Doctor of Philosophy / Department of Chemical Engineering / James H. Edgar / The effects of process conditions on the material’s properties were investigated for the sublimation growth of aluminum nitride and the epitaxial growth of silicon carbide. Since the mid 1990’s, these semiconductors have made new types of high power electronics and short wavelength optoelectronics that were never before feasible. The sublimation growth of AlN crystals on SiC seeds was carried out to produce high quality AlN bulk crystals. Si-face, 3.5 º off-axis 6H-SiC (0001) and 8 º off-axis 4H-SiC (0001) wafers were used as the substrates. An investigation of the initial growth demonstrated 1800 – 1850ºC was the optimum temperature for AlN growth. By optimizing the temperature gradient, large area AlN layer was deposited. Consecutive growths and continuous growth were performed to enlarge the crystal thickness. Single-crystalline AlN layers, each with a thickness of 2 mm and a diameter of 20 mm, were produced. X-ray diffraction confirmed the grown AlN had good crystal quality. Approximately 3 – 6 at% of Si and 5 – 8 at% of C were detected in the crystals by x-ray photoelectron spectroscopy, which came from the decomposition of SiC seeds and the degradation of the graphite components in the furnace. Molten KOH/NaOH etching revealed the dislocation density decreased from 108 cm-2 to 106 cm-2 as the AlN layer thickness increased from 30 μm to 2 mm. Epitaxial growth of SiC was carried out in a chemical vapor deposition system. High-quality 6H-SiC and 4H-SiC homoepitaxial films were produced at growth rates up to 80 μm/hr by using a novel single precursor, methyltrichlorosilane (MTS). Inclusions of 3C-SiC were circumvented by employing 8º mis-orientated substrates. Adjusting the H2/Ar flow ratio in the carrier gas effectively changed the C/Si ratio in the gas phase due to the reaction between H2 and the graphite heater; thereby, influencing surface roughness and dislocation density. Low H2/Ar ratios of 0.1 and 0.125 produced smooth surfaces without step-bunching. Higher H2/Ar ratios of 0.2 and 0.33 enhanced the conversion of basal plane dislocations into threading edge dislocations, and reduced the density of basal plane dislocations to approximately 600 cm-2.

Cette thèse est consacrée à l'étude des métaux-N-H des matériaux pour le stockage d'hydrogène de solide. Le but est de caractériser la synthèse mechanochemical, structurelle et les propriétés d'hydrogénation de Li-N-H, Li-Mg-N-H et des systèmes Li-Mg-B-N-H. Premièrement, l'assimilation hydrogène pendant mechanochemistry de Li3N sous 9 MPA de H2 a été analysée au moyen de l'absorption solide-à-gaz in situ et la Diffraction de Radiographie d'ex-situ (XRD) des mesures. Deux étapes de H-sorption menant à une assimilation hydrogène globale de 9.8wt le % ont été obtenus. La première étape de réaction comprend la transformation de polymorphe-li3n (S.G.P6/mmm) dans li3n (S.G.P63/mmc) métastable la phase et la réaction du dernier avec l'hydrogène pour former lithium imide :-li3n + H2 Li2NH + LiH. La deuxième étape absorbant est lithium imide des convertis à lithium amide / This thesis is dedicated to the study of novel metal-N-H materials for solid state hydrogen storage. The aim is to characterize the mechanochemical synthesis, structural and hydrogenation properties of Li-N-H, Li-Mg-N-H and Li-Mg-B-N-H systems. Firstly, hydrogen uptake during mechanochemistry of Li3N under 9 MPa of H2 has been analyzed by means of in-situ solid-gas absorption and ex-situ X-Ray Diffraction (XRD) measurements. Two H-sorption steps leading to an overall hydrogen uptake of 9.8wt% was obtained. The first reaction step comprises the transformation of polymorph -Li3N (S.G.P6/mmm) into -Li3N (S.G.P63/mmc) metastable phase and the reaction of the latter with hydrogen to form lithium imide: -Li3N + H2 Li2NH + LiH. The second absorption step is lithium imide converts to lithium amide following the reaction scheme Li2NH + H2 LiNH2 + LiH. The assessment of reaction paths in this system as well as of the appraisal of the underlying reaction mechanisms was under taken. Secondly, reactive ball milling (RBM) under H2 of Li3N and Mg powder with a molar ratio of 2:1 was taken on to destabilize Li-N-H system and accelerate its sorption kinetics. The onset dehydrogenation temperature of the as-milled 2Li3N+Mg mixture was detected at 125°C, which is about 75°C lower than that of the Li-N-H system. The structural and phases evolution of the Li-Mg-N-H system during both the synthesis and subsequent hydrogenation/dehydrogenation cycling were characterized by combined analysis of in-situ XRD and neutron powder diffraction (NPD) measurements. It was found step wised for the both processes depending on mainly the temperature and hydrogen pressure to the system. Finally, the effect of the addition of Co-based compounds, lithium borohydides and the combination of them to Li-Mg-N-H system were systematically investigated by XRD, scanning electron microscopy (SEM), fourier transform infra-red (FTIR), differential scanning calorimetry (DSC) and hydrogen storage properties measurements with the aim to overcome the kinetic barriers and further decrease the dehydrogenation temperature. The Li-Mg-B-N-H/3wt% ZrCoH3 composite synthesized by RBM has the best hydrogen storage properties. It is shown that the activation energy was decreased and the N-H bonds were weakened, which could be the main reasons for improving the hydrogen storage properties of Li-Mg-N-H system

Le travail présenté ici est une contribution à l’étude des propriétés de photoluminescence (PL) d’ions de terre rare (Erbium) insérés dans des matrices grand gap (AlN) de différentes morphologies et déposées sous forme de films minces. Une méthode de dépôt PVD magnétron rf a été utilisée pour obtenir des dépôts minces de nitrure d’aluminium dont les morphologies cristallines couvrent une gamme allant de la morphologie colonnaire classique jusqu’à l’état nano cristallisé et amorphe. On montre comment, plus la puissance magnétron est élevée plus les cristallites colonnaires d’AlN sont de grande dimension et comment l’application d’une polarisation négative sur les substrats de silicium permet l’obtention de dépôts nano cristallisés. Différents taux de dopage, de 0.1 à 6 at. %, sont obtenus avec une cible composite Al+Er.La PL à 1.54 [micro]m de l’atome d’Er a été étudiée en fonction des valeurs des paramètres « procédé » et donc en fonction des morphologies de AlN. Il a été montré que le maximum d'émission de PL a lieu pour un dopage de 1 at. %. L’étude montre que l'intensité de PL augmente avec la puissance magnétron et diminue avec l’intensité de polarisation des substrats. Ces deux résultats montrent que l'intensité PL est fortement corrélée à la morphologie des films. Plus les cristallites sont importantes, plus l'émission de PL est efficace. Cette corrélation entre la PL et la morphologie des matrices a permis de mettre en évidence le rôle des champs cristallins des défauts non radiatifs dans les cristallites. Le rôle des défauts a été confirmé par des mesures de luminescence résolue en temps, des mesures sur dépôts recuits et des mesures de PL à basse température. L’effet de diminution de la PL avec la température est très faible ce qui rend le matériau très prometteur pour des applications en optoélectronique et en photonique / The work presented here is a contribution to the study of the photoluminescence (PL) properties of a rare earth ions (Erbium) inserted inside wide gap matrices (AlN) of different morphologies and deposited as thin films. A physical vapour deposition magnetron rf technique has been used to obtain thin layers of aluminium nitride whose crystalline morphologies are ranging from the classical columnar morphology to the nanocrystalline state or amorphous. One shows how, the higher the magnetron power, the larger are the columnar crystallites and how the use of a negative polarization on the silicon substrates allows obtaining nano crystallized layers. Different doping rates (from 0.1 to 6 at. %) have been achieved using a Al+Er composite target.The PL of the Er atom at 1.54 [micro]m has been studied versus the process parameters and so as a function of the different AlN morphologies. It was shown that the maximum of PL emission is achieved for a rate of 1 atomic %. PL intensity was shown to increase with the magnetron power and decrease with the polarization intensity of the substrates. These two results demonstrate that PL intensity is strongly correlated to the matrix morphology. The larger the crystallites, the most efficient are the PL emission allows evidencing the role of the non radiative defects crystalline fields in the crystallites. The role of the defects was confirmed by time resolved photoluminescence measurements and by PL measurements performed on annealed samples or at low temperature. The decrease of PL with temperature is very weak, making this way the material very promising for optoelectronic and photonic applications

No description available.

The behaviour of mould fluxes used in continuous casting of two Ti-stabilised stainless steels was investigated in terms of the level of titanium pick-up by the flux and the effect of this absorption of titanium on the viscosity of the fluxes. The two fluxes considered are respectively used for the casting of a ferritic steel (type 409) and an austenitic steel (type 321). Concerning the titanium pick-up (expressed as Ti02), the Ti02 content of the flux stabilised at about 3-4% for the mould flux of the ferritic steel and at about 6% for the mould flux of the austenitic steel after 20 minutes of casting. At the same time due to the reduction of Si02 in the molten flux by TiN and Ti in the steel the basicity of the mould flux of the ferritic steel increased from 0.8 to 0.9 while it increased from 0.95 to 1.2 for the mould flux of the austenitic steel. The SEM/EDS analysis of the sampled flux during casting showed only some spherical metallic droplets in the case of the mould flux of the ferritic steel but for the mould flux of the austenitic steel apart from the metallic droplets, some precipitates rich in Ca, Ti and O were identified in the glassy phases. Rotational viscometry carried out on the two fluxes showed that there is a decrease in the viscosity of the fluxes with the absorption of Ti02, Ti2O3 and Ti3O5 in the range of 2 to 10 wt%, for temperatures from 1400°C to 1200°C. The effect of Ti02 and Ti2O3 has been tested with the mould flux of the austenitic steel at a basicity of 1.2 to match the basicity which arises during casting. For temperatures of 12500C and below, the apparent viscosity of the flux increased markedly with the absorption of 10 % of Ti02 or Ti2O3. In both cases precipitation of perovskite (Ca2 Ti2O6 or Ca2 Ti2O5) was found to be responsible for the increase of the apparent viscosity of the flux of the austenitic steel. / Dissertation (M Eng (Metallurgical Engineering))--University of Pretoria, 2006. / Materials Science and Metallurgical Engineering / unrestricted

Hydroxyapatite (HA) has received wide attention in orthopedics, due to its biocompatibility and osseointegration ability. Despite these advantages, the brittle nature and low fracture toughness of HA often results in rapid wear and premature fracture of implant. Hence, there is a need to improve the fracture toughness and wear resistance of HA without compromising its biocompatibility. The aim of the current research is to explore the potential of nanotubes as reinforcement to HA for orthopedic implants. HA- 4 wt.% carbon nanotube (CNT) composites and coatings are synthesized by spark plasma sintering and plasma spraying respectively, and investigated for their mechanical, tribological and biological behavior. CNT reinforcement improves the fracture toughness (>90%) and wear resistance (>66%) of HA for coating and free standing composites. CNTs have demonstrated a positive influence on the proliferation, differentiation and matrix mineralization activities of osteoblasts, during in-vitro biocompatibility studies. In-vivo exposure of HA-CNT coated titanium implant in animal model (rat) shows excellent histocompatibility and neobone integration on the implant surface. The improved osseointegration due to presence of CNTs in HA is quantified by the adhesion strength measurement of single osteoblast using nano-scratch technique. Considering the ongoing debate about cytotoxicity of CNTs in the literature, the present study also suggests boron nitride nanotube (BNNT) as an alternative reinforcement. BNNT with the similar elastic modulus and strength as CNT, were added to HA. The resulting composite having 4 wt.% BNNTs improved the fracture toughness (~85%) and wear resistance (~75%) of HA in the similar range as HA-CNT composites. BNNTs were found to be non-cytotoxic for osteoblasts and macrophages. In-vitro evaluation shows positive role of BNNT in osteoblast proliferation and viability. Apatite formability of BNNT surface in ~4 days establishes its osseointegration ability.

No description available.

Two technologies, namely Laser Technology and Surface Modification Technology, have made rapid strides in the last few decades. The lasers have evolved from a simple laboratory curiosity to a matured industrial tool and its applications are limited only by imagination. Intense, coherent and monochromatic laser sources with power outputs ranging over several orders of magnitude have found innumerable applications in the realm of materials engineering. Reactive Pulsed Laser Deposition (PLD) is a powerful technique that utilises the power of a nanosecond pulsed laser for materials synthesis. Unlike conventional PLD, which require high density targets that are difficult to synthesize at a reasonable cost, the RPLD circumvents the need for one such ceramic target. This thesis presents a detailed and judicious use of this technique for synthesis of hard ceramic multilayer coatings using elemental metal targets. Transition metal nitrides having rock salt structure are known to exhibit superior properties such as hardness and wear resistance and hence formed the basis for the development of first generation coatings. Further improvements through alloying of these binary compounds with metal or metalloid components lead to the development of second generation coatings. As the demand for functional materials increased, surface modification technology alias surface engineering, grew in leaps and bounds. As the large number of coating requirements for optimal performance could not be fulfilled by a single homogeneous material, third generation coatings, comprising multilayer coatings, were developed. It is this aspect of combining the advantages of RPLD process to synthesize ceramic multilayer coatings, provides the main motivation for the present research work. In this thesis, a systematic study presented for synthesis of nanocrystalline and stoichiometric TiN and NbN thin films using RPLD through ablation of high purity titanium and niobium targets, in the presence of low pressure nitrogen gas. A novel Secondary Ion Mass Spectrometry (SIMS) based analysis was developed to effectively deduce the important process parameters in minimum trials to arrive at desired composition. The validity of this SIMS based method, for optimization of process parameters to get stoichiometric nitride films, was proved beyond any speculation by corroborative Proton Elastic Backscattering Spectrometric (PEBS) analysis. SIMS was also used to characterize the [NbN/TiN] multilayers. The feasibility of growing nanocrystalline multilayers with varying thicknesses has been demonstrated. Nanomechanical properties including hardness and adhesion strength of monolithic TiN and NbN films and multilayers were evaluated. The thesis is organised into six chapters. The first chapter gives a brief account on the history and development of ‘surface engineering’. The second chapter provides a comprehensive description of the experimental facility developed in-house to pursue research on PLD grown ceramic thin films and multilayers. Thin film synthesis procedure for ex-situ SIMS and TEM analyses is described. Brief introduction is also presented on the characterization techniques used in this study to investigate the surface, interface and microstructural aspects of PLD grown films with underlying basic principles. The third and fourth chapter describes the synthesis and characterization of titanium nitride and niobium nitride thin films using RPLD technique, respectively. SIMS was used in depth profiling mode, for optimization of three important process parameters, viz., nitrogen gas pressure, substrate temperature and laser pulse energy, to get stoichiometric nitride films. Further, films were characterized using GIXRD, TEM, XPS and PEBS for their structure and composition. AFM measurements were made to elucidate the surface morphological features. PEBS was effectively used to estimate the nitrogen concentration in a quantitative manner and the results corroborate well with the SIMS measurements. Having succeeded in synthesizing stoichiometric TiN and NbN films, further studies on the nanomechanical properties of monolithic TiN and NbN films and their multilayers were carried out and these results form the contents of the fifth chapter. The findings of the work reported in this thesis are concluded in Chapter 6 and few possible suggestions were presented as future directions. Both the monolithic TiN and NbN coatings showed a deposition pressure dependent hardness variation. The hardness of these monolithic films was found to be around 30 GPa, higher than the hardness values obtained by other conventional techniques. Keeping total thickness of the multilayers constant at 1 μm, [NbN/TiN] multilayers having bilayer periods ranging from 50 nm to 1000 nm, were synthesized. A systematic enhancement in hardness upto ~ 40 GPa was observed for [NbN/TiN]10 with the modulus of the multilayer remaining almost constant. The pileup observed around the indentation edge is indicative of toughening in multilayers. The tribological properties of multilayer films showed a better performance in terms of low coefficient of friction and regeneration of coating surfaces as revealed from the nanotribological studies. Overall, the multilayer coatings exhibited better performance in terms of hardness, toughness and adhesion with the substrate material.

As firearms continuously become more sophisticated, there have been commensurate efforts to optimize the ballistic performance of armours, with ceramic materials currently at the forefront of such studies. These efforts have focused on improving processing and microstructural design with reinforcements using dispersion particles, carbon nanotubes (CNT) and boron nitride nanotubes (BNNT). In most studies, ballistic testing has been used to identify parameters affecting the performance. The research documented here focuses on: (1) the investigation of two commercial ceramics, namely silicon carbide (SiC) and zirconia toughened alumina (ZTA). The primary material properties evaluated for the characterization included: hardness, fracture toughness, flexural strength and Young’s modulus. Other properties investigated included the microstructure, porosity/density, and mode of failure or fracture. (2) Ballistic depth of penetration (DOP) testing for six candidate ceramic armour systems including three monolithic ceramics (Al2O3, SiC and B4C) and three nanotube toughened ceramic composites (Al2O3-BNNT, Al2O3-single walled CNT and SiC-BNNT). SiC showed a hardness of 2413 HV, which is far beyond the requirements for armour ceramic. In contrast, ZTA barely met the hardness requirement of 1500 HV, but showed improved toughness of 4.90 MPa m1/2 beyond values reported for monolithic alumina. SiC and ZTA showed that microstructural design improves fracture toughness but processing introduces defects that can substantially reduce other armour related properties such as the strength. The results of the Charpy and drop tower impact tests are in agreement with indentation fracture toughness results suggesting a great degree of reliability of this cost efficient method. The addition of nanotubes produced an increase in toughness and a decrease in hardness in the ceramics, which resulted in an overall drop in performance during ballistic depth of penetration (DOP) tests. A microstructure-quasi-static mechanical properties-ballistic performance relationship was established which led to the development of a novel ballistic performance index and a new DOP model. The proposed ballistic performance index yielded a ranking, which agrees better with experimental observations than the currently published indices. The developed semi-empirical model suggests that the ballistic performance of ceramics is improved with increased fracture toughness, reduced flaw size and higher density.

Multi-junction photovoltaic devices based on III-V semiconductors have applications in space power systems and terrestrial concentrating photovoltaics, as well as in power-over-fibre and optical power conversion systems. These devices have between two and twenty junctions arranged in tandem, connected in series with optically transparent tunnel diodes. In some cases, they may include as many as eight different materials, including ternary and quaternary alloys, and >100 epitaxial layers in total. A general method for simulating performance of these devices using drift-diffusion based device simulation tools is reviewed. This includes discussion of the geometry, discretization, and physical equations to be solved. A set of material parameters for some important materials is listed, and solutions are shown for an example of a lattice-matched four-junction GaInP / (In)AlGaAs / InGaAsN(Sb) / Ge solar cell including a dilute nitride based p-i-n junction with ∼ 0.9 eV band gap. A sample of this dilute nitride junction with a 650 nm absorber layer was grown by molecular beam epitaxy and was shown to have short-circuit current density of 15.1 mA/cm2, sufficient for use in the 4-junction structure, while transmitting sufficient light through to the bottom (germanium) junction. Open-circuit voltage was up to 0.186 V at 1-sun, increasing to 0.436 V under 1500 suns concentration. The device simulation methodology was extended to include effects of luminescent coupling and photon recycling. These effects are included by adding a term to the electron and hole continuity equations, and the resulting coupled system of equations is solved. No external iterative loop is required, as has been the case in other efforts to model these effects. A five-junction photonic power converter (PPC) is simulated and it is shown that the quantum efficiency of the device is significantly broadened through luminescent coupling. There is a 350 mV reduction in simulated open-circuit voltage (70 mV per junction) if luminescent coupling is neglected. This work was later extended to a 12-junction PPC device, where the simulation predicts a wavelength sensitivity of -1.1%/nm in the absence of luminescent coupling; this is reduced to -0.4%/nm when luminescent coupling is included in the calculation. The latter result, and the overall shape of the simulated quantum efficiency curve agree closely with experimental measurements. Finally, two specific applications of PPCs are demonstrated. The first is in a step-up DC-to-DC converter, where a linear regulator combined with a laser/PPC pair can convert a 3.3 V input (commonly available from a single lithium polymer battery cell) into 12 V. Unlike conventional switching boost converters, this ‘photonic boost converter’ is not a source of ripple. In testing, a >80 dB reduction in ripple was measured compared with an equivalent switching boost converter, limited only by input noise of the instrument.The second application is in a 60 kW, 650 V switching circuit such as might be found in a hybrid or electric vehicle drivetrain. These circuits need several isolated power supplies to power gate drivers for the IGBT or SiC MOSFET switching components. This isolation is commonly provided by a small transformer, which inherently has a parasitic capacitance between primary and secondary windings and creates a path for EMI currents to flow from the high-power components to the power supply and control circuitry. By using a laser/PPC pair to provide the needed isolation, this parasitic capacitance can be largely eliminated; a 20 dB reduction in EMI current reaching the control FPGA is demonstrated.