En rupture avec les approches classiques de métallurgie consistant à allier un ou deux éléments majoritaires avec d'autres éléments en proportions minoritaires, un nouveau concept de matériaux est né : des alliages multi-composants formant une solution solide et pour lesquels tous les composants sont fortement concentrés. Ces nouveaux alliages, appelés alliages à haute entropie, présentent des propriétés mécaniques prometteuses, telles qu'une résistance mécanique élevée combiné à une grande ductilité. Par définition, ce nouveau concept de matériau rend possible l'exploration d'un champ quasi-infini de compositions chimiques. Toutefois, la stabilité thermodynamique de ces systèmes est mal connue, limitant fortement le choix des compositions. Dans ce contexte, le premier objectif de cette étude était de déterminer le domaine d'existence de la solution solide cubique à faces centrées (cfc) pour le système Co-Cr-Fe-Mn-Ni. Pour cela, la stabilité de phase cfc a été étudiée théoriquement et expérimentalement. En utilisant l'approche Calphad (Calculation of PHAse Diagram) et une nouvelle base de données (TCHEA-1), les phases stables de 10 626 compositions ont pu être calculées, à plusieurs températures. La comparaison entre calculs et résultats expérimentaux indique que la solution solide cfc est correctement décrite par cette base de données. Ainsi, il a été montré que la phase cfc est stable sur une large gamme de composition, décrite intégralement. Il est désormais possible de choisir une composition formant une solution solide stable à haute température pour ce système. Des calculs DFT (Density Functional Theory) ont ensuite permis d'analyser l'évolution de l'enthalpie de mélange en fonction de la composition mais aussi du nombre d'éléments. Des différences notables ont pu être constatées avec les prédictions faites par la base de données TCHEA-1. De plus, ces calculs ont mis en avant l'absence d'interaction ternaire et quaternaire pour le système d'étude. Ensuite, l'influence de la composition sur le durcissement par solution solide a été étudiée, pour permettre l'optimisation des propriétés mécaniques. Ainsi, l'évolution des propriétés structurelles et mécaniques des alliages multi-composants a été étudiée expérimentalement. Vingt-cinq alliages du système Co-Cr-Fe-Mn-Ni formant une solution solide cfc ont été traités. Le paramètre de maille a été mesuré par rayons X tandis que la dureté et le module d'élasticité ont été étudiés par nano-indentation. Le rôle de chaque élément sur le comportement mécanique fut ainsi explicité. Finalement, un modèle permettant d'estimer le durcissement de solution solide pour ce système est étudié / For a long time, development of alloys was restricted to one principal element, or two, with minor elements added for performance optimization. In 2004, a new concept of materials was born: multi-component alloys forming a solid-solution and in which all components are very concentrated. These new alloys, named high entropy alloys, can combine high mechanical resistance and large ductility. By definition this new material concept should make it possible to explore an almost infinite field of chemical compositions. But in the meantime, the thermodynamic stability of these systems was poorly known and severely limits the choice of alloy compositions. In this context, the first objective of this study was to fully determine the composition range of existence of a unique fcc solid solution within the multi-component Co-Cr-Fe-Mn-Ni system. To address this problem, the phase stability was theoretically and experimentally investigated. Using the Calphad approach and a new database (TCHEA-1), the stable phases of 10 626 compositions could be calculated, at several temperatures. The comparison between calculation and experimental results indicates that the fcc solid solution is accurately described by this database. Finally, it was shown that the fcc phase is stable over a wide range of composition, which was completely described. Now, it is possible to choose a priori a composition which will form a solid solution within this system. The heat of mixing of the fcc phase were compared between density functional theory (DFT) and Calphad calculations for binaries, ternaries, quaternaries and quinary systems. Significant differences were found with the predictions made by the TCHEA-1 database. In addition, these calculations have highlighted the absence of ternary and quaternary interaction for the Co-Cr-Fe-Mn-Ni system. However, the influence of the composition on the fcc solid solution strengthening was not fully understood, which limits mechanical optimization. So, the evolution of structural and mechanical properties of multi-components alloys was experimentally investigated. Several alloys from the Co-Cr-Fe-Mn-Ni system forming a unique fcc solid solution were processed. The lattice parameter was measured by XRD while the hardness and elastic modulus were measured by nano-indentation. The role of each element on the mechanical behaviour is presented. Finally, a model to assess the solid solution strengthening for this system is studied

Fitas amorfas ferromagnéticas apresentam um decaimento com o tempo da susceptibilidade magnética. Tal fenômeno é conhecido como aftereffect ou desacomodação (DA). Para explicar esse fenômeno em ligas amorfas existem dois modelos importantes. O modelo de Allia e Vinai prevê uma dependência do decaimento relativo da permeabilidade A?/? com a magnetostricção de saturação ?s. Construímos um sistema de medidas adequado para realizar tais experimentos. Fabricamos e caracterizamos magneticamente três séries de composições Co77-x MnxSi14B9 (série 1: x = O, 2, 4, 5, 6, 7, 8, 9; série 2: x = 0, 2, 4, 6, 8, 10, 15); Co75-xMnx Fe1Mo1Si14B9 (série 3: 1, 3, 4, 5, 6, 7). Preocupados em evitar a dispersão de dados frequentemente observada na literatura, mantivemos os parâmetros de fabricação da fita constantes, bem como também a proporção de metalóides. Apesar dos cuidados, nossos resultados ainda apresentaram certa dispersão. Mesmo assim, foi possível concluir que nossos resultados são bem descritos pelo modelo. A caracterização magnética das fitas de Co-Mn e o estudo da dependência da DA com ?s nessas ligas deram origem a um artigo que se tornou nosso primeiro trabalho publicado em revista internacional. O modelo proposto por Kronmüllerer dá maior ênfase à cinética dos processos responsáveis pelo decaimento da susceptibilidade. Por isso foi necessário construir um novo sistema que nos permitisse realizar medidas em diferentes temperaturas. Realizamos medidas de desacomodação em Co67Fe4Mo1Si12B16. Conseguimos eliminar as contribuições irreversíveis da DA através de um tratamento térmico seguido de um processo de estabilização. Os resultados das medidas de DA foram ajustados de acordo com a expressão prevista pelo modelo, fornecendo um valor de ?0 ~ 10-12 segundos, que é da ordem do inverso da frequência de Debye nesses materiais. Concluímos que os dois modelos estudados são igualmente úteis no estudo da desacomodação e devem ser tratados como aspectos complementares do mesmo problema. / Amorphous ferromagnetic alloys show a decay of magnetic susceptibility. This phenomenon is known as aftereffect or disaccomodation (DA). There are two major models which explain this effect in amorphous materials. According to Allia et al., the decay of susceptibility presents a dependence on the saturation magnetostriction ?s. We built an adequate system for measurement of DA based on this model. Ribbons of compositions: Co77-x MnxSi14B9 (series 1: x = O, 2, 4, 5, 6, 7, 8, 9; series 2: x = 0, 2, 4, 6, 8, 10, 15); Co75-xMnx Fe1Mo1Si14B9 (series 3: 1, 3, 4, 5, 6, 7), were produced by melt-spinning. Production parameters were held constant as well as the metalloid concentration in order to prevent the data dispersion which is commonly observed in the literature. Despite our cane, results show a certain dispersion, although it is possible to confirm the validity of this model in describing such alloys The magnetic characterization and study of the dependence of DA on ?s on these alloys originated our first international publication. Kronmülller proposes another model which emphasizes the kinetics of the processes originating such decay. We built another system which allows measurements at, higher temperatures. Measurements were made in Co67Fe4Mo1Si12B16. Irreversible contributions were eliminated by a heat treatment followed by a stabilization process. Fitting of the resulting data to the theoretical expression yields a value of ?0 ~ 10-12 s, which corresponds in order of magnitude to the inverse of Debye frequency in these materials. We conclude that both models are useful in the study of DA in amorphous and should be treated as complementary aspects of the same problem.

>Magister Scientiae - MSc / The purpose of this study was to develop a high performance-lower cost catalyst to be applied in Direct Methanol Fuel Cells (DMFC). The study also aimed to prepare plurimetallic supported platinum (Pt), platinum-ruthenium (PtRu), platinum-ruthenium-vanadium (PtRuV) and platinum ruthenium-vanadium-iron (PtRuVFe) upon multi-walled carbon nanotube (MWCNT) as well as upon multiwalled carbon nanotube-titanium oxide (MWCNT/TiO2) supports. Platinum is very active but prone to poisoning by carbon monoxide (CO), which may be present in the fuel used in fuel cells. The focus on the use of methanol was because of its better reaction kinetics, and better performance in direct methanol fuel cells (DMFC) better than proton exchange membrane fuel cell (PEMFC). When Pt is alloyed with another platinum group metals (PGM) the alloying decreases the over-potential for reactions critical in the fuel cells. Proton exchange membrane fuel cell (PEMFC) performance may be improved at low metal loading, when supported pluri-metallic catalysts are applied since the trimetallic catalysts may promote high catalyst utilisation. In practice, DMFC require electrodes with a Pt loading to achieve acceptance fuel cell (FC) power performance. The aim of this study was therefore the reduction of the catalyst loading through further improvement of mass activity of Pt based catalysts by partial substitution of the noble metal/metals, and the use of a carbon support that will provide high surface area, good electrical conductivity and high stability. MWCNT supported pluri-metallic (PtRuVFe,) and bimetallic (PtRu) nanoparticles possessed characteristic of increased surface area, improved electron transfer rate, enhance electro-catalytic activity and promoted stability.

Many technologically important alloys such as Ni base superalloys and Ti-Al base alloys benefit from the precipitation of an ordered β phase from a disordered α matrix. When the crystallographic symmetry of the β phase is a subgroup of that of the disordered α phase, the microstructure may contain multiple orientational variants of the β phase, each with its own (anisotropic, crystallographically equivalent) misfit (lattice parameter mismatch) with the matrix phase. Examples include orthorhombic precipitates in a hexagonal matrix in Ti-Al-Nb alloys, and tetragonal precipitates in a cubic matrix in ZrO2-Y2O3. We have studied two-phase microstructures containing multiple variants of the precipitate phase. In particular, we have used phase field simulations to study the effect of elastic stresses in a two dimensional system containing a disordered matrix and three different orientational variants of the precipitate phase, with a view to elucidate the effect of different levels of anisotropy in misfit. We consider a two dimensional, elastically homogeneous and isotropic model system in which the matrix (α) and precipitate (β) phases have hexagonal and rectangular symmetries, respectively, giving rise to three orientational variants of the β phase. Therefore, our phase field model has composition (c) and three order parameters (η1, η2, η3) as the field variables.Due to the difference in crystallographic symmetry, the precipitate-matrix misfit strain tensor, ε*, can be anisotropic. ε*maybe represented in its principal form as ε *= (ε xx 0 ) 0 εyy where ε xx and ε yy are the principal components of the misfit tensor. We define t= εyy/εxx as the parameter representing anisotropy in the misfit. In this thesis, we report the results of our systematic study of microstructural evolution in systems with different values of t, representing different levels of anisotropy in misfit: •Case A: t=1 (dilatational or isotropic misfit) • Case B: 0 <t<1 (principal misfit components are unequal but have the same sign) • Case C: t=0 (the principal misfit along the y direction is zero) • Case D: -1 <t<0 (principal misfit components have opposite signs and unequal magnitudes) • Case E: t= -1 (principal misfit components are equal, but with opposite signs; pure shear) In Cases D and E, there is an invariant line along which the normal misfit is zero. In Case D, this invariant line is at ±54.72◦, and in Case E, it is at ±45◦, with respect to the x-axis. Our simulations of microstructural evolution in this system are based on numerical integration of the Cahn-Hilliard and Cahn-Allen equations which govern the evolution of composition and order parameter fields, respectively. In each case, we have studied two different situations: isolated particle (single variant) and many interacting particles (multivariant). Dynamical growth shape of an isolated precipitate In systems with an isotropic misfit (Case A), the precipitate shape remains circular at all sizes. In Cases B and C, the precipitate shape is elongated along the y-axis, which is also the direction in which the magnitude of the misfit strain is lower. In all these cases, the symmetry of the particle shape remains unaltered at all sizes. In contrast, in Cases D and E, the particle shape exhibits a symmetry-breaking transition. In Case D, the precipitate elongates initially along the y direction (i.e. the direction of lower absolute misfit), before undergoing a transition in which the mirror symmetry normal to x and yaxes is lost. In Case E, the particle has an initial square-like shape (with its sides normal to the 11directions) before losing its four-fold rotation axis to become rectangle-like with its long axis along one of the the 11directions. The critical precipitate size at which the symmetry-breaking shape transition occurs is obtained using bifurcation diagrams. In both Cases D and E, the critical size for the dynamical growth shapes is larger than those for equilibrium shapes[1].This critical size is larger when the matrix supersaturation is higher or shear modulus is lower. Microstructural Evolution In all the five cases, the elastic stresses have a common effect: they lead to microstructures in which the precipitate volume fraction is lower than that in a system with no misfit. This observation is consistent with the results from the thermodynamics of stressed solids that show that a precipitate-matrix misfit increases the interfacial composition in both the matrix and the precipitate phase. In systems with isotropic misfit (Case A), the microstructure consists of isolated circular domains of the precipitate phase that retain their circular shape during growth and subsequent coarsening. In Cases B and C with anisotropic misfit with t≥0, the three orientational variants of the precipitate phase are elongated along the directions of lower misfit (y-axis and ±120◦to y-axis). At a given size, particles in Case C (in which one of the principal misfits is zero) are more elongated than those in Case B. Systems with a higher shear modulus enhance the effect of misfit stresses, and therefore, lead to thinner and longer precipitates. When the precipitate volume fraction is increased, these elongated precipitates interact with (and impinge against) one another to a greater extent, and acquire a more jagged appearance. For Cases D and E, each orientation domain is associated with an invariant line along which the normal misfit is zero. Thus, in Case D, early stage microstructures show particles elongated along directions of lower absolute misfit (y-axis and ±120°to y-axis). At the later stages, the domains of the precipitate phase tend to orient along the invariant lines; this leads some of the particles to acquire a ‘Z’ shape before they completely re-orient themselves along the invariant line. In Case E, each variant grows as a thin plate elongating along the invariant line. The growth and impingement of these thin plates leads to a microstructure exhibiting complex multi-domain patterns such as stars, wedges, triangles, and checkerboard. These patterns have been compared (and are in good agreement) with experimental observations in Ti-Al-Nb alloys containing the precipitate (O) and matrix (α2)phases[2]. Since in Case E the sum of misfit strains of the three variants is zero, elastic energy considerations point to the possibility of compact, self-accommodating clusters of the three variants, sharing antiphase boundaries (APBs). Thus, if the APB energy is sufficiently low, the microstructure may consist of such compact clusters. Our simulations with such low APB energy do show triangle shaped clusters with six separate particles (two of each variant)in a self-accommodating pattern. (Refer PDF file)

Os Aluminetos de Ferro tem, dentre muitas características predominantes, excelente resistência à corrosão a altas temperaturas devido à formação de uma camada protetora de alumina que favorece a sua aplicação em ambientes agressivos. Este trabalho tem por objetivo estudar a produção de ligas a partir de matéria-prima reciclada e a cinética de oxidação em alta temperatura de 800 graus Celsius a 1100 graus Celsius em forno mufla sem atmosfera protetora com tempo de permanência no forno de 10, 50, 100 e 200h. As ligas estudadas se baseiam na composição básica Fe30Al6Cr (os números representam a fração molar dos componentes). Duas ligas, nomeadas (A) e (B), foram obtidas seguindo a mesma rota de processamento, porém, diferenciando os cadinhos de fundição o que resultou em concentrações de carbono diferentes e conseqüente diferença na fração volumétrica de carbonetos. As ligas foram analisadas através de difração de Raio X para determinação das fases presentes e microscopia eletrônica de varredura para caracterização microestrutural. Foram também, submetidas ao ensaio de solubilização por 10 horas a uma temperatura de 1200 graus Celsius e precipitação a 800 graus Celsius por 10 min para determinação da evolução microestrutural. O resultados das análises de microdureza Vickers no material em estados bruto de fusão e tratado termicamente serviram para caracterizar os carbonetos presentes, bem como a resistência intrínseca da matriz. Os resultados do ensaio de oxidação realizado em 16 amostras de cada liga são apresentados sob forma de curvas de ganho de massa por unidade de área, (deltam/S), versus tempo de oxidação, (t). A avaliação feita das curvas dos gráficos não foi suficiente para determinar à cinética de formação de óxidos. / Iron aluminides have, among many outstanding characteristics, excellent resistance to high temperature oxidation due to the formation of a protective alumina layer which favors its use in harsh environments. This work aims at producing iron aluminides-based alloy using only recycled raw material and characterizing the results of studies of oxidation kinetic at high temperatures of 800 Celsius to 1100 Celsius in muffle furnace without protective atmosphere with residence time in oven 10, 50, 100 and 200h. The investigated alloy are based on the nominal composition Fe30Al6Cr (The numbers refer to the molar fraction of alloys elementes). Two alloys, namely (A) and (B), were obtained following the same processing route using, however, different crucibles which resulted in different carbon concentrations and consequently in different carbide volume fractions. The alloys were analyzed by X-ray diffraction to determine the phases and scanning electron microscopy for microstructural characterization. Sample taken from both alloys were also subjected to solubilization for 10 hours at 1200 Celsius and precipitation at 800 Celsius for 10 min to determine the microstructural evolution. The analytical results of Vickers microhardness of the material both in the as cast state as well as in the heat treated states were used to characterize the carbides and matrix mechanical properties. Oxidation results carried out in 16 samples of each alloy are presented in the form of mass gain per unit area (deltam / S) versus oxidation time (t) curves. The evaluation of the graphics curves used to observe the linear behavior was not enough to determine the oxidation kinetics law.

Neste trabalho foram estudados os efeitos do tratamento térmico e da adição de zircônio, vanádio, titânio e manganês nas propriedades mecânicas em alta temperatura de uma liga AlSi12CuMgNi, comumente utilizada em pistões automotivos. Os resultados de tração a 300°C mostram que a adição de elementos de liga reduz o alongamento sem aumentar o limite de escoamento. Os ensaios de fadiga a 300°C mostram que a aplicação de um tratamento de solubilização a 525°C por 15 minutos é duas vezes melhor que a aplicação de um tratamento de solubilização a 500°C por uma hora. Estes resultados foram atribuídos ao arredondamento das partículas de silício que, por serem partículas frágeis, quando arredondadas ocupam menor área por volume, reduzindo a velocidade de propagação de trincas. Os ensaios de fadiga a 300°C mostram também que a adição de elementos de liga combinados a um tratamento de solubilização a 525°C por 15 minutos é cerca de 30% pior que o mesmo tratamento aplicado a uma liga sem a adição destes elementos de liga. Este fenômeno foi atribuído à fragilização dos intermetálicos que, por consequência, aumentam a velocidade de propagação das trincas de fadiga. / The effects of heat treatment and the addition of zirconium, vanadium, titanium and manganese on the high temperature properties of an AlSi12CuMgSi alloy, usually applied to cast automotive pistons, were studied. The tensile test results at 300°C show that the addition of alloying elements decreases the elongation without significantly increasing the yield strength. The fatigue tests at 300°C show that a solution heat treatment at 525°C for 15 minutes is two times better than a solution heat treatment at 500°C for one hour. These results are due to the spheroidization of the silicone particles that are brittle and, when spheroidized, have a smaller area/volume ratio, slowing the crack propagation speed. The fatigue tests at 300°C also show that the addition of alloying elements combined with a solutionizing treatment at 525°C for 15 minutes is 30% worse than the same treatment applied to an alloy without these alloying elements. This behavior is due to the embrittlement of the intermetallic particles containing these alloying elements, increasing the fatigue crack propagation speed.

>Magister Scientiae - MSc / In the past few decades, the studies of f-electron materials have revealed unusual physical properties such as Fermi-liquid, non-Fermi-liquid behaviour at low temperatures, heavy- Fermion behaviour, valence fluctuation, Kondo effect, superconducting and magnetic ordering. These materials include binary and ternary compounds and alloys with Cerium (Ce) or Ytterbium (Yb) based rare earth elements or Uranium (U) based actinide element. In these systems the localized magnetic moments formed by Ce, Yb or U ions transform the electronic properties of these compounds leading to quasiparticles with masses in excess to 1000 times the bare electron mass. These materials are known as heavy-fermion materials. Two well known heavy – Fermion compounds with Ce based rare earth elements of interest in this thesis are CePt₂Si₂ and CeCu₅In. The effect of substituting Ce with moment bearing Tb or Dy in these two compounds, are reported through measurements of electrical resistivity, magnetic susceptibility and magnetization. The three alloy systems (Ce₁₋ₓREₓ)Pt₂Si₂ (RE = Tb, Dy) and (Ce₁₋ₓTbᵪ)Cu₅In under investigation in the present thesis, was synthesized and characterized by x-ray diffraction. The alloy systems (Ce₁₋ₓREₓ)Pt₂Si₂ (RE = Tb, Dy, 0≤ ᵡ ≤1) formed a single phase in the P4/nmm tetragonal CaBe₂Ge₂ – type structure across the whole series while the (Ce₁₋ₓTbᵪ)Cu₅In alloy system formed a single phase in the Pnma orthorhombic CeCu₆ – type crystal structure up to 40% Ce substitution. The physical properties of these systems is reported and discussed through the measurements of electrical resistivity, magnetic susceptibility and magnetization. The variables of this study are: the doping concentration of Tb or Dy, the applied magnetic field and the sample temperature. Electrical resistivity studies for all the systems revealed coherence effect at Ce – rich alloys (0≤ ᵡ ≤0.2) and single-ion Kondo scattering with further increased RE concentration ( ᵡ ≥ 0.3). The magnetic property studies indicate antiferromagnetic ordering only for the (Ce₁₋ₓREₓ)Pt₂Si₂ alloy system in the concentration range 0.7≤ ᵡ ≤ 1. The present thesis is comprised of six chapters, which are arranged as follows: The first chapter deals with the theoretical background of the physical properties of Ce based intermetallics compounds and alloys. Experimental techniques constitutes chapter II and explains the techniques used in this study. The theoretical overview of the two parent compounds of interest in this thesis (CePt₂Si₂ and CeCu₅In) is presented in chapter III. The fourth and the fifth chapters of this study deals with results and discussion. The thesis is completed with a conclusion in chapter six.

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Please read the abstract in the section 00front of this document / Dissertation (M Eng (Metallurgical Engineering))--University of Pretoria, 2005. / Materials Science and Metallurgical Engineering / unrestricted

Strand et al. (2002) discovered small metal alloy grains rich in Cu, Co, and Sn (maximum size 150 µm) in vesicles of lava from Kilauea Volcano. These alloys are also found in basaltic rocks of several Italian volcanoes. To better understand the origin of these metal-rich grains, bombs from Stromboli Volcano were examined. Two bomb types were collected from Stromboli: pumiceous bombs and scoriaceous bombs. Bulk rock trace element geochemistry indicates that there are no significant differences in Cu, Co, or Sn (the three major components of the metal alloys) between the pumiceous and scoriaceous bombs. Comparison of olivine melt inclusion and matrix glass concentrations from these rocks shows that the pumiceous bombs are more primitive (melt inclusions: MgO 2.7-5.8 wt. %; matrix glass: MgO 5.1-6.50 wt. %) and are more S-rich (melt inclusions: maximum 0.13 wt. %; matrix glass: maximum 0.06 wt. % ) than the scoriaceous bombs. The melt inclusions and matrix glass in the scoriaceous bombs are more evolved (melt inclusions: MgO 3.0-4.3 wt. %; matrix glass: MgO 2.7-3.7 wt. %) and are S-poor (melt inclusions: maximum 0.06 wt. %; matrix glass: b.d.l. ). However, Cl concentrations in melt inclusions and matrix glass are more similar for both bomb types. Metal alloys were counted in thin section for each sample. The crystallized interiors of the bombs contain more metal grains than the glassy exteriors. Pumiceous bombs (from more primitive, S-rich magma) contain more metal grains of a larger size than the scoriaceous bombs (from more fractionated, S-poor magma). This indicates that S (and Cl) are probable transport ligands for the metals in the alloys. As S (and Cl) move through the glass of an erupted cooling bomb, they complex with volatile chalcophile metals (Cu, Co, and Sn). These vapor-phase metal sulfides and chlorides move to inflating vesicles. Here the sulfide and chloride complexes become reduced and metal alloys condense, as S and Cl escape as gas. Non-degassed primitive magma may provide more S (but not necessarily more metals) to create the higher abundance of alloys hosted by the vesicles of the pumiceous bombs.