Silicon carbide and silicon nitride turbine engine components are susceptible to hot corrosion by molten sodium sulfate salts which are formed from impurities in the engine's fuel and air intake. Several oxide materials were identified which may be able to protect these components from corrosion and preserve their structural properties. Ta20, coatings were identified as one of the most promising candidates. Thermochemical calculations showed that the chemical vapor deposition(CVD) of tantalum oxide from O2 and TaCI5 precursors is thermodynamically feasible over a range of pressures, temperatures, and reactant concentrations. The deposition of Ta205, as a single phase is predicted in regions of excess oxygen, where the reaction is predicted to yield nearly 100% efficiency. CVD experiments were carried out to deposit tantalum oxide films onto SiC substrates. Depending on the deposition conditions, a variety of coating morphologies have been produced, and conditions have been identified which produce dense, continuous Ta205 deposits. Preliminary corrosion tests on these coatings showed no apparent degradation of the CVD deposited tantalum oxide coatings. The feasibility of depositing ZrTi04 as a coating material was also investigated based on thermochemical considerations. Since no data were available for this material, thermodynamic values were estimated. Thermochemical calculations indicated the chemical vapor deposition of zirconium titanate from O2, ZrCl4, and TiCl4 occurs over a range of temperatures in a very narrow region of the phase diagram. Deviations from the single phase region predicted the codeposition of either Zr02 or Ti02 with ZrTi04. These results suggested that the chemical vapor deposition of ZrTi04 may be difficult from a process handling perspective. Additionally, the process is predicted to be very inefficient, leaving substantial amounts of unreacted chlorides in the reactor exhaust. / Master of Science

Yes / Less than optimal particle isolation techniques have impeded analysis of orthopaedic wear debris in vivo. The purpose of this research was to develop and test an improved method for particle isolation from tissue. A volume of 0.018 mm3 of clinically relevant CoCrMo, Ti-6Al-4V or Si3N4 particles was injected into rat stifle joints for seven days of in vivo exposure. Following sacrifice, particles were located within tissues using histology. The particles were recovered by enzymatic digestion of periarticular tissue with papain and proteinase K, followed by ultracentrifugation using a sodium polytungstate density gradient. Particles were recovered from all samples, observed using SEM and the particle composition was verified using EDX, which demonstrated that all isolated particles were free from contamination. Particle size, aspect ratio and circularity were measured using image analysis software. There were no significant changes to the measured parameters of CoCrMo or Si3N4 particles before and after the recovery process (KS tests, p > 0.05). Titanium particles were too few before and after isolation to analyse statistically, though size and morphologies were similar. Overall the method demonstrated a significant improvement to current particle isolation methods from tissue in terms of sensitivity and efficacy at removal of protein, and has the potential to be used for the isolation of ultra-low wearing total joint replacement materials from periprosthetic tissues.

This thesis presents a computational study of water and ion dynamics in modified hydrophobic silicon nitride (Si3N4) nanopores, aimed at enhancing protein sequenc- ing technologies. By employing molecular dynamics (MD) simulations, the research investigates the wetting-dewetting behavior within nanopores as an indirect measure of amino acid residue hydrophobicity, focusing on how post-translational modifications (PTMs) of lysine, particularly the acetylation of lysine residues, influence nanopore hydrophobicity and ionic conductance. The study reveals that nanopore radius and hydrophobicity significantly affect water and ion permeation, with smaller nanopores oscillating between open and closed states, while larger ones remain open.  Using umbrella sampling and the Weighted Histogram Analysis Method (WHAM), the potential of mean force (PMF) for potassium (K+), chloride (Cl−), and water within the nanopores was determined, showing distinct PMF profiles based on lysine and acetyl- lysine presence. The modulation of ionic currents as a tool for protein sequencing was explored, demonstrating that different amino acid residues affect ionic currents by par- tially blocking the pore and altering local permeability, thereby enabling differentiation based on size, shape, charge, and hydrophobicity.  The findings suggest that silicon nitride pore hydrophobicity can be tailored for nanopore sequencing, correlating changes in ionic currents with amino acid residue translocation. This research enhances the understanding of interactions within nanopore environments, potentially leading to more precise nanopore-based sequencing methods.

In the rapidly advancing field of quantum technologies, integrated quantum photonics merges quantum mechanics with photonics, promising breakthroughs in communication, sensing, computing, and security. This doctoral thesis investigates the generation of correlated photons via spontaneous four-wave mixing (sFWM) on silicon-based platforms. Through a comparative analysis of various intramodal and intermodal sources, the research focuses on two main areas: applications in sensing within the 2 μm region and the development of sources and other integrated structures in the visible-near infrared region for quantum algorithms, such as variational quantum eigensolver and boson sampler. For sensing, the study enhances quantum ghost spectroscopy to enable efficient gas detection using non-degenerate intermodal silicon sFWM. In the context of quantum simulation, silicon-nitride-based integrated photonic structures were realized to generate and manipulate quantum light within a photonic integrated circuit. Additionally, a proof-of-concept implementation of a two-qubit SWAP test in silicon nitride material showcased significant potential in quantum machine learning.

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[Truncated abstract] This study investigates the thermal stability of Plasma Enhanced Chemical Vapor Deposited (PECVD) silicon nitride thin films. Effects of heat-treatment in air on the chemical composition, atomic bonding structure, crystallinity, mechanical properties, morphological and physical integrity are investigated. The chemical composition, bonding structures and crystallinity are studied by means of X-ray Photoelectron Spectroscopy (XPS), Fourier Transform Infrared (FTIR) Spectroscopy and Transmission Electron Microscopy (TEM). The mechanical properties, such as hardness and Young’s modulus, are determined by means of nanoindentation. The morphological and physical integrity are analyzed using Scanning Electron Microscopy (SEM) . . . The Young’s modulus (E) and hardness (H) of the film deposited at 448 K were measured to have E=121±1.8 GPa and H=11.7±0.25 GPa. The film deposited at 573 K has E=150±3.6 GPa and H=14.7±0.6 GPa. For the film deposited at 573 K, the Young’s modulus is not affected by heating up to 1148 K. Heating at 1373 K caused significant increase in Young’s modulus to 180∼199 GPa. This is attributed to the crystallization of the film. For the film deposited at 448 K, the Young’s modulus showed a moderate increase, by ∼10%, after heating to above 673 K. This is consistent with the much lower level of crystallization in this film as compared to the film deposited at 573 K. In summary, low temperature deposited PECVD SiNx films are chemically and structurally unstable when heated in air to above 673 K. The main changes include oxidation to SiO2, crystallization of Si3N4 and physical cracking. The film deposited at 573 K is more stable and damage and oxidation resistant than the film deposited at 448 K.

Doctor of Philosophy / Department of Industrial & Manufacturing Systems Engineering / Shuting Lei / Laser-assisted machining (LAM) is a promising non-conventional machining technique for advanced ceramics. However, the fundamental machining mechanism which governs the LAM process is not well understood so far. Hence, the main objective of this study is to explore the machining mechanism and provide guidance for future LAM operations. In this study, laser-assisted milling (LAMill) of silicon nitride ceramics is focused. Experimental experience reveals that workpiece temperature in LAM of silicon nitride ceramics determines the surface quality of the machined workpiece. Thus, in order to know the thermal features of the workpiece in LAM, the laser-silicon nitride interaction mechanism is investigated via heating experiments. The trends of temperature affected by the key parameters (laser power, laser beam diameter, feed rate, and preheat time) are obtained through a parametric study. Experimental results show that high operating temperature leads to low cutting force, good surface finish, small edge chipping, and low residual stress. The temperature range for brittle-to-ductile transition should be avoided due to the rapid increase of fracture toughness. In order to know the temperature distribution at the cutting zone in the workpiece, a transient three-dimensional thermal model is developed using finite element analysis (FEA) and validated through experiments. Heat generation associated with machining is considered and demonstrated to have little impact on LAM. The model indicates that laser power is one critical parameter for successful operation of LAM. Feed and cutting speed can indirectly affect the operating temperatures. Furthermore, a machining model is established with the distinct element method (or discrete element method, DEM) to simulate the dynamic process of LAM. In the microstructural modeling of a β-type silicon nitride ceramic, clusters are used to simulate the rod-like grains of the silicon nitride ceramic and parallel bonds act as the intergranular glass phase between grains. The resulting temperature-dependent synthetic materials for LAM are calibrated through the numerical compression, bending and fracture toughness tests. The machining model is also validated through experiments in terms of cutting forces, chip size and depth of subsurface damage.

The global energy market is continuously changing due to changes in demand and fuel availability. Amongst the technologies considered as capable of fulfilling these future energy requirements, Photovoltaics (PV) are one of the most promising. Currently the majority of the PV market is fulfilled by crystalline Silicon (c-Si) solar cell technology, the so called 1st generation PV. Although c-Si technology is well established there is still a lot to be done to fully exploit its potential. The cost of the devices, and their efficiencies, must be improved to allow PV to become the energy source of the future. The surface of the c-Si device is one of the most important parts of the solar cell as the surface defines the electrical and the optical properties of the device. The surface is responsible for light reflection and charge carrier recombination. The standard surface finish is a thin film layer of silicon nitride deposited by Plasma Enhanced Chemical Vapour Deposition (PECVD). In this thesis an alternative technique of coating preparation is presented. The HiTUS sputtering tool, utilising a remote plasma source, was used to deposit the surface coating. The remote plasma source is unique for solar cells application. Sputtering is a versatile process allowing growth of different films by simply changing the target and/or the deposition atmosphere. Apart from silicon nitride, alternative materials to it were also investigated including: aluminium nitride (this was the first use of the material in solar cells) silicon carbide, and silicon carbonitride. All the materials were successfully used to prepare solar cells apart from the silicon carbide, which was not used due to too high a refractive index. Screen printed solar cells with a silicon nitride coating deposited in HiTUS were prepared with an efficiency of 15.14%. The coating was deposited without the use of silane, a hazardous precursor used in the PECVD process, and without substrate heating. The elimination of both offers potential processing advantages. By applying substrate heating it was found possible to improve the surface passivation and thus improve the spectral response of the solar cell for short wavelengths. These results show that HiTUS can deposit good quality ARC for silicon solar cells. It offers optical improvement of the ARC s properties, compared to an industrial standard, by using the DL-ARC high/low refractive index coating. This coating, unlike the silicon nitride silica stack, is applicable to encapsulated cells. The surface passivation levels obtained allowed a good blue current response.

Spark plasma sintering (SPS) is a powder consolidation technique used to rapidly densify a variety of material systems. SPS is capable of precisely controlling material microstructures and achieving non-equilibrium phases due to rapid heating and cooling rates through the simultaneous application of pressure and direct current. Due to these characteristics, SPS is an ideal processing technique for high temperature ceramics which require processing at temperatures greater than 1500°C. Due to the desirable properties obtained on small diameter materials processed by SPS, larger and more complex geometries are desired while maintaining sample microstructures. In order to accurately scale ceramics produced by SPS, a finite element model must be developed that can be used as a predictive tool. My research focuses on developing a finite element model for the spark plasma sintering furnace at the University of Arizona and validating modeled results using experimentally obtained data. Electrical and thermal conductivity as functions of temperature vary widely among different grades of commercially available electrode grade graphite at constant density. Modeled material properties are optimized in order to calibrate modeled results to experimentally obtained data (i.e. measured current, voltage, and temperature distributions). Sensitivity analysis is performed on the model to better understand model physics and predictions. A calibrated model is presented for 20mm ZrB2 and Si3N4 discs. Sample temperature gradients are experimentally confirmed using grain size and β-Si3N4 phase composition. The model is used to investigate scale up from 20mm to 30mm discs and 30mm rings as well as effects of processing conditions on β-Si3N4 content.