No description available.

No description available.

No description available.

No description available.

Cette étude s’inscrit dans le cadre du projet européen IMPRESS, "Intermetallic Materials Processing in Relation to Earth and Space Solidification". Elle porte sur la compréhension des mécanismes fondamentaux qui contrôlent la solidification de l’alliage Ti-46Al-8Nb envisagés pour le développement d’aubes de turbines. La première partie de cette étude caractérise l’influence de l’oxygène sur le comportement à la solidification d’alliages de base TiAl coulés et contenant de 40 a 48 at.% d’aluminium. L’addition d’oxygène augmente la fraction volumique de phase [alpha] formée pendant la solidification péritectique et conduit au changement de la phase primaire de solidification de la phase [bêta] à la phase [alpha] dans les alliages ternaires Ti-44,3Al-1,5O, Ti-47,7Al-0,8O et Ti-47,3Al-1,5O (at.%). Les coefficients de partage pour l’aluminium et l’oxygène kAl[alpha]/l= 0,9 et kO[alpha]/l = 1,29, ont été déterminés pour l’alliage ayant [alpha] comme phase primaire de solidification. Dans un deuxième temps, l’étude du comportement à la solidification de l’alliage Ti-46Al-8Nb, est décrite en portant une attention particulière sur les effets de la contamination et des conditions de croissance sur la formation des microstructures et des microségrégations. Deux comportements différents ont été mis en évidence : dans la phase primaire de solidification [alpha] rencontrée pour des hauts niveaux de contamination en oxygène, une très faible rétrodiffusion est observée. Pour de faibles quantités d’oxygène, la phase primaire de solidification est la phase [bêta]. Dans ce cas la présence d’oxygène induit une augmentation de l’amplitude de ségrégation malgré une forte rétrodiffusion dans la structure cubique centrée / This study was performed in the framework of the IMPRESS, "Intermetallic Materials Processing in Relation to Earth and Space Solidification", and is dedicated to the understanding of the fundamental mechanisms that control solidification in a Ti-46Al-8Nb alloy selected for TiAl-based alloy turbine blade development. The first part of this work is devoted to study the influence of oxygen on the solidification behaviour of cast TiAl-based alloys containing from 40 to 48 at.% of Al. Increasing the oxygen content affects significantly the macrostructure of the as-cast ingots, increases volume fraction of the phase formed during the peritectic solidification and leads to a change of the [bêta] primary solidification phase to the [alpha] phase in the ternary Ti-44.2Al-1.4O, Ti-47.3Al-0.9O and Ti-47.2Al-1.5O (at.%) alloys. When [alpha] is the primary solidification phase, the partition coefficients has been determined as kAl[alpha]/l= 0,9 and kO(alpha]/l = 1,29. In a second part, the solidification behaviour of Ti-46Al-8Nb alloy is investigated, with a particular attention to the contamination and growth conditions effects on microstructures and microsegregation formations. For high contamination levels, the solidification phase is [alpha] where oxygen reduces solute mobility, leading to limited backdiffusion. In low oxygen containing alloys, [bêta] is the primary solidification phase, and oxygen leads to an extent of the segregation amplitude despite high level of back-diffusion in the bcc structure

Orientador: Fernando Luis Fertonani / Resumo: Neste trabalho voltametria cíclica, análise térmica (TG/DTG), e análise de superfície (Microanálise por EDX, mapeamento dos elementos, obtenção das imagens SEM e XRD), foram utilizadas para o estudo das reações em estado sólido entre a liga de composição Pt-Rh 80:20%(m/m) e o Hg. A partir das técnicas de voltametria cíclica e termogravimetria-termogravimetria derivada (TG/DTG), foi possível evidenciar o ataque efetivo do Hg sobre o substrato, e ainda, a formação de compostos de caráter covalente, do tipo: PtHg, PtHg2, RhHg2 e PtHg4, caracterizados através da técnica de difratometria de Raios X (XRD). As análises de superfície, permitiram revelar, a presença de um filme de intermetálicos sobre a superfície do substrato, e uma distribuição homogênea do Hg sobre a superfície do substrato. O sistema Pt-Rh 80:20%(m/m)-Hg apresentou um comportamento térmico (TG) e eletroquímico (VC), similar ao sistema Pt-Rh 85:15%(m/m)-Hg, e também apresentou um ataque considerável ao substrato quando comparado à liga de Pt-Rh 70:30%, esta, por sua vez, não apresenta a formação do intermetálico PtHg4. Desta forma, o comportamento observado para o sistema Pt-Rh 80:20% (m/m)- Hg, apresenta reatividade intermediária aos sistemas Pt-Rh 85:15%(m/m)-Hg e Pt- Rh 70:30%(m/m)-Hg, devido ao teor do elemento modificador, Rh, na matriz de Pt, como o esperado. / Abstract: In this work, ciclic voltametry, thermal analysis (TG/DTG), and analysis of surface (EDX Microanalysis, Mapping, and XRD), were utilized for the study of the reactions in solid state between the Pt-Rh 80:20% alloy and the Hg. The CV and TG showed an effective Hg attack on the alloy, and the formation of covalent compounds such as PtHg, PtHg2, RhHg2 and PtHg4, characterized by XRD technique. From the techniques of ciclic voltametry and termogravimetry-derived termogravimetry (TG/DTG), was possible show up an effective Hg attack on the alloy, and the covalent compounds formation as PtHg, PtHg2, RhHg2 and PtHg4, characterized by X-Rays Difratometry (XRD). The surface analysis showed an intermetallic film on the alloy surface, and the Hg homogeneous distribution on the surface. The Pt-Rh 80:20%(m/m)-Hg system presented an eletrochemical (VC) and thermal behavior (TG), similar to Pt-Rh 85:15%(m/m)-Hg system, and presented also a considerable Hg attack to the alloy when compared to the Pt-Rh 70:30% alloy, this system, doesn't present the intermetallic PtHg4 formation. In this way, the behavior observed for the system Pt-Rh 80:20% (m/m)-Hg, presents an intermediate reactivity to the systems Pt-Rh 85:15%(m/m)-Hg and Pt-Rh 70:30%(m/m)-Hg, due to the content of the modificator element, Rh, in the matrix of Pt, as him expected. Keywords: intermetallic compounds; platinum; rhodium; mercury. / Mestre

Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 1980. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Includes bibliographical references. / by Pierre Leon Jacques Chemelle. / M.S.

Dissimilar metal joining was performed with the main goal being maximization of the strength of the joined samples, but because of some potential applications of the dissimilar joints, analyzing their corrosion behavior also becomes crucial. Starting with materials that initially have suitable corrosion resistance, ensuring that the laser processing does not diminish this property is necessary. Conversely, the laser shock peening processing was implemented with a complete focus on improving the corrosion behavior of the workpiece. Thus, many commonalities occur between these two manufacturing processes, and this thesis goes on to analyze the thermal and mechanical influence of laser processing on materials’ corrosion resistances. Brittle intermetallic phases can form at the interfaces of dissimilar metal joints. A process called autogenous laser brazing has been explored as a method to minimize the brittle intermetallic formation and therefore increase the fracture strength of joints. In particular, joining of nickel titanium to stainless steel wires is performed with a cup/cone interfacial geometry. This geometry provides beneficial mechanical effects at the interface to increase the fracture strength and also enables high-speed rotation of the wires during irradiation, providing temperature uniformity throughout the depth of the wires. Energy dispersive X-ray spectroscopy, tensile testing, and a numerical thermal modelling are used for the analysis. The material pair of nickel titanium and stainless steel have many applications in implantable medical devices, owing to nickel titanium’s special properties of shape memory and superelasticity. In order for an implantable medical device to be used in the body, it must be ensured that upon exposure to body fluid it does not corrode in harmful ways. The effect that laser autogenous brazing has on the biocompatibility of dissimilar joined nickel titanium to stainless steel samples is thus explored. While initially both of these materials are considered to be biocompatible on their own, the laser treatment may change much of the behavior. Thermally induced changes in the oxide layers, grain refinement, and galvanic effects all influence the biocompatibility. Nickel release rate, polarization, hemolysis, and cytotoxicity tests are used to help quantify the changes and ascertain the biocompatibility of the joints. To directly exert a beneficial influence on materials’ corrosion properties laser shock peening (LSP) is performed, with a particular focus on the stress corrosion cracking (SCC) behavior. Resulting from the combination of an applied load on a susceptible material exposed to a corrosive environment, SCC can cause sudden material failure. Stainless steel, high strength steel, and brass are subjected to LSP and their differing corrosion responses are determined via cathodic charging, hardness, mechanical U-bend, Kelvin Probe Force Microscopy, and SEM imaging. A description accounting for the differing behavior of each material is provided as well as considerations for improving the effectiveness of the process. SCC can occur by several different physical processes, and to fully encapsulate the ways in which LSP provides mitigation, the interaction of microstructure changes induced by LSP on SCC mechanisms is determined. Hydrogen absorbed from the corrosive environment can cause phase changes to the material. Cathodic charging and subsequent X-ray diffraction is used to analyze the phase change of sample with and without LSP processing. Lattice dislocations play an important role, and transmission electron microscopy helps to aid in the analysis. A finite element model providing spatially resolved dislocation densities from LSP processing is performed.

Two different aluminium alloys, AA6111 (Al-Mg-Si) and AA7055 (Al-Mg-Zn), were chosen as the aluminium alloys to be welded with DC04, and two welding methods (USW and FSSW) were selected to prepare the welds. Selected pre-welded joints were then annealed at T=400 - 570oC for different times. Kinetics growth data was collected from the microstructure results, and the growth behaviour of the IMC layer was found to fit the parabolic growth law. A grain growth model was built to predict the grain size as a function of annealing time. A double-IMC phase diffusion model was applied, together with grain growth model, to predict the thickness of each phase as a function of annealing time in the diffusion process during heat treatment. In both material combinations and with both welding processes a similar sequence of IMC phase formation was observed during the solid state welding. η-Fe2Al5 was found to be the first IMC phase to nucleate. The IMC islands then spread to form a continuous layer in both material combinations. With longer welding times a second IMC phase, θ-FeAl3, was seen to develop on the aluminium side of the joints. Higher fracture energy was received in the DC04-AA6111 joints than in the DC04-AA7055 joints. Two reasons were claimed according to the microstructure in the two joints. The thicker IMC layers were observed in the DC04-AA7055 joints either before or after heat treatment, due to the faster growth rate of the θ phase. In addition, pores were left in the aluminium side near the interface as a result of the low melting point of AA7055.The modelling results for both the diffusion model and grain growth model fitted very well with the data from the static heat treatment. Grain growth occurred in both phases in the heat treatment significantly, and was found to affect the calculated activation energy by the grain boundary diffusion. At lower temperatures in the phases with a smaller grain size, the grain boundary diffusion had a more significant influence on the growth rate of the IMC phases. The activation energies for the grain boundary diffusion and lattice diffusion were calculated as 240 kJ/mol and 120 kJ/mol for the η phase, and 220 kJ/mol and 110 kJ/mol for the θ phase, respectively. The model was invalid for the growth of the discontinuous IMC layers in USW process. The diffusion model only worked for 1-Dimensional growth of a continuous layer, which was the growth behaviour of the IMC layer during heat treatment. However, due to the highly transient conditions in USW process, the IMC phases were not continuous and uniform even after a welding time of 2 seconds. Therefore, the growth of the island shaped IMC particles in USW was difficult to be predicted, unless the nucleation stage was taken into consideration.

Orientador: Pascoal José Giglio Pagliuso / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-09-24T15:46:53Z (GMT). No. of bitstreams: 1 Adriano_Cris_D.pdf: 6784336 bytes, checksum: d7c200af40255398764228130bc8b93d (MD5) Previous issue date: 2009 / Resumo: Este trabalho apresenta estudos sistemáticos das propriedades magnéticas dos compostos Ce2MIn8 (M = Rh, Ir) dopados com Cd, Sn e Ga no sítio cristalográfico do In. Foram utilizadas as técnicas de medidas macroscópicas de susceptibilidade magnética, calor específico e resistividade elétrica, além de medidas de caracterização estrutural pelo método de difração de pó de raios-x e medidas microscópicas da determinação da estrutura magnética usando a técnica de espalhamento magnético de raios-x e nêutrons para os compostos dopados com Cd. Os compostos Ce2MIn8 (chamados de 218) são tetragonais (grupo espacial P4/mmm) e são a versão bi-camada da família de férmions pesados supercondutores Cem MnIn3m+2n(M = Co, Rh, Ir; m = 1,2; n = 0,1), na qual os compostos do tipo CeMIn5 (chamados de 115) foram muito estudados por apresentarem uma variedade de propriedades físicas interessantes, tais como efeito Kondo, supercondutividade não convencional, ordenamento magnético, comportamento non-Fermi-Liquid, e ocorrência de pontos críticos quânticos. Mais interessante ainda é o fato de que estas propriedades podem ser controladas por dopagem, pressão externa e/ou campo magnético gerando diagramas de fases bastante interessantes. O objetivo de se estudar os parentes Ce2MIn8 é entender o papel da dimensionalidade nas propriedades físicas destes compostos e comparar os resultados encontrados com aqueles observados para os 115. Foram construídos os diagramas de fase inéditos para as séries de Ce2RhIn8-xCdx, Ce2IrIn8-xCdx, C e2Rh0.5Ir0.5In8-xC dx, Ce2RhIn8-xSnx e Ce2RhIn8-xGax a partir de dados obtidos utilizando as técnicas mencionadas acima. Foi visto que a dopagem de Cd nos compostos Ce2MIn8 favorece o AFM através do aumento da TN em função da concentração de Cd. Os resultados sugerem que o Cd está agindo de modo a diminuir a densidade de carga local e isso está favorecendo o ordenamento magnético. Porém, resultados da variação da temperatura do máximo da resistividade elétrica em função da concentração de Cd, sugerem que efeitos de campo cristalino também estão presentes nestes compostos. A estrutura magnética dos compostos de Ce2RhIn8-xCdx e C e2IrIn8-xCdx dopados com x = 2.6 % de Cd foram estudados em baixas-T e encontrou-se um vetor de propagação do tipo (½ ½ 0) consistente com ordenamento AFM abaixo de TN. Verificou-se que a orientação do momento magnético tende a ir na direção do plano-ab com dopagem de Cd nestes compostos. A substituição de In por Sn nos compostos de Ce2MIn8 mostrou que esta dopagem está desfavorecendo o ordenamento magnético através da diminuição do valor da TN em função da concentração de Sn. Os resultados sugerem que o Sn está favorecendo o efeito Kondo e que efeitos de campo cristalino são menos observáveis nos compostos dopados com Sn. Foi visto que a dopagem com Ga no sítio do In igualmente diminui a temperatura de ordenamento magnético e favorece o efeito Kondo. Porém, os resultados sugerem que efeitos de campo cristalino estão presentes pela variação não usual da temperatura do máximo das curvas de resistividade elétrica em função da dopagem com Ga. Neste trabalho também são apresentados estudos da evolução do magnetismo dos elétrons 4f, em compostos relacionados que não são férmions pesados para R2CoGa8, para R = Gd, Tb, Dy, Ho, Er e Tm. Nestes compostos podemos observar a evolução do magnetismo e dos efeitos de campo cristalino sem a presença do efeito Kondo / Abstract: This thesis describes the investigation of the physical properties of the (Cd, Sn, Ga)-doped Ce2MIn8 (M = Rh, Ir) intermetallic compounds. Temperature dependent magnetic susceptibility, heat capacity and electrical resistivity measurements were performed to characterize the macroscopic properties of the synthesized compounds. X-ray powder diffraction were used to determine their phase purity and crystal structure and X-ray and neutron magnetic scattering techniques were used to study the microscopic magnetic structure in low temperature. The Ce2MIn8 (M = Rh, Ir) compounds belong to the family of the heavy-fermions Ce-based compounds CenMIn3n+2 (M = Co, Rh, Ir; n = 1, 2), where the occurrence of unconventional superconductivity (USC) in many of its members has been motivating intense work in past few years. In particular these compounds present a wide range of interesting properties as Kondo effect, USC, magnetism, non Fermi liquid and Fermi liquid behavior and the occurrence of quantum critical points. Particularly interesting is the tunability of their ground state by pressure and chemical doping that revealed very interesting and rich phase diagrams with properties that are unprecedented for this class of compounds. Indeed the study of the 218 parent compounds is a great opportunity to further study the relationship between magnetism, USC and crystal structure in this family. We report in this work five unpublished phase diagrams of this family: Ce2RhIn8-xCdx, Ce2IrIn8-xCdx, Ce2Rh0.5Ir0.5 In8-xCdx, Ce2RhIn8-xSnx e Ce2RhIn8-xGax. Our results revealed that Cd-doping Ce2MIn8 enhances the antiferromagnetic ordering temperature as a function of the Cd concentration. The results suggest that the Cd-doping in these compounds is inducing an electronic tuning by locally decreasing the Ce 3+ density of states and this is favoring the AFM ordering according com a Doniach-like scenario. However the evolution of the maximum in the resistivity as a function of the Cd concentration and the small variation of the magnetic moment orientation of the doped compounds suggest that Cd-doping is also changing the crystal field (CEF) parameters in these compounds. The magnetic structure studied by X-ray and neutron magnetic scattering showed the Cd-doped samples present just below TN a commensurate antiferromagnetic structure with a propagation vector (½ ½ 0). The magnetic structure determination indicates that the magnetic moment orientation of the Cd doped samples tend going to the ab-plane. The Sn chemical substitution in Ce2MI n8 (M = Rh, Ir) showed Sn-doping is decreasing the magnetic order by favoring the Kondo effect. This is the opposite of the Cd-doping effect because Sn is now increasing the local density of states of the Ce3+ions. As Sn-doping drives 4f to a more itinerant character the CEF effect are less important for this compounds. On the other hand, the Ga-doped Ce2RhI n8 similarly show a decreasing of the magnetic order due to the enhancement of the Kondo effect by chemical pressure. However the unexpected evolution of the maximum in the resistivity as a function of the Ga suggests in this dopant is changing the crystal field is still an important effect in this compound. Finally we present the 4f magnetism evolution studies on the series of the Ga-based R2CoGa8 for R = Gd ¿ Tm compounds, where one can follow the evolution of the magnetism and the CEF parameters without the presence of the Kondo effect / Doutorado / Física da Matéria Condensada / Doutor em Ciências