Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Boron nitride (BN) is a compound formed by covalent bonds between boron and nitrogen atoms. In the crystalline phase it can be found in different structures, such cubic (c-BN), simgle hexagonal (h-BN), wurtzite (w-BN) and rhombohedral (r- BN). Similarly to graphite h-BN can form two dimensional structures, which can be cut to form tubes. Otherwise, c-BN has hardness similar to diamond, which is retained up to 2000 °C while diamond turns into to graphite at about 900 °C. These properties make BN a promissor material for nanoelectronics in a hot environment. Here, we investigate structural and electronic properties of BN nanotubes. Our study is directed not only to BN nanotubes in the pristine form (no defects), but also when topological defects (vacancies) and dopant impurities (Carbon) are present. The first principles calculations are based on the density functional theory with the generalized gradient approximation for the exchange-correlation term. The calculations were performed using the SIESTA computer code using gaussian functions to expand the Khon-Sham orbitals. We observe that C impurities have low formation energies when compared to vacancies have high formation energies. All the pristine BN nanotubes studied are non magnetic semiconductor with a band gap energy around 3.5 eV, which is almost independent of the tube chirality and diameter. Carbon impurities introduce localized electronic levels into the band gap while vacancies give magnetic moments to the BN nanotubes. Calculations for complex defects (carbon impurities and vacancies) show that the formation of these complex defects have lower formation energies when compared to the sum of the formation energies for isolated defects, indicating that these defects have higher probability of occurring. Double vacancies have formation energies close to those for single vacancies and in the equilibrium geometry, occurs a reconstruction where a pentagon-octagon-pentagon (5−8−5) structure is present. In the optimal geometry dangling bonds are not present and the magnetic moment is zero, but non-spin-polarized electronic levels are present in the band gap. / O nitreto de boro (BN) é formado por ligações covalentes entre B e N. Na fase cristalina pode ser encontrado nas diferentes estruturas: cúbica (c-BN), hexagonal (h-BN), wurtzita (w-BN) e romboédrica (r-BN). Similar ao grafite, o h-BN pode formar estruturas bidimensionais (planos ou camadas), as quais podem ser cortadas formando tubos. O c-BN tem uma dureza semelhante à do diamante, que é mantida até 2000 °C, enquanto que o diamante se desfaz em grafite a cerca de 900 °C. Estas propriedades fazem do BN um material promissor para nanoeletrônica em ambientes abrasivos. Neste trabalho, estudamos as propriedades estruturais e eletrônicas de nanotubos de BN. Nosso estudo é dirigido não só para os nanotubos de BN na forma pristina (sem defeitos), mas também quando defeitos topológicos (vacâncias) e impurezas (carbono) estão presentes. Os cálculos de primeiros princípios são baseados na teoria do funcional da densidade (TFD) com a aproximação do gradiente generalizado para o termo de troca-correlação (AGG). Utilizamos o código computacional SIESTA com funções gaussianas para expandir os orbitais de Khon-Sham. Observamos que as energias de formação para impurezas de carbono (C) são menores que para vacâncias. Os nanotubos de BN na fase pristina estudados são semicondutores não magnéticos com um gap de energia de cerca de 3,5 eV e praticamente independente do diâmetro e da quiralidade do tubo. Impurezas de carbono introduzem níveis eletrônicos localizados no gap enquanto que vacâncias geram momentos magnéticos para os nanotubos de BN. Cálculos para defeitos complexos (impurezas de C e vacâncias) mostram uma menor energia de formação quando comparados com defeitos isolados, indicando maior probabilidade de ocorrer. Vacâncias duplas têm energias de formação similares as de vacâncias simples e na geometria de equilíbrio ocorre uma reconstrução onde uma estrutura pentágono-octógono-pentágono (5−8−5) está presente. Não existem ligações pendentes e o momento magnético é zero, mas níveis eletrônicos de spin não polarizados estão presentes no gap.

Master of Science / Department of Chemical Engineering / James H. Edgar / Hexagonal boron nitride has been used as an inert, refractory material with excellent resistance to thermal decomposition and oxidation for more than fifty years. In the past few years, hBN has been targeted for potential electrical and optical devices such as neutron detectors, ultraviolet light emitters, deep ultraviolet light detectors, and substrates for graphene and other atomically-thin two-dimensional materials. All of these potential applications benefit from high quality, single crystals, with thicknesses varying from nanometers to microns. This research was undertaken to investigate four aspects of hBN crystal growth and recovery. (1) In an effort to optimize hBN crystal growth from a nickel-chromium flux, a series of stepped cooling experiments were undertaken. The temperature profile was stepped in a way as to promote growth in both the a and c directions, at their optimal growth conditions. Crystals were found to be typically 100-500 µm across and thickness of approximately 20-30 µm with a pyramid-like crystal habit. (2) A method for the removal of hBN crystals prior to freezing of the metal flux was demonstrated using a specialized hot pressed boron nitride crucible capable of removing hBN crystals from the flux in situ. (3) Growth of isotopically pure hBN crystals was undertaken. By modifying the crucible material for solution growth, enrichment of hBN crystals over 90% was accomplished. (4) Exfoliation of hBN has many potential applications, specifically as graphene-hBN heterostructures where layers approaching thicknesses of single atoms are most effective surface to interact with graphene as an electronic device. Several methods were tested toward exfoliating a single crystal resulting in few-layered hexagonal boron nitride nanosheets. As a result of these investigations a greater understanding of hBN bulk growth, its isotopic enrichment, its recovery, and its exfoliation was obtained.

Dans le cadre de la fabrication de pièces structurales pour l’industrie aéronautique, de nouveaux matériaux composites à matrice céramique sont envisagés par le motoriste Safran. Lors de l’utilisation dans des environnements sévères de combustion, et sous chargement mécanique, la matrice pourra s’endommager par fissuration et la capacité du matériau à s’auto-protéger sera réduite. Les travaux présentés dans cette thèse ont pour but d'identifier les mécanismes prépondérants de ruine de ce type de matériaux composites en fonction de différentes sollicitations thermiques, mécaniques et environnementales. Une démarche multi-échelle a été adoptée, de manière à considérer les phénomènes à une échelle microscopique (chaque constituant) et macroscopique (synergie entre les constituants au sein du matériau). Le comportement en oxydation/corrosion du matériau composite et de chacun de ses constituants a été caractérisé puis modélisé pour être extrapolé à des environnements de combustion. Différents domaines de protection du matériau ont ainsi été mis en évidence. Dans cette même optique, le comportement thermomécanique des constituants matriciels et du composite a fait l’objet d’essais de fluage pour déterminer les paramètres d’une première modélisation, et analyser les dégradations associées. En couplant les différents résultats obtenus, il est ainsi possible d’évaluer la criticité des différents phénomènes de ruine. Des scenarii de ruine sont donc présentés. / To design and manufacture CMC structural components for aeronautics, Safran develops a new CMC grade, provided to resist severe combustion environments. Understanding this new composite material damaging and failure mechanisms is essential: environmental conditions, mechanical loading, and matrix damages, can lead to a decrease in its self-protective properties. The aim of this work is to identify prevailing high temperature degradation mechanisms of those MI SiC/SiC CMCs, depending of different thermal, mechanical and environmental stresses. To fulfill that outcome, a multi-scale approach was considered, by examining phenomena from single constituents to complex composite architecture (effects of constituents’ synergy). High temperature oxidation/corrosion behaviors of the composite material and each of its constituents were characterized, and modeled to meet representative combustion environment. Different operating areas of efficient self-protection of the composite material were therefore highlighted. In the same perspective, themomechanical behaviors of both matrix constituents and composite were experimentally explored, enabling the determination of behavior laws. Related degradations in the composite material were also analyzed. Crossing all results, it was thereby possible to evaluate kinetics and criticality of failure mechanisms: different damaging scenarios are thus proposed, depending on environmental conditions.

Made available in DSpace on 2015-05-14T12:14:08Z (GMT). No. of bitstreams: 1 parte1.pdf: 2147467 bytes, checksum: 06d61abcd760c3d3a8cc6b1d61af88fa (MD5) Previous issue date: 2008-08-21 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In this work, we performed an analysis of the structural and electronic stability of nanostructures of Boron Nitride (BN), such as layers, tubes and cones, when doped with Carbon, through first-principles calculations as implemented in code SIESTA. We found that substitutional doping of Carbon for either a single Boron or a single Nitrogen atom produces significant changes in the conductive properties of each material. Such replacement process transforms the formerly insulating material, in a n-type conductor, donnor of electrons, for Boron replaced by Carbon, and the p-type, acceptor of electrons, for the Nitrogen substitution. Furthermore, we also performed calculations with spin-polarization and found occurrence of spontaneous magnetization of 1μB for all doped structures, except for tube (6,0), which presented a magnetic moment of 0;2μB. This magnetization is attributed to the unpaired electron located in the pz orbital of carbon. It was also noted that the doped layers become more energetically stable as the number of atoms increases. To the tubes, increased stability occurs with the increase in diameter combined with the consequent increase in the number of atoms. At the cones, stability energy is reduced with the increase in the angle of disclination. These effects are the result of a combination of percentage concentration of the defect and the greater or lesser degree of hybridization. / Neste trabalho, fizemos uma análise da estabilidade estrutural e eletrônica de nanoestruturas de Nitreto de Boro (BN), tais como planos, tubos e cones, quando dopadas com carbono, através do uso de cálculos de primeiros princípios como implementado no código SIESTA. Encontramos que a dopagem substitucional de carbono por boro ou nitrogênio provoca mudanças significativas nas propriedades condutoras de cada material. Tais substituições transformam o material que antes era isolante, em condutor do tipo n, doador de elétrons, para o boro substituído pelo carbono, e do tipo p, receptor de elétrons, para a substituição do nitrogênio. Além disso, realizamos cálculos com polarização de spin e verificamos a ocorrência de um momento magnético de 1μB para todas as estruturas dopadas, com exceção do tubo (6;0) que apresentou um momento magnético de 0;2μB. Essa magnetização é atribuída ao elétron desemparelhado localizado no orbital pz do carbono. Foi verificado também que os planos dopados se tornam mais estáveis energeticamente à medida que o número de átomos aumenta. Para os tubos, o aumento da estabilidade ocorre com o aumento do diâmetro combinado com o consequente aumento do número de átomos. Já nos cones, a estabilidade energética é diminuída com o aumento do ângulo de disclinação. Esses efeitos são fruto de uma combinação entre porcentagem de concentração do defeito e do maior ou menor grau de hibridização.

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.

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.

In the past few years, led by graphene, a large variety of two dimensional (2D) materials have been discovered to exhibit astonishing properties. By assembling 2D materials with different designs, we are able to construct novel artificial van der Waals (vdW) heterostructures to explore new fundamental physics and potential applications for future technology. This thesis describes several novel vdW heterostructures and their fundamental properties. At the beginning, the basic properties of some 2D materials and assembled vdW heterostructures are introduced, together with the fabrication procedure and transport measurement setups. Then the graphene based capacitors on hBN (hexagonal Boron Nitride) substrate are studied, where quantum capacitance measurements are applied to determine the density of states and many body effects. Meanwhile, quantum capacitance measurement is also used to search for alternative substrates to hBN which allow graphene to exhibit micrometer-scale ballistic transport. We found that graphene placed on top of MoS2 and TaS2 show comparable mobilities up to 60,000cm2/Vs. After that, the graphene/hBN superlattices are studied. With a Hall bar structure based on the superlattices, we find that new Dirac minibands appear away from the main Dirac cone with pronounced peaks in the resistivity and are accompanied by reversal of the Hall effects. With the capacitive structure based on the superlattices, quantum capacitance measurement is used to directly probe the density states in the graphene/hBN superlattices, and we observe a clear replica spectrum, the Hofstadter-butterfly fan diagram, together with the suppression of quantum Hall Ferromagnetism. In the final part, we report on the existence of the valley current in the graphene/hBN superlattice structure. The topological current originating from graphene’s two valleys flows in opposite directions due to the broken inversion symmetry in the graphene/hBN superlattice, meaning an open band gap in graphene.

Cubic boron nitride (cBN) synthesis has gained lot of interest during the past decade as it offers outstanding physical and chemical properties like high hardness, high wear resistance, and chemical inertness. Despite of their excellent properties, every application of cBN is hindered by high compressive stresses and poor adhesion. The cost of equipment is also high in almost all the techniques used so far. This thesis deals with the synthesis of cubic phase of boron nitride on Si (100) wafers using electron beam evaporator, a low cost equipment that is capable of depositing films with reduced stresses. Using this process, need of ion beam employed in ion beam assisted processes can be eliminated thus reducing the surface damage and enhancing the film adhesion. Four sets of samples have been deposited by varying substrate temperature and the deposition time. scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR) techniques have been used to determine the structure and composition of the films deposited. X-ray diffraction (XRD) was performed on one of the samples to determine the thickness of the film deposited for the given deposition rate. Several samples showed dendrites being formed as a stage of film formation. It was found that deposition at substrate temperature of 400oC and for a period of one hour yielded high quality cubic boron nitride films.

The SRV test rig was used to evaluate the friction and wear properties of a lubricant in a laboratory setup. Normally, the coefficient of friction and the amount of wear that occurred are measured while the wear scar surface is also evaluated. Special attention was paid to factors that affect the repeatability. The test fluid was subjected to a friction and wear test on the SRV test rig in order to determine what factors affect the repeatability of the coefficient of friction, the amount of wear that occurred and the wear scar appearance. The test fluid used was based on rapeseed oil and white mineral oil. The fluid also contained an extreme pressure additive in the form of sulphurised ester. This was also compared for the same test fluid with dispersed hexagonal-boron nitride (h-BN) nanoparticles. The standard test method as described by ASTM D 6425, was used as test method. Instead of the standard temperature, the block temperature was increased to 100 °C in order to simulate harsher operating environments. The load was set at 200 N It was found that:  The rapid load increase from 50 to 200 N at the end of the running-in period (as described in the standard test method) caused poor repeatability. The test was modified with a more gradual load application for the duration of the running-in period (30 N/min), which resulted in improvement in the repeatability of the tests conducted.  The moisture content in the atmosphere also affected the repeatability of the friction and wear tests. This was most likely due to the formation of a corrosion layer that involves water and by keeping the relative humidity constant, a further improvement in the repeatability was observed. The addition of the h-BN nanoparticles resulted in an improvement of the repeatability of the coefficient of friction (COF), wear scar surface (WSS) and wear scar volume (WSV), since the wear scar surfaces indicated that the particles remove the corrosion layers. This could have led to more consistent wear surfaces for the duration of the test.  The particles also influenced the corrosion layer formation. For both fluids, Raman spectroscopy indicated that greigite (Fe3S4) and goethite (α-FeOOH) were found on the surface, while additional corrosion products were found on the wear scar surface for the test fluid with dispersed particles. These compounds were melanterite (FeSO4.7H2O) and rozenite (FeSO4.4H2O). All these corrosion products were most likely formed due to the reaction of iron from the specimens with sulphurised esters in the test fluid. / Dissertation (MEng)--University of Pretoria, 2015. / tm2015 / Chemical Engineering / MEng / Unrestricted

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