The influence of mechanical alloying (MA) milling time, temperature, sintering method and microstructure on the mechanical properties of a tungsten carbide-cobalt (WC-Co) hardmetal, based on 10wt% Co, has been established. The effects of high-energy milling for 30, 60, 180 and 300 min and the interrelation between milling time and powder properties, and the resultant effects on the mechanical properties of the consolidated WC-10Co material, has been obtained for a horizontally designed ball mill. Nanostructured WC-10Co powder was synthesised after 60 min cyclic milling at room temperature with an average WC domain size of 21 nm. In direct comparison, a WC-10Co composition MA at -30°C for 60 min produced an average WC domain size of 26 nm with a higher lattice strain. WC domain size showed a slight increase with milling time, measured at 27 nm after 300 min ball milling. Extended ball milling (300 min) reduced the mean particle size from 0.148 μm for 60 min milling to 0.117 μm. Thermal analysis showed that the onset temperature of the WC-Co eutectic was related to particle size with increased milling time reducing the onset temperature from 1344°C after 60 min milling to 1312°C after 300 min milling. Onset temperature was further reduced by the addition of vanadium carbide (VC), reducing the onset temperature to 1283°C after 300 min milling. Powder contamination increased with increased milling time with Fe content measured at ~ 3wt% after 300 min ball milling. Milling at -30°C reduced Fe contamination to an almost undetectable level. Increased ball milling time resulted in decreased levels of green density with the powders milled for 30 and 300 min achieving 62.5% and 59.5% TD, respectively. Relative density increased for the powder milled at -30°C compared to the RT milled powder due to its flattened, slightly rounded morphology. A large difference in VC starting particle size compared to WC and Co led to non-uniform dispersion of the inhibitor during milling. Densification and hardness reached optimum levels for the 60 min milled powder for both pressureless sintering and sinter-HIP. Both properties decreased with increased milling time, regardless of the sintering method. Low temperature milling resulted in a higher hardness value of 1390 HV30 compared to 1326 HV30 for the 60 min, RT milled material after pressureless sintering. Densification levels of the doped materials were restricted to < 90% TD for both sintering methods due to inhomogeneity in the microstructures. Palmqvist fracture toughness (WK) of the RT milled powders increased with increased milling time and increasing WC grain size for both sintering methods. WK reached 11.6 MN.m3/2 with 300 min milling after pressureless sintering but reached 16.1 MN.m32 for the same material after sinter-HIP due to the effect of mean WC grain size and binder phase mean free path. The -30°C milled powder exhibited higher fracture toughness for both sintering methods than the 60 min, RT milled material. Spark plasma sintering (SPS) showed that the onset of densification was dependent upon particle size with the powder from 300 min milling showing an onset temperature of ~ 800°C compared to ~ 1000°C for the 60 min milled powder. The low temperature milled powder showed an onset temperature of ~ 980°C, which suggested that low temperature milling provided enhanced densification kinetics.

published_or_final_version / abstract / Mechanical Engineering / Doctoral / Doctor of Philosophy

published_or_final_version / abstract / Mechanical Engineering / Master / Master of Philosophy

The magnetic properties, coercivity, Hc, and weight-specific magnetic saturation, CoM, are two important quality characteristics in cemented carbides and ceramic metals, cermets. These properties give information about grain size and binder phase content, and are influenced by the different stages in the sintering process. This master thesis aim to investigate how the magnetic properties in cemented carbides are influenced by the top temperature during sintering and how the sintering processes used for cermets can be optimized in order to gain better magnetic properties in the final products. During the first part of the project, the temperature range investigated was 1380°C–1520°C. The results indicate that Hc in cemented carbides has a strong temperature dependence, where increasing top temperature results in lower Hc. In order to have approval limits for the furnace control pieces that follow the process directives, the limits used today need to become narrower. Furthermore, the results show that CoM also has a temperature dependence, although not as strongly as Hc. During the second part of the project, already existing data of the magnetic properties in four different cermet grades were evaluated. The results indicate that the two sintering processes used in the DDK furnace are generating too high results in Hc and CoM. Optimization tests were conducted and changes implemented in order to gain better results, where the DJ1430 process now has an increased time during the solid state sintering and the DF1480 process now has an increased time during the liquid phase sintering.

Multiscale (analytical and computational) models have been developed based on a thermodynamic variational principle (TVP) to model sintering and eventual mudcracking in thermal barrier coatings (TBCs) made using the electron beam physical vapour deposition (EB-PVD) process. It is assumed that the sintering occurs by interfacial diffusion at local contacts between columns and driven by changes in interface free energy and elastic stored energy of the coating. The models link diffusional processes at the scale of contacting feathery columns with the macroscopic deformation and sintering response. In service, the columns can come into contact and sinter together. As sintering progresses there is a build up of strain energy in the system which reduces the driving force for sintering and leads to either complete or incomplete sintering of the TBC depending on the magnitude of effective modulus (E) of the coating. By seeding the coating with initial imperfections, different types of behaviour are observed depending on the value of E and the spacing between imperfections. For compliant coatings, the response is insensitive to the presence of imperfections and the coating fully sinters. At higher values of E, strain energy is released by the development of intercolumnar cracks in the coating, which can propagate to the interface with the TGO (thermally grown oxide), deflect into the interface and propagate, leading to spallation of regions of the coating and loss of thermal protection. It is observed that cracks develop at initial imperfections in the structure. The greater the spacing between imperfections the faster the development of cracks at these locations. If a TBC contains a distribution of imperfections there is progressive formation of cracks, with the average spacing decreasing with time, after an initial incubation period. The crack density eventually saturates to a constant value, which depends on the mechanical properties of the TBC. Initially, a crack spacing, CS, in the range 1.5H ≤ CS ≤ 3H has been predicted based on trapezoidal contact models. Here H is the thickness of the coating. Crack spacing predicted using this model is consistent in the lower range of experimentally observed crack spacing. However, axisymmetric contact models predict a crack spacing, CS, in the range 4H ≤ CS ≤ 8H, which is in good agreement with experimentally observed crack spacing range 3H ≤ CS ≤ 10H reported in the literature. Compared to the trapezoidal contact models, axisymmetric contact models more accurately predict the sintering response.

Pour les applications aéronautiques, les fibres en céramique piézoélectrique à âme métallique permettent d'imaginer des solutions pour avoir des dispositifs actifs et des capteurs complétement intégrés dans des structures, telles que les composites renforcés par des fibres.La démarche de cette étude est d'élaborer et de caractériser de telles fibres qui présentent de nombreux avantages : l'activation en mode radial permet d'utiliser de faibles tensions de commandes, l'utilisation d'un cœur et d'une matrice conducteurs permet de s'affranchir du dépôt d'électrodes et de garantir leur continuité, la présence d'un coeur métallique améliore la résistance mécanique de la fibre, l'utilisation sous forme de fibres fines et longues permet de l'intégrer à des profils de formes complexes sur de grandes longueurs. Dans un premier temps, le procédé d'enduction est utilisé pour la réalisation de ces fibres en déposant des particules céramiques à base de titano-zirconate de plomb (PZT) sur des fils de platine. Le développement et l'optimisation d'un procédé multicouche permet de réaliser des fibres avec des épaisseurs parfaitement contrôlées pour obtenir les capacités de déformations optimales en alternant des cycles dépôt/traitement thermique avant une opération de frittage finale. La caractérisation d'échantillons massifs traités dans les mêmes conditions permet de s'assurer des propriétés piézoélectriques atteintes pendant les différents traitements thermiques. Les caractérisations électromécaniques réalisées sur les fibres permettent de vérifier le comportement en tant qu'actionneur et que capteur, bien qu'il s'avère difficile de remonter aux caractéristiques intrinsèques des fibres.Dans un second temps, une réflexion est menée sur les moyens à mettre en oeuvre pour envisager un développement à grande échelle de ce type de fibre. Dans ce sens, des expérimentations sur la mise en place du procédé continu de coextrusion avec un polymère chargé sont menées, de même que sur la réduction de la température de frittage à l'aide d'additifs pour substituer les fils en platine, mais aussi sur la réduction du temps de frittage à l'aide de techniques non conventionnelles comme le frittage laser et le frittage micro-ondes. Ces investigations ouvrent des pistes sérieuses pour imaginer une production continue de fibres piézoélectriques à âme métallique.Enfin, des travaux de modélisation par éléments finis du comportement de ces fibres, intégrées ou non dans une structure, permettent de mettre en évidence l'influence du dimensionnement des fibres sur les déformations résultantes, en fonction notamment de l'épaisseur du matériau actif déposée et des propriétés élastiques des différents éléments. Différentes configurations sont imaginées pour utiliser ces fibres dans des structures en tant qu'actionneur et capteur. / Metal core piezoelectric fibres are suitable for active devices and sensors fully embedded in structuresas fibres reinforced polymers for aeronautic applications.The aim of this study is to develop and characterize such fibres that have many advantages: radial mode activation allows the use of low voltage control, the use of a core and a conductive matrix eliminates the deposition of electrodes and the necessity to maintain their continuity, the presence of a metal core improves the mechanical strength of the fibre, the use of thin and long fibres permits their integration in profiles with complex shapes over long distances.In a first step, a dip-coating process is used to realize such fibres by depositing ceramic particles based on lead zirconium titanate (PZT) on platinum wire. The development and optimization of a multilayer process, by alternating deposition cycles / heat treatment prior to the final sintering step, lead to the production of fibres with perfectly controlled thickness in order to obtain optimal strain capability. Characterization of bulk samples under the same thermal conditions allows to measure equivalent piezoelectric properties as fibres submitted to the same heat treatments. Electromechanical characterizations performed on the fibres confirm their behaviour as actuator and sensor, although it is still difficult to determine the effective piezoelectric properties of the fibres.In a second step, the possibility to develop a large-scale production of this type of fibre is investigated.In this regard, experiments are carried on coextrusion process with a PZT loaded polymer, as well as the reduction of the sintering temperature by using additives to replace the platinum core. In addition, reducing the sintering time using unconventional techniques such as laser sintering and microwave sintering are investigated. It is then open serious leads to imagine a continuous production of metal core piezoelectric fibres.Finally, a finite element modelling approach of the behaviour of these fibres, integrated or not in a structure, allows to highlight the influence of fibre sizing on the resulting strains, in particular according to the thickness of the active deposited material and elastic properties of the individual elements (metal core, matrix). Different configurations are analysed to use these fibres in structures as actuator and sensor.

Cerâmicas porosas combinam baixa condutividade térmica com elevada estabilidade química, dimensional e refratariedade. Devido a isso, seu uso como isolante térmico em altas temperaturas (T >1000°C) tem se apresentado como uma importante solução para reduzir o consumo energético. Dentre as diversas matérias primas utilizáveis nessa aplicação, o hexaluminato de cálcio (CaAl12O19 ou CA6) é um novo tipo promissor de refratário leve. Entre suas características mais importantes, destacam-se o alto ponto de fusão (1875°C) e a dificuldade intrínseca para densificar, devido à morfologia dos cristais em forma de placas que permite manutenção da porosidade em altas temperaturas, e por longos tempos. Apesar do grande interesse tecnológico e dos diversos estudos relatando propriedades e aplicações, há poucos trabalhos descrevendo a evolução da microestrutura de estruturas porosas formadas \"in situ\" a partir de fontes de Al2O3 e CaO. Sabendo que essa rota de processamento permite significativa economia de energia e tempo, compreender os mecanismos e variáveis envolvidos torna-se um importante ponto de investigação. Neste trabalho, foram preparadas composições com diferentes proporções de Al2O3 e CaCO3 por meio de prensagem uniaxial. Após tratamento térmico (500-1500°C), as amostras foramcaracterizadas em relação à porosidade total, resistência à ruptura por flexão, módulo elástico, fases numeralógicas formadas, dilatação térmica linear e morfologia. Os principais fatores que afetaram a evolução da microestrutura porosa foram o teor de CaCO3 adicionado ao sistema, o tamanho médio dessas partículas e a temperatura final de tratamento térmico. Para todas as composições com CaCO3, verificou-se que a formação de poros após a decomposição do CaCO3 (650-720°C) não afetou o nível total de porosidade da estrutura. Entre 1300-1400°C ocorreu a formação de fases intermediárias (CaAl2O4 e CaAl4O7) com composição eutética e baixo ponto de fusão ao redor dos poros. Em 1500°C, essas fases líquidas adquiriram a composição do hexaluminato e se cristalizaram, gerando estruturas porosas e com razoável resistência mecânica. / Porous ceramics combine low thermal conductivity with high chemical and dimensional stability and refractoriness. Therefore, their use as insulators at high temperatures (T>1000°C) has emerged as an important solution for the reduction ofenergy consumption. Among the various raw materials to be used for such a purpose, calcium hexaluminate (CaAl12O19 or CA6) is a promising new type of lightweight refractory material. Some ofits most important features include high melting point (1875°C) and intrinsic difficulty to densify due to the morphology of its plate-like crystals that enables the maintenance of porosity at higher temperatures and for longer times. Despite the great technological interest it has drawn and the development of studies on its properties and applications, the literature reports few studies on the evolution of its microstructure formed in situ from Al2O3 and CaO sources. Because this processing route significantly saves energy and time, the mechanisms involved must be understood. This dissertation addresses the preparation of compositions with different proportions of Al2O3 and CaCO3 by uniaxial pressing. After heat treatment (500-1500°C), samples were characterized regarding total porosity, tensile strength by bending, elastic modulus, formed phases, dilatometric analyzis and scanning electron microscopy. The main factors that affected the evolution of the porous microstructure were the CaCO3 content added to the system, average size of the particles and the final temperature of the heat treatment. The formation of pores after the CaCO3 (650-720°C) decomposition did not affect the level of total porosity significantly. The formation of intermediate phases (CaAl2O4 and CaAl4O7) with eutectic composition and low melting point surrounding the pores was observed between 1300-1400°C. At 1500°C, such liquid phases displayed a hexaluminate composition and crystallized, which resulted in porous structures of reasonable strength.

O objetivo do trabalho foi fabricar ferramentas de corte para usinagem a partir de materiais em gradação funcional (Functionally Graded Materials FGM), fazendo uso da técnica de sinterização por plasma pulsado (Spark Plasma Sintering SPS), a qual permite taxa de aquecimento e resfriamento maior do que as técnicas tradicionais, menor temperatura e tempo de operação, melhor controle energético e alta repetibilidade. Os materiais utilizados foram pós cerâmicos a base de alumina (Al2O3-ZrO2 e Al2O3-TiC) e metal duro (WC-Co), de modo que dois insertos foram desenvolvidos, um de cerâmica branca (Al2O3-ZrO2) em gradação com metal duro e outro de cerâmica mista (Al2O3-TiC) em gradação com metal duro. A metodologia experimental levou em conta a aplicação de um modelo termomecânico para estimar a tensão residual térmica ao longo da espessura da ferramenta, estudo da influência dos parâmetros de sinterização por SPS (Temperatura e Pressão) sobre a qualidade do sinterizado (caracterização da propriedade física, densidade), com base nesses dados foi escolhida a melhor condição de operação para fabricar corpos de prova (CPs) para os ensaios mecânicos de resistência à flexão, dureza e tenacidade à fratura, além de insertos em FGM para os ensaios de usinagem em ferro fundido cinzento fazendo uso da operação de torneamento. Os resultados mostraram que o parâmetro de máquina que mais influenciou a densidade foi a Temperatura, os FGMs de AlTiC e AlZr obtiveram um aumento de 126 e 73% na resistência à flexão em relação às suas respectivas cerâmicas homogêneas, seguindo a sequência dos materiais, a dureza foi avaliada em 13,8 e 15,8 GPa, enquanto a tenacidade à fratura em 4,91 e 5,04 MPa.m1/2. Quanto aos ensaios de usinagem, as ferramentas de FGM AlZr apresentaram menor desgaste do que as de FGM AlTiC, as forças de corte foram influenciadas pelas variáveis Avanço e Velocidade de corte, finalmente, o Avanço foi a variável que mais influenciou os resultados de rugosidade. / The aim was fabricating cutting tools from functionally graded materials (FGM) by spark plasma sintering method (SPS), which allow heating and cooling rates higher than traditional methods, lower temperature and shorter time sintering, better energy control and high reproducibility. The materials used were ceramic powders based on alumina (Al2O3-ZrO2 and Al2O3-TiC) and cemented carbide (WC-Co), so that two inserts were developed, one of white ceramic (Al2O3-ZrO2) graded with cemented carbide and the other of mixed ceramic (Al2O3- TiC) graded with cemented carbide. The experimental methodology was developed from thermo-mechanical model application to estimate thermal residual stress along with tool thickness, study into the influence of SPS sintering parameters (Temperature and Pressure) over sintered quality (physical properties characterization, density), on the basis of these data, the best operating condition was chosen to fabricate workpieces for mechanical tests of flexural strength, hardness and fracture toughness, besides FGM inserts to machining tests in grey cast iron using turning operation. The results showed the machine parameter that mostly influenced density was Temperature; the AlTiC and AlZr FGMs got an increase of 126 and 73% in flexural strength in relation to their homogeneous ceramics. Following the materials sequence, the hardness was evaluated at 13.8 and 15.8 GPa, whereas the fracture toughness was 4.91 and 5.04 MPa.m1/2. For the machining tests, FGM AlZr cutting tools showed lower wear than FGM AlTiC ones; the cutting forces were influenced by Feed Rate and Cutting Speed. Finally, the Feed Rate was the variable that mostly influenced the roughness results.

Os objetivos deste trabalho foram a implantação e a otimização da técnica de sinterização por varredura a laser de filmes espessos, o estudo da cinética do processo e a avaliação das propriedades do composto BaTi0.85Zr0.15O3 (BTZ) sinterizado a laser, em comparação com os filmes sinterizados em forno. Pós nanocristalinos de BTZ foram sintetizados em baixas temperaturas com sucesso pela primeira vez (600ºC), por meio do método dos precursores poliméricos modificado. Foram obtidos pós nanométricos com tamanho de partículas primárias de ~20 nm e com aglomeração controlada, uma inovação para pós de BTZ preparados por rotas químicas. Para a deposição dos filmes, a estabilidade das suspensões de partida foi estudada e filmes espessos com excelente homogeneidade foram depositados utilizando a técnica de eletroforese (EDP). O desenvolvimento da técnica permitiu o controle da espessura do filme a partir dos parâmetros de deposição. A montagem experimental para a sinterização a laser foi otimizada de modo a permitir a sinterização de filmes com dimensões de até 70 mm de comprimento por 10 mm de largura e espessuras variáveis. Os tempos de patamares em cada etapa foram dependentes da velocidade e do número de varreduras. A temperatura máxima que se pode atingir no filme espesso, durante cada varredura e para uma potência nominal do laser fixa, foi correlacionada com a densidade relativa. Os processos térmicos envolvidos durante a varredura a laser atuaram de modo similar á sinterização em duas etapas (two step sintering). Com o intuito de melhorar a densificação dos filmes, passamos a adicionar o composto Bi4Ti3O12 (BIT) (1 e 2 mol %) ao BTZ durante a deposição. A utilização do sistema desenvolvido para a sinterização por varredura a laser em conjunto com o acréscimo do aditivo BIT resultou em uma diminuição no tamanho de grão dos filmes e uma importante diminuição da porosidade aparente. Para a aditivação com 2 mol% de BIT obtivemos filmes de ótima densidade (porosidade aparente de ~4%) e reduzido tamanho de grão (~200 nm), resultado inédito em se tratando de filmes espessos. A sinterização a laser resultou em filmes com maior permissividade dielétrica em relação ao filme sinterizado em forno elétrico. As reações que ocorrem entre o BTZ e o BIT foram exploradas usando conjuntamente as técnicas de espectroscopia de impedância, análise térmica e difratometria de raios-X. / The goals of this work were the implantation and optimization of the technique of sintering by laser scan of thick films, the kinetic study of the process and the evaluation of the physical properties of the laser sintered compound BaTi0.85Zr0.15O3 (BTZ), compared to thick films sintered in conventional furnace. Nanocrystalline powders of BTZ were for the first time, successfully synthesized at low temperatures (600ºC) using the modified polymeric method. Nanometric powders with primaries particles of ~20nm sizes and controlled agglomeration were obtained which was an innovation for BTZ powders prepared by chemical methods. For the films deposition, the suspensions stability was studied and thick films with excellent homogeneity were deposited using the electrophoresis technique (EDP). The developing of the technique allowed the thicknesses control using the deposition parameters. The characteristics of the experimental apparatus were optimized in such a way as to allow the sintering of thick films whose dimensions were up to 70mm in length, 10mm in width and variable thicknesses. The step times in each stage were dependent on the velocity and scan number. The maximum temperature that can be achieved in the thick film, during each scan, and for a fixed rated laser power was correlated with the relative density. The related thermal process during the continuous laser scan acted in a similar way as a two-step sintering. To improve the densification of the films, we started to add the compound Bi4Ti3O12 (BIT) (1 e 2 mol %) to BTZ during the deposition. The utilization of the system developed for the sintering by laser scan alongwith the adding of the BIT resulted in a grain size decrease and a significant decrease in apparent porosity. For the 2mol% additivation we obtained films with excellent density (apparent porosity of ~4%) and reduced grain size (~200nm), which is an unpublished result for thick films. The laser sintering resulted in films with a higher dielectric permittivity in relation to the conventionally sintered film. The reactions between BTZ and BIT were explored using the techniques of impedance spectroscopy, thermal analysis and X-ray diffraction.

A study has been made of the enhancement of the mechanical strength of bricks fabricated from five Sri Lankan Quaternary and post-Quaternary brick clays with the objective of identifying and optimising those factors which control the quality and performance characteristics of fired clay products of this type. Mineralogical investigations have shown that the clays are predominantly kaolinitic. Of the accessory minerals, feldspars and gibbsite are the chief constituents. The experimental programme involved the development of feasible processing techniques for clay bodies, the establishment of optimum heat treatments for their firing, and the testing and evaluation of material properties of the fired products. The microstructures of fired materials have been characterized using optical and electron microscopical techniques, as well as X-ray diffraction, electron probe microanalysis and chemical analysis. A limited study was also made of the durability of laboratory fired specimens. Methods of strength enhancement included use of the reactions of phosphates with natural clays, use of mineralizers to induce mullitization and surface coating by an efflorescence process. A kinetic analysis based on the first order kinetics is proposed for the estimation of optimum firing conditions for kaolinitic clays. The study has shown that surface coating of bricks increases the load at the elastic limit by up to 30% and the ultimate failing load by 19% in the clays examined. The measured increases in modulus of rupture and modulus of elasticity are over 33% and 40% respectively. A fabrication technique which requires the incorporation of phosphates has been developed. This provides the possibility of lowering the peak temperature of firing to 500°C. Flexural strength increase of up to 60% over the normally fired unbonded specimens can be achieved using this technique. Relevant compatibility relations in the ternary system Si02- P205-AI203 at 500'C are proposed. The presence of an optimum amount of mineralizer in a clay body may alter its sintering characteristics resulting in an increase in modulus of rupture up to 55%. However, uncontrolled additions exceeding 4 wt% cause deleterious effects. Microstructural analysis provides evidence that liquid phase sintering, development of mullite, development of pores and bloating are the dominant strength determining features in these clays. An empirical equation correlating the functional relation between modulus of rupture, mullite content and porosity is proposed. Mechanisms of strength development are discussed in the light of these findings.