Le développement de protections balistiques toujours plus légères et performantes reste un sujet de recherche très actif. Malgré de très hautes performances, la difficulté de mise en forme du SiC conduit généralement à l’utilisation d’aides au frittage en quantité importante, favorisant la formation de phases secondaires pouvant fragiliser le matériau. De plus, les hautes températures de mise en forme induisent la présence de phase α, conférant au matériau des propriétés mécaniques anisotropes et inférieures à celles de la phase cubique β.Dans ces travaux de thèse, l’objectif a été d’élaborer un matériau SiC cubique de très haute pureté, avec une densité de 100% et une stœchiométrie Si/C idéale afin d’optimiser les performances de cette céramique. Deux types de précurseurs ont été envisagés : une poudre commerciale et une poudre issue de la conversion d’un précurseur polymère précéramique.Dans un premier temps, une étude paramétrique de frittage par SPS a permis d’atteindre des densités de 95% pour les 2 précurseurs, tout en conservant la phase cubique seule. Ces résultats, bien qu’encourageants mais n’étant pas suffisants pour l’application visée, l’étude s’est tournée vers l’ajout d’aides au frittage. Des densités de 100% ont ainsi été obtenues sur des échantillons préparés à partir de poudre commerciale, même pour de très faibles teneurs en additif. Un second aspect de ces travaux a permis de mettre en évidence une dépendance de la température de transition β -> α du SiC vis-à-vis de la pression de frittage mais également vis-à-vis du type de précurseur, l’utilisation du précurseur polymère étant plus favorable à la stabilité de la structure cubique. Enfin des mesures de dureté ont été réalisées sur les meilleurs échantillons et ont permis de souligner le rôle prépondérant de la densité sur cette propriété. / The development of light and high performance ballistic protections is currently a sensitive subject of research. Despite promising mechanical characteristics, the complexity of SiC shaping generally leads to the use of high content of sintering aids, favouring secondary phases formation which could weaken the material. Nevertheless, high sintering temperatures induce the presence of the α form of SiC, conferring to the material anisotropical and lower mechanical properties than the one obtained with the cubic β phase.The goal of this PhD work is the development of high purity cubic SiC, with density close to 100% and perfect Si:C stoichiometry to optimize the performances of this ceramic. Two kinds of precursors were considered: a commercial powder and a powder from the conversion of preceramic polymer precursor.Firstly, the parametric study of SPS sintering allowed to reach densities of 95% for both precursors, while conserving only the cubic phase. These encouraging results being not sufficient, this study switched to the use of sintering aids. Densities close to 100% were thus reached on samples sintered with prepared mixtures from commercial powder, even for very low content of additive. The second subject of this thesis highlighted a dependence of the β -> α transition temperature of SiC as a function of sintering pressure, but also according to the kind of precursor. Indeed, the use of polymer precursor is favourable to cubic structure stability. Then, hardness measurements were performed on the most promising samples and allowed to highlight the major role of density on this property.

15-5PH stainless steel is an important alloy in the aerospace, chemical, and nuclear industries for its high strength and corrosion resistance at high temperature. Thus, this material is a good candidate for processing development in the direct metal laser sintering (DMLS) branch of additive manufacturing. The chemistry and microstructure of this alloy processed via DMLS was compared to its conventionally cast counterpart through various heat treatments as part of a characterization effort. The investigation utilized optical microscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-Ray diffractometry (XRD), energy dispersive X-Ray spectroscopy (EDS) and glow discharge atomic emission spectrometry (GDS) techniques. DMLS processed samples contained a layered microstructure in which the prior austenite grain sizes were relatively smaller than the cast and annealed prior austenite grain size. The largest of the quantifiable DMLS prior austenite grains had an ASTM grain size of approximately 11.5-12 (6.7?m to 5.6?m, respectively) and the cast and annealed prior austenite grain size was approximately 7-7.5 (31.8µm to 26.7µm, respectively), giving insight to the elevated mechanical properties of the DMLS processed alloy. During investigation, significant amounts of retained austenite phase were found in the DMLS processed samples and quantified by XRD analysis. Causes of this phase included high nitrogen content, absorbed during nitrogen gas atomization of the DMLS metal powder and from the DMLS build chamber nitrogen atmosphere. Nitrogen content was quantified by GDS for three samples. DMLS powder produced by nitrogen gas atomization had a nitrogen content of 0.11 wt%. A DMLS processed sample contained 0.08 wt% nitrogen, and a conventionally cast and annealed sample contained only 0.019 wt% nitrogen. In iron based alloys, nitrogen is a significant austenite promoter and reduced the martensite start and finish temperatures, rendering the standard heat treatments for the alloy ineffective in producing full transformation to martensite. Process improvements are proposed along with suggested future research.

Thesis (M. Tech.) - Central University of Technology, Free State, 2008 / A company’s ability to produce products faster and more economically may lead to a competitive edge in the international market. The reduction of development costs and shortened development time will undeniably depend on effective organisational structures that are based on effective information- and communication techniques and manufacturing technologies. An innovative manufacturing technology that impacts on rapid product development is Rapid Prototyping (RP). The Centre for Rapid Prototyping and Manufacturing (CRPM) works closely with South African companies, supporting them with common mechanical engineering solutions and specialising in the manufacturing of prototypes. One of the options offered in the manufacture of prototypes is the Laser Sintering (LS) process. It is however, difficult to determine the product cost for the building volume used to manufacture the prototypes. Prototypes from different clients can be manufactured at the same time in the same process. The problem however, is how to calculate the costs for each prototype and to offer the clients an accurate quotation for the manufacture of the prototype. Therefore, it is necessary to design a calculation concept, which includes all accrued costs and allocate these to the different parts/prototypes. As it is problematic to calculate the manufacturing cost of prototypes, it is necessary to analyse all the effects, parameters and influences on the manufacturing process in order to determine the manufacturing time, and ultimately the machine costs. This is needed to calculate the total cost of one platform and the cost of each individual part. The project, through various experiments determined how to allocate the costs, through a correlation between part volume and platform height. The aim of the study was to determine a calculation concept to estimate the total platform cost and the cost of each individual part. Furthermore, the estimated cost was compared with the actual cost to determine the deviation between the calculation methods, and lead to a calculation concept that can be used to predict and reduce the manufacturing costs. The results obtained from the research were used for an exact calculation and reduction of prototype unit costs manufactured on LS machines, which gave three basic advantages: * Manufacturing costs were reduced to benefit clients, which meant that they could invest more in the design of new prototypes and products, to improve customer satisfaction * Prototype manufacturing on expensive RP machines could be optimised by using more prototypes and lower costs for entering the market. * The calculation risk could be minimised, which lowered the risk of losing money on a project and resulted in better planning for available resources.

Published Article / In this paper the time and cost parameters of tooling manufacturing by metal casting in rapid prototyping sand moulds are assessed and comparison is made with alternative tool making processes such as computer numerical control machining and investment casting (Paris Process). To that end two case studies obtained from local companies were carried out. The tool manufacturing was conducted according to a five steps process chain referred to as Rapid Casting for Tooling (RCT). These steps include CAD modelling, casting simulation, rapid prototyping, metal casting and finishing operations. In particular the Rapid Prototyping (RP) step for producing the sand moulds was achieved with the aid of an EOSINT S 550 Laser Sintering machine and a Spectrum 510 Three Dimensional Printer. The results indicate that RP is the rate determining step and cost driver of the proposed tooling manufacturing technique. In addition it was found that this tool making process is faster but more expensive than machining and investment casting.

Published Article / Rapid Manufacturing (RM) has emerged over the past few years as a potential technology to successfully produce patient-specific implants for maxilla/facial and cranial reconstructive surgeries. However, in the area of spinal implants, customization has not yet come to the forefront and with growing capabilities in both software and manufacturing technologies, these opportunities need to be investigated and developed wherever possible. The possibility of using Computed Tomography (CT) and Rapid Manufacturing (RM) technologies to design and manufacture a customized, patient-specific intervertebral implant, is investigated. Customized implants could aid in the efforts to reduce the risk of implant subsidence, which is a concern with existing standard implants. This article investigates how accurately the geometry of a customized artificial intervertebral disc (CAID) can represent the inverse geometry of a patient's vertebral endplates. The results indicate that the endplates of a customized disc implant can be manufactured to a calculated average error of 0.01mm within a confidence interval of 0.022mm, with 95% confidence, when using Direct Metal Laser Sintering.

Current fossil fuel based energy sources have a huge shortcoming when one discusses their efficiency. The conversion efficiency of fossil fuel-based technologies is less than 40% in best cases. Therefore, until the renewable energy section is mature enough to handle all the energy demand one has to research and develop the technologies available to harvest the energy from the waste heat generated in fossil fuel-based supply sources. One of these emerging technologies is the use of thermoelectric (TE) devices to achieve this goal, which are solid-state devices capable of directly interconverting between heat and electrical energy. In the past decade there has been a significant scientific and financial investment within the field to enhance their properties and result in time/energy efficient fabrication processes of TE materials and devices for a more sustainable environment. In this thesis with use of chemical synthesis routes for nanostructured bulk thermoelectric materials iron antimonide (FeSb2), skutterudites (based on general formula of RzMxCo1-xSb3-yNy) and copper selenide (Cu2Se) are developed. These materials are promising candidates for use in thermoelectric generators (TEG) or for sensing applications. Using chemical synthesis routes such as chemical co-precipitation, salt melting in marginal solvents and thermolysis, fabrication of these TE materials with good performance can be performed with high degree of reproducibility, in a much shorter time, and easily scalable manner for industrial processes. The TE figure of merit ZT of these materials is comparable to, or better than their conventional method counterparts to ensure the applicability of these processes in industrial scale. Finally, through thorough investigation, optimized consolidation parameters were generated for compaction of each family of materials using Spark Plasma Sintering technique (SPS). As each family of TE nanomaterial investigated in this thesis had little to no prior consolidation literature available, specific parameters had to be studied and generated. The aim of studies on compaction parameters were to focus on preservation of the nanostructured features of the powder while reaching a high compaction density to have positive effects on the materials TE figure of merit. / Dagens fossilbränslebaserade energikällor har en enorm brist gällande effektivitet. Effektiviteten av fossilbränslebaserade teknologiers omvandling är mindre än 40 % i bästa fall. Därför tills förnybar energi är mogen nog att hantera alla energibehov, måste man forska och utveckla teknik för att skörda energi från spillvärme i fossilbränslebaserade försörjningskällor. En av dessa nya tekniker är tillämpning av termoelektriska (TE) material för att uppnå målet. Nämnde material är Soldi-State materialer som kan transformera mellan värme och elektrisk energi. Under det senaste decenniet har det pågått en stor vetenskaplig och ekonomisk investering inom området för att förbättra termoelektriska materials egenskaper. Dessutom ville man ta fram tid/energieffektiva TE material och komponenter för en mer hållbar miljö. I denna avhandling utvecklades och producerades termoelektriska material såsom järn antimonid (FeSb2), skutterudit (baserat på allmänna formeln RzMxCo1-xSb3-YNY) och koppar selenid (Cu2Se) med hjälp av kemiska syntesmetoder. Genom att Använda kemiska syntesmetoder som kemisk samutfällning, salt smältning i marginella lösningsmedel och termolys, kan material med hög grad av reproducerbarhet och ställbar för industriella processer tillverkas.   Termoelektrisk omvandling effektivitet hos uppnådde material är betydligt högre än resultat av andra studier. I och med detta kan man säga att materialet kan användas inom industri. Slutligen, genom en grundlig undersökning optimerades packningsparametrar som genererades för packning av varje materialgrupp med hjälp av Spark Plasma Sintring teknik (SPS). Eftersom ingen relevant studie finns för varje grupp av termoelektriska nanomaterial som undersökts i denna avhandling, studerades och genererades dessa specifika parametrar. Syftet med studien är att fokusera på bevarande av nanostrukturerade egenskaperna hos pulvret och att samtidigt nå en hög packningstäthet för att ha positiva effekter på materialens termoelektriska omvandlingseffektivitet. / <p>QC 20160503</p> / NEXTEC / SCALTEG

The term Nanoceramics is well known in the ceramic field for at least two decades. In this project a detailed study was performed on the synthesis of α-alumina nanopowders. High solids content nanoalumina suspensions were prepared and used to form green bodies using both wet and dry forming routes. The green bodies were then sintered using both conventional single and two-step sintering approaches. Synthesis: Two different synthesis methods, viz. precipitation and hydrothermal treatment, were used to synthesize fine α-alumina powders from aluminium chloride, ammonia solution and TEAH (Tetraethyl ammonium hydroxide). XRD, TEM and FEG-SEM were used to characterise the powders produced. The presence of commercial α-alumina powder as seed particles did not affect the transformation to α-alumina phase during the hydrothermal treatment at 220˚C in either basic or acidic environments. The results obtained from the precipitation route showed that the combined effect of adding α-alumina seeds and surfactants to the precursor solution could lower the transformation temperature of α-alumina from about 1200˚C for unseeded samples to 800˚C, as well as reducing the level of agglomeration in the alumina powders. The difference in transformation temperature mainly resulted from the nucleation process by the α-alumina seeds, which enhanced the θ → α transformation kinetics. The lower level of agglomeration present in the final powders could be due to the surface modifying role of the surfactants preventing the particles from growing together during the synthesis process. By introducing a further high-temperature step for a very short duration (1 minute) to the low-temperature heat treatment route (800˚C/12 h), the unseeded sample with added surfactant transformed into pure α-alumina phase. The newly-added step was shown to be an in-situ seeding step, followed by a conventional nucleation and growth process. The best final powder was compared with a commercial α-alumina nanopowder. Processing of alumina ceramics: The effect of low-molecular weight ammonium dispersants including Dispex-A40, Darvan-C and Dolapix-CE64, on high solids content nanoalumina suspensions was investigated. The nanosuspension prepared using the most suitable dispersant, Dolapix-CE64, was slip cast into ~53% dense, very homogeneous green bodies. This nanosuspension was also spray freeze dried into crushable granules using Freon as a foaming agent. Green compacts with density of ~53.5% were then formed by dry pressing the 2 vol% Freon-added spray freeze dried granules at 40 MPa. Both slip cast and die pressed green bodies were sintered using conventional single-step and two-step routes followed by characterising the density and grain size measurement of final dense compacts. The results have been compared with that of a submicron alumina ceramic prepared using a commercial α-alumina suspension. Highly dense alumina with an average grain size of ~0.6 μm was fabricated by means of spark plasma sintering at 1200˚C. The application of 500 MPa allowed achieving almost fully dense alumina at temperature as low as 1200˚C for 30 minutes with no significant grain growth.

<p>In this project, nano powder of CoSb₃ thermoelectric material was synthesized using chemical alloying novel co-precipitation method. This method involved co-precipitation of TE precursor compounds in controlled pH aqueous solutions followed by thermo-chemical treatments including calcination and reduction to produce nano-particulates of CoSb₃. The nano powder was consolidated using rapid solid state spark plasma sintering (SPS) and the processing time was of the order of few minutes. On a result very high densities were achieved and grain growth was almost negligible.</p><p>Various batches of the CoSb₃ nano powder were produced to achieve high purity, minimum particle size and compensate Sb evaporation during thermo-chemical reduction. For de-agglomeration, powder was grinded before and after calcination. Samples were characterized at each stage during synthesis using XRD and SEM (with EDX). Thermal gravimetric analysis (TGA) was done before thermochemical treatments to observe weight losses with heating the powder at high temperatures and other physiochemical changes. Thermal diffusivity of the samples was measured at room temperature using Laser Flash Apparatus (LFA) and heat capacity was measured using Differential Scanning Calorimetry (DSC).   Thermal conductivities are calculated using these thermal diffusivities, heat capacities and densities of the sintered pellets. Average grain size is measure using image size J software.</p><p>It was observed that powder purity and size is affected by batch size, reduction conditions like holding temperature and time.  During sintering with SPS; heating and cooling rates, sintering temperature, holding pressure and time were the main variables. Grain size and morphology was analyzed using SEM.</p><p>It was observed that larger the grain size higher will be the thermal diffusivity, which leads to increase in thermal conductivity. Hence, grain size has affected on thermal conductivity and also on TE performance.</p> / QC 20100708

<p>A whisker is a common name of single crystalline inorganic fibre of small dimensions, typically 0.5-1 μm in diameter and 20-50 μm in length. Whiskers are mainly used as reinforcement of ceramics. This work describes the synthesis and characterisation of new whisker types. Ti0.33Ta0.33Nb0.33CxN1-x, TiB2, B4C, and LaxCe1-xB6 have been prepared by carbothermal vapour–liquid–solid (CTR-VLS) growth mechanisms in the temperature range 900-1800°C, in argon or nitrogen. Generally, carbon and different suitable oxides were used as whisker precursors. The oxides reacted via a carbothermal reduction process. A halogenide salt was added to form gaseous metal halogenides or oxohalogenides and small amount of a transition metal was added to catalyse the whisker growth. In this mechanism, the whisker constituents are dissolved into the catalyst, in liquid phase, which becomes supersaturated. Then a whisker could nucleate and grow out under continuous feed of constituents. </p><p>The syntheses of TiC, TiB2, and B4C were followed at ordinary synthesis conditions by means of mass spectrometry (MS), thermogravimetry (TG), differential thermal analysis (DTA) and quenching. The main reaction starting temperatures and reaction time for the different mixtures was revealed, and it was found that the temperature inside the crucible during the reactions was up to 100°C below the furnace set-point, due to endothermic nature of the reactions. Quench experiments showed that whiskers were formed already when reaching the temperature plateau, but the yield increased fast with the holding time and reached a maximum after about 20-30 minutes. Growth models for whisker formation have been proposed.</p><p>Alumina based composites reinforced by (2-5 vol.%) TiCnano and TiNnano and 25 vol.% of carbide, and boride phases (whiskers and particulates of TiC, TiN, TaC, NbC, (Ti,Ta)C, (Ti,Ta,Nb)C, SiC, TiB2 and B4C) have been prepared by a developed aqueous colloidal processing route followed by hot pressing for 90 min at 1700°C, 28 MPa or SPS sintering for 5 minutes at 1200-1600°C and 75 MPa. Vickers indentation measurements showed that the lowest possible sintering temperature is to prefer from mechanical properties point of view. In the TiNnano composites the fracture mode was typically intergranular, while it was transgranular in the SiCnano composites. The whisker and particulate composites have been compared in terms of e.g. microstructure and mechanical properties. Generally, additions of whiskers yielded higher fracture toughness compared to particulates. Composites of commercially available SiC whiskers showed best mechanical properties with a low spread but all the other whisker phases, especially TiB2, exhibited a great potential as reinforcement materials. </p>

Chalcogenide glasses and glass-ceramics present a high interest for the production of thermal imaging lenses transparent in the 3-5 μm and 8-12 μm windows. However, chalcogenide glasses are conventionally synthesized in sealed silica ampoules which have two major drawbacks. First, the low thermal conductivity of silica limits the sample dimensions and second the silica tubes employed are single use and expensive, and represent up to 30% of the final cost of the material. The present work therefore addresses the development of innovative synthesis methods for chalcogenide glass and glass-ceramics that can present an alternative to the silica tube route. The method investigated involves melting the raw starting elements in reusable silica containers. This method is suitable for the synthesis of stable chalcogenide glasses compositions such as GeSe₄ but uncontrolled crystallization and homogenization problems are experienced for less stable compositions. The second approach involves preparation of amorphous chalcogenide powders by ball milling of raw elements. This mechanosynthesis step is followed by consolidation of the resulting powders to produce bulk glasses. Hot Uniaxial Pressing is suitable for compositions stable against crystallization. However, uncontrolled crystallization occurs for the unstable 80GeSe₂-20Ga₂Se₃ glass composition. In contrast consolidation through Spark Plasma Sintering (SPS) allows production of bulk glasses in a short duration at relatively low temperatures and is appropriate for the synthesis of unstable glasses. A sintering stage of only 2 min at 390°C is shown to be sufficient to obtain infrared transparent 80GeSe₂-20Ga₂Se₃ bulk glasses. This method enables the production of lenses with a 4-fold increase in diameter in comparison to those obtained by melt/quenching technique. Moreover, increasing the SPS treatment duration yielded infrared transparent glass-ceramics with enhanced mechanical properties. This innovative synthesis method combining mechanosynthesis and SPS has been patented in the framework if this study. The controlled etching of 80GeSe₂-20Ga₂Se₃ glass-ceramics in acid solution yields nanoporous materials with enhanced surface area. The porous layer created on the surface of the glass-ceramic is shown to play the role of anti-reflection coating and increase the optical transmission in the infrared range by up to 10%. These materials may have potential for the production of sensors with increased sensitivity in the infrared. The influence of indium and lead addition on the thermal and optical properties of the 80GeSe₂-20Ga₂Se₃ glass has also been assessed. Increased In or Pb contents tend to decrease the Tg of the glasses and shift the optical band gap toward higher wavelengths. A systematic ceramization study emphasizes the difficulty of controlling the crystallization for glasses in the systems GeSe₂-Ga₂Se₃-In₂Se₃ and GeSe₂-Ga₂Se₃-PbSe. No crystallization of the In₂Se₃ and PbSe crystalline phase was obtained. Finally, the possibility of producing rare-earth doped 80GeSe₂-20Ga₂Se₃ glass-ceramics transparent in the infrared region up to 16 μm is demonstrated. Enhanced photoluminescence intensity and reduced radiative lifetimes are observed with increased crystallinity in these materials.