Deux nouveaux alliages à base de TiAl (le Ti-46Al-8Nb et le Ti-46Al-8Ta) développés dans le cadre du projet européen IMPRESS pour des applications dans les turbines aéronautiques de Rolls Royce plc. ont été étudiés au cours de ce travail de thèse. Ils ont été caractérisés du point de vue de leur microstructure, leur résistance à l'oxydation et leurs propriétés mécaniques en traction. La microstructure dite convolutée mise en œuvre lors des traitements thermiques effectués par différents partenaires du projet a été caractérisée par microscopie optique, microscopie électronique à balayage et en transmission. A la différence de la microstructure lamellaire classique dont les lamelles d'un même grain sont orientées dans la même direction, les grains convolutés possèdent plusieurs orientations des colonies de lamelles. Ces orientations multiples ont été attribuées aux orientations possibles des plans de la phase gamma (obtenue après transformation massive) sur lesquelles la phase a2 est susceptible de précipiter et de croître. Le comportement à l'oxydation isotherme de ces alliages a été étudié à 700°C sous air et il a été montré que les cinétiques d'oxydation de l'alliage au Nb sont inférieures à celles de l'alliage au tantale, traduisant ainsi le fait que le Nb confère d'avantage plus de résistance à l'oxydation que le Ta. La structure de la couche d'oxyde au bout de 50 h est faite de deux sous-couches dans le cas de l'alliage au Nb : une sous-couche externe riche en alumine amorphe et une sous-couche interne constituée d'alumine amorphe renfermant de nombreuses petites cristallites de rutile. Dans le cas de l'alliage au tantale, la couche d'oxyde après 50 h d'oxydation est constituée d'une monocouche d'oxyde amorphe riche en aluminium renfermant des cristallites de rutile. L'alliage au Nb présente 2 sous couches : une sous couche externe d'oxyde amorphe riche en aluminium et une sous couche interne d'oxyde amorphe renfermant des cristallites de rutile. Au bout de 1000 h d'oxydation, la composition et la structure des couches d'oxyde ont complètement changé. L'oxyde est complètement cristallisé et se présente sous forme de deux sous-couches dans le cas de l'alliage au Nb. Une sous-couche externe d'alumine gamma et une sous-couche interne de rutile. Quant à l'alliage au tantale, l'on a 3 ou 4 sous couches selon que l'oxyde se soit formé à partir des lamelles de la phase g ou de la phase a2. La sous-couche externe reste continue et uniforme, et est constituée par de l'alumine gamma. En suite l'on a une sous-couche également continue de rutile. Les deux sous-couches se mélangent sur une épaisseur d'environ 20 à 30 nm et forment ainsi une zone d'oxydes mixtes de rutile et d'alumine. Cette sous-couche d'oxydes mixte se prolonge jusqu'à l'interface dans le cas de l'oxydation des lamelles de la phase gamma. En revanche, dans le cas de l'oxydation des lamelles de la phase a2, une quatrième couche de rutile est présente en dessous de la couche d'oxyde mixte. Dans tous les cas, l'interface entre l'oxyde et le substrat est faite d'une couche continue de nitrures de titane après 1000 h d'oxydation. Ces nitrures sont très localisés après les temps d'oxydation courts (50 h). L'influence de la température et de la vitesse de déformation sur les propriétés mécaniques en traction a été étudiée, et il a été relevé que plusieurs modes de rupture présents dans la plage de température étudiée (25-900°C). Pour la vitesse de 10-4s-1, en dessous de 750°C la rupture est fragile et à partir de 800°C elle est ductile. Le domaine de transition ductile fragile a été donc établi entre 750 et 800°C pour cette gamme de vitesse de déformation. A vitesse de déformation plus faible (10-5s-1), les ductilités obtenues sont accrues et l'on atteint près de 1% de déformation à température ambiante. Les essais de fragilisation de l'alliage au Ta ont été réalisés par des essais de fluage interrompus et des recuits à 700°C sous différents environnements, suivis de la traction à froid. Il a été montré qu'indépendant du pré-traitement subi, la déformation plastique est complètement perdue. Cette perte de ductilité a été attribuée à la formation des précipités riches en Ta présents aux joints de grains et aux joints de lamelles des deux phases en présence. Lesdits précipités se forment par décomposition de la phase a2 et du rejet du Ta aux joints de grains et aux interfaces inter-lamellaires lors du maintient à 700°C. / This study was performed within the frame-work of the European integrated IMPRESS project and two different new TiAl based alloys (namely Ti-46Al-8Nb and Ti-46Al-8Ta) were studied as potential materials for applications in low pressure turbine blades. They were characterized in terms of their microstructure, their oxidation resistance at service temperature (namely 700°C) and their tensile properties. The so-called convoluted microstructure (obtained during heat treatments performed by different project partners) has been characterized by optical microscopy, scanning electron microscopy and transmission electron microscopy. Unlike the classical lamellar microstructure in which the lamellae of a given grain are oriented in the same direction, the convoluted microstructure shows different orientations of lamellae colonies and these were attributed to the possible orientations of the (111) planes of the “gamma phase” (g-TiAl) obtained after massive transformation, on which the basal plane of the « alpha 2 phase” (a2-Ti3Al) is likely to precipitate and grow during heat treatments. Isothermal oxidation of these alloys was studied in air at 700°C and it was shown that the oxidation kinetics of the Nb-alloy is lower compared to that of the Ta-alloy, suggesting that niobium provides greater oxidation resistance compared to tantalum. The structure of the oxide layer after 50 h oxidation is made of two sub-layers in the case of the Nb-alloy, with an outer amorphous aluminum enriched oxide layer and an inner sub-layer made of amorphous aluminum enriched oxide containing many small crystallites of rutile. In the case of the Ta-alloy, after the same oxidation period of time, the oxide layer is made of a unique amorphous aluminum enriched oxide layer containing crystallites of rutile. After 1000 h of oxidation, the composition and structure of the oxide have completely changed. The oxide layer is now completely crystallized and is made of two sub-layers in the case of the niobium alloy, with an outermost gamma alumina (g-Al2O3) layer and an inner layer made exclusively of rutile (TiO2) crystallites. As for the alloy with tantalum, 3 or 4 sub-layers could be found depending on the initial phase of the substrate (g or a2) from which the oxide is formed. The same as for the previous alloy, the two external sub-layers are continuous with an outermost uniform g-Al2O3 and an inner sub-layer made of rutile crystallites. These two sub-layers are interconnected within a 20 to 30 nm thick sub-layer made of mixed oxides of gamma alumina and rutile. This sub-layer of mixed oxides extends to the interface with the substrate in front of “gamma phase” lamellae. When the oxidized lamellae are the ones of the “alpha 2 phase”, a fourth sub-layer of rutile is present below the mixed oxide layer. For the two alloys, a continuous layer of titanium nitride (TiN) is present at the interface between the oxide and substrate after 1000 h oxidation, while isolated nitrides are observed at the interface after shorter oxidation time (50 h). The influence of temperature and strain rate on tensile properties was investigated, and it was noted that within the temperature domain explored (25-900°C), several failure modes occur with increasing temperature. For a strain rate of 10-4s-1 the failure mode is brittle below 750°C and is ductile above 800°C. The brittle to ductile transition domain was then established between 750 and 800°C for this strain rate. At much lower strain rate (10-5s-1), the ductility increases significantly and reaches nearly 1% strain at room temperature. Embrittlement testing of the alloy with tantalum was also performed by doing interrupted creep tests and pre-annealed tests under different environments at 700°C. These tests where then followed by straining the samples to failure at room temperature. Regardless of pre-treatment, all the tested samples show a total loose of their ductility and the tensile tests resulted in their early failure in the elastic domain. This loose of ductility was attributed to the formation of tantalum enriched precipitates which are present at grain boundaries and also at the interface between the lamellae of the different phases of the substrate. Such precipitates are formed by decomposition of the "alpha 2 phase" and the rejection of tantalum at grain boundaries and at inter-lamellar interfaces during elevated temperature holding (700°C).

Estudos anteriores de precipitação, em outros aços superferríticos, constataram a ocorrência de precipitação das fases sigma, qui, de Laves e até de austenita, que no posterior resfriamento pode se transformar em martensita. O objetivo principal do presente trabalho foi estudar a precipitação de fases de Laves no aço inoxidável superferrítico X 1 CrNiMoNb 28 4 2 (Werkstoff-Nr. 1.4575). Para isto foram utilizadas algumas técnicas complementares de análise microestrutural, tais como microscopia óptica, eletrônica de varredura (MEV) e eletrônica de transmissão (MET). A composição química das fases foi estudada por análise de raios X por dispersão de energia tanto no MEV como no MET. A estrutura cristalina das fases foi estudada por difração de elétrons em área selecionada no MET. A fase que se precipita em maior quantidade no aço 1.4575 é a fase sigma. No entanto, também foram identificadas de maneira inequívoca, nos contornos de grãos, após envelhecimento a 850 ºC, pequenas quantidades de fase de Laves do tipo MgZn2, com estrutura hexagonal compacta e composição química (Fe,Cr,Ni)2(Nb,Mo,Si). O crescimento da fase de Laves é inibido pelo envolvimento da fase sigma, que também precipita nos contornos de grãos, mas em maior quantidade. Não foram detectadas as presenças das fases qui e austenita na temperatura estudada. / Previous precipitation studies in other superferritic stainless steels observed the occurrence of precipitations of sigma, chi and Laves phases and even of austenite, which on subsequent cooling may transform into martensite. The main objective of the present work was to study the Laves phase precipitation in a X 1 CrNiMoNb 28 4 2 (Werkstoff- Nr. 1.4575) superferritic stainless steel. Therefore, several complementary techniques have been employed such as optical microscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The chemical composition of the phases has been studied using X-ray energy dispersive analysis both in SEM and TEM. Crystal structure of the phases has been analyzed using selected area electron diffraction in the TEM. The phase that precipitates in larger quantity in the 1.4575 steel is the sigma phase. However, it has been identified, in an unequivocal manner, on grain boundaries, after aging at 850 ºC, small quantities of Laves phase of the MgZn2 type, with a compact hexagonal structure and a chemical composition of (Fe,Cr,Ni)2(Nb,Mo,Si). Growth of the Laves phases is inhibited through the involvement of the sigma phase, which precipitates in higher quantities on grain boundaries. No chi and austenite phases have been detected in the studied temperature.

Os compostos intermetálicos do tipo R IND. 6 Fe IND. 14-X Al IND. X (R = Nd, La) são antiferromagnéticos e apresentam uma transição do tipo metamagnética em campos da ordem de 2-3 Tesla. Com objetivo de caracterizar suas propriedades magnéticas, amostras policristalinas forma investigadas via medidas de magnetização, magneto-resistência, magnetostricção e difração de nêutrons. As amostras foram preparadas por meio de forno a arco e submetidas a tratamentos térmicos de 750 GRAUSC por 4 semanas. A estrutura cristalina foi identificada como sendo tetragonal do tipo La IND. 6 Co IND. 11 GA IND. 3 (grupo especial 14/mcm). Em contraste com os compostos baseados em La, as amostras de Nd apresentaram uma grande histerese magnética e um efeito dependente da história magnética na região de T<30 K, e um ordenamento dos momentos magnéticos de Nd a 70 K. As T IND. N foram determinadas por meio de medidas de suscetibilidade magnética e se encontram na região de 150-310 K e 100-230 K para os compostos de Nd e La, respectivamente. A transição metamagnética foi observada em todas as amostras analisadas, e foi observada uma variação de 3-5% da resistência elétrica no momento da transição, sugerindo uma estrutura magnética em forma de camadas magnéticas. Infelizmente através das medidas de difração de nêutrons, não foi possível determinar a estrutura magnética das amostras. Entretanto, no composto Nd IND. 6 Fe IND. 10 Al IND. 4, essas medidas nos indicaram uma mudança da estrutura espacial por meio da alteração do grupo espacial do 14/mcm para P42/mcm na região de temperatura de 70 K, onde foi observado um pico bastante saliente em nossas medidas de suscetibilidade. Por meio de medidas de espectroscopia Mössbauer não foi observado nenhum comportamento anômalo nos parâmetros hiperfinos do Fe, indicando ser esta um fenômeno isolado dos momentos do Nd. ) Um outro resultado obtido por difração de nêutrons foi a presença de uma reflexão magnética (001) que cresce na região abaixo de 30 K, indicando a existência de uma componente dos spins paralela ao plano basal. Nenhuma anomalia magnética foi observada nas amostras de La. Esse crescimento do pico (001) sugere uma tendência dos momentos do Nd a se alinharem na direção do plano basal, podendo ser esta a explicação para o efeito de irreversibilidade observado nesta região de temperatura / Rare earth-based intermetallic compounds R IND.6Fe IND.14-xAl IND.x with R=(Nd, La) are antiferromagnetic and undergo a metamagnetic transition at 2~3 T applied fields. In order to further characterize their magnetic behavior, polycrystalline samples were investigated with magnetometry, magneto resistance, magnetostriction and neutron diffraction. Samples have been prepared by arc melting under argon and annealed at 750°C for four weeks. The crystal structure is tetragonal of La IND.6Co IND.11Ga IND.3-type (space group 14/mcm). In contrast to La-based compounds, Nd IND.6Fe IND.14-xAl IND.x exhibits a large transition hysteresis and magnetic history effects at T<30 K, and antiferromagnetic ordering of Nd moments at 70 K. The T IND.N was determined by magnetic susceptibility measurements in the 150-310 K and 100-230 K range for the Nd and La compounds, respectively. The metamagnetic transition was observed for all samples and a ~3-5% resistivity drop was found to occur concomitantly, suggesting a magnetic multilayer-like structure. Unfortunately the magnetic structure of this compound could not be determined in this work by neutron diffraction. However, neutron diffraction measurements in the Nd IND.6Fe IND.10Al IND.4 compound revealed a change of space group from 14/mcm to P4 IND.2/mcm at 70 K, where the magnetic susceptibility exhibits a sharp peak. Mossbauer spectroscopy measured in the 4.2-100 K range has shown no evidence of Fe spin rotation, suggesting an isolated Nd phenomenon. Another result from neutron diffraction measurements was the presence of a magnetic (001) reflection that grows below 30 K, indicating the development of a spin component parallel to the basal plane. No such effect was observed with La-based samples. This increase is likely to be due to a canting of Nd moments towards the basal plane. The coincidence of this effect with the onset temperature for irreversible behavior in magnetic measurements is consistent with this interpretation.

A auto-organização é uma das principais características de sistemas naturais. Os fenômenos auto-organizados podem emergir em sistemas suficientemente afastados do equilíbrio termodinâmico. A não-linearidade intrínseca aos sistemas eletroquímicos, permite inúmeros exemplos de comportamento complexo, sendo, grande parte, em eletrocatálise. Apesar do considerável progresso no entendimento dos aspectos mecanísticos da eletro-oxidação oscilatória de moléculas orgânicas pequenas, aparentemente não existe nenhum estudo sistemático do impacto de modificadores superficiais na dinâmica oscilatória. Nesta tese de doutorado, a eletro-oxidação oscilatória do ácido fórmico em bimetálicos de platina, com estanho ou bismuto, é comparada com aquela obtida em platina policristalina. A modificação da superfície afeta drasticamente a dinâmica oscilatória. As oscilações auto-organizadas de potencial foram usadas como sonda para a atividade eletrocatalítica dos eletrodos bimetálicos de platina. Em intermetálicos ordenados de platina e estanho, a velocidade de envenenamento diminui significativamente, o que retarda a desativação da superfície e promove oscilações de longa duração, sem precedentes, com estabilização de mais de 2200 ciclos. Isto corresponde a 30-40 vezes mais estável com relação ao eletrodo de platina. A presença de estanho na superfície do eletrodo tem grande impacto na produção de CO2, como observado em experimentos, modelagem e simulações numéricas, com aumento na velocidade das etapas produtoras de CO2. Com as informações adicionais obtidas em regime oscilatório, frente os experimentos em estado estacionário, foi possível estimar o efeito catalítico dos modificadores como estanho ou bismuto em eletrodos de platina, bem como, alguns aspectos mecanísticos da eletro-oxidação de formaldeído, ácido fórmico, metanol e etanol. / The self-organization is one of the most important features of nature. The self-organization phenomenon can emerge in sufficiently far from thermodynamic equilibrium systems. The non-linearity laws of the electrochemistry systems, allows several examples of complex behavior, most of them in electrocatalysis. Despite the considerable progress in understanding of the mechanistic aspects of the oscillatory electro-oxidation of C1 molecules, there is a apparently no systematic studies concerning the impact of surfaces modifiers on the oscillations dynamics. In this doctoral thesis the electro-oxidation of formic acid on platinum bimetallic electrodes, with tin and bismuth, was compared to that observed on polycrystalline platinum electrodes. Overall, the obtained results were very reproducible, robust and allowed a detailed analysis on the correlation between the catalytic activity and the oscillation dynamics. The modified surfaces promote drastic effect on the oscillatory dynamics. The self-organized oscillations were used as a probe to the electrocatalytic activity of bimetallic electrodes. In ordered intermetallic electrodes of the platinum and tin, the rate of surface poisoning significantly decrease, which slow the surface deactivation and promotes long-lasting oscillations, unprecedented stabilization of more than 2200 oscillatory cycles. This corresponds to 30-40 fold stabilization with respect to the behavior of platinum electrodes. The adsorbed tin affects the reaction pathways that produce CO2, as observed in experiments, modeling and numerical simulations. Further information obtained in oscillatory regime permitted the estimative of the catalytic effect of the surface modifiers, such as tin and bismuth, and some mechanistic aspects of the electro-oxidation of formaldehyde, formic acid, methanol and ethanol.

This thesis presents the formation mechanism of intermetallics formed at Fe-Al film interfaces. Al thin films with different initial film thicknesses were coated on low carbon steel substrates by physical vapor deposition (PVD). By annealing the system at different temperatures and for different time intervals, several intermetallic phases were observed. X-Ray, SEM and EDS studies showed that intermetallic phases FeAl2 and Fe2Al5 are most dominant phases which were observed and they formed sequentially on the contrary of intermetallics which formed synchronous in bulk materials.

Titanium carbide (TiC) and titanium carbonitride (Ti(C,N)) are both common components in hard, wear resistant ceramic-metal composites, or cermets. In this study the intermetallic nickel aluminide (Ni3Al) has been used as a binder for the production of TiC and Ti(C,N) based cermets. These cermets offer several improved characteristics relative to conventional WC-based ‘hardmetals’, such as lower mass and improved oxidation resistance, which are also combined with high fracture resistance, hardness and wear resistance. The cermets were produced using an in-situ, reaction sintering procedure to form the stoichiometric Ni3Al binder, with the binder contents varied from 20 to 40 vol%. However, for high N content Ti(C,N) cermets, the wettability of molten Ni3Al is relatively poor, which leads to materials with residual porosity. Therefore various amounts of Mo2C (1.25, 2.5, 5 and 10 vol%) were incorporated into the Ti(C0.3,N0.7)-Ni3Al cermets, with the aim of improving the densification behaviour. Mo2C was found to improve upon the wettability during sintering, thus enhancing the densification, especially at the lower binder contents. The tribological behaviour of TiC and Ti(C,N) cermets have been evaluated under reciprocating sliding conditions. The wear tests were conducted using a ball-on-flat sliding geometry, with a WC-Co sphere as the counter-face material, for loads from 20 to 60 N. The wear response was characterised using a combination of scanning electron microscopy, energy dispersive X-ray spectroscopy, and focused ion beam microscopy. Initially, two-body abrasive wear was observed to occur, which transitions to three-body abrasion through the generation of debris from the cermet and counter-face materials. Ultimately, this wear debris is incorporated into a thin tribolayer within the wear track, which indicates a further transition to an adhesive wear mechanism. It was found that Mo2C additions had a positive effect on both the hardness and indentation fracture resistance of the samples, but had a detrimental effect on the sliding wear response of the cermets. This behaviour was attributed to increased microstructural inhomogeneity with Mo2C additions.

Dans ce travail on a étudié l’insertion d’éléments légers dans des intermétalliques TRMX(TR = Terre-Rare, M = métal de transition, X = Si ou Ge) qui cristallisent dans le type structural CeScSi.Cette structure contient deux types de sites interstitiels dans lesquels il est possible d’insérer deséléments légers : un site tétraédrique TR4 et un site octaédrique TR2M4.Pour tous les composés étudiés au cours de ce travail (GdScGe, NdScSi, CeTiGe,...) on a observésystématiquement une insertion des atomes d’hydrogène dans les sites tétraédriques TR4. Danscertains cas les atomes d’hydrogène occupent également les sites octaédriques TR2M4. Ceci aconduit à l’obtention de deux type d’hydrures : TRMXH et TRMXH1,5 pour lesquels on observe unetrès forte diminution de l’ordre magnétique et des changements significatifs des propriétés deconduction électrique par rapport aux phases initiales.L’insertion de carbone par fusion des éléments à l’aide d’une procédure en plusieurs étapes permetd’obtenir des phases TRScSiCx avec un taux de carbone variable (0 ≤ x ≤ 0,5) qui correspond à unremplissage plus ou moins partiel du site octaédrique TR2M4. Cette insertion de carbone induitégalement une diminution des températures d’ordre magnétique (de Curie et de Néelrespectivement pour NdScSi et CeScSi).Dans une deuxième étape on a montré qu’il est possible d’insérer partiellement de l’hydrogène dansles sites TR4 laissés vacants. Des changements de type d’ordre magnétique ont été observéscontrairement aux hydrures et carbures précédents. Des études systématiques de diffractionneutronique ont permis de déterminer les structures magnétiques à basse température de la plupartde ces nouvelles phases d’insertion. / Rare earth based intermetallics RTX (R = rare earth, T = transition metal, X = Si, Ge)crystallising in the layered CeScSi structure type contain vacant interstitial sites that can be filled bylight elements to modify the initial physical properties. Hydrogenation studies on CeScSi-typecompounds show that hydrogen atoms are inserted in the tetrahedral (R4) sites and sometimes inthe octahedral (R2Sc4) sites. This causes an anisotropic expansion of the unit cell with a decreasingand c strongly increasing. It also drastically lowers the magnetic ordering temperatures of the parentmaterials and changes their resistivity behaviour.We developed a multi-step process to synthesise intermetallic carbides (RTXCX) with controllable Ccontent. Neutron diffraction shows that C occupies only the R2Sc4 sites of the RScSi compounds (R =La-Nd and Gd) causing the increase of the a cell parameter and the decrease of the c one. We obtainRScSiCX solid solutions with 0.0 ≤ x ≤ 0.5 for R = Ce and 0.25 <̰ x ≤ 0.5 for R = Nd. Carburation reducesthe Curie and Néel temperature of the NdScSi and CeScSi pristine phases, respectively.As the R4 tetrahedra are empty in the RScSiCX carbides, we have succeeded in hydrogenating thesematerials (R = Ce and Nd). However, due to the antagonistic structural distortion induced by C and Hinsertion respectively, only around 15 % of the R4 sites could be filled for a final composition ofRScSiC0.5H~0.15. It also changes the type of magnetic behaviour from a ferromagnetic order to anantiferromagnetic order in NdScSiC0.5.Neutron diffraction experiments have been performed to determine the magnetic structures ofthese new insertion compounds.

Submitted by FRANCIELLE BORTOLOTI null (franciellebortoloti@yahoo.com.br) on 2016-03-31T18:13:57Z No. of bitstreams: 1 Dissertação_Defesa_pronto.pdf: 3622072 bytes, checksum: 8e76232a4bb6cbf4c06ed6197450b404 (MD5) / Approved for entry into archive by Felipe Augusto Arakaki (arakaki@reitoria.unesp.br) on 2016-04-05T13:41:27Z (GMT) No. of bitstreams: 1 bortoliti_f_me_bauru.pdf: 3622072 bytes, checksum: 8e76232a4bb6cbf4c06ed6197450b404 (MD5) / Made available in DSpace on 2016-04-05T13:41:27Z (GMT). No. of bitstreams: 1 bortoliti_f_me_bauru.pdf: 3622072 bytes, checksum: 8e76232a4bb6cbf4c06ed6197450b404 (MD5) Previous issue date: 2016-03-24 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Atualmente uma quantidade demasiadamente grande de glicerol tem sido produzida. O desenvolvimento de materiais que consigam eletro-oxidar essa molécula é de extrema importância, para que assim, este composto possa ter aplicações na geração de energia ou mesmo produzir produtos de interesse industrial. No presente trabalho foram estudadas as reações de oxidação do glicerol sobre as nanopartículas intermetálicas ordenadas PtSn/C, PdSn/C e as ligas PtSn/C, PdSn/C em meio alcalino. A caracterização físico-química dos materiais foi realizada por Difração de Raios-X, Espectroscopia de Energia Dispersiva por Raios-X, Microscopia Eletrônica de Transmissão de Alta Resolução e Espectroscopia de Absorção de Raios-X. Estas análises indicaram a formação de fases intermetálicas quando utilizado o método de redução por poliol, e a formação de ligas metálicas quando empregado o método da microemulsão. O desempenho eletroquímico foi avaliado pelas técnicas de voltametria cíclica e cronoamperometria. Todas as nanopartículas apresentaram atividade frente à reação de oxidação do glicerol, sendo que os materiais à base de Pt se destacaram em relação aos de Pd. Além disso, foi o intermetálico ordenado PtSn/C que demonstrou melhor desempenho eletroquímico, o que pode ser atribuído ao efeito eletrônico provocado pela adição do segundo metal (Sn). Através das análises dos espectros de massas foi identificado que para os materiais PtSn/C os produtos formados durante a eletrólise foram gliceraldeído, ácido glicólico e ácido fórmico, evidenciando a clivagem entre as ligações C-C. Em relação a PdSn/C, a quebra entre as ligações C-C não ocorreu, e os produtos formados foram gliceraldeído ou dihidroxiacetona para o intermetálico ordenado PdSn/C, e ácido tartrônico para a liga PdSn/C. Foi sugerido o mecanismo da reação de oxidação do glicerol nos materiais estudados. / Nowadays, the huge amount of glycerol produced from biodiesel obtaining process becomes an important environmental concern in our country. So, development of new and improvement of ancient methods of using glycerol urges to avoid the unappropriated discard of this compound and the consequent environmental pollution. Among the several methods early proposed, the enhancement of electrode materials able to electrooxidize glycerol appears as viable alternative to produce energy and/or high aggregated value chemicals. In the present work, it was investigated the performance of ordered intermetallic nanoparticles PtSn/C and PdSn/C and the alloys PtSn/C and Pd/Sn/C as anode materials to electrooxidize glycerol molecule in alkaline medium. The physical-chemical characterization of the synthesized nanoparticles was performed by using X-Ray Diffraction, Energy-Dispersive Spectrometry, High Resolution Transmission Electronic Microscopy and X-ray Absorption Spectroscopy techniques. The physical-chemical characterization confirmed the prevalence of ordered intermetallic structure from the synthetic route via polyol-modified protocol as well as the alloy structure prevalence as the materials were synthesized via micro-emulsion protocol. The electrochemical performance of the materials was investigated by using cyclic voltammetry and chronoamperometry techniques. All materials proved to be active for the glycerol electrooxidation reaction and it was observed the superior performance of the materials based on Pt as compared to the similar ones based on Pd. Moreover, ordered intermetallic PtSn/C presented the best performance among all the studied materials, which was proposed to be a consequence of the electronic effect of the neighbor Sn atom towards the Pt adsorption site. From mass spectra analysis, glyceraldehyde, glycolic acid and formic acid were detected as main products as the electrooxidation took place at Pt surfaces, evidencing the C-C bond cleavage. On the other hand, the same phenomenon was not observed for the reaction at Pd materials and the main products detected were glyceraldehyde or dihydroxyacetone for ordered intermetallic PdSn/C and tartronic acid for PdSn/C alloy. The corresponding electrooxidation mechanisms were proposed for the reaction occurring on all materials. / CNPq: 130452/2014-9

Following the continually increasing demand for high-density interconnection and multilayer packaging for chips, solder bump size has decreased significantly over the years, this has led to some challenges in the reliability of interconnects. This thesis presents research into the resulting effects of miniaturization on the interconnection with Sn-solder, especially focusing on the full intermetallics (IMCs) micro-joints which appear in the 3D IC stacking packaging. Thereby, systematic studies have been conducted to study the microstructural evolution and reliability issues of Cu-Sn and Cu-Sn-Ni IMCs micro-joints. (1) Phenomenon of IMCs planar growth: The planar IMCs interlayer was asymmetric and composed of (Cu,Ni)6Sn5 mainly in Ni/Sn (2.5~5 μm)/Cu interconnect. Meanwhile, it was symmetric two-layer structure in Cu/Sn (2.5~5 μm)/Cu interconnect with the Cu3Sn fine grains underneath Cu6Sn5 cobblestone-shape-like grains for each IMCs layer. Besides, it is worth noticing that the appearance of Cu-rich whiskers (the mixture of Cu/Cu2O/SnOx/Cu6Sn5) could potentially lead to short-circuit in the cases of ultra-fine ( < 10 μm pitch) interconnects for the miniaturization of electronics devices. (2) Microstructural evolution process of Cu-Sn IMCs micro-joint: The simultaneous solidification of IMCs interlayer supressed the scalloped growth of Cu6Sn5 grains in Cu/Sn (2.5 μm)/Cu interconnect during the transient liquid phase (TLP) soldering process. The growth factor of Cu3Sn was in the range of 0.29~0.48 in Cu-Cu6Sn5 diffusion couple at 240~290 °C, which was impacted significantly by the type of substrates. And the subsequent homogenization process of Cu3Sn grains was found to be consistent with the description of flux-driven ripening (FDR) theory. Moreover, Kirkendall voids appeared only in the Cu3Sn layer adjacent to Cu-plated substrate, and this porous Cu3Sn micro-joint was mechanically robust during the shear test. (3) Microstructural evolution of Cu-Sn-Ni IMCs micro-joint: There was obvious inter-reaction between the interfacial reactions in Ni/Sn (1.5 μm)/Cu interconnect. The growth factor of (Cu,Ni)3Sn on Cu side was about 0.36 at 240 °C, and the reaction product on Ni side was changed from Ni3Sn4 into (Cu,Ni)6Sn5 with the increase of soldering temperature. In particular, the segregation of Ni atoms occurred along with phase transformation at 290 °C and thereby stabilized the (Cu,Ni)6Sn5 phase for the high Ni content of 20 at.%. (4) Micro-mechanical characteristics of Cu-Sn-Ni IMCs micro-joint: The Young s modulus and hardness of Cu-Sn-Ni IMCs were measured by nanoindentation test, such as 160.6±3.1 GPa/ 7.34±0.14 GPa for (Cu,Ni)6Sn5 and 183.7±4.0 GPa/ 7.38±0.46 GPa for (Cu,Ni)3Sn, respectively. Besides, in-situ nano-compression tests have been conducted on IMCs micro-cantilevers, the fracture strength turns out to be 2.46 GPa. And also, the ultimate tensile stress was calculated to be 2.3±0.7 GPa from in-situ micro-bending tests, which is not sensitive with the microstructural change of IMCs after dwelling at 290 °C.

Os compostos intermetálicos do tipo R IND. 6 Fe IND. 14-X Al IND. X (R = Nd, La) são antiferromagnéticos e apresentam uma transição do tipo metamagnética em campos da ordem de 2-3 Tesla. Com objetivo de caracterizar suas propriedades magnéticas, amostras policristalinas forma investigadas via medidas de magnetização, magneto-resistência, magnetostricção e difração de nêutrons. As amostras foram preparadas por meio de forno a arco e submetidas a tratamentos térmicos de 750 GRAUSC por 4 semanas. A estrutura cristalina foi identificada como sendo tetragonal do tipo La IND. 6 Co IND. 11 GA IND. 3 (grupo especial 14/mcm). Em contraste com os compostos baseados em La, as amostras de Nd apresentaram uma grande histerese magnética e um efeito dependente da história magnética na região de T<30 K, e um ordenamento dos momentos magnéticos de Nd a 70 K. As T IND. N foram determinadas por meio de medidas de suscetibilidade magnética e se encontram na região de 150-310 K e 100-230 K para os compostos de Nd e La, respectivamente. A transição metamagnética foi observada em todas as amostras analisadas, e foi observada uma variação de 3-5% da resistência elétrica no momento da transição, sugerindo uma estrutura magnética em forma de camadas magnéticas. Infelizmente através das medidas de difração de nêutrons, não foi possível determinar a estrutura magnética das amostras. Entretanto, no composto Nd IND. 6 Fe IND. 10 Al IND. 4, essas medidas nos indicaram uma mudança da estrutura espacial por meio da alteração do grupo espacial do 14/mcm para P42/mcm na região de temperatura de 70 K, onde foi observado um pico bastante saliente em nossas medidas de suscetibilidade. Por meio de medidas de espectroscopia Mössbauer não foi observado nenhum comportamento anômalo nos parâmetros hiperfinos do Fe, indicando ser esta um fenômeno isolado dos momentos do Nd. ) Um outro resultado obtido por difração de nêutrons foi a presença de uma reflexão magnética (001) que cresce na região abaixo de 30 K, indicando a existência de uma componente dos spins paralela ao plano basal. Nenhuma anomalia magnética foi observada nas amostras de La. Esse crescimento do pico (001) sugere uma tendência dos momentos do Nd a se alinharem na direção do plano basal, podendo ser esta a explicação para o efeito de irreversibilidade observado nesta região de temperatura / Rare earth-based intermetallic compounds R IND.6Fe IND.14-xAl IND.x with R=(Nd, La) are antiferromagnetic and undergo a metamagnetic transition at 2~3 T applied fields. In order to further characterize their magnetic behavior, polycrystalline samples were investigated with magnetometry, magneto resistance, magnetostriction and neutron diffraction. Samples have been prepared by arc melting under argon and annealed at 750°C for four weeks. The crystal structure is tetragonal of La IND.6Co IND.11Ga IND.3-type (space group 14/mcm). In contrast to La-based compounds, Nd IND.6Fe IND.14-xAl IND.x exhibits a large transition hysteresis and magnetic history effects at T<30 K, and antiferromagnetic ordering of Nd moments at 70 K. The T IND.N was determined by magnetic susceptibility measurements in the 150-310 K and 100-230 K range for the Nd and La compounds, respectively. The metamagnetic transition was observed for all samples and a ~3-5% resistivity drop was found to occur concomitantly, suggesting a magnetic multilayer-like structure. Unfortunately the magnetic structure of this compound could not be determined in this work by neutron diffraction. However, neutron diffraction measurements in the Nd IND.6Fe IND.10Al IND.4 compound revealed a change of space group from 14/mcm to P4 IND.2/mcm at 70 K, where the magnetic susceptibility exhibits a sharp peak. Mossbauer spectroscopy measured in the 4.2-100 K range has shown no evidence of Fe spin rotation, suggesting an isolated Nd phenomenon. Another result from neutron diffraction measurements was the presence of a magnetic (001) reflection that grows below 30 K, indicating the development of a spin component parallel to the basal plane. No such effect was observed with La-based samples. This increase is likely to be due to a canting of Nd moments towards the basal plane. The coincidence of this effect with the onset temperature for irreversible behavior in magnetic measurements is consistent with this interpretation.