Neste trabalho foram avaliados os efeitos da adição de polímeros precursores na sinterização, microestrutura, dureza e na tenacidade à natura de materiais cerâmicos à base de carbeto de silício e de AI2O3. As matérias-primas cerâmicas foram caracterizadas por análise semi-quantitativa por espectrometria de fluorescência de raios X, difração por laser, adsorção gasosa e microscopia eletrônica de varredura. Para os polímeros utilizou-se análise termogravimétrica. A cinética de sinterização das amostras compactadas foi estudada por dilatometria. A caracterização dos materiais sinterizados incluiu medidas de densidade aparente pelo princípio de Arquimedes e/ou por picnometria de He, porosimetria por intrusão de Hg, análises de difração de raios X, de carbono total, avaliação da microestrutura e por microscopia eletrônica de varredura e de transmissão, análise por espectrometria de raios X por dispersão de energia, ensaios de impressão Vickers para determinação de dureza e tenacidade à fiatura. No estudo de cerâmica à base de carbeto de silício foram utilizados os aditivos óxidos AI2O3 (4% em peso) e Y2O3 (4% em peso) e os aditivos poliméricos PMHS (polimetilhidrogenossiloxano) e polimetilhidrogenossiloxano com D4Vi. O processamento envolveu a cura do material, pirólise e sinterização (1850 °C e 1950 °C/l h. Ar ou N2). Nas amostras à base de carbeto de silício houve elevada perda de massa, principalmente quando a atmosfera de sinterização foi argônio. As amostras à base de carbeto de silício, com adição de polímeros atingiram densidade de até 3,15 g/cm3 quando pirolisadas a 900 °C em N2 e sinterizadas a 1950 °C, em atmosfera de nitrogênio. Para as amostras à base de alumina foram utilizados os aditivos poliméricos PMHS, PMS (polimetilsilsesquioxano) e PPS (polifenihnetilvinilhidrogenosilsesquioxano) e as sinterizações foram realizadas a 1650 °C e 1700 °C, não havendo variações significativas nas densidades obtidas nas duas temperaturas. Nos materiais com adição de PMHS foram obtidos compósitos de alumina e mulita, sendo que os grãos de mulita foram formados intergranularmente. Nas amostras contendo PMS ou PPS a distribuição das feses formadas, Si2Al4O4N4 e Si2ON2, foi bastante heterogênea, A obtenção de compósitos cerâmicos utilizando pequenas adições de polímeros precursores cerâmicos mostrou-se viável para materiais à base de alumina, sendo uma rota simples de conformação, com grande potencial para a obtenção de peças com geometria complexa. / The effects of the addition of precursor polymers on sintering, microstructure, hardness and fiacture toughness of silicon carbide and alimiina ceramics were studied. The ceramic raw materials were characterized by semi-quantitative analysis by X-ray fluorescence, particle size by laser diffraction, specific surface area by gas adsorption and microstructural analysis by scanning elecfron microscopy. The polymers were analyzed by thermogravimetry. The sintering kinetics of cold-pressed specimens was studied by dilatometry. The sintered materials were characterized by evaluation of apparent density by the Archimedes technique and/or helium picnometry, by mercury porosimetry, by X-ray diflftaction, by evaluation of total carbon content, by scanning and transmission electron microscopy, by enetgy dispersion X-ray spectrometry, and by Vickers indentation analysis for determining hardness and fiacture toughness. AI2O3 (4wt.%) and Y2O3 (4wt.%) and polymetylhydrogenosiloxane and polymetylhydrogenossiloxane with D4Vi were the sintering aids for SiC. The processing procedures were material cure, pyrolysis and sintering (1850 X and 1950 °C/1 h, Ar or N2). High mass loss was measured in silicon carbide based ceramics, mainly under argon. Silicon carbide based ceramics with polymer sintering aids achieved 3.15 g/cm3 density after pyrolysis at 900 °C under N2 and sintering at 1950 °C under nitrogen. PMHS, PMS and PPS polymer sintering aids were used for almnina based ceramics sintering carried out at 1650 °C and 1700 °C, without significant difference in the final density. Addition of PMHS yielded alumina and mullite composites, with intergranular mullite grains. Heterogeneous Si2AI4O4N4 and Si2ON2 phases were obtained in specimens with PMS or PPS, The preparation of ceramic composites using small amounts of precursor polymers showed a suitable process for alumina-based ceramics, a simple forming route, with high potential for the fabrication of complex shape pieces.

La protection des gaines de combustible de réacteur nucléaire contre l’oxydation à haute température en conditions accidentelles est essentielle pour garantir leur intégrité, c’est-à-dire celle de la première barrière de confinement. Celle-ci peut s’effectuer par le dépôt d’un revêtement sur leur paroi interne et ce sont les procédés CVD qui sont les plus à même de le faire. Il s’agit plus précisément du procédé DLI-MOCVD qui a été utilisé ici pour déposer des revêtements à base de chrome (chrome métallique Cr(S) cristallisé) et de carbures de chrome (carbures de chrome CrxCy amorphes non recyclés, recyclés et CrxSizCy dopés au Si), réputés pour leur bonne résistance à l’oxydation. Afin d’améliorer la qualité des revêtements, le procédé de dépôt a été optimisé à l’aide de simulations numériques. Après une réflexion sur le mécanisme chimique, un modèle cinétique réactionnel du dépôt d’un revêtement CrxCy amorphe a pu être ajusté et validé. Il a aussi été montré que la solution utilisée de précurseur organométallique bis(arène)chrome et de solvant toluène pouvait être directement recyclée, augmentant ainsi le potentiel d’industrialisation du procédé. Les propriétés physico-chimiques et structurales des revêtements déposés avec ce procédé ont été caractérisées. Une étude des propriétés mécaniques de ces revêtements a par ailleurs été entreprise. Il en ressort que, comparés à des revêtements apparentés déposés par d’autres procédés, ceux déposés par DLIMOCVD possèdent notamment une dureté élevée (jusqu’à une trentaine de GPa), des contraintes résiduelles en compression, une bonne adhérence avec leur substrat et enfin une résistance à l’usure abrasive différente suivant la température. L’évaluation de leur résistance à l’oxydation à 1200 °C a révélé les excellentes performances des revêtements en carbures de chrome amorphes, qui permettent de retarder l’oxydation catastrophique de plus de deux heures pour une épaisseur de 10 µm. Tous les autres revêtements augmentent la tenue en température des substrats en zircaloy mais ne retardent pas autant l’oxydation catastrophique. / Nuclear fuel cladding tubes resistance against high temperature oxidation during accident conditions is crucial because it means protecting the first containment barrier. This can be done by coating the inner wall of the cladding tube with CVD processes, which are most likely to do so. More specifically, we used DLI-MOCVD to grow chromium based (Cr(S), metallic crystalline chromium) and chromium carbides based (amorphous chromium carbides CrxCy, recycled CrxCy, silicon doped CrxSizCy) coatings, known for their good oxidation resistance. The coating process was optimized using numerical modelling to improve coatings performance. A reaction kinetics model of the deposition process of amorphous CrxCy coatings was adjusted and validated after the identification of the chemical mechanism. It was also shown that the liquid solution containing organometallic precursor (bis(arene)chromium) and solvent (toluene) could be directly recycled, thereby increasing the industrialization potential of such process. Physical, chemical and structural properties of coatings deposited with this process were characterized. A study of the coatings mechanical properties has also been undertaken. It shows that compared to related coatings grown with other processes, those deposited by DLI-MOCVD exhibit a particularly high hardness (up to 30 GPa), compressive residual stresses, good adhesion with the substrate and finally a different abrasive wear resistance depending on the temperature. The assessment of their oxidation resistance at 1200 °C revealed excellent performances of amorphous chromium carbides coatings, which can delay catastrophic oxidation up to two hours with only a 10 µm thickness. All the other coatings only increase the thermal resistance of zircaloy substrates.

The aim of this thesis is a complex processing of obtained technical findings in the area of cutting materials, especially the evaluation and comparison of work possibilities recommended by prime world manufacturers for effective usage and application of coated and uncoated cemented carbides. Characteristics of cemented carbides in terms of production, marking method, physical and mechanical properties and application. Comparison of cemented carbides in the range of production of the most significant world tool and cutting material producers. Cutting efficiency evaluation of the tool. Recommended areas and operating conditions for effective usage of cemented carbides and their technical economic evaluation.

Orientador: Eduardo Carlos Bianchi / Resumo: Aços-rápidos são materiais que exibem elevada resistência ao desgaste abrasivo, aliada a uma tenacidade relativamente alta, propriedades estas que os tornam adequados para se fabricar ferramentas de corte. Grande parte de suas propriedades se deve a presença de carbonetos na microestrutura. Ao mesmo tempo que estas propriedades mecânicas são favoráveis para a utilização como ferramentas, tornam-se desafios na sua fabricação. O processo de retificação é empregado nas últimas etapas de fabricação de ferramentas de corte como machos e brocas e a presença dos carbonetos afetam a eficiência dos rebolos. Neste contexto, este trabalho visa investigar o quanto a diferença de microestrutura de aços-rápidos classe AISI M3:2, obtidos de diferentes fornecedores, influencia na retificação, levando em consideração a integridade superficial. Os materiais, aqui nomeados como M-A, M-B e M-C, foram avaliados sob três aspectos: características da microestrutura, resistência à abrasão e integridade da superfície após a retificação. Da microestrutura os carbonetos tipo MC e M6C, foram descritos quanto à forma e a distribuição, utilizando para isso MEV e EDS. A resistência à abrasão dos materiais foi medida recorrendo ao método de ensaio tribológico pino-lixa. Após esta caracterização, foram realizados ensaios de retificação tangencial plana com rebolo de Carboneto de Silício (SiC) em várias penetrações de trabalho (entre 10 µm e 30 µm). As superfícies das amostras foram avaliadas mensurando a rug... (Resumo completo, clicar acesso eletrônico abaixo) / High-Speed Steels are materials that exhibit high abrasive wear resistance coupled withrelatively high toughness, properties that make them suitable for making cutting tools. Much ofits properties are due to the presence of carbides in the microstructure. While these mechanicalproperties are favorable for use as tools, they impose challenges in their manufacture. Thegrinding process is employed in the final stages of the cutting tools manufacturing, such as tapsand drills and the presence of carbides affects the efficiency of the grinding wheels. In thiscontext, this work aims to investigate how the microstructure difference of class AISI M3: 2steel, obtained from different suppliers, influences the grinding, taking into consideration thesurface integrity. The materials, here named M-A, M-B, and M-C, were evaluated under threeaspects: microstructure characteristics, abrasion resistance, and surface integrity after grinding.From the microstructure, carbides type MC and M6C were described regarding the shape anddistribution, using for this purpose SEM and EDS. The abrasive wear resistance of the materialswas measured using the pin-abrasive tribological test. After this characterization, flat tangentialgrinding tests were performed, using silicon carbide grinding wheel (SiC), in various workdepths (between 10 μm and 30 μm). The ground samples surfaces were evaluated by measuringthe roughness parameters, evaluated by SEM, and the microhardness profil / Doutor

Solar selective coatings based on carbon transition metal carbide nanocomposite absorber layers were designed. Pulsed filtered cathodic arc was used for depositing amorphous carbon: metal carbide (a-C:MeC, Me = V, Mo) thin films. Composition and structure of the samples were characterized by ion beam analysis, X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. The optical properties were determined by ellipsometry and spectrophotometry. Three effective medium approximations (EMA), namely Maxwell-Garnett, Bruggeman, and Bergman, were applied to simulate the optical behaviour of the nanocomposite thin films. Excellent agreement was achieved between simulated and measured reflectance spectra in the entire wavelength range by using the Bergman approach, where in-depth knowledge of the nanocomposite thin film microstructure is included. The reflectance is shown to be a function of the metal carbide volume fraction and its degree of percolation, but not dependent on whether the nanocomposite microstructure is homogeneous or a self-organized multilayer. Solar selective coatings based on an optimized a-C:MeC absorber layer were designed exhibiting a maximum solar absorptance of 96% and a low thermal emittance of ~5 and 15% at 25 and 600ºC, respectively. The results of this study can be considered as predictive design tool for nanomaterial-based optical coatings in general.

The average size of hot-work tools has gradually increased over the past years.This affects the effective temperature cycle tools experience during hardening,as large dimensions prevent uniform and rapid cooling, and thereby the resulting microstructures and properties. In order to avoid the formation of coarse structures or cracking during heat treatment it has become common practise to lower the austenitising temperature below that recommended by the steel manufacturer.In this work, therefore, the effects of austenitising at temperatures lower thancommonly recommended are investigated. Three 5% Cr hot-work tool steelsalloyed with Mo and V were heat treated, resulting microstructures andtempering carbides were studied and transformation characteristics determined for different austenitising temperatures and different cooling rates. The temperatures and cooling rates have been chosen to be representative for heat treatments of different sizes of tools. Bainite rather than martensite formed during slow cooling regardless of austenitising temperature. A lowered austenitising temperature produced largeramounts of both bainite and retained austenite while a higher caused graingrowth. Carbon partitioning during the bainitic transformation resulted in anincrease of the carbon content in the retained austenite of at least 0.3 wt.%. The austenitising temperature influences also the type and amount of tempering carbides that precipitate, which affects the properties of the steel. Higher austenitising temperatures favour the precipitation of MC carbides during tempering. The Mo rich M2C type carbides were proven to be more prone to coarsening during service at 560°C-600°C, while V rich MC carbides preserve their fine distribution. A best practice heat treatment needs to balance the increase of grain size with increasing austenitising temperatures, with the possibility to form more tempering carbides. Higher austenitising temperatures also give less retained austenite, which can affect dimensional stability and toughness negatively after tempering

In this Master Thesis work, the effect of pressure on sintering of cemented carbides is investigated. Special focus hasbeen given to the residual porosity after sintering. It is well known that sintering shrinkage depends on binder phasecontent, grain size, temperature and pressure. Thus 4 different cemented carbides grades were selected. The gradeswere pressed into standard products and TRS (Tensile Rupture Strength) rods with two different shrinkage factors.These were then sintered at different pressures and temperatures. Thereafter the impact of pressure on propertiessuch as Density, Coercivity, Porosity and TRS were analyzed. The observations were further supported with Weibullprobability analysis and fracture surface analysis in SEM.It has been shown that there exists a distinct threshold pressure at which significant reduction in porosity occurs forgiven compacted densities. For 3 out of 4 cemented carbide grades it has been observed that P2 sintering pressure issufficient to meet desired product characteristics. The fourth grade required a minimum sintering pressure of P4 toachieve desired quality criteria. Moreover it has been concluded that an increased sintering pressure increasesmaterial strength, as compared to vacuum sintering, thereby reducing the amount of early failures caused by poresduring TRS test.                                    Keywords: Cemented Carbides, Pressurized Sintering, Tungsten carbide, Porosity, Vacuum sintering, TensileRupture Strength, Weibull analysis, Fracture surface analysis.

A fundamental quantum mechanical modelling approach is used for calculating liquid diffusion parameters in cemented carbides. Up to now, no detailed description of diffusion for alloying elements in a liquid Co matrix is available. Neither are experimental measurements found in the literature for the self- or impurity diffusion in the liquid Co system. State of the art application is the description of gradient formation in cemented carbide systems using DICTRA. In this work it is assumed that diffusion during sintering of cemented carbides takes place mainly in the liquid Co binder phase. With this assumption one can calculate the diffusion coefficient for different alloying elements like W, Ti, N and C in a liquid Co matrix phase. The mean square displacement (MSD) of the diffusing atoms is used to obtain the diffusion coefficients which could be simulated by Ab initio Molecular Dynamics (AIMD). By fitting the computed temperature dependence with the Arrhenius relation one can determine the frequency factor and the activation energy which allows to give a quantitative description of the diffusion. Three methods will be used for validating the data from this work. Available estimated literature values based on calculations (scaling laws, a modified Sutherland equation and classical molecular dynamics) will be used to compare the results in a first instance. The general agreement for diffusion in liquid metals will be done by comparison with experimental data for the liquid Fe system. In a last step, the diffusion values obtained by this work will be used to create a kinetic database for DICTRA. The gradient simulations will be compared with experimentally measured gradients. The AIMD simulations are performed for binary diffusion systems to investigate the diffusion between the liquid Co matrix and one type of alloying element. In a second approach the diffusion for a multicomponent systems with Co, W, Ti and C has been performed. The results from the present AIMD simulations could be shown to be in good agreement with the literature. Only two DICTRA simulations could be performed within the timeframe of this work. Both are predicting a ~3 times bigger gradient zone whereas the initial choice of the labyrinth factor λ = f could be identified as a possible source of disagreement. A labyrinth factor of λ = f2 with the calculated mobility values from the AIMD calculations should give improved results. Although the results from those simulations are not available to this date. The two approaches of the diffusion simulations in the binary and multicomponent system are giving matching results. The non-metallic elements C and N are diffusing two times faster than the fastest metallic element Co. The diffusivity of Ti is slightly lower than Co and W could be identified as the element with the slowest diffusion within the liquid Co matrix. Further investigations of the liquid structure could indicate the tendency to form bonds between C and W and between C and Ti. This gives slowed down diffusion of C in the multicomponent system compared to the diffusion in the binary Co-C system.

No description available.

The objective of this study was to produce a metal matrix composite (MMC). This compositematerial proves highly suitable for scenarios involving abrasive wear, owing to the exceptionalhardness of carbide particles, in conjunction with the remarkable ductility and capacity for workhardening found in Hadfield steel. Therefore, the effect of WC and TiC on the microstructure,mechanical properties, and wear resistance was investigated. The X-Ray Diffraction (XRD)technique and Scanning Electron Microscope coupled with Energy X-ray Dispersive Spectroscopy(SEM-EDS) were employed to examine the phase transformation and microstructurecharacteristics of the MMCs. The grain size of carbides was calculated using ImageJ software.The wear test was conducted using a mini jaw crusher equipped with a stationary jaw (SJ) andmovable jaw (MJ). The wear characterization involved assessing volume loss, hardness profile,and the worn surface. The microstructures showed the formation of carbides particles dispersedwithin the matrix. Compared to the hardness of the manganese steel matrix, the MMCs exhibiteda significant increase in hardness. Regarding the wear performances, the movable jaw (MJ)demonstrated greater resistance (lower volume loss) compared to the stationnary jaw (SJ), indicatingdifferent wear mechanisms between the two jaws. The worn surface exhibited a texturedappearance with visible grooves, scratches, and embedded abrasive fragments. The hardnessprofile from the worn surface towards the core displayed a gradual decrease for both the SJ andMJ, indicating the work hardening capacity of manganese steel.