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This dissertation discusses the synthesis, processing, and characterization of titanium carbide (TiC) and titanium diboride (TiB2) based materials for structural and electronic application. A series of TiB2 and TiC-TiB2 powders was prepared through a novel carbon coated precursors method. Reaction process, phase evolution, and microstructures were analyzed and characterized. The synthesized powders have the advantages of fine particle size (nano to submicron grade, 100nm to 800nm), high purity (low levels of contaminations such as free carbon and oxygen), loose agglomeration, and high surface area (~2.5 m2/g to 7.2 m2/g). Using the synthesized powders, three categories of composites were prepared: (1) TiB2-TiC-Ni composites with improved mechanical properties for structural applications; (2) TiB2-TiNiFeCrCoAl high-entropy alloy (HEA) composites with enhanced hardness and toughness for structural application; (3) TiC-Ti3Al based composites with good electrical and oxidation properties as the interconnect in solid oxide fuel cell. The author focuses on the sintering mechanism, microstructure and interface, reactions, and properties characterizations of above three types of composites. Correlations of processing-microstructures-properties are discussed and established based on scientific observation.

Alumina-titanium diboride (Al2O3-TiB2) composites have high temperature, wear, and impact resistance that could be useful in high performance applications. Determining the effect of processing parameters on relative bond strength and effective plasticity may contribute to optimization and predictability of performance in the Al2O3-TiB2 system. Al2O3-TiB2 composites were obtained from a collection of samples that were created during a separate ongoing research program being conducted by Dr. Kathryn V. Logan. The Logan samples were initially formed by hot pressing powders produced using Self-Propagating High Temperature synthesis (SHS) of Al, TiO2, and B2O3 powders or manual mixing (MM) of Al2O3 and TiB2 powders. Samples were then fractured using standard single edge notched beam (SENB) fracture toughness testing. The obtained fractured surfaces were examined using Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDS). Relative amounts of transgranular and intergranular fracture of Al2O3 and TiB2 grains were determined. Transgranular fracture was used as a measure of relative bond strength. Other samples were obtained from the Logan collection to conduct nano-indentation measurements on polished sample surfaces in Al2O3 grains and in TiB2 grains. Indent locations were verified using SEM. Reduced modulus, final displacements, and fracture toughness for indents in Al2O3 grains and in TiB2 grains were determined from nano-indentation curves. Reduced modulus was used as a measure of relative bond strength. Final displacement and fracture toughness were used as measures of relative effective plasticity. Analysis of Variance (ANOVA) using Taguchi arrays was conducted using the powder processing factor (SHS vs. MM) and the predominant microstructure factor (TiB2 grains surrounding Al2O3 grains vs. TiB2 grains distributed amongst Al2O3 grains) when examining the effect of processing parameters on relative bond strength as measured by amount of transgranular fracture. Analysis of Variance (ANOVA) using Taguchi arrays was conducted using the powder processing factor (SHS vs. MM), the predominant microstructure factor (TiB2 grains surrounding Al2O3 grains vs. TiB2 grains distributed amongst Al2O3 grains), and the indented phase factor (Al2O3 vs. TiB2) when examining the effect of processing parameters on relative bond strength as measured by nano-indentation reduced modulus and both measures of relative effective plasticity. Powder processing was significant for the relative bond strength measures, but was not significant for the relative effective plasticity measures. Predominant microstructure was significant for all measures except relative effective plasticity as measured by fracture toughness, for which none of the factors and interactions were significant. The interaction between powder processing and predominant microstructure was significant for most of the relative bond strength measures and for relative effective plasticity as measured by final displacements. Indented phase was significant for the nano-indentation measures except nano-indentation fracture toughness, although the significance for nano-indentation fracture toughness was just below the critical level. The interaction between powder processing and indented phase and the interaction between predominant microstructure and indented phase were only significant for the relative bond strength measure using nano-indentation reduced modulus. The interaction between powder processing, predominant microstructure, and indented phase was significant for the nano-indentation measures except nano-indentation fracture toughness. The optimum level for powder processing was predominantly manual mixing. The optimum level for predominant microstructure was predominantly TiB2 grains surrounding Al2O3 grains. The optimum level for indented phase was predominantly TiB2. / Master of Science

The stoichiometric Self-propagating High-temperature Synthesis (SHS) thermite reaction involving magnesium oxide (MgO), titanium dioxide (TiO₂), and boron oxide (B₂O₃) forms titanium diboride (TiB₂) and MgO as final products. Selective acid leaching is used to remove the MgO leaving high purity TiB₂ powder. The SHS method to produce TiB₂ is attractive because of the relatively low temperature required to initiate the reaction, fast reaction time, and product purity. This study investigates the acid leaching of SHS produced MgO/TiB2 and a stoichiometric mixture of commercial MgO and TiB₂ powders. Leaching was conducted at 90° C, 60° C, and 30° C at pH levels of 4.0, 2.5, and 1.0 by introduction of concentrated aliquots of HNO₃. This method maintains a minimum pH target throughout the leaching process, thereby sustaining a dynamic concentration to remove the oxide. The optimal leaching conditions were determined to be at 90° C at a minimum pH target of 2.5 for the SHS produced product. At these conditions, conversion percentages of 83%-84% of MgO were measured with only trace amounts of TiB2 measured in the solution (less than 100 ppm). Conversion percentages for each leaching condition and dissolution mass of solid MgO and TiB₂ at each pH are also reported. Results from powder XRD confirm the removal of MgO and minimal dissolution of TiB₂, and indicate the formation of unidentified compounds. Inductively coupled plasma mass spectrometry (ICP) was used to analyze the ionic composition and extent of leaching. Scanning electron microscopy (SEM) was used to observe the particle morphology of the leached powders. / Master of Science

Reaction synthesis is a processing technique where the thermal activation energy needed to form a compound is provided by the exothermic heat of formation of the thermodynamically stable product. This type of synthesis has been used to form a variety of ceramics, intermetallics, and in-situ composites. In this work, the effects of changing the stoichiometry of the titanium aluminide matrix, and the effects of extrinsic reaction variables on the behavior of the reaction were studied and compared to theoretical predictions. It was shown that changing the stoichiometry of the titanium aluminide did have an effect on the measured heat of reaction; however this did not match the prediction. Changing the extrinsic variables of titanium and aluminum particle sizes also showed a significant effect on the behavior of the reaction. / Master of Science

The aim of this study was to understand the processing – structure – property relationships in spark plasma sintered (SPS) boron carbide (B4C) and B4C-titanium diboride (TiB2) ceramic composites. SPS allowed for consolidation of both B4C and B4C-TiB2 composites without sintering additives, residual phases, e.g., graphite, and excessive grain growth due to long sintering times. A selection of composite compositions in 20% TiB2 feedstock powder increments from 0% to 100%, was sintered at 1900°C for 25 minutes hold time. A homogeneous B4C-TiB2 composite microstructure was determined with excellent distribution of TiB2 phase, while achieving ~99.5% theoretical density. An optimum B4C-23 vol.% TiB2 composite composition with low density of ~3.0 g/cm3 was determined that exhibited ~30-35% increase in hardness, fracture toughness, and flexural bend strength compared to commercial armor-grade B4C. This is a result of a) no residual graphitic carbon in the composites, b) interfacial microcrack toughening due to thermal expansion coefficient differences placing the B4C matrix in compression and TiB2 phase in tension, and c) TiB2 phase aids in crack deflection thereby increasing the amount of intergranular fracture. Collectively, the addition of TiB2 serves as a strengthening and toughening agent, and SPS shows promise for the manufacture of hybrid ceramic composites.

[pt] O presente trabalho teve como objetivo central o estudo das modificações nas propriedades estruturais, mecânicas e tribológicas causadas pela incorporação de nitrogênio em filmes de diborato de titânio (TiB2) crescidos pela técnica de erosão catódica assistida por um campo magnético. Os revestimentos de Ti-B-N com diferentes conteúdos de nitrogênio foram depositados em substratos de silício cristalino (100) a partir da erosão de um alvo de diborato de titânio mediante o uso da técnica de erosão catódica em uma atmosfera de argônio e nitrogênio e com tensões de polarização variando entre +100V e - 100V. Os efeitos do conteúdo de nitrogênio e a influência da tensão de polarização na estrutura e no comportamento tribológico foram investigados com o uso da técnica nuclear de retroespalhamento Rutherford (RBS), espectroscopia de fotoelétrons induzida por raios-x (XPS), difração por raios-x (XRD), perfilometria (medidas de tensão interna), microscopia de força atômica (AFM) e de ângulo de contato. Os resultados do presente trabalho mostraram que a incorporação de nitrogênio produz filmes com tensões internas cada vez mais compressivas. No entanto a mudança da tensão de autopolarização a valores positivos provocou uma relaxação na tensão interna. Nesses casos, foi observada uma melhor adesão dos filmes aos substratos de silício. Os resultados de XPS mostraram que as fases, TiB2, BN e TiN, estão presentes nos filmes de Ti-B-N e a caracterização por XRD determinou a estrutura nanocristalina desses revestimentos. Medidas de AFM indicaram valores de rugosidade superficial entre 1 e 2nm. / [en] The main purpose of the present work was the study of the effects on the structural, mechanical and tribological properties of the incorporation of nitrogen in titanium diboride films (TiB2) grown by reactive dc magnetron sputtering. Ti-BN coatings with different N contents were deposited on Si (100) substrates from a TiB2 target. The sputtering was carried out in an Ar-N2 gas mixture with a substrate bias voltage in the range between +100V e -100V. The effects of the nitrogen content and the influence of substrate bias voltage on the coatings properties were studied by Rutherford Backscattering Spectrometry (RBS), XRay photoelectron spectroscopy (XPS), X-Ray diffraction (XRD), profilometry (internal stress measurements), atomic force microscopy (AFM) and contact angle measurements. The results of the present work show that nitrogen incorporation produces films with higher compressive internal stress. However, a positive substrate bias reduces the compressive stress, thus resulting in a better adhesion to the substrate. The XPS results showed that the TiB2, TiN and BN phases are present in the Ti-B-N films. Characterization by XRD determined the nanocrystalline structure of Ti-B-N coatings. Measurements by AFM revealed low surface roughness values.

Titanium diboride was produced both by volume combustion synthesis (VCS) and by mechanochemical synthesis through the reaction of TiO2, B2O3 and metallic Mg. Reaction products were expected to be composed of TiB2 and MgO. However, side products such as Mg2TiO4, Mg3B2O6, MgB2 and TiN were also present in the products obtained by volume combustion synthesis. Formation of TiN could be prevented by conducting the volume combustion synthesis under argon atmosphere. Mg2TiO4 did not form when 40% excess Mg was used. Wet ball milling of the products before leaching was found to be effective in removal of Mg3B2O6 during leaching in 1M HCl. When stoichiometric starting mixtures were used, all of the side products could be removed after wet ball milling in ethanol and leaching in 5 M HCl. Thus, pure TiB2 was obtained with a molar yield of 30%. Pure TiB2 could also be obtained at a molar yield of 45.6% by hot leaching of VCS products at 75oC in 5 M HCl, omitting the wet ball milling step. By mechanochemical processing, products containing only TiB2 and MgO were obtained after 15 hours of ball milling. Leaching in 0.5 M HCl for 3 minutes was found to be sufficient for elimination of MgO. Molar yield of TiB2 was 89.6%, much higher than that of TiB2 produced by volume combustion synthesis. According to scanning electron microscope analyses, produced TiB2 had average particle size of 0.27&plusmn / 0.08 &amp / #956 / m.