Orientador: Flávio César Guimarães Gandra / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-19T11:06:30Z (GMT). No. of bitstreams: 1 Monteiro_JoseCarlosBotelho_M.pdf: 5466679 bytes, checksum: 3148a9c0487d05fa44922d063e525114 (MD5) Previous issue date: 2011 / Resumo: Neste trabalho apresentamos os resultados das medidas de magnetização e calorimetria em policristais da série RZn (R= Tb, Gd, Er e Ho). Através da análise das curvas de magnetização em função da temperatura, obtidas em campos de até 5 T, avaliamos e obtemos o efeito magnetocalórico (EMC) para os compostos da série, expresso através da variação isotérmica da entropia. O composto GdZn é o mais simples da série sendo o único que não apresenta efeitos inerentes à anisotropia magnética. Pelas medidas de magnetização observamos uma transição de ordenamento magnético em 260 K. Para este composto utilizamos um hamiltoniano simples, considerando apenas as contribuições devido à interação de troca e ao efeito Zeeman para simular curvas de calor específico e magnetização. Com os dados obtidos observamos uma variação de entropia máxima de 3,49 mJ/gK para um campo de 5 T em torno de Tc. O ErZn apresenta transição ferromagnética em 18 K e uma queda na magnetização em temperaturas abaixo de Tc, que é resultado de uma transição de reorientação de spin (TRS) induzida por campo. Essa transição é um efeito da anisotropia do sistema e é observada apenas em curvas obtidas em baixos campos magnéticos. Para simular as curvas de magnetização do ErZn e dos demais compostos da série adicionamos ao hamiltoniano utilizado a contribuição devido ao campo cristalino. Ao avaliarmos o EMC do ErZn vemos que existe uma pequena anomalia, resultado da TRS, em torno de 11K para variações em até 2 T de campo. Em campos maiores a anomalia desaparece e obtemos um ?S de até 14,83 mJ/gK em campos de 5 T. Os compostos TbZn e HoZn apresentam transições ferromagnéticas em 195 e 66 K, respectivamente, e ambos apresentam transições de reorientação de spin em temperaturas abaixo de Tc. Diferentemente do ErZn, porém, nesses compostos as TRS não são induzidas por campo, sendo resultado apenas da anisotropia do sistema, mostrando efeitos muito mais pronunciados nas curvas de magnetização e calor específico. Ao calcularmos o EMC desses compostos, observamos dois picos pronunciados relativos à mudança da entropia no material, um devido ao ordenamento magnético em Tc e outro devido à reorientação de spin no material. Essa característica faz com que o EMC nesses compostos tenha uma área de atuação muito maior do que em materiais que só apresentam um ?Smax em Tc, tornando materiais desse tipo fortes candidatos à refrigeração magnética / Abstract: This work presents the results of calorimetric and magnetization measurements on polycrystalline RZn series (R = Tb, Gd, Er and Ho). By analyzing the curves of magnetization as a function of temperature, obtained under fields up to 5 T (6 T for TbZn), we obtain and evaluate the magnetocaloric effect (MCE) for compounds of the series, expressed by the isothermal entropy change. The GdZn compound is the simplest of the series being the only one that has no inherent magnetic anisotropy effects. Through magnetization measurements we observe a magnetic ordering transition at 260 K. For this compound we use a simple Hamiltonian, considering only the contributions due to exchange interaction and the Zeeman Effect to simulate curves of specific heat and magnetization. With the data obtained, GdZn presented a maximum entropy change of 3.49 mJ/gK for a magnetic field of 5 T around Tc. The ErZn presents a ferromagnetic transition at 18 K and a drop in magnetization at temperatures below Tc, which is the result of a spin reorientation transition (SRT) induced by magnetic field. This transition is an effect of the system¿s anisotropy and is observed only in curves at low magnetic fields. To simulate the magnetization curves of ErZn and the other compounds of the series we added to the Hamiltonian the contribution due to the crystalline field. In evaluating the MCE of ErZn we find that there is a small anomaly, the result of SRT, around 11K for field variations up to 2 T. In larger fields the anomaly disappears and we get ?S up to 14.83 mJ / gK at fields of 5 T. The compounds HoZn and TbZn have ferromagnetic transitions at 195 and 66 K, respectively, and both have spin reorientation transitions at temperatures below Tc. Unlike the ErZn compound, however, those SRT are not field-induced, being the sole result of anisotropy of the system and showing effects much more pronounced in the curves of magnetization and specific heat. In calculating the EMC of these compounds, we observe two pronounced peaks on the entropy change in the material, one due to a magnetic ordering at Tc and the other due to spin reorientation in the material. This feature shows that the MCE in these compounds act in a much wider range than the usual materials that shows a peak only in Tc, making them strong candidates for magnetic refrigeration / Mestrado / Física da Matéria Condensada / Mestre em Física

When joining steel to aluminium there is a reaction between iron and aluminium which results in the formation of brittle intermetallic compounds (IMC). These compounds are usually the reason for the poor mechanical strength of the dissimilar metallic joints. The research on dissimilar metal joining is vast but is mainly focused on the automotive industry and therefore, the material in use is very thin, usually less than 1 mm. For materials with thicker sections the present solution is a transition joint made by explosion welding which permits joining of steel to aluminium and avoids the formation of IMCs. However, this solution brings additional costs and extra processing time to join the materials. The main goals of this project are to understand the mechanism of formation of the IMCs, control the formation of the IMCs, and understand their effects on the mechanical properties of the dissimilar Fe-Al joints during laser welding. Laser welding permits accurate and precise control of the welding thermal cycle and thereby the underpinning mechanism of IMC formation can be easily understood along with the factors which control the strength of the joints. The further goal of this project is to find an appropriate interlayer to restrict the Fe-Al reaction. The first stage of the work was focused on the formation and growth of the Fe-Al IMCs during laser welding. The understanding of how the processing conditions affect the IMC growth provides an opportunity to act and avoid its formation and thereby, to optimize the strength of the dissimilar metal joints. The results showed that even with a negligible amount of energy it was not possible to prevent the IMC formation which was composed of both Fe2Al5 and FeAl3 phases. The IMC growth increases exponentially with the applied specific point energy. However, for higher power densities the growth is more accentuated. The strength of the Fe-Al lap-joints was found to be not only dependent on the IMC layer thickness but also on the bonding area. In order to obtain sound joints it is necessary to achieve a balance between these two factors. The thermal model developed for the laser welding process in this joint configuration showed that for the same level of energy it is more efficient to use higher power densities than longer interaction iv times. Even though a thicker IMC layer is formed under this condition due to higher temperature there is also more melting of aluminium which creates a larger bonding area between the steel and the aluminium. The joint strength is thus improved ... [cont.].

These thesis deals with electromigration in solder joint. In theoretical part are described lead-free solders, surface finish, formation of solder joint, intermetallic compounds a electromigration. In practical part is investigated a effect of electromigration on growth intermetallic compounds in solder jsoint.

The main focus of this work is the preparation, chemical and structural characterization along with the investigation of physical properties of intermetallic clathrates. Starting from the history of clathrate research, classification of clathrate types, their structural properties and possible application areas are evaluated in chapter 2. The methodologies of sample preparation and materials characterization as well as quantum chemical calculations are discussed in chapter 3. The complete characterization of Ba8Ge433 ( is a Schottky-symbol standing for vacancies),12-14 which is a parent compound for the variety of ternary variants, is the subject of chapter 4. Ba8Ge433 is a high temperature phase,12 which was prepared for the first time as single phase bulk material in this work.15, 16 In this way, the intrinsic transport properties could be investigated without influence of grain boundary and impurity effects. The transport behavior is analyzed at low and high temperatures and referred to the former results. In addition, crystal structure and vacancy ordering in terms of the reaction conditions are discussed. Chemical bonding in Ba8Ge433 is investigated by topological analysis of the electron localizability indicator and the electron density. Chapter 5 deals with the preparation, phase analysis, crystal structure and physical properties of BaGe5, which constitutes a new clathrate type oP60.17, 18 So far, two clathrate types were known in the binary system Ba – Ge, namely the clathrate cP124 Ba6Ge25,19-21 and the clathrate-I Ba8Ge433. Originally, BaGe5 was detected by optical and scanning electron microscopy within the grains of Ba8Ge433.12 Once the preparation of phase-pure Ba8Ge433 was achieved, it became possible to make detailed investigations of its decomposition along with the formation of BaGe5. A detailed theoretical and experimental analysis on the relation between crystal structure and physical properties of BaGe5 is presented. In chapter 6, a thorough structural characterization and the physical properties of clathrates in the system Ba – Ni – Ge is presented based on the subtle relation between the crystal structure containing vacancies and the thermoelectric properties. During the investigations in this system, a large single crystal was grown by Nguyen et al. 22, 23 from the melt with the composition Ba8Ni3.5Ge42.10.4. A systematic reinvestigation of the phase relations in this system was performed and the influence of different Ni content to the crystal structure and physical properties is evaluated. The Si-based ternary clathrate with composition Ba8–δNixySi46–x–y is the subject of chapter 7. The phase relations and the homogeneity range are established. The crystal structure taking into account vacancies in the framework is discussed. Physical properties of bulk pieces are analyzed and the results are related to the sample composition. In addition, first-principles electronic structure calculations are carried out to assess variations in the electronic band structure, phase stability and chemical bonding.24 Chapter 8 reports on the intermetallic compound Ba3Si4,25, 26 which was encountered during the investigations on the Ba – Ni – Si phase diagram. The discussion covers issues related to preparation, crystal structure, phase diagram analysis, electrical and magnetic properties, NMR measurements, quantum mechanical calculations and oxidation to nanoporous silicon with gaseous HCl. Besides my contributions to the NoE CMA, I studied under the Priority Program 1178 of Deutsche Forschungsgemeinschaft “Experimental electron density as the key for understanding chemical interactions” with the project of “Charge distribution changes by external electric fields: investigations of bond selective redistributions of valence electron densities”. Chapter 9 deals with the preparation of chalcopyrites ZnSiP2 and CuAlS2 for experimental charge density analysis. Both phases show semiconducting properties and have non-centrosymmetric structures with high space group symmetry as needed to investigate the structural changes induced by external electric field. In this chapter, I describe the preparation and the crystal structure analyses of ZnSiP2 and CuAlS2 including issues related to the data collection as well as the results of NMR investigation.

This research demonstrates the use of friction stir welding (FSW) to join dissimilar (Al-Mg) metal alloys. The main challenges in joining different, dissimilar metal alloys is the formation of brittle intermetallic compounds (IMCs) in the stir zone affecting mechanical properties of joint significantly. In this present study, FSW joining process is used to join aluminum alloy AA2139 and magnesium alloy WE43. The 9.5 mm thick plates of AA2139 and WE43 were friction stir butt welded. Different processing parameters were used to optimize processing parameters. Also, various weldings showed a crack at interface due to formation of IMCs caused by liquation during FSW. A good strength sound weld was obtained using processing parameter of 1200 rev/min rotational speed; 76.2 mm/min traverse speed; 1.5 degree tilt and 0.13 mm offsets towards aluminum. The crack faded away as the tool was offset towards advancing side aluminum. Mostly, the research was focused on developing high strength joint through microstructural control to reduce IMCs thickness in Al-Mg dissimilar weld joint with optimized processing parameter and appropriate tool offset.

Die vorliegenden Dissertation berichtet von der Entdeckung ungewöhnlicher magnetischer, elektronischer und struktureller Eigenschaften in einer Reihe von neuen intermetallischen Verbindungen auf Selten-Erd-Basis. Die untersuchten Systeme vom Typ RET2X bestehen aus den Selten-Erd-Elementen (RE) Yb oder Lu, den Übergangsmetallen (T) Pt oder Pd sowie den weiteren Liganden (X) Sn oder In. Die Synthese der verwendeten Proben, deren kristallografische Analyse und die Untersuchung ihrer physikalischen Eigenschaften werden im Detail vorgestellt. Diese Arbeit liefert Resultate, die sowohl für die Grundlagenforschung als auch für technische Anwendungen eine große Relevanz besitzen. Die Untersuchungen der neuen Verbindungen YbPt2Sn und YbPt2In zeigen, dass die magnetische Kopplung zwischen benachbarten Yb-Ionen extrem schwach ist. Dies führt zu einem riesigen magnetokalorischen Effekt im Bereich von 0.05 K bis 2 K. Damit besitzen beide metallischen Materialien optimale Eigenschaften, um als Kühlkörper in Entmagnetisierungskryostaten Verwendung zu finden. Zwei zu Testzwecken aufgebaute Kühleinsätze auf YbPt2Sn-Basis bestätigen die Eignung dieser Verbindung als metallisches Kühlmaterial. Die Untersuchungen der Substitutionsreihe Lu(Pt1-xPdx)2In offenbaren einen Ladungsdichtewelle (CDW)-Phasenübergang mit außergewöhnlichen Eigenschaften. Im Gegensatz zu Beobachtungen in den meisten anderen bekannten CDW-Systemen ist der Übergang in LuPt2In kontinuierlich, d. h. zweiter Ordnung. Durch Ersetzen von Pt mit isovalenten Pd kann die Übergangstemperatur T_CDW kontinuierlich zum absoluten Temperaturnullpunkt geführt werden. Die beobachteten Eigenschaften zeigen, dass der Phasenübergang dabei zweiter Ordnung bleibt. Damit wird experimentell bewiesen, dass Lu(Pt1-xPdx)2In eines der seltenen Systeme ist, in denen ein CDW quantenkritischer Punkt in Erscheinung tritt. Noch außergewöhnlicher ist die Beobachtung von Supraleitung mit einem ausgeprägten Maximum in der Sprungtemperatur T_c genau am quantenkritischen Punkt. Das deutet auf eine neuartige Kopplung zwischen quantenkritischer CDW und Supraleitung hin.

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Les applications portables et stationnaires des accumulateurs Ni-MH nécessitent sans cesse des autonomies de plus en plus importantes. Cet accroissement d’autonomie peut être obtenu en développant de nouveaux composés intermétalliques hydrurables de type ABx (3<x<4) de plus grande capacité massique. Le groupe A de ces composés est constitué de La partiellement substitué par du Mg, qui est beaucoup plus léger et diminue la masse molaire de l’alliage, et le groupe B contenant du Ni partiellement substitué par d’autres éléments de transition. Après une étude bibliographique approfondie, le travail de cette thèse consiste à rechercher tout d’abord les conditions optimales d’élaboration d’intermétalliques de composition La1-yMgyNix (0<y<1 ; 3<x<4). Puis ces composés sont caractérisés du point de vue structural et physico chimique (diffraction des rayons X et microsonde électronique), et leurs propriétés vis-à-vis de l’hydrogène (réaction solide-gaz et électrochimique) sont étudiées / Mobile and stationary applications for Ni-MH batteries require continuously more and more energy density. This increased autonomy can be obtained by developing new hydride-forming compounds of ABx-type (3<x<4) with larger weight capacities. The A element of these compounds is constituted of La partially substituted by light Mg, allowing a reduced molar weight. The B element is made of Ni that can be partially substituted by other transition metals. After an extensive bibliographic study, this thesis presents the research work to find optimum conditions for the synthesis of Mg-containing intermetallic compounds La1-yMgyNix (0<y<1; 3<x<4). These compounds are then characterized from the structural and chemical point of views (X-ray diffraction and microprobe analysis) and their hydrogen-related properties are studied and compared (solid-gas and electrochemical reactions)

O objetivo dessa tese é contribuir para o entendimento da precipitação de compostos intermetálicos e da reversão da martensita por meio de modelos cinéticos, tanto em experimentos isotérmicos no aço maraging 350 (350B) como em estudos não-isotérmicos nos aços maraging 300 (300A), maraging 350 (350C). Além da cinética das transformações de fase, foram estudadas também as mudanças da microestrutura e dos mecanismos de endurecimento decorrentes de tratamentos térmicos de envelhecimento para o aço maraging 350B. Para estas finalidades, foram usadas diversas técnicas complementares de caracterização microestrutural, como microscopia ótica (MO), microscopia eletrônica de varredura (MEV) com espectroscopia por dispersão de energia de raios X (EDS), microdureza Vickers, difração de raios X (DRX) e ferritoscopia. Já a calorimetria exploratória diferencial (DSC) foi usada para estudar a precipitação de compostos intermetálicos e reversão da martensita em experimentos não-isotérmicos. Os resultados dos experimentos não-isotérmicos de DSC com os aços maraging 300 e 350 evidenciaram que a precipitação ocorre em duas etapas. A primeira relacionada à difusão de soluto no volume com energia de ativação próxima da difusão do níquel e molibdênio na ferrita, enquanto a segunda acontece por meio da difusão de soluto ao longo das discordâncias com energia de ativação menor que a difusão do níquel e do molibdênio na ferrita. Observou-se também que a reversão da martensita pode ocorrer em duas etapas. A primeira etapa foi associada à difusão de soluto, enquanto a segunda foi relacionada ao mecanismo de cisalhamento. Já as observações microestruturais, por meio de microscopia óptica e de microscopia eletrônica de varredura, evidenciaram que a austenita revertida formou-se nas regiões de interface, como os contornos de grão, contornos de pacote e contornos de ripas da estrutura martensítica para temperaturas a partir de 520 °C, enquanto a austenita revertida encontrada no interior das ripas da martensita formou-se a partir de 560 °C. O estudo da cinética de precipitação e do comportamento da curva de envelhecimento em um aço maraging 350 (350B), para tratamentos isotérmicos entre 440 e 600 °C, mostrou que as medidas de microdureza podem ser muito úteis para estudos dessa natureza nesses aços. A análise cinética da precipitação, realizada por meio do ajuste dos dados experimentais aos modelos JMAK e Austin-Rickett, mostrou que eles se ajustam bem a esses modelos com coeficiente de correlação próximo de 1. Entretanto, a interpretação dos valores de n, obtidos pela equação Austin-Rickett, mostrou que eles têm maior concordância com as mudanças microestruturais observadas nos aços maraging, em estudos anteriores, se comparados com aqueles estimados por meio da equação JMAK. A interpretação das constantes n, usando a equação Austin-Rickett, permitiu estabelecer diversas etapas para a precipitação. Na primeira ocorre a precipitação nas discordâncias para 440 °C, seguida pelo crescimento de cilindros longos e finitos em comparação com a distância de separação deles para 480 °C e, por fim, o crescimento de precipitados partindo de dimensões pequenas com taxa de nucleação zero para 520 e 560 °C. Já o estudo do comportamento da curva de envelhecimento para diversos tempos entre 440 e 600 °C em aço maraging 350 (350B) mostrou que esse aço apresenta uma etapa de endurecimento e outra de amolecimento. Essa etapa de endurecimento, comumente atribuída à formação de fases intermetálicas coerentes e semicoerentes, pode subdividir-se em dois estágios para as temperaturas de envelhecimento de 440 e 480 ºC ou apresentar um único estágio para 520 e 560 ºC. Já a etapa de amolecimento é associada não somente ao mecanismo clássico de superenvelhecimento em que a queda na resistência mecânica ocorre em virtude da perda de coerência e do engrossamento de precipitados, mas também como consequência da formação de austenita revertida a partir da martensita, especialmente, para temperaturas entre 520 e 600 ºC. / The purpose of this thesis is to contribute to the understanding of precipitation of intermetallic compounds and reversion of martensite through kinetic models, as in isothermal experiments in maraging 350 steel (350B) as in non-isothermal studies in maraging steels 300 (300A) maraging 350 (350C). In addition to kinetics of phase transformation, they were also investigated both the changes of the microstructure and the mechanisms of hardening due to aging heat treatments for the maraging steel 350B. For these purposes, we used several complementary techniques for microstructural characterization, such as optical microscopy (OM), scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS), Vickers hardness, X-ray diffraction (XRD) and feritscope, while differential scanning calorimetry (DSC) was used to study the precipitation of intermetallic compounds and reversion of martensite in non-isothermal experiments. The results of the non-isothermal DSC experiments with the maraging steel 300 and 350 showed that precipitation occurs in two steps. First stage related to the diffusion of solute in bulk with activation energy next to nickel diffusion and molybdenum in the ferrite, while second stage occurs through the solute diffusion along dislocations with lower activation energy than the diffusion of nickel and molybdenum in ferrite. It was also observed that the reversion of the martensite can occur in two steps. First stage was associated with the solute diffusion, while the second stage is related to the shear mechanism. Microstructural observations by optical microscopy and scanning electron microscopy showed that austenite reverted was formed in the interface regions, such as grain boundaries, packet boundaries and lath boundaries of martensitic structure for temperatures from the 520 °C, while the reverted austenite found within the martensite laths formed from 560 °C. Study of the kinetics of precipitation and aging hardening behavior in a 350 maraging steel (350B), by isothermal treatments between 440 and 600 °C, showed that the microhardness measurements can be very useful for such studies in these steels. Kinetics of precipitation analysis was carried out by adjusting the experimental data to JMAK and Austin-Rickett models. It showed that they fit well to these models with a correlation coefficient close to 1. However, the interpretation of the n values, obtained by Austin-Rickett equation, they have showed higher agreement with the observed microstructural changes in the maraging steel, in previous studies, when compared with those estimated by JMAK equation. The interpretation of the constants, using the Austin-Rickett equation, revealed several steps to precipitation. In the first precipitates on dislocations for 440 °C followed by growth of long and finite cylinders in comparison with the distance their separation for 480 °C and, finally, the growth of precipitates starting from small dimensions with nucleation rate zero for 520 and 560 °C. Study of aging hardening behavior curve for various times between 440 and 600 °C in maraging steel 350 (350B) showed that the steel has a hardening step and another softening. This step of hardening, commonly attributed to the formation of intermetallic phases coherent and semicoerentes, it can be divided into two stages to the aging temperatures of 440 and 480 °C or present a single stage 520 and 560 °C. Since the softening stage is associated not only to classic overaging mechanism in which a drop in mechanical strength occurs due to loss of coherence and precipitate coarsening, but also as a consequence of austenite formation reverted from the martensite especially to temperatures between 520 and 600 °C.