by Tang Wing Chi = 碳-碳化鈦生物陶器之合成與表徵 / 鄧詠芝. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2006. / Includes bibliographical references. / Text in English; abstracts in English and Chinese. / by Tang Wing Chi = Tan-tan hua tai sheng wu tao qi zhi he cheng yu biao zheng / Deng Yongzhi. / Acknowledgement --- p.i / Abstract --- p.ii / 摘要 --- p.iv / Table of contents --- p.vi / List of figures --- p.xi / Chapter Chapter 1 --- Introduction / Chapter 1.1 --- Biomorphic materials --- p.1-1 / Chapter 1.2 --- Synthesis of biomorphic ceramics --- p.1-1 / Chapter 1.2.1 --- Pyrolysis --- p.1-2 / Chapter 1.2.1.1 --- Pyrolysis conditions --- p.1-3 / Chapter 1.2.2 --- Infiltration --- p.1-4 / Chapter 1.2.2.1 --- Vapor or gas infiltration --- p.1-4 / Chapter 1.2.2.2 --- Liquid infiltration --- p.1-4 / Chapter 1.2.2.3 --- Chemical vapor infiltration (CVI) --- p.1-5 / Chapter 1.2.2.4 --- Sol-gel processing --- p.1-5 / Chapter 1.2.3 --- Sintering --- p.1-6 / Chapter 1.3 --- Potential applications of biomorphic ceramics --- p.1-7 / Chapter 1.3.1 --- Homogenous porosity structures --- p.1-7 / Chapter 1.3.2 --- Heterogeneous porosity structures --- p.1-7 / Chapter 1.4 --- Methods and raw materials --- p.1-8 / Chapter 1.4.1 --- Infiltration --- p.1-8 / Chapter 1.4.2 --- Starting materials --- p.1-8 / Chapter 1.4.2.1 --- Ti source --- p.1-8 / Chapter 1.4.2.2 --- Biotemplates --- p.1-9 / Chapter 1.5 --- Objectives and approaches --- p.1-9 / Chapter 1.6 --- Thesis layout --- p.1-10 / References --- p.1-11 / Figures --- p.1-13 / Chapter Chapter 2 --- Methodology and Instrumentation / Chapter 2.1 --- Introduction --- p.2-1 / Chapter 2.2 --- Synthesis --- p.2-1 / Chapter 2.2.1 --- Biomorphic C-TiC ceramics from dragon tree --- p.2-1 / Chapter 2.2.2 --- Biomorphic C-TiC ceramics from wool sponge --- p.2-2 / Chapter 2.3 --- Characterization methods --- p.2-3 / Chapter 2.3.1 --- Differential thermal analyzer (DTA) --- p.2-3 / Chapter 2.3.2 --- Scanning electron microscopy (SEM) --- p.2-4 / Chapter 2.3.3 --- X-Ray powder diffractometry (XRD) --- p.2-4 / Chapter 2.3.4 --- Transmission electron microscopy (TEM) --- p.2-4 / Chapter 2.3.5 --- X-ray photoelectron spectroscopy (XPS) --- p.2-6 / Chapter 2.3.6 --- Compression tests --- p.2-6 / References --- p.2-9 / Figures --- p.2-8 / Chapter Chapter 3 --- The starting materials / Chapter 3.1 --- Introduction --- p.3-1 / Chapter 3.2 --- Fresh dragon tree --- p.3-1 / Chapter 3.2.1 --- SEM results --- p.3-1 / Chapter 3.2.2 --- Discussions --- p.3-2 / Chapter 3.3 --- Fresh sea wool sponge --- p.3-2 / Chapter 3.3.1 --- SEM results --- p.3-3 / Chapter 3.3.2 --- Discussions --- p.3-3 / Chapter 3.4 --- Tyzor-LA solution --- p.3-3 / Chapter 3.4.1 --- Physical properties --- p.3-4 / Chapter 3.4.2 --- DTA results --- p.3-4 / Chapter 3.4.3 --- XRD results --- p.3-5 / Chapter 3.4.4 --- Discussions --- p.3-5 / Chapter 3.5 --- Conclusions --- p.3-6 / References --- p.3-7 / Figures --- p.3-8 / Chapter Chapter 4 --- Results and discussions of biomorphic products fabricated from dragon tree / Chapter 4.1 --- Introduction --- p.4-1 / Chapter 4.2 --- Fabrication of biomorphic C-TiC ceramics --- p.4-1 / Chapter 4.2.1 --- Biotemplates from dragon tree --- p.4-1 / Chapter 4.2.1.1 --- XRD results --- p.4-1 / Chapter 4.2.1.2 --- SEM results --- p.4-2 / Chapter 4.2.1.3 --- Discussions --- p.4-2 / Chapter 4.2.2 --- Biomorphic C-TiC ceramics --- p.4-3 / Chapter 4.2.2.1 --- XRD results --- p.4-3 / Chapter 4.2.2.1.1 --- Effects of sintering temperature --- p.4-3 / Chapter 4.2.2.1.2 --- Effects of time duration --- p.4-3 / Chapter 4.2.2.2 --- SEM results --- p.4-4 / Chapter 4.2.2.3 --- TEM results --- p.4-4 / Chapter 4.2.2.3.1 --- Sample sintered at 1400。C for 6 hours --- p.4-4 / Chapter 4.2.2.3.2 --- Sample sintered at 1200°C for 6 hours --- p.4-5 / Chapter 4.2.2.3.3 --- Sample sintered at 1100。C for 6 hours --- p.4-5 / Chapter 4.2.2.3.4 --- Sample sintered at 900°C for 32 hours --- p.4-6 / Chapter 4.2.2.4 --- XPS results --- p.4-6 / Chapter 4.2.2.5 --- Results of compression tests --- p.4-7 / Chapter 4.2.2.6 --- Discussions --- p.4-7 / Chapter 4.3 --- Biomorphic C-TiC ceramics by repeated infiltration --- p.4-10 / Chapter 4.3.1 --- XRD results --- p.4-10 / Chapter 4.3.2 --- Discussions --- p.4-10 / Chapter 4.4 --- Conclusions --- p.4-11 / References --- p.4-12 / Figures --- p.4-13 / Chapter Chapter 5 --- Results and discussions of biomorphic products fabricated from sea wool sponges / Chapter 5.1 --- Introduction --- p.5-1 / Chapter 5.2 --- Fabrication of C-TiC biomorphic ceramics with sea wool sponges --- p.5-1 / Chapter 5.2.1 --- XRD results --- p.5-1 / Chapter 5.2.2 --- SEM results --- p.5-2 / Chapter 5.2.3 --- TEM results --- p.5-3 / Chapter 5.2.4 --- Discussions --- p.5-3 / Chapter 5.3 --- Dilution of Tyzor-LA solution --- p.5-5 / Chapter 5.3.1 --- XRD results --- p.5-5 / Chapter 5.3.2 --- SEM results --- p.4-5 / Chapter 5.3.3 --- Discussions --- p.5-6 / Chapter 5.4 --- Further annealing of biomorphic C-TiC ceramics in air --- p.5-6 / Chapter 5.4.1 --- XRD results --- p.5-7 / Chapter 5.4.2 --- SEM results --- p.5-7 / Chapter 5.4.3 --- TEM results --- p.5-8 / Chapter 5.4.4 --- Discussions --- p.5-9 / Chapter 5.5 --- Conclusions --- p.5-11 / References --- p.5-12 / Figures --- p.5-13 / Chapter Chapter 6 --- Conclusions and future works / Chapter 6.1 --- Conclusions --- p.6-1 / Chapter 6.2 --- Future works --- p.6-2 / References --- p.6-4

M.S. / Materials Science and Engineering / The goal of this thesis is to determine the corrosion behavior of a new class of advanced materials, namely: titanium carbide reinforced iron composites containing chromium (Fe-Cr-TiC) and chromium and manganese (Fe-Cr-Mn-TiC). TiC has excellent physical properties, such as high melting point, low density, high Vickers hardness value, high electrical resistivity and low thermal expansion. Due to their great wear resistance characteristics and toughness, these materials show potential applications in pulp and paper industries, mining and mineral processing industries, metallurgical industries, cement industries, and electric industries. Some components made of these materials may work under a combined action of corrosion and wear. This study is aimed at determining the corrosion behavior using electrochemical methods such as potentiodynamic and potentiostatic. Two different electrolytes were used in this research: 1N (0.5 M) sulfuric acid (H2SO4) and 1N (0.5 M) sodium sulfate (Na2SO4). The experiments were performed on the following materials; Fe-TiC, Fe-Cr-TiC, Fe-Cr-Mn- TiC and their matrix materials.

The sintering behavior to form TiC-Ni-Mo cermet using a nano-size TiC powders was investigated in flowing Argon gas at 1500°C. Nano-sized titanium carbide powders with high purity, high surface area, and low cost were synthesized from carbon coated Ti containing precursors utilizing a patented process. The sintering studies showed that an increase in theoretical density (TD) with increasing molybdenum content. TiC based cermets were characterized using X-ray diffraction (XRD), Vickers hardness, and scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS). Mechanical properties, electrical conductivity and oxidation resistance results shows potential applications as interconnect for Low/Intermediate Temperature Solid Oxide Fuel Cells (SOFC) and machining tool tips.

Materials for studies related to nanoscience and nanotechnology have gained tremendous attention owing to their unique physical, chemical and electronic properties. Among various anisotropic nanostructures, one dimensional (1D) materials have received immense interest in numerous fields ranging from catalysis to electronics. Imparting multi-functionality to nanostructures is one of the major areas of research in materials science. In this direction, use of nanosized materials in energy systems such as fuel cells has been the subject of focus to achieve improved performance. Tuning the morphology of nanostructures, alloying of catalysts, dispersing catalytic particles onto various supports (carbon nanotubes, carbon nanofibers, graphene, etc.) are some of the ways to address issues related to electrochemical energy systems. It is worth mentioning that highly stable and corrosion resistant electrodes are mandatory as electrochemical cells operate under aggressive environments. Additionally, carbon, which is often used as a support for catalysts, is prone to corrosion and is subsequently implicated in reduced performance due to poor adherence of catalyst particles and loss in electrochemically active area. Hence, there is a quest for the development of stable and durable electrocatalysts / supports for various studies including fuel cells. The present thesis is structured in exploring the multi-functional aspects of titanium carbide (TiC), an early transition metal carbide. TiC, a fascinating material, possesses many favorable properties such as extreme hardness, high melting point, good thermal and electrical conductivity. Its metal-like conductivity and extreme corrosion resistance prompted us to use this material for various electrical and electrochemical studies. The current study explores the versatility of TiC in bulk as well as nanostructured forms, in electrical and electrochemical studies towards sensing, electrocatalytic reactions and active supports. 1D TiC nanowires (TiC-NW) are prepared by simple solvothermal method without use of any template and are characterized using various physico-chemical techniques. The TiC-NW comprise of 1D nanostructures with several µm length and 40 ± 15 nm diameter (figure 1). Electrical properties of individual TiC-NW are probed by fabricating devices using focused ion beam deposition (FIB) technique. The results depict the metallic nature of TiC-NW (figure 2). Figure 1. (a) SEM, (b) TEM and (c) HRTEM images of TiC-NW prepared by solvothermal method. Figure 2. (a) SEM image and (b) I-V characteristics of TiC-NW - based device as a function of temperature. The contact pads are made of Pt. Subsequently, oxidized TiC nanowires are prepared by thermal annealing of TiC-NW, leading to carbon - doped TiO2 nanowires (C-TiO2-NW) (figure 3). Photodetectors are fabricated with isolated C-TiO2-NW and the device is found to respond to visible light (figure 3) radiation with very good responsivity (20.5 A/W) and external quantum efficiency (2.7 X 104). The characteristics are quite comparable with several reported visible light photodetectors based on chalcogenide semiconductors. Figure 3. (a) HRTEM, (b) EDAX, (c) Scanning TEM-DF images of C-TiO2-NW along with (d) Ti (e) O and (f) C mapping. (g) Current – voltage curves of single C-TiO2-NW recorded in dark (black) and in presence of visible light radiation (red) of intensity 57.7 mW/cm2 at 25oC. Inset of (g) shows the SEM image of the device (top) and schematic illustration of fabricated photodetector (bottom). The next chapter deals with the electrochemical performance of TiC demonstrated for studies involving oxygen reduction and borohydride oxidation reactions. Electrochemical oxygen reduction reaction (ORR) reveal that TiC-NW possess high activity for ORR and involves four electron process while it is a two electron reduction for bulk TiC particles (figure 4). The data has been substantiated by density functional theory (DFT) calculations that reveal different modes of adsorption of oxygen on bulk and nanowire morphologies. Stable performance is observed for several hundreds of cycles that confirm the robustness of TiC. The study also demonstrates excellent selectivity of TiC for ORR in presence of methanol and thus cross-over issue can be effectively addressed in direct methanol fuel cells. In the chapter on borohydride oxidation, bare TiC electrode is explored as a catalyst for the oxidation of borohydride. One of the major issues in direct borohydride fuel cells (DBFC) is the hydrolysis of borohydride that happens on almost all electrode materials leading to low efficiency. The present study reveals that TiC is a very good catalyst for borohydride oxidation with little or no hydrolysis of borohydride [figure 5 (a)] under the experimental conditions studied. Further, shape dependant activity of TiC has been studied and fuel cell performance is followed [figure 5 (b)]. Polarization data suggests that the performance of TiC is quite stable under fuel cell experimental conditions. Figure 4. (a) Linear sweep voltammograms for ORR recorded using (i) bulk TiC particles and (ii) TiC-NW in O2-saturated 0.5 M KOH at 1000 rpm. Scan rate used is 0.005 Vs-1. (b) Variation of number of electrons with DC bias. Black dots correspond to TiC bulk particles while red ones represent nanowires. Figure 5. (a) Cyclic voltammograms of borohydride oxidation on TiC coated GC electrode in 1 M NaOH containing 0.1 M NaBH4. Scan rate used is 0.05 Vs-1. (b) Fuel cell polarization data at 70oC for DBFC assembled with (i) bulk TiC particles and (ii) TiC-NW as anode catalysts and 40 wt% Pt/C as cathode. Anolyte is 2.1 M NaBH4 in 2.5 M NaOH, and catholyte is 2.2 M H2O2 in 1.5 M H2SO4. Anode loading is 1.5 mg cm-2 and cathode loading is 2 mg cm-2. The corrosion resistance nature of TiC lends itself amenable to be used as an active support for catalytic particles (Pt and Pd) for small molecules oxidation reactions. In the present study, electro-oxidation of methanol, ethanol and formic acid have been studied. As shown in figure 6 (a), the performance of Pd loaded TiC (Pd-TiC) is found to be higher than that of Pd loaded carbon (Pd-C) suggesting the active role of TiC. The catalytic activities of TiC-based supports are further improved by tuning their morphologies. Figure 6 (c) reveals that the activities are higher in case of Pd-TiC-NW than that of Pd-TiC. Figure 6. (a) Cyclic voltammograms of Pd-TiC and Pd-C for ethanol oxidation, (b) T EM image of Pd-TiC-NW and (c) voltammograms of Pd-TiC-NW in N2-saturated 1 M ethanol in 1 M KOH medium, scan rate used is 0.05 Vs-1. The next aspect explored, is based on the preparation of C-TiO2 and its use as a substrate for surface enhanced Raman spectroscopy (SERS). Carbon doped titanium dioxide is prepared by thermal annealing of TiC. It is observed that the amount of dopant (carbon content) is dependent on the experimental conditions used. SERS studies using 4¬mercaptobenzoic acid (4-MBA) as the analyte, indicates that C-TiO2 [figure 7 (a)] enhances Raman signals based on chemical interactions between the analyte and the substrate. Raman signal intensities can be tuned with the amount of carbon content in C¬TiO2. Enhancement factors are calculated to be (7.7 ± 1.2) x 103 (for 4-MBA) and (1.7 ± 1.2) x 103 (for 4-nitrothiophenol). The SERS substrates are found to be surface renewable using visible light, a simple strategy to re-use the substrate [figure 7 (b)]. The regeneration of SERS substrates is based on self cleaning action of TiO2 that produces highly reactive oxygen containing radicals known to degrade the molecules adsorbed on TiO2. Thus, the versatility of TiC has been demonstrated with various studies. In addition to using TiC-based materials, nanoparticles of Rh, Ir and Rh-Ir alloy structures have also been used for borohydride oxidation reaction. This is explained in the last section. In Appendix-I, preliminary studies on the preparation of TiC-polyaniline (PANI) composites using liquid-liquid interfacial polymerization is explained. Raman spectroscopy results suggest that the presence of TiC-NW makes PANI to assume preferential orientation in the polaronic (conducting) form. Appendix-II discusses the role of TiC-NW as a fluorescence quencher for CdS semiconductor nanoparticles.

Philosophiae Doctor - PhD / Metal matrix composites harness the superior attributes of their individual constituents to form high performance materials that would rather be impossible from monolithic substances. Owing to many possible combinations, a myriad of metal matrix composite systems can be fabricated with a metal (or a metal alloy) as a matrix (continuous) phase and a ceramic as a reinforcement (discontinuous) phase. The current study focuses on two matrices, namely Nickel Aluminide and Austenitic Steel as well as two reinforcements namely, Titanium Carbide and Oxynitrides. NiAl alloys are candidates for high temperature structural materials due to their high melting temperature, low density, good thermal conductivity, and excellent oxidation resistance.

This thesis is concerned with the deposition of nanoparticle films onto boron-doped diamond and tin-doped indium oxide (lTO) surfaces and the characterisation of the films using electron microscopy, powder diffraction methods and quartz crystal microbalance (QCM) data. The redox behaviour of the porous films was examined using cyclic voltammetry in various media to investigate potential electroanalytical applications. TiOz (anatase) mono-layer films were immobilised onto an inert boron-doped diamond substrate. Cyclic voltammetry experiments allowed two distinct steps in the reduction - protonation processes to be identified that are consistent with the formation of Ti(III) surface sites accompanied by the adsorption of protons. Preliminary data for electron transfer processes at the reduced TiOz surface such as the dihydrogen evolution process and the 2 electron - 2 proton reduction of maleic acid to succinic acid are discussed. Novel multi-layer TiOz films were deposited with a variety of organic binder molecules onto ITO substrates. The redox reactivity of Cuz+ with 1,4,7,10- tetraazacyclododecane- 1,4,7, IO-tetrayl- tetrakis (methyl-phosphonic acid) in solution and immobilised on an electrode surface are investigated. The influences of film thickness, scan rate, and pH on the electrochemistry of immobilised pyrroloquinoline quinone was investigated with two possible electron transport processes observed. The thickness of TiOz phytate films was found to change the shape of the resulting cyclic voltammograms dramatically. Computer simulation and impedance spectroscopy allowed insights into the diffusion of electrons to be obtained. 1, 1 ~Ferrocenedimethanol was employed as an adsorbing redox system to study the voltammetric characteristics of carboxymethyl-y-cyclodextrin films and evidence for two distinct binding sites is considered. The apparent transport coefficients for dopamine and Ru(NHJ)6J+ are estimated for TiOz Nafion® films. The electrochemical processes in biphasic electrode systems for the oxidation of water-insoluble N,N-didodecyl-N;N~diethyl-benzene-diamine (DDPD) pure and dissolved in di-(2-ethyl-hexyl)phosphate (HDOP) immersed in aqueous electrolyte media are described. Transfer of the anion from the aqueous electrolyte phase into the organic phase accompanies the oxidation of pure DDPD. In the presence of HOOP, oxidation is accompanied by proton exchange. The electrochemically driven proton exchange process occurs over a wide pH range. Organic microdroplet deposits of OOPD in HDOP at basal plane pyrolytic graphite electrodes are studied using voltammetric techniques and compared to the behaviour of organic microphase deposits in mesoporous Ti02 thin films. Two types of Ti02 thin film electrodes were investigated, (i) a 300-400 nm film on ITa and (ii) a 300-400 nm film on ITa sputter-coated with a 20 nm porous gold layer. The latter biphasic design is superior. Titanium carbide (TiC) nanoparticies were deposited onto ITa electrodes. Partial anodic oxidation and formation of novel core-shell TiC-Ti02 nanoparticies was observed at applied potentials positive of 0.3 V vs. SCE. Significant thermal oxidation of TiC nanoparticies by heating in air occurs at 250 °c leading to coreshell TiC-Ti02 nanoparticies, then Ti02 (anatase) at ca. 350 °c, and Ti02 (rutile) at temperatures higher than 750 °c. The electrocatalytic properties of the core-shell TiC-Ti02 nanoparticulate films were surveyed for the oxidation of hydroquinone, ascorbic acid, dopamine and nitric oxide (NO) in aqueous buffer media. Mono- and multi-layer Ce02 deposits on ITa are shown to be electrochemically active. A reduction assigned to a Ce(IV/III) process has been observed and followup chemistry in the presence of phosphate discovered. The interfacial formation of CeP04 has been proven and effects of the deposit type, pH and phosphate concentration on the process analysed. The electrochemistry of multi-layer Ce02 nanoparticulate films in organic solvent is shown to be more stable.

Ce travail de thèse s'inscrit dans le cadre de l'étude et du développement de matériaux céramiques de type carbure pouvant être utilisés dans l'assemblage combustible des réacteurs nucléaires du futur. Depuis l'accident de Fukushima, ces céramiques réfractaires sont envisagées afin d'améliorer la sûreté dans les centrales à eau pressurisée actuelles. Sous forme de revêtements ou de gaines, ces matériaux pourraient en effet permettre de garantir une meilleure résistance de l'assemblage combustible notamment en conditions accidentelles à haute température. Le principal frein à l'utilisation en réacteur de céramiques carbures sous forme frittée est leur faible ténacité qui a conduit à envisager l'utilisation de matériaux composites à matrice céramique. Ces matériaux sont constitués de fibres ou de tubes insérés dans une matrice céramique. Depuis quelques années, des techniques complexes permettant d'envisager la fabrication de gaines étanches aux produits de fission gazeux ont été perfectionnées (Procédés CVI et NITE®, utilisation d'un liner…). Quel que soit le procédé ou la forme finale du matériau envisagé, la mise en oeuvre d'une matrice céramique à nanograins peut présenter un gain en termes de résistance à l'irradiation notamment. Certains matériaux sont à l'étude comme le carbure de titane qui présente l'avantage de présenter une très haute température de fusion et également une conductivité thermique relativement conservée sous irradiation et à haute température. Dans cette étude, nous avons choisi de nous intéresser à l'impact de la taille de grains sur certaines propriétés du matériau TiC. Notre démarche a été de synthétiser trois microstructures différentes par la technique SPS avec trois tailles de grains moyennes. Dans un premier temps, nous avons déterminé les meilleures conditions de dispersion d'une poudre commerciale nanométrique (≈40 nm). Nous avons ensuite défini les conditions optimales de frittage afin d'obtenir les trois microstructures souhaitées / In the context of generation IV reactors, refractory ceramics such as carbides are developed for the fuel cladding. Titanium carbide (TiC) exhibits good mechanical properties such as hardness and wear resistance, a high thermal conductivity even under irradiation and a good stability over a wide range of stoichiometry which is an asset for irradiation resistance. Due to these properties, TiC appears to be an interesting candidate for nuclear applications. Titanium carbide samples were prepared by spark plasma sintering. Three different microstructures were prepared with average grain sizes of about 0.3, 1.3 and 25.0 µm. Each microstructure was irradiated with 500 keV 40Ar+ ions at a high fluence of 3.2X10[exposant]17 at.cm[exposant]-2. Irradiations were carried out at room temperature (RT) or at 1000°C. Post-irradiation annealing was performed on some samples to follow the surface modification. In fact, clusters and nanocracks were observed at depth in the nanometric grains (<100nm) whereas more extended cracks were found in larger grains (>1 µm). Microcracks can induce localized surface blistering after irradiation at RT. The size, shape and density of the blisters were proposed to depend on the crystallographic orientation of each grain. The microstructure with sub-micrometric grains exhibited increased surface roughness after irradiation, with grain removal and grain boundary abrasion but no blistering. In this article, we highlight the role played by gastight grain boundaries and porosity to explain the distinct behavior of microstructures

This thesis describes a new Laser-Assisted Spray Pyrolysis technique developed to grow nanoparticle coatings with controllable particle sizes. In this method, droplets of a precursor formed by a nebulizer are injected into a growth chamber using SF6 carrier gas. An experimental study and a computational model to investigate the particle size dependence on various growth parameters have been carried out. The results show that heating of 1.5and#61549;m droplets of metalorganic precursor in a carrier gas using a CO2 laser resulted in the formation of TiC and Fe3O4 particles with diameters in the range of 50-60nm. Also the results show that by reducing the concentration of the metal organic precursor the diameter of the deposited particles can be reduced.

Lithium-ion batteries are most commonly employed as power sources for portable electronic devices. Limited capacity, high cost, and safety problems associated with the commercially used graphite anode materials are hampering the use of lithium-ion batteries in larger-scale applications such as the electric vehicle. Nanocomposite alloys have shown promise as new anode materials because of their better safety due to higher operating potential, increased energy density, low cost, and straightforward synthesis as compared to graphite. The purpose of this dissertation is to investigate and understand the electrochemical properties of several types of nanocomposite alloys and to assess their viability as replacement anode materials for lithium-ion batteries. Tin and antimony are two elements that are active toward lithium. Accordingly, this dissertation is focused on tin-based and antimony-based nanocomposite alloy materials. Tin and antimony each have larger theoretical capacities than commercially available anodes, but the capacity fades dramatically in the first few cycles when metallic tin or antimony is used as the anode in a lithium-ion battery. This capacity fade is largely due to the agglomeration of particles in the anode material and the formation of a barrier layer between the surface of the anode and the electrolyte. In order to suppress agglomeration, the active anode material can be constrained by an inactive matrix of material that makes up the nanocomposite. By controlling the surface of the particles in the nanocomposite via methods such as the addition of additives to the electrolyte, the detrimental effects of the solid-electrolyte interphase layer (SEI) can be minimized, and the capacity of the material can be maintained. Moreover, the nanocomposite alloys described in this dissertation can be used above the voltage where lithium plating occurs, thereby enhancing the safety of lithium-ion batteries. The alloy anodes in this study are synthesized by high-energy mechanical milling and furnace heating. The materials are characterized by X-ray diffraction, scanning and transmission electron microscopies, and X-ray photoelectron spectroscopy. Electrochemical performances are assessed at various temperatures, potential ranges, and charge rates. The lithiation/delithiation reaction mechanisms for these nanocomposite materials are explored with ex-situ X-ray diffraction. Specifically, three different nanocomposite alloy anode materials have been developed: Mo3Sb7-C, Cu2Sb-Al2O3-C, and Cu6Sn5-TiC-C. Mo3Sb7-C has high gravimetric capacity and involves a reaction mechanism whereby crystalline Mo3Sb7 disappears and is reformed during each cycle. Cu2Sb-Al2O3-C with small particles (2 - 10 nm) of Cu2Sb dispersed in the Al2O3-C matrix is made by a single-step ball milling process. It exhibits long cycle life (+ 500 cycles), and the reversibility of the reaction of Cu2Sb-Al2O3-C with lithium is improved when longer milling times are used for synthesis. The reaction mechanism for Cu2Sb-Al2O3-C appears to be dependent upon the size of the crystalline Cu2Sb particles. The coulombic efficiency of Cu2Sb-Al2O3-C is improved through the addition of 2 % vinylethylene carbonate to the electrolyte. With a high tap density of 2.2 g/cm3, Cu6Sn5-TiC-C exhibits high volumetric capacity. The reversibility of the reaction of Cu6Sn5-TiC-C with lithium is improved when the material is cycled above 0.2 V vs. Li/Li+. / text

Densification behaviour and mechanical properties (hardness, fracture toughness and flexural strength) of the SiC-TiC composite system were studied. Pressureless sintering experiments were conducted on samples containing 0 to 30 vol % TiC created through an in-situ reaction between TiO2 and C: TiO2 + 3C -> TiC + 2CO. Sintering of the compacts was carried out in the presence of Al2O3 and Y2O3 sintering additives which promoted densification at sintering temperatures ranging from 1825 to 1925°C. It was determined that the presence of synthesized TiC particles served to effectively toughen the composite through crack deflection, impedance and bridging. An increase in fracture strength and hardness was also observed. Densities in excess of 98 % theoretical density were achieved depending on the sintering conditions and volume fraction of TiC phase. The SiC grain size and morphology was analyzed as a function of TiC volume fraction. The presence of TiC particles in the SiC matrix inhibited the exaggerated grain growth of the SiC grains and activated additional toughening mechanisms. The SiC grains were found to be roughly equiaxed with very fine TiC particles preventing significant elongation. The optimal sintering conditions for room temperature mechanical properties required slow heating through the reaction zone (1300 to 1520°C) followed by a 1 h dwell at 1885°C. At this temperature, the maximum flexural strength of 566 MPa was measured in samples containing 5 vol % TiC. Conversely, a maximum fracture toughness of 5.7 MPa·m0.5 was measured in samples containing 10 vol % TiC sintered at 1900°C. The hardness was shown to increase very little, from ~19.8 GPa in the monolithic SiC samples to 20.1 GPa in samples containing 5 vol % TiC. A theoretical analysis was conducted to model the effect of porosity and grain morphology on the mechanical properties of the SiC matrix and was experimentally verified. / Thesis (Master, Mechanical and Materials Engineering) -- Queen's University, 2010-09-21 15:20:02.797