Matching Items (32)

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Synthesis and Characterization of Laser Plasma that Produces Pseudocarbyne Using Laser Pulses

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Carbon allotropes are the basis for many exciting advancements in technology. While sp² and sp³ hybridizations are well understood, the sp¹ hybridized carbon has been elusive. However, with recent advances made using a pulsed laser ablation in liquid technique, sp¹

Carbon allotropes are the basis for many exciting advancements in technology. While sp² and sp³ hybridizations are well understood, the sp¹ hybridized carbon has been elusive. However, with recent advances made using a pulsed laser ablation in liquid technique, sp¹ hybridized carbon allotropes have been created. The fabricated carbon chain is composed of sp¹ and sp³ hybridized bonds, but it also incorporates nanoparticles such as gold or possibly silver to stabilize the chain. The polyyne generated in this process is called pseudocarbyne due to its striking resemblance to the theoretical carbyne. The formation of these carbon chains is yet to be fully understood, but significant progress has been made in determining the temperature of the plasma in which the pseudocarbyne is formed. When a 532 nm pulsed laser with a pulsed energy of 250 mJ and pulse length of 10ns is used to ablate a gold target, a peak temperature of 13400 K is measured. When measured using Laser-Induced Breakdown spectroscopy (LIBS) the average temperature of the neutral carbon plasma over one second was 4590±172 K. This temperature strongly suggests that the current theoretical model used to describe the temperature at which pseudocarbyne generates is accurate.

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2019-05

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Study of Exhaust Throttling Effects on SI Engine Performance

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To determine the effects of exhaust heat recovery systems on small engines, an experiment was performed to measure the power losses of an engine with restricted exhaust flow. In cooperation with ASU's SAE Formula race team, a water brake dynamometer

To determine the effects of exhaust heat recovery systems on small engines, an experiment was performed to measure the power losses of an engine with restricted exhaust flow. In cooperation with ASU's SAE Formula race team, a water brake dynamometer was refurbished and connected to the 2017 racecar engine. The engine was mounted with a diffuser disc exhaust to restrict flow, and a pressure sensor was installed in the O2 port to measure pressure under different restrictions. During testing, problems with the equipment prevented suitable from being generated. Using failure root cause analysis, the failure modes were identified and plans were made to resolve those issues. While no useful data was generated, the project successfully rebuilt a dynamometer for students to use for future engine research.

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2017-05

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Growth, characterization, and thermodynamics of III-nitride semiconductors

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III-nitride alloys are wide band gap semiconductors with a broad range of applications in optoelectronic devices such as light emitting diodes and laser diodes. Indium gallium nitride light emitting diodes have been successfully produced over the past decade. But the

III-nitride alloys are wide band gap semiconductors with a broad range of applications in optoelectronic devices such as light emitting diodes and laser diodes. Indium gallium nitride light emitting diodes have been successfully produced over the past decade. But the progress of green emission light emitting devices has been limited by the incorporation of indium in the alloy, mainly due to phase separation. This difficulty could be addressed by studying the growth and thermodynamics of these alloys. Knowledge of thermodynamic phase stabilities and of pressure - temperature - composition phase diagrams is important for an understanding of the boundary conditions of a variety of growth techniques. In this dissertation a study of the phase separation of indium gallium nitride is conducted using a regular solution model of the ternary alloy system. Graphs of Gibbs free energy of mixing were produced for a range of temperatures. Binodal and spinodal decomposition curves show the stable and unstable regions of the alloy in equilibrium. The growth of gallium nitride and indium gallium nitride was attempted by the reaction of molten gallium - indium alloy with ammonia at atmospheric pressure. Characterization by X-ray diffraction, photoluminescence, and secondary electron microscopy show that the samples produced by this method contain only gallium nitride in the hexagonal phase. The instability of indium nitride at the temperatures required for activation of ammonia accounts for these results. The photoluminescence spectra show a correlation between the intensity of a broad green emission, related to native defects, and indium composition used in the molten alloy. A different growth method was used to grow two columnar-structured gallium nitride films using ammonium chloride and gallium as reactants and nitrogen and ammonia as carrier gasses. Investigation by X-ray diffraction and spatially-resolved cathodoluminescence shows the film grown at higher temperature to be primarily hexagonal with small quantities of cubic crystallites, while the one grown at lower temperature to be pure hexagonal. This was also confirmed by low temperature photoluminescence measurements. The results presented here show that cubic and hexagonal crystallites can coexist, with the cubic phase having a much sharper and stronger luminescence. Controlled growth of the cubic phase GaN crystallites can be of use for high efficiency light detecting and emitting devices. The ammonolysis of a precursor was used to grow InGaN powders with different indium composition. High purity hexagonal GaN and InN were obtained. XRD spectra showed complete phase separation for samples with x < 30%, with ~ 9% indium incorporation in the 30% sample. The presence of InGaN in this sample was confirmed by PL measurements, where luminescence from both GaN and InGaN band edge are observed. The growth of higher indium compositions samples proved to be difficult, with only the presence of InN in the sample. Nonetheless, by controlling parameters like temperature and time may lead to successful growth of this III-nitride alloy by this method.

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2011

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Thermodynamics and kinetics of DNA tile-based self-assembly

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Deoxyribonucleic acid (DNA) has emerged as an attractive building material for creating complex architectures at the nanometer scale that simultaneously affords versatility and modularity. Particularly, the programmability of DNA enables the assembly of basic building units into increasingly complex, arbitrary

Deoxyribonucleic acid (DNA) has emerged as an attractive building material for creating complex architectures at the nanometer scale that simultaneously affords versatility and modularity. Particularly, the programmability of DNA enables the assembly of basic building units into increasingly complex, arbitrary shapes or patterns. With the expanding complexity and functionality of DNA toolboxes, a quantitative understanding of DNA self-assembly in terms of thermodynamics and kinetics, will provide researchers with more subtle design guidelines that facilitate more precise spatial and temporal control. This dissertation focuses on studying the physicochemical properties of DNA tile-based self-assembly process by recapitulating representative scenarios and intermediate states with unique assembly pathways.

First, DNA double-helical tiles with increasing flexibility were designed to investigate the dimerization kinetics. The higher dimerization rates of more rigid tiles result from the opposing effects of higher activation energies and higher pre-exponential factors from the Arrhenius equation, where the pre-exponential factor dominates. Next, the thermodynamics and kinetics of single tile attachment to preformed “multitile” arrays were investigated to test the fundamental assumptions of tile assembly models. The results offer experimental evidences that double crossover tile attachment is determined by the electrostatic environment and the steric hindrance at the binding site. Finally, the assembly of double crossover tiles within a rhombic DNA origami frame was employed as the model system to investigate the competition between unseeded, facet and seeded nucleation. The results revealed that preference of nucleation types can be tuned by controlling the rate-limiting nucleation step.

The works presented in this dissertation will be helpful for refining the DNA tile assembly model for future designs and simulations. Moreover, The works presented here could also be helpful in understanding how individual molecules interact and more complex cooperative bindings in chemistry and biology. The future direction will focus on the characterization of tile assembly at single molecule level and the development of error-free tile assembly systems.

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2016

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Thermodynamics and kinetics of DNA nanostructure assembly

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ABSTRACT The unique structural features of deoxyribonucleic acid (DNA) that are of considerable biological interest also make it a valuable engineering material. Perhaps the most useful property of DNA for molecular engineering is its ability to self-assemble into predictable, double

ABSTRACT The unique structural features of deoxyribonucleic acid (DNA) that are of considerable biological interest also make it a valuable engineering material. Perhaps the most useful property of DNA for molecular engineering is its ability to self-assemble into predictable, double helical secondary structures. These interactions are exploited to design a variety of DNA nanostructures, which can be organized into both discrete and periodic structures. This dissertation focuses on studying the dynamic behavior of DNA nanostructure recognition processes. The thermodynamics and kinetics of nanostructure binding are evaluated, with the intention of improving our ability to understand and control their assembly. Presented here are a series of studies toward this goal. First, multi-helical DNA nanostructures were used to investigate how the valency and arrangement of the connections between DNA nanostructures affect super-structure formation. The study revealed that both the number and the relative position of connections play a significant role in the stability of the final assembly. Next, several DNA nanostructures were designed to gain insight into how small changes to the nanostructure scaffolds, intended to vary their conformational flexibility, would affect their association equilibrium. This approach yielded quantitative information about the roles of enthalpy and entropy in the affinity of polyvalent DNA nanostructure interactions, which exhibit an intriguing compensating effect. Finally, a multi-helical DNA nanostructure was used as a model `chip' for the detection of a single stranded DNA target. The results revealed that the rate constant of hybridization is strongly dominated by a rate-limiting nucleation step.

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2011

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First-principles study of thermodynamic properties in thin-film photovoltaics

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This thesis focuses on the theoretical work done to determine thermodynamic properties of a chalcopyrite thin-film material for use as a photovoltaic material in a tandem device. The material of main focus here is ZnGeAs2, which was chosen for the

This thesis focuses on the theoretical work done to determine thermodynamic properties of a chalcopyrite thin-film material for use as a photovoltaic material in a tandem device. The material of main focus here is ZnGeAs2, which was chosen for the relative abundance of constituents, favorable photovoltaic properties, and good lattice matching with ZnSnP2, the other component in this tandem device. This work is divided into two main chapters, which will cover: calculations and method to determine the formation energy and abundance of native point defects, and a model to calculate the vapor pressure over a ternary material from first-principles. The purpose of this work is to guide experimental work being done in tandem to synthesize ZnGeAs2 in thin-film form with high enough quality such that it can be used as a photovoltaic. Since properties of photovoltaic depend greatly on defect concentrations and film quality, a theoretical understanding of how laboratory conditions affect these properties is very valuable. The work done here is from first-principles and utilizes density functional theory using the local density approximation. Results from the native point defect study show that the zinc vacancy (VZn) and the germanium antisite (GeZn) are the more prominent defects; which most likely produce non-stoichiometric films. The vapor pressure model for a ternary system is validated using known vapor pressure for monatomic and binary test systems. With a valid ternary system vapor pressure model, results show there is a kinetic barrier to decomposition for ZnGeAs2.

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2011

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Theoretical and empirical investigations of ecosystem development in boreal wetlands

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Despite the breadth of studies investigating ecosystem development, an underlying theory guiding this process remains elusive. Several principles have been proposed to explain ecosystem development, though few have garnered broad support in the literature. I used boreal wetland soils as

Despite the breadth of studies investigating ecosystem development, an underlying theory guiding this process remains elusive. Several principles have been proposed to explain ecosystem development, though few have garnered broad support in the literature. I used boreal wetland soils as a study system to test a notable goal oriented principle: The Maximum Power Principle (MPP). The MPP posits that ecosystems, and in fact all energy systems, develop to maximize power production or the rate of energy production. I conducted theoretical and empirical investigations to test the MPP in northern wetlands.

Permafrost degradation is leading to rapid wetland formation in northern peatland ecosystems, altering the role of these ecosystems in the global carbon cycle. I reviewed the literature on the history of the MPP theory, including tracing its origins to The Second Law of Thermodynamics. To empirically test the MPP, I collected soils along a gradient of ecosystem development and: 1) quantified the rate of adenosine triphosphate (ATP) production--literally cellular energy--to test the MPP; 2) quantified greenhouse gas production (CO2, CH4, and N2O) and microbial genes that produce enzymes catalyzing greenhouse gas production, and; 3) sequenced the 16s rRNA gene from soil microbes to investigate microbial community composition across the chronosequence of wetland development. My results suggested that the MPP and other related theoretical constructs have strong potential to further inform our understanding of ecosystem development. Soil system power (ATP) decreased temporarily as the ecosystem reorganized after disturbance to rates of power production that approached pre-disturbance levels. Rates of CH4 and N2O production were higher at the newly formed bog and microbial genes involved with greenhouse gas production were strongly related to the amount of greenhouse gas produced. DNA sequencing results showed that across the chronosequence of development, the two relatively mature ecosystems--the peatland forest ecosystem prior to permafrost degradation and the oldest bog--were more similar to one another than to the intermediate, less mature bog. Collectively, my results suggest that ecosystem age, rather than ecosystem state, was a more important driver for ecosystem structure and function.

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Date Created
2015

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Thermodynamics and biological applications of DNA nanostructures

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DNA nanotechnology is one of the most flourishing interdisciplinary research fields. Through the features of programmability and predictability, DNA nanostructures can be designed to self-assemble into a variety of periodic or aperiodic patterns of different shapes and length scales, and

DNA nanotechnology is one of the most flourishing interdisciplinary research fields. Through the features of programmability and predictability, DNA nanostructures can be designed to self-assemble into a variety of periodic or aperiodic patterns of different shapes and length scales, and more importantly, they can be used as scaffolds for organizing other nanoparticles, proteins and chemical groups. By leveraging these molecules, DNA nanostructures can be used to direct the organization of complex bio-inspired materials that may serve as smart drug delivery systems and in vitro or in vivo bio-molecular computing and diagnostic devices. In this dissertation I describe a systematic study of the thermodynamic properties of complex DNA nanostructures, including 2D and 3D DNA origami, in order to understand their assembly, stability and functionality and inform future design endeavors. It is conceivable that a more thorough understanding of DNA self-assembly can be used to guide the structural design process and optimize the conditions for assembly, manipulation, and functionalization, thus benefiting both upstream design and downstream applications. As a biocompatible nanoscale motif, the successful integration, stabilization and separation of DNA nanostructures from cells/cell lysate suggests its potential to serve as a diagnostic platform at the cellular level. Here, DNA origami was used to capture and identify multiple T cell receptor mRNA species from single cells within a mixed cell population. This demonstrates the potential of DNA nanostructure as an ideal nano scale tool for biological applications.

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2014

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A Steady State Thermodynamic Model of Concentrating Solar Power with Thermochemical Energy Storage

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Fluids such as steam, oils, and molten salts are commonly used to store and transfer heat in a concentrating solar power (CSP) system. Metal oxide materials have received increasing attention for their reversible reduction-oxidation (redox) reaction that permits receiving, storing,

Fluids such as steam, oils, and molten salts are commonly used to store and transfer heat in a concentrating solar power (CSP) system. Metal oxide materials have received increasing attention for their reversible reduction-oxidation (redox) reaction that permits receiving, storing, and releasing energy through sensible and chemical potential. This study investigates the performance of a 111.7 MWe CSP system coupled with a thermochemical energy storage system (TCES) that uses a redox active metal oxide acting as the heat transfer fluid. A one-dimensional thermodynamic model is introduced for the novel CSP system design, with detailed designs of the underlying nine components developed from first principles and empirical data of the heat transfer media. The model is used to (a) size components, (b) examine intraday operational behaviors of the system against varying solar insolation, (c) calculate annual productivity and performance characteristics over a simulated year, and (d) evaluate factors that affect system performance using sensitivity analysis. Time series simulations use hourly direct normal irradiance (DNI) data for Barstow, California, USA. The nominal system design uses a solar multiple of 1.8 with a storage capacity of six hours for off-sun power generation. The mass of particles to achieve six hours of storage weighs 5,140 metric tonnes. Capacity factor increases by 3.55% for an increase in storage capacity to eight hours which requires an increase in storage volume by 33% or 737 m3, or plant design can be improved by decreasing solar multiple to 1.6 to increase the ratio of annual capacity factor to solar multiple. The solar reduction receiver is the focal point for the concentrated solar energy for inducing an endothermic reaction in the particles under low partial pressure of oxygen, and the reoxidation reactor induces the opposite exothermic reaction by mixing the particles with air to power an air Brayton engine. Stream flow data indicate the solar receiver experiences the largest thermal loss of any component, excluding the solar field. Design and sensitivity analysis of thermal insulation layers for the solar receiver show that additional RSLE-57 insulation material achieves the greatest increase in energetic efficiency of the five materials investigated.

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2017

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Design and Additive Manufacturing of Copper Heat Sinks for Microelectronics Cooling

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Thermal management is a critical aspect of microelectronics packaging and often centers around preventing central processing units (CPUs) and graphics processing units (GPUs) from overheating. As the need for power going into these processors increases, so too does the need

Thermal management is a critical aspect of microelectronics packaging and often centers around preventing central processing units (CPUs) and graphics processing units (GPUs) from overheating. As the need for power going into these processors increases, so too does the need for more effective thermal management strategies. One such strategy is to utilize additive manufacturing to fabricate heat sinks with bio-inspired and cellular structures and is the focus of this thesis. In this study, a process was developed for manufacturing the copper alloy CuNi2SiCr on the 100w Concept Laser Mlab laser powder bed fusion 3D printer to obtain parts that were 94% dense, while dealing with challenges of low absorptivity in copper and its high potential for oxidation. The developed process was then used to manufacture and test heat sinks with traditional pin and fin designs to establish a baseline cooling effect, as determined from tests conducted on a substrate, CPU and heat spreader assembly. Two additional heat sinks were designed, the first of these being bio-inspired and the second incorporating Triply Periodic Minimal Surface (TPMS) cellular structures, with the aim of trying to improve the cooling effect relative to commercial heat sinks. The results showed that the pure copper commercial pin-design heat sink outperformed the additive manufactured (AM) pin-design heat sink under both natural and forced convection conditions due to its approximately tenfold higher thermal conductivity, but that the gap in performance could be bridged using the bio-inspired and Schwarz-P heat sink designs developed in this work and is an encouraging indicator that further improvements could be obtained with improved alloys, heat treatments and even more innovative designs.

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2021