The effect of ultra-high temperature (UHT) on production of polycyclic aromatic hydrocarbons (PAHs) on the surface of beef steaks was determined. Beef steaks were treated with five treatments, raw, UHT, UHT/grill marks, UHT/grill marks/microwave, and charcoal grilled. Four PAHs, benzo[a]pyrene, benz[a]anthracene, benzo[b]fluoranthene, and benzo[k]fluoranthene, were quantified. High performance liquid chromatography (HPLC) and gas chromatography (GC) were used to purify and analyze the PAH extracts, respectively. Levels of PAH found on charcoal-grilled steaks were higher than those observed in the literature. A balanced incomplete block design was used to analyze the data. There were no significant differences among the treatments in the production of the benzofluoranthenes. There were significant increases in production of benzo[a]pyrene and benz[a]anthracene when grill marks were applied to the UHT steak. Microwaving significantly decreased the levels of benzo[a]pyrene and benz[a]anthracene. The production of these PAHs on UHT/grill mark/microwave steak did not differ significantly from the charcoal-grilled steak in the levels of PAH quantified.

Yogurts were made from intermediate-high temperature (100, 110, 120, and 130°C for 4 or 16 s), ultra-high temperature (140°C for 4 or 16 s), and vat heat (82°C for 20 min) treatments of skim milk fortified to 5% protein by either ultrafiltration or the addition of nonfat dry milk (NOM). Whey protein denaturation in heated milks increased with temperature and holding time from indirect plate heating and was highest in vat-heated milks. Whey protein denaturation and yogurt water-holding capacity increased with protein levels in the fortified milks compared to skim milk. Penetrometer gel strength and stirred viscosity in 21 day-old yogurt made from heated ultrafiltered skim milk exceeded those of yogurts made from NOM-fortified skim milk, even though the NOM yogurts contained more solids (13.0 vs 11.4%). Maximum gel strength and viscosity, and least syneresis of yogurts from ultrafiltered and NOM fortified yogurts occurred following intermediate-high temperature treatments of 1 00°C for 16 s, 110°C for 4 or 16 s, and 120°C for 4 s. There was significantly lower whey protein denaturation at these intermediate-high temperatures compared to UHT or vat heating. Gel strength and viscosity were lower and syneresis greater in yogurts from ultrafiltered or NOM-fortified skim milk following UHT treatment compared to yogurts made with intermediate-high temperature treatments or vat heating. The water-holding capacity of yogurts from fortified milks treated at intermediate-high temperatures was comparable to that of yogurts from vatheated milks. Fortification by ultrafiltration, to lower total solids (and without use of stabilizers) resulted in yogurt with higher gel strength and viscosity, and reduced syneresis compared to yogurt from NOM fortification. Yogurt prepared by intermediate-high temperature treatment had comparable or better gel strength and viscosity, and reduced syneresis compared to yogurt prepared by traditional vat heating.

The purpose of this research was to investigate the effect of ultra-high temperature process parameters on age gelation of milk concentrate. Skim milk was concentrated to 2X (volume reduction) using reverse osmosis. The milk concentrate was preheated at 75 or 90°C for 20 or 50 s and UHT-processed at 138 or 145°C for 4 or 16 s. Sterilizing methods used were direct steam injection and indirect plate heat exchanger. The samples were aseptically collected in presterilized plastic containers and stored at 15 or 35°C. At 15°C storage temperature, the steam-injected samples gelled in 5 months when 4 s UHT time was used. When UHT time was increased to 16 s, the samples gelled in 6 months. Of the samples that were UHT processed by indirect plate heat exchanger for 4 s and stored at 15°C, all gelled after 7 months. When UHT time was increased to 16 s, all the 138°C samples gelled after 7 months as did the samples that were preheated for 50 s and UHT-processed at 138°C. The samples preheated at 75°C for 50 sand UHT-processed at 145°C gelled after 8 months, whereas at 90°C preheat temperature the samples gelled after 9 months. The samples stored at 35°C did not gel but showed different sedimentation levels. The sediment depth in the container was always greater for the steam-injected samples. The samples that received higher heat treatments by the two processing methods had a higher sedimentation depth. The pH decreased during storage and the extent of reduction was higher at 35°C storage temperature . Maillard browning occurred at both storage temperatures. Browning was greater in samples stored at 35°C and processed by indirect plate heat exchanger.

This study investigated the manufacturing procedures and texture attributes of direct acid set of an unripened, shelf-stable cheese variety produced by the combined technologies of ultrafiltration and ultra-high temperature processing. Product evaluation included physical and chemical properties such as gel strength, syneresis, pH, moisture, protein, and fat. Whole milk was concentrated by ultrafiltration to 30, 35, and 40% total solids. Milk retentate was ultra-high temperature-processed by preheating to 65 or 77°C, sterilized at 141°C for 4 s by direct steam injection, flash cooled to approximately 62 or 72°C, homogenized in two stages at either 13.8/2.1 or 27.6/4.1 MPa, cooled to 38°C, and aseptically packaged. iv sterilized sodium chloride was aseptically added and dissolved in the ultra-filtrated and ultra-high temperature processed retentate to produce .5% final concentration. Autoclaved solutions of citric and lactic acids, or glucono-delta-lactone were added aseptically to the salted retentate to form a soft gel by lowering the pH range from 4.3 to 4.6. The coagulated retentates were stored at room temperature for 6 months. The effects of total solids, homogenization pressures, preheat temperatures, acidulants, and storage time on selected physicochemical properties of the acid gels were determined. Taste panels evaluated selected soft cheese characteristics after 6 months' storage. No statistically significant effect of the total milk solids level on gel firmness was observed. High homogenization pressure and the interaction of high preheat temperature and homogenization pressure produced significantly firmer gel and caused less syneresis. Acidulant types influenced significantly gel strength, syneresis, appearance, and texture. Soft cheeses prepared with citric acid were firmer than those acidified with lactic acid or gluconodelta-lactone. Lactic acid samples produced more syneresis than citric acid cheese samples. Cheese samples prepared with glucono-delta-lactone had the smoothest and least grainy texture, shiny appearance, little or no wheying-off, and a gel strength intermediate between the two other acidulants.

Zirconium carbide (ZrC) is a high modulus ceramic with an ultra-high melting temperature and, consequently, is capable of withstanding extreme environments. Carbon-carbon composites (CCCs) are important structural materials in future hypersonic aircraft; however, these materials may be susceptible to degradation when exposed to elevated temperatures during extreme velocities. At speeds of exceeding Mach 5, intense heating of leading edges of the aircraft triggers rapid oxidation of carbon in CCCs resulting in degradation of the structure and probable failure. Environmental/thermal barrier coatings (EBC/TBC) are employed to protect airfoil structures from extreme conditions. Yttria stabilized zirconia (YSZ) is a well-known EBC/TBC material currently used to protect metallic turbine blades and other aerospace structures. In this work, 3 mol% YSZ has been studied as a potential EBC/TBC on CCCs. However, YSZ is an oxygen conductor and may not sufficiently slow the oxidation of the underlying CCC. Under appropriate conditions, ZrC can form at the interface between CCC and YSZ. Because ZrC is a poor oxygen ion conductor in addition to its stability at high temperatures, it can reduce the oxygen transport to the CCC and thus increase the service lifetime of the structure. This dissertation investigates the thermodynamics and kinetics of the YSZ/ZrC/CCC system and the resulting structural changes across multiple size scales. A series of experiments were conducted to understand the mechanisms and species involved in the carbothermal reduction of ZrO2 to form ZrC. 3 mol% YSZ and graphite powders were uniaxially pressed into pellets and reacted in a graphite (C) furnace. Rietveld x-ray diffraction phase quantification determined that greater fractions of ZrC were formed when carbon was the majority mobile species. These results were validated by modeling the process thermochemically and were confirmed with additional experiments. Measurements were conducted to examine the effect of carbothermal reduction on the bond lengths in YSZ and ZrC. Subsequent extended x-ray absorption fine structure (EXAFS) measurements and calculations showed Zr-O, Zr-C and Zr-Zr bond lengths to be unchanged after carbothermal reduction. Energy dispersive spectroscopy (EDS) line scan and mapping were carried out on carbothermaly reduced 3 mol% YSZ and 10 mol% YSZ powders. Results revealed Y2O3 stabilizer forming agglomerates with a very low solubility in ZrC.

The manufacturing of UHTC materials has significantly advanced over recent years, allowing for the development of new microstructures, architectures, shapes, and geometries to explore new properties and applications for these materials beyond aerospace. One of the UHTCs, titanium diboride (TiB2) exhibits high electrical and thermal conductivity that could satisfy the needs of functional ceramic component applications, like battery cathodes, by tailoring its microstructure and architecture. This thesis represents one of the first detailed studies to understand how the processing-microstructure-properties relationship of TiB2 can be shifted to explore new applications. In order to do that, TiB2 has been manufactured with a processing technique never used before, with significant porosity, exploration of which has been very limited for this material. Additionally, this thesis also explores the synthesis and utilization of novel anisotropic particles to further explore this material relationship. In this work, aqueous tape casting of TiB2 has been investigated. Zeta potential measurements and suspension rheology were used to understand the role of dispersant, binder and plasticizer in the suspension and their interaction with the surface chemistry of the TiB2 particles to develop a stable, homogenous suspension, with minimum additive amounts (0-2 wt%). Homogeneous, flexible and strong TiB2 tapes were prepared using suspensions with 30 vol% solids and characterized to compare different compositions, mixing methods, and thicknesses. The characterization shows the tailoring of the properties as a function of the controlled suspension formulation with minimum amount of additives. Green tapes with 2 wt% dispersant, 1 wt% binder, and 2 wt% plasticizer had similar microstructure to those with half the plasticizer but quintuple the Young's modulus (1.96 GPa). The effect on other relevant properties is also discussed. Tape casting aligns anisotropic particles along the direction of casting, which can be taken advantage of for increasing fracture toughness directionally or producing aligned pore networks using sacrificial fillers. The relationship between alignment, porosity, and the mechanical properties of titanium diboride has not been studied. In this work, we characterize the porous sintered bodies produced through aqueous tape casting of non-spherical TiB2 particles of aspect ratio close to 1, as well as composites with an added high aspect ratio particle (2 wt% PCN-222). Synthesis of uniform, spherical ZrC is difficult and generally not cost-effective, as is the case for most ultra-high temperature ceramics. High aspect ratio particles for reinforcement of ceramic composites are even more difficult to synthesize. Metal organic frameworks (MOF) are crystalline coordination polymers composed of multidentate organic linkers bridging metal nodes to form porous structures. Thermal decomposition of MOFs presents a new and cost-effective route to synthesis of ZrC. In this study, heat treatment at 2000°C of MOF PCN-222 produces zirconium carbide (ZrC) within a highly anisotropic particle. The resulting rod-shaped, glass-like carbon matrix embedded with ZrC crystals is described. These rods have potential as reinforcements for iii high temperature applications and as a synthetic route for ultra-high temperature ceramics with unique morphologies. It is the first time that this type of transformation from a MOF into a UHTC has been reported. We have determined through analysis of SEM images that regardless of tape casting speed, about 57% of the TiB2 particles are aligned with the tape casting direction. The mechanical properties are dominated by the effects of the porosity (38%), but the alignment exhibited here could be further exploited for anisotropic behavior across the sintered tapes. Composites cast with high aspect ratio particles exhibited strong alignment in the casting direction. Further work is required to understand the interplay between alignment and porosity and their effects on material properties. / Doctor of Philosophy / Titanium diboride (TiB2) is an ultra-high temperature ceramic with a melting point of 3225°C. Many applications for this material require fully dense structural ceramics, such as cutting tools,1 armor,2 and high temperature structural supports.2,3 These applications rely mainly on the high mechanical strength of TiB2, which is maintained in extreme thermal and chemical environments. The field of knowledge surrounding TiB2 lacks information about the ways that porosity affects its otherwise well-known properties;4,5 to bridge this gap could open up applications for functional and porous ceramics such as lithium-air batteries,6 electrochemical components,7 semiconductors,8 and more. This work intends to provide a foundation for this endeavor by developing for the first time a colloidal suspension formulation that allows for the tape casting of TiB2 and characterizing the resulting porous ceramics. Among these new potential applications, many require thin ceramics less than 1 mm thick—a result which has been accomplished for other materials via tape casting.4,9 This is a wet route of producing ceramics that provides the ability to tailor the surface chemistry of the particles, giving greater control over the stability of the suspension (TiB2 particles suspended in water) and quality of the end product than is afforded by dry processing routes.10 This also allows for more complex shaping than simple pressing, which ultimately saves costs; by producing the near-net shape in the green body before firing, less machining must be done to the sintered body when it is removed from the high temperature furnace.11 In tape casting, the suspension is spread over a substrate by a doctor blade to the desired thickness. It is known that tape casting tends to align anisotropic particles along the direction of casting due to a nonuniform velocity imparted by the shear force of the doctor blade spreading the suspension, an advantage which can provide directional properties in the final ceramic.9 While this process is well known, it has never been applied to the material TiB2 prior to this work. In this work, a suspension is formulated to allow for the tape casting of TiB2 with minimum organic additive content, which is cost-effective and reduces potential for defects. Porosity and alignment in the tape cast specimens are characterized. For comparison, a highly anisotropic or rod-shaped particle (PCN-222, a metal organic framework material) was included in the TiB2 suspensions for tape casting. This metal organic framework (MOF) has been transformed into a high temperature material after thermal treatment at the sintering temperature of 2000°C, showing that the resulting particle is made of glass-like carbon embedded with zirconium carbide (ZrC) crystallites. This particle could be used as a reinforcement for ultra-high temperature ceramics, and in this work was shown to align strongly in the tape casting direction. At the level of porosity (38%) and alignment (57%) in the TiB2 specimens in this study, porosity dominates the mechanical properties. This relationship is shown to be more complicated than lowering the strength by the same proportion that the density is lowered, and various models for understanding the role of porosity on the elastic modulus are explored.

<p>For many applications within the defense, aerospace, and electricity-producing industries, available material choices for high-performance devices that fulfill necessary requirements are limited. Choosing a metallic material or a ceramic material may be optimal for only some of the required properties. For instance, choosing a metal may optimize ductility but compromise oxidation resistance, yield strength, or creep resistance. Of potential interest, ceramic-metal (cermet) composites can address several fundamental concerns such as high temperature mechanical toughness and stiffness and oxidation/corrosion resistance. However, cost-effective, scalable manufacturing of complex-shaped, high-temperature cermets can be challenging.</p> <p>A cermet of interest is niobium and yttrium oxide, Y2O3. Both materials exhibit high melting points with similar coefficients of thermal expansion. Basic thermodynamic calculations suggest that these materials are chemically compatible, and that Y2O3/Nb cermets may be generated by reactive melt infiltration using the patented Displacive Compensation of Porosity (DCP) process. With the DCP process, a liquid fills a porous perform, and a displacement reaction occurs to produce products of larger solid volume. This reaction yields the cermet of interest, formed in a reduced-stress condition, while maintaining a generally near net shape and high relative density.</p> <p>In order to get to the point of designing cermet components for various applications, a focus of this work has been to create a Y2O3/Nb composite by hot pressing powders at high temperatures at the predicted stoichiometric ratios, and then characterizing the thermal and mechanical properties. The reduction reaction between liquid yttrium and solid niobium (IV) oxide (NbO2) was then characterized to evaluate kinetic mechanisms affecting the reaction rate which is necessary for future DCP-based cermet component manufacturing.</p> <p>Lastly, the mechanical behavior of this cermet was modeled and compared to another cermet processed using liquid metal infiltration using a temperature-dependent elasto-visco-plastic self-consistent model. The effects of cooling from processing temperatures, as well as thermally cycling of these cermets, were quantified. As high temperature experiments can be time intensive with high costs, it is advantageous to have a computationally efficient, desktop design tool to quantify the impacts of changing processing and use conditions on material performance.</p>

From space exploration and advanced aircraft to next generation weapons, achieving hypersonic speed is becoming increasingly important across a range of research domains. The immense challenge associated with this goal involves the development of suitable materials and systems for the different components of a hypersonic vehicle, each of which must have the inherent capability to resist extreme temperatures, high thermal shock due to high heat flux, and high oxidation and ablation. First, the ultra-high temperature ceramic (UHTC) zirconium diboride or ZrB2 was sintered by ultra-fast high temperature sintering (UHS). The UHS process was optimized and the sintering parameters for ZrB2 and other UHTCs were studied. ZrB2 is an ultra-high temperature ceramic (UHTC) with a very high melting point; thus, its densification is difficult, energy intensive, and time-consuming. Commercial ZrB2 powders were rapidly densified via UHS to >90% relative density within 60 second in vacuum without pressure. The effect of sintering time on densification and final grain size were studied. An innovative process for manufacturing bulk UHTC materials was studied and is detailed herein. Second, the work function (W_f) of electron emitting materials was reduced to improved performance. A reduction of W_f in multicomponent hexaborides was achieved by doping with highly electropositive Ba, which enhances electron emission. Single-phase bulk multicomponent polycrystalline hexaborides of La0.5Ba0.5B6, Ce0.5Ba0.5B6, and BaB6 powders were first synthesized and then densified by UHS sintering. W_f measurements were obtained by Kelvin probe force microscopy. Ba-substitution was found to lower W_f (~25%) in synthesized multicomponent hexaborides. The specific techniques required to engineer the W_f of these materials are also provided herein. Finally, combining low W_f materials with UHTCs was explored for thin film systems for the exterior surface of hypersonic vehicles. The thin films of CeB6, a low W_f material, was deposited on sintered ZrB2 by RF-sputtering and single crystalline SrTiO3 (STO) substrates. Epitaxial thin films of SrHfO3 (SHO) were also deposited on (100), (110) and (111) STO substrates at 600°C. X-ray diffraction (XRD) results confirmed the formation of epitaxial layer, and reciprocal space mapping (RSM) was used to characterize film's mosaicity / texture on different substrates. XRD and RSM data demonstrated that the most favorable film growth direction was (110). As detailed herein, an inexpensive thin film production process, RF-sputtering, was exploited to manufacture various epitaxial and non-epitaxial layers of low W_f materials on UHTC and single-crystal substrates for hypersonic vehicles. To summarize, a range of bulk UHTCs and low W_f materials were prepared by UHS, and various thin films of low W_f material were produced on UHTC. Thereafter, the properties of synthesized materials were studied to develop new material systems for hypersonic applications. The findings from this research shed light on the development of suitable materials for implementation of electron transpiration cooling for hypersonic vehicle development. / Doctor of Philosophy / Rapid sintering of ultra-high temperature ceramics (UHTCs) and synthesis of low work-function electron emitting materials have been performed by ultra-fast high temperature sintering technique (UHS). Sintering of UHTCs is a difficult process, due to their high melting temperature, presence of covalent bond, and slower diffusion coefficient. A long sintering duration is used to achieve a high relative density along with adding sintering aid, using fine powder (produced by milling), and utilizing pressure (such as field assisted sintering and hot-pressing technology) during sintering. Synthesis and densification of multicomponent hexaboride is difficult, involves multi-steps and complicated processes. These long and complicated processes not only prolong development of new materials but also cause chemical wastes. To overcome all the aforementioned processing issues, an advanced processing technique, UHS, is used and densified pure and commercially available UHTCs to >90% within 60 second without applying sintering aid, powder milling, and pressure. The outcome of this research demonstrates the potential for a simple, cost-effective, fast, and adjustable processes, UHS, to develop a wide range of bulk UHTCs and other technical ceramics, and it gives new insight into the mechanisms of rapid sintering of UHTCs by rapid heating. The first detailed studies (experimental report) on rapid sintering of ZrB2 (and other UHTCs) by UHS technique and a through characterizations of the UHS sintered sample were performed to understand rapid sintering mechanism and how the processing effects the microstructure and properties of UHS ZrB2. The rapid microstructural evolution during the UHS sintering is investigated at 10, 30, and 60 second sintering interval. The UHS technique enables a heating rate of 103 - 104 °C/min and reaches a sintering temperature of 2600 °C in 30 seconds. Microstructural analysis was conducted on polished sample surfaces by using ImageJ software (National Institutes of Health, version 1.53e), measuring the grain size perpendicular to two diagonals of each grain. A comparison of grain size from sample center and periphery showed a homogeneous microstructure after sintering. Furthermore, the rapid sintering did not change/effect crystallinity, boron to metal stoichiometry, and grain boundary elemental composition as observed by XRD and EDS analysis. Additional characterization of the UHS sintered ZrB2 shows a hardness and elastic modulus of 30 GPa and 412 GPa respectively by nanoindentation method. Finally, the oxidation test at 1100 °C in isothermal condition showed a weight gain of 1.4% in air. The low work-function (W_f) materials are famous for electron emitting applications like electron guns for scanning electron microscopy. DFT simulation predicts the W_f of the widely used electron emitters (such as LaB6 and CeB6) can be reduced by changing their compositions, which increase electron generation efficiency of those materials. Previously, those materials were synthesized by long processes that involved multiple processing steps, which required expensive starting materials and yielded chemical wastes. The advantages of rapid sintering technique, UHS, had been exploited to synthesize low work function electron emitting materials. Single-phase bulk polycrystalline hexaborides were produced by using electrically powered UHS technique using a vacuum atmosphere. A reaction synthesis route: B4C reduction technique was first used to form pure phase hexaboride. Then, the synthesized compositions were densified to ~90% theoretical density in 180 seconds by UHS densification. After UHS sintering, XRD analysis confirmed the presence of a phase pure cubic BaB6, La0.5Ba0.5B6, and Ce0.5Ba0.5B6. Additional analyses were conducted to determine an optimum reaction temperature 1500 and 2100 °C for the formation BaB6 and multi-component hexaborides. Microstructural analyses were conducted to observe both reaction-synthesized and densified products. EDS compositional analysis and elemental mapping revealed a stoichiometric reaction product with homogeneous metal cation and boron distributions. The W_f of BaB6, La0.5Ba0.5B6, and Ce0.5Ba0.5B6 was determined to be 1.95 ± 0.1, 2.05 ± 0.1 and 2.0 ± 0.1 eV, respectively. The addition of BaB6 in La0.5Ba0.5B6, and Ce0.5Ba0.5B6 resulted in a 25% decrease in W_f for LaB6 from 2.7 ± 0.1 to 2.00 ± 0.1 eV and a 23% decrease in W_f for CeB6 from 2.68 ± 0.08 to 2.05 ± 0.1 eV. Ba substitution is shown to be a general method for lowering W_f in a variety of multicomponent hexaborides. Finally, the polycrystalline thin films of CeB6, a low W_f material, was deposited on sintered ZrB2 by RF-sputtering technique. Additionally, epitaxial thin films of SrHfO3 (SHO) were also deposited on (100), (110) and (111) STO single crystalline substrates. Both types of thin films were deposited at 600 °C temperature and at a vacuum pressure of 10-3 Torr. After deposition of the SHO films, X-ray diffraction (XRD) was conducted to confirm the formation of epitaxial layer, and reciprocal space mapping (RSM) was used to characterize film's mosaicity / texture on different substrates. XRD and RSM data demonstrated that the most favorable film growth direction was (110). The XRD of the CeB6 film showed highly crystalline film was formed. For both the films, a detailed microstructural analysis was performed by scanning electron microscopy and film smoothness was characterized by atomic force microscopy method. As detailed herein, an inexpensive thin film production process, RF-sputtering, was exploited to manufacture various epitaxial and non-epitaxial layers of low W_f materials on UHTC and single-crystal substrates for hypersonic vehicles applications.

The use of electrospun polystyrene (PS) fibers to create continuous long range ordered multi-scale porous structures in titanium diboride (TiB2) is investigated in this work. The introduction of electrospun PS fibers as a sacrificial filler into a colloidal suspension of TiB2 allows for easy control over the pore size, porosity, and long range ordering of the porous structures of the sintered ceramic. Green bodies were formed by vacuum infiltrating an electrospun-fiber-filled mold with the colloidal TiB2 suspension. The size, volume, distribution, and dispersion of the pores were optimized by carefully selecting the sacrificial polymer, the fiber diameter, the solvent, and the solid content of TiB2. The green bodies were partially sintered at 2000 C in argon to form a multiscale porous structure via the removal of the PS fibers. Aligned continuous cylindrical pores were derived from the PS fibers in a range of ~5 - 20 μm and random porosity was revealed between the ceramic particles with the size of ~0.3 - 1 μm. TiB2 near-net-shaped parts with the multi-scale porosities (~50 to 70%) were successfully cast and sintered. The multi-scale porous structure produced from electrospun fibers was characterized both thermally and mechanically, at room temperature. The conductivity ranged from 12-31 W m^(-1) K^(-1) at room temperature and the compressive strength ranged from 2-30 MPa at room temperature. Analytical thermal and mechanical models were employed to understand and verify he processing-structure-properties relationship. Finally, a method was devised for estimating the effective thermal conductivity of candidate materials for UHTC applications at relevant temperatures using a finite difference model and a controlled sample environment. This low-cost processing technique facilitates the production of thermally and mechanically anisotropic structures into near-net shape parts, for extreme environment applications, such as ultra high temperature insulation and active cooling components. / MS / Society is on the cusp of hypersonic flight which will revolutionize defense, space and transport technologies. Hypersonic flight is associated with conditions like that of atmospheric re-entry, high heat and force or specific locations of a space craft. The realization of hypersonic flight relies on innovative materials to survive the harsh conditions for repeated flight. We have created a new material with tiny holes that can help prevent heat flow from the harsh atmosphere from damaging the hypersonic craft. Thesis tiny holes are made from placing a polymer fiber in an advanced ceramic (which withstand high temperatures) and removing the fiber to leave holes. The tiny hole’s effect on strength and heat flow have been studied, to understand how the tiny holes can be made better. It is difficult to test materials in the harsh atmosphere associated with hypersonic flight, so a program has been written to estimate thermal properties of candidate materials for hypersonic flight.

The effects of oxidation in the thermomechanical response of porous titanium diboride have been investigated. An in-house quasi-static material point method tool was used to perform two -dimensional plane strain simulations on unoxidized hexagonal representative volume elements (RVEs) with macroporosity volume fractions of 10%, 40% and 70% to establish a baseline for the response due to geometric effects. Compressive strains of up to 30% were applied at room temperature. The 10% and 40% RVEs showed shear banding and subsequent shear failure of the inter-pore struts, while shear banding in 70% RVE weakened the struts, which lead to buckling failure. A snapshot oxidation model was then applied to the hexagonal RVEs in place of a transient, diffusion-based oxidation solver. Compressive strain simulations were performed on RVEs with oxide layers ranging from 5 to 50 μm. In RVEs with porosity of 40% or higher, oxide percolation in the struts reduced the effective elastic modulus and compressive strength, though further oxidation beyond the percolation point did not have a significant impact. Ramped and cyclic thermal loads were applied and the damage due to thermal expansion coefficient mismatch at the oxide-substrate interface decreased as the oxide layer was increased. Finally, the snapshot oxidation modeling approach was applied to large porous RVEs derived from micro-computed tomography images of titanium diboride foam. The effective elastic modulus decreased by 47% when the 5 μm layer was applied due to many thin, flexible struts becoming fully oxidized. Subsequent oxidation did not have a significant impact on the thermomechanical response. / Master of Science / Thermal loading experienced by hypersonic flight vehicles has posed significant design challenges in the development of platforms for military and re-entry applications. The advent of hypersonic strike weapons and waveriders has led to an interest in utilizing ceramics with melting points above 3000°C, called ultra-high temperature ceramics (UHTCs), that offer improved resistance to high-temperature oxidation. Beyond load-carrying applications, UHTCs imbued with macroscale porosity have been introduced as candidates for providing thermal insulation of sensitive on-board components. This thesis presents a first pass at modeling the coupled effects of oxidation and continuum damage in the thermomechanical response of such materials. Using an in-house material point method tool, two-dimensional compressive strain simulations were performed on hexagonal representative volume elements (RVEs) of titanium diboride foam with varying levels of macroporosity, along with large porous RVEs derived from micro-computed tomography images of titanium diboride foam. A snapshot oxidation model was applied to these RVEs in place of a transient, diffusion-based oxidation solver, then simulations with applied compressive strains of up to 30% were performed on RVEs with oxide layers ranging from 5 to 50 μm. Ramped and cyclic thermal loads were applied to explore the effects of thermal expansion mismatch between the substrate and oxide phases. The oxide layers were shown to reduce the effective stiffness, compressive strength, and thermal conductivity of the RVEs, with the oxidation state of the inter-pore struts having a large impact on the overall material response.