This thesis investigates the effect of microstructural strengthening mechanisms on the overall mechanical performance of micro-truss periodic cellular metals (PCMs). Prior to the author’s work, the primary design considerations of micro-truss PCMs had been topological issues, i.e. the architectural arrangement of the load-supporting ligaments. Very little attention had been given to investigate the influence of microstructural effects within the cellular ligaments. Of the four broad categories of strengthening mechanisms in metals, only solute and second phase strengthening had previously been used in micro-trusses; the potential for strengthening micro-truss materials by work-hardening or grain size reduction had not been addressed. In order to utilize these strengthening mechanisms in micro-truss PCMs, two issues needed to be addressed. First, the deformation-forming method used to produce the micro-trusses was analyzed in order to map the fabrication-induced (in-situ) strain as well as the range of architectures that could be reached. Second, a new compression testing method was developed to simulate the properties of the micro-truss as part of a common functional form, i.e. as the core of a light-weight sandwich panel, and test the effectiveness of microstructural strengthening mechanisms without the influence of typical high-temperature sandwich panel joining processes, such as brazing. The first strengthening mechanism was achieved by controlling the distribution of plastic strain imparted to the micro-truss struts during fabrication. It was shown that this strain energy can lead to a factor of three increase in compressive strength without an associated weight penalty. An analytical model for the critical inelastic buckling stress of the micro-truss struts during uniaxial compression was developed in terms of the axial flow stress during stretch forming fabrication. The second mechanism was achieved by electrodeposition of a high-strength nanocrystalline metal sleeve around the cellular ligaments, producing new types of hybrid nanocrystalline cellular metals. It was shown that despite the added mass, the nanocrystalline sleeves could increase the weight-specific strength of micro-truss hybrids. An isostrain model was developed based on the theoretical behaviour of a nanocrystalline metal tube network in order to predict the compressive strength of the hybrid materials.

<div>Magnesium alloys are regarded as the most promising structure materials in transportation and aerospace fields because of their low densities and high specific strengths. However, the unsatisfactory mechanical performance and corrosion resistance restrict their applications. Grain refinement is an effective way to improve the mechanical properties and widen the applications. Among which, ultrasonic shot peening shows a great potential in producing refined grains or even nanocrystalline. A nanocrystalline forms at the surface after ultrasonic shot peening treatment. The formed nanocrystalline has been proved to dramatically affect the mechanical properties, such as hardness, mechanical stress, wear resistance and fatigue life. </div><div><br></div><div> </div><div>In this dissertation, the microstructure evolution of AZ31 Mg alloy after the ultrasonic shot peening as well as its effect on the mechanical properties are investigated. The grain size, the twin structure, the surface roughness and the residual stress distribution after ultrasonic shot peening are characterized. A gradient nanostructure is achieved through ultrasonic shot peening and the thickness of this gradient nanostructure increases with prolonging the treated time. The grains at the top surface after 5 min treatment is refined to 45 nm and further refined to 42 nm for 10 min and 37nm for 15 min treatment from the XRD result. A lamellar nanocrystaline is below the top surface and a lot of tensile twins are found at the heavily deformed grains below the nanocrystalline layer. Below the twinned layer, a residual stress is distributed as deep as 400 $\mu$m in the matrix. A rough surface is obtained and the surface roughness of the 5 min treated sample was 5.934 $\mu$m, increased to 6.161 $\mu$m for10 min and 6.236 $\mu$m for 15 min. The nanocrystalline leads to the improvement of the microhardness, from 65 HV of the as-received to 123 HV, 127 HV and 145 HV for 5 min, 10 min and 15 min treatment, respectively. The tensile stress and compression stress are also improved remarkably. The yield stress is increased from 127.7 MPa of as-received to 198 MPa of 10 min treated sample and the compression stress is improved from 73 MPa to 100 MPa. The improved yield stress is attributed to the grain refinement and the work hardening of the nanocrystalline. </div><div><br></div><div> </div><div> </div><div>The wear resistance of AZ31 Mg alloy is improved greatly after ultrasonic shot peening process. The coefficient of friction and the wear rate of the ultrasonic shot peening treated sample are both lower than that of as-received. The width of the wear track of ultrasonic shot peening treated is also narrower than that of as-received, and the worn surface has a lower surface roughness. In as-received samples, abrasion and oxidation dominate the wear mechanism at low sliding speed and low applied load. The increase of sliding speed or applied load resulted in the delamination. Severe wear such as thermal softening happens with the further increase of load value or sliding speed. In ultrasonic shot peening treated samples, oxidation, the abrasion and delamination are also existing while no severe wear is found. The improved wear resistance of the ultrasonic shot peened sample is due to the improved hardness and a higher activity of oxidation during wear process. The nanocrystalline on the top surface leads to the the transition boundary between the mild wear and severe wear to a higher sliding speed and higher applied load. </div><div><br></div><div><br></div><div>The corrosion resistance of AZ31 Mg alloy before and after ultrasonic shot peening is tested in 3.5 $\%$ NaCl solution. The corrosion resistance after ultrasonic shot peening is reduced greatly because of the Fe particles at the top surface, which was exfoliated from the shot during the treating process. After a 40 $\mu$m thick polishing, Fe particles are removed totally and the corrosion resistance is improved, compared with that of as-received. The anodic current density of the nanocrystallized surface after polishing is reduced because of the compression residual stress and a rapid formation of protective layer. Meanwhile, the grain boundary acts as a physical barrier for corrosion and reduces the corrosion rate. </div><div><br></div><div><br></div><div>The bending behavior of AZ31 Mg alloy before and after ultrasonic shot peening is studied by a V-bending test. The ultrasonic shot peening treated sample has a similar bending performance even though the ductility has been reduced after ultrasonic shot peening. A single side ultrasonic shot peening (either at the inner side or the outer side) changed the bending behavior because of its asymmetric structure. The ultrasonic shot peening at the inner side for 5 min improves the bendability and longer treated, such as 10 min and 15 min degenerates the bendability to as-received. The improved bendability of 5 min treated sample is due to the drawing back of the neutral layer. The ultrasonic shot peening at the outer side for 5 min also improves the bending performance and a longer treatment of 15 min further enhanced the bendability. The improved bendability after outer side treatment is due to the high yield stress of nanocrystalline at the convex, resulting in the smaller strain here. </div>

Materiais cerâmicos obtidos a partir de pós nanocristalinos permitem a obtenção de excelentes propriedades após sinterização, devido à possibilidade de redução da temperatura final de sinterização com conseqüente refinamento microestrutural e excelente densificação. Nesse contexto, a zircônia tetragonal (ZrO2 (t)) tem um importante papel, pois suas características intrínsecas, tais como a transformação martensítica (ZrO2 (t-m)), permitem o desenvolvimento de excelentes propriedades, destacando-se a elevada tenacidade à fratura e resistência a flexão, tornando-a um material diferenciado visando aplicações nobres onde propriedades mecânicas e confiabilidade sejam pré-requisitos. Visando otimizar estas aplicações, se faz necessário conhecer as correlações entre as propriedades mecânicas e a microestrutura. Sendo assim, é de extrema importância promover a revelação microestrutural desses materiais, de forma padronizada e com representatividade estatística, o que exige cuidados nas técnicas de preparação ceramográfica. Nesse trabalho pretende-se caracterizar microestruturalmente cerâmicas a base de ZrO2(Y2O3) nanométrica, visando estudar os efeitos da temperatura e do tempo de sinterização na cinética de crescimento de grão. Foi definida uma rota de preparação e análise ceramográfica propondo seqüência de lixas e panos de polimento, assim como cargas e tempos em cada etapa. As amostras foram atacadas termicamente e micrografias foram obtidas. As micrografias foram processadas por rotinas de análise digital de imagens, visando definir padronizações para determinação de parâmetros microestruturais de interesse, tais como distribuição de tamanhos de grãos, densidade de grãos por unidade de área, razão de aspecto, etc. Foi estudado o efeito das condições de sinterização (temperatura final e tempo de isoterma) no crescimento de grãos. / Ceramic materials obtained from nanocrystalline powders enable the obtaining of excellent properties after sintering, due to the possibility of reducing the final sintering temperature with consequent microstructural refinement and excellent densification. In this context, tetragonal zirconia (ZrO2 (t)) has an important role, since their intrinsic characteristics, such as the martensitic transformation (ZrO2 (t-m)), allow the development of excellent properties, highlighting the high tenacity to fracture and resistance to bending, making it a differentiated material aiming noble applications where mechanical properties and reliability are prerequirements. In order to optimize these applications, it is necessary to know the correlations between the mechanical properties and microstructure. Thus, it is extremely important to promote the microstructural disclosure of these materials, in a standardized manner and with statistical representativeness, which requires care with the ceramographic preparation techniques. This work aims to microstructurally characterize ceramics based on nanometric ZrO2(Y2O3), looking for the study of the effects of the sintering temperature and time on the graingrowth kinetics. It was defined a route for ceramographic preparation and analysis proposing a sequence of sandpapers and polishing cloths, as well as loads and times at each stage. The samples were thermally etched and micrographs were obtained. The micrographs were processed through routines of digital image analysis, aiming the definition of standards for the determination of microstructural parameters of interest, such as distribution of grain sizes, density of grains per unit of area, aspect ration, and others. It was studied the effects of the sintering conditions (final temperature and time of isotherm) on the grain growth.

As nonoceluloses são partículas com pelo menos uma dimensão menor que 100 nm. A produção delas a partir de materiais lignocelulósicos tem obtido grande destaque nos últimos anos. A celulose nanocristalina (CNC) é tradicionalmente produzida através da hidrólise ácida, utilizando alta concentração de ácido, grande volume de água e com baixo rendimento. A celulose nanofibrilada (CNF) é produzida pela desfibrilação mecânica de polpas celulósicas com alto consumo de energia. Por outro lado, embora a produção industrial de etanol 2G já tenha começado, com as primeiras plantas de produção em escala espalhadas pelo mundo, a hidrólise enzimática completa da celulose para este fim não é economicamente viável e gera um resíduo rico em celulose e altamente recalcitrante, que poderia ser utilizado para produzir nanoceluloses, que tem alto valor agregado. Neste contexto, este estudo investigou a viabilidade técnica da produção das nanoceluloses (CNC e CNF) integradas ao processo de produção de açúcares fermentescíveis para a produção de etanol 2G a partir do bagaço de cana-de-açúcar. Incialmente, em uma planta piloto de produção de etanol 2G, o bagaço foi pré-tratado por explosão a vapor, que gerou a celulignina que foi deslignificada com NaOH. A polpa celulósica gerada foi tratada com peróxido de hidrogênio em meio alcalino para realizar a remoção da lignina residual. Os materiais gerados pelo pré-tratamento e pelo processo de polpação em meio alcalino foram caracterizados quando sua composição química e hidrolisados com diferentes cargas de enzimas. Os resultados mostraram a eficiência dos pré-tratamentos aplicados ao bagaço de cana-de-açúcar causando o enriquecimento em celulose e a diminuição do teor lignina e de hemiceluloses, acarretando um maior acesso das enzimas a celulose. O estudo do efeito das cargas enzimáticas, do aumento da carga de sólidos e do sistema de agitação, resultou em conversões de celulose em torno de 80%, atingindo concentrações acima de 120 g/L. Utilizando o resíduo de hidrólise da polpa celulósica, foram obtidas as nanoceluloses. A CNC apresentou tamanho médio de partículas de 679 nm, índice de cristalinidade de 54%, diâmetros mais frequentes entre 55 e 65 nm e rendimento de aproximadamente 48%. A CNF apresentou tamanho médio de 722 nm e diâmetros com maior frequência em torno de 60 nm, e rendimento de aproximadamente 38%. As suspensões aquosas de CNC e CNF apresentaram baixa estabilidade, quando monitoradas através do potencial zeta. / Nanocelluloses are particles with at least one dimension smaller than 100 nm. Their production from lignocellulosic materials has gained prominence in recent years. Cellulose nanocrystals (CNC) is traditionally produced through acid hydrolysis using high acid concentration, high water volume and results in low yield. Cellulose nanofibrils (CNF) is produced by mechanical defibrillation of cellulosic pulps with high energy consumption. On the other hand, despite the fact the production of 2G ethanol has already reached commercial production, with the first commercial facilities around the worldwide, complete enzymatic hydrolysis of cellulose for this purpose is not economically viable and generates a highly recalcitrant residue rich in cellulose and, which could be used to produce nanocelluloses, high-added value products. In this context, this study investigated the technical viability of obtaining nanocelluloses integrated into the production process of fermentable sugars to obtain 2G ethanol from sugarcane bagasse. Initially, at a pilot plant for production of2G ethanol, sugarcane bagasse was pre-treated by steam explosion, generating cellulignin, which was delignified with NaOH. The resulting cellulosic pulp was treated with hydrogen peroxide in an alkaline medium to remove residual lignin. The materials generated after the pre-treatment and the pulping process in alkaline medium were characterized regarding their chemical composition and then hydrolyzed with different loads of enzymes. The results showed that the pre-treatments applied to the bagasse caused the enrichment in cellulose and the decrease of lignin and hemicelluloses contents, leading to a greater access of the enzymes to cellulose. The enzymatic charges used in the experiments, which were evaluated in combination with the increase of the solids loading together with the change of the agitation system, resulted in a cellulose conversion of around 80%, reaching concentrations above 120 g/L. Using the hydrolysis residue of the cellulosic pulp, nanocelluloses were obtained. The CNC showed a mean particle size of 679 nm, crystallinity index of 54%, diameters between 55 and 65 nm and a yield of about 48%. The CNF displayed an average particle size of 722 nm and diameters with higher frequency around 60 nm. The aqueous suspensions of CNC and CNF showed low stability when monitored through the zeta potential.

As superligas à base de cobalto são bem conhecidas por sua excelente resistência ao desgaste. Muitas pesquisas reportadas na literatura abordam o comportamento do desgaste destas ligas, seja no desgaste por deslizamento, erosivo ou abrasivo. Não obstante, o desgaste microabrasivo destas ligas não tem sido muito investigado, apesar dos danos causados por este tipo de solicitação. O comportamento do desgaste microabrasivo de três superligas à base de cobalto: a) 48% Co, 29 %Cr, 19 % Fe; b) uma liga com composição química próxima à da liga comercial Tribaloy T400 (Co 56 %, Cr 8.5%, Mo 29% Si 3.3 %) e c) uma liga com composição próxima à da liga comercial Stellite 6 (Co 64%, Cr 24 %, W 4.2 %, C 2,3%) foram investigadas. Os ensaios de microabrasão foram conduzidos com três abrasivos SiO2, Al2O3, e SiC em suspensão em água destilada, com concentração de 0,1 g/cm3. A carga aplicada foi de 0,3 N, a velocidade angular 20 rpm e a distância total de deslizamento, 48 metros. A análise das superfícies desgastadas por microscopia óptica, eletrônica de varredura e por perfilometria de contato mostraram que o tamanho, forma e dureza dos abrasivos podem influenciar significativamente os coeficientes de desgaste. Os ensaios conduzidos com partículas abrasivas de SiC e Al2O3 apresentaram maiores coeficientes de desgaste que os conduzidos com partículas de SiO2. A Liga Co-Cr-Fe mostrou os maiores coeficientes de desgaste quando comparada com as demais ligas, devido à baixa fração volumétrica de partículas de segunda fase, duras, precipitadas em sua microestrutura. Durante os ensaios, as três ligas, ensaiadas com os três diferentes abrasivos, apresentaram coeficientes de desgaste crescentes com o aumento da dureza do abrasivo; observou-se uma variação linear dos coeficientes de desgaste com a razão entre a dureza do abrasivo (Ha) e a dureza composta da liga (Hs), com R2 = 0.74. O micromecanismo dominante em todos os ensaios foi o desgaste abrasivo a dois corpos (grooving wear). A liga com composição próxima à da liga comercial Tribaloy T400, contendo fases de Laves dispersas em sua microestrutura, apresentou uma transição de micromecanismo de desgaste dúctil para frágil, quando submetida a ensaios com partículas abrasivas de Al2O3. Assim sendo, o volume de material removido nesta liga foi ligeiramente maior que o observado no ensaio com partículas de SiC. Na liga contendo baixa fração volumétrica de partículas de segunda fase, com matriz constituída por Co (CFC), observou-se uma camada subsuperficial nanocristalina de aproximadamente 1 µm de espessura, severamente deformada, imediatamente abaixo da superfície desgastada. Concluiu-se que o desgaste microabrasivo induziu a recristalização a frio do material encruado, com formação de grãos equiaxiais de dimensões nanométricas. / Cobalt alloys are well known for their excellent wear resistance. Many investigations are reported in literature related to the behavior of erosive, abrasive or sliding wear of these alloys. Nevertheless, the micro-abrasive wear of these alloys has not been thoroughly investigated, despite the damage caused by this type of wear. The microabrasive wear behavior of three cobalt alloys: a) 48 wt.% Co, 29 wt.% Cr, 19 wt.% Fe; b) an alloy with chemical composition close to Tribaloy T400 (56 wt.% Co, 8.5 wt.% Cr, 29% wt. Mo, 3.3 wt. %Si) and c) an alloy with chemical composition close to Stellite 6 (64wt.% Co 24 wt.% Cr, 4.2 wt.% W, 2,3 wt.% C were investigated. The tests were carried out using three 0,1 g/cm3 slurries composed by SiO2, Al2O3, and SiC particles, in suspension in distilled water. The applied load was 0.3 N, the rotational speed 20 rpm and the total sliding distance 48 m. Analysis of the worn surfaces of the tested alloys by Optical Microscopy, Scanning Electron Microscopy and Contact Stylus Profilometry showed that abrasive size, shape and hardness could significantly influence the wear coefficients. The tests carried out with SiC and Al2O3 slurries resulted in greater wear rates than those carried out in SiO2 slurry. Stellite 250, showed the greatest wear coefficient, compared to the two other experimental alloys, due to a very low volume fraction of hard second phase particles in the microstructure. Wear coefficients decreased with increasing abrasive particles hardness. An approximate linear correlation with the ratio between the hardness of the abrasives (Ha) and the compound hardness of the alloys (Ha) with a correlation factor R2= 0.74. The dominant wear micromechanism observed in all tests was two-body abrasion (grooving wear). The modified T400 alloy, containing Laves phase showed a transition from ductile to brittle wear mechanisms when testing with alumina slurries. The worn volume was slightly greater than the one observed with SiC. A severely deformed nanocrystalline layer was identified, immediately below the worn surface. It was concluded that cold recrystallization of the work-hardened material occurred, with the formation of nano sized equiaxed grains.

Materiais cerâmicos obtidos a partir de pós nanocristalinos permitem a obtenção de excelentes propriedades após sinterização, devido à possibilidade de redução da temperatura final de sinterização com conseqüente refinamento microestrutural e excelente densificação. Nesse contexto, a zircônia tetragonal (ZrO2 (t)) tem um importante papel, pois suas características intrínsecas, tais como a transformação martensítica (ZrO2 (t-m)), permitem o desenvolvimento de excelentes propriedades, destacando-se a elevada tenacidade à fratura e resistência a flexão, tornando-a um material diferenciado visando aplicações nobres onde propriedades mecânicas e confiabilidade sejam pré-requisitos. Visando otimizar estas aplicações, se faz necessário conhecer as correlações entre as propriedades mecânicas e a microestrutura. Sendo assim, é de extrema importância promover a revelação microestrutural desses materiais, de forma padronizada e com representatividade estatística, o que exige cuidados nas técnicas de preparação ceramográfica. Nesse trabalho pretende-se caracterizar microestruturalmente cerâmicas a base de ZrO2(Y2O3) nanométrica, visando estudar os efeitos da temperatura e do tempo de sinterização na cinética de crescimento de grão. Foi definida uma rota de preparação e análise ceramográfica propondo seqüência de lixas e panos de polimento, assim como cargas e tempos em cada etapa. As amostras foram atacadas termicamente e micrografias foram obtidas. As micrografias foram processadas por rotinas de análise digital de imagens, visando definir padronizações para determinação de parâmetros microestruturais de interesse, tais como distribuição de tamanhos de grãos, densidade de grãos por unidade de área, razão de aspecto, etc. Foi estudado o efeito das condições de sinterização (temperatura final e tempo de isoterma) no crescimento de grãos. / Ceramic materials obtained from nanocrystalline powders enable the obtaining of excellent properties after sintering, due to the possibility of reducing the final sintering temperature with consequent microstructural refinement and excellent densification. In this context, tetragonal zirconia (ZrO2 (t)) has an important role, since their intrinsic characteristics, such as the martensitic transformation (ZrO2 (t-m)), allow the development of excellent properties, highlighting the high tenacity to fracture and resistance to bending, making it a differentiated material aiming noble applications where mechanical properties and reliability are prerequirements. In order to optimize these applications, it is necessary to know the correlations between the mechanical properties and microstructure. Thus, it is extremely important to promote the microstructural disclosure of these materials, in a standardized manner and with statistical representativeness, which requires care with the ceramographic preparation techniques. This work aims to microstructurally characterize ceramics based on nanometric ZrO2(Y2O3), looking for the study of the effects of the sintering temperature and time on the graingrowth kinetics. It was defined a route for ceramographic preparation and analysis proposing a sequence of sandpapers and polishing cloths, as well as loads and times at each stage. The samples were thermally etched and micrographs were obtained. The micrographs were processed through routines of digital image analysis, aiming the definition of standards for the determination of microstructural parameters of interest, such as distribution of grain sizes, density of grains per unit of area, aspect ration, and others. It was studied the effects of the sintering conditions (final temperature and time of isotherm) on the grain growth.

Borides and carbides of tantalum and hafnium are of great interest due to their ultrahigh temperature applications. Properties of these ceramics including oxidation resistance and mechanical properties might be further improved through solid solution/composite formation. Synthesis of single-phase TaxHf1-xC and TaxHf1-xB2 solid solution powders including nanopowders via carbothermal reduction (CTR) is complicated due to noticeable difference in reactivity of parent oxides with carbon, and also the low solubility of those oxides in each other. Moreover, for TaC-HfC system the solid solution may go through phase separation due to the presence of a miscibility gap at temperatures below 887°C.In this study, a method of low-cost aqueous solution processing followed by CTR was used to synthesize TaxHf1-xC and TaxHf1-xB2 solid solution powders. In fact, method was first used to synthesize boron carbide (B4C) powders as it paves the way for a detailed study on the synthesis of TaxHf1-xC and TaxHf1-xB2 solid solutions powders considering the fact that B4C contains both carbon and boron in its structure. Particular emphasis was given to investigate the influences of starting compositions and processing conditions on phase separation during the formation of both carbide and boride phase(s). It was found that individual TaC-HfC and TaB2-HfB2 phases always form quickly but separately during the CTR process (e.g., at 1600 °C within a few minutes). Those carbides and borides remain phase-separated unless heated to much higher temperatures for long time due to the slow inter-diffusion between them. It was also found that for TaxHf1-xC applying a DC electric field through the use of spark plasma sintering (SPS) system significantly accelerates the inter-diffusion of Ta and Hf leading to formation of a single-phase TaxHf1-xC solid solution at 1600 °C for 15 minutes. On the other hand, for borides alkali metal reduction reaction (AMR) method appears to be an excellent alternative to CTR-based method for formation of a single-phase TaxHf1-xB2 solid solution. In this method, chlorides of tantalum and hafnium are directly reduced using sodium borohydride (NaBH4) giving rise to formation of a single-phase Ta0.5Hf0.5B2 solid solution nanopowders in one step at much lower temperatures (e.g., 700 °C) by avoiding the oxides formation and the associated phase separation of individual borides as observed in the CTR-based process.

<p>Thin films of refractory metals and carbides have been studied extensively over many years because of their wide range of application. The two major techniques used are Chemical Vapour Deposition (CVD) and Physical Vapour Deposition (PVD). These can result in the deposition of two-dimensional blanket or patterned thin films. Laser-assisted Chemical Vapour Deposition (LCVD) can provide a maskless alternative for localised deposition in two and three dimensions. This thesis describes LCVD of micrometer-sized tungsten, molybdenum and tungsten carbide rods. The kinetics, phase composition and microstructure have been studied as a function of in situ measured laser induced deposition temperature.</p><p>Tungsten and molybdenum rods were deposited by hydrogen reduction of their corresponding hexafluorides, WF6 and MoF6, respectively. Single crystal and polycrystalline tungsten rods were obtained, depending on the H2/WF6 molar ratio and deposition temperature. The molybdenum rods were either single crystals or dendritic in form depending on experimental conditions. The field emission characteristics of the tungsten single crystals were investigated. The results showed LCVD to be a potential fabrication technique for field emitting cathodes.</p><p>Nanocrystalline tungsten carbide rods were deposited from WF6, C2H4 and H2. TEM analysis showed that the carbide rods exhibited a layered structure in terms of phase composition and grain size as a result of the temperature gradient induced by the laser beam. With decreasing WF6/C2H4 molar ratio, the carbon content in the rods increased and the phase composition changed from W/W2C to WC/WC1-x and finally to WC1-x/C.</p>

<p>Electrical transport properties of nanoparticle gold films made by the gas evaporation method were analysed using resistivity measurements. Low temperature electrical transport measurements showed a cross-over from a temperature range dominated by inelastic scattering to a temperature range dominated by elastic scattering, presumably by grain boundaries. This cross-over shifted towards lower temperatures with increasing grain size. </p><p>High temperature in-situ electrical transport measurements were carried out in isothermal annealing experiments. Four types of samples, prepared at different deposition rates, were analysed. Samples prepared at low deposition rate displayed a higher thermal stability than samples prepared at high deposition rate. A relaxation model was fitted to the in-situ electrical transport data. The model included an activation energy, which was found to increase with increasing annealing temperature for all samples, thus pointing at the presence of pinning mechanisms in the samples.</p><p>Optical properties of nanoparticle gold films were investigated in the 0.3 < λ < 12.5 µm wavelength range. A model taking grain boundary scattering into account was successfully fitted to the experimental data and it was shown that the infrared reflectance decreased with decreasing grain size as a consequence of increased grain boundary scattering.</p><p>Nanoparticle tin-doped indium oxide films were made by spin-coating a dispersion containing the nanoparticles onto a substrate. The tin-doped indium oxide particles were prepared by a wet-chemical method. Optical properties were investigated in the 0.3 < λ < 30 µm wavelength range by reflectance and transmittance measurements. Effective medium theory was employed in the analyses of the optical data and information regarding film porosity and charge carrier concentration and mobility within the individual nanoparticles was obtained. It was found that ionized impurity scattering of the conduction electrons dominates within the particles. The temperature-dependent film resistivity was found to be governed by insulating barriers between clusters containing a large number of nanoparticles, thereby giving a negative temperature coefficient of resistivity.</p>

Thin films of refractory metals and carbides have been studied extensively over many years because of their wide range of application. The two major techniques used are Chemical Vapour Deposition (CVD) and Physical Vapour Deposition (PVD). These can result in the deposition of two-dimensional blanket or patterned thin films. Laser-assisted Chemical Vapour Deposition (LCVD) can provide a maskless alternative for localised deposition in two and three dimensions. This thesis describes LCVD of micrometer-sized tungsten, molybdenum and tungsten carbide rods. The kinetics, phase composition and microstructure have been studied as a function of in situ measured laser induced deposition temperature. Tungsten and molybdenum rods were deposited by hydrogen reduction of their corresponding hexafluorides, WF6 and MoF6, respectively. Single crystal and polycrystalline tungsten rods were obtained, depending on the H2/WF6 molar ratio and deposition temperature. The molybdenum rods were either single crystals or dendritic in form depending on experimental conditions. The field emission characteristics of the tungsten single crystals were investigated. The results showed LCVD to be a potential fabrication technique for field emitting cathodes. Nanocrystalline tungsten carbide rods were deposited from WF6, C2H4 and H2. TEM analysis showed that the carbide rods exhibited a layered structure in terms of phase composition and grain size as a result of the temperature gradient induced by the laser beam. With decreasing WF6/C2H4 molar ratio, the carbon content in the rods increased and the phase composition changed from W/W2C to WC/WC1-x and finally to WC1-x/C.