Degenerative disorders of the rotator cuff tendons account for nearly 75% of all shoulder pain, causing considerable pain and morbidity. Given the strong correlation between age and tendinopathy, and unprecedented population aging, these disorders will become increasingly prevalent. Improved understanding of tendon degeneration will guide the development of future diagnostic and treatments, and is therefore urgently needed. However, the aetiology and pathology of rotator cuff tendinopathy remain unclear. The complicated mechanical environment of the rotator cuff is hypothesised to influence the susceptibility of the tendons to degeneration and tearing. Studies have reported biological adaptations in torn cuff tendons indicative of increased compressive loading within the tendon. The material adaptations of healthy and degenerative cuff tendons are largely unreported but will provide further insight into the role of the mechanical environment in rotator cuff aetiology and pathology. This thesis examined the material adaptations of healthy and diseased tendons to explore the role of mechanical loading in rotator cuff pathology. The material adaptations of healthy animal tendons, and healthy and delaminated human cadaveric rotator cuff tendons, in response to different loading environments were characterised. The effects of age, tears, steroid injection and subacromial decompression surgery on the structural adaptations of human cuff tendons were also studied, as was the effect of tendon cell proliferation on the mechanical properties and degradation behaviour of collagen scaffolds. Loading environment significantly affected the structural adaptations of healthy tendons. Regions exposed to compressive and shear strains exhibited thinner fibres, shorter crimp lengths and thinner, less aligned fibrils compared with regions exposed to tensile strains alone. In healthy rotator cuff tendons, the inhomogeneous loading environment produced topographically inhomogeneous structural adaptations. The tendons of a delaminated rotator cuff exhibited less topographical variation in properties and thinner, less aligned fibrils compared with healthy cuff tendons. Torn cuff tendons exhibited thinner fibrils and shorter crimp lengths compared with control samples. These adaptations were identifiable early in the disease progression, and neither steroid injection nor subacromial decompression surgery significantly influenced these adaptations at seven weeks post‐treatment. Significant correlations between decreasing dimensions and increasing tear size were found when age was included as a confounding factor, reflecting the importance of age and tear size in determining the material properties of tendons. Tendon cell proliferation influenced the mechanical properties and degradation behaviour of the collagen scaffolds, emphasising the integral role of cells in the functional adaptation of biological materials. These results demonstrate the effect of mechanical environment on the material adaptations of tendons. They also indicate the importance of the complicated mechanical environment experienced by the rotator cuff tendons in predisposing the tendons to degeneration and tearing. The observed material adaptations of degenerative and torn tendons suggest that rotator cuff pathology is associated with increased levels of compressive and/or shear strains within the tendon. These changes begin early in the disease progression and neither steroid injection nor sub‐acromial decompression surgery are capable of reversing the changes in the timeframe investigated. These findings highlight the urgent clinical need for pre‐rupture diagnostic techniques for the detection of early pathological changes in the rotator cuff. They also emphasize the requirement for new intervention strategies that restore the healthy mechanical environment and reverse early pathological adaptations in order to prevent catastrophic failure of the tendons.

Austenitic stainless steels are frequently used in the cooling circuits of nuclear reactors. It has been found that cold-worked 304 stainless steels can be particularly susceptible to stress corrosion cracking at the operating conditions of such reactors. Despite more than 130 years of research underlying mechanisms are still not properly understood. For this reason, the effects of cold-work and applied stress on the oxidation behaviour of 304SS have been studied in this thesis. A set of samples with/without prior cold-work, and with/without stress applied during oxidation, were oxidized in autoclaves under simulated pressurised water reactor primary circuit conditions. Atom-probe tomography and analytical transmission electron microscopy were used to investigate the local chemistry and microstructure in the different samples tested. Regions containing grain boundaries, deformation bands, and matrix material in contact with the environment, were extracted from the coupon specimens with a focused ion beam machine. Cross-sections of crack tips were studied with secondary ion mass spectrometry and electron backscatter diffraction. The compositions of oxides grown along the surface and the different microstructural features were analysed. Fe-rich spinels were found at the surface and Cr-rich spinels were observed along fast diffusion paths. Ni-enrichment was found at the metal/oxide interfaces and a Ni-rich phase was detected in precipitates ahead of grain boundary oxides. Li was observed in all oxidised regions and B segregation, originating from impurities in the alloy, was observed in grain boundaries and crack tip oxides. Cavities and hydrogen associated with Ni-rich regions were found ahead of the bulk Cr-rich oxide in some of the samples. The implications of these findings for the understanding of SCC mechanisms are discussed. It is suggested that Ni precipitation as well as the presence of deformation bands may play an important role in controlling SCC susceptibility in 304 stainless steel. A modification of the film-rupture model including internal oxidation and fast diffusion along H-stabilised vacancies in strain fields at the crack front is proposed.

This thesis presents an investigation of the dynamic properties of wide range of interfacial systems, from colloidal particles in solution, through the realm of aerosols and onto studies of molecular adsorption at an interface. The primary experimental technique utilized is optical tweezers. An exploration of the history of the use of radiation pressure to manipulate matter is presented, followed by an introduction to how optical tweezers work. Some of the more advanced methods of tweezing are discussed, with an emphasis on the use of spatial light modulators (SLMs) to realise dynamic holographic optical tweezers (DHOTs), an example of which has been constructed within our laboratory using off-the-shelf optical components, and combined with a spectrometer to facilitate high resolution spectroscopic studies of microscopic systems. The spectroscopic analysis of microparticles is greatly enhanced by optical feedback generated when the wavelength of light utilized is an integer number of wavelengths around the circumference of the microsphere. Enhanced signal occurs at these wavelengths, termed whispering gallery modes (WGMs). The absolute position of these resonances depends strongly upon the shape, size and refractive index of the particle, and is predicted by Mie theory. A discussion of the concepts behind Mie theory, as well as how to use an experimental WGM spectrum to deduce the size and composition of a microparticle, is provided. This technique is then put to use in a detailed study on the properties of single aerosols, comprised of sodium chloride solution, and generated using a handheld medical nebulizer. Studies have been carried out on both evaporating and growing droplets trapped with a Gaussian beam; in the latter case, periods of size stability are observed, owing to resonant absorption of radiation at the trapping laser wavelength. The SLM can be used to change the trapping laser to a Laguerre-Gaussian (LG) mode, and an investigation of how this affects the dynamics of the droplet is presented. It is found that the use of LG modes with $ellgeq10$ produced Raman spectra with significantly more intense WGMs, and also suppressed droplet evaporation. Through observations made with fluorescent polystyrene microspheres, it is argued that the LG modes are more efficient at coupling into WGMs of the droplets. Leading on from these experiments on salt water droplets, experiments have been conducted using ionic liquids (ILs). These fluids have many fascinating properties and potential applications. The optical trapping of droplets comprised of aqueous solutions of the ionic liquid ethylammonium nitrate (EAN) and water has been demonstrated for the first time. These droplets are analysed spectroscopically by illuminating them with the output from a broadband LED; WGMs that are observed in the backscattered light are used to determine their size and composition. The response of the droplets to conditions of varying relative humidity has also been investigated. In order to characterise the relative humidity experienced by both the salt water and IL droplets, the concentration of water vapour within the trapping cells has been measured using diode laser absorption spectroscopy. The spatially modulated laser beam is then utilized in a different fashion; instead of optically tweezing a sample, a low numerical aperture objective lens is utilized to focus the laser onto the surface of a gold coated microscope slide. When a colloidal sample is placed on this surface, the thermal gradients cause the particles to form two dimensional crystals. The SLM is utilized to form multiple nucleation sites, and the dynamics of the crystals are directly observed in real time using video microscopy. It is found that grain rotation-induced grain coalescence (GRIGC) occurs, with the rotation of both crystals before coalescence. Control over the grain size is achieved by altering the separation of the laser spots, and shows that the time scale for grain boundary annealing in our system is in good agreement with theoretical expressions formulated for nanocrystal growth. Finally, as a complimentary technique to the microparticle spectroscopy previously discussed, a bulk interface is probed by using evanescent wave broadband cavity enhanced absorption spectroscopy (EW-BBCEAS) specifically to study the adsorption of cytochrome c (cyt c) to a fused silica surface. Visible radiation from a supercontinuum source is coupled into an optical cavity consisting of a pair of broadband high reflectivity mirrors, and a total internal reflection (TIR) event at the prism/water interface. Aqueous solutions of cyt c are placed onto the TIR footprint on the prism surface and the subsequent protein adsorption is probed by the resulting evanescent wave. The time integrated cavity output is directed into a spectrometer, where it is dispersed and analysed. The broadband nature of the source allows observation of a wide spectral range (ca 250 nm in the visible). The system is calibrated by measuring the absorption spectra of dyes of a known absorbance. Absorption spectra of cyt c are obtained for both S and P polarized radiation, allowing information about the orientation of the adsorbed protein to be extracted.

Hardness measurements and Three-Dimensional Atom Probe (3DAP) were used to characterize the early stages of precipitation in three different Al-Mg-Si alloys (Al-0.50 wt%Mg-1.00 wt%Si) with different Cu contents (0.03 wt%, 0.15 wt%, or 0.80 wt% Cu). Heat treatments were chosen to simulate an industrial production line for car body-sheet material and included natural ageing (NA), pre-ageing at 80 °C (PA), paint-bake ageing at 180 °C (PB) and 10 second ageing at 180 °C (spike). The Cu content and the chosen heat treatments were found to influence the microstructural evolution of the alloy considerably. Based on the determined microstructures and matrix solute concentrations, mechanisms for the effect of NA, PA and Cu additions were proposed. NA had a deleterious effect on the PB hardening response, which was delayed dramatically after 20 minutes NA or longer. When the NA time was 1 minute, β" precipitates were formed within 30 minutes PB resulting in high hardness of the alloy. The delay with NA time was caused by a decrease in the nucleation rate of elongated precipitates during the subsequent PB. This decrease was thought to be due to a combination of a decrease in the matrix solute concentrations and clusters acting as vacancy sinks. PA before NA improved the PB response due to the formation of a high density of short elongated precipitates. Small Mg-Si clusters were detected after both NA and PA. Clusters formed during PA were found to be, on average, Mg-richer and larger than those formed during NA. Larger clusters were found to be more stable during PB and, upon PB, to grow into nucleation sites for elongated precipitates. Application of a spike before PA resulted in faster growth of clusters during PA. Growth of clusters and nucleation of short elongated precipitates during PB was found to be enhanced with increasing Cu content when no PA was given. Cu was found to be present in all precipitates and clusters in the alloy with the highest Cu content. These precipitates were thought to be precursors to the Q' phase.

Experimental investigations of the optical properties of GaN nanostructured light emitting diode (LED) arrays are presented. Microphotoluminescence spectroscopy with pulsed and continuous wave lasers was used to probe the carrier dynamics and emission mechanisms of nanorod LED arrays fabricated by a top down etching method. Results show a possible reduction in internal electric field as nanorod diameter decreases. Localisation effects were also observed, affecting the spectral shape of the nanorod emission. Under two-photon excitation, quantum dot-like sharp spectral peaks in the PL spectra are found to exist in abundance amongst all the nanorod samples. The optical properties of these localised states, which are shown to be associated with the nanorod free-surfaces, are characterised using non-linear and time resolved spectroscopy. An investigation into spatially resolved single nanorods was also carried out. Single nanorods were isolated, and characterised using pulsed lasers. The etching is shown to increase the carrier decay life-time at extended intervals over several hundred ns. The temporal evolution and excitation power density dependence of the quantum dot-like states are also presented for the first time. The long lived localised states are thought to arise from surface effects, in particular Fermi-surface pinning, causing localisation and spatial separation of carriers. Additional work on nano-pyramid array LEDs, with quantum wells on semi-polar surfaces is also presented. Optical properties using micro-photoluminescence are compared to cathodoluminescence studies. An uneven distribution of emission wavelengths across the pyramid facet is thought to lead to an emission mechanism involving carriers transferring between multiple spatially localised states. Finally, experimental techniques and fabrication methods for future work are documented in detail.

Graphene has unrivalled properties and is heralded as a revolutionary material for the 21^st century. Chemical vapour deposition (CVD) on metals is a promising method to produce large-area graphene. Controlling the properties of CVD graphene is vital for its integration in a wide-range of future applications. Many factors can influence the CVD growth of graphene and its properties, therefore further investigations will be beneficial to fully understand and control this technique. In this thesis I expand the knowledge about the growth of pure and heteroatom-doped graphene by low pressure chemical vapour deposition (LPCVD) and atmospheric pressure chemical vapour deposition (APCVD) on commercially available Cu and Pt foils. Using a range of characterisation techniques, I investigate the influence of the substrate’s properties and the synthesis conditions on the growth of graphene, in pursuit of improved, controlled or optimised production, which can promote high quality, large-area, single-layer graphene, or other as desired. By characterising the topography, surface roughness, crystallographic orientations, and chemical composition of six Cu foils, I find that their properties vary greatly and this influences the growth of CVD graphene. I elucidate that the commonly used 99.8 % Alfa Aesar Cu foil has a surface coating composed of calcium, chromium, and phosphorus, which detrimentally influences graphene growth. Cleaning Cu foils with CH₃COOH is shown to reduce the concentration of surface contaminants, consequently reducing the nucleation density and increasing the growth rate of CVD graphene. I also demonstrate that the shape, orientation, edge-geometry and thickness of CVD graphene domains can be controlled by the Cu crystallographic orientations. Single layer LPCVD graphene domains align with zigzag edges parallel to a single <101> direction on Cu{111} and Cu{101}, while bilayer domains align to two directions on Cu{001}. Hexagonal APCVD domains also preferentially align with edges parallel to the <101> direction(s). This discovery resolves a key challenge of controlling the orientation of individual graphene domains and opens a new avenue for tailored production of large-area CVD graphene with improved properties. By controlling the synthesis conditions of APCVD graphene on Pt foils I optimise production of ~0.5 mm single layer graphene domains with reduced nucleation density and increased growth rate of ~100 &mu;m/min by synthesis at 1150°C, a higher temperature than previously reported. The absence of large, hexagonal, single-crystal domains on pristine Pt foil, and observation of a reaction between quartz and Pt that promotes hexagonal domains, suggests that a silicon or platinum silicide surface layer may be advantageous for improved growth of graphene. Finally, I demonstrate that the dopant concentration of nitrogen-doped graphene is increased at lower synthesis temperatures and higher NH₃ concentration, up to 1.3 %, but with an associated decrease in the growth rate. Direct visualisation, elemental confirmation, and electronic characterisation of individual nitrogen atoms is shown for the first time using aberration corrected scanning transmission electron microscopy and electron energy loss spectroscopy. Boron-doped graphene is also synthesised. The implications of these findings, and many additional minor contributions, are wide-ranging and of considerable importance for the future understanding of CVD growth of graphene on metals, and more generally for the advancement of scientific knowledge for manufacturing large-area graphene. Collectively, these discoveries represent a significant body of work that can improve the efficiency of production and assist with controlling the properties of large-area CVD graphene.

The commercial polycrystalline superalloy RR1000 developed for turbine disc applications contains a large number of alloying elements. This complex alloy chemistry is required in order to produce appropriate microstructures and the required mechanical properties, such that the most important strengthener γʹ displays complex alloy chemistry. The broad aim of this project is to develop an approach to measuring the composition of γʹ precipitates at a broad range of length scales from nanometres to hundreds of nanometres, and subsequently develop a better understanding of the role of thermodynamics and diffusion kinetics on γʹ phase separation and precipitate growth. A solution of the absorption-corrected EDX spectroscopy to spherical particles was developed in our work, therefore enabling the quantitative analysis of precipitates' composition using an absorption-corrected Cliff-Lorimer approach. By performing this quantification, size-dependent precipitate compositional variations were obtained. Examination of this quantitative approach was compared to thermodynamic calculations of primary γ' precipitates possessing equilibrium compositions. Given the development of semi-quantitative compositional measurements for spherical γʹ precipitates and that cooling is one of the most common and critical regimes in physical metallurgy of Ni-based superalloys, this approach was then applied to study the local compositional variations that are induced in γ' precipitates when the alloy RR1000 undergoes different cooling rates. These measured compositions have been compared to detailed thermodynamic calculations and provide new experimental evidence of the importance of the dominant role of aluminium antisite diffusion in determining the low-temperature growth kinetics of fine-scale γ' precipitates. We have applied a similar analysis approach to study the compositional variations of γʹ cores within the class of secondary precipitates upon cyclic coarsening and reversal coarsening. It was shown that supersaturated Co in secondary γʹ exhibits an overall trend towards the equilibrium but Co content can significantly increase as γʹ coarsens. It was demonstrated that the limited elemental diffusivity in γ and γʹ compared to the observed coarsening rate in the coarsening regime results in the long-lasting Co supersaturation in γʹ and builds up elemental enhancements or depletions. These inhomogeneous elemental distributions produce compressive elastic constraints on large-scale secondary γʹ, therefore inducing morphological instability of these γʹ and causing the reversal coarsening. These results enable us to better understand the role that both thermodynamics and limited diffusion kinetics plays in controlling the complex microstructures of γ' precipitates.

A tese proposta teve por objetivo caracterizar óxidos e hidróxidos de alumínio sintéticos comerciais por métodos óptico-eletrônicos ( microscopia eletrônica de varredura e de transmissão, difração de elétrons, microanálise por espectrometria dispersiva em comprimento de onda e por espectrometria dispersiva em energia), além da difração de raios-X e análise térmica diferencial. Os quatro hidróxidos de alumínio estudados foram gibsitas, de fórmula química Al(OH) IND.3 , três dos quais sintetizados industrialmente pelo processo Bayer ( cujo recursor é o aluminato de sódio) e o outro resultante do processo Weiser, de laboratório (com o aluminato de potássio como precursor ). Os onze óxidos de alumínio, ou aluminas (de fórmula química Al IND.2 0IND. 3 ), estudados foram sintetizados por vários processos: baixa e alta calcinação, redução aluminotérmica, calcinação de alumen de amônio e eletrofusão; variando no teor de sódio presente. No caso desta Tese, a microscopia eletrônica de varredura permitiu uma descrição morfológica dos materiais analisados e, quando acoplada à microanálise de raios-X, permitiu uma análise química elementar. A microscopia eletrônica de transmissão possibilitou uma descrição da morfologia da fração de dimensões coloidais; sendo, também, utilizado como câmara de difração para a identificação cristalográfica das amostras. Os melhores dados de composição quantitativos foram obtidos por microanálise, através de espectrometria dispersiva em energia obtidos em EDS/MEA. A difração de raios-X possibilitou a identificação dos compostos cristalinos presentes nas amostras; enquanto a análise térmica diferencial forneceu dados sobre reações exotérmicas e endotérmicas que as amostras sofrem durante o aquecimento, que transforma a gibsita nas aluminas de transição e alumina-alfa. O microscópio analítico, que permite imagens morfológicas assim como informações sobre a estrutura cristalina e a composição química elementar, firmou-se como a mais poderosa ferramenta de caracterização para uma indústria dedicada à produção de hidróxidos e óxidos de alumínio. / The aim of the present Thesis was the characterization of commercial synthetic aluminum hydroxides and oxides by electron-optical methods (scanning and transmission electron microscopy, electron diffraction, energy dispersive spectrometry and wavelength dispersive spectrometry) besides X-ray diffraction and differential thermal analysis. The four aluminum hydroxides studied were gibbsite (Al(OH)3), three of which were sythetized by the Bayer process ( sodium aluminate as precursor ) and the other resulting from the Weiser process ( potassium aluminate as precursor). The eleven aluminum oxides or aluminas (Al203) were synthetized by several processes: low and high calcination aluminothermic redution, amonium alum calcination and electromelting; all of them with varying sodium content. In this Thesis the scanning electron microscoy allowed a morphological description of the samples, and when associated to X-ray microanalysis allowed an elemental chemical analysis. The transmission electron microscopy allowed a morphological descripition of the coloidal dimensions fraction; it was also used as a diffraction camera for crystallographic identification. The better quantitative analysis results were obtained by X-ray microanalysis using EDS/ AEM. The X-ray diffraction allowed the identification of crystalline compounds; the differential thermal analysis gave data about the exo and endothermical reactions suffered by the gibbsite, by the transition aluminas and by the alpha-alumina. The analytical microscope, wbich allowed morpbological images as well as information about the crystalline structure and the elemental cbemical composition, was established as the most powerful tool for the cbaracterization in an industry dedicated to the production of aluminum hydroxides and oxides.

A tese proposta teve por objetivo caracterizar óxidos e hidróxidos de alumínio sintéticos comerciais por métodos óptico-eletrônicos ( microscopia eletrônica de varredura e de transmissão, difração de elétrons, microanálise por espectrometria dispersiva em comprimento de onda e por espectrometria dispersiva em energia), além da difração de raios-X e análise térmica diferencial. Os quatro hidróxidos de alumínio estudados foram gibsitas, de fórmula química Al(OH) IND.3 , três dos quais sintetizados industrialmente pelo processo Bayer ( cujo recursor é o aluminato de sódio) e o outro resultante do processo Weiser, de laboratório (com o aluminato de potássio como precursor ). Os onze óxidos de alumínio, ou aluminas (de fórmula química Al IND.2 0IND. 3 ), estudados foram sintetizados por vários processos: baixa e alta calcinação, redução aluminotérmica, calcinação de alumen de amônio e eletrofusão; variando no teor de sódio presente. No caso desta Tese, a microscopia eletrônica de varredura permitiu uma descrição morfológica dos materiais analisados e, quando acoplada à microanálise de raios-X, permitiu uma análise química elementar. A microscopia eletrônica de transmissão possibilitou uma descrição da morfologia da fração de dimensões coloidais; sendo, também, utilizado como câmara de difração para a identificação cristalográfica das amostras. Os melhores dados de composição quantitativos foram obtidos por microanálise, através de espectrometria dispersiva em energia obtidos em EDS/MEA. A difração de raios-X possibilitou a identificação dos compostos cristalinos presentes nas amostras; enquanto a análise térmica diferencial forneceu dados sobre reações exotérmicas e endotérmicas que as amostras sofrem durante o aquecimento, que transforma a gibsita nas aluminas de transição e alumina-alfa. O microscópio analítico, que permite imagens morfológicas assim como informações sobre a estrutura cristalina e a composição química elementar, firmou-se como a mais poderosa ferramenta de caracterização para uma indústria dedicada à produção de hidróxidos e óxidos de alumínio. / The aim of the present Thesis was the characterization of commercial synthetic aluminum hydroxides and oxides by electron-optical methods (scanning and transmission electron microscopy, electron diffraction, energy dispersive spectrometry and wavelength dispersive spectrometry) besides X-ray diffraction and differential thermal analysis. The four aluminum hydroxides studied were gibbsite (Al(OH)3), three of which were sythetized by the Bayer process ( sodium aluminate as precursor ) and the other resulting from the Weiser process ( potassium aluminate as precursor). The eleven aluminum oxides or aluminas (Al203) were synthetized by several processes: low and high calcination aluminothermic redution, amonium alum calcination and electromelting; all of them with varying sodium content. In this Thesis the scanning electron microscoy allowed a morphological description of the samples, and when associated to X-ray microanalysis allowed an elemental chemical analysis. The transmission electron microscopy allowed a morphological descripition of the coloidal dimensions fraction; it was also used as a diffraction camera for crystallographic identification. The better quantitative analysis results were obtained by X-ray microanalysis using EDS/ AEM. The X-ray diffraction allowed the identification of crystalline compounds; the differential thermal analysis gave data about the exo and endothermical reactions suffered by the gibbsite, by the transition aluminas and by the alpha-alumina. The analytical microscope, wbich allowed morpbological images as well as information about the crystalline structure and the elemental cbemical composition, was established as the most powerful tool for the cbaracterization in an industry dedicated to the production of aluminum hydroxides and oxides.

O NbAl3 e algumas ligas intermetálicas do sistema Nb-Ni-AI foram sintetizadas por combustão a partir dos pós de seus elementos constituintes. O efeito de variáveis de processo, como o tamanho de partícula dos pós, a composição química, a pressão de compactação, o tratamento de desgaseificação e a taxa de aquecimento, foram investigados na síntese do NbAl3 na forma de pastilhas cilíndricas. A síntese de ligas do sistema Nb-Ni-AI foi realizada a partir de misturas com as composições Nb10Ni70AI, Nb20Ni65AI e Nb30Ni60AI. A microestrutura das amostras reagidas foi caracterizada por microscopia óptica, microscopia eletrônica de varredura, EDS e difração de raios-X (método de Rietveld). Foram obtidas pastilhas de NbAl3 com 98,5 % da densidade teórica, superior ao valor encontrado na literatura (95%), mediante o controle de variáveis de processo. Nas pastilhas contendo níquel, a combustão ocorreu nas pastilhas de todas as composições. Fases metaestáveis, presentes na microestrutura das pastilhas baitas de reação, foram transformadas após tratamento térmico, originando ligas trifásicas com diferentes concentrações de fases (NbAl3, NiAI e NbNiAI), conforme a composição inicial do compactado. Algumas propriedades mecânicas de amostras brutas de reação e tratadas termicamente foram determinadas pela técnica da impressão (microdureza e tenacidade). Os resultados obtidos são comparáveis aos da literatura, salvo algumas discrepâncias atribuídas a processos de fabricação distintos. As etapas de reação da síntese do NbAl3 e de ligas Nb-Ni-AI foram posteriormente investigadas mediante interrupção da reação durante sua propagação ao longo de barras paralelepipédicas compactadas. Verificou-se que a síntese do NbAl3 ocorre pela dissolução de nióbio no alumínio fundido, seguida da precipitação do NbAl3. Nas amostras contendo níquel, a síntese ocorre em dois estágios: no primeiro estágio formam-se o Ni2Al3 ou o NiAl3, em quantidades relativas dependentes da composição geral. As reações deste primeiro estágio podem disparar as reações do segundo estágio, referentes à síntese do NbAl3. / NbAl3 and Nb-Ni-AI intermetallic alloys have been obtained by pressureless combustion synthesis from elemental powders. The effects of process variables as powder particle size, composition, compaction pressure (green density), degassing treatment and heating rate on the combustion (thermal explosion mode) of NbAl3 cylindrical pellets were studied. Combustion synthesis of Nb-Ni-AI alloys was performed on powder mixtures with nominal compositions Nb10Ni70AI, Nb20Ni65AI and Nb30NI60AI. The microstructure of reacted samples was characterized by optical microscopy, scanning electron microscopy, EDS and X-ray diffraction (Rietveld method). It was shown that careful control of the processing conditions allowed near full (98,5%) dense pellets of NbAl3. In the nickel containing pellets, reaction occurred for all the compositions investigated. Metastable phases were seen to be present in the as reacted pellets, which were transformed after a heat treatment, producing a three phase alloy (NbAl3, NiAI and NbNiAI) with different phase concentrations, depending on the initial compact composition. Some mechanical properties, like microhardness and tenacity were measured by microidentation technique on the as reacted and heat-treated samples. The results are comparable with the literature, excepted for some discrepancies caused by different fabrication processes. The reaction sequence for both cases (NbAl3 and Nb-Ni-AI alloys) was further investigated by DSC analysis and also by interrupting the reaction during its propagation along compacted parallelopipedal bars. It was found that the NbAl3 synthesis occurs through niobium dissolution in molten aluminum and precipitation of NbAl3. In the nickel containing samples, synthesis occurs as two-stage reaction: Ni2Al3 or NiAl3 are formed in the first stage, with relative amounts depending on the general composition. This first stage reaction can trigger the second one, related to the formation of NbAl3.