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- All Subjects: Density Functional Theory
- All Subjects: Molecular Dynamics
- Creators: Muhich, Christopher
- Creators: Singh, Arunima
Description
Titanium dioxide is an essential material under research for energy and environmental applications, chiefly through its photocatalytic properties. These properties allow it to be used for water-splitting, detoxification, and photovoltaics, in addition to its conventional uses in pigmentation and sunscreen. Titanium dioxide exists in several polymorphic structures, of which the most common are rutile and anatase. We focused on anatase for the purposes of this research, due to its promising results for hydrolysis.
Anatase exists often in its reduced form (TiO2-x), enabling it to perform redox reactions through the absorption and release of oxygen into/from the crystal lattice. These processes result in structural changes, induced by defects in the material, which can theoretically be observed using advanced characterization methods. In situ electron microscopy is one of such methods, and can provide a window into these structural changes. However, in order to interpret the structural evolution caused by defects in materials, it is often necessary and pertinent to use atomistic simulations to compare the experimental images with models.
In this thesis project, we modeled the defect structures in anatase, around oxygen vacancies and at surfaces, using molecular dynamics, benchmarked with density functional theory. Using a “reactive” forcefield designed for the simulation of interactions between anatase and water that can model and treat bonding through the use of bond orders, different vacancy structures were analyzed and simulated. To compare these theoretical, generated models with experimental data, the “multislice approach” to TEM image simulation was used. We investigated a series of different vacancy configurations and surfaces and generated fingerprints for comparison with TEM experiments. This comparison demonstrated a proof of concept for a technique suggesting the possibility for the identification of oxygen vacancy structures directly from TEM images. This research aims to improve our atomic-level understanding of oxide materials, by providing a methodology for the analysis of vacancy formation from very subtle phenomena in TEM images.
Anatase exists often in its reduced form (TiO2-x), enabling it to perform redox reactions through the absorption and release of oxygen into/from the crystal lattice. These processes result in structural changes, induced by defects in the material, which can theoretically be observed using advanced characterization methods. In situ electron microscopy is one of such methods, and can provide a window into these structural changes. However, in order to interpret the structural evolution caused by defects in materials, it is often necessary and pertinent to use atomistic simulations to compare the experimental images with models.
In this thesis project, we modeled the defect structures in anatase, around oxygen vacancies and at surfaces, using molecular dynamics, benchmarked with density functional theory. Using a “reactive” forcefield designed for the simulation of interactions between anatase and water that can model and treat bonding through the use of bond orders, different vacancy structures were analyzed and simulated. To compare these theoretical, generated models with experimental data, the “multislice approach” to TEM image simulation was used. We investigated a series of different vacancy configurations and surfaces and generated fingerprints for comparison with TEM experiments. This comparison demonstrated a proof of concept for a technique suggesting the possibility for the identification of oxygen vacancy structures directly from TEM images. This research aims to improve our atomic-level understanding of oxide materials, by providing a methodology for the analysis of vacancy formation from very subtle phenomena in TEM images.
ContributorsShindel, Benjamin Noam (Author) / Crozier, Peter (Thesis director) / Anwar, Shahriar (Committee member) / Singh, Arunima (Committee member) / Materials Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2019-05
Description
This honors thesis is focused on two separate catalysis projects conducted under the mentorship of Dr. Javier Pérez-Ramírez at ETH Zürich. The first project explored ethylene oxychlorination over supported europium oxychloride catalysts. The second project investigated alkyne semihydrogenation over nickel phosphide catalysts. This work is the subject of a publication of which I am a co-author, as cited below.
Project 1 Abstract: Ethylene Oxychlorination
The current two-step process for the industrial process of vinyl chloride production involves CuCl2 catalyzed ethylene oxychlorination to ethylene dichloride followed by thermal cracking of the latter to vinyl chloride. To date, no industrial application of a one-step process is available. To close this gap, this work evaluates a wide range of self-prepared supported CeO2 and EuOCl catalysts for one-step production of vinyl chloride from ethylene in a fixed-bed reactor at 623 773 K and 1 bar using feed ratios of C2H4:HCl:O2:Ar:He = 3:3 6:1.5 6:3:82 89.5. Among all studied systems, CeO2/ZrO2 and CeO2/Zeolite MS show the highest activity but suffer from severe combustion of ethylene, forming COx, while 20 wt.% EuOCl/γ-Al2O3 leads to the best vinyl chloride selectivity of 87% at 15.6% C2H4 conversion with complete suppression of CO2 formation and only 4% selectivity to CO conversion for over 100 h on stream. Characterization by XRD and EDX mapping reveals that much of the Eu is present in non-active phases such as Al2Eu or EuAl4, indicating that alternative synthesis methods could be employed to better utilize the metal. A linear relationship between conversion and metal loading is found for this catalyst, indicating that always part of the used Eu is available as EuOCl, while the rest forms inactive europium aluminate species. Zeolite-supported EuOCl slightly outperforms EuOCl/γ Al2O3 in terms of total yield, but is prone to significant coking and is unstable. Even though a lot of Eu seems locked in inactive species on EuOCl/γ Al2O3, these results indicate possible savings of nearly 16,000 USD per kg of catalyst compared to a bulk EuOCl catalyst. These very promising findings constitute a crucial step for process intensification of polyvinyl chloride production and exploring the potential of supported EuOCl catalysts in industrially-relevant reactions.
Project 2 Abstract: Alkyne Semihydrogenation
Despite strongly suffering from poor noble metal utilization and a highly toxic selectivity modifier (Pb), the archetypal catalyst applied for the three-phase alkyne semihydrogenation, the Pb-doped Pd/CaCO3 (Lindlar catalyst), is still being utilized at industrial level. Inspired by the very recent strategies involving the modification of Pd with p-block elements (i.e., S), this work extrapolates the concept by preparing crystalline metal phosphides with controlled stoichiometry. To develop an affordable and environmentally-friendly alternative to traditional hydrogenation catalysts, nickel, a metal belonging to the same group as Pd and capable of splitting molecular hydrogen has been selected. Herein, a simple two-step synthesis procedure involving nontoxic precursors was used to synthesize bulk nickel phosphides with different stoichiometries (Ni2P, Ni5P4, and Ni12P5) by controlling the P:Ni ratios. To uncover structural and surface features, this catalyst family is characterized with an array of methods including X-ray diffraction (XRD), 31P magic-angle nuclear magnetic resonance (MAS-NMR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Bulk-sensitive techniques prove the successful preparation of pure phases while XPS analysis unravels the facile passivation occurring at the NixPy surface that persists even after reductive treatment. To assess the characteristic surface fingerprints of these materials, Ar sputtering was carried out at different penetration depths, reveling the presence of Ni+ and P-species. Continuous-flow three-phase hydrogenations of short-chain acetylenic compounds display that the oxidized layer covering the surface is reduced under reaction conditions, as evidenced by the induction period before reaching the steady state performance. To assess the impact of the phosphidation treatment on catalytic performance, the catalysts were benchmarked against a commercial Ni/SiO2-Al2O3 sample. While Ni/SiO2-Al2O3 presents very low selectivity to the alkene (the selectivity is about 10% at full conversion) attributed to the well-known tendency of naked nickel nanoparticles to form hydrides, the performance of nickel phosphides is highly selective and independent of P:Ni ratio. In line with previous findings on PdxS, kinetic tests indicate the occurrence of a dual-site mechanism where the alkyne and hydrogen do not compete for the same site.
This work is the subject of a publication of which I am a co-author, as cited below.
D. Albani; K. Karajovic; B. Tata; Q. Li; S. Mitchell; N. López; J. Pérez-Ramírez. Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-Hydrogenation. ChemCatChem 2019. doi.org/10.1002/cctc.201801430
Project 1 Abstract: Ethylene Oxychlorination
The current two-step process for the industrial process of vinyl chloride production involves CuCl2 catalyzed ethylene oxychlorination to ethylene dichloride followed by thermal cracking of the latter to vinyl chloride. To date, no industrial application of a one-step process is available. To close this gap, this work evaluates a wide range of self-prepared supported CeO2 and EuOCl catalysts for one-step production of vinyl chloride from ethylene in a fixed-bed reactor at 623 773 K and 1 bar using feed ratios of C2H4:HCl:O2:Ar:He = 3:3 6:1.5 6:3:82 89.5. Among all studied systems, CeO2/ZrO2 and CeO2/Zeolite MS show the highest activity but suffer from severe combustion of ethylene, forming COx, while 20 wt.% EuOCl/γ-Al2O3 leads to the best vinyl chloride selectivity of 87% at 15.6% C2H4 conversion with complete suppression of CO2 formation and only 4% selectivity to CO conversion for over 100 h on stream. Characterization by XRD and EDX mapping reveals that much of the Eu is present in non-active phases such as Al2Eu or EuAl4, indicating that alternative synthesis methods could be employed to better utilize the metal. A linear relationship between conversion and metal loading is found for this catalyst, indicating that always part of the used Eu is available as EuOCl, while the rest forms inactive europium aluminate species. Zeolite-supported EuOCl slightly outperforms EuOCl/γ Al2O3 in terms of total yield, but is prone to significant coking and is unstable. Even though a lot of Eu seems locked in inactive species on EuOCl/γ Al2O3, these results indicate possible savings of nearly 16,000 USD per kg of catalyst compared to a bulk EuOCl catalyst. These very promising findings constitute a crucial step for process intensification of polyvinyl chloride production and exploring the potential of supported EuOCl catalysts in industrially-relevant reactions.
Project 2 Abstract: Alkyne Semihydrogenation
Despite strongly suffering from poor noble metal utilization and a highly toxic selectivity modifier (Pb), the archetypal catalyst applied for the three-phase alkyne semihydrogenation, the Pb-doped Pd/CaCO3 (Lindlar catalyst), is still being utilized at industrial level. Inspired by the very recent strategies involving the modification of Pd with p-block elements (i.e., S), this work extrapolates the concept by preparing crystalline metal phosphides with controlled stoichiometry. To develop an affordable and environmentally-friendly alternative to traditional hydrogenation catalysts, nickel, a metal belonging to the same group as Pd and capable of splitting molecular hydrogen has been selected. Herein, a simple two-step synthesis procedure involving nontoxic precursors was used to synthesize bulk nickel phosphides with different stoichiometries (Ni2P, Ni5P4, and Ni12P5) by controlling the P:Ni ratios. To uncover structural and surface features, this catalyst family is characterized with an array of methods including X-ray diffraction (XRD), 31P magic-angle nuclear magnetic resonance (MAS-NMR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Bulk-sensitive techniques prove the successful preparation of pure phases while XPS analysis unravels the facile passivation occurring at the NixPy surface that persists even after reductive treatment. To assess the characteristic surface fingerprints of these materials, Ar sputtering was carried out at different penetration depths, reveling the presence of Ni+ and P-species. Continuous-flow three-phase hydrogenations of short-chain acetylenic compounds display that the oxidized layer covering the surface is reduced under reaction conditions, as evidenced by the induction period before reaching the steady state performance. To assess the impact of the phosphidation treatment on catalytic performance, the catalysts were benchmarked against a commercial Ni/SiO2-Al2O3 sample. While Ni/SiO2-Al2O3 presents very low selectivity to the alkene (the selectivity is about 10% at full conversion) attributed to the well-known tendency of naked nickel nanoparticles to form hydrides, the performance of nickel phosphides is highly selective and independent of P:Ni ratio. In line with previous findings on PdxS, kinetic tests indicate the occurrence of a dual-site mechanism where the alkyne and hydrogen do not compete for the same site.
This work is the subject of a publication of which I am a co-author, as cited below.
D. Albani; K. Karajovic; B. Tata; Q. Li; S. Mitchell; N. López; J. Pérez-Ramírez. Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-Hydrogenation. ChemCatChem 2019. doi.org/10.1002/cctc.201801430
ContributorsTata, Bharath (Author) / Deng, Shuguang (Thesis director) / Muhich, Christopher (Committee member) / Chemical Engineering Program (Contributor, Contributor) / School of Sustainability (Contributor) / Barrett, The Honors College (Contributor)
Created2019-05
Description
Graph neural networks (GNN) offer a potential method of bypassing the Kohn-Sham equations in density functional theory (DFT) calculations by learning both the Hohenberg-Kohn (HK) mapping of electron density to energy, allowing for calculations of much larger atomic systems and time scales and enabling large-scale MD simulations with DFT-level accuracy. In this work, we investigate the feasibility of GNNs to learn the HK map from the external potential approximated as Gaussians to the electron density 𝑛(𝑟), and the mapping from 𝑛(𝑟) to the energy density 𝑒(𝑟) using Pytorch Geometric. We develop a graph representation for densities on radial grid points and determine that a k-nearest neighbor algorithm for determining node connections is an effective approach compared to a distance cutoff model, having an average graph size of 6.31 MB and 32.0 MB for datasets with 𝑘 = 10 and 𝑘 = 50 respectively. Furthermore, we develop two GNNs in Pytorch Geometric, and demonstrate a decrease in training losses for a 𝑛(𝑟) to 𝑒(𝑟) of 8.52 · 10^14 and 3.10 · 10^14 for 𝑘 = 10 and 𝑘 = 20 datasets respectively, suggesting the model could be further trained and optimized to learn the electron density to energy functional.
ContributorsHayes, Matthew (Author) / Muhich, Christopher (Thesis director) / Oswald, Jay (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor) / School of Mathematical and Statistical Sciences (Contributor)
Created2023-05
Description
This research seeks to answer the question if there is a singular relationship between stishovite nucleation and the atomistic structure of the preshocked amorphous SiO$_2$. To do this a stishovite manufacturing method is developed in which 1,152 samples were produced. The majority of these samples did crystallize. The method was produced through two rounds of experiments and fine-tuning with the pressure damp, temperature damp, shock pressure using an NPHug fix, and sample origin. A new random atomic insertion method was used to generate a new and different SiO$_2$ amorphous structure not before seen within the research literature. The optimal values for shock were found to be 60~GPa for randomly atom insertion samples and 55~GPa for quartz origin samples. Temperature damp appeared to have a slight effect optimizing at 0.05~ps and the pressure damp had no visible effect, testing was done with temperature damp from 0.05 to 0.5~ps and pressure damp from 0.1 to 10.0~ps. There appeared to be significant randomness in crystallization behavior. The preshocked and postnucleated samples were transformed into Gaussian fields of crystal, mass, and charge. These fields were divided and classified using a cut-off method taking the number of crystals produced in portions of each simulation and classifying each potion as nucleated or non-nucleated. Data in which some nucleation but not a critical amount was present was removed constituting 2.6\% to 20.3\% of data in all tests. A max method was also used which takes only the maximum portions of each simulation to classify as nucleating. There are three other variables tested within this work, a sample size of 18,000 or 72,728~atoms, Gaussian variance of 1 or 4~\AA, and Convolutional neural network (CNN) architecture of a garden verity or all convolution along with the portioning classification method, sample origination, and Gaussian field type. In total 64 tests were performed to try every combination of variable. No significant classifications were made by the CNNs to nucleation or non-nucleation portions. The results clearly confirmed that the data was not abstracting to atomistic structure and was random by all classifications of the CNNs. The all convolution CNN testing did show smoother outcomes in training with less fluctuations. 59\% of all validation accuracy was held at 0.5 for a random state and 84\% was within $\pm0.02$ of 0.5. It is conclusive that prenucleation structure is not the sole predictor of nucleation behavior. It is not conclusive if prenucleation structure is a partial or non-factor within nucleation of stishovite from amorphous SiO$_2$.
ContributorsChristen, Jonathan Scorr (Author) / Oswald, Jay (Thesis advisor) / Muhich, Christopher (Committee member) / Zhuang, Houlong (Committee member) / Arizona State University (Publisher)
Created2021
Description
Past experiments have revealed several unusual properties about interstitial hydrogen atoms in niobium. Absorption isotherms showed that niobium absorbs a large amount of hydrogen without changing its crystal structure. These isotherms also revealed that the interactions between hydrogen atoms in niobium are a combination of long-range attraction and short-range repulsion and exhibit many-body characteristics. Other experiments reported the facile thermal diffusion of hydrogen and deuterium in niobium. Contrary to the classical theory of diffusion, these experiments revealed a break in the activation energy of hydrogen diffusion at low temperatures, but no such break was reported for deuterium. Finally, experiments report a phenomenon called electromigration, where hydrogen atoms inside niobium respond to weak electric fields as if they had a positive effective charge. These experimental results date back to when tools like density functional theory (DFT) and modern high-performance computing abilities did not exist. Therefore, the current understanding of these properties is primarily based on inferences from experimental results. Understanding these properties at a deeper level, besides being scientifically important, can profoundly affect various applications involving hydrogen separation and transport. The high-level goal of this work is to use first-principles methods to explain the discussed properties of interstitial hydrogen in niobium. DFT calculations were used to study hydrogen atoms' site preference in niobium and its effect on the cell shape and volume of the host cell. The nature and origin of the interactions between hydrogen atoms were studied through interaction energy, structural, partial charge, and electronic densities of state analysis. A phenomenological model with fewer parameters than traditional models was developed and fit to the experimental absorption data. Thermodynamic quantities such as the enthalpy and entropy of hydrogen dissolution in niobium were derived from this model. The enthalpy of hydrogen dissolution in niobium was also calculated using DFT by sampling different geometric configurations and performing an ensemble-based averaging. Further work is required to explain the observed isotope effects for hydrogen diffusion in niobium and the electromigration phenomena. Applications of the niobium-hydrogen system require studying hydrogen's behavior on niobium's surface.
ContributorsRamcahandran, Arvind (Author) / Lackner, Klaus S. (Thesis advisor) / Zhuang, Houlong (Thesis advisor) / Muhich, Christopher (Committee member) / Singh, Arunima (Committee member) / Arizona State University (Publisher)
Created2021
Description
Using DFT calculations and GAMESS computational software, porphine and its derivatives were analyzed for unique sites to accept the adsorbates As(III), As(V) and P(V) in order to compare resulting adsorption energies and determine if any of these molecules prefer arsenic oxyanions over phosphate. Pure porphine preferred As(III) over P(V) with a resulting adsorption energy of -0.7974 eV. Of the functionalized porphyrins tested, carboxyl porphyrin preferred As(V) over P(V) with a total adsorption energy of -0.7345 eV. Ethyl, methyl, chlorine and amino porphyrin all preferred As(III), with energies of -0.7934, -0.8239, -0.7602, and -0.8508 eV, respectively. Of the metalated porphyrins tested, copper and vanadium porphyrin preferred As(V) over P(V) with adsorption energies of -0.7645 and -2.0915 eV. Chromium, iron and magnesium porphyrin all preferred As(III) over P(V) with energies of -0.5993, -1.4539, and - 1.0790 eV, respectively.
ContributorsKusbel, Ashley (Author) / Muhich, Christopher (Thesis director) / Jin, Kailong (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2023-05
Description
Ionic liquids (ILs), or low-temperature liquid salts, are a class of materials with unique and useful properties. Made up entirely of ions, ILs are remarkably tunable and diverse as cations and anions can be mixed and matched to yield desired properties. Because of this, IL/water systems range widely—from homogeneous mixtures to multiphasic systems featuring ionic liquid/liquid interfaces. Even more diversity is added when particles are introduced to these systems, as hard particles or soft-matter microgels interact with both ILs and water in complex ways. This work examines both miscible ionic liquid/water mixture and two-phase, immiscible ionic liquid/water systems. Extensive molecular dynamics (MD) simulations are utilized in conjunction with physical measurements to inform theoretical understanding of the nature of these systems, and this theoretical understanding is related to practical applications—in particular, the development of a low-temperature liquid electrolyte for use in molecular electronic transducer (MET) seismometers, and particle self-assembly and transport at ionic liquid/liquid interfaces such as those in Pickering emulsions.
The homogenous mixture of 1-butyl-3-methylimidazolium iodide and water is examined extensively through MD as well as physical characterization of properties. Molecular ordering within the liquid mixture is related to macroscopic properties. These mixtures are then used as the basis of an electrolyte with unusual characteristics, specifically a wide liquid temperature range with an extremely low lower bound combined with relatively low viscosity allowing excellent performance in the MET sensor. Electrolyte performance is further improved by the addition of fullerene nanoparticles, which dramatically increase device sensitivity. The reasons behind this effect are explored by testing the effect of graphene surface size and through MD simulations of fullerene and a silica nanoparticle (for contrast) in [BMIM][I]/water mixtures.
Immiscible ionic liquid/water systems are explored through MD studies of particles at IL/water interfaces. By increasing the concentration of hydrophobic nanoparticles at the IL/water interface, one study discovers the formation of a commingled IL/water/particle pseudo-phase, and relates this discovery to previously-observed unique behaviors of these interfaces, particularly spontaneous particle transport across the interface. The other study demonstrates that IL hydrophobicity can influence the deformation of thermo-responsive soft particles at the liquid/liquid interface.
The homogenous mixture of 1-butyl-3-methylimidazolium iodide and water is examined extensively through MD as well as physical characterization of properties. Molecular ordering within the liquid mixture is related to macroscopic properties. These mixtures are then used as the basis of an electrolyte with unusual characteristics, specifically a wide liquid temperature range with an extremely low lower bound combined with relatively low viscosity allowing excellent performance in the MET sensor. Electrolyte performance is further improved by the addition of fullerene nanoparticles, which dramatically increase device sensitivity. The reasons behind this effect are explored by testing the effect of graphene surface size and through MD simulations of fullerene and a silica nanoparticle (for contrast) in [BMIM][I]/water mixtures.
Immiscible ionic liquid/water systems are explored through MD studies of particles at IL/water interfaces. By increasing the concentration of hydrophobic nanoparticles at the IL/water interface, one study discovers the formation of a commingled IL/water/particle pseudo-phase, and relates this discovery to previously-observed unique behaviors of these interfaces, particularly spontaneous particle transport across the interface. The other study demonstrates that IL hydrophobicity can influence the deformation of thermo-responsive soft particles at the liquid/liquid interface.
ContributorsNickerson, Stella Day (Author) / Dai, Lenore L (Thesis advisor) / Yu, Hongyu (Committee member) / Lind, Mary Laura (Committee member) / Mu, Bin (Committee member) / Emady, Heather (Committee member) / Arizona State University (Publisher)
Created2016
Description
Losses in commercial microwave dielectrics arise from spin excitations in paramagnetic transition metal dopants, at least at reduced temperatures. The magnitude of the loss tangent can be altered by orders of magnitude through the application of an external magnetic field. The goal of this thesis is to produce “smart” dielectrics that can be switched “on” or “off” at small magnetic fields while investigating the influence of transition metal dopants on the dielectric, magnetic, and structural properties.
A proof of principle demonstration of a resonator that can switch from a high-Q “on state” to a low-Q “off state” at reduced temperatures is demonstrated in (Al1-xFex)2O3 and La(Al1-xFex)O3. The Fe3+ ions are in a high spin state (S=5/2) and undergo electron paramagnetic resonance absorption transitions that increase the microwave loss of the system. Transitions occur between mJ states with a corresponding change in the angular momentum, J, by ±ħ (i.e., ΔmJ=±1) at small magnetic fields. The paramagnetic ions also have an influence on the dielectric and magnetic properties, which I explore in these systems along with another low loss complex perovskite material, Ca[(Al1-xFex)1/2Nb1/2]O3. I describe what constitutes an optimal microwave loss switchable material induced from EPR transitions and the mechanisms associated with the key properties.
As a first step to modeling the properties of high-performance microwave host lattices and ultimately their performance at microwave frequencies, a first-principles approach is used to determine the structural phase stability of various complex perovskites with a range of tolerance factors at 0 K and finite temperatures. By understanding the correct structural phases of these complex perovskites, the temperature coefficient of resonant frequency can be better predicted.
A strong understanding of these parameters is expected to open the possibility to produce new types of high-performance switchable filters, time domain MIMO’s, multiplexers, and demultiplexers.
A proof of principle demonstration of a resonator that can switch from a high-Q “on state” to a low-Q “off state” at reduced temperatures is demonstrated in (Al1-xFex)2O3 and La(Al1-xFex)O3. The Fe3+ ions are in a high spin state (S=5/2) and undergo electron paramagnetic resonance absorption transitions that increase the microwave loss of the system. Transitions occur between mJ states with a corresponding change in the angular momentum, J, by ±ħ (i.e., ΔmJ=±1) at small magnetic fields. The paramagnetic ions also have an influence on the dielectric and magnetic properties, which I explore in these systems along with another low loss complex perovskite material, Ca[(Al1-xFex)1/2Nb1/2]O3. I describe what constitutes an optimal microwave loss switchable material induced from EPR transitions and the mechanisms associated with the key properties.
As a first step to modeling the properties of high-performance microwave host lattices and ultimately their performance at microwave frequencies, a first-principles approach is used to determine the structural phase stability of various complex perovskites with a range of tolerance factors at 0 K and finite temperatures. By understanding the correct structural phases of these complex perovskites, the temperature coefficient of resonant frequency can be better predicted.
A strong understanding of these parameters is expected to open the possibility to produce new types of high-performance switchable filters, time domain MIMO’s, multiplexers, and demultiplexers.
ContributorsGonzales, Justin Michael (Author) / Newman, Nathan (Thesis advisor) / Muhich, Christopher (Committee member) / Tongay, Sefaattin (Committee member) / Arizona State University (Publisher)
Created2020
Description
Single-layer pentagonal materials have received limited attention compared with their counterparts with hexagonal structures. They are two-dimensional (2D) materials with pentagonal structures, that exhibit novel electronic, optical, or magnetic properties. There are 15 types of pentagonal tessellations which allow plenty of options for constructing 2D pentagonal lattices. Few of them have been explored theoretically or experimentally. Studying this new type of 2D materials with density functional theory (DFT) will inspire the discovery of new 2D materials and open up applications of these materials in electronic and magnetic devices.In this dissertation, DFT is applied to discover novel 2D materials with pentagonal structures. Firstly, I examine the possibility of forming a 2D nanosheet with the vertices of type 15 pentagons occupied by boron, silicon, phosphorous, sulfur, gallium, germanium or tin atoms. I obtain different rearranged structures such as a single-layer gallium sheet with triangular patterns. Then the exploration expands to other 14 types of pentagons, leading to the discoveries of carbon nanosheets with Cairo tessellation (type 2/4 pentagons) and other patterns. The resulting 2D structures exhibit diverse electrical properties. Then I reveal the hidden Cairo tessellations in the pyrite structures and discover a family of planar 2D materials (such as PtP2), with a chemical formula of AB2 and space group pa ̄3. The combination of DFT and geometries opens up a novel route for the discovery of new 2D materials. Following this path, a series of 2D pentagonal materials such as 2D CoS2 are revealed with promising electronic and magnetic applications. Specifically, the DFT calculations show that CoS2 is an antiferromagnetic semiconductor with a band gap of 2.24 eV, and a N ́eel temperature of about 20 K. In order to enhance the superexchange interactions between the ions in this binary compound, I explore the ternary 2D pentagonal material CoAsS, that lacks the inversion symmetry. I find out CoAsS exhibits a higher Curie temperature of 95 K and a sizable piezoelectricity (d11=-3.52 pm/V). In addition to CoAsS, 34 ternary 2D pentagonal materials are discovered, among which I focus on FeAsS, that is a semiconductor showing strong magnetocrystalline anisotropy and sizable Berry curvature. Its magnetocrystalline anisotropy energy is 440 μeV/Fe ion, higher than many other 2D magnets that have been found.
Overall, this work not only provides insights into the structure-property relationship of 2D pentagonal materials and opens up a new route of studying 2D materials by combining geometry and computational materials science, but also shows the potential applications of 2D pentagonal materials in electronic and magnetic devices.
Overall, this work not only provides insights into the structure-property relationship of 2D pentagonal materials and opens up a new route of studying 2D materials by combining geometry and computational materials science, but also shows the potential applications of 2D pentagonal materials in electronic and magnetic devices.
ContributorsLiu, Lei (Author) / Zhuang, Houlong (Thesis advisor) / Singh, Arunima (Committee member) / Jiao, Yang (Committee member) / Arizona State University (Publisher)
Created2020
Description
Polyurea is a highly versatile material used in coatings and armor systems to protect against extreme conditions such as ballistic impact, cavitation erosion, and blast loading. However, the relationships between microstructurally-dependent deformation mechanisms and the mechanical properties of polyurea are not yet fully understood, especially under extreme conditions. In this work, multi-scale coarse-grained models are developed to probe molecular dynamics across the wide range of time and length scales that these fundamental deformation mechanisms operate. In the first of these models, a high-resolution coarse-grained model of polyurea is developed, where similar to united-atom models, hydrogen atoms are modeled implicitly. This model was trained using a modified iterative Boltzmann inversion method that dramatically reduces the number of iterations required. Coarse-grained simulations using this model demonstrate that multiblock systems evolve to form a more interconnected hard phase, compared to the more interrupted hard phase composed of distinct ribbon-shaped domains found in diblock systems. Next, a reactive coarse-grained model is developed to simulate the influence of the difference in time scales for step-growth polymerization and phase segregation in polyurea. Analysis of the simulated cured polyurea systems reveals that more rapid reaction rates produce a smaller diameter ligaments in the gyroidal hard phase as well as increased covalent bonding connecting the hard domain ligaments as evidenced by a larger fraction of bridging segments and larger mean radius of gyration of the copolymer chains. The effect that these processing-induced structural variations have on the mechanical properties of the polymer was tested by simulating uniaxial compression, which revealed that the higher degree of hard domain connectivity leads to a 20% increase in the flow stress. A hierarchical multiresolution framework is proposed to fully link coarse-grained molecular simulations across a broader range of time scales, in which a family of coarse-grained models are developed. The models are connected using an incremental reverse–mapping scheme allowing for long time scale dynamics simulated at a highly coarsened resolution to be passed all the way to an atomistic representation.
ContributorsLiu, Minghao (Author) / Oswald, Jay (Thesis advisor) / Muhich, Christopher (Committee member) / Jiang, Hanqing (Committee member) / Peralta, Pedro (Committee member) / Jiao, Yang (Committee member) / Arizona State University (Publisher)
Created2020