Next generation aerospace vehicles require thermal protection system (TPS) materials that are capable of withstanding the extreme aerothermal environment during hypersonic flight (>Mach 5 [>1700 m/s]). Ultra-high temperature ceramics (UHTC) such as zirconium diboride (ZrB₂) are candidate TPS materials due to their high-temperature thermal and mechanical properties and are often the basis for advanced composites for enhanced oxidation resistance. However, ZrB₂ matrix impurities in the form of boron trioxide (B₂O₃) and zirconium dioxide (ZrO₂) limit the high-temperature capabilities. Electric based sintering techniques, such as spark plasma sintering (SPS), that use joule heating have become the preferred densification method to process advanced ceramics due to its ability to produce high density parts with reduced densification times and limit grain growth. This study focuses on a combined experimental and thermodynamic assisted processing approach to enhance powder purity through a carbo- and borocarbo-thermal reduction of oxides using carbon (C) and boron carbide (B₄C). The amount of oxides on the powder surface are measured, the amount of additive required to remove oxides is calculated, and processing conditions (temperature, pressure, environment) are controlled to promote favorable thermodynamic reactions both during thermal processing in a tube furnace and SPS. Untreated ZrB₂ contains 0.18 wt%O after SPS. Additions of 0.75 wt%C is found to reduce powder surface oxides to 0.12 wt%O. A preliminary Zr-C-O computational thermodynamic model shows limited efficiency of carbon additions to completely remove oxygen due to the solubility of oxygen in zirconium carbide (ZrC) forming a zirconium oxycarbide (ZrCₓOᵧ). Scanning electron microscopy (SEM) and scanning transmission electron microscopy (STEM) with atomic scale elemental spectroscopy shows reduced oxygen content with amorphous Zr-B oxides and discreet ZrO₂ particle impurities in the microstructure. Processing ZrB₂ with minimal additions of B₄C (0.25 wt%) produces high purity parts after SPS with only 0.06 wt%O. STEM identifies unique “trash collector” oxides composed of manufacturer powder impurities of calcium, silver, and yttrium. A preliminary Zr-B-C-O thermodynamic model is used to show the potential reaction paths using B₄C that promotes oxide removal to produce high-purity ZrB₂ with fine grains (3.3 𝜇m) and superior mechanical properties (flexural strength of 660MPa) than the current state-of-the-art ZrB₂ ceramics. Due to the desirable properties produced using SPS, there is growing interest to advance processing techniques from lab-scale (20 mm discs) to large-scale (>100 mm). The advancement of SPS technologies has been stunted due to the limited power and load delivery of lab-scale furnaces. We use a large scale direct current sintering furnace (DCS) to address the challenges of producing industrially relevant sized parts. However, current-assisted sintering techniques, like SPS and DCS, are highly dependent on tooling resistances and the electrical conductivity of the sample, which influences the part uniformity through localized heating spots that are strongly dependent on the current flow path. We develop a coupled thermal-electrical finite element analysis model to investigate the development and effects of tooling and current density manipulation on an electrical conductor (ZrB₂) and an electrical insulator, silicon nitride (Si₃N₄), at the steady-state where material properties, temperature gradients and current/voltage input are constant. The model is built based on experimentally measured temperature gradients in the tooling for 20 mm discs and validated by producing 30 mm discs with similar temperature gradients and grain size uniformity across the part. The model aids in developing tooling to manipulate localize current density in specific regions to produce uniform 100 mm discs of ZrB₂ and Si₃N₄.

Spark plasma sintering (SPS), also known as direct current sintering (DCS) is an advanced sintering technique that and uses a continuous pulsed direct current to rapidly process materials through Joule heating and offers significant advantages and versatility over conventional sintering methods. The technique features in energy saving owing to high heating rates and is very suitable for consolidation as well as diffusion bonding of electrical conductive advanced ceramic materials such as ultra high temperature ceramics (UHTCs). However, cooling rate in SPS also plays an important role as it directly influences the generation of residual stress especially for specimens consist of dissimilar phases such as composites and laminates primarily due to CTE mismatch. Therefore, in order to produce high quality materials, a zirconium diboride with addition of silicon carbide (ZrB2-SiC) ultra high temperature ceramic composite is selected to investigate the effect of cooling rate in SPS on microstructure and mechanical properties. After being densified at the target temperature, ZrB2-25vol%SiC specimens are cooled from 1800°C using controlled cooling rates of 10 °C/minute to ~225.5 °C/minute (free cooling). A time dependent finite element analysis (FEA) model is used to simulate the temperature gradients across the specimens at dwell times and during the cooling processes. The residual stress within the specimens are experimentally verified using X-ray diffraction (XRD) and Raman spectrometry, and found maximum residual stress within the specimen cooled at 225.5 °C/minute. Peak Hardness and moderate elastic modulus is found for specimen sintered at 1800 °C and cooled at 100 °C/minute, which make this temperature and cooling rate appropriate conditions for future fabrication of UHTCs with similar thermal and electrical properties. These materials are of great interest for their excellent high-temperature capabilities, wear and corrosion resistance, and are regarded as material candidates for engineering applications in extreme environments. Therefore, development of an effective joining technique is important since near-net shape fabrication is challenging, and joints formed by brazing or conventional solid-state diffusion bonding limit the mechanical strength and high temperature applications of the base materials. Using SPS we have rapidly and successfully joined ZrB2 to hafnium diboride (HfB2) at 1750 and 1800 °C within a minute through electric current assisted solid-state diffusion bonding. The electric current enables localized Joule heating as well as plastic deformation of the mating surface asperities, and enhances the elemental interdiffusion process at the HfB2/ZrB2 interfaces owing to electromigration, which leads to the formation of ZrxHf1-xB2 solid solution. A series of characterization and analytical techniques including scanning electron microscopy (SEM), wavelength dispersive spectroscopy (WDS), electron backscatter diffraction (EBSD), and scanning transmission electron microscopy (S/TEM) are employed to study the microstructure and chemical composition at of the HfB2/ZrB2 interfaces. Apart from enhanced diffusion as a result of electromigration, the applied electric current can also be use to promote plastic deformation in ZrB2, which does not go through gross plastic deformation due to its extremely high melting point and brittle nature even when elevated temperature and pressure are applied. Through “electroplastic effect” (an effect based on electromigration) the mobility and multiplication of the existing dislocations in ZrB2 is enhanced, and a “metal-like” primary recrystallization phenomenon in the ZrB2 is observed meaning the material has experienced a sufficient amount of plastic deformation and reached the critical dislocation density and configuration for nucleation of “strain-free” grains. The average grain size of the recrystallized grain is only ½ of its original value. These findings suggest great potentials in microstructural tailoring and grain refinement of conductive advanced ceramics using SPS, and provide promising ideas for future fabrications and applications.

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.

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 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.

Ultra-high temperature ceramics (UHTCs) are a class of materials that maintain their structural integrity at high temperatures, e.g. 2000 °C. They have been limited in their aerospace applications because of their relatively high density and the difficulty involved in forming them into complex shapes, like leading edges and inlets. Recent advanced processing techniques have made significant headway in addressing these challenges, where the introduction of multiscale porosity has resulted in lightweight UHTCs dubbed multiscale porous UHTCs. The effect of multiscale porosity on material properties must be characterized to enable design, but doing so experimentally can be costly, especially when attempting to replicate hypersonic flight conditions for relevant testing of selected candidate samples. As such, this dissertation seeks to computationally characterize the thermomechanical properties of multiscale porous UHTCs, specifically titanium diboride, and validate those results against experimental results so as to build confidence in the model. An implicit quasi-static variant of the Material Point Method (MPM) is developed, whose capabilities include intrinsic treatment of large deformations and contact which are needed to capture the complex material behavior of the as-simulated porous UHTC microstructures. It is found that the MPM can successfully obtain the elastic thermomechanical properties of multiscale porous UHTCs over a wide range of temperatures. Furthermore, characterizations of post-elastic behavior are found to be qualitatively consistent with data obtained from uniaxial compression experiments and Brazilian disk experiments. / Doctor of Philosophy / This dissertation explores a class of materials called ultra-high temperature ceramics (UHTCs). These materials can sustain very high temperatures without degrading, and thus have the potential to be used on hypersonic aircraft which routinely experience high temperatures during flight. In lieu of performing experiments on physical UHTC specimens, one can perform a series of computer simulations to figure out how UHTCs behave under various conditions. This is done here, with a particular focus what happens when pores are introduced into UHTCs, thus rendering them more like a sponge than a solid block of material. Doing computer simulations instead of physical experiments is attractive because of the flexibility one has in a computational environment, as well as the significantly decreased cost associated with running a simulation vs. setting up and performing an experiment. This is especially true when considering challenging operating environments like those experienced by high-speed aircraft. The ultimate goal with this research is to develop a computational tool than can be used to design the ideal distribution of pores in UHTCs so that they can best perform their intended functions.

<p dir="ltr">The technological drive of humanity to explore the cosmos, travel at hypersonic speeds, and pursue clean energy solutions requires ceramic scientists and engineers to constantly push materials to their functional, behavioral, and chemical extremes. Ultra-high temperature ceramics, and particularly transition metal carbides, are promising materials to meet the demands of extreme environment materials with their >4000 °C melting temperature and impressive thermomechanical behaviors in extreme conditions. The advent of the 2D version of these transition metal carbides, known as MXenes, added a new direction to design transition metal carbides for energy, catalysis, flexible electronics, and other applications. Toward extreme conditions, although MXenes remain yet unexplored, we believe that the ~1 nm flakes of MXenes gives ceramics scientists and engineers the ability to truly engineer transition metal carbides layer-by-layer at the nanoscale to endure the extreme conditions required by future harsh environment technology. Although MXenes have this inherent promise, fundamental study of their behavior in high-temperature environments is necessary to understand how their chemistry and 2D nature affects the high-temperature stability and phase behavior of MXenes toward application in extreme environments.</p><p dir="ltr">In this dissertation, we investigate the high-temperature phase behavior of 2D MXenes in high temperature inert environments to understand the stability and phase transition behavior of MXenes. In this work, we demonstrate that 1) MXenes’ transition at high-temperatures is to highly textured transition metal carbides is due to the homoepitaxial growth of these phases onto ~1-nm-thick MXenes’ highly exposed basal plane, 2) the MXene to MXene interface plays a major role in the phase behavior of MXenes, particularly toward building layered transition metal carbides using MXenes as ~1-nm-thick building blocks, and 3) Defects are the primary site at which atomic migration begins during phase transition of MXenes into these highly textured transition metal carbides, and these defects can be engineered for different phase stability of MXenes. To do so, we investigate the phase behavior of Ti₃C₂T_<em>x</em>, Ta₄C₃T_<em>x</em>, Mo₂TiC₂T_<em>x</em>, and other MXenes using a combination of <i>in situ</i> x-ray diffraction and scanning transmission electron microscopy and other <i>ex situ</i> methods, such as secondary ion mass spectrometry and x-ray photoelectron spectroscopy, with other methods. By investigating the fundamentals of the high-temperature phase behavior of MXenes, we hope to establish the basic principles behind use of MXenes as the ideal material for application in future extreme environments.</p>

Hypersonic aerospace vehicles are severely limited by the lack of adequate high temperature materials that can withstand the harsh hypersonic environment. Tantalum carbide (TaC), with a melting point of 3880°C, is an ultrahigh temperature ceramic (UHTC) with potential applications such as scramjet engines, leading edges, and zero erosion nozzles. However, consolidation of TaC to a dense structure and its low fracture toughness are major challenges that make it currently unviable for hypersonic applications. In this study, Graphene NanoPlatelets (GNP) reinforced TaC composites are synthesized by spark plasma sintering (SPS) at extreme conditions of 1850˚C and 80-100 MPa. The addition of GNP improves densification and enhances fracture toughness of TaC by up to ~100% through mechanisms such as GNP bending, sliding, pull-out, grain wrapping, crack bridging, and crack deflection. Also, TaC-GNP composites display improved oxidation behavior over TaC when exposed to a high temperature plasma flow exceeding 2500 ˚C.

Pour améliorer la durée de vie des matériaux à haute température et sous atmosphère oxydante, une solution est l’utilisation d’une protection de surface constituée de matériaux ultra réfractaires non oxydes. Un des objectifs principaux de cette thèse est la sélection et la validation expérimentale de nouvelles compositions chimiques de revêtements utilisés en condition oxydante et corrosive à ultra haute température. Les recherches s’appuient sur une démarche expérimentale physico-chimique se basant sur une approche thermodynamique et thermochimique menée au préalable pour choisir les composés. Les revêtements doivent être stables chimiquement, compatibles thermomécaniquement avec le substrat et adhérent de la température ambiante à celle d’utilisation. De plus, Ils doivent jouer le rôle de barrière environnementale et/ou de barrière thermique.Des tests d’oxydation sont réalisés au four solaire sur les systèmes de matériaux non oxydes massifs élaborés par frittage flash. En parallèle, des composites modèles constitués d’une fibre de carbone revêtue par PVD d’un revêtement métallique ultra réfractaire ont été élaborés puis chauffés par effet Joule afin de réaliser des tests d’oxydation. La compréhension des mécanismes entrant en jeu lors de l’oxydation de ces « nouveaux » revêtements est aussi un des challenges de ce manuscrit. Par ailleurs, elle aide à la classification de ces matériaux selon leur résistance à l’oxydation. / In order to improve material’s lifetime used at a temperature above 2500°C and under oxidizing atmosphere, a solution is to use a surfacing protection constituted of non oxide refractory materials. One of the main objectives of this thesis is to select and experimentally validate new chemical coating compositions which will be used under corrosive and oxidizing atmosphere at ultra high temperature (more than 2000°C). A preliminary thermodynamic and thermo-chemical study aims to select compounds. These compounds are then analyzed with physic-chemical tests. Coatings have to be chemically stable, thermo-mechanically compatible with the substrate and have to stick to the substrate from ambient temperature to more than 2000°C. Moreover, coatings have to act as an environmental barrier and/or as a thermal barrier.Two kinds of oxidation tests are made. On one hand, non oxide massive material’s systems are fabricated by spark plasma sintering in order to be tested at the solar furnace. On the other hand, composite models are fabricated by PVD. A carbon fiber is covered with ultra refractory metallic coating by PVD. Then, these composite models are heated by Joule effect in order to realize oxidation tests. Understanding mechanisms at work during the oxidation of these new coatings is another main objective of this thesis. This understanding will be also useful to classify these materials regarding their resistance to oxidation.

Les composites de type Cf/C sont utilisés en tant que pièces structurales dans les propulseurs spatiaux du fait de leurs excellentes propriétés mécaniques dans le domaine des très hautes températures. Néanmoins, l’atmosphère oxydante et corrosive créée lors du décollage des lanceurs et les hauts flux gazeux dégradent ces matériaux. Afin d’améliorer les performances de ces matériaux vis-à-vis de l’oxydation/corrosion, une protection composée de céramiques ultra-réfractaires (dites UHTC) peut être appliquée. Pour une efficacité de protection optimale, des phases UHTC ont été introduites en tant que constituants de la matrice. Dans ces travaux de thèse, la matrice a été réalisée par l’intermédiaire d’un procédé d’élaboration en phase liquide combinant : (i) l’introduction de poudres et (ii) la densification par infiltration réactive d’un métal fondu. La composition de la matrice appartient au système (B;C;Si;Zr). La caractérisation des matériaux après élaboration a permis de comprendre les mécanismes d’infiltration et les réactions permettant de mieux contrôler la composition chimique et la répartition des phases. Des essais sous torche oxyacétylénique ont été utilisés pour se placer dans des conditions proches de l’application visée. La caractérisation post-test des matériaux a permis d’évaluer l’efficacité de la protection dans le cas d’une utilisation unique et également d’une possible réutilisation. Les résultats en oxydation/corrosion ont permis de classer les matériaux en fonction de leur efficacité de protection. / Since many decades, Carbon/Carbon composites are used as structural parts in rocket engines due to their excellent thermomechanical properties. However, under highly oxidizing/corrosive atmosphere and high gas flow rates, carbon suffers from severe oxidation. To improve oxidation resistance of these composites, Ultra High Temperature Ceramics (UHTC) can be used as a protection. To protect the whole composite, the introduction of UHTC as a matrix has been done using a liquid phase process combining: (i) slurry infiltration process and (ii) reactive melt infiltration. Matrix constituents belong to the (B;C;Si;Zr) system. Material characterisation allowed a better understanding of the infiltration mechanisms and of the phase distribution and composition in respect to the processing conditions. To select the best composition, oxyacetylene torch testing has been done to recreate spacecraft launch environmental conditions. Post-test characterisation has been done to evaluate protection efficiency of each matrix composition for single use and possible reuse. Finally, advantages and drawbacks assessment of each composition allowed to highlight the most protective composition and phase distribution.