Ti-6Al-4V alloy has been used as biomedical implants for decades because of its superior mechanical properties, good biocompatibility, lack of allergic problems and good corrosion resistance. It is widely used as the tibial components in total knee arthroplastry and hip cup in total hip replacement. However, the mechanical properties of Ti-6Al-4V implant can be deteriorated due to corrosion pits. In the past decades, the rapid developments in additive manufacturing have broadened their applications in biomedical area due to the high geometrical freedom in fabricating patient-friendly implants. However, the high-localized thermal input and fast cooling rate during laser processing usually result in non-equilibrium phase with high residual stress. Therefore, it is necessary to apply proper post-treatments on the as-printed parts to ensure better properties. In this work, various post-treatments (e.g. post-heat treatments, hot isostatic pressing) were applied aim to improve the corrosion behavior of direct metal laser sintered Ti-6Al-4V parts. The effect of post-treatment temperature on the mechanical properties and corrosion behavior were examined experimentally. A discussion on factors influencing corrosion rate was presented, and the corrosion mechanism on the Ti-6Al-4V part in simulated body fluid was proposed. Based on the electrochemical measurement results, enhanced corrosion resistance was observed in the samples after high temperature HIPing at the annealing temperature (α+β region) of 799°C.

In recent years, sintering of powdered materials in microwaves has emerged as a manufacturing technique with many potential advantages over conventional sintering methods, including the possibility of faster processing and finer microstructure, along with the potential for vast energy savings. However, the technique remains on the level of laboratory studies and is underutilized in industry, mostly due to the difficulty of controlling the process: the intrinsically nonuniform temperature pattern that results from microwave heating routinely induces nonuniform mechanical deformation. Mathematical models and computer simulations can help to clarify the factors that influence this process and aid experimentalists in the design of efficient processing equipment. Although a number of modelling techniques have been reported to this end, they appear to inadequately represent the entire chain of related physical phenomena, which involves interaction of the electromagnetic field with the material, heat transfer, and mechanical deformation, each of which is coupled with both of the others, and all of which occur on different time scales. In this work, we present an original comprehensive mathematical formulation that accounts for the chain of physical processes comprising microwave sintering in one- and two-dimensional scenarios. We develop models for simulating the coupled electromagnetic, thermal, and mechanical phenomena at their appropriate time and spatial scales, and in addition, we account for the temperature and density dependence of the full set of thermal and dielectric properties of the material undergoing sintering. The electromagnetic and temperature fields are approximated using finite difference methods, and the mechanical problem is solved using the Master Sintering Curve representation of the density kinetics, which gives a way of accounting for the effect of microscale transport on the macroscopic property of relative density. For constant-rate sintering trials, we use the exponential integral to compute the work of sintering, which reduces computation time. The presented algorithms are all implemented and shown in MATLAB and Python. Simulation of density and temperature evolution of the sintered sample shows processing times and shrinkage rates comparable to experimental results. This work lays a theoretical and computational foundation for modelling the general three-dimensional problem and computer-aided design of efficient sintering processes.

The present study focuses on the physical and chemical mechanisms of lubricant removal during the first step of the sintering process during powder metallurgy (P/M) processing of ferrous systems. Previous works on the kinetics of delubrication made it possible to develop an empirical model which accounts for the typical weight loss profile observed upon heating of green compacts. It has been established that the rate at which the parts are heated dictates the overall process kinetics, and fitting curve methods yield two parameters which contain the corresponding information: (i) TMAX is the temperature of 50% lubricant removal, and (ii) b is representative of the slope of the curve during weight loss stage. Phase I of this study aims at determining the dependencies of these two parameters with respect to a series of physical variables: green density of the compacts; presence of an alloying element potentially catalytic for the reaction of lubricant pyrolysis; and procedure of compaction and geometry of the compacts. Also, it is suggested that the two parameters obtained from the fitting curve methods can be related to the main two mechanisms of delubrication: evaporation of the lubricant and conversion of the lubricant molecules into smaller hydrocarbons, assuming that these two mechanisms are the kinetically limiting mechanisms. Furthermore, recent studies of the delubrication process have been opening the way to the potential development of gas sensors, which could eventually allow the direct monitoring of the emissions of gaseous species. Several key features have been reported in the literature, including a peak emission of hydrocarbons at the delubrication temperature, as well as strong emissions of CO and CO2 at temperatures above 700°C. The scope of Phase II of this project was thus to verify that these features were retained under various processing conditions, so that the development of a sensor suitable for various sintering environments is viable. Variations in the emission profiles of gaseous species were observed as the processing conditions were changed, and when possible, potential justifications for these changes have been proposed.

This work was on the effect of electric current on the processing of ceramics. The focus was on electromigration/electrochemistry and plasma effects. While there is no solid evidence that there is plasma in Spark Plasma Sintering, (SPS), newer techniques e.g. flash, use different conditions so there is an interest in understanding the conditions under which a plasma forms. The minimum arcing voltage was found from literature to be from 10-15V for materials of interest. This is above that found in SPS (10V). However, due to the many contact points in a powder compact much higher voltages (50V) were required in practical experiments. Optical spectroscopy was used to verify the formation of a plasma, and emission peaks from the powder compact material were visible implying they were vaporised and formed the plasma. Electromigration was exploited to alter the oxidation of zirconium diboride, by passing current through the oxide layer (120μm zirconia base grown at 1200°C) oxygen could be pumped either away or toward the diboride bulk. Small cubes (3mm) of diboride had platinum foil electrodes applied on both sides and oxidation was performed at 1400°C for 5hr. Without a field the oxide grew to 360μm, by applying 10V and 100mA the oxide grew to 150μm under the +ve electrode but 1400μm under the -ve electrode. Electrochemical reduction was believed to have occurred due to the electrical properties of the material changing during oxidation and visible blackening of the oxide. Combining the techniques from both earlier works, a contactless flash sintering setup was developed. This used two plasma arcs as electrodes to heat and pass current through the sample. Various materials, currents and times were used, but the best result was with SiC:B4C which was sintered in 3s with 6A, the microstructure showed sharp grains, no segregation and limited grain growth ( initially 0.7μm SiC and 0.5μm B4C, this grew to 1.1μm and 1.4μm). This was the first recorded case of contactless flash sintering and the technique has the potential to sinter ceramics in a continuous manner.

Monolithic composites are needed that combine low friction and wear, high mechanical hardness, and high fracture toughness. Thin films and coatings are often unable to meet this engineering challenge as they can delaminate and fracture during operation ceasing to provide beneficial properties during service life. Two material systems were synthesized by spark plasma sintering (SPS) and were studied for their ability to meet these criteria. A dual hybrid composite was fabricated and consisted of a nickel matrix for fracture toughness, TiC for hardness and graphite for solid/self‐lubrication. An in‐situ reaction during processing resulted in the formation of TiC from elemental Ti and C powders. The composition was varied to determine its effects on tribological behavior. Stellite 21, a cobalt‐chrome‐molybdenum alloy, was also produced by SPS. Stellite 21 has low stacking fault energy and a hexagonal phase which forms during sliding that both contribute to low interfacial shear and friction. Samples were investigated by x‐ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive x‐ray spectroscopy (EDS), and electron back‐scattered diffraction (EBSD). Tribological properties were characterized by pin on disc tribometry and wear rates were determined by profilometry and abrasion testing. Solid/self‐lubrication in the TiC/C/Ni system was investigated by Raman and Auger mapping. A tribofilm, which undergoes a stress‐induced phase transformation from polycrystalline graphite to amorphous carbon, was formed during sliding in the TiC/C/Ni system that is responsible for low friction and wear. TiC additions help to further decrease wear. Stellite 21 was also found to exhibit acceptably low friction and wear properties arising from the presence of Cr23C6 in the matrix and work hardening of the cobalt and chromium during sliding.

Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 1982. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Vita. / Includes bibliographical references. / by Joseph Michael Dynys. / Ph.D.

A técnica de sinterização por plasma, também conhecida como processo SPS (Spark Plasma Sintering), é um processo para consolidação e sinterização de pós, em que corrente elétrica alternada pulsada e pressão de compactação são aplicadas simultaneamente aos componentes ferramentais (molde, punções, etc.). O molde utilizado neste processo tradicionalmente é cilíndrico, composto por grafite e permite a fabricação de amostras com geometria circular. Esse processo também possibilita a sinterização de um grande número de materiais, em especial, Materiais com Gradação Funcional (MGF). Tendo em vista os aspectos de geometria e composição da amostra, um projeto de otimização de moldes pode ser desenvolvido visando a fabricação de amostras com geometrias e gradação complexas. Com isso, é possível adequar a geometria do molde ao formato e composição da amostra que se deseja sinterizar, visando uma sinterização uniforme. Portanto, o objetivo deste trabalho é o desenvolvimento de uma metodologia para projetos de moldes utilizados na sinterização por plasma. Esta metodologia consiste na implementação de um algoritmo de otimização baseado no Método de Otimização Topológica (MOT), considerando três tipos de abordagem: a primeira abordagem, a qual visa a geometria da amostra, busca obter um molde prismático considerando amostras com geometria arbitrária, como por exemplo quadrada, triangular ou em cruz, com o objetivo de uniformizar o campo de temperaturas na amostra: na segunda abordagem, que considera moldes para a fabricação de amostras (MGF, os moldes podem ser projetados de modo a produzirem um gradiente de temperatura, na direção axial, através da variação da espessura da parede do molde; a terceira abordagem considera um molde constituído por material compósito. Nesta última abordagem é proposto um novo conceito de molde, onde se busca trabalhar não apenas com a geometria, como também com a microestrutura do molde dada por um material anisotrópico. Para a implementação do algoritmo de otimização, um modelo computacional baseado no Método dos Elementos Finitos (MEF), é desenvolvido considerando o processo SPS como um problema de acoplamento eletrotérmico. Na implementação do MOT utiliza-se um modelo de material baseado no SIMP (Solid Isotropic Material with Penalization) e Programação Linear Sequencial (PLS) para resolver o problema de otimização do molde. Todo algoritmo de otimização é implementado na linguagem própria do ambiente Matlab® e o pós-processamento, para verificação e validação dos resultados, é executado no software comercial Comsol®. / The Spark Plasma Sintering (SPS) technique is a powder consolidating and sintering process, in which pulsed DC electric current and pressure loads are applied simultaneously in the tool system components (graphite die, punchers, etc.) in order to perform the sintering process. Generally, a cylindrical graphite die is used for circular samples manufacturing and through this process the sinterization of a large number of materials, including Functionally Graded Materials (FGM), is possible. Considering the geometry and sample material aspects, an optimization die design technique can be developed based on the manufacturing of samples with complex geometry and gradation. Thus, it is possible to adjust the die geometry to the sample geometry or gradation in order to achieve a uniform sinterization. Therefore, the aim of this work is the development of a methodology to be applied in the design of dies used in SPS sintering process. This methodology consists of implementing an optimization algorithm based on the Topology Optimization Method (TOM), considering three approaches: in the first one a prismatic die is designed to process a sample with arbitrary geometry, for example square, triangular and cross sample; in the second approach the change of the die wall thickness is considered to achieve a predefined temperature gradient in the gradation direction of MGF samples and the third approach the same previous objective is considered, however the focus is the optimization of thermal conductive fibers. In the latest approach, a new die concept is proposed, where the objective is to optimize not only the die geometry but he microstructure considering a die composed by an anisotropic material. T implement the optimization algorithm a computational model based on the Finite Element Method (FEM) is developed considering the SPS process as an electrothermal coupled problem. In the TOM implementation a material model based on SIMP (Solid Isotropic Material with Penalization) is adopted and the Sequential Linear Programming is used to solve the optimization problem. The optimization algorithm is implemented using the Matlab® environment and the pos-processing, for verification and validation of the obtained results is carried out by using Comsol®.

Este trabalho teve por objetivo desenvolver um processo de sinterização a plasma utilizando gaiola catódica para a sinterização de amostras de alumínio, para atmosferas de argônio, hidrogênio e nitrogênio. Avanços recentes na sinterização a plasma motivaram a investigação sobre seus benefícios para o alumínio e se a técnica de tela ativa, em particular com o uso de gaiola catódica, é capaz de contornar alguns problemas encontrados na sinterização deste material, como a presença de uma camada passiva de óxido e a expansão volumétrica após a sinterização para certos parâmetros de processo. A sinterização foi realizada em três processos: convencional, plasma direto e plasma com gaiola catódica. Para o processo convencional utilizou-se atmosferas de argônio e nitrogênio e, para os processos a plasma, utilizou-se atmosferas de argônio, hidrogênio e nitrogênio. Houve queda na densificação média após a sinterização em todos os processos. Tanto o processo a plasma direto e com gaiola catódica resultaram na menor queda de densificação. A atmosfera de nitrogênio mostrou-se a mais efetiva nos processos avaliados, indo ao encontro com o reportado na literatura consultada. Houve aparente endurecimento superficial das amostras sinterizadas a plasma direto. As amostras sinterizadas a plasma com gaiola catódica obtiveram homogeneidade nos valores de microdureza superficial e transversal entre as atmosferas, concordando com o esperado do uso desta técnica. O processo a plasma direto produziu amostras com maior rugosidade em comparação com os outros processos, não havendo influência significativa da atmosfera de sinterização neste aspecto. Foi detectada a presença de zinco na superfície de amostras provenientes do processo convencional com nitrogênio e do processo a plasma com gaiola catódica utilizando argônio e nitrogênio, sendo confirmado pela análise química. Houve formação de nitreto de alumínio apenas no processo convencional com nitrogênio. O processo a plasma com gaiola catódica mostrou-se o mais promissor por apresentar bons resultados em relação aos obtidos nos outros processos avaliados e por ser capaz de preservar a integridade superficial das amostras. É possível promover a melhora das propriedades superficiais do alumínio com o uso de gaiola catódica através de tratamentos termoquímicos concomitantes com a sinterização, tendo em vista os benefícios relatados na literatura. / This study aimed to develop a plasma sintering process using cathodic cage for sintering aluminum samples for argon, hydrogen and nitrogen atmospheres. Recent advances in plasma sintering motivated the research into its benefits for the aluminum and if the active screen technique, in particular the use of cathodic cage, can overcome some problems encountered in the sintering of this material, as the presence of a passive oxide layer and volumetric expansion after sintering for certain process parameters. Sintering was carried out in three processes: conventional, direct plasma and plasma with cathodic cage. For the conventional process was used argon and nitrogen atmospheres and for the plasma processing was used argon, hydrogen and nitrogen atmospheres. There was a decrease in average densification after sintering in all processes Both the direct plasma and cathodic cage plasma processes resulted in the smallest drop of densification. The nitrogen atmosphere proved to be the most effective in al processes evaluated, meeting with the reported in the literature. There was apparent superficial hardening of the samples sintered in direct plasma. Samples sintered in cathodic cage plasma obtained homogeneity in values of surface and cross section hardness between the atmospheres, according to the expected use of this technique. The direct plasma process produced samples with higher surface roughness compared with other processes, with no apparent influence of the atmosphere in this respect. It was detected the presence of zinc in the sample surface from the conventional process with nitrogen and cathodic cage plasma process with argon and nitrogen being confirmed by chemical analysis. The phase analysis on the sintered samples with nitrogen accused the formation of aluminum nitride for the conventional process. The cathodic cage plasma process proved to be the most promising for showing good results compared to those obtained in the other processes evaluated and to be able to preserve the surface integrity of the samples. It is possible to promote the improvement of the surface properties of aluminum with the use of active screen via thermochemical treatments concomitant with the sintering, in view of the benefits reported in the literature.

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.

by Li, Kowk Cheung = 利用木材製作具有生物形態的碳化矽 / 李國彰. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references. / Abstracts in English and Chinese. / by Li, Kwok Cheung = Li yong mu cai zhi zuo ju you sheng wu xing tai de tan hua xi / Li Guozhang. / Abstract --- p.i / 摘要 --- p.iii / Acknowledgements --- p.v / Table of contents --- p.vi / List of figure captions --- p.x / List of table captions --- p.xiv / Chapter Chapter 1 --- Introduction / Chapter 1.1 --- Biomorphic products and their potential applications --- p.1 / Chapter 1.2 --- Structures and mechanical behaviors of wood --- p.1 / Chapter 1.3 --- Characteristics and applications of SiC --- p.2 / Chapter 1.4 --- Common methods of producing biomorphic SiC from wood --- p.2 / Chapter 1.4.1 --- Chemical vapor deposition --- p.3 / Chapter 1.4.2 --- Melt infiltration --- p.3 / Chapter 1.4.3 --- Sol-gel process --- p.4 / Chapter 1.5 --- Carbothermal reduction process of silica --- p.5 / Chapter 1.6 --- Objectives of present work --- p.5 / Chapter 1.6.1 --- Comments on the previous works --- p.5 / Chapter 1.6.2 --- Current approaches --- p.6 / References --- p.8 / Chapter Chapter 2 --- Experimental procedures / Chapter 2.1 --- Wood biotemplates --- p.10 / Chapter 2.1.1 --- Balsa --- p.10 / Chapter 2.1.2 --- Flame tree --- p.10 / Chapter 2.2 --- Sol Gel process --- p.11 / Chapter 2.2.1 --- Precursor --- p.11 / Chapter 2.2.2 --- Reaction mechanisms --- p.11 / Chapter 2.2.3 --- "Effects of pH, temperature, and environment" --- p.12 / Chapter 2.3 --- Preparation of biomorphic SiC / Chapter 2.3.1 --- HC1 pretreatment --- p.13 / Chapter 2.3.2 --- Infiltration of silica via sol gel process --- p.13 / Chapter 2.3.2.1 --- Balsa --- p.14 / Chapter 2.3.2.2 --- Flame tree --- p.15 / Chapter 2.3.3 --- Sintering --- p.15 / Chapter 2.3.4 --- Removal of carbon --- p.15 / Chapter 2.4 --- Characterization methods --- p.16 / Chapter 2.4.1 --- Scanning electron microscope and energy dispersive x-ray spectroscopy --- p.16 / Chapter 2.4.2 --- X-ray diffractometry --- p.16 / Chapter 2.4.3 --- Differential thermal analysis --- p.16 / Chapter 2.4.4 --- Compressive strength analysis --- p.17 / Chapter 2.5 --- Summary --- p.17 / References --- p.18 / Figures --- p.19 / Chapter Chapter 3 --- Results and discussions / Chapter 3.1 --- Balsa --- p.21 / Chapter 3.1.1 --- HC1 pretreatment --- p.21 / Chapter 3.1.2 --- Infiltration behaviors --- p.21 / Chapter 3.1.2.1 --- By the standard method --- p.21 / Chapter 3.1.2.2 --- Modified sol-gel process --- p.21 / Chapter 3.1.3 --- SiC products --- p.22 / Chapter 3.1.3.1 --- Volumetric shrinkage and weight loss --- p.22 / Chapter 3.1.3.2 --- Compositions --- p.23 / Chapter 3.1.3.3 --- Morphology and structure --- p.24 / Chapter 3.1.4 --- Optimal infiltration conditions --- p.25 / Chapter 3.2 --- Flame tree --- p.25 / Chapter 3.2.1 --- HC1 pretreatment --- p.26 / Chapter 3.2.2 --- Infiltration behaviors --- p.26 / Chapter 3.2.3 --- SiC products --- p.26 / Chapter 3.2.3.1 --- Volumetric shrinkage and weight loss --- p.26 / Chapter 3.2.3.2 --- Composition --- p.27 / Chapter 3.2.3.3 --- Morphology and structure --- p.27 / Chapter 3.3 --- Mechanisms for the formation of SiC cell walls --- p.30 / Chapter 3.4 --- Compressive strength --- p.31 / Chapter 3.5 --- Summary --- p.34 / References --- p.35 / Tables --- p.36 / Figures --- p.38 / Appendix --- p.65 / Chapter Chapter 4 --- Conclusions and future works / Chapter 4.1 --- Summary --- p.67 / Chapter 4.2 --- Suggestions for future work --- p.68 / References --- p.70