From isomorphism to polymorphism: connecting interzeolite transformations to structural and graph similarity

Zeolites are nanoporous crystalline materials with abundant industrial applications. Despite sustained research, only 235 different zeolite frameworks have been realized out of millions of hypothetical ones predicted by computational enumeration. Structure-property relationships in zeolite synthesis are very complex and only marginally understood. Here, we apply structure and graph-based unsupervised machine learning to gain insight on zeolite frameworks and how they relate to experimentally observed polymorphism and phase transformations. We begin by describing zeolite structures using the Smooth Overlap of Atomic Positions method, which clusters crystals with similar cages and density in a way consistent with traditional hand-selected composite building units. To also account for topological differences, zeolite crystals are represented as multigraphs and compared by isomorphism tests. We find that fourteen different pairs and one trio of known frameworks are graph isomorphic. Based on experimental interzeolite conversions and occurrence of competing phases, we propose that the availability of kinetic-controlled transformations between metastable zeolite frameworks is related to their similarity in the graph space. When this description is applied to enumerated structures, over 3,400 hypothetical structures are found to be isomorphic to known frameworks, and thus might be realized from their experimental counterparts. Using a continuous similarity metric, the space of known zeolites shows additional overlaps with experimentally observed phase transformations. Hence, graph-based similarity approaches suggest a venue for realizing novel zeolites from existing ones by providing a relationship between pairwise structure similarity and experimental transformations.Comment: 11 pages, 6 figure

Composite cathodes for lithium rechargeable batteries

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2007.Includes bibliographical references.The utility of incorporating continuous, nanoscale vanadium oxide phases within preferred domains of self-organizing copolymers was investigated towards the fabrication of composite, nanoarchitectured electrode materials for solid-state rechargeable batteries. In situ growth of cathodic phases within ion-conducting copolymer domains was explored as a means to control morphology and to increase the surface-area-to-volume ratio, thereby increasing the specific electrode area for faradaic reactions and decreasing ion diffusion distances within the electrode-active material. Copolymers of microphase-separating rubbery block and graft copolymers, previously developed as solid electrolytes, provide a matrix for directing the synthesis of an inorganic battery-active phase. The copolymers include poly[(oxyethylene)9 methacrylate]-block-poly(butyl methacrylate) (POEM-b-PBMA) with a domain periodicity of -35 nm made by atom transfer radical polymerization, and poly[(oxyethylene)9 methacrylate]-graft-poly(dimethyl siloxane) (POEM-g-PDMS) with a domain periodicity of-17 nm made by free radical polymerization. The resulting microphase-separated polymer is a structure of alternating hydrophilic (Li-ion conducting) and hydrophobic regions.(cont.) Sol-gel chemistry involving a vanadium alkoxide precursor enabled the in situ growth of cathode-active vanadium oxide within the continuous ion-conducting POEM domains of the microphase-separated copolymers. Resulting films, termed POEM-b-PBMA/VOx and POEM-g-PDMS/VOx, were freestanding and mechanically flexible. Small angle x-ray scattering and transmission electron microscopy revealed the nanoscale morphology of the composite and confirmed the spatially-selective incorporation of up to 34 wt% VO, in POEM-b-PBMA and 31 wt% in POEM-g-PDMS. Electronically conductive components, necessary for wiring of the lithium-active vanadium oxide domains to the external circuit, were added through a variety of methods. Dispersions of acid-treated and cryo-ground carbon black within POEM-b-PBMA/VOx enabled the cycling of this material as a cathode. Reversible capacities of-~ 40 mAh/g were measured for batteries fitted with a polymer electrolyte doped with LiCF3SO3 and a lithium foil anode. Electrolyte thickness studies indicated battery performance was limited by the ionic conductivity of the solid electrolyte.(cont.) Using liquid electrolyte resulted in improved capacity (at higher currents) over conventional composite cathodes made from sol-gel derived vanadium oxide without the polymer matrix. The vanadium oxide nanoarchitecture was preserved upon removal of the polymer by heat treatment. The resulting templated vanadium oxide, when repotted with carbon black and binder, exhibited improved capacity at high current over non-templated vanadium oxide cathodes.by Elsa A. Olivetti.Ph.D

Manufacturing-focused emissions reductions in footwear production

What is the burden upon your feet? With sales of running and jogging shoes in the world averaging a nontrivial 25 billion shoes per year, or 34 million per day, the impact of the footwear industry represents a significant portion of the apparel sector's environmental burden. A single shoe can contain 65 discrete parts that require 360 processing steps for assembly. While brand name companies dictate product design and material specifications, the actual manufacturing of footwear is typically contracted to manufacturers based in emerging economies. Using life cycle assessment methodology in accordance with the ISO 14040/14044 standards, this effort quantifies the life cycle greenhouse gas emissions, often referred to as a carbon footprint, of a pair of running shoes. Furthermore, mitigation strategies are proposed focusing on high leverage aspects of the life cycle. Using this approach, it is estimated that the carbon footprint of a typical pair of running shoes made of synthetic materials is 14 ± 2.7 kg CO[subscript 2]-equivalent. The vast majority of this impact is incurred during the materials processing and manufacturing stages, which make up around 29% and 68% of the total impact, respectively. Other similar studies in the apparel industry have reported carbon footprints of running shoes ranging between 18 and 41 kg CO[subscript 2]-equivalent/pair (PUMA, 2008; Timberland, 2009). For consumer products not requiring electricity during use, the intensity of emissions in the manufacturing phase is atypical; most commonly, materials make up the biggest percentage of impact. This distinction highlights the importance of identifying mitigation strategies within the manufacturing process, and the need to evaluate the emissions reduction efficacy of each potential strategy. By suggesting a few of the causes of manufacturing dominance in the global warming potential assessment of this product, this study hypothesizes the characteristics of a product that could lead to high manufacturing impact. Some of these characteristics include the source of energy in manufacturing and the form of manufacturing, in other words the complexity of processes used and the area over which these process are performed (particularly when a product involves numerous parts and light materials). Thereby, the work provides an example when relying solely on the bill of materials information for product greenhouse gas emissions assessment may underestimate life cycle burden and ignore potentially high impact mitigation strategies

Database, Features, and Machine Learning Model to Identify Thermally Driven Metal-Insulator Transition Compounds

Metal-insulator transition (MIT) compounds are materials that may exhibit insulating or metallic behavior, depending on the physical conditions, and are of immense fundamental interest owing to their potential applications in emerging microelectronics. There is a dearth of thermally-driven MIT materials, however, which makes delineating these compounds from those that are exclusively insulating or metallic challenging. Here we report a material database comprising temperature-controlled MITs (and metals and insulators with similar chemical composition and stoichiometries to the MIT compounds) from high quality experimental literature, built through a combination of materials-domain knowledge and natural language processing. We featurize the dataset using compositional, structural, and energetic descriptors, including two MIT relevant energy scales, an estimated Hubbard interaction and the charge transfer energy, as well as the structure-bond-stress metric referred to as the global-instability index (GII). We then perform supervised classification, constructing three electronic-state classifiers: metal vs non-metal (M), insulator vs non-insulator (I), and MIT vs non-MIT (T). We identify two important descriptors that separate metals, insulators, and MIT materials in a 2D feature space: the average deviation of the covalent radius and the range of the Mendeleev number. We further elaborate on other important features (GII and Ewald energy), and examine how they affect classification of binary vanadium and titanium oxides. We discuss the relationship of these atomic features to the physical interactions underlying MITs in the rare-earth nickelate family. Last, we implement an online version of the classifiers, enabling quick probabilistic class predictions by uploading a crystallographic structure file

Advancing Alternative Analysis: Integration of Decision Science.

Decision analysis-a systematic approach to solving complex problems-offers tools and frameworks to support decision making that are increasingly being applied to environmental challenges. Alternatives analysis is a method used in regulation and product design to identify, compare, and evaluate the safety and viability of potential substitutes for hazardous chemicals.Assess whether decision science may assist the alternatives analysis decision maker in comparing alternatives across a range of metrics.A workshop was convened that included representatives from government, academia, business, and civil society and included experts in toxicology, decision science, alternatives assessment, engineering, and law and policy. Participants were divided into two groups and prompted with targeted questions. Throughout the workshop, the groups periodically came together in plenary sessions to reflect on other groups' findings.We conclude the further incorporation of decision science into alternatives analysis would advance the ability of companies and regulators to select alternatives to harmful ingredients, and would also advance the science of decision analysis.We advance four recommendations: (1) engaging the systematic development and evaluation of decision approaches and tools; (2) using case studies to advance the integration of decision analysis into alternatives analysis; (3) supporting transdisciplinary research; and (4) supporting education and outreach efforts

REWAS 2022: Developing Tomorrow’s Technical Cycles

Abstract REWAS, a sustainability driven conference within The Minerals, Metals & Materials Society (TMS), has a long history of bringing together academia and industry to exchange and reflect on the latest technology developments in the process optimization and waste management fields. The first edition of REWAS (REcycling and WASte symposium) took place in 1999. The scope of the conference has since then broadened to include environmental sustainability, resource management and manufacturing efficiency, liaising these developments to the metallurgical industry in a broader societal and systemic context. The 2022 edition of REWAS which will be hosted at the TMS 2022 Annual Meeting & Exhibition in Anaheim, California, provides a resolute outlook towards Developing Tomorrow’s Technical Cycles. Within the metals and materials industry, technical cycles refer to the ensemble of strategies and processes applied to the development of sustainable product loops with the intent to eliminate waste and instead rethink, reuse and upcycle products. The success of technical cycles requires strengthening our circular approach for product life cycle design by providing guidelines and implementation examples to the developers, designers, policy makers and business managers. REWAS promotes such strategies within a priority sector identified for Circular Economy enablement: raw materials supply and management. REWAS 2022 consists of six symposia, and abstract submissions are expected in summer 2021. Topics include recycling and sustainability within the aluminum industry, specifically on casting technologies, recovery of metals from complex products and systems, decarbonization of the metallurgical and manufacturing industry, sustainable production and development perspectives, as well as automatization and digitalization for advanced manufacturing. REWAS 2022 will also include an honorary symposium for Dr. Diran Apelian, whose contributions in metals processing, aluminum and battery recycling, sustainability, education in materials science and more have shaped the path for sustainable materials processing

Sustainable development of materials: Broadening stakeholder engagement

Abstract We present a transformative vision for future materials selection, processing, and design decisions in the context of sustainability. Specifically, we highlight the concept of sustainable development of materials and the need to broaden the range of stakeholders engaged in materials design decisions. For instance, beyond the traditional structure–processing–performance triangle, there is a critical need to incorporate sustainability metrics into materials design. Such metrics embrace concepts of green chemistry and chemicals management, critical materials and materials circularity, materials substitution and alternatives assessment. Implementation requires broad engagement beyond the traditional materials science and engineering boundaries, including global perspectives on public policy, governance, economics, and public health. Educational norms clearly must also change, together with workforce development programs and comprehensive industrial buy-in. This vision is further expanded upon in the articles in this issue, which we summarize here, providing highlights of each article and identifying critical intersections among the topics presented, thereby providing a framework to realize our vision. Graphical Abstrac

Manufacturing scalability implications of materials choice in inorganic solid-state batteries

© 2020 Elsevier Inc. The pursuit of scalable and manufacturable all-solid-state batteries continues to intensify, motivated by the rapidly increasing demand for safe, dense electrical energy storage. In this perspective, we describe the numerous, often conflicting implications of materials choices that have been made in the search for effective mitigations to the interfacial instabilities plaguing solid-state batteries. Specifically, we show that the manufacturing scalability of solid-state batteries can be governed by at least three principal consequences of materials selection: (1) the availability, scaling capacity, and price volatility of the chosen materials’ constituents, (2) the manufacturing processes needed to integrate the chosen materials into full cells, and (3) the cell performance that may be practically achieved with the chosen materials and processes. While each of these factors is, in isolation, a pivotal determinant of manufacturing scalability, we show that consideration and optimization of their collective effects and trade-offs is necessary to more completely chart a scalable pathway to manufacturing. With examples pulled from recent developments in solid-state batteries, we illustrate the consequences of materials choice on materials availability, processing requirements and challenges, and resultant device performance. We demonstrate that while each of these factors is, by itself, essential to understanding manufacturing scalability, joint consideration of all three provides for a more comprehensive understanding of the specific factors that could impede the scale up to production. Much of the recent activity in solid-state battery research has been aimed at mitigating the various interfacial instabilities that currently prevent the fabrication of a low-cost, high-performance device. With such a wide breadth of options, it can be difficult for researchers to identify the most promising or scalable pathways forward. As such, we aim to empower researchers to make more informed decisions by providing them with insights into how their materials choices are likely to impact the manufacturing scalability of different interfacial mitigation alternatives. In doing so, we hope that generalizable lessons about scalability can be extracted and applied to subsequent challenges in solid-state battery development, thereby accelerating their scale up to manufacturing. In the design of solid-state batteries, a considerable range of materials is under investigation for both the solid electrolyte as well as for mitigations to the numerous interfacial instabilities that hamper device performance. The choices made for these material and device design decisions have many, often conflicting, effects on manufacturing scalability. By modeling example cells reported in the literature, we show that collective evaluation of these trade-offs is imperative to accurately assess potential barriers to manufacturing scale up

Econometric modeling of recycled copper supply

Fu, Xinkai, et al. “Econometric Modeling of Recycled Copper Supply.” Resources, Conservation and Recycling, vol. 122, July 2017, pp. 219–26.National Science Foundation (U.S.) (Award 1605050