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.

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.

No description available.

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.

The research focus was to determine diffusion mechanisms responsible for densification behavior of SHS produced Al2O3/TiB2 Ceramic Matrix Composites (CMCs). Previous research has shown SHS produced Al₂O₃/TiB₂ composites exhibited unique microstructural properties that contributed to high strength, fracture toughness, and hardness properties. Pressureless densification of SHS produced Al₂O₃/TiB₂ composites would provide a cost savings because the equipment for pressureless densification is less expensive and less complicated than equipment required for densification with pressure. Models for sintering of CMCs and calculation of Sintering Time Constants (STC) were used to predict the densification behavior of the SHS produced Al2O3/TiB2 composite. The Levin, Dirnfeld, Shwam equation was used to determine the Rate Controlling Diffusion Mechanism (RCDM) and activation energy for sintering. X-Ray Diffraction (XRD) analysis of the as-milled reaction product powder revealed the presence of an aluminum borate (Al₁₈B₄O₃₃) as a third phase, as well as, in pressureless heat treated samples. Based on experimental results and analysis, it seemed possible the Al₁₈B₄O₃₃ compound may have formed by reaction of Al₂O₃ with TiB2 along their interfaces. Aluminum borates have been observed to form Al₁₈B₄O₃₃ (s) + B₂O₃ (l) at temperatures above 1000°C. The RCDM for densification of SHS produced Al₂O₃/TiB₂ was found to be liquid phase diffusion with volume diffusion also likely being active during densification. In addition, Al₁₈B₄O₃₃ seemed to be the preferred compound formed during oxidation. Further research should be performed to control formation of Al₁₈B₄O₃₃; as well as, on the oxidation behavior of the SHS produced Al2O3/TiB2. / Master of Science

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.

Made available in DSpace on 2017-07-21T20:42:42Z (GMT). No. of bitstreams: 1 Cristiano da Silva.pdf: 5271302 bytes, checksum: 25a5bdf4a3671c9a497d93fa788662df (MD5) Previous issue date: 2014-01-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This work aims at verifying the influence of processing by high energy ball milling of titanium diboride (TiB2), to increase the effect of grain refining of high-purity aluminum. Various mills were carried out by varying the ratio of the initial TiB2 and aluminum charges. After obtaining the milling products, they were compressed in a cylindrical array as a uniaxial compressive stress of 100MPa, some were later sintered at 600°C for 30 minutes. The tablets were introduced in the metal bath of aluminum and castings at 800°C in thermal analysis cups. In metal baths, experiments with and without the presence of titanium as a solute, in addition to the variation of the content of TiB2 (0.15 and 0.30 wt%) can be observed. The results indicate a significant reduction in grain size, especially in the samples were nucleated with pellets which were sintered before being added to the bath. / Este trabalho, tem por objetivo, verificar a influência do processamento por moagem de alta energia em moinho de bolas, do diboreto de titânio (TiB2), visando aumentar o efeito de refino de grãos do alumínio de alta pureza. Várias moagens foram realizadas, variando-se a razão de alumínio e TiB2 das cargas iniciais. Após a obtenção dos produtos de moagem, os mesmos foram compactados em uma matriz cilíndrica uniaxial como uma tensão de compressão de 100MPa, algumas posteriormente foram sinterizadas à 600°C por 30 minutos. As pastilhas foram introduzidas no banho metálico de alumínio e vazadas à 800°C em copos para análise térmica. Nos banhos metálicos, experimentos sem e com a presença de titânio como soluto, além da variação do teor de TiB2 (0,15 e 0,30%p) também podem ser observados. Os resultados indicam uma redução significativa no tamanho de grão, especialmente nas amostras que foram nucleadas por pastilhas que foram sinterizadas antes de serem adicionadas ao banho.

The mechanical properties of boron carbide (B4C) with 10 and 20 vol% particulate inclusions of commercially available nano-sized alpha-phase silicon carbide (a-SiC) or micron-sized titanium diboride (TiB2) were investigated so as to produce a fine-grained material with high hardness, toughness, and overall strength in order to increase the effectiveness of B4C as a structural ceramic, whose use in the field has been limited because of the extreme brittle nature of the material. Full density sintering of the ceramics (≥99% theoretical) was completed using the novel Plasma Pressure Compaction (P²C®) technique, which limited grain growth due to a reduced processing temperature and a significantly reduced consolidation time. The reinforced ceramic composites had particulate grains homogeneously distributed within the B4C matrix. X-ray diffraction patterns confirmed that the constituents did not interdiffuse. The four-point flexure strength for the monolithic B4C ceramic was found to be significantly larger than any recorded value found in scientific literature, and was most likely attributed to the fine-grained microstructure resulting from the P²C® processing. The mechanical properties of the nano-sized a-SiC-B4C ceramics showed a slight increase in the Chevron-notched four-point bend fracture toughness due to the crack deflection toughening mechanism. A slight decrease in the Vickers microhardness and the static elastic modulus values were also observed. A significant increase in the fracture toughness as well as a slight increase in the microhardness and elastic modulus of the micron-sized TiB2-B4C materials was found. The toughening mechanism of this composite was attributed to the slight chemical bond between the B4C matrix and the ultra-small, ultra-tough TiB2 particulates, which forced a propagating crack to completely rip apart the TiB2 reinforcing particles. This cleaving nature resulted in significant amounts of energy being absorbed by the micron-sized particulates. It was concluded that the composite with 20 vol% TiB2 allowed for the largest gain in toughness because it possessed the largest number of ultra small, ultra tough particulate-cracktip interactions.