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Item Broken-symmetry phases of matter and their effects on electronic and magnetic properties(Montana State University - Bozeman, College of Letters & Science, 2023) Peterson, Sean Fahlman; Chairperson, Graduate Committee: Yves U. Idzerda; This is a manuscript style paper that includes co-authored chapters.Physical symmetries inherent to a material are often reflected in its electronic and magnetic properties. The in-plane four-fold rotational symmetry of thin-film ferromagnets inherent to their tetragonal lattice is also exhibited by their cubic anisotropy. The magnetization as a function of applied magnetic field can be calculated via the Stoner- Wohlfarth model. These calculated hysteresis loops were fit to measured hysteresis loops to determine anisotropy constants consistent with known values. An electronic nematic state reduces the in-plane four-fold rotational symmetry of materials by inducing a structural transition from tetragonal to orthorhombic/monoclinic, with two-fold symmetry. This reduced symmetry persists in the electronic thermal transport. Nematicity enhances nearest-neighbor hopping along one axis and reduces it along the other. This results in a deformed Fermi surface compressed (elongated) along the axis of stronger (weaker) electron hopping. This drags van Hove singularities through the Fermi level, affecting quasiparticle lifetimes. Calculating conductivity from the Boltzmann kinetic equation, nematicity enhances thermal transport along one axis and diminishes it along the other. Additionally, s-wave superconductivity coexisting with nematicity creates a feedback on the superconducting gap with a d-wave instability, which can lead to gapless excitations. In the case of weak feedback, nematic superconductors behave like fully-gapped superconductors along both axes, where transport decreases exponentially with temperature. Once gapless excitations form, transport along both axes becomes T -linear at low-T . Similarly, striped antiferromagnetism (AFM2 and AFM3) reduces the rotational symmetry of a square unit cell to a larger two-fold symmetric magnetic cell. Modeling the band structure with a tight- binding model and considering a smaller periodicity in momentum-space, gaps the Fermi surface along one axis. Calculating conductivity reveals diminished transport along one axis and enhanced thermal transport along the other. Considering d-wave superconductivity in this model results in two cases. One has highly anisotropic transport with greatly enhanced T -linear transport along one axis and diminished transport decreasing exponentially with temperature along the other. The second has weakly anisotropic transport with diminished T -linear conductivity along both axes. The symmetry of a material's properties, such as magnetic anisotropy and thermal transport, are intrinsically linked to their crystalline, electronic, and magnetic symmetries.Item Biochar as a renewable carbon additive for biodegradable plastics(Montana State University - Bozeman, College of Engineering, 2022) Kane, Seth Douglas; Chairperson, Graduate Committee: Cecily Ryan; This is a manuscript style paper that includes co-authored chapters.Biochar - a carbon material produced from pyrolysis of biomass - is a promising alternative to petroleum-derived filler materials in biobased and biodegradable plastics. In this application, biochar can replace materials such as carbon black, with a material that is compatible with end-of-life degradation of bioplastics, while reducing costs and improving material properties. Specifically, high electrical conductivity biochar has the potential to be applied to create highly electrically conductive and biodegradable biochar-bioplastic composite materials. Herein, two critical gaps to development of biochar-bioplastic composites are addressed: the high variation in biochar electrical conductivity and poor thermal interactions between bioplastics and biochar that reduce the bioplastics molecular weight and mechanical properties. To this end, biochars are produced from a variety of feedstocks and their chemical structure and electrical conductivity are extensively characterized. The relationship between feedstock chemical properties, biochar chemical properties, and biochar electrical conductivity is examined. Feedstock oxygen and inorganic content are found to play a critical role in developing highly electrically conductive biochar. The impact of these biochars on the thermal behavior of bioplastics is then examined in detail, and multiple hypotheses for the reduction in thermal behavior that have been proposed in past studies are tested. Biochar moisture content is found to have a limited impact on polymer thermal degradation, while alkali and alkaline earth metals present in biochar reduce the thermal degradation temperature of common bioplastics. A simple washing method was developed to remove these metals and improve the thermal stability of biochar-bioplastic composites. Finally, the environmental benefits of biochar-plastic composites are examined with life cycle assessment methodology, and the developed biochar is examined as a conductive additive in lithium-ion batteries. This work addresses two critical issues that limited the potential of biochar to reduce environmental impacts of rapidly growing classes of materials, as well as demonstrating its applicability in critical applications of petroleum-derived materials. Biochar-bioplastic composites show a unique combination of high electrical conductivity and biodegradability, with strong potential for development of applications in diverse industries from agriculture to biomedical applications.Item Multi-component oxide powder processing dynamics & synergy towards multi-functionality(Montana State University - Bozeman, College of Engineering, 2022) Heywood, Stephen Kevin; Chairperson, Graduate Committee: Stephen W. Sofie; This is a manuscript style paper that includes co-authored chapters.Multi-component or multi-cation ceramic oxides are particularly sensitive to processing-properties variation, in which a single defined chemical stoichiometry can embody dramatic variability in measured properties simply through the steps of synthesis and processing to reach the desired form. Hence, the tailoring of complex oxides is often convoluted by chemical doping and changes in stoichiometry when the influence of processing is not understood. Mixed conducting, multi-valent double perovskite Sr 2-x V Mo O 6-delta (SVMO) shows extraordinary electrical conductivity relative to comparable double perovskites. The technical hurdles of synthesizing and processing bulk powders of SVMO to optimize studies of fundamental electrical transport mechanisms otherwise convoluted by porosity in prior literature were overcome. The basis of various synthesis conditions via rapid microwave assisted sol-gel synthesis were discerned for their contribution to either open porosity of SVMO or enhanced densification. Enhanced resistance to particle coarsening under reducing contrast to inert atmosphere and a means to generate electrical percolation via solid-solution stability of SVMO were two key discoveries among fundamental breakthroughs understanding particle consolidation behaviors. It was discovered that SVMO's elastic modulus was well in excess of other oxide materials, approaching 300 GPa and in correspondence with the mixed V/Mo valency system provides an explanation for low thermal diffusion during sintering. The advanced solid lithium conducting garnet Li 6.25 La 3 Zr 2 Al 0.25 O 12 (LLZO) demonstrates high ionic conductivity for all solid-state batteries, however, it must be paired with an active cathode and anode to enable high energy storage capacity. The study presented here identifies methods to process LLZO materials into dense and porous constituents to satisfy the design architecture of a solid-state battery emphasizing the sensitivity of LLZO performance to lithium content and the desired cubic phase. The aim was to calibrate synthesis techniques towards minimizing sensitivity to thermal processing that contributes towards lithium loss. Studies of sintering optimization and excess lithium content in conjunction with novel freeze based tape casting methods to generate low tortuosity pores were explored. Development of these novel microstructures represents a backbone of processing methodology necessary to incorporate multivalent double perovskites in fuel-electrolysis cells and improve solid state lithium battery technologies.Item Hall effect and electrical conductivity studies of some MHD and fuel cell related materials(Montana State University - Bozeman, College of Letters & Science, 1978) Snyder, Stuart CodyItem Electrical conductivity of MHD coal slags to 2025 K(Montana State University - Bozeman, College of Letters & Science, 1978) Westpfahl, David JohnItem Sr 2-x VMoO 6-Y double perovskites : a new generation of solid oxide fuel cell anodes(Montana State University - Bozeman, College of Letters & Science, 2013) Childs, Nicholas Brule; Chairperson, Graduate Committee: Richard J. Smith; Cameron Law, Richard Smith, Stephen Sofie, Camas Key, Michael Kopcyzk and Michael Lerch were co-authors of the article, 'Electronic current distribution calculation for a NI-YSZ solid oxide fuel cell anode' in the journal 'Fuel cells' which is contained within this thesis.Fuel cells are an attractive power source due to their ability to efficiently convert chemical energy stored in fuel directly into electricity. The ability of Solid Oxide Fuel Cells (SOFCs) to reform hydrocarbons at the anode provides for fuel flexibility, an advantage over other types of fuel cell technologies. The primary goals of this dissertation were to investigate the limitations of the currently used anode cermet material, synthesize a double perovskite material (Sr ₂₋xVMoO ₆₋y) without these limitations and investigate the electrical conduction properties of this mixed ionic and electronic conductor (MEIC) in a SOFC anode environment. The electronic current density limitation of a Ni-YSZ anode was determined through the development of a computer simulation and use of experimental data. The electronic current density distribution for nickel particles in a Ni-YSZ anode was calculated via a Monte-Carlo percolation model. Experiments were performed to determine the failure current densities of thin nickel wires in a SOFC anode environment. The results show a current density limitation of Ni-YSZ anodes that is not expected with MEIC anodes. A MEIC anode material, Sr ₂₋xVMoO ₆₋y, was synthesized and characterized using a variety of techniques. The expected MEIC nature of this perovskite material eliminates a potential anode limitation, while adding other benefits over Ni-YSZ. X-ray diffraction (XRD) was used to verify crystal structure. In contrast to the trace amounts of secondary insulating phases found through XRD, XPS shows a high percentage (85-90%) of these secondary phases at the surface. The electrical conductivity of Sr ₂₋xVMoO ₆₋y was found to exceed that reported for Ni-YSZ anodes in a typical SOFC anode environment. Polycrystalline Sr 1.9VMoO ₆₋y'' samples exhibited higher electrical conductivity than that reported for SrMoO ₃ polycrystalline samples, making it a candidate for being the highest electrical conducting oxide known. These conduction values were only measured after specific thermal treatments in a reducing atmosphere. These treatments reduced secondary surface phases, Sr ₃V ₂O ₈ and SrMoO ₄, into their more conducting counterparts, SrVO ₃ and SrMoO ₃. Vanadium and molybdenum valence state XPS fitting parameters for primary and secondary phases are reported.