, when air was removed carefully, the sample decomposed as well and contained besides 54 wt.% of Ti2InN, 25 wt. % TiN, 20 wt.% In, and 1 wt.%TiO2 It seems unlikely that using nitrogen instead of argon would allow to overcome this problem (i.e. that 130 bar Ar pressure can prevent In from sublimation from Ti2InN). All our samples contain TiN in the form of separate inclusions (with a small amount of oxygen and a very small amount of indium,). The beginning of the SC transition of all our samples was approximately 5K. The SC transition temperature of TiN was reported to be 5.3-6 K. We did not find a clear correlation between the amount of TiN and the magnetization of the materials. However, the grains of TiN phase are still a candidate for the superconducting phase in our materials. A detailed study of the Ti2InN materials structures which demonstrated Tc=7.3 K would be of great interest. Especially in view of the transition temperatures reported for g-Ti3O5 (7.1 K) and TiO (7.4 K) films.
References:
[1] A. D. Bortolozo, G. Serrano, A. Serquis, D. Rodrigues Jr., C. A. M. dos Santos, Z. Fisk, A.J.S. Machado , Solid State Commun. 150 (2010) 1364-1366. doi:10.1016/j.ssc.2010.04.036
As the global leaders grapple with their stated goals to achieve Net Zero Carbon Emissions (NZE) by 2050 or 2060, one must take a serious look at the trends and what needs to be done in the future. Despite all the trends in the right direction, both International Renewable Energy Agency (IRENA) and International Energy Agency (IEA) project that we will fall woefully short of achieving the NZE2050 or limiting the global temperature rise to 1.50C if we continue with the current policies of the countries. While IEA and IRENA, project future estimates of energy based on the present technologies and some incremental improvements, they are not in a position to foresee what innovative new technologies will be available in the future, which might completely change our predictions. As an example, about 25% of all the energy used in the U.S. is for cooling of buildings. Although that percentage is lower for the rest of the world, it is rapidly increasing. Since buildings are cooled exclusively by electrical power, at present we can only hope to replace that electricity with power from renewable energy. However, a very promising innovation on the horizon in scientific and engineering research is to develop coatings for building skins that will emit long wavelength infra-red radiation in the atmospheric window (8–13 mm wavelength) to deep space, which is at a temperature close to absolute zero. The technology known as plasmonic cooling, when developed, will cool the buildings simply by transferring the heat from the buildings to the outer space by radiation. When this technology becomes practical and commercially available, there might not be any need for mechanical cooling or heating of buildings in many parts of the world. Just as we have seen developments in computer and information technologies in the last two decades that we could not even imagine 30 years back, we will see developments in solar and ambient energy space that we can barely imagine today. The presentation will describe some of the transformative developments, including plasmonic cooling that we expect to see in the future. Such transformative information is being communicated via a new open access journal, Solar Compass, journal of the International Solar Alliance.
| SESSION: AdvancedMaterialsWedPM3-R5 | 7th Intl Symposium on New & Advanced Materials and Technologies for Energy, Environment, Health and Sustainable Development |
| Wed. 29 Nov. 2023 / Room: Heliconia | |
| Session Chairs: Fernand Marquis; Session Monitor: TBA | |
The increasing demand for the application of hydrogen in different domains of the Global Industry should bring these technologies to the next level of development and contribute with important solutions to significant logistic and energy challenges as well, such as the transportation of gas or liquid hydrogen (LH2). The boiling temperature of LH2 is 20 K, what makes promising application of high temperature superconductors. It has been proposed [1] to construct a centrifugal type LH2-pump (with superconducting bearings, immersed in liquid hydrogen, with an impeller diameter of 32 mm and rotating speed 15 000 rpm.) to fill a 100 l mobile Dewar in about 5 mins. Because of this it is of great importance to understand which comparatively well developed superconducting material can be more stable and efficient in such working conditions. We analyzed the functional superconducting characteristics of MgB2-based bulks without and with additions of Ti, Ti-O and TiC, prepared by hot pressing (30 MPa), spark plasma sintering (50-96 MPa) and under high quasy-hydrostatic pressure (2 GPa) conditions. Their stability in gas hydrogen under 4.2 bar pressure was under the study. The trapped magnetic fields were studied using hollow cylinders of the same geometry prepared from magnesium diboride-based materials and MT-YBCO. The high critical current densities and critical magnetic fields should ensure high trapped fields in all these materials. Indeed all materials demonstrated the required performance; however, flux jumps are a serious issue in MgB2 even in crack free cylinders and impeded higher trapped fields. An inhomogeneous and porous MgB2 structure was found to be less stable against flux jumps. On the other hand, deviations of the material matrices from MgB2 stoichiometry did not impede high Jc and trapped fields. The superconducting properties of all materials investigated in this study occurred to be sufficient for magnets in submersible liquid hydrogen pumps with a required trapped field of about 500-600 mT.
References:
[1] S Kloeppel1 et al. Superconducting bearings for a LHe transfer pump, IOP Conf. Series: Materials Science and Engineering 278 (2017) 012029 doi:10.1088/1757-899X/278/1/012029
As the function of strain, the second derivatives of free energy to strain form a matrix, of which the eigenvalues are directly related with elastic properties. By adjusting temperature, pressure and shape change properly, those eigenvalues can increase, or become non-zero from the initial zero value, which thus inhibit the occurance of martensitic phase transformation. Meanwhile, elastic constants increase and many elastic properties are strengthened, therefore, the elasticity and safety of glass is improved. In summary, we can expect that the smash danger of glass will be reduced greatly due to this anti-martensitic phase transformation.
| SESSION: AdvancedMaterialsThuAM-R5 | 7th Intl Symposium on New & Advanced Materials and Technologies for Energy, Environment, Health and Sustainable Development |
| Thu. 30 Nov. 2023 / Room: Heliconia | |
| Session Chairs: Fernand Marquis; Session Monitor: TBA | |
Orthogonal frequency division multiplexing (OFDM) with offset quadrature amplitude modulation (OQAM) has been widely discussed in the literature and is considered a popular waveform for 5th generation (5G) wireless telecommunications and beyond. In this work, we show that OFDM-OQAM can be generated using the Hilbert transform and is equivalent to single sideband modulation (SSB), that has roots in analog telecommunications [1]. The symbol density in time-frequency space is greater than unity. OFDM-OQAM is also known as filter bank multicarrier (FBMC). One of the key advantages of OFDM-OQAM/FBMC over OFDM [2, 3, 4] is its immunity against frequency offsets. In other words, it may not be necessary for an OFDM-OQAM/FBMC system to estimate and cancel the frequency offset, unlike OFDM. The other important feature of OFDM-OQAM is the spectral containment of each subcarrier using a transmit filter, which is absent in OFDM. However, OFDM is more attractive than OFDM-OQAM in terms of implementation simplicity. The transmit filter for OFDM-OQAM is complex valued and is given by 
where 
is a real-valued pulse shape that satisfies the zero intersymbol interference (ISI) condition, 
is its Hilbert transform and 
. The real-valued digital data (message) are transmitted through 
and frequency division multiplexed on orthogonal subcarriers. The message bandwidth corresponding to each subcarrier is assumed to be narrow enough so that the channel can be considered ideal. Therefore, at the receiver, a matched filter can used to recover the message. Turbo coding is used to achieve bit-error-rate (BER) as low as 10-5 at an average signal-to-noise ratio (SNR) per bit close to 0 db. The system has been simulated in discrete time.
References:
[1] K Vasudevan, Gyanesh Kumar Pathak, Surendra Kota and Lov Kumar, “OFDM-OQAM using the Hilbert Transform”, Invited Talk, WCAM-2023, 8 – 10 May, Tokyo, Japan.
[2] K Vasudevan, “Coherent Detection of Turbo Coded OFDM Signals Transmitted through Frequency Selective Rayleigh Fading Channels”, IEEE International Conference on Signal Processing Computing and Control, 26—28 Sept. 2013, Shimla.
[3] K Vasudevan, “Coherent Detection of Turbo-Coded OFDM Signals Transmitted Through Frequency Selective Rayleigh Fading Channels with Receiver Diversity and Increased Throughput”, Wireless Personal Communications, Springer, vol. 82, no. 3, pp. 1623—1642, June 2015.
[4] K Vasudevan, “Near Capacity Signaling over Fading Channels using Coherent Turbo Coded OFDM and Massive MIMO”, International Journal On Advances in Telecommunications, issn 1942-2601, vol. 10, no. 1 & 2, year 2017, 22:37, http://www.iariajournals.org/telecommunications/.
Air pollution is one of the largest health and environmental problems in the world. It is a treat for the human and animal health and is one of the leading risk factors for death. In fact, the air pollution is responsible for more than 6.5 million deaths each year globally [1].In this study, we are presenting sustainable and biodegradable materials, which can be used as sorbents for air pollutants, such as CO2, CO, CH4, NOx, SOx, volatile organic compounds (VOC) and others. The presented sorbent materials are composed of agricultural by-products in a network of fungal threads (mycelia), named My-Com™. My-Com™ composites can be easily made in any shape, form and size. Preliminary life-cycle assessments show negative CO2 emissions for the composite production, i.e. the material production uses CO2 from the environment to produce the “mycelium-wrapped” agricultural by-product composites [2]. My-Com™ composites in their original state, as well as the amine-functionalized My-Com™ composites efficiently adsorb the small-molecule environmental pollutants, viz. CO, CO2, CH4 and others [3]. The studies of the VOC-adsorption on My-Com™ materials are in progress. Overall, My-Com™ composites are promising sustainable materials for removing pollutants from the environment, and at the end of their use, when disposed, they are completely biodegradable.
References:
[1] Air Pollution and Your Health (nih.gov)
[2] Achiya Livne et al., Fungal Mycelium Bio-Composite Acts as a CO2-Sink Building Material with Low Embodied Energy, ACS Sustainable Chem. Eng. 2022, 10, 37, 12099–12106
[3] Taekyoung Lee, Jaeyun Choi, Mycelium-composite panels for atmospheric particulate matter adsorption, Results in Materials 11 (2021) 100208
The idea concerning the control strategy of a Solid Oxide Fuel Cell (SOFC) functioning to meet the electrical demand of a public utility building is meticulously detailed. This innovative strategy was thoughtfully designed and structured with the integral assistance of an Artificial Neural Network, a type of artificial intelligence that models human brain function and can adapt to new data.This complex network, the Artificial Neural Network, was employed for a critical function; it was used to forecast the electricity demand, a task requiring significant computational intelligence and adaptability. These intricate calculations and simulations were performed specifically using the example of a prominent structure, the building of the Institute of Heat Engineering at Warsaw University of Technology.The control strategy's effectiveness and operation aren't static, they are significantly influenced by a multitude of diverse factors. These factors could be internal or external, varying with the dynamic changes in market conditions, as well as the operating characteristics of the SOFC itself. As a result, we can effectively define several different objective functions tailored to meet the circumstances. These objectives can range from operating solely for self-sustenance, to functioning for maximum profitability, and even to achieving the longest possible service life.Moreover, the article goes on to showcase a comprehensive simulation of the SOFC's operation, specifically tailored to the electricity demand profile of the aforementioned Institute of Heat Engineering (IHE) building. The simulation takes into account the data from a selected period of time, providing a rich and detailed view of the SOFC's potential capabilities and performances under various operating conditions and demand scenarios. This case study acts as a demonstration of the practical application of the control strategy and offers potential insights for its broader implementation.
References:
[1] Solid oxide fuel cell
X rays are high-energy ionizing rays, which can cause severe damage to the human body if the proper protection is not in place. Traditionally, lead-containing radiation shielding materials have been used for protection of both, the patients and the operators, in medical X ray diagnostic and interventional settings. Lead is known to be a good X ray attenuation metal due to its high atomic number (Z), high density and low cost, but its weight and toxicity have prompted the search for light-weight and lead-free shielding materials [1, 2]. In this study, recyclable non-lead radiation shielding materials with superior protection in an extended range of diagnostic X ray energies from 50 to 150 kV are presented. The radiation protective materials consist of optimized elastomeric matrix filled with non-lead protective metal particles, such as antimony, bismuth, tungsten, barium, etc. Light-weight radiation shielding materials were made by selecting the proper combination of metals with certain Z, density and K-adsorption edge, and by optimizing their loading level, particle sizes and particle size distributions. The materials showed a superior attenuation level against primary and scatter X rays compared to competitive materials, as tested in a modified broad beam geometry (BBG*) according to the IEC 61331-1: 2014 standard [3]. The attenuation level of the presented lead-free materials is comparable to that of lead-containing shielding materials [4]. Moreover, the materials have improved mechanical properties, viz. tensile strength, toughness and elongation, which enable applications in various medical settings, such as protective aprons, caps, sleeves, vests, thyroid shields, drapes, blankets, and other protective garments. Lastly, but not least, the presented lead-free protective materials are recyclable and can be re-processed in the same manufacturing processes used for their original production.
References:
[1] Shahzad, K.; Kausar, A.; Manzoor, S.; Rakha, S.A.; Uzair, A.; Sajid, M.; Arif, A.; Khan, A.F.; Diallo, A.; Ahmad, I. Views on Radiation Shielding Efficiency of Polymeric Composites/ Nano-composites and Multi-Layered Materials: Current State and Advancements. Radiation 2023, 3, 1–20.
[2] Gilys, L.; Griškonis, E.; Griškevicius, P.; Adlien˙ e, D. Lead Free Multilayered Polymer Composites for Radiation Shielding. Polymers 2022, 14, 1696.
[3] H. Eder, H.; Schlattl, H. IEC 61331-1: A new setup for testing lead free X-ray protective clothing, Physica Medica 45 (2018) 6–11.
[4] Trajkovska-Petkoska, A. Assessment of the Protective Efficiency of Commercial Lead-Free Protective Materials Against Diagnostic X Rays, Materials (MDPI), 2023, in progress.
| SESSION: AdvancedMaterialsFriAM1-R5 | 7th Intl Symposium on New & Advanced Materials and Technologies for Energy, Environment, Health and Sustainable Development |
| Fri. 1 Dec. 2023 / Room: Heliconia | |
| Session Chairs: Fernand Marquis; Session Monitor: TBA | |
The reliability of the future electronics and photonics products, including the micro-electro-mechanical systems (MEMS) and MOEMS (optical MEMS), will depend, first of all, on the performance of their materials, devices and packages [1]. The forty years old highly accelerated life testing (HALT) (see, e.g., [2]) has many merits, but is unable to predict the probability of failure of the product in the field. The recently suggested probabilistic design for reliability (PDfR) concept [3,4] in electronics and photonics engineering is based on 1) highly focused and highly cost-effective failure oriented accelerated testing (FOAT) [5], aimed at understanding the physics of the anticipated failures and at quantifying, on the probabilistic basis, the outcome of the FOAT conducted for the most vulnerable element(s) of the product of interest (such as, e.g., solder joint interconnections); 2) predictive modeling (PM) aimed at evaluating the reliability in actual operation conditions from the FOAT data and for the most likely operation conditions; and 3) subsequent sensitivity analyses (SA) that enables changing, if necessary, using the developed models, the obtained information, so that the acceptable probability of failure is assured. The PDfR concept proceeds from the recognition of the fact that the difference between a highly reliable and an insufficiently reliable product is “merely” the level of the never zero probability of their failure. If this probability, evaluated for the anticipated loading conditions and the given time in operation, is not acceptable, SA can be effectively employed to determine what could/should be changed to improve the situation. The PDfR can be used also to make sure that the product of interest is not made more robust than necessary for the accepted level of the probability of failure. The operational reliability cannot be low, of course, but does not have to be higher than necessary either: it has to be adequate for the given product and application. Both reliability and cost-effectiveness are imperative, of course. To get the best reliability "bang for the buck" is an obvious challenge for a product designer and manufacturer. The total cost of a product can be computed as the sum of its initial (manufacturing) cost and the cost of maintenance (repair). It has been found [4] that this sum can be minimized, if the product's availability (i.e., the probability that the device is available to the user when he/she needs it) is maximized. The design-stage FOAT is intended to be carried out when developing a new design or a new manufacturing technology and when high operational reliability, like the one required, e.g., for aerospace, military, or long-haul communication applications, or the future medical device engineering, is imperative. The recently suggested multi-parametric Boltzmann-Arrhenius-Zhurkov (BAZ) [6] equation could be used to predict the probability of FOAT failure and the field failure from the FOAT data. The equation can be effectively used to analyze and design products with the predicted, quantified, assured, and, if appropriate and cost-effective, even maintained and specified probability of operational failure. These concepts and methodologies can be accepted as an effective means for the evaluation of the operational reliability of EP materials and products, and that the next generation of qualification testing (QT) specifications and practices for such products could be viewed and conducted as a quasi-FOAT that adequately replicates the initial non-destructive segment of the previously conducted comprehensive full-scale FOAT. Burn-in-testing (BIT) [7], the chronologically final HALT that is routinely conducted at the manufacturing stage of almost every IC product is also of a FOAT type: it is aimed at eliminating the infant mortality portion (IMP) of the bathtub curve (BTC) [8] by getting rid of the low reliability "freaks" prior to shipping the hopefully “healthy” products, i.e., those that survived BIT, to the customer(s). All the indicated analyses were carried out using analytical ("mathematical") predictive modeling [9]. It 2 is suggested that physically meaningful predictive modeling, preferably of the PDfR type, should always be considered and conducted prior to and during the actual testing procedure and that analytical modeling should always complement computer simulations. Future work should be focused, in the author's view, on the experimental verification of the obtained findings and recommendations and should be conducted in application to particular devices, designs, manufacturing technologies, products and applications.
References:
[1] E. Suhir, “Microelectronics and Photonics – the Future”, Microelectronics Journal, vol.31, No.11-12, 2000
[2] E. Suhir, A. Bensoussan, J. Nicolics, and L. Bechou,
[3] E. Suhir, “Probabilistic Design for Reliability”, Chip Scale Reviews, 14(6), 2010
[4] E.Suhir, “Probabilistic Design for Reliability of Electronic Materials, Assemblies, Packages and Systems: Attributes, Challenges, Pitfalls”, Plenary Lecture, MMCTSE 2017, Cambridge, UK, Feb. 24-26, 2017
[5] E. Suhir,
[6] E. Suhir and S. Kang, “Boltzmann-Arrhenius-Zhurkov (BAZ) Model in Physics-of-Materials Problems”, Modern Physics Letters B (MPLB), vol.27, April 2013
[7] E. Suhir, “To Burn-in, or not to Burn-in: That’s the Question,” Aerospace, 6(3), 2019
[8] E. Suhir,
[9] E. Suhir,
Porous bulbs made from slip-cast kaolin as catalyst supports for microchannel reactors are described. The platelike surfaces of the naturally occurring kaolinite mineral are decorated with catalyst by infiltration with metal salts, decomposed and reduced in situ for nucleation and growth. The process of making the ceramic bulbs with nanoparticles using nickel acetate is described in detail. High catalyst loading up to 75 mg/cm3 was achieved, giving on the order of 1015 25 nm nanoparticles per cm3 with high total surface area on the order of 2 x 106 m2/m3, making these catalytic membranes competitive with the best microchannel reactors. The microstructure of ceramic bulbs made from two different types of clays, before and after nickel infusion is investigated, and the gas permeation flux as a function of applied differential pressure is presented.
References:
[1] W. David Kingery; Pamela B. Vandiver. Ceramic Masterpieces – Art, Structure and Technology; The Free Press a division of MacMillan, Inc.: 866 Third Ave, New York, NY, 1986; p. 244.
[2] Haydn H. Murray. Applied Clay Mineralogy – Occurrences, Processing and Application of Kaolins, Bentonites, Palygorskite Sepiolite and Common Clays, Developments in Clay Science 2, 1st ed., Elsevier B.V.: Amsterdam, The Netherlands, 2007.
[3] Hewitt Wilson, Ceramics Clay Technology, 1st ed. McGraw-Hill Book Company, Inc. New York and London, 1927
[4] Lopez, E., Divins, N.J., Anzola, A., Schbib, S., Borio, D., Llorca, J.; Ethanol steam reforming for hydrogen generation over structured catalysts. I. J. Hyd. Energy, 2013, 38, 4418-4428
[5] Ricote, S.; Coors, W.G. Ni-Infiltrated Spherical Porcelain Support as Potential Steam Reforming Microchannel Reactor. Materials 2023, 16, 1519. https://doi.org/10.3390/ma16041519
Green chemistry started for the search of benign methods for the development of nanoparticles from nature and their use in the field of antibacterial, antioxidant, and antitumor applications. Bio wastes are eco-friendly starting materials to produce typical nanoparticles with well-defined chemical composition, size, and morphology. Cellulose, starch, chitin and chitosan are the most abundant biopolymers around the world. Cellulose nanoparticles (fibers, crystals and whiskers) can be extracted from agrowaste resources. Chitin is the second most abundant biopolymer after cellulose, it is a characteristic component of the cell walls of fungi, the exoskeletons of arthropods and nanoparticles of chitin (fibers, whiskers) can be extracted from shrimp and crab shells. Starch nano particles can be extracted from tapioca and potato wastes. These nanoparticles can be converted into smart and functional biomaterials by functionalization through chemical modifications due to presence of large amount of hydroxyl group on the surface. The preparation of these nanoparticles includes both series of chemical as well as mechanical treatments; crushing, grinding, alkali, bleaching and acid treatments. Since large quantities of bio wastes are produced annually, further utilization of cellulose, starch and chitins as functionalized materials is very much desired. The cellulose, starch and chitin nano particles are currently obtained as aqueous suspensions which are used as reinforcing additives for high performance environment-friendly biodegradable polymer materials. These nanocomposites are being used as biomedical composites for drug/gene delivery, nano scaffolds in tissue engineering and cosmetic orthodontics. The reinforcing effect of these nanoparticles results from the formation of a percolating network based on hydrogen bonding forces. The incorporation of these nano particles in several bio-based polymers have been discussed. The role of nano particle dispersion, distribution, interfacial adhesion and orientation on the properties of the ecofriendly bio nanocomposites have been carefully evaluated.
References:
1.Patanair, B., Saiter-Fourcin, A., Thomas, S., Thomas, M. G., Parathukkamparambil Pundarikashan, P., Gopalan Nair, K., ... & Delpouve, N. (2021). Promoting interfacial interactions with the addition of lignin in poly (lactic acid) hybrid nanocomposites. Polymers, 13(2), 272.
2.Jose, C., Chan, C. H., Winie, T., Joseph, B., Tharayil, A., Maria, H. J., ... & Thomas, S. (2021). Thermomechanical Analysis of Isora Nanofibril Incorporated Polyethylene Nanocomposites. Polymers, 13(2), 299.
3.Amalraj, A., Raj, K. J., Haponiuk, J. T., Thomas, S., & Gopi, S. (2020). Preparation, characterization, and antimicrobial activity of chitosan/gum arabic/polyethylene glycol composite films incorporated with black pepper essential oil and ginger essential oil as potential packaging and wound dressing materials. Advanced Composites and Hybrid Materials, 3(4), 485-497.
4.Varghese, R. J., Parani, S., Adeyemi, O. O., Remya, V. R., Maluleke, R., Thomas, S., & Oluwafemi, O. S. (2020). Green Synthesis of Sodium Alginate Capped-CuInS 2 Quantum Dots with Improved Fluorescence Properties. Journal of Fluorescence, 30(6), 1331-1335.
5.Nourbakhsh, M., Zarrintaj, P., Jafari, S. H., Hosseini, S. M., Aliakbari, S., Pourbadie, H. G., ... & Saeb, M. R. (2020). Fabricating an electroactive injectable hydrogel based on pluronic-chitosan/aniline-pentamer containing angiogenic factor for functional repair of the hippocampus ischemia rat model. Materials Science and Engineering: C, 117, 111328.
Due to the increased specific area-to-volume ratio (S/V), silica-based nanomaterials may have different and in many cases better chemical and physical characteristics than bulk materials. Many of these properties can be improved by surface modification and functionalization of nanomaterials, which can be done by altering the functionality and features of their surfaces, such as roughness, hydrophilicity/hydrophobicity, surface charge, biocompatibility, and reactivity. In this way, the functionality of nanomaterials can be adapted to the desired application. Due to their extremely fascinating and useful chemical and physical properties, nanomaterials exhibit an interest in many fields of applications such as sensor technology, biomedicine and biotechnology, environmental protection, photonics, and, the production of paints and varnishes, textiles, footwear, packaging, electronics, aerospace and automotive, etc. Although nanomaterials, on the one hand, offer technical and commercial opportunities and challenges, on the other hand, they can pose a risk to the environment and raise concerns about the health and safety of humans and animals, as regulation of nanomaterials is debated, and many questions related to the risks of exposure to nanomaterials are still unanswered. This presentation will introduce some recent examples from our Sensor Research Group demonstrating the use and challenges that may be tackled by functional nanomaterials, and some risks will be briefly mentioned.
References:
[1] [1] N. Frančič, A. Košak, A. Lobnik. J. of Sol-Gel Sci. and Technol. 79 (2016) 3. [2] P. Nedeljko, M. Turel, A. Košak, A. Lobnik. J. of Sol-Gel Sci. and Technol. 79 (2016) 3, [3] A. Košak, M. Lakić, A. Lobnik. GB2526659 (B). London: Intellectual Property Office, (2017).
| SESSION: AdvancedMaterialsFriAM2-R5 | 7th Intl Symposium on New & Advanced Materials and Technologies for Energy, Environment, Health and Sustainable Development |
| Fri. 1 Dec. 2023 / Room: Heliconia | |
| Session Chairs: Fernand Marquis; Session Monitor: TBA | |
The concept of viscosity is one of the central themes in rheology. There are many factors, including temperature T, pressure P, shear velocity , mass of polymer M and branching, which have great impacts on the shear viscosity of polymer solution. Based on the analysis and principle of each factor’s influence on the viscosity of polymer solution, a unified expression for the viscosity of polymer solution is put forward in this work. This new formula has two adjustable parameters (A and B), as well as three polymer constants ( M , n, C M ), where M is mass of polymer, n stands for the non-Newtonian index and C M is threshold mass for chain entanglememt of polymer.
10:45: [AdvancedMaterialsFriAM206] OS KeynoteSupercritical fluids (SCFs) represent the state of matter that exists whenever pressure of fluids reach above their critical point. This state holds a special diffusivity similar to gases with combined dissolving power comparable to liquids. SCFs provide an effective reaction environment for the synthesis of novel types of polymer materials and their modification into composites, blends, useful nanostructures ,nanocomposites and nanohybrids. Tuning supercritical conditions allows for precise regulation of filler size, shape, aspect ratios, infusion, deposition, dispersion, and exfoliation. Carbon dioxide offers as the source of the most useful supercritical fluid, so called supercritical carbon dioxide. The primary objectives of the talk will pertain to the salient characteristics of SCFs and their applications in the production of technologically valuable polymer materials used to make durable structures, sensors, energy storage, and items of biomedical importance.[1-6]. Final thoughts on simplicity, diversity, and the marketplace of supercritical fluid technology in material science and engineering will be presented.
References:
[1] Shubham Sharma, Sameena Mehtab & MGH Zaidi(2023).Supercritical processing of thermally stable multiwalled carbon nanotube/boron nitride nanohybrids with synergistically improved electrical conductivity. Materials Chemistry & Physics 12728
[2] Pragati Joshi, Sameena Mehtab & M.G.H.Zaidi (2022). “Electroanalysis of simazine release from supercritically derived nanoferrogels over polypyrrole graphene oxide electrodes.” Bulletin of Chemical Society of Japan, 95(6):855-861
[3] Gunjan Bisht, M.G.H. Zaidi & K.C. Biplab (2018). “In vivo acute cytotoxicity study of poly (2-amino ethyl methacrylate-co-methylene bis-acrylamide) magnetic composite synthesized in supercritical carbon dioxide.” Macromolecular Research, 1-11
[4] Harish Mudila, Sweta Rana & M.G.H. Zaidi (2017).“Supercritical carbon dioxide aided polyindole-graphene nanocomposites for high power density electrode.” Advanced Materials Letters,8(3):269-275
[5] M.G.H.Zaidi, Aparna Thakur, Tithi Agarwal & Sarfaraz Alam (2014). “Synthesis of polypyrrole/ polythiophene copolymers in supercritical carbon dioxide.” Iranian Polymer Journal, 23:365–374
[6] M.G.H.Zaidi, Sanjeev Kumar. Joshi, Manoj Kumar, Deepak Sharma, Ashawani Kumar, Sarfaraz Alam & Prakash Lal Sah (2013). “Modifications in mechanical, thermal and electrical characteristics of epoxy through dispersion of multiwalled carbon nanotube in supercritical carbon dioxide.” Carbon Letters 14(4):218-227
As the use of radiation increased from last few decades, the need for the study of radiation effects on materials, a phantom etc is most important. We know nowadays the radioisotopes or radioactive substances used in many fields like in medical field, nuclear power plants, and radiation research etc. Many researchers did a lot of experiments in this field and found different conclusions. In the present study we used the polymeric materials which can be available easily, having low cost, can be used at large scale. The results investigated and calculated were most useful in the fields of gamma radiation shielding, dosimetry, material science etc. Also radiation is widely used in biomaterial science for the surface modification, sterilization and to improve bulk properties of materials.In the present work we investigated the gamma radiation parameters as mass attenuation coefficient, the total atomic scattering cross-sections, the electronic scattering cross-sections, the effective atomic numbers, and the effective electron densities for some polymers such as polyoxymethylene (CH2O), poly acrylonitrile (C3H3N), natural rubber (C5H8), poly ethyl acrylate (C5H8O2 ), polyphenyl methacrylate (C10H10O2 ), and polyethylene tetraphthalate (C10H8O4 ). The gamma ray photons were detected by NaI(Tl) detector with resolution of 8.2 % at 662 keV, using radioactive gamma ray sources 57Co, 133Ba, 137Cs, 54Mn, 60Co, and 22Na at energies 122, 356, 511, 662, 840, 1170, 1275, and 1330 keV. Values of m/e for the chosen polymers decrease with increasing energy. The results of investigated data are useful in plastic industry, building materials, agriculture fields radiation shielding, accelerator centers, polymer industry, medical field, etc.
11:35: [AdvancedMaterialsFriAM208] OSThe physical safety of people and the protection of infrastructure from accidents caused by man-made, accidental and terrorist acts are still one of the major challenges for humanity. The most common of the many causes of accidents are industrial and terrorist explosions and fires, often accompanied by toxic gases and uncontrolled sources of radiation. Therefore, fast / rapid identification of such threats, processing the information and timely informing of emergency or other structures are the only way to prevent them, minimize and/or avoid the serious negative consequences. In this regard under high-risks are all kind of critical infrastructure facilities (tunnels, underground structures and confined spaces) and crowded civilian/ social places (transportation hubs, airports, shopping malls, etc.) Georgia (as well as European countries) has adopted the National Security Concept (NSC-GEO (1) .pdf), where in the first place in the list of main threats is "terrorist acts organized by the Russian Federation from the occupied territories of Georgia" and at the fifth place is " International Terrorism and Transnational Organized Crime. " The situation is further complicated due to the ongoing Russia-Ukraine war in the Black Sea region and its consequences in future. In the civil field, the most dangerous increased threat spaces in terms of technogenic (man-made) and accidental explosions are tunnels, in particular coal mines, nuclear power plants, radiation sources and waste storage areas. As annual statistics show, many miners around the world die due to methane and coal dust explosions in coal mines. Cases of toxic gas poisoning are frequent. During a single explosion in a Turkish (Soma) mine killed 301 miners. Recently the one of the last such accident occurred on January 31 of this year, 2022 in the Tkibuli (Georgia) coal mine. Besides there are also very serious consequences due to the fires at radiation sources, provoked by emergency or accidents, which leads to dangerous increases in radiation levels and environmental pollution.Protecting facilities (especially tunnels and underground spaces) from accidental and terrorist explosions and fires, taking into account their accompanying toxic gases, and in some cases from increased radiation, still remains as highly topical problem.
References:
[1] M. Chikhradze, E. Mataradze, N. Bochorishvili, N. Chikhradze, Multifunctional device for explosion detection, Conference: EFEE- 8th World Conference on Explosives & Blasting, At: Lyon, France, Volume: Proceedings of 8th World Conference on Explosives & Blasting, editor: R.Famfield et al
[2] 17. M. Chikhradze, E.Mataradze, K.Tavlalashvili, N.Bochorishvili, Sh. Marjanishvili. Development of Device for Identification Explosions and Fires. Proceedings of the Signal Processing Symposium SPS-2015, 10-12 June 2015, Debe, Poland, pp. 293-296
[3] 18. M. Chikhradze, N. Bochorishvili, I. Akhvlediani, E. Mataradze. Analysis of EMP Generated by Explosion in tunnels. Authors: Photonics Applications in Communications, Industry, and High-Energy Physics Experiments, 2010, Vol. 7745
[4] 19. M. Chikhradze, E. Mataradze, Sh. Marjanishvili, N. Bochorishvili, I. Akhvlediani. Study and processing of the signals generated in tunnels. Proceedings of the Signal Processing Symposium. Poland, 3-7 June, 2013
| SESSION: AdvancedMaterialsFriPM1-R5 | 7th Intl Symposium on New & Advanced Materials and Technologies for Energy, Environment, Health and Sustainable Development |
| Fri. 1 Dec. 2023 / Room: Heliconia | |
| Session Chairs: Fernand Marquis; Session Monitor: TBA | |
The MCFFP are an eco-efficient disruptive invention in industrial production processes that has industrial applicability in several industrial segments. It is an incorporation and productive modernization that manages to make a new lean manufacturing technique and has its management philosophy focused on a few items (quality, waste, overproduction, inventory, logistics, transport, customization, reuse). In short, it is a division and decentralization of production where products are made in two production stages, providing a competitive advantage and making an evolution of the production processes of current industries.
With this, innovations occurred in the production process, organization, marketing, and product. Covering the purposes of an industry 4.0, circular economy, smart cities, SDG, the supra secular decline, the industrialization and green reindustrialization of countries that do not have productive capacity (industries), offering a new dynamic of industrialization of industrialized countries, break of the state of art, change the status quo, create a masterpiece of contemporary industry, create a new industrial ERA and a new future for mankind.
There is no literature for the production process because it is unique and pioneering, the literature is still being written. The proof of the non-existence of literature is associated with supra-secular decline. The supra-secular decline is a study done by Harvard, Ohio, British Bank, and others in relation to the fall in the average real (world) interest rate that has been falling since it was created (change from feudalism to capitalism (1300)). In the thesis of the MCFFP, this decline will be contained because the problem comes from the productive processes that were made in a centralized way and the invention in the productive process of the MCFFP is the decentralization of this production model.
References:
[1] https://wipogreen.wipo.int/wipogreen-database/articles/10783?query=biocerr&type=BASIC&&pagination.page=0&pagination.size=10&sort.0.field=ALL&sort.0.direction=DESC&
[2] http://www.incobra.eu/en/object/news/466.html
[3] https://www.businessforplasticstreaty.org/
[4] https://globeeawards.com/golden-bridge-awards/winners/
[5] https://aliancapeloimpacto.org.br/wp-content/uploads/2020/03/ice-estudo-negocios-de-impacto-2019-web.pdf
Air quality is deteriorating throughout the world due to emissions from power plants, automobiles and industrial processes. In addition, organics used in indoor building materials, carpets, paints and surface finishes add to the indoor air quality problems. According to USEPA, indoor air can be 5 times more polluted than outdoor air. Filtration of air has been the dominant way of improving the indoor air quality, HEPA filters being the standard for air filters. However, many recent studies, especially from the medical literature have shown that filtration of air is not enough to take care of the indoor air quality problems. This is because particles smaller than the pore sizes of the filters, especially, Volatile Organic Chemicals (VOCs) are able to pass through the filters and any micro-organisms trapped on the filters continue to multiply on the filters and eventually get back into the air. Photo-electrochemical oxidation (PECO) technology was introduced in the market by Molekule in 2016, which does not just capture the pollutants but destroys them by oxidation process. The technology has been shown to be effective against biological pollutants, such as, bacteria, viruses and spores and also against molecular pollutants, such as, VOCs. The latest innovative technology for indoor air disinfection and detoxification is Plasmonic Photonic technology. This technology uses nanoparticles to generate surface plasmons, which when subjected to an incident light of the same frequency causes resonance to multiply the effect of incident light to disinfect the indoor air by phtoctalysis. This technology is being introduced to the market as an integral part of the air conditioning system in buildings, as a protection against next viral pandemic.The lecture will describe the science and technology behind each innovation and its impact on indoor air quality and in keeping indoor air disinfected and alleviating the allergy and asthma symptoms of patients.
13:50: [AdvancedMaterialsFriPM111] OS KeynoteIncreased concentrations of greenhouse gases (GHGs) in the atmosphere due to both natural and anthropogenic activities have resulted in severe environmental consequences threatening the biosphere of the Earth due to global warming and sea level rise. Therefore, strategies to reduce GHG emissions in both global and local contexts is mandatory. In this lecture, the terms ecological footprint (EFP), carbon footprint (CFP), global warming potential (GWP), and climate footprint will be defined and factors contributing to these terms discussed. The different strategies to reduce CFP include improving and promoting energy conservation and efficiency, using fuels with low carbon output such as nuclear and hydrogen fuels, changing to renewable energy (solar, hydropower, wind, and bioenergy), promoting carbon capture and storage, and using and promoting geoengineering approaches (reforestation, afforestation).The global GHG emissions by sector include energy, direct industrial processes, waste, and agriculture, forestry, and land use. The energy sector includes electricity, heat and transport which accounts for 73.2% and direct industrial processes, waste, and agriculture, forestry and land use contribute to 5.2%, 3.2% and 18.4%, respectively, as per 2016 data [1]. The countries contributing to GHG in 2020 are in the order China > USA > India > EU27 > Indonesia > Russian Federation > Brazil and the international transportation coming to next place. However, as per capita GHG emissions, the order is USA > Russian Federation > China > Brazil > Indonesia > EU27 > World > India. In EU countries, in 2020, the fuel combustion in energy industries, transportation including international aviation, households, commercial and other institutions, and manufacturing and construction industries account for 23.3%, 23.2%, 15.4%, and 12.1% GHG emissions thus totalling to 74.0%. In EU countries, there is a considerable reduction in GHG emissions from 1990 to 2020 in most sectors except fuel combustion in transport, including international aviation. The fuel combustion in transportation has a significant increase in by 50 million tonnes of CO2-equivalents [2].According to the World Resources Institute Climate Analysis Indicators Tool (WRI CAIT), the contributions to Sri Lanka’s GHG emissions, in 2011, are from energy sector (40%), waste (28%), land use change and forestry (LUCF) (15%), agriculture (14%) and industrial processes (3%). Energy sector emissions include transportation (39%), electricity and heat (28%), other fuel combustion (27%), and manufacturing and construction (5%). However, the energy sector which includes power generation and transport dominates over all other sectors [3]. The R&D activities currently in action in Sri Lanka such as developing carbon capture methods, conversion of carbon dioxide to useful chemicals, green energy technologies (hydropower, wind power, solar energy conversion and storage, hydrogen generation, fuel cells and supercapacitors), floating solar panels fixed under NORPART programme, development of all electric sport car “VEGA” and electric three wheeler vehicles and carbon negative vehicle body parts, alternative to cement in concrete production, carbon-negative construction materials, waste management and conversion of sludges to organic fertilizer will be discussed.
14:15: [AdvancedMaterialsFriPM112] OSE-mobility advancements and green power generation are central to achieving Green Deal's goals toward a low-carbon society. High-performing rare earth elements-transition metals permanent magnets (REE-TM PMs), such as Nd-Fe-B and Sm-Co, vital in e-motors and generators, are thus indispensable to meet these aims. Thus, in-depth study into REE-TM PMs is essential to boost their performance. However, the challenge lies in the limited availability of REEs, as they're flagged as critical for EU. Comprehensive solutions in recourse efficient magnet processing and reprocessing, including recycling, should now be integral to future PMs development. We are actively researching ways to make Nd-Fe-B and PMs reprocessing and recycling more viable [1]. Applying the electrochemical separation of anodic oxidation showed that the Nd-Fe-B scrap magnets can be successfully recycled either to matrix Nd2Fe14B matrix phase grains or be separated down to rare earth precursors [2]. Additionally, we have found that Sm-Co PMs can also be effectively recycled using electrochemical methods [3]. A step towards upscaling of Nd-Fe-B recycling principles is realized by selective chemical leaching of the Nd-rich secondary phase out of Nd-Fe-B feedstocks via organic acid which is considered as environmentally friendly approach [4]. These recycling routes open up new possibilities for reengineering Nd-Fe-B magnets from scratch, breaking away from conventional approaches and potentially improving magnet performance, such as energy products. In ongoing work related to the Nd-Fe-B system, we are exploring fast consolidation techniques through spark plasma sintering. These techniques hold promise in advancing the perspective of Nd-Fe-B magnet development.
References:
[1] X. Xu, K. Zuzek Rozman et al, A facile method for the simultaneous recovery of rare-earth elements and transition metals from Nd-Fe-B magnets. Green chem., 22, 1105-1112.
[2] X. Xu, K. Zuzek Rozman et al, 2019, Direct recycling of Nd-Fe-B magnets based on the recovery of Nd2Fe14B grains by acid-free electrochemical etching. ChemSusChem, 12, 21, 4754-4758.
[3] X. Xu, K. Zuzek Rozman et al., Electrochemical routes for environmentally friendly recycling of rare-earth-based (Sm-Co) permanent magnets. Journal of Applied Electrochemistry, 2022, 52, 4, pp10.
[4] S. Khoshima, S. K. Zuzek et al. Environmentally friendly approach for Nd2Fe14B magnetic phase extraction by selective chemical leaching : a proof-of-concept study. Materials, ISSN 1996-1944, 2023, vol. 16, no. 14, pp14
| SESSION: AdvancedMaterialsFriPM2-R5 | 7th Intl Symposium on New & Advanced Materials and Technologies for Energy, Environment, Health and Sustainable Development |
| Fri. 1 Dec. 2023 / Room: Heliconia | |
| Session Chairs: Fernand Marquis; Session Monitor: TBA | |
Today when Moore law gradually loses its effect and conventional charge-based electronics will soon come to the end development of high speed and low energy consuming information systems is urgently needed. Up to now, many new methodologies have been proposed, such as molecular electronics, nanoelectronics, spintronics, magnetronics, optronics, etc. Modern Electronics (Micro Nano Spin Electronics) and its future mainly based on novel materials (metals and nonmetals), their preparation technologies and new properties. Perfection and ultra-purity are not the only parameters characterized materials usefulness for quantum devices. Modification of material properties by different structural nonperfections (structural defects: impurities, isotopes, etc.) is the smart instrument for regulation of their characteristics. Based on difference from conventional electronics e electron’s which uses the electron’s charge degree of freedom for information processing, spintronics is devoted to incorporating the electron’s spin degree of freedom. Despite its great potential advantages, spintronics now faces a number of challenges, such as generation of fully spin-polarized carriers (pure spins) and injection of spin into devices, long distance spin transport, and manipulation and detection of carriers’ spin orientation. The solutions to these issues rely on the development of device fabrication and designing new spintronics materials with specific properties. [1]. Pure spin generation and injection mainly depends on the degree of spin polarization in the used semiconductors or metals. Thanks to the discovery of carbon based nanomaterials such as graphene [2] and carbon nanotubes, the challenge of long distance spin transport is likely to be solved in the near future. Because of their very weak spin–orbit coupling (SOC), carbon-based nanomaterials can have a long spin coherence length up to a few micrometers, thus are very good spin transportation materials. According to their electronic and magnetic properties, spintronics materials can be classified as magnetic metals, topological insulators, and magnetic semiconductors In a spintronic device, magnetic metals and topological insulators, serve as spin sources and drains, while magnetic semiconductors constitute the central region of the device.[3]. At the same time usage of electron spins as quantum bits for quantum information processing in so called quantum computers, were a qubit exists in more than one state simultaneously, is clear. Qubits in this state display a degree of correlations impossible in classical physics. This phenomenon is called entanglement and is crucial property of quantum computing. The main requirements of quantum computation are: Scalable physical systems with well characterized qubits (Zeeman Spliting); Long decoherence time: Existence of qubits at the ground state; Set of quantum gates; measurement capabilities, etc. Candidate for a qubit needs longer decoherence time than gate operation time. The transformation of digital computers from bulky machines to portable systems has been enabled by new materials and advanced processing technologies that allow ultrahigh integration of solid- state electronic switching devices. As this conventional scaling pathway has approached atomic- scale dimensions, the constituent nanomaterials increasingly possess properties that are dominated by quantum physics. [4]. The convergence between quantum materials properties and prototype quantum devices is especially apparent in the field of 2D materials, which offer a broad range of materials properties, high flexibility in fabrication pathways and the ability to form artificial states of quantum matter. Along with the quantum properties and potential of 2D materials as solid- state platforms for quantum- dot qubits, single- photon emitters, superconducting qubits and topological quantum computing elements it is necessary to select a the best method of their preparation. Potential of laser plasma process for 2D materials preparation, particularly its usefulness for organization of nanostructures applicable in spintronic and quantum computing devices novadays is actively developing. Laser plasma formed under the ionizing effect of powerful laser radiation on the thing. For example, LP arises during optical breakdown in gaseous media, laser radiation on top solid body, in laser thermonuclear targets. LP can exist in a wide range of temperatures - from 1 eV to 104 eV (104–108 K) and arising as a result of ionization of the electron impact with the subsequent image electronic avalanche, or as a result of many photon ionization. The impact of a light wave on LP leads to the formation of plasma waves (coil -ny electronic and ionic densities), which interact with the primary and scattered light. As a result, electric magnetic waves are formed with a frequency that is a multiple of the frequency of the incident light this wave (the so-called harmonics). The probability of generating high harmonics increases with an increase in intensity of laser radiation.
The properties of nanomaterials prepared by laser plasma technique are unique, and they are not reproducible by any other method including chemical ones. The usage of resonance light heat creates the opportunity to energize the selected atoms as well as their groups (assemble) and to produce plasma with the necessary properties relevant to structures which must be prepared This technique was successfully used by the authors of the project to study the conditions for obtaining diamond-like films, as well as thin layers of boron carbide. In the last two decades, the Laser plasma method was used to form both homogeneously doped GaAs:Mn layers and two-dimensional structures, including a δ-doped GaAs:Mn layer and a InxGa1 – xAs quantum well separated by a GaAs spacer with a thickness of d = 3–6 nm. It is obvious that only Mn ions, which are part of the GaMnAs solid solution and are distributed almost uniformly in it, can noticeably exchange with quantum well carriers, leading to their spin polarization and, consequently, to the anomalous Hall effect [5].. We are looking for farther development of LP processes aim of preparation the next (higher) level of spintronic nanostructures based on above mentioned and some other diluted semiconductors. Our works shown that the LP method and technology is very useful for preparation of semiconductor silicon and graphene nanosystem in one sandwich for creation of a new highly effective multiqubit element. Selection of laser sources and their parameters is giving the possibility to vary the energy of ionized atoms in plasma plum, activate them to the necessary level and deposit the hot atoms and their clusters on substrates of different origin (semiconductors: Silicon, GaAs, etc.; Metals: Fe, Ni, etc.; Insulators: Al2O3, etc). For organization of these processes it is also possible to use the resonance wavelength of the light sources in order to have the direct and strong interaction with electron’s bonding energies.
References:
[1] P. Kervalishvili. Semiconducting Nanostructures - Materials for Spintronics. Nanotechnology Perceptions, Vol. 1, N 3, 2005.
[2] K.S. Novoselov, A.K. Geim and S.V Morozov et al. Electric field effect in atomically thin carbon films. Science 2004; 306: 666–9.
[3] A. Fert, The origin, development, and future of spintronics, Nobel Lecture, December 8, 2007, Stockholm, Sweden
[4] P. Kervalishvili. Philosophy of quantum information science. NATO Science series, IOS press, v.93, 2012, 55-73.
[5] P. Kervalishvili and A. Lagutin, Nanostructures, magnetic semiconductors and spintronics, Microelectronics Journal, 39 (2008), pp.1060–1065.
| SESSION: BatteryTueAM-R6 | Kumar international Symposium (8th Intl. Symp. on Sustainable Secondary Battery Manufacturing & Recycling) |
| Tue. 28 Nov. 2023 / Room: Orchid | |
| Session Chairs: Athan Fox; Claudio Capiglia; Session Monitor: TBA | |
Lithium-ion batteries (LIBs) represent a massive shift beginning from personal electronic to energy storage in electrification of transportation, uninterrupted power supply and in supporting power generation from renewable energy technologies. Next generation of research in LIBs are making rapid progress in low-to zero cobalt cathodes, solid state batteries, safety, increased energy and power densities, fast charging and the use of 2D materials and metallic lithium as the anode. (1-3))
Looking into the near future, many other battery chemistries are also staking their claims within a mix of battery chemistry portfolios. In addition to LIBs, aspects of Lead Acid, Li-S, Sodium, Zinc, Aluminium, Potassium, and Redox battery systems will be discussed. Understanding battery chemistry basics is critical to unlocking the issues of energy, power, costs, safety, resources, and sustainability, as this talk will explore.(4,5)
• Some key areas of progress in the Battery Revolution will be addressed:
• Acceleration of research & innovation.
• Use of Artificial Intelligence & Machine Learning.
• Battery Supply Chain – implication for resources; Life Cycle Analysis.
• Optimization of Materials and Energy with minimal environmental degradation with the battery eco-system.
• Re-use, Recovery, Recycling and Upgrading of Battery Materials.
References:
1. Rechargeable Ion Batteries; Eds: Katerina Aifantis, RV Kumar, Hu Pu; Jan 2023, RV Kumar has co-authored 4 chapters on (i) Introduction to Batteries (ii) Primary Batteries (iii) Secondary Batteries and (iv) Li-S Batteries; Wiley-VCH Print ISBN: 978-3-527-35018-6; ePDF ISBN: 978-3-527-83669-7
2. Leapfrogging to sustainable power, R.V. Kumar, Chapter in “Smart Villages: New Thinking for Off-Grid Communities Worldwide; Published by Banson (Lavenham Press, UK), 2015, pp. 35-41; ISBN 978-0-9932932-0-7(paperback); 978-0-9932932-1-4 (hardback)
3. Lithiated metallic molybdenum disulfide nanosheets for high-performance lithium-sulfur batteries, Z. Li, I. Sami, J Yang, J Li, RV Kumar and M Chhowalla, Nature Energy; 8, 84-93, 2022
4.Lead Recycling, PCT filed on 6 Nov 2007. RV Kumar, S Sonmez and VP Kotzeva; PCT/GB2007/004222; EU 07824458.9; RU 2009117620; US 12/513707; CN 200780041628.4; IN 2216/KOLNP/2009.
5.Recycling of Lead Containing Waste, V Selvaraj, M Yiao, RV Kumar (UCAM), Athan Fox, R Liu(AEL), , British Patent Application P60233GB, Jan 2019; PCT/GB2020/050132; TW109102253 Jan 2020; PCT/GB2020/050132; TW109102253
Lithium-ion batteries (LIBs) represent a massive shift beginning from personal electronic to energy storage in electrification of transportation, uninterrupted power supply and in supporting power generation from renewable energy technologies. Next generation of research in LIBs are making rapid progress in low-to zero cobalt cathodes, solid state batteries, safety, increased energy and power densities, fast charging and the use of 2D materials and metallic lithium as the anode.
Looking into the near future, many other battery chemistries are also staking their claims within a mix of battery chemistry portfolios. In addition to LIBs, aspects of Lead Acid, Li-S, Sodium, Zinc, Aluminium, Potassium, and Redox battery systems will be discussed. Understanding battery chemistry basics is critical to unlocking the issues of energy, power, costs, safety, resources, and sustainability, as this talk will explore.
• Some key areas of progress in the Battery Revolution will be addressed:
• Acceleration of research & innovation.
• Use of Artificial Intelligence & Machine Learning.
• Battery Supply Chain – implication for resources; Life Cycle Analysis.
• Optimization of Materials and Energy with minimal environmental degradation with the battery eco-system.
• Re-use, Recovery, Recycling and Upgrading of Battery Materials.
References:
1. Rechargeable Ion Batteries; Eds: Katerina Aifantis, RV Kumar, Hu Pu; Jan 2023, RV Kumar has co-authored 4 chapters on (i) Introduction to Batteries (ii) Primary Batteries (iii) Secondary Batteries and (iv) Li-S Batteries; Wiley-VCH Print ISBN: 978-3-527-35018-6; ePDF ISBN: 978-3-527-83669-7
2. Leapfrogging to sustainable power, R.V. Kumar, Chapter in “Smart Villages: New Thinking for Off-Grid Communities Worldwide; Published by Banson (Lavenham Press, UK), 2015, pp. 35-41; ISBN 978-0-9932932-0-7(paperback); 978-0-9932932-1-4 (hardback)
3. Lithiated metallic molybdenum disulfide nanosheets for high-performance lithium-sulfur batteries, Z. Li, I. Sami, J Yang, J Li, RV Kumar and M Chhowalla, Nature Energy; 8, 84-93, 2022
4.Lead Recycling, PCT filed on 6 Nov 2007. RV Kumar, S Sonmez and VP Kotzeva; PCT/GB2007/004222; EU 07824458.9; RU 2009117620; US 12/513707; CN 200780041628.4; IN 2216/KOLNP/2009.
5.Recycling of Lead Containing Waste, V Selvaraj, M Yiao, RV Kumar (UCAM), Athan Fox, R Liu(AEL), , British Patent Application P60233GB, Jan 2019; PCT/GB2020/050132; TW109102253 Jan 2020; PCT/GB2020/050132; TW109102253
Sulfide based solid electrolytes are attracting attention because they have better electrochemical performances compared to other types of solid electrolytes. In addition, they have higher formability enabling favorable interfaces between the active material and solid electrolyte. Even though the sulfide based electrolyte shows better electrochemical characteristics among the various solid electrolytes, it poses some problems that have to be resolved such as poor compatibility of sulfide SEs against oxide-based cathode active materials and its instability against air and moisture. This study presents the findings of a comparative analysis on the stability of two different sulfide solid electrolytes (SEs) which are glass-ceramic Li7P3S11 and crystalline Li6P5SCl. We synthesized both SEs using the same mechanical milling method in order to compare them under identical conditions. Then, the composite cathodes were prepared by simply mixing the SEs with the active materials and additives. We tried to observe any side reactions that occur during the charging and discharging process. Additionally, electrochemical characterization of the composite cathode were conducted using each SEs. Also, it is aimed to continuously monitor the degradation mechanism of the composite cathodes during the charging and discharging process, as well as evaluate their thermal stability under high-temperature conditions, utilizing X-ray based analytical techniques. The details will be discussed at the meeting.
12:50: [BatteryTueAM04] OS InvitedAmong various battery chemistries, Zn and Al batteries stand out due to their safety, availability, high volumetric capacity, ease of handling and recyclability. [1, 2] Compared to Li/Na battery chemistries, both Zn and Al batteries have been developed using aqueous/ionic liquid electrolytes which has shown relatively stable performance. [3, 4] However, challenges exist in tuning the electrolyte chemistries along with developing suitable cathodes due to multi-ion storage process. In the last couple of years, we have looked into the electrolyte and cathode chemistries for both batteries and have progressed in developing a stable battery system.In this presentation, I will show the progress in both batteries which involves modification of aqueous electrolytes using ionic liquids/bio-ionic liquids which in-turn changes the electrochemical reactions at the cathode and anode. The addition of ionic liquids leads to dendrite-free metal deposition at the anode and improves the overall battery capacity. By tuning the electrolyte composition, we have improved both the capacity and stabilities of Zn and Al batteries.
References:
[1] Faegh et al, Nat. Energy, 2021, 6, 21
[2] Jia et al, Chem Rev., 2020, 120, 7785
[3] Lahiri et al, ACS Appl. Mater. Interface., 2019, 11, 45098
[4] Lahiri et al, Materials Advances, 2021, 2, 2676
| SESSION: BatteryTuePM1-R6 | Kumar international Symposium (8th Intl. Symp. on Sustainable Secondary Battery Manufacturing & Recycling) |
| Tue. 28 Nov. 2023 / Room: Orchid | |
| Session Chairs: Amr Henni; Hyun-Kyung Kim; Session Monitor: TBA | |
In this presentation we celebrate the contributions of distinguished scientist Professor R Vasant Kumar in the field of battery recycling and upcycling battery-active materials. A green hydrometallurgical process for the recycling of lead-acid battery paste has been developed. The background intellectual property, invented by Professor R Vasant Kumar, was licensed to Ever Resource where Dr Fox and colleagues worked in partnership with Professor Kumar to scale up the technology. The technology uses chelating organic acids to capture lead in the form of a metal-organic framework (MOF). The intermediate MOF is converted into highly advanced, nanostructured, battery-grade oxides which exhibit enhanced energy and power densities, among other properties. In a recent 3rd party-trial, it has been shown that energy densities can increase by as much as 40% - this is due to the high surface area of the oxides made by the process. By controlling the conditions, we have been able to convert the MOF into battery alpha oxide; beta oxide; and controlled mixtures of alpha and beta. Moreover, it is possible to produce red lead or lead sesquioxide as the final product. This level of control could enable fine-tuning of battery plate for specific applications (e.g. more power in automotive batteries, more cycling for stationary batteries and renewable energy storage, etc). Meanwhile, the quantity of lead in these leady oxides can be controlled to anything from negligible (less than 1% lead) to greater than 20%. The wet chemistry has been scaled up to 5 tonnes per hour continuous treatment of spent paste (modular), while the life-cycle analysis shows potential for reducing the carbon footprint of traditional recycling by approximately 85% and waste by more than 90%. The process saves considerable energy by not relying on a traditional furnace or electro-process – saving the equivalent of at least 3,000 tonnes of coal per 10,000 tonnes of batteries processed.
14:30: [BatteryTuePM106] OSOne of the most pressing environmental concerns facing humanity today is the limitation of carbon dioxide emissions. In the field of natural gas sweetening, carbon capture is equally critical. The solubility of carbon dioxide (CO2) and ethane (C2H6) in three ionic liquids (ILs) with the same anion, [C3C1pip][FSI], [C3C1pyrr] [FSI] and [N1223][FSI], was measured at (303.15, 323.15, and 343.15) K and at pressures up to 1.1 MPa.Experimental data were correlated with Peng-Robinson (PR) equation of state using three different mixing rules: (i) van der Waals one (vdW1, based on a single binary interaction parameter), (ii) van der Waals two (vdW2, based on two binary interaction parameters), and (iii) Wong-Sandler mixing rules combined with NRTL model. Henry's law constants, enthalpy and entropy for the absorption of Carbon dioxide and ethane in these ILs were also estimated. No significant change was found in the values of Henry's law constants of C2H6 in these three ILs which indicates a negligible effect of cations of these ILs on C2H6 solubility. The selectivity towards carbon dioxide (CO2) over C2H6 for these ILs was also reported. [FSI]-based ILs seem to have higher selectivity than all the other ILs, except for [C4C1Im][BF4] and possibly [C4C1Im][PF6], which may qualify them as promising solvents for CO2 removal from natural gas streams.
References:
[1] Carbon Dioxide, Ethane, Solubility, Selectivity, Ionic Liquids
Lithium-ion batteries are widely used as energy storage devices for electric vehicles and large-scale energy storage systems. Nevertheless, there are growing concerns about the limited availability of lithium resources, which could result in depletion and increased prices in the future. To tackle this issue, scientists have been extensively investigating alternative secondary battery systems that can replace commercial lithium-ion batteries. Sodium-ion batteries have attracted considerable interest among these alternatives due to the abundance of sodium resources and its economic feasibility compared to lithium. [1]
Although hard carbon has been recognized as a reversible anode material that enables sodium-ion insertion and extraction, the demand for high-capacity anode materials is imperative to achieve the desired energy density in sodium-ion batteries. Conversion- and alloy-based materials are considered highly promising alternatives due to their substantial theoretical capacity for sodium storage. [2,3] However, these materials encounter challenges such as notable volume changes of the active components, slow reaction kinetics, and instability at the electrode interfaces during the sodiation and desodiation processes. Overcoming these obstacles is essential to effectively implement these materials in high-performance sodium-ion batteries. [4]
In order to address these challenges, we devised a novel approach in this study, which involved the design of heterostructured anodes with a unique architecture. This was achieved by combining conversion- or alloy-based active materials with a porous silicon oxycarbide (SiOC) nanocoating layer, which is known for its exceptional surface capacitive reactivity and mechanical strength. We synthesized heterostructured composite anodes (MoS2@SiOC and Sn@SiOC) by controlling the dispersion of precursors in silicon oil and subsequent heat treatment. To investigate the properties of these composites, we conducted extensive physicochemical and electrochemical characterization, as well as post-mortem analysis. Our focus was particularly on understanding how the heterostructure influenced the battery performance of these composites. By adopting this heterostructure approach, we anticipate that new possibilities will arise for the development of innovative and high-performance anode materials for sodium-ion batteries.
References:
[1] C. Vaalma, D. Buchholz, M. Weil, S. Passerini, Nat. Rev. Mater. 3 (2018) 1-11.
[2] P. Tao, J. He, T. Shen, Y. Hao, J. Yan, Z. Huang, X. Xu, M. Li, Y. Chen, Adv. Mater. Interfaces 6 (2019) 1900460.
[3] H.T. Tan, D. Chen, X.H. Rui, Y. Yu, Adv. Funct. Mater. 29 (2019) 1808745.
[4] S.Z. Liang, Y.J. Cheng, J. Zhu, Y.G. Xia, P. Muller-Buschbaum, Small Methods 4 (2020) 2000218.
Recycling and reuse of batteries has increased its importance in recent years. In this study, recycling strategies of both lead acid batteries (LABs) and lithium-ion batteries (LIBs) were investigated comprehensively. Pyrometallurgical processes such as smelting and carbothemic reduction and hydrometallurgical processes such as desulphurisation and electrowinning were evaluated in detail for the recovery of lead in spent lead acid batteries [1-3]. Effects of the battery structure and recycling technologies such us hydrometallurgical, bio-hydrometallurgical and solvo-metallurgical methods on the energy and sustainability of lithium ion batteries were discussed [4]. Opportunities, challenges, and future prospects for the recycling of lead acid batteries and lithium ion batteries were evaluated. Recycling plays an important role for the sustainability of lead acid batteries and lithium ion considering the battery characteristics, environmental issues and critical raw materials. Green sustainable recycling and circular economy were emphasized for spent batteries [5-7]. Future perspectives for sustainable recycling of both lead acid batteries and lithium ion batteries were outlined.
References:
[1] M.S. Sonmez, R.V. Kumar, Leaching of waste battery paste components. Part 1: Lead citrate synthesis from PbO and PbO2, Hydrometallurgy, 95, 1–2, 2009, 53-60 (https://doi.org/10.1016/j.hydromet.2008.04.012.).
[2] M.S. Sonmez, R.V. Kumar, Leaching of waste battery paste components. Part 2: Leaching and desulphurisation of PbSO4 by citric acid and sodium citrate solution, Hydrometallurgy, 95, 1–2, 2009, 82-86, (https://doi.org/10.1016/j.hydromet.2008.04.019).
[3] Hengyu Pan, Yong Geng, Huijuan Dong, Mustafa Ali, Shijiang Xiao, Sustainability evaluation of secondary lead production from spent lead acid batteries recycling, Resources, Conservation and Recycling, 140, 2019, 13-22, (https://doi.org/10.1016/j.resconrec.2018.09.012).
[4] Lívia Salles Martins, Lucas Fonseca Guimarães, Amilton Barbosa Botelho Junior, Jorge Alberto Soares Tenório, Denise Crocce Romano Espinosa, Electric car battery: An overview on global demand, recycling and future approaches towards sustainability, Journal of Environmental Management, 295, 2021, 113091, (https://doi.org/10.1016/j.jenvman.2021.113091).
[5] Ersha Fan, Li Li, Zhenpo Wang, Jiao Lin, Yongxin Huang, Ying Yao, Renjie Chen, and Feng Wu, Sustainable Recycling Technology for Li-Ion Batteries and Beyond: Challenges and Future Prospects, Chemical Reviews 2020 120 (14), 7020-7063, (DOI: 10.1021/acs.chemrev.9b00535).
[6] Jędrzej Piątek, Semih Afyon, Tetyana M. Budnyak, Serhiy Budnyk, Mika H. Sipponen, Adam Slabon, Sustainable Li-Ion Batteries: Chemistry and Recycling, Adv. Energy Mater. 2021, 11, 2003456, (DOI: 10.1002/aenm.202003456).
[7] Joseph Jegan Roy, Saptak Rarotra, Vida Krikstolaityte, Kenny Wu Zhuoran, Yang Dja-Ia Cindy, Xian Yi Tan, Michael Carboni, Daniel Meyer, Qingyu Yan, and Madhavi Srinivasan, Green Recycling Methods to Treat Lithium-Ion Batteries E-Waste: A Circular Approach to Sustainability, Adv. Mater. 2022, 34, 2103346, (DOI: 10.1002/adma.202103346).
| SESSION: BatteryTuePM2-R6 | Kumar international Symposium (8th Intl. Symp. on Sustainable Secondary Battery Manufacturing & Recycling) |
| Tue. 28 Nov. 2023 / Room: Orchid | |
| Session Chairs: Claudio Capiglia; Satheesh Krishnamurthy; Session Monitor: TBA | |
Current process simulators such as ASPEN, PRO-II, gPROMS etc. do not have thermo-physical and transport property database of the materials used or produced in the battery industry. The process simulators lack physics-based models for modelling unit operations such as mixing, wet milling, coating, drying, calendaring. It is thus hard for process simulators to capture the effect of process variables in materials manufacturing or in cell manufacturing units on cell performance. Therefore, the process development and control in the battery industry is mostly done using a trial-and-error approach which makes it time and cost intensive. The recent advances in machine learning, artificial intelligence and sensing technologies can be leveraged to reduce the cost, accelerate the development and retuning of plants in the battery industry [1, 2]. The data from the pilot lines or from the manufacturing lines could be used to develop data-based models. There are only a few academic groups who have worked on data-based models for cell manufacturing units [2]. However, there is no work on developing data-based models for battery materials manufacturing unit. The biggest bottleneck in developing data-based model for cell manufacturing and battery materials manufacturing units is the availability of feature rich and diverse dataset.The scarcity of data could be mitigated by coupling multiscale modelling with data driven approach. Multiscale modelling gets computationally intensive when models are built to scale. Plant data still is orders of magnitude expensive and hence exists in much smaller volumes. One possible solution is to build multiscale models with the help of plant data and run these simulations for different scenarios creating a diverse enough dataset [3,4]. The simulated data along with plant data could then be expanded using generative AI to a much larger data set enabling higher accuracies of the data-based model. However, this concept still needs to be tested and validated.
References:
[1] Sinha, A.; Radhakrishnan, V.; Vadari, R.; Capiglia, C. Scaling up Li-ion cell production: Building a Gigafatory. Sustainable Industrial Processing Summit and Exhibition 2022, 14.
[2] Bockwinkel, K.; Nowak, C.; Thiede, B.; Nöske, M.; Dietrich, F.; Thiede, S.; Haselrieder, W.; Dröder, K.; Kwade, A.; Herrmann, C. Enhanced Processing and Testing Concepts for New Active Materials for lithium‐Ion Batteries. Energy Technology 2019, 8 (2).
[3] Duquesnoy, M.; Liu, C.; Dominguez, D. Z.; Kumar, V.; Ayerbe, E.; Franco, A. A. Machine Learning-Assisted Multi-Objective Optimization of Battery Manufacturing from Synthetic Data Generated by Physics-Based Simulations. Energy Storage Materials 2023, 56, 50–61.
[4] Turetskyy, A.; Thiede, S.; Thomitzek, M.; von Drachenfels, N.; Pape, T.; Herrmann, C. Toward Data‐driven Applications in lithium‐Ion Battery Cell Manufacturing. Energy Technology 2019, 8 (2).
The advent of printed large area electronics has started delivering exciting innovations over the last few years. A key enabler for fully thin devices are printed energy storage devices. Over the last few years, Zinergy has embarked on a mission to develop simple, low cost, printed energy storage devices which are compatible with other printed electronic devices. Printing is a very versatile technique for batteries. It allows to control not only size and shape of devices, but also via thickness control and ink formulations there is a toolkit to adapt the battery´s energy and power requirements to a large set of applications, optimising for energy, power or mechanical properties. Printing batteries allows a degree of freedom in design generally not possible with more traditional production methods. In this paper we discuss the use of a printed co-planar battery electrode layout, constructed in a polymer casing which allows the in-situ observation of electrode/electrolyte dynamics. The effects during discharge at various current rates was done by visual time lapsed observation of the formation of compound residues which crystallise and re-dissolve during the discharge process. An aqueous, acidic Zinc/MnO2 system is used and the spatial observation of reactants allows also the visualisation of electrolyte/ion movement. In addition, it is noted that the presence of the separator plays a critical role in providing nucleation sites for crystallisation. Electrical discharge curves and optical measurements are complemented with in-situ X-ray synchrotron data, allowing the observation of the components formed and as a result provide a better understanding of the discharge process, leading to and overall improved battery design. This paper provides an overview of the learnings from in situ measurements of co-planar aqueous zinc batteries, and it is hoped that this system may be more generally applied to observe reaction dynamics in different battery systems, contributing to the electrochemical energy storage field in general.
16:50: [BatteryTuePM211] OSAqueous zinc ion batteries (AZIBs) have emerged as one of the promising next-generation secondary batteries, offering affordability and inherent safety features. However, AZIBs face limitations associated with the use of water-based electrolytes, which result in low operating voltages and subsequently low energy density. Additionally, challenges such as dendrite growth and hydrogen gas evolution at the interface between the zinc metal anode and electrolyte further hinder the commercialization of AZIBs. To address these issues, this study focuses on implementing two interfacial modification strategies. In the first study, we tried to enhance the depth of discharge (DOD) by using a zinc powder electrode instead of thick zinc foils as the anode, thereby reducing the N/P ratio. However, the high surface area of zinc powder accelerates dendrite growth and corrosion. To address these challenges, we applied a uniform SnO2 coating layer on the zinc powder using the atomic layer deposition (ALD) technique. The SnO2 coating effectively inhibits dendrite growth and corrosion on the zinc powder surface. When we implemented this interfacial modification strategy in a full-cell configuration, we observed an increase in discharge capacity from 163 mAh g-1 to 221 mAh g-1, indicating improved cycling performance. Ultimately, by using zinc powder anodes with a low N/P ratio similar to that of commercial lithium-ion batteries. As a result, by applying SnO2 coating as a protective layer, we not only increased the zinc utilization rate but also achieved an increase in volumetric energy density. Secondly, we introduced tetrabutylammonium iodide (TBAI) as an electrolyte additive to the mildly acidic ZnSO4 electrolyte. This approach combines the zincophobic repulsion effect of cationic TBA+ ions and the corrosion inhibition effect of the anionic I- ions. TBA+ ions form a protective layer on the zinc anode surface, preventing localized deposition of Zn2+ ions. I- ions act as corrosion inhibitors, suppressing the detrimental corrosion at the interface. By effectively addressing these issues at the interface, we achieved improved capacity retention in the full-cell system with a Zn0.25V2O5 cathode. After 5000 cycles, the capacity retention rate increased from 44.7% to 58.3% upon the incorporation of the TBAI additive.
17:15: [BatteryTuePM212] OSRecycling has become an absolute necessity. Spent Lithium-ion batteries (LIBs) are hazardous waste but a potential source of purified minerals. The industrial focus on LIB recycling is mostly centered on costly and scarce cathode materials recovery. Graphite is often overlooked as it fails to generate useful revenue. Herein, the waste LIBs are recycled following an all-components-recovery route that minimizes cross-contamination. However, the surface of the recovered graphite is covered with solid electrolyte interphase (SEI) formed during its first life application. Solvent wash followed by thermal treatment revives graphite for second-life applications. Three important things to consider here are the interaction of solvent media with the preformed SEI, the role of leftover SEI in forming the second-life SEI, and the effect of regenerated SEI on second-life electrochemistry. Therefore, the nature of the solvent plays a vital role in the overall process. Utilizing water is the go-to alternative but the obtained electrochemistry from water-washed graphite is below the mark. Organic solvent dimethyl carbonate (DMC) modifies the chemical composition of the interphase in such a way that it improves second-life electrochemistry. Strong inorganic acid HCl results in the highest carbon purity and makes recovered graphite suitable for non-electrochemical applications too. Electrochemically superior DMC-washed graphite is repurposed into a dual-ion full cell that delivers an average voltage of 4.5 V and an energy density of 110 Wh kg-1.
| SESSION: BatteryTuePM3-R6 | Kumar international Symposium (8th Intl. Symp. on Sustainable Secondary Battery Manufacturing & Recycling) |
| Tue. 28 Nov. 2023 / Room: Orchid | |
| Session Chairs: Claudio Capiglia; Session Monitor: TBA | |
Electrochemical energy storage devices can offer a number of great potentials for meeting future energy demands, such as of renewable energy, electric vehicles, portable electronics, that require high energy density, high power density and long cycle life. Among the various electrode materials available for energy storage devices, graphene, a one-atom-thick, two-dimensional sp2 carbon structure, has attracted considerable interest as a next-generation electrode material. This can be attributed to a number of interesting properties of graphene, such as its good mechanical/chemical stability, high electrical/thermal conductivity, and a large surface area due to its high surface-to-volume ratio.[1] The combination of these unique physical and chemical properties means that graphene has significant potential to act as an electrochemically active material for use in energy storage devices such as Li-ion batteries and electrochemical capacitors.[2,3]
In this study, we report on the synthesis and electrochemical characterization of nanoperforated graphene-based electrode materials for energy storage applications. More details will be discussed at the meeting.
References:
[1] A. K. Geim and K. S. Novoselov, Nat. Mater. 6 (2007) 183.
[2] Y. J. Choi, G-W. Lee, Y. H. Kim, H-K. Kim, K-B. Kim, Chemical Engineering Journal, 455 (2022) 140770.
[3] Y. J. Choi, G-W. Lee, Y. H. Kim, H-K. Kim, K-B. Kim, Chemical Engineering Journal, 432 (2022) 134260.
| SESSION: LawsWedAM-R6 | Carter International Symposium (3rd Intl Symp on Laws & their Applications for Sustainable Development) |
| Wed. 29 Nov. 2023 / Room: Orchid | |
| Session Chairs: Malcolm McNeil; Samuel Berger; Session Monitor: TBA | |
New technology development can easily push borders of existing habit and understanding of the world. With it frequently new previously unthought borders are openly or hiddenly or unconsciously push and this can adversely affect the human rights. In this presentation the author vast experience in human rights protections is used through different examples to make the point that science and technology in their new inventions and discoveries do not go against human rights. A particular case mind reading devises and the landmark ruling of the Chilean Supreme court against a mind-reading device that will have significant repercussions in regulating such devices and protecting “neural rights.” Analysis is carried out and conclusions are drawn.
12:00: [LawsWedAM02] OS PlenaryThe concept of sustainability has been somehow politized in terms of unilaterally extracting it from its core basis. Following the definition of FLOGEN Sustainability Framework the 3 criteria of sustainability that must be reached simultaneously are economic growth, environmental protection, and social development. As per this definition there are 3 factors that can help or hinder sustainability: Science and Technology, Governance and Management and education of civil society. In this paper a depoliticized sensible approach to a balance in environment and energy considerations of sustainability will be presented, depoliticizing its concept.
12:25: [LawsWedAM03] OS PlenaryData Science focuses on the mathematics and statistical relationships to help filter the data and make accurate analysis as raw data can prove deceptive not by design, but by the methods of collection, processing and interpretation. Analyzing data is its own science for many inherent reasons such as understanding of how to normalize the data using Relational Algebra [1]. The importance of creating precise data structures when handling, processing and manipulating mass amounts of data cannot be understated and can only be achieved accurately using Relational Algebra for a host of reasons. You must also master how to query the data using standard query language and how to analyze the data using advanced statistical methods such as regression testing, etc.In this lecture you will see a major universal world-wide problem [2] analyzed from a different prospective. We will also look at other objective related data [3] [4] to see if the raw data may prove to be misleading prior to initializing our studies. This data you have all seen in raw form and now you will see how a data scientist brakes down and analyzes the underlying data to give new insights and even point to new studies and research.
References:
[1] IDEAS Data Science Conference in 2019 – “Data Architecture for the Extreme Data Scientist” (https://www.youtube.com/watch?v=AOnilawQWys)
[2] Climate Change: Global Temperature (https://www.climate.gov/news-features/understanding-climate/climate-change-global-temperature)
[3] U.S. Hurricane Strikes by Decade (https://www.nhc.noaa.gov/pastdec.shtml)
[4] World of Change: Antarctic Sea Ice (https://earthobservatory.nasa.gov/world-of-change/sea-ice-antarctic)
Companies have long taken environmental and social and governance (ESG) factors into account when managing businesses as a way to reduce risk, address mission and respond to stakeholder priorities. However, in recent years what has been a rather loose, subjective set of principles has morphed into something different. Touting good ESG practices can be an important marketing strategy, but critics can point to examples when the marketing hype fell short of reality, so-called “green-washing”. Other critics question whether non-monetary considerations should be used when considering business decisions or argue that ESG is purely a political tool with no commercial merit. Many businesses now are believed to be “green-hushing”, meaning that they continue to use the ESG metrics to operate their businesses but are speaking about it less openly. At the same time, investment mandates for “green” are not going away. Regulators are taking greater notice of ESG-related disclosures, and the consequences for misstatements are increasing. Accordingly, for companies managing their ESG compliance, they will need to consider business operations, communications, marketing, strategy and legal issues. The speaker intends to lead a spirited discussion of the appropriate uses of ESG in business decision-making, risk mitigation and the roles of lawyers in advising clients about these issues.
| SESSION: LawsWedPM1-R6 | Carter International Symposium (3rd Intl Symp on Laws & their Applications for Sustainable Development) |
| Wed. 29 Nov. 2023 / Room: Orchid | |
| Session Chairs: Malcolm McNeil; Hunter Carter; Session Monitor: TBA | |
A sustainably developing world that strives to simultaneously achieve environmental protection, economic development and social development will depend upon more effective and responsive systems for protecting human rights. The author will review his experience in a pair of significant human rights cases in the InterAmerican system and will focus on problems of justice delayed, as a lack of respect of human rights. One case involves the torture of Chilean Air Force officials by leaders of the coup against President Salvador Allende and the other involves marriage equality that also rises from Chile. A detailed analysis will be carried out and proper conclusions will be drawn.
14:30: [LawsWedPM106] OS PlenaryJudicial systems around the world may be divided in two major groups: common and civil law system. Common Law systems are mainly used in UK, USA, Canada and the civil law systems are used in Europe and other countries. There are also countries or states/provinces that have mix systems like Quebec where criminal matters use mainly common law system and civil matters use civil law systems and in manty cases both methods of both systems are used interchangeably. A somewhat indirect product of the systems is the way that the judges are appointed or elected. In this paper a comparative analysis of both systems and their elected or appointed judges is carried out with all his advantaged and disadvantages.
14:55: [LawsWedPM107] OS KeynoteTwitter, Microsoft, Target, Ebay, Equifax, JPMorgan Chase, Home Depot, First American Financial Corp., Facebook, eBay, Equifax, Heartland Payment Systems, LinkedIn, Marriott International, Yahoo and countless more have all been victims of major cybercrime [1]. Ransomware has become a well-known household term. How did cyber criminals become so effective so quickly? How do you protect your mission critical data and intellectual properties? How much are cyber criminals costing the world and is this problem going to get even worse [2]?The advanced techniques covered in this lecture can be understood by everyone and applied universally. You do not need to be an IT guru or data specialist or a security administrator to understand and appreciate these concepts, but once you do have this knowledge you can better identify your weaknesses including the people you hire to protect your most valuable assets [3]. You cannot hire and fire security administrators effectively without knowing the right questions to ask and have an understanding of their mission.
References:
[1] Biggest Data Breaches in US History (https://www.upguard.com/blog/biggest-data-breaches-us)
[2] Estimated cost of cybercrime worldwide 2017-2028 (https://www.statista.com/forecasts/1280009/cost-cybercrime-worldwide)
[3] Cybersecurity Best Practices (https://www.cisa.gov/topics/cybersecurity-best-practices)
Background:Amy Antoniolli will speak about the policy success stories from the Illinois Clean Enegy Jobs Act ("CEJA"), which was legislation based on sustainability. CEJA, passed in 2021, includes a first-in-the-nation fleet transformation under the Illinois Coal to Solar program and Energy Transition Act. This framework allows the fleet to develop solar and energy storage at nine existing plant sites in a way that supports equitable clean energy jobs and transitions communities dependent on a legacy coal fleet to renewable energy. CEJA also created additional incentives to develop renewable energy facilities on brownfields, including former ash ponds at coal-fired power plants, to further support a just transition for communities dependent on revenue from a legacy coal fleet.Learning Objectives: Learn about one of the most equitable clean energy jobs bills in history from a firm that participated in its drafting. Effective September 15, 2021, the Climate & Equitable Jobs Act sets an ambitious decarbonization goal, requiring Illinois to be reliant on 100% renewable energy by 2050 and is currently in the height of the implementation process. The legislation also created the Illinois Coal to Solar program to transition communities reliant on Illinois’ coal fleet to carbon-free sources of energy.Methodology: The CEJA created a pathway for Illinois to build a diverse clean energy workforce; build wealth, capacity and employment opportunities in minority and women-owned businesses; and ensure that the benefits of energy efficiency and clean energy programs reach environmental justice communities and communities that have experienced historic disinvestment. The presenter will prepare Powerpoint slides to illustrate and describe case studies, summarize the statewide incentives for transitioning impacted communities and increasing diversity in clean jobs, and explain how Illinois has been a leader in equitable energy policy.
| SESSION: LawsWedPM2-R6 | Carter International Symposium (3rd Intl Symp on Laws & their Applications for Sustainable Development) |
| Wed. 29 Nov. 2023 / Room: Orchid | |
| Session Chairs: Wilson Ferreira Santos Jr.; Session Monitor: TBA | |
Modern corporate compliance systems have considerably affected the way the modern multinational business corporations work. These systems have replaced the culture of existing corruption and have become significant tools to prevent transnational crime and political corruption, including the replacement of corrupt governments practices that result on the theft of resources from their people and worsen the economic and social development by channelling the money for the enrichment of a few numbers of people. Various examples on the above will be given and proper conclusions will be drawn.
16:25: [LawsWedPM210] OSHuman sustainability requires freedom of movement. Freedom to choose where to live your life and put down roots. That freedom is restricted by immigration laws and requirements. Businesses are desperate to find the most talented human resources and most lucrative markets, and individuals are desperate to find the most rewarding employment and environments for themselves and their families. Both of these needs must be met for human sustainability. Satisfying these needs often crosses borders, implicating the local immigration systems and authorities. To better human sustainability, immigration systems must be scrutinized to see what avenues can be enabled to ease freedom of movement. Foreign entrepreneurs and international businesses must have routes to establish and operate businesses in new global markets, generating revenue and offering employment opportunities locally and globally. Individuals need feasible ways to obtain visas in a timely manner to accept global employment assignments and to establish themselves in new settings. More transparency is needed in the visa adjudication process so that all involved understand more clearly the criteria and reasoning used in adjudications. This will allow applicants to better prepare their visa petitions, which will increase efficiency and effectiveness all around, and will increase the feeling that there is fairness and trust in the immigration system. Improving immigration systems will improve human sustainability and happiness.
16:50: [LawsWedPM211] OSDrawback is characterized as a special regime, whose scope is to allow the suspension, exemption and refund of some taxes levied on the acquisition of inputs and intermediate products incorporated in the manufacturing process and industrialization of products intended to increase our foreign exchange with their exports.
17:15: [LawsWedPM212] OLA PUNISHING and challenging climate change is here. With the global temperature rising - from the melting of the arctic zones to the frequent flooding in the tropics, and cyclical droughts in the deserts of Africa, to the worst desertification in India and China and the sea-level rise in lowland states --- the reality is pervasive and destructive to both poor and rich citizens of the world. Both Developed and Developing countries experiences these destructive weather patterns. No one country is spared from scorching heat and raging waters.In fact, the global corona virus pandemic and these on-going climate crises has prompted Inger Andersen, the United Nations Environment Chief to say that “Nature is sending us a message” and that “humanity, was placing too many pressures on the natural world with damaging consequences”, and she warned that “failing to take care of the planet meant not taking care of ourselves”.It has been established that human activities, particularly massive development and infrastructure works caused the temperature rise in the atmosphere. Greenhouse gas emissions from pollutive industries and extensive corporate agricultural activities , as well as motor vehicles pollution indexes have increased for the last five decades. A question maybe asked, What have we, the humanity, done, so far, to address these problems and introduce counter-measures in order to cushion the impact of environmental destruction?A review and evaluation of the legal frameworks are necessarily important, in order to determine that these dynamic and fast moving changes in nature are effectively addressed, properly or distinctively. Climate control, climate resiliency, disaster preparedness become the byword. Do we really have to live with these cyclical weather patterns or do we make concrete actions to preserve mother earth, including precious lives.Thus, the following legal frameworks must be identified, clustered and reviewed to pinpoint whether the whole of humanity have instituted reforms and established proper and corrective climate control mechanisms to manage and limit these environmental destruction. These frameworks are as follows: a. International Treaties or Conventions; b. Regional Treaties or Agreements; and c. Domestic or National Laws.
| SESSION: BatteryThuAM-R6 | Kumar international Symposium (8th Intl. Symp. on Sustainable Secondary Battery Manufacturing & Recycling) |
| Thu. 30 Nov. 2023 / Room: Orchid | |
| Session Chairs: Vasant Kumar; Session Monitor: TBA | |
A hybrid energy storage system (HESS) can combine the efficiency and quick response of batteries with the energy density and cost of synthetic (e-)fuel storage. Exergy analysis is a valuable tool in optimising the efficiency of the electrochemical process chains needed to produce and consume e‑fuels. In the paper we present our ongoing efforts on using exergy analysis and exergy gravimetric analysis in battery- fuel cell integrated energy systems. A couple of case studies are presented. A hybrid energy storage system case in detail and others briefly. An algorithm for optimal sizing of HESS-supported electrical grids in various locations, powered purely by renewable energy is introduced [1]. Efficient process chains have been developed for several fuels such as hydrogen, methane and ammonia. These process chains were combined with storage sizing algorithms to make design choices for large scale energy storage in the Netherlands [2]. Exergy analysis combined with HESS-sizing algorithms can also be used for exergy gravimetric analysis, which is an approach that seeks to optimise efficiency simultaneously with energy density. This approach can be useful for several applications, particularly weight-sensitive applications such as long-range sustainable transport. The use of exergy-gravimetric approaches for designing an optimal minimized-mass power plant for aircraft applications is presented [3-5]. Additionally, ongoing efforts on using the same approach in developing road transport systems are also introduced
References:
[1] A. Amladi, S. Singh, T. Woudstra, P.V. Aravind, ECS Trans. 103 (2021) 393
[2] A. Amladi, F. Resink, O. el Tambouli, V. Venkataraman, T. Woudstra, P.V. Aravind, ECS Trans. 111 (2023) 1803
[3] C. Haynes, R. Miller, Proceedings of the ASME 2013 11th International Conference on Fuel Cell Science, Engineering and Technology V001T02A003
[4] Y. Tambi, MSc Thesis, Delft University of Technology, 2019
[5] A. Flapper, MSc Thesis, University of Groningen, 2023
The sustainable advancement of green energy storage technologies hinges on the efficient utilisation of readily available and cost-effective materials. In this context, here, I delve into the eco-friendly conversion of natural minerals and biomass into functional materials tailored for metal-ion energy storage applications. Particular emphasis is placed on the mechanochemical, thermal, and molten salt modification techniques developed at E2MC to nanostructuring minerals such as molybdenum disulfide, ilmenite, and natural graphite, as well as biomass. These processes result in the creation of nanostructured electrode materials with enhanced electrochemical performances for use in Li-ion and/or Na-ion batteries. The phase transformations that occur during these modification processes are explored and their consequential impact on key factors such as metal-ion storage capacity, diffusion coefficients, and surface pseudocapacitive behaviors are discussed. Furthermore, I would underscore the economic benefits stemming from the utilisation of abundant and economical materials in the development of highly efficient battery systems.
References:
[1] A.R. Kamali*, S. Li, Applied Energy 334 (2023) 120692
[2] A.R. Kamali*, H. Zhao, Journal of Alloys and Compounds 949 (2023) 169819
[3] W. Zhu, A.R. Kamali*, Journal of Water Process Engineering 53 (2023) 103903
[4] W. Zhu, A.R. Kamali*, Journal of Alloys and Compounds 932 (2023) 167724
[5] W. Zhu, A.R. Kamali*, Journal of Alloys and Compounds 968 (2023) 171823
[6] R. Li, A.R. Kamali*, Chemical Engineering Science 265 (2023) 118222
[7] A.R. Kamali*, J. Ye, Minerals Engineering 172 (2021) 107175
[8] A.R. Kamali, W. Zhu, China Patent CN110498446 (2020)
Hybrid organic-inorganic perovskites have attracted significant attention in the past two decades owing to their enormous application potential in energy. Like their oxide counterparts, these hybrid organic-inorganic systems exhibit abundant phase transitions which can often lead to significant changes in the electrical, magnetic, and optical properties that are of vital importance for the design and fabrication of functional devices. However, the atomistic driving forces and underlying mechanism need to be well understood for these hybrid perovskite systems. In this talk, I shall present our recent advances in the thermally and pressure-driven phase transitions and their microscopic mechanisms of some three-dimensional and two-dimensional hybrid organic-inorganic perovskites. At the same time, I shall discuss the symmetry alternation at the interface and corresponding atomic origin of some two-dimensional hybrid organic-inorganic perovskites.
References:
1. Y. Qin, Z.-G. Li, F.-F. Gao, H. Chen, X. Li, B. Xu, Q. Li, X. Jiang, W. Li*, X. Wu, Z. Quan, L. Ye, Y. Zhang*, Z. Lin, L. Pedesseau, J. Even*, P. Lu, X.-H. Bu*, Adv. Mater., 2022, 2201666.
2. K. Li, Z.-G. Li, J. Xu, Y. Qin, W. Li*, A. Stroppa, K. T. Butler*, C. J. Howard, M. T. Dove, A. K. Cheetham, X.-H. Bu*, J. Am. Chem. Soc., 2022, 144, 816.
3. W.-J. Wei, X.-X. Jiang, L.-Y. Dong, W.-W. Liu, X.-B. Han, Y. Qin, K. Li, W. Li*, Z.-S. Lin*, X.-H. Bu*, P. Lu*, J. Am. Chem. Soc., 2019, 141, 9134.
4. W. Li*, L. Ji, Science, 2018, 361, 132.
5. W. Wei, W. Li*, K. Butler*, G. Feng, C. J. Howard, M. Carpenter*, P. Lu*, A. Walsh, A. K. Cheetham, Angew. Chem. Int. Ed., 2018, 57, 8932.
6. W. Li*, Z.-M. Wang, F. Deschler, S. Gao*. R. H. Friend*, A. K. Cheetham*, Nat. Rev. Mater., 2017, 2, 16099.
| SESSION: CarbonTueAM-R7 | 6th Intl. Symp. on Sustainable Carbon and Biocoke and their Industrial Application |
| Tue. 28 Nov. 2023 / Room: Sunflower | |
| Session Chairs: David Scheiblehner; Gustav Hanke; Session Monitor: TBA | |
Despite all modern technologies and innovative developments, carbon is still of major importance in metallurgy. Not only for iron and steel production, but also for nonferrous metals. In many pyrometallurgical processes, coal and coke are the main reducing agents and important energy sources. However, one product of carbon application is always CO2, which is known as one major problem in climate change. As such, it is indispensable to develop and use new sustainable technologies that reduce or eliminate the CO2 discharge to the atmosphere. In metal production, carbon is still the most important reducing agent and essential for most modern pyrometallurgical processes, and this will not change in near future. In the short- and mid-term, until entirely new processes that are not carbon-based are introduced, the use of coke out of biomass can help to minimize the CO2 footprint. However, coke must meet several requirements in terms of reactivity, stability, grain size, etc. to be used in specific processes. Here, the influence on the process caused by the much higher reactivity and different impurities needs to be studied and defined, to optimize existing treatment procedures, if necessary.For replacing fossil coke, which is in use today, the coke produced out of biomass must be as similar as possible so that in best case, no changes in the processes are necessary.For an environment-friendlier solution, the origin of the biomass is also critical. Preferably, the material is locally available and not of any other use. Depending on the location, this could be agricultural residues like olive stones and fruit tree cuttings or waste wood for example.Until now, the use of biocoke in lead production and in the Waelz kiln was in the focus of research at Montanuniversitaet Leoben. While the application in lead metallurgy is less problematic and was tested successfully, the substitution of coke in the Waelz kiln is more difficult and places higher demands on the properties of the carbon carrier, especially in terms of reactivity. For this, the reduction of reactivity is now in focus and will be critical for the future of biocoke in this process. Trials showed that an increase of the grainsize (pellets) and a treatment with additives like bentonite, has a positive impact on the properties of the coke and could lead to an efficient application.
12:00: [CarbonTueAM02] OSHydrogen represents a pivotal element in transforming the current energy system as its application as a fuel or reducing agent in critical industrial sectors, including transportation and metallurgy, can enhance energy diversity and availability while offering the opportunity to reduce greenhouse gas emissions [1]. However, producing H2 using conventional methods is associated with the generation of high volumes of carbon dioxide [2]. Therefore, extensive research activities concentrate on developing alternative processes with decreased CO2 footprints.Methane pyrolysis in liquid metallic catalysts is an attractive process that shows excellent potential, as its specific energy demand is comparable to that of steam methane reforming, but no CO2 is emitted due to the base reaction [3], [4]. Furthermore, generated pyrolysis carbon is a valuable product with many possible applications [5].This work investigates the influence of different compositions of the utilized metal bath on produced pyrolysis carbon. The focus is on modulating its physical properties, especially with regard to marketability and impact on the overall process economics while sustaining sufficient hydrogen yield.
References:
[1] IEA. Global Hydrogen Review 2022, IEA: Paris, 2022
[2] Machhammer, O., Bode, A. and Hormuth, W. Financial and Ecological Evaluation of Hydrogen Production Processes on Large Scale. Chem. Eng. Technol. 2016, 39, 6, pp. 1185–1193. doi:10.1002/ceat.201600023
[3] Scheiblehner, D., Neuschitzer, D., Wibner, S., Sprung, A. and Antrekowitsch, H. Hydrogen production by methane pyrolysis in molten binary copper alloys. International Journal of Hydrogen Energy 2022. doi:10.1016/j.ijhydene.2022.08.115
[4] Scheiblehner, D., Antrekowitsch, H., Neuschitzer, D., Wibner, S. and Sprung, A. Hydrogen Production by Methane Pyrolysis in Molten Cu-Ni-Sn Alloys. Metals 2023, 13, 7, pp. 1310. doi:10.3390/met13071310
[5] R.A. Dagle, V. Dagle, M.D. Bearden, J.D. Holladay, T.R. Krause and S. Ahmed. An Overview of Natural Gas Conversion Technologies for Co-Production of Hydrogen and Value-Added Solid Carbon Products, 2017. doi:10.2172/1411934
In the context of the growing interest in hydrogen as an energy carrier and reducing agent, numerous industries, including the iron and steel sector, are contemplating an increased adoption of hydrogen. To meet the escalating demand in energy-intensive industries, it becomes imperative to significantly expand and further develop hydrogen production. However, the present hydrogen production methods heavily rely on fossil fuels, resulting in a substantial environmental burden, with approximately 10 tons of CO2 emissions per ton of hydrogen generated. [1], [2]To address this challenge, methane pyrolysis has emerged as a promising approach to produce clean hydrogen with reduced CO2 emissions. This process involves the dissociation of methane into hydrogen and solid carbon, leading to a substantial reduction in the carbon dioxide footprint associated with hydrogen production. [3], [4]The Montanuniversitaet Leoben (Austria) is currently actively engaged in research concerning methane pyrolysis and the development of a liquid metal bubble column reactor (LMBCR) specifically dedicated to this purpose. While the resulting H2-rich product gas from methane pyrolysis may have potential applications in various processes, such as iron ore reduction, the carbon product, on the other hand, has stricter requirements in terms of impurities, depending on its intended field of use. Many applications demand very low threshold values for impurities in the carbon product [5]. Therefore, the main objective of this study is to investigate the chemical properties of carbon produced via methane pyrolysis in an LMBCR concerning impurities and to propose process technological improvements to enhance the overall product quality.
References:
[1] International Energy Agency. Net Zero by 2050. https://www.iea.org/reports/net-zero-by-2050 (accessed on 25.08.2023)
[2] International Energy Agency. Global Hydrogen Review 2021. https://www.iea.org/reports/global-hydrogen-review-2021 (accessed on 25.08.2023)
[3] Patlolla, S.R., Katsu, K., Sharafian, A., Wei, K., Herrera, O.E. and Mérida, W. A review of methane pyrolysis technologies for hydrogen production. Renewable and Sustainable Energy Reviews 2023, 181, pp. 113323. doi:10.1016/j.rser.2023.113323
[4] Sánchez-Bastardo, N., Schlögl, R. and Ruland, H. Methane Pyrolysis for Zero-Emission Hydrogen Production: A Potential Bridge Technology from Fossil Fuels to a Renewable and Sustainable Hydrogen Economy. Industrial & Engineering Chemistry Research 2021, 60, 32, pp. 11855–11881. doi:10.1021/acs.iecr.1c01679
[5] R.A. Dagle, V. Dagle, M.D. Bearden, J.D. Holladay, T.R. Krause and S. Ahmed. An Overview of Natural Gas Conversion Technologies for Co-Production of Hydrogen and Value-Added Solid Carbon Products, 2017
The catalytic decomposition of methane in molten metals represents a promising complementary methodology to water electrolysis for the production of CO2-free hydrogen. In this process, methane is introduced into a liquid, catalytically active molten metal and cracked, whereby the resulting solid carbon is transported to the surface of the metal bath. In order to be able to investigate fundamental issues surrounding the production of hydrogen in this strategically important research segment, the corresponding infrastructure is created in the form of a technical centre (Hydrogen Research Centre, HRC) at the University of Leoben in Austria. In this paper, the relevant equipment is explained in detail and the influence of the scale-up stages of the methane pyrolysis process up to demonstration scale on the products hydrogen and carbon is described. The demonstration plant planned at the HRC consists of different aggregates, which are necessary for a comprehensive investigation of various process parameters affecting methane pyrolysis in the metal bath. The central metallurgical unit is an induction furnace, which can be operated in a metallurgical vacuum and at pressures of up to 10 bar. A hot gas filter with heat exchanger is planned for the subsequent product flow treatment to separate the solid carbon produced during methane decomposition. By means of a membrane separator, the particle-free gas stream, which mainly consists of hydrogen and unreacted CH4, can be divided in order to enrich H2. Furthermore, by using a thermal afterburning system, it is possible to completely neutralise all of the products created in this process.
| SESSION: RecyclingTuePM1-R7 | 9th Intl. Symp. on Sustainable Materials Recycling Processes & Products |
| Tue. 28 Nov. 2023 / Room: Sunflower | |
| Session Chairs: Florian Kongoli; Juergen Antrekowitsch; Session Monitor: TBA | |
Slags from primary lead industry are well known as potential resource for zinc which is accumulated in the slag during lead smelting. At some of the smelters a subsequent fuming process is installed to recover zinc which is usually present in a range between 4 to 16 %.However, at many lead producers this is not the case and the slag is landfilled. Out of this, over the years, a huge number of dumps was generated worldwide. The Chair of Nonferrous Metallurgy at Montanuniverstaet Leoben has developed possible strategies to treat such slags in a way that zinc and lead can be recovered and the remaining mineral phase containing first of all typical slag components can also be utilized. These concepts allow a full remediation of a dumpsite or a zero waste treatment of slag from ongoing smelter operations.The present paper describes the reduction process which is performed under CO2-neutral conditions, utilizing either hydrogen or charcoal. Furthermore, possibilities for slag modification and optimization are explained, allowing a utilization of the slag in building and construction industry. Results from various test campaigns in lab- and technical scale are discussed.Finally, an overview of the worldwide potential and some process scenarios including economic considerations are presented.
References:
[1] Auer M., C. Wölfler and J. Antrekowitsch: Inflluence of different carbon content on reduction of zinc oxide via metal bath. Applied Sciences (2022), 12, 2, 4180
[2] Hanke G., J. Antrekowitsch, F. Castro and H. Krug: Maximizing the efficiency of by-product treatment by multi-metal recovery and slag valorization. Rewas 2022 – Developing tomorrow‘s technical cycles (2022), Anaheim, Kalifornien, USA, 201–211
[3] Leuchtenmueller M., C. Legerer, U. Brandner U. and J. Antrekowitsch: Carbothermic Reduction of Zinc Containing Industrial Wastes: A Kinetic Model, Metallurgical and Materials Transactions B: Process Metallurgy and Materials Processing Science (2021), 548-557
Rotary Kiln is a rotating cylindrical reactor that reduces the oxide feed minerals or dusts with carbon reductants and/or natural gas in order to extract a specific component from the feed by volatilization and produce a waste oxide material or to preliminary reduce the feed material into a pre-reduced one to be subsequently used in a specific reactor. Because of the specificity of these rotating reactors the number of shutdowns to clean the reactors are numerous and as such they constitute a big source of productivity loss. This work presents a unique control of process operations of rotary kilns, concentrating in one of the most difficult ones, the Waelz Process through the unique proprietary FLOGEN CONTOP design, decision making, control, optimization and automation system that made possible a considerable increase of the zinc recovery by volatilization and a drastic decrease of the numbers of shutdowns.
14:55: [RecyclingTuePM107] OSThe Concept of Industrial and Innovative Development of the Republic of Kazakhstan for 2021-2025 includes the development of production of rare and rare earth metals among the priority areas. The latter, unfortunately, is associated with the emissions of organic compounds into the environment. To avoid this, it is necessary to purify solutions of rare-metal production from organic pollutants.
Sorption with carbon sorbents of a novel type is considered to be the most effective way of removing organic impurities during the hydrometallurgy process of non-ferrous metals [1]. However, there are no data on the behavior of these sorbents in the hydrometallurgy of rare metals. Carbon sorbents active against the ions of rare, precious and heavy metals have been obtained from the waste of rice and coke production such as rice husk and special fine coke. It is known that activated carbons from rice husk are effective to remove organic pollutants [2-4]. But their production is associated with the formation of secondary waste.
The purpose of the current work is to use rice husk and special fine coke to generate a new selective composite sorbent and resource-saving high-temperature material for use in hydro- and pyrometallurgical sectors of industry.
Carbon and silica-containing components are isolated from the both waste. The carbon components are used to produce a composite sorbent. The silica-containing components are used to produce a high-temperature material. The combination of a finely dispersed rice husk carbon material with a large specific surface area and a more durable, meso- and macroporous special coke carbon material contributes to the formation of a carbon-carbon matrix when obtaining a composite sorbent. The combination of stoichiometric amounts of amorphous silicon dioxide isolated from rice husk, special fine coke ash and original rice husk is used to ensure the formation of highly refractory silicon carbide. The burning of rice husk contributes to the forming of a porous structure of the prepared material. The formation, on the one hand, of highly refractory phases and, on the other hand, of a porous system enhances the strength, durability and thermal insulation properties of the resulting refractory material.
So, rice husk and special fine coke (some of the most common waste types) are promising raw materials for creating a selective composite sorbent of a novel type. In order to ensure the complex processing of special fine coke and rice husk, it seems practical to use silica-containing waste from composite sorbent production mixed with raw rice husk to synthesize a resource-saving high-temperature material.
This research is funded by the Science Committee of the Ministry of Science and Higher Education of the Republic of Kazakhstan (grant number AP 19677767).
References:
[1] Yu.V. Surovikin, V.A. Likholobov, V.V. Sergeev, I.V. Makarov, Solid Fuel Chemitry 6 (2014) 47-56.
[2] Y. Deng, X. Wang, Y. Li, J. Shao, H. Yang, H. Chen, Sheng Wu Gong Cheng Xue Bao (Chinese Journal of biotechnology) 10 (2015) 1492-500.
[3] M. Akhtar, M.I. Bhanger, S. Iqbal, S.M. Hasany, Journal of Hazardous Materials 1 (2006) 44-52.
[4] S.L. Ng, C.E. Seng, P.E. Lim, Chemosphere 10 (2009) 1392-400.
Skin is the most vulnerable organ to different kinds of injuries due to its large surface and potential for exposure to biological, mechanical, thermal, and radiation factors. In this context, the demand for innovative biomaterials for chronic wounds, skin burns, or skin disease treatment is high [1].
Collagen is a consecrated biomaterial for different skin wound healing formulations like powders, creams, films, hydrogels, and microspheres, due to high biocompatibility and non-toxicity as compared to synthesis polymers [2]. Recent research reported the advanced efficiency of gelatin and collagen hydrolysate in wound healing as compared to native collagen [1], due to the more available peptides and binding sites for the regeneration mechanism in the wound healing process.
The presentation will explore the potential of gelatins of different origins extracted from bovine and donkey hides, rabbit skin or fish scales to be processes as collagen nanofibers with preserved bioactivity and high efficiency in skin restoration due to the scaffold structure with increased surface area-to-volume ratio as compared to gelatin [3-7].
The main properties of these gelatins such as dry substance, ash and protein content, conductivity, viscosity, and molecular weight will be presented in connection to spinnable properties in view of manufacturing collagen nanofibers for new biomaterials used in wound healing.
The electrospinning parameters for fabrication of wound healing mats based on gelatins of different origins will be presented and the influence of solvents will be highlighted. The antimicrobial properties were improved by adding active substances from essential oils to metal and oxide nanoparticles. Coaxial electrospinning was used for volatile essential oils encapsulation and slow release in interaction with skin wounds.
The properties of collagen nanofibers manufactured from different gelatins will be presented in connection with their specific structure and origin: size dimension and morphology (SEM), surface composition (EDX), antioxidant properties, phenol releasing, cytotoxic concentrations, in vivo biocompatibility, and antimicrobial properties.
Finally, the behavior of gelatin nanofibers as compared to gelatins to preservation treatments by different gamma radiation doses will be discussed.
Different gelatin nanofibers successfully fabricated from different raw materials showed the huge potential for biomaterials innovation as compared to the use of classical native collagen in skin wound healing.
References:
[1] Prelipcean, A.-M.; Iosageanu, A.; Gaspar-Pintiliescu, A.; Moldovan, L.; Craciunescu, O.; Negreanu-Pirjol, T.; Negreanu-Pirjol, B.; Mitran, R.-A.; Marin, M.; D’Amora, U. Marine and Agro-Industrial By-Products Valorization Intended for Topical Formulations in Wound Healing Applications. Materials 2022, 15, 3507. https://doi.org/10.3390/ma15103507
[2] Deaconu, M.; Prelipcean, A.-M.; Brezoiu, A.-M.; Mitran, R.-A.; Isopencu, G.; Matei, C.; Berger, D.Novel Collagen-Polyphenols-Loaded Silica Composites for Topical Application. Pharmaceutics 2023, 15, 312. https://doi.org/10.3390/pharmaceutics15020312
[3] Maria Râpă , Traian Zaharescu, Laura Mihaela Stefan, Carmen Gaidău,*, Ioana Stănculescu ,*, Rodica Roxana Constantinescu and Maria Stanca, Bioactivity and Thermal Stability of Collagen–Chitosan Containing Lemongrass Essential Oil for Potential Medical Applications, Polymers 2022, 14, 3884, https://doi.org/10.3390/polym14183884
[4] Maria Râpa , Carmen Gaidau2,* , Liliana Mititelu-Tartau , Mariana-Daniela Berechet , Andrei Constantin Berbecaru, Irina Rosca, Aurica P. Chiriac , Ecaterina Matei, Andra-Mihaela Predescu, Cristian Predescu, Bioactive Collagen Hydrolysate-Chitosan/Essential Oil Electrospun Nanofibers Designed for Medica lWound Dressings, Pharmaceutics 2021, 13, 1939, https://doi.org/10.3390/pharmaceutics13111939
[5] Ecaterina Matei, Carmen Gaidau, Maria Râpă, Laura Mihaela Stefan, Lia-Mara Ditu ,
Andra Mihaela Predescu , Maria Stanca , Mircea Cristian Pantilimon , Daniela Berechet , Cristian Predescu and Anamaria Mosutiu, Sustainable Coated Nanostructures Based on Alginate and Electrospun Collagen Loaded with Antimicrobial Agents, Coatings 2021, 11, 121, https://doi.org/10.3390/coatings11020121
[6] Ecaterina Matei, Carmen Gaidau2*, Maria Râpă1*, Roxana Constantinescu, Simona Savin, Mariana Daniela Berechet, Andra Mihaela Predescu, Andrei Constantin Berbecaru, George Coman, Cristian Predescu, Sustainable Rabbit Skin Glue to Produce Bioactive Nanofibersfor Non-Active Wound Dressings, Materials 2020, 13(23), 5388; https://doi.org/10.3390/ma13235388
[7] Maria Râpă , Carmen Gaidău*, Laura Mihaela Stefan, Ecaterina Matei, Mihaela Niculescu, Mariana Daniela Berechet, Maria Stanca, Cristina Tablet, Mădălina Tudorache, Raluca Gavrilă, Cristian Predescu, Ruxandra Vidu, New Nanofibers based on Protein By-Products with Bioactive Potential for Tissue Engineering, Materials 2020, 13(14), 3149; https://doi.org/10.3390/ma13143149
| SESSION: Biochar_CementTuePM2-R7 | 8th International Symposium on Sustainable Biochar, Cement and Concrete Production and Utilization |
| Tue. 28 Nov. 2023 / Room: Sunflower | |
| Session Chairs: Andrej Ivanic; Mauro Giorcelli; Session Monitor: TBA | |
Biochar is a carbonaceous material derived from the pyrolysis of biomass, which is often considered a waste material with the associated disposal problems. In this work will be summarises the latest research developments in biochar materials, a field that is gaining increasing popularity due to biochar's potential to replace carbon materials derived from non-renewable sources. The work explores emerging and innovative applications of biochar, covering all aspects of the field, from production [1] to applications, including details on the techniques used. Special attention is given to biochar as a material for composites and sensors [2]. The applications of biochar in the field of cement-based composites will also be discussed as it is expected that the cement industry will have a high demand for biochar in the coming years as biochar has proven to be an excellent substitute for both inert material and cement itself without altering the properties of the final composite.This work has been reported in the first book [3] to address the emerging applications of biochar as an innovative, versatile and renewable carbon-based material, going beyond its traditional uses in agriculture. The book is a valuable reference for all researchers in the field of biochar and carbon-based materials, including practitioners.
References:
[1] M.Bartoli, M.Troiano, P.Giudicianni, D. Amato, M. Giorcelli, R. Solimene, A. Tagliaferro, Applications in Energy and Combustion Science (2022), Elsevier
[2] A. Noori, M. Bartoli, A. Frache, E. Piatti, M. Giorcelli, A. Tagliaferro, Micromachines 11 (4), 339 (2020)
[3] A. Tagliaferro, C.Rosso, M.Giorcelli, “Bochar emergin applications”, IOP Science (2020) ISBN: 978-0-7503-2660-5
The concrete industry is one of the major consumers of natural resources. Sustainable development aims to find alternative resources that could decrease the concrete industry's adverse effects on the environment and contribute to preserving natural resources. Vast amounts of waste tires accumulated worldwide are recognized as a good supplement for natural aggregates in concrete [1]. Shredded rubber is generally used as a substitute for coarse aggregate, irregularly shaped crumb rubber is used as a fine aggregate, and powdered rubber can be used as a filler, binder, or fine sand in concrete [2]. Concrete with recycled rubber has many advantages over standard concrete, such as more excellent ductility, lower thermal conductivity, and better resistance to freezing and thawing [3]. However, mechanical strength is generally reduced when the natural aggregates in standard concrete are replaced by rubber.This study aimed to design load-bearing concrete in which fine aggregate was partially replaced by crumb rubber in the 5-20 % range by volume. Workability, compressive strength, density, dynamic modulus of elasticity, freeze-thaw resistance, and induced volume changes were comprehensively evaluated. The consistency of the rubberized concrete and the strength loss in the hardened state was compensated by adding a superplasticizer and silica fume. The results show that the modified concrete maintains its compressive strength and provides better freeze-thaw protection than standard concrete.
References:
[1] D. Bjegović, A. Baričević, M. Serdar, Durability Properties of Concrete with Recycled Waste Tyres, International Conference on Durability of Building Materials and Components, Porto, Portugal, 2011.
[2] E. Ganjian, M. Khorami, A.A. Maghsoudi, Scrap-tire-rubber replacement for aggregate and filler in concrete, Constr. Build. Mater. 23 (2009) 1828-1836.
[3] R. Siddique, T.R. Naik, Properties of concrete containing scrap-tire rubber – an overview, Waste Management, 24 (2004) 563-569.
This case study provides a holistic perspective on the emerging biochar production industry in Mexico, focusing on the industry as a whole rather than individual companies. The study explores the industry's initiatives to harness agricultural waste for sustainable biochar product creation, with shared objectives of boosting local economic development, addressing climate change, and capitalizing on carbon markets.Leveraging successful experiences in various emerging markets [2], the industry recognized the promise of biochar in supply chain innovation and systems optimization. Mexico, endowed with an ample supply of agricultural waste, emerged as a promising market. However, the challenge remained in familiarizing the market with biochar, an unfamiliar product in this context.The industry embraced a proactive approach by collaborating with farming organizations and local communities, aiming to garner support and introduce biochar to the Mexican market through consistent communication, education, and practical demonstrations.The study addresses the economic viability of biochar production in Mexico, driven by secure feedstock sources and anticipated revenue from carbon credits. The timeline for biochar production, its primary application in traditional agriculture, and ongoing experiments for efficiency optimization are presented as common industry practices.Biochar producers in Mexico are exploring non-agricultural markets [1], such as the construction sector, where biochar can enhance construction materials and reduce carbon emissions. Collaborations with industry associations and research institutions support these initiatives.The study discusses the projection of carbon credit revenue growth, on the expanding voluntary market and the increasing confidence in testing and data disclosure, which can boost biochar's financial sustainability.The report concludes with a set of recommendations for aspiring biochar producers, emphasizing the importance of securing feedstock, assessing local market potential, and conducting studies to foster industry growth..
References:
[1] [1] A. Bates, K. Draper, Burn Using Fire to Cool the Earth (2018) 61-69
[2] [2] David Lefebvre1, Samer Fawzy2,3, Camila A. Aquije 4, Biomass residue to carbon dioxide removal: quantifying the global impact of biochar (2023) 5-8
Research in biochar concrete has advanced considerably in the last 11 years or so. However, there is not yet any study examining the effects of biochar on the mechanical strength, net embodied carbon and effectiveness of accelerated carbonation of a relatively new and more sustainable type of concrete - limestone calcined clay concrete (LC3). This work represents a pioneering effort in examining the influence that rice husk- and wood-based biochar, produced at a temperature range of 300-500C, have on the aforementioned qualities of LC3-70, in which 30% of the Ordinary Portland Cement (OPC) was replaced with the combination of limestone, calcined clay and sustainable additives. Four types of additives were examined: rice husk ash (RHA), rice husk biochar, wood sawdust protected with titanium dioxide shell, and sawdust biochar. These samples were further categorized into two groups - those dosed with CO2 (i.e. accelerated carbonation at 20% over 24 hours) and those that were not dosed. It was observed that accelerated carbonation marginally increased the compressive strength (by 2-5%) of all samples containing the aforementioned sustainable additives at 28 days. However, all these samples had marginally lower strength than the control LC3-70, except when RHA was used (a 1.6% increased strength was observed). Furthermore, the compressive strength of the samples was not correlated to the quantities of calcium hydroxide produced from hydration of the binder. The most notable result in this study was that carbonation of these LC3 samples made them more resilient to heat - thermogravimetric analyses reviewed that carbonation substantially reduced the disintegration of the calcium carbonate (calcite) present in all the LC3-70 samples. This unusual phenomenon can be attributed to the production of additional amounts of alumina and silica gels in the matrix, which increased the internal thermal resistance of the microstructure of the LC3-70. These results show that substituting OPC in LC3-70 with the proposed sustainable additives does not affect the strength significantly, but it can reduce the net carbon emission of the concrete while rendering the mix more resistant against thermal disintegration. This special characteristic implies that our mixes can potentially be used as indoor lightweight non-structural panels that can be used to prevent fire from spreading within a particular confined indoor space.
| SESSION: Biochar_CementTuePM3-R7 | 8th International Symposium on Sustainable Biochar, Cement and Concrete Production and Utilization |
| Tue. 28 Nov. 2023 / Room: Sunflower | |
| Session Chairs: TBA Session Monitor: TBA | |
In recent years, biochar has been successfully investigated to improve the mechanical properties, internal curing, and CO2 capture of cementitious materials [1]. Thus, the aim of this work was to study the sensing ability of commercial biochar (Nera biochar) made from certified wood wastes as a strain sensor in mortar samples.The as-received material was first characterized by laser granulometry, X-ray diffraction, x-ray fluorescence and scanning electron microscopy. Later, the biochar particles were manually ground and sieved at 125 microns with a steel mesh. The passing fraction was first dispersed in distilled water using a bath sonicator and then, added to a commercial resin for restoration (Primal B60 from Rohm & Haas, a copolymer of ethyl acrylate/methyl methacrylate) under magnetic stirring. Multiwalled carbon nanotubes (CNTs, Nanocyl 7000) were also used to increase the sensitivity of the sensors because of their higher aspect ratio. Different compositions were investigated: pure biochar, 85% biochar/15% CaCO3, 80% biochar/20% CaCO3, 65% biochar/15% CaCO3/20% CNTs and 60% biochar/20% CaCO3/20% CNTs. Two stainless steel mesh (1 × 2 cm2) were manually inserted as electrodes into mortar prisms (4 × 4 × 16 cm3) prepared with standard sand immediately after casting and vibrating (1:2 water to cement ratio and 3:1 sand to cement ratio). The samples were demolded after 24 hours and cured under water for 28 days. After drying, the sensing materials were finally painted by brush on the cementitious samples (strip of 1 cm in width between the two stainless steel electrodes at a distance of about 10 cm). The prisms were tested in three-point bending, and the sensing films were alimented with a 1 V AC current at 1 kHz frequency using an impedancemeter (Hioki 3301). The change in the impedance value was monitored during mechanical testing. The measurements were first done on samples with a certain humidity content and then on fully dried ones. The best results were obtained with the sensing film containing 60% biochar/20% CaCO3/20% CNTs, which showed a 23% change in the impedance value under a force of 2000 N.
References:
[1] S. Gupta, J.M. Tulliani, H.W. Kua, Carbonaceous admixtures in cementitious building materials: Effect of particle size blending on rheology, packing, early age properties and processing energy demand, Science of the Total Environment, 807 (2022) Article number 150884
| SESSION: MineralWedAM-R7 | Torem International Symposium (8th Intl. Symp. on Sustainable Mineral Processing) |
| Wed. 29 Nov. 2023 / Room: Sunflower | |
| Session Chairs: Marcos De Campos; Session Monitor: TBA | |
Electroflotation is a potencial and suitable procedure to be well-thought-out alternative for the mineral processing development. This electrochemical technique is capable of float fine particles, using micro-bubbles oxygen and hydrogen with diameters smaller than 100 μm generated from the electrolysis of aqueous solutions [1,2,3]. Another important factor that has been studied is the use of a biorreagent in the concentration of minerals [4]. Research in biotechnology indicates that biosurfactants can be used to replace chemical surfactants because they offer functional characteristics, such as negative electric charge and hydrophobicity, and have low toxicity and higher degradation capacity than surfactants [5]. In this way the aim of this work was to evaluate the electroflotation of fines particles of an itabiritic iron ore using a biosurfactant extracted from Rhodococcus opacus strain. The tests were carried out with an iron ore in a specific particle size range of -38 + 20 μm containing 77,12% Fe2O3 and 22,65% SiO2. The assays were conducted in a modified Partridge-Smith binary electroflotation cell. The parameters used in these tests were iron ore mass (1g), agitation (500 rpm), conditioning time (5 min), flotation time (10 min), electrolyte concentration (Na2SO4 - 0.20 mol/L) and current density around 16mA/cm2. Moreover, the pH and biosurfactant concentration were respectively in the range of 3 to 11 and 50 to 800mg/L. The results of the interaction study indicated a possible interaction of the biosurfactant with hematite. After conditioning of the hematite with the biosurfactant, the spectrum (FTIR) showed characteristic functional groups of the biosurfactant (NH, CH2, C=O, COO and PO2-). The measurements of zeta potential suggest a possible electrostatic interaction between the hematite and the biosurfactant, by shifting the isoelectric point from 5.3 to 3.5. Contact angle measurements suggest that after interaction, hematite may have become more hydrophobic, changing the contact angle from 40° to 60°. According to the surface tension analysis, a reduction in surface tension from 71 mN/m to 40 mN/m was demonstrated in the presence of 25 mg/L biosurfactant. The electroflotation experiments validated an encouraging form of hematite recovery. The best results occurred at pH 3, this behavior can be attributed to electrostatic interactions that occur in this pH range. The increase of the biosurfactant concentration favored metallurgical recovery and the iron grade, this behavior remained up to 300 mg/L, above this value occurred a decline probably caused by the formation of micelles. The maximum metallurgical recovery was 80% and the iron content 59%.
References:
[1] HACHA, R. R., MERMA, A. G., COUTO, H. J. B., TOREM, M. L. Measurement and analysis of H2 and O2 bubbles diameter produced by electroflotation processes in a modified Partridge-Smith cell. Powder Technology, 342, 308-320, 2019.
[2] FARROKHPAY, S. et al. Flotation of fine particles in the presence of combined microbubbles and conventional bubbles. Minerals Engineering, v. 155, p. 106439-106445, ago. 2020
[3] LIU, An; FAN, Pan-Pan; HAN, Feng; HAN, Hua; LI, Zhi-Hong; WANG, Huai-Fa; FAN, Min-Qiang. Effect of electroflotation on quartz and magnetite and its utilization on the reverse flotation of magnetic separation concentrate. Minerals Engineering, [S.L.], v. 175, p. 107292, jan. 2022
[4] DWYER, R. et al. Bioflotation and biofloculation review: microorganisms relevant for mineral beneficiation. Minerals Processing and Extractive Metallurgy, 121 (2). p. 65-71, 2012.
[5] CAMARATE, M. C., MERMA, A. G., HACHA, R. R., TOREM, M. L. Selective bioflocculation of ultrafine hematite particles from quartz using a biosurfactant extracted from Candida stellata yeast. Separation Science and Technology, 57(1), 36-47, 2022.
Mining dams tailing are the waste of mining processes that pollute and badly affect the environment around the mining sites. To find a sustainable solution of mining tailing a new technology has been developed to process the tailing to produce special bricks that can be used for the construction replacing the usual high-cost bricks. This paper will present this technology and its potential to turn mining tailings into special bricks with goods properties and considerable low cost.
12:25: [MineralWedAM03] OS KeynoteProducing concentrates from graphite ores with the highest possible grade of graphite flakes is an important goal to increase the efficiency of the use graphite ores in the framework of sustainability. Participating in Balama Graphite Project from Syrah Resources Company in Mozambique, Fundação Gorceix, through its Mining and Metallurgy Department carried out initial characterisation of graphite ores, carried out bench test works in laboratory and pilot plants using a large sample of graphite ore provided by the company. As a result, it was possible to obtain concentrates with a high grade of graphite flakes, above 93%, compatible with market demand for use in electric car batteries. The subsequent work included the definition of the process flowsheet adopted for the characteristics of the current industrial exploitation in Mozambique. This paper will present this work and the results achieved.
12:50: [MineralWedAM04] OS KeynoteGenerating high iron containing concentrates is an important goal to ensure the efficiency of their Direct Reduction subsequent treatment in the framework of sustainability. This was the main objective of Fundação Gorceix when undertaking, through its Mining and Metallurgy Department two major industrial iron ore projects: (1) BAMIN's Pedra de Ferro project, which plans the production of 25 million tons of pellets per year, in the State of Bahia, outside the Ferriferous Quadrangle, with an expected start up in 2025 and (2) Compact Ores Arcelor Mittal project–Serra Azul Mine, in Minas Gerais state. During the course of the projects a complete research investigation was carried out including mineralogical characterization, bench scale tests and pilot plant studies. The major result of the work was the generation of a premium concentrate for Direct Reduction with iron content as high as 66.5% and with a high competitive metallurgical recovery. The industrial processing flowsheet in a compatible industrial metallurgical complex was also developed. This paper will present this work and the results achieved.
| SESSION: MineralWedPM1-R7 | Torem International Symposium (8th Intl. Symp. on Sustainable Mineral Processing) |
| Wed. 29 Nov. 2023 / Room: Sunflower | |
| Session Chairs: Fernando Jose Gomes; Session Monitor: TBA | |
The market of rare-earths is reviewed. The rare-earth market is driven by three main applications: permanent magnets, luminescent phosphors and catalysis. The market is currently driven by iron based rare-earth magnets. Luminescent phsophors are a relevant application, but in this case the rare-earth acts as a dopant and the demand volume is not so high as in rare-earth magnets. Cheaper rare-earths as cerium and lanthanum are used in catalysis. Lanthanum is used for oil cracking, for stabilizing zeolites . Other applications are also reviewed. Yttrium demand increased recently, probably due to increased production of yttria stabilized zirconia.Electrical cars use typically 1-2 kg of permanent magnets of the NdFeB type, based on the NBd2Fe14B, with partial replacement of Nd by Pr, and by Dy and Tb to increase the operation temperature. In many applications, there is the possibility of replacement of NdFeB magnets by hard ferrites as Sr2Fe12O19 or BaFe12O19. However, for electric cars, NdFeB-type magnets are preferrable because they increase the machine efficiency. Many rare-earth extraction projects were recently announced in Brazil. One of the main drawbacks is the lack of technology for rare-earth concentration, and also for rare-earth oxide separation. Here, it is discussed the roadmaps to be followed to overcome such problems. China developed better technology for rare-earth oxide separation [1], and this possibly is the reason for the Chinese leadership in the rare-earth market.Ores containing rare-earth are very abundant along the globe. The main problem is cheap technology for rare-earth concentration and also for rare-earth oxide separation. Brazil has potential for becoming a significant producer of rare-earths, by using the tailings of niobium and tin mines. However, proper technology has to be developed for using these tailings.
References:
[1] https://newsen.pku.edu.cn/news_events/news/people/9479.html
Producing concentrates from spodumene ores with the highest possible grade of lithium is an important goal to increase the efficiency of the use lithium ores in the framework of sustainability. Participating in Brazilian society project, Fundação Gorceix, through its Mining and Metallurgy Department carried out initial characterization of lithium ores, carried out bench test works in laboratory and pilot plants using a sample provided by the company. As a result, it was possible to obtain concentrates with a high grade of lithium, above 5,7%, (target 6,0%) compatible with market demand. The subsequent work included the simplification and proposition of the new industrial process flowsheet (flotation of micas/feldspathe has been excluded). This paper will present this work and the results achieved.
14:55: [MineralWedPM107] OSThe decreasing of CO2 emissions on the ironmaking industries is a challenging issue. The massive use of granulated biomass and biogas in the iron ore sintering process are promising technological solutions to mitigate the environmental impacts on the steel plant. We focused on the development of a computational tool to analyze and suggest new practices for the sintering process using an integrated modeling approach by applying the multiphase and multicomponent theory. New phases, chemical species and rate equations are included. The model predictions were confronted with industrial data showing good adherence. New scenarios for utilizing the combined technologies of granulated biomass and biogas injection are investigated. The model predictions indicated that the high performance of the process with suitable sinter quality could be achieved. The sintering process fully operating with renewable energy sources is demonstrated.
References:
[1] J. A. Castro, E. M. Oliveira, M. F. Campos, C. Takano and J. Yagi: Journal of Cleaner Production 198(2018), 654. https://doi.org/10.1016/j.jclepro.2018.07.082
[2] J. A. Castro, N. Nath, A. B. França, V. S. Guilherme and Y. Sasaki: Ironmaking & Steelmaking 39(2012), 605.
[3] J. A. Castro, C. J. L. Pereira, V. S. Guilherme, E. P. Rocha and A. B. França: J. Mater Res Technol, 2 (2013), 323. http://dx.doi.org/10.1016/j.jmrt.2013.06.002.
A rapid microwave preparation method that is a combination of alkali fusion and acid digestion (4.5 h turn-around time) was developed for the determination of REEs (Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Eb, Tm, Yb and Lu) and selected non-REEs ((Ba, Ca, Co, Cu, Fe, Mn, Ni, Sr, Th, Ti, U, V, Zn, Zr) by inductively coupled plasma optical emission spectrometry (ICP-OES). Uranium and Th, although investigated could not be determined by ICP-OES. The aim of this method was to provide cost effective REE and selected non-REE analysis within an acceptable turn-around time to industry. The microwave method of preparation was twin streamed with a manual method entailing alkali fusion and open vessel wet acid digestion on a hotplate. The data from both methods demonstrated comparable recoveries of REEs and non-REEs (between 95 % and 105 %) with an LOQ of 10 mg L-1. The methods were validated using two certified reference materials, CGL 124 and CGL 111.
| SESSION: MineralWedPM2-R7 | Torem International Symposium (8th Intl. Symp. on Sustainable Mineral Processing) |
| Wed. 29 Nov. 2023 / Room: Sunflower | |
| Session Chairs: Marcos De Campos; Session Monitor: TBA | |
This paper asks two fundamental questions: 1) How can we have international cooperation on climate mitigation in a world of geo-political confrontation? 2) Is the impact of the international trade system on the environment only negative?By doing so, the paper takes a comprehensive approach over how the trading system can help mitigate climate change and enhance sustainable energy. The paper brings together a top-down and bottom-up approach to the governance of sustainability. Furthermore, it analyzes two of the most relevant global regulatory trends in recent international trade agreements, namely climate change and sustainable energy.The paper takes the novel approach of bringing together law, international political economy (IPE) and international relations (IR) to explain sustainable energy as an academic discipline. It is interdisciplinary and inter-sectoral, combining an analysis of international trade and sustainable energy from the perspectives of law, IPE, and IR—an approach that makes the paper ground-breaking and unconventional. It applies methods of legal analysis, namely a comprehensive analysis of treaties, case law, and academic writings from scholars as well as literature from other social science disciplines, such as IR and IPE, to help explore the challenges addressed.This paper challenges the view that trade’s only impact on the environment is negative. It takes the unconventional view that the trading system goes beyond benefiting the economy and society in that it can also contribute to environmental protection, with a specific focus on decarbonization. In this sense, this paper proposes a paradigm shift in how we approach trade and develops a new theory based on the triple benefit of trade. This paper incorporates the current trend of bottom-up, rather than top-down, solutions to today’s global challenges. It: • Investigates how trade agreements may be more effective legal instruments than environmental agreements for environmental-protection purposes—a possibility that is both counter-intuitive and surprising;• Identifies opportunities to promote sustainable energy and environmental protection in future trade agreements; and• Explores the potential role of citizens in trade policy the same way prosumers are the new actors on the energy market towards the achievement of energy transition via energy decentralization and democratization. This approach shifts the paradigm from a top-down to a bottom-up perspective in sustainability governance.
16:25: [MineralWedPM210] OSEconomic recovery of REEs is recognized as one of the greatest challenges of industrial inorganic separation. This challenge originates from the unique mineralogy, occurrence, and physicochemical properties of REEs. Amongst the identified 20 critical raw materials for the entire global economy, the rare earth elements (REE) have the highest risk of secure supply issues. REE are a group of 17 elements comprising 15 lanthanides plus Yttrium (Y) and Scandium (Sc). These elements are strategic and critical for both green-tech (solar/fuel cells, electric vehicles, wind turbines, low emission engines, high-strength magnets, energy-efficient lighting) and high-tech (electronic and electric devices, hard disk drives, advanced alloys, catalysts). REE are also used by the defence sector in precision-guided munitions, smart bombs, sonars, and radars. The state-of-the-art of industrial REE extraction is to concentrate REE minerals using froth flotation aided by physical separation methods such as multi-gravity, magnetic and electrostatic techniques. The concentrate is then treated with a mineral acid to leach out REE, followed by further purification using a hydrometallurgical method, typically solvent extraction. Unfortunately, both froth flotation and solvent extraction are the antitheses of green chemistry, which severely limits their future in the 21st century. However, green surfactants produced from renewable sources or by bioprocesses offer important benefits compared to the conventional (petroleum-based) counterpart, such as biodegradability, better recyclability, and non-toxicity. Emerging greener approaches to make REE extraction more environmentally acceptable are presented and discussed, including their advantages and limitations with respect to conventional REE extraction methods. An alternative cutting-edge foam flotation separation method, a proposed hybrid of froth flotation and solvent extraction, (where the organic solvent is replaced by air, the surfactant acts as an extracting agent, and the stripping step is replaced by physical collection of the cation-enriched foam). This technology is environmentally more sustainable than the conventional and emerging methods of REE extraction.
16:50: [MineralWedPM211] OSSodium cyanide (NaCN) is a solubilizer that improves gold uptake in phytomining [1]. However, concerns have been expressed about the persistence of this adjuvant and their associated detrimental repercussions for environment. Therefore, evaluating the persistence of residual CN in the remained substrates is relevant [2]. In order to assess the loss of CN in a gold phytoextraction process with Helianthus annuus L. (sunflower) on a gold mining waste. Pots containing 3.5 kg of substrate were prepared for this study. Sunflower plants were cultivated in a homemade greenhouse. Temperature range was 24-38° C and environment humidity range was of 40-60%. Twelve weeks after seeding, all containers were treated with a dose of 250 mg.kg-1 of NaCN in solution. Seven days later, plants were harvested. Samples with 30 g of substrate were obtained in all containers at time of plant harvest 7, 14, 21, 28, 35, and 42 days after harvest. Samples were prepared and analyzed in laboratory to determine the total content of CN. We found that 7 days after the application, the CN total concentration was reduced in a 91.7% for containers without plants and 90.8%, for containers with plants, respectively. Plants cultivated in mine waste produces a small increase in loss of adjuvant[3]. These results suggest that concerns about CN could be reduced, because it is enough one week of natural intemperization processes, to reduce significantly the CN in soil. This study could be applied to the mining waste management and the environmental impact of CN application in the gold mining industry.
References:
[1] Wilson-Corral, V., et al., Gold concentrations in mine tailings. Potential application of phytomining, in Ecology in an Era of Globalization: Challenges and Opportunities for Environmental Scientist in the Americas. 2006, ESA. p. 156-157.
[2] Ebbs, S.D., et al., Initial loss of cyanide, thiocyanate, and thiosulfate adjuvants following amendment to an oxidic gold ore. Minerals Engineering, 2011. 24(14): p. 1641-1643.
[3] Cañón-Cortázar, R.G., L.M. Avellaneda-Torres, and E. Torres-Rojas, Associated microorganisms to the nitrogen cycle in soils under three systems of use: potato crop, livestock and páramo, in Los Nevados National Natural Park, Colombia. Acta Agronómica, 2012. 61(4): p. 371-379.
Mining industry annually generates millions of tons of waste that needs to be adequately managed in order to prevent environmental risks. Assisted phytoremediation with chelating agents has been proposed as a viable alternative for cleaning of Cu-contaminated soils [2]. Particularly, ethylenediaminedisuccinic acid (EDDS) has been suggested as an option because it has shown the ability to increase the bioavailability of metals such as Cu [3]. In assisted phytoremediation EDDS has been characterized by a short half-life in the environment [4], and as not leaching chemical. In this study, the efficiency of 4 doses of EDDS in the phytoremediation of Cu lodged in a mine waste substrate was evaluated. Helianthus annuus L. (sunflower) plant species was cultivated in homemade greenhouse for 10 weeks in a previously prepared mining waste substrate. After this period, 4 treatments (0, 0.2, 0.4 and 0.8 mMol/kg) of EDDS were applied to the substrate to improve the bioavailability of Cu. One week later, plants were harvested, prepared, and analyzed by atomic absorption spectrometry to determine Cu concentrations in plant tissue. According to results, the dose of 0.8 mMol/kg showed the highest efficiency. In this case, the translocation factor was equivalent to 0.65, which was 116% higher than recorded in the plants used as control (0.30). In addition, the Cu bioconcentration factor, in the aerial part of plant, for the dose of 0.8 mMol/kg was 8.32, which is 407% higher than recorded in the aerial part of the controls (1.64). Regarding the underground part of the plants, the bioconcentration factor occurred in the dose of 0.8 mMol/kg was 12.85, which was 137% higher than registered in the underground part of the plants used as a control (5.42). Our results suggest that a phytoremediation process of mine waste substrate, assisted with EDDS, could be viable using H. annuus. This study provides useful data for the design of efficient strategies in Cu phytoremediation processes, for waste substrates generated by the mining industry.
References:
[1] Helser, J., E. Vassilieva, and V. Cappuyns, Environmental and human health risk assessment of sulfidic mine waste: Bioaccessibility, leaching and mineralogy. Journal of Hazardous Materials, 2022. 424: p. 127313.
[2] Ju, W., et al., Co-inoculation effect of plant-growth-promoting rhizobacteria and rhizobium on EDDS assisted phytoremediation of Cu contaminated soils. Chemosphere, 2020. 254: p. 126724.
[3] Wang, X., et al., Biodegradation and effects of EDDS and NTA on Zn in soil solutions during phytoextraction by alfalfa in soils with three Zn levels. Chemosphere, 2022. 292: p. 133519.
[4] Tandy, S., et al., Extraction of Heavy Metals from Soils Using Biodegradable Chelating Agents. Environmental Science & Technology, 2004. 38(3): p. 937-944.
| SESSION: MineralWedPM3-R7 | Torem International Symposium (8th Intl. Symp. on Sustainable Mineral Processing) |
| Wed. 29 Nov. 2023 / Room: Sunflower | |
| Session Chairs: Fernando Jose Gomes; Session Monitor: TBA | |
Science and Technology as described in the FLOGEN Sustainability Framework is the first and most efficient and important pillar to achieve sustainability. The National Center on Complex Processing of Mineral Raw Materials of the Republic of Kazakhstan as the largest scientific institution in the mining and metallurgical industry of the Republic of Kazakhstan and Central Asia countries has used the scientific research and developed new technologies to solve the global problems of traditional deposits depletion, treatment of off-grade and man-grade raw materials, achievement of integrated processing of primary minerals, and achieving the transition to deep and ultra-deep horizons in order to reduce environmental pollution and improve the quality of life of current and future generations. This presentation will describe some of these achievements with special emphasis on the following developments.A new technology that produces an alloy of two incompatible metals – iron and aluminum that simultaneously deoxidizes and inoculates in steel. Developed as part of "Kazakhstani Alloy" project in cooperation ThyssenKrupp (Germany) and Posco (South Korea) the technology has been patented in numerous countries. A new technology for thermomagnetic beneficiation and dephosphorization of high-phosphorous brown iron ores and concentrates which for the first time treats low-quality brown iron ores and produces a prime concentrate with an iron content of 65% and phosphorus content of no more than 0.25% that fully meets the requirements of metallurgical treatment in terms of chemical and mineral compositions, as well as physical properties.An unusual new technology has been proposed to obtain ferrosilicon with a low content of aluminum and titanium based on the processing of large-tonnage renewable raw materials unconventional for metallurgy - rice husk. A new technology for processing of low-quality, complex oxidized and mixed gold-copper ores with poor gold content based on which more than 20 Kazakhstani and foreign gold processing enterprises have been created. Combined beneficiating and hydrometallurgical technologies for processing low-grade copper-containing raw materials have been introduced at a number of domestic deposits. A new technology and pilot-plant production facilities for the production of stable isotope of osmium, iodine and their compounds that put Kazakhstan on the top 3 countries leading in the production of stable isotopes.New safe mining technologies, the latest innovative automated systems for positioning people and equipment, managing a geotechnological complex at open pit (Jetygara) have been implemented at a number of mines in Kazakhstan.The above new technologies are added to the existing Kazakistani technology for lead smelting, using the KIVCET flash-cyclone-oxygen-electric smelting method, that has been implemented in Bolivia, Italy, Canada, and China that overall, today smelt a tenth of the world's primary lead output.The implementation of these technologies has been made possible by a volume of investments of more than $3.5 billion and the annual output of commodity products at these enterprises at today's prices exceeds $4.0 billion while the total amount of investments in new production facilities based on them in the next 2-3 years will reach $2-2.5 billion. These success stories have tremendously helped achieving sustainability through science and technology and it is an important confirmation of the role of science and technology as forecasted by FLOGEN Sustainability Framework
18:20: [MineralWedPM314] OS KeynoteThe industrial development, globalization and increased population in the world have significantly affected the food production and food consumption in such ways that negatively impact the ecosystem and the health of the people. Most of the current food systems are not sustainable, nor resilient. Many households in the developed world do not cook their food, traditional cooking practices are vanishing from the family kitchens, and people are shifting towards ultra-processed ready-to-eat food choices with poor nutritional profiles. Regardless of the fact that there is plenty of food for consumption, these nutrient-poor food choices have become the number one cause of health issues in the modern world, such as obesity, diabetes, and other metabolic syndrome problems, as well as cancers and cardiovascular diseases, which is an enormous health and economic burden for every society. The developing countries are also facing the problem of “double burden” – a combination of under-nutrition and non-communicable diseases.Sustainable and resilient food systems can be the key factors towards a more sustainable planet and the well-being of all people. Such food systems offer not only reduced environmental pollution, but have the potential to end the hunger and yield healthier nations. A good representative of a resilient food system is the Mediterranean diet – an affordable diet with numerous science-backed health benefits, which is easily transferable to regions outside the Mediterranean basin. Mediterranean diet (MD) refers to the dietary patterns and the lifestyle habits of the people living around the Mediterranean Sea. MD is mainly a plant-based diet, which emphasizes abundant consumption of seasonal and local unprocessed (or minimally processed) fruits, vegetables, whole grains, nuts, legumes, seeds, herbs and spices, followed by moderate consumption of fish, poultry, eggs, dairy and fermented products. Extra virgin olive oil is the main source of healthy fats, while the consumption of red meat products and products with refined sugars is low. The food is consumed together with family and friends, which along with the other social aspects and the sense of community are integral parts of the Mediterranean way of living. Numerous studies have associated the MD with a reduced risk of cardiovascular diseases, cancers, dementia, Alzheimer’s disease, Parkinson’s disease and others, but also have linked it to improved longevity and quality of life of the people who adhere to this diet.Due to its importance, MD was recognized as an intangible cultural heritage by UNESCO in 2010, where it is defined as “a set of skills, knowledge, rituals, symbols and traditions concerning crops, harvesting, fishing, animal husbandry, conservation, processing, cooking, and particularly the sharing and consumption of food”.In this study, different aspects of the MD will be considered with an emphasis on the nutrient-dense, antioxidant, and anti-inflammatory character of the diet, which are responsible for the diet’s health benefits. The resiliency of the diet, which originally was “a diet of the poor”, its environmental impact and the potential this diet holds for the future of the mankind and the planet will be discussed, too.
References:
[1] 1. Trajkovska Petkoska and A. Trajkovska-Broach, Mediterranean Diet: A Nutrient-Packed Diet and a Healthy Lifestyle for a Sustainable World, Journal of the Science of Food and Agriculture, 2020. DOI: 10.1002/JSFA.10907.
[2] 2. Trajkovska Petkoska, A.T. Broach, Sustainable food systems and healthy diets: the case of mediterranean diet, Acta hort regiotec, 24, (2): 110–118. 2021.
[3] 3. Trajkovska-Broach A. and Trajkovska Petkoska A. Mediterranean Diet Ingredients: Their Antioxidant and Anti-Inflammatory Potential. Austin J Biotechnol Bioeng. 2021; 8(2): 1114.
[4] 4. Trajkovska-Broach A. and Trajkovska Petkoska A. Mediterranean Herbs, Spices and Medicinal Plants – Natural Therapeutics and Rich Sources of Bioactive Compounds, JSFA Reports, 2023.
[5] 5. Trajkovska Petkoska, Can We Solve the Problem of Global Syndemic? Mediterranean Diet as a Potential Solution, Acta Scientific Nutritional Health, 5.2 (2021): 137-145.
| SESSION: MineralThuAM-R7 | Torem International Symposium (8th Intl. Symp. on Sustainable Mineral Processing) |
| Thu. 30 Nov. 2023 / Room: Sunflower | |
| Session Chairs: Marcos De Campos; Session Monitor: TBA | |
Bioparticles, like other biological objects, are characterized not only by different biological properties, but also purely physical. Physical parameters can be include their mass, speed of movement, mechanical, electrical, magnetic characteristics, etc. Since the biosystems like viruses travel much less than the speed of light, are small in size and mass, vibrate with a certain frequency relative to a fixed coordinate systemSpectroscopic methods have the characteristic of providing fast results and reliable information related to the composition of the samples. The studies presented have shown promising results in a field of science that needs to be better explored. It has been shown that multivariate analysis techniques are of great importance to analyze spectroscopic data, providing the potential to identify and classify biological samples.[1-3]. We do hope that with advancement in this field of study, spectroscopic methods and tools will be used in bio medicine in the nearest future. Methods of light therapy of different diseases based on estimation of EM field characteristics and resonant wave ranges based on computer simulation of nanobioparticles characterization will be widely implemented, and possibility of determination of resonant (own) frequencies of entire system of molecules including virions will be a key point for that. Recent frontiers in technology are exploring the possibility of using external excitations to vibrate a virus to its death. The genetic material of virus is DNA/RNA enclosed within the protective protein shell (Capsid). Every cell in human body has a natural tendency to vibrate at frequency known as the natural frequency, and so the virus. Natural frequency values of these vibrations are very high compared to healthy cells, and depend on the molecular structure and differ from virus to virus.In our opinion the concept and relevant methods of resonance therapy will be basis of different viral deceases treatment in the nearest future of practical medicine.
References:
[1] Kervalishvili P., Bzhalava T, Computer Simulation Study of Oscillation Mechanisms and Physical Properties of Nanosized Biostructures, Published in book: Innovative Smart Healthcare and Bio-Medical Systems, CRC Press – Taylor and Francis, New York, 2020, Chapter 6, 8 pages.
[2] Tamar Berberashvili, Paata Kervalishvili. Experimental Methods of Investigation of Vibrational Properties of Nanobioobjects. The international scientific conference: Modern research methods of bionanoagents, RMB-2021, Batumi, Georgia, 24-26 November, 2021.
[3] Kervalishvili P. Study of Vibrational Properties of Viral Particles by Computer Modeling. Egyptian Computer Science Journal Vol. 45 No.2 May 2021, pp 44-65. ISSN-1110-2586
The convergence between quantum materials properties and prototype quantum devices is especially apparent in the field of 2D materials, which offer a broad range of material’s properties, high flexibility in fabrication pathways and the ability to form artificial states of quantum matter. Along with the quantum properties and potential of 2D materials as solid- state platforms for quantum- dot qubits, single- photon emitters, superconducting qubits and topological quantum computing elements it is necessary to select the best method of preparation spinqubit nanosystems [1].Leptons are fermions - particles with ½ and they are an important part of the Standard Model. Following the spin-statistics (spin-communication theorem) - theorem which states that one fermion can exist in a given quantum state and no two leptons of the same species can be in the same state at the same time lepton can have only two possible spin states - up or down. The charged lepton is the electron; the next lepton to be observed was the muon, which was classified as a meson at the time. After investigation, it was realized that the muon has not the expected properties of a meson, but rather behaved like an electron, but with higher mass. Another lepton the first neutrino, the electron neutrino, was proposed in order to explain certain characteristics of beta decay.When we are choosing the particles for quantum computing we should consider that the candidate for a qubit generally needs to have the quantum properties of superposition and entanglement. There are also the main technical requirements of quantum computation which are: scalable physical systems with well characterized qubits (Zeeman Splitting); long decoherence time higher than gate operation one; existence of qubits at the ground state; set of quantum gates; measurement capabilities, etc. Leptons – fermions (electrons, protons, neutrons, muons, tauon and even neutrinos) as we know have that kind of properties. Concerning the photons – bosons particles with frequency-dependent energy collecting into the same energy state (Bose-Einstein condensation), they also could acting as a qubits because of polarization effects they characterized.[2,3]. The usefulness the other boson particles as quantum information carriers is the very interesting task current and future research works.
References:
[1] P. Kervalishvili. Nuclear spin based model of quantum information system. Book of abstracts of International conference of Nanosensory Systems and Nanomaterials, June 6-9, 2013, EU-ISTC-GTU, Tbilisi, Georgia. 2013, p. 28-3
[2] Paata Kervalishvili. Photons, InformationTransfer and Speed of Light (Invitrd Lecture), International Conference eRA -7 The Synenergy Forum, TEIPIR, Athens, Greece, 2012.
[3] Paata J. Kervalishvili, Quantum information technology: Theory and applications. Published in: IEEE Seventh International Conference on Intelligent Computing and Information Systems (ICICIS), IEEE Xplore: 04 February 2016, DOI: 10.1109/IntelCIS.2015.7397187, Publisher: IEEE. 15p.
Due to the current climate crisis, growing social inequities, and continued exploitation of the environment and its inhabitants, there is a dire need to incorporate education for sustainability (EfS) into mainstream education globally. STEM education is a popular educational initiative that has been integrated into curricula worldwide, which has some overlap with the pedagogies as EfS. A scoping literature review was conducted to examine the parallels between STEM education and EfS pedagogies in K-12 education. A total of 35 articles from 2012 to 2022 were reviewed. When comparing both sets of literature, the use of digital technology was a top pedagogical practice in both STEM and EfS. While design-based instruction was a common element of STEM education literature, it was only found in one of the EfS studies. Digital-technology based instruction was the most common pedagogy in the EfS literature followed by inquiry-based instruction and collaborative methods. Future research can be conducted in these areas to examine educator effectiveness at integrating EfS and STEM education by using these areas as bridges between the educational initiatives, allowing EfS to become more mainstream in K-12 education globally.
References:
[1] P21 Partnership for 21st-century Learning. (2019). Framework for 21st-century Learning Definitions. Battelle for Kids. https://static.battelleforkids.org/documents/p21/P21_Framework_DefinitionsBFK.pdf
[2] UNESCO. (2017). Education for Sustainable Development Goals Learning Objectives. https://www.iau-hesd.net/sites/default/files/documents/247444e.pdf
[3] Martin-Paez, T., Aguilera, D., Perales-Palacios, F. J., & Vilchez-Gonzalez, J. M. (2019). What are we talking about when we talk about STEM education? A review of literature. Science Education, 103(4), 799–822. https://doi.org/10.1002/sce.21522
[8] McLoughlin, E., Butler, D., Kaya, S., & Costello, E. (2020). STEM education in schools: What can we learn from the research? (ATS STEM Report #1). Dublin City University. https://doi.org/10.5281/zenodo.3673728
[9] Corres, A., Rieckmann, M., Espasa, A., & Ruiz-Mallen, I. (2020). Educator competences in sustainability education: A systematic review of frameworks. Sustainability, 12(1958). http://dx.doi.org/10.3390/su12239858
[10] Redman, A., & Wiek, A. (2021). Competencies for advancing transformations towards sustainability. Frontiers in Education, 6(785163), 1–11. https://doi.org/10.3389/feduc.2021.785163
Over the past decade, there have been increasing concerns about climate change[1]. This phenomenon affects various aspects of society. In this paper, we examine the nexus between climate change, sustainable agricultural practices, and rural migration in Africa. This area of research is particularly important because the majority of the population living in rural areas in Africa depend on local agriculture for livelihood concerns.[2] The trajectory of climate change and environmental degradation is having a drastic impact on food security at the local and regional level, and this is precipitating rural exodus across the continent. We focus on how hydrological climate conditions such as water shortage, flooding, and reduced rainfall hinder agricultural productivity, consequently inducing food insecurity, forced rural emigration, inter-ethnic conflicts, and internal displacement. Findings shows that this trend further threatens rural population retention and sustainable development. To mitigate these challenges, we propose policy recommendations based on sustainable land-use and indigenous farming practices. This paper aims at developing a strategic plan for utilizing bio-waste for agricultural land re-generation. Also, we aim at developing a strategic adaptation mechanism for communities specifically impacted by hydrological hazards. This paper relevant because the outcome of our selected case studies can be adopted by other communities facing similar climate and migration challenges.
References:
[1] 1] Zeng, Z., Y. Wang and C. Wu (2007), «Environmental dynamical control of tropical cyclone intensity: An observational study" Monthly Weather Review, vol. 135, N° 1.
[2] [2] AfDN (African Development Bank) and Others (2007), Poverty and climate change: Reducing the Vulnerability of the poor through adaptation, Word Bank.
| SESSION: MineralFriAM1-R7 | Torem International Symposium (8th Intl. Symp. on Sustainable Mineral Processing) |
| Fri. 1 Dec. 2023 / Room: Sunflower | |
| Session Chairs: Fernando Jose Gomes; Session Monitor: TBA | |
The San Gabriel (SG) orebody is an intermediate sulphidation epithermal deposit with mainly Au, Ag and Cu mineralization. The geometallurgical modelling of San Gabriel project was based on the geological model which describe the mineralization as a genetic relationship with breccia lithology. Breccia was subclassified in phreatomagmatic, monomictic and polymictic. From a geometallurgical point of view, only monomictic and polymictic breccias are important as these host the economic mineralization.
To flowsheet development and parameters definition it was performed several metallurgical tests during the last decade using CIL cyanidation, gravity concentration and froth flotation of the head ore and tailings also. Finally, it was decided to apply gravity concentration and CIL cyanidation due to the effectiveness in gold recovery.
The geometallurgical modelling to support the Feasibility Study was made over a total of 162 tests results that assess their representativeness, considering main features as geochemistry, lithology, alteration, mineral composition, and structure type.
As per the metallurgical test results, polymictic breccia has an amenable metallurgical behavior with higher metal recovery, on the other hand, part of monomictic breccia is associated with a lower metallurgical recovery. There is not any relation of low recovery ore with any metal element or geochemical characteristic other than the presence and high concentration of organic matter.
Geometallurgical domains are defined in function of gold extraction and there is a strong relationship between metallurgical recovery and the silver grade in the ore as a predictor of gold extraction. Furthermore, gold recovery together with silver head grade allows to define the geometallurgical units (UGM as per its Spanish acronym) into the orebody to apply the recovery criteria in the block model. Overall gold extraction algorithms regarding to each defined UGM were defined for this modelling.
Gold metallurgical extraction were loaded to the resources block model using algorithms defined during this work and the production program and gold extraction predicted for the Feasibility Study are based on the inventory of economically exploitable mineral resources and the aforementioned considerations.
References:
[1] R. Baumgartner, M. Dusci, J. Gressier, A. Trueman, S. Poos, M. Brittan and P. Mayta. Building a Geometallurgical Model for Early-Stage Project Development – A Case Study from the Canahuire Epithermal Au-Cu-Ag Deposit, Southern Peru (2011). The First AUSIMM International Geometallurgy Conference – Brisbane, QLD.
[2] J. Li1, and J. Zhou. Geometallurgical and Mineralogical Characterization of Gold Ores (2017). The Conference of Metallurgists hosting World Gold & Nickel Cobalt Proceedings.
[3] J. Vann, J. Jackson, S. Coward and S. Dunham. The Geomet Curve – A Model for Implementation of Geometallurgy (2011). The First AUSIMM International Geometallurgy Conference – Brisbane, QLD.
[4] R. Dunne, W. P. Staunton and K. Afewu. A Historical Review of the Treatment of Preg-Robbing Gold Ores – What has Worked and Changed (2013). World gold CONFERENCE/Brisbane, QLD.
[5] R. Kim, A. Ghahreman, and M. Epiney. E1ffect of Dissolved Oxygen on Pre-oxidation and Cyanidation of Gold Ore Containing Sulfide Minerals: A Review (2017). The Conference of Metallurgists hosting World Gold & Nickel Cobalt Proceedings.
In recent years, many nanostructures are gaining more and more acceptance for advanced applications due to their responsiveness to desired properties, workability, self-renewal, environmental compatibility, and low cost. These materials have been found to be more efficient than conventional materials in many cases. Within this group, hydrogels which consisted a polymeric materials are received high interest. The hydrophilic structure of which renders them capable of holding large amounts of water in their three-dimensional networks. Especially in the form of nanocomposite, the addition of inorganic solid nanoparticles (typically in the form of fibers, flakes, spheres or fine particles) into polymer matrix leads to increase in their physical, structural and mechanical properties which made them preferable material. They are able to degrade easily after their service life. Furthermore, apart from typical hydrogel beads, they can able to be produced with properties that allow a significant volume phase change or gel-sol phase transition in response to certain physical and chemical stimuli (temperature, electric and magnetic fields, solvent composition, light intensity, and pressure). These properties make them indispensable alternative materials especially for biomedical applications. In this article, the fundamental concepts, production methods and applications together with kinetics approach was reviewed on the base of composite hydrogel.
09:05: [MineralFriAM103] OLAnthropogenic and industrial wastes are resources for metals of high economic significance. These metals being the foremost aspect for development and national security fall in the high risk zone of critical metals. Developing countries like India is devoid of many of those critical metals due to lack of primary resources and hence the secondary resources play a pivotal role, to augmenting their supply. Wastes generated from iron & steel, aluminium, copper, zinc, and the anthropogenic wastes like WEEEs (batteries, magnets, catalysts), etc contain high risk & high economic importance critical metals like Rare earths, Se, Te, Co, Ni, Li, etc, which are worthy of exploitation for recovery. Most of these metals in their metal wheel have very minute concentration; but their concentrations are highly increased in their relevant wastes. Recycling those wastes and concurrently extracting these critical metals shall be very advantageous for developing econmies to be self-reliant in many of these net imported metals. This overview shall discuss on the various technological options to replenish these metals from the global cum Indian perspective, and the advent of indigenous technologies to exploit such resources.
09:30: [MineralFriAM104] OS Though the sustainable development debatediscourse for most of human history, the impetus and made it a household name in development discourses (WCED 1987). Ever since, development schemes focus on holistic development paradigm that tries to address social, economic, political, and cultural discourse is the interface between poverty, environment, and resources use. This paper contributes to the ongoing debate on the povertyenvironment nexus. The interface between poverty and environment has seen an endless debate in Africa. Connection between poverty and environmental degradation with contested concepts. While some scholars place the blame of unsustainable development on the poor, others also ascribe it to the noncomplex link between economic status and environment degradation. For anenhanced appreciation environmental degradation scrutinize the institutional, historical, and structural factors that influence how resources are appropriaterequires government, civil society, and cooperatattempts to establish a link between people and binaries likes poor/nonrelationships both at the local and way they do.
References:
[1] siakwa
| SESSION: MineralFriAM2-R7 | Torem International Symposium (8th Intl. Symp. on Sustainable Mineral Processing) |
| Fri. 1 Dec. 2023 / Room: Sunflower | |
| Session Chairs: TBA Session Monitor: TBA | |
The presence of high concentrations of dissolved ions in groundwater, sea water or recycled water may alter the water structure, particle surface wettability and colloidal interactions between bubbles and particles and can have a significant effect on mineral flotation [1]. While the impact of water quality on the flotation of precious and base metal minerals is well established [2], [3], there is a lack of relevant published studies regarding the effect of water salinity on the flotation of rare earth bearing minerals. This study aims to investigate the effects of using saline water and water with high concentration of dissolved salts on the flotation of rare earth bearing minerals. Specifically, this paper attempts to quantify the effect of water quality variation on flotation recovery and grade of rare earth minerals and gain an understanding on which ions existing in saline water affect flotation behaviour. The results showed that the presence of divalent metal ions such as Mg2+ and Ca2+ leads to significant depression of monazite flotation while the presence of monovalent metal ions such as Na+ affected monazite flotation recovery to a lesser extent. Comparison of various water systems for flotation showed that bore water from Western Australia resulted in decrease in recovery of >40% after two stages of cleaning.
References:
[1] Wang, B., & Peng, Y., (2014). The effect of saline water on mineral flotation – A critical review. Minerals Engineering, 66-68, 13-24.
[2] Peng, Y., Seaman, D., 2011. The flotation of slime-fine fractions of Mt. Keith pentlandite ore in de-ionised and saline water. Minerals Engineering 24 (5), 479–481.
[3] Moreno, P.A., Aral, H., Cuevas, J., Monardes, A., Adaro, M., Norgate, T., & Bruckard, W., 2011. The use of seawater as process water at Las Luces copper–molybdenum beneficiation plant in Taltal (Chile). Minerals Engineering, 24(8), 852-858.
Salinity is defined as accumulation of different salts in soil which are injurious to Plant’s health. Heavy metals salts presence in soil and irrigation water are great threat to different types of crops especially underground stems like potato’s tubers. Heavy metals contamination in underground stems is one of major issue that arises due to frequent urbanization in growing cities which are injurious to the health of humans. Heavy metals salts pose a serious threat to potato crop. Salicylic acids detoxify the poisonous effect of heavy metals and improve the growth of plant under abiotic stresses in climate change scenario. The research was designed to investigate the effect of salicylic acid on morphological, physiological and anatomical responses of potato (Solanum tuberosum L.). A pot experiment was conducted to investigate the three levels of salicylic acid (0, 0.5 and 1mM) against four different concentrations of sewage water (0, 2, 4 and 6% contamination of heavy metals salts). Foliar application of salicylic acid was applied at vegetative stage. Various growth parameters and soil analysis were done. The results showed application of salicylic on tomato plants significantly improved all studies traits like shoot length, shoot fresh weight, no. of leaves, no. of shoots, leaves area, root length, root weight, tuber volume, tuber diameter, tuber numbers and fresh weight, heavy metal analysis and protein analysis in leaves with H2O2 content. This study proved that SA treatment improved morphology and anatomical structure of potato plants. It had potential to reduce the adverse effects of heavy metal stress.
| SESSION: GeochemistryTueAM-R8 | Navrotsky International Symposium (2nd Intl. Symp. on Geochemistry for Sustainable Development) |
| Tue. 28 Nov. 2023 / Room: Coral Reef | |
| Session Chairs: Wenhao Sun; Manisha Rane-Fondacaro; Session Monitor: TBA | |
Though the abundances of elements in our galaxy arise from nuclear physics, the materials they form in planetary systems reflect their chemistry, with complex reactions involving gases, liquids, fluids, melts and solids. On Earth we have inherited, from billions of years of geologic processes, mostly at high temperature and pressure, a suite of rocks and minerals which are the source of all materials we make and use. After use, the elements are eventually returned to the Earth as “waste” or “contamination”. This cycle of mining, processing, use, and disposition can be referred to as “cradle to grave” technology. More sustainable technology, involving reuse of “waste” in technology, is sometimes called “cradle to cradle”. In either case, the feasibility of each step is determined by thermodynamics, and its rate by kinetics. Using rare earths and actinides as examples, this lecture addresses thermodynamic constraints on mining, extraction, separation, fabrication, corrosion and disposal. Current interest in space exploration and planetary missions, as well as the discovery of myriads of exotic and highly variable exoplanets, place these thermodynamic questions in a much broader context for materials of the universe.
12:00: [GeochemistryTueAM02] OS KeynoteThe climate change time bomb is waiting to explode its fury with frequent and severe droughts, heatwaves, and rainfall unless we limit the global temperature increase to below 1.5°C above pre-industrial levels. To avert this situation we have to reduce the greenhouse gas emissions by 43% by 2030 [1], and we can if the entire world works together—collaborating and exchanging knowledge and technology. Globally, all nations trying to expand their renewable energy portfolio are facing the same problems regardless of their geographic location— NIMBY or not in my backyard—public resistance to renewable energy installations for aesthetic reasons and fear of loss in property value Siting delays for environmental reasons, or inadequate or nonexistent policies on renewable energy installations on government and municipal lands, and inadequately trained workforce Interconnection delays due to inadequate transmission bandwidth to carry renewable electricity Intermittency in renewable power and the need for fossil fuel power to bridge that gap Opposition from the fossil fuel industry and lobby who stand to lose the most in terms of profits and jobs.In 2019, globally 41 million people were employed by fuel supply & power generation sectors [2], and assuming one dependent per employee makes 82 million (~1%) of the world population supported by the fossil fuel industry in 2023. Moreover, after information technology and the financial sector, energy is the most profitable sector on the global stock market and is a major component of most state-sponsored retirement plans and U.S. social security. Hence going cold turkey on fossil fuel energy is not an option. We need a well-orchestrated transition from the fossil fuel industry that repurposes its manpower, infrastructure, and value chain to the maximum, and ensures continuity and amplification of tax revenue generation from renewable energy.And through economy of scales, a one-size-fits-all solution can deeply discount the levelized cost of clean energy and green hydrogen as compared to other renewable energy technologies, making it affordable for every nation and expediting its adoption.I will present how we can expand a network of solar microgrids comprising solar, electrolyzer, fuel cell, and hydrogen & energy storage in New York State to: Produce the cheapest electricity and green hydrogen to collectively end the “Tale of Two Grids” which has resulted in 92.7% zero emissions electric supply (and the remainder from fossil fuel) in upstate New York, and merely 5.5% zero emissions electric supply (and rest from fossil fuel) in downstate due to transmission congestion [3] Build a clean hydrogen network to offset the intermittency in renewable electricity from solar and wind power to deliver weather-resistant electricity in New York State with 6σ reliability without investing in expensive transmission system upgrade Decarbonize hard-to-decarbonize sectors including fertilizer, steel & concrete, ammonia, methanol production, etc. Facilitate expansion of EV charging infrastructure, and Discuss how we can implement this model worldwide to achieve the economic prosperity of every nation through energy independence.
References:
[1] The Paris Agreement | UNFCCC
[2] World Energy Employment Report (windows.net)
[3] Power Trends - NYISO (2022 report)
The climate change time bomb is waiting to explode its fury with frequent and severe droughts, heatwaves, and rainfall unless we limit the global temperature increase to below 1.5°C above pre-industrial levels. To avert this situation we have to reduce the greenhouse gas emissions by 43% by 2030 [1], and we can if the entire world works together—collaborating and exchanging knowledge and technology. Globally, all nations trying to expand their renewable energy portfolio are facing the same problems regardless of their geographic location— NIMBY or not in my backyard—public resistance to renewable energy installations for aesthetic reasons and fear of loss in property value Siting delays for environmental reasons, or inadequate or nonexistent policies on renewable energy installations on government and municipal lands, and inadequately trained workforce Interconnection delays due to inadequate transmission bandwidth to carry renewable electricity Intermittency in renewable power and the need for fossil fuel power to bridge that gap Opposition from the fossil fuel industry and lobby who stand to lose the most in terms of profits and jobs.In 2019, glo