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Creators/Authors contains: "Bowman, William_J"

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  1. Abstract Entropy‐stabilized oxide (ESO) research has primarily focused on discovering unprecedented structures, chemistries, and properties in the single‐phase state. However, few studies discuss the impacts of entropy stabilization and secondary phases on functionality and in particular, electrical conductivity. To address this gap, electrical transport mechanisms in the canonical ESO rocksalt (Co,Cu,Mg,Ni,Zn)O are assessed as a function of secondary phase content. When single‐phase, the oxide conducts electrons via Cu+/Cu2+small polarons. After 2 h of heat treatment, Cu‐rich tenorite secondary phases form at some grain boundaries (GBs), enhancing grain interior electronic conductivity by tuning defect chemistry toward higher Cu+carrier concentrations. 24 h of heat treatment yields Cu‐rich tenorite at all GBs, followed by the formation of anisotropic Cu‐rich tenorite and equiaxed Co‐rich spinel secondary phases in grains, further enhancing grain interior electronic conductivity but slowing electronic transport across the tenorite‐rich GBs. Across all samples, the total electrical conductivity increases (and decreases reversibly) by four orders of magnitude with heat‐treatment‐induced phase transformation by tuning the grains’ defect chemistry toward higher carrier concentration and lower migration activation energy. This work demonstrates the potential to selectively grow secondary phases in ESO grains and at GBs, thereby tuning the electrical properties using microstructure design, nanoscale engineering, and heat treatment, paving the way to develop many novel materials. 
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  2. We present Turnstile+, a high-level, macros-based metaDSL for building dependently typed languages. With it, programmers may rapidly prototype and iterate on the design of new dependently typed features and extensions. Or they may create entirely new DSLs whose dependent type ``power'' is tailored to a specific domain. Our framework's support of language-oriented programming also makes it suitable for experimenting with systems of interacting components, e.g., a proof assistant and its companion DSLs. This paper explains the implementation details of Turnstile+, as well as how it may be used to create a wide-variety of dependently typed languages, from a lightweight one with indexed types, to a full spectrum proof assistant, complete with a tactic system and extensions for features like sized types and SMT interaction. 
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  3. Abstract Deploying energy storage and carbon capture at scale is hindered by the substantial endothermic penalty of decomposing CaCO3to CaO and CO2, and the rapid loss of CO2absorption capacity by CaO sorbent particles due to sintering at the high requisite decomposition temperatures. The decomposition reaction mechanism underlying sorbent deactivation remains unclear at the atomic level and nanoscale due to past reliance on postmortem characterization methods with insufficient spatial and temporal resolution. Thus, elucidating the important CaCO3decomposition reaction pathway requires direct observation by time‐resolved (sub‐)nanoscale methods. Here, chemical and structural dynamics during the decomposition of CaCO3nanoparticles to nanoporous CaO particles comprising high‐surface‐area CaO nanocrystallites are examined. Comparing in situ transmission electron microscopy (TEM) and synchrotron X‐ray diffraction experiments gives key insights into the dynamics of nanoparticle calcination, involving anisotropic CaCO3thermal distortion before conversion to thermally dilated energetically stable CaO crystallites. Time‐resolved TEM uncovered a novel CaO formation mechanism involving heterogeneous nucleation at extended CaCO3defects followed by sweeping reaction front motion across the initial CaCO3particle. These observations clarify longstanding, yet incomplete, reaction mechanisms and kinetic models lacking accurate information about (sub‐)nanoscale dynamics, while also demonstrating calcination of CaCO3without sintering through rapid heating and precise temperature control. 
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