Made available in DSpace on 2014-10-09T12:26:37Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:22Z (GMT). No. of bitstreams: 0 / A reconstrução tridimensional de superfícies de fratura de materiais compósitos do tipo CFRP é apresentada neste trabalho como um método possível para análise fractográfica desse material, cuja superfície de fratura pode apresentar uma rugosidade acentuada, com grande variação em altura. Dois métodos são apresentados para esse propósito: a reconstrução por foco variável, realizada com imagens de microscopia óptica e a reconstrução por paralaxe, realizada com par de imagens estéreo, obtidas por microscopia eletrônica de varredura. Uma avaliação é realizada para cada um dos dois métodos, discutindo seus limites e a eficiência de cada um deles, perante as dificuldades de análise de materiais compósitos unidirecionais e multidirecionais. O método de foco variável apresentou um excelente resultado de reconstrução, mas tem a necessidade de um número grande de imagens, tempo de dedicação do instrumento e limite de ampliação das imagens como fatores a serem considerados na escolha de melhor método. As inclinações da amostra, durante o método da paralaxe, revelam alterações nos histogramas das imagens adquiridas no sentido horário que limitam o uso do método para materiais com alta rugosidade. A obtenção de imagens em um único sentido e a construção de uma região de interesse, posicionada no centro da imagem são sugestões para tornar o método mais abrangente. A linearidade das projeções de características na imagem inclinada também sugere a possibilidade de realizar a reconstrução utilizando, em vez de apenas duas, múltiplas imagens obtidas no sentido anti-horário. As alterações propostas para modificar a rotina, são sugeridas para que o programa possa ser aplicado de forma mais abrangente, independente da qualidade da superfície de fratura observada. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:43:55Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:08:49Z (GMT). No. of bitstreams: 1 06768.pdf: 7929582 bytes, checksum: 40b065a53d2b28d5924616b854124430 (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Submitted by Pedro Silva Filho (pfsilva@ipen.br) on 2017-11-17T17:01:48Z No. of bitstreams: 0 / Made available in DSpace on 2017-11-17T17:01:48Z (GMT). No. of bitstreams: 0 / Os ímãs permanentes de terras-raras tem um papel relevante na indústria de dispositivos eletromagnéticos, principalmente no que se refere à produção de motores para veículos híbridos e elétricos e geradores para turbinas eólicas. Com a recente restrição chinesa a exportação de terras-raras, os altos preços e a necessidade de substituição do Dy nesses ímãs, há um interesse mundial por alternativas a essas questões. A adição de elementos de liga em ímãs permanentes de terras raras tem como objetivo a melhora das propriedades magnéticas. O presente trabalho avalia a influência do Ti, V, Cr, Ni, Zr, Nb e Mo na microestrutura e nas propriedades magnéticas de ímãs sinterizados. Os ímãs foram preparados via metalurgia do pó, a partir de pós obtidos pelo processo de decrepitação por hidrogênio (HD). Na produção do ímã Pr16Fe66,9Co10,7B5,7Cu0,7, sem adição de elementos de liga, foi utilizada a mistura das ligas Pr20Fe73B5Cu2 (33% em peso) e Pr14Fe64Co16B6 (67% em peso). Para avaliar a influência das adições foi utilizada a liga Pr14Fe64Co16B6M0,1, onde M = Ti, V, Cr, Ni, Zr, Nb e Mo (67% em peso). As ligas utilizadas e os ímãs produzidos foram caracterizados por Microscopia Eletrônica de Varredura (MEV) e Difração de Raios-X (DRX), e as propriedades magnéticas foram obtidas por meio de Permeâmetro. O ímã com adição de Cr (iHc = 836 KA.m-1) apresentou coercividade intrínseca 11,8% superior ao ímã sem adição de elemento de liga (iHc = 748 KA.m-1). A maior remanência foi observada para o ímã com adição de Nb (Br = 1,04 T). Os ímãs com as adições de Ti, V e Zr apresentaram os maiores valores de produto de energia (BHmáx = 145, 145 e 144 KJ.m-3, respectivamente). Já o ímã com adição de Mo apresentou o maior fator de quadratura (FQ = 0,73) entre todas as amostras, 28% superior ao ímã sem adição de elementos de liga. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

Pós magnéticos foram produzidos utilizando o processo de hidrogenação, desproporção, dessorção e recombinação (HDDR). A primeira parte deste trabalho envolveu o estudo do efeito da adição de Co na liga Pr14FebalCoxB6Nb0.1 (x= 0, 4, 8, 10, 12, 16) variando a de temperatura de dessorção/ recombinação de 800° a 900°C, com o objetivo de otimização do tratamento HDDR. A liga Pr14Fe80B6 foi utilizada como padrão. As ligas foram tratadas termicamente a 1100°C por 20 horas para eliminação do Fe- exixtente na liga em estado bruto de fusão. A temperatura de dessorção/ recombinação afetou a microestrutura e as propriedades magnéticas dos ímãs moldados com polímeros. A liga com baixa adição de cobalto (4 at.%) exigiu a temperatura de reação mais alta (880°C) entre os demais ímãs. As temperaturas ótimas para as ligas com 8 at.% Co e 10 at.% Co foram 840°C e 820°C, respectivamente. Ligas com altas concentrações de cobalto (12 at.% and 16 at.%) foram processadas a 840°C. A temperatura de dessorção/ recombinação que apresentou alta anisotropia nas ligas Pr14Fe80B6 e Pr14Fe79,9B6Nb0,1 foi de 820°C. O ímã que apresentou melhor remanência (862mT) foi processado com a liga Pr14Fe67,9Co12B6Nb0,1. Cada liga apresentou uma temperatura de reação otimizada e exibiu uma microestrutura particular, de acordo com a composição. A segunda parte deste trabalho envolveu a caracterização, dos pós HDDR de Pr14Fe80B6, que foram analisadas por difração de raios X com fonte síncrotron para a identificação e quantificação de fases cristalinas, e ainda para a determinação do tamanho médio de cristalitos da fase principal. A microscopia eletrônica de varredura (MEV) foi utilizada para revelar a morfologia dos pós HDDR. / Fine magnetic powders were produced using the hydrogenation disproportionation desorption and recombination (HDDR) process. The first stage in this work involved an investigation of the effect of the Co content and range of desorption/ recombination temperatures between 800 and 900°C with the purpose of optimizing the HDDR treatment for Pr14Fe80B6 and Pr14FebalCoxB6Nb0,1 (x= 0, 4, 8, 10, 12, 16) alloys. The cast alloys were annealed at 1100°C for 20 hours for homogenization. The processing temperature (desorption/ recombination) affected the microstructure and magnetic properties of the bonded magnets. The alloy with low cobalt content (4 at.%) required the highest reaction temperature (880°C) to yield anisotropic bonded magnets. The optimum temperature for alloys with 8 at.% Co and 10 at.% Co were 840°C and 820°C, respectively. Alloys with high cobalt content (12 at.% and 16 at.%) were processed at 840°C. The optimum desorption temperature for achieving high anisotropy for Pr14Fe80B6 and Pr14Fe79,9B6Nb0,1 was 820°C. The best remanence (862mT) was achieved with the Pr14Fe67,9B6Co12Nb0,1 magnet, processed at 840°C. Each alloy required an optimum reaction temperature and exhibited a particular microstructure according to the composition. The second stage of the work involved the characterization, for each temperature, of the Pr14Fe80B6 HDDR powder processed using X-ray diffraction analysis. The samples of the HDDR material were studied by synchrotron radiation powder diffraction using the Rietveld method for cell refinement, phase quantification and crystallite sizes determination. Scanning electron microscopy (SEM) has also been employed to reveal the morphology of the HDDR powder.

No description available.

The iron-group metals and alloys are of interest because of their excellent soft magnetic properties. They have found a wide application field in the storage technology, especially for reading/writing elements in the hard drive head, and in microelectromechanical systems (MEMS). Especially the CoFe system, which possesses the highest, among others, saturation magnetisation of 2.45 T and a relatively low coercivity of about 2×10^-5 T, is of interest. These properties are crucial for the further development in the storage technology. Electrodeposition is a very promising alternative to the physical vapour deposition techniques (PVD) to produce soft magnetic layers and microstructures. The advantage of electrodeposition in comparison to PVD processes is the fact that it is an inexpensive method. Moreover, electrodeposition is the most appropriate process for the writing head fabrication since it allows to deposit high aspect ratio layers with a thickness ranging from a few monolayers up to more than 1 um onto a complex geometry substrate. A superposition of an external magnetic field during the electrodeposition can affect the deposit properties. Mainly the morphology of the deposited layers is influenced. This is mostly caused by the Lorentz force driven convection, i.e. the magnetohydrodynamic (MHD) effect. Whilst the knowledge of uniform external magnetic field effects on the electrodeposition of single metals has been greatly improved during the past decade, an alloy deposition is still a challenging task. Due to a lack of understanding of mechanisms of a magnetic field impact on the deposition of CoFe alloys and their technological importance a detailed investigation is of demand. The aim of this work is to analyse in detail the effects induced by a homogeneous magnetic field with different strength and relative to the electrode surface orientation on the electrodeposition of thin CoFe alloy films of different composition. This study is divided into three major parts: an analysis of the electrochemical behaviour (1), nucleation and growth processes (2) and the determination of the morphology and the physical properties of the deposited layers (3). 1. A detailed analysis of the electrochemical processes is performed. The influence of the magnetic field with respect to its flux density and relative to the electrode surface orientation on the reactions rates has been investigated. A special attention has been given to the side reactions accompanying the metal reduction, i.e. the hydrogen evolution reaction (HER). Which has a significant impact on the layer’s properties. It has been shown that the electrochemical reaction rates are improved in the parallel to the electrode magnetic field due to the classical MHD effect. On the contrary, in the perpendicular to the electrode magnetic field nearly no effect on the metal reduction is observed, whilst the HER rate is significantly increased. The reason of that is seen in the improved desorption of hydrogen bubbles from the electrode surface due to a localized convection in a bubble vicinity, the so called micro- MHD effect. Moreover, the additional convection introduced by a magnetic field, regardless of its relative to the electrode surface orientations, leads to a reduced interface pH value. This, in turn, results in an improved layer quality, i.e. the hydroxides precipitation is inhibited. 2. The nucleation and the very beginning of the layer growth are of particular importance for thin film deposition. Since the deposit properties are determined by these processes an extensive study of the very initial stages of electrocrystallisation is presented. This was performed by an analysis of the current density vs. time transients. It was found that the nucleation behaviour can be altered by a magnetic field. The changes in the nucleation behaviour have been studied on the basis of theoretical models by an current density-time transients analysis. Regardless of the electrolyte chemistry, the magnetic field strength, and its relative to the electrode orientation, similar features in the current density-time transients have been observed. The nucleation and growth are characterised by a layer-by-layer mode. The first nucleation and growth step at the very beginning of the potential step has been attributed to the 2D (most probably epitaxial) layer formation (up to a few monolayers), which was found unaffected by a magnetic field superposition. The 2D step is then followed by the next nucleation and growth step indicated by the occurrence of a maximum in the current density-time transients. This is attributed to the nucleation and 3D diffusion controlled growth and is altered by a magnetic field applied in the parallel-to-electrode configuration. The experimental dependencies have been examined by known theoretical models. This analysis revealed that the superposition of the parallel magnetic field leads to a retardation of the steady state nucleation rate (AN0) due to the MHD effect acting in the electrolyte. A qualitative model was proposed in order to explain this phenomenon. In contrast, the perpendicular to the electrode magnetic field does not change the nucleation behaviour. However, the growth mode of the layer is remarkably changed, i.e. a columnar growth is observed. 3. The magnetic field impact on the electrochemical reaction rates, on the desorption of hydrogen from the electrode surface, and on the nucleation behaviour has strong consequences for the resulting layer characteristics. This can be summarized as follows: • The most pronounced effect is noticed for the morphology of the layers. The quality of the layers deposited in a magnetic field, irrespective of its relative to the electrode orientation, is strongly improved. The reason of this is an enhanced desorption of hydrogen from the electrode surface. As a result large holes left by hydrogen bubbles observed for the layers deposited without a field disappear for the layers deposited under the influence of a magnetic field. The layers deposited under an influence of the parallel to the electrode magnetic field appear denser and more homogeneous than the ones obtained without a magnetic field. On the contrary, the layers deposited in the perpendicular to the electrode magnetic field appeared more diverse. The most remarkable effect has been observed for the layers deposited from the Fe and the CoFe(A) electrolyte in a perpendicular magnetic field where the grains tend to grow as separated columns in the direction of the magnetic field. A scaling analysis has revealed a smoothing effect of a parallel magnetic field manifested in a reduced value of the roughness exponent in comparison to the layers deposited without a magnetic field. On the contrary, the roughness exponent has increased for the layers obtained in the perpendicular to the electrode magnetic field, i.e. a roughening effect of the perpendicular magnetic field is observed. • No magnetic field effects neither on the crystal structure nor on the texture of the deposits have been observed. All layers irrespective of the deposition parameters develop a fibre texture. Nevertheless, the internal stress state of the deposited layers is affected by a magnetic field. A magnetic field applied during the deposition of alloy layers from buffered electrolytes, irrespective of its relative to the electrode orientation, reduces the internal stress of the layer. This effect is attributed to an improved desorption of hydrogen from the electrode surface, which is observed under the influence of a magnetic field. • The chemical composition of the deposited alloy layers, irrespective of the deposition parameters, is unchanged by magnetic fields. • The magnetic properties of the deposits are found to be affected by a magnetic field applied during the deposition. These effects are caused by microstructural changes induced by the magnetic field, i.e. the roughness of the layer, the internal stress state, and the chemical composition of the deposit. A good correlation between the coercivity and the roughness is found. Moreover, an in-plane magnetic anisotropy is observed in the alloy layers deposited under the influence of the parallel to the electrode magnetic field, where, according to the XRD investigations, isotropic properties were expected. The origin of this phenomenon is seen in a preferential same atom couples formation in the magnetic field direction. / Metalle und Legierungen der Eisengruppe sind von großem Interesse insbesondere wegen ihrer exzellenten weichmagnetischen Eigenschaften. Ein breites Anwendungsgebiet liegt in der Speichertechnologie, sie finden vorrangig Einsatz in Lese- und Schreibköpfen und in mikroelektromechanischen Systemen (MEMS). Besonders das CoFe-System, das u.a. die höchste Sättigungsmagnetisierung von 2,45 T bei einer relativ niedrigen Koerzitivfeldstärke von ca. 2×10^-5 T aufweist, ist interessant für zukünftige Entwicklungen in der Speichertechnologie. Im Vergleich zu physikalischen Abscheideverfahren, wie PVD (physical vapor deposition) ist die Elektrokristallisation eine einfache und preiswerte Alternative zur Herstellung von weichmagnetischen Schichten und Strukturen, die sich im Herstellungsprozess von Schreib-und Leseköpfen durchgesetzt hat. Es ist möglich Schichten und komplexe geometrische Strukturen mit einer Stärke von einigen Monolagen bis zu mehr als 1µm und in hohen Aspektverhältnissen abzuscheiden. Durch Überlagerung von externen Magnetfeldern während der Elektrodeposition können die Eigenschaften und insbesondere die Morphologie der Schichten signifikant beeinflusst werden. Die Ursache dafür besteht im Wesentlichen in der durch Lorentzkräfte angetriebenen Konvektion, die als magnetohydrodynamische Konvektion (MHD) bezeichnet wird. Während im letzten Jahrzehnt durch grundlegende Untersuchungen der Kenntnisstand bezüglich der elektrochemischen Abscheidung einzelner Metalle in überlagerten Magnetfeldern vertieft wurde, ist das Verständnis zum Mechanismus der Legierungsabscheidung wenig erforscht und eine Herausforderung. Es besteht kaum Kenntnis zum Mechanismus der CoFe Abscheidung unter dem Einfluss externer Magnetfelder und deren Bedeutung für technologische Prozesse. Das Ziel dieser Arbeit ist es, den Einfluss homogener Magnetfelder unterschiedlicher Stärke und Orientierung bezüglich der Elektrodenoberfläche während der Elektrokristallisation von CoFe Legierungen unterschiedlicher Zusammensetzung zu untersuchen und die magnetfeldinduzierten Effekte detailliert und grundlegend zu analysieren. Die Arbeit ist in drei wesentliche Abschnitte gegliedert, (1) die Analyse des elektrochemischen Verhaltens, (2) die Untersuchung von Keimbildungs- und Wachstumsprozessen, (3) die Charakterisierung der Morphologie und der physikalischen Eigenschaften der Schichten. 1. Die elektrochemischen Prozesse und Abscheideraten wurden in Abhängigkeit von der magnetischen Flussdichte und Orientierung bezüglich der Elektrodenanordnung detailliert analysiert. Besondere Berücksichtigung fand die die Metallabscheidung begleitende Nebenreaktion, die Wasserstoffreduktion (HER), die signifikant die Eigenschaften der Schichten beeinflusst. Es konnte gezeigt werden, dass die Rate der Metallabscheidung in einem Magnetfeld, welches parallel zur Elektrode ausgerichtet ist, erhöht wird, was auf den klassischen MHD-Effekt zurückzuführen ist, der im Elektrolyten eine Strömung generiert. Im Gegensatz dazu wurde in einem homogenen Magnetfeld das senkrecht auf die Probe gerichtet ist, nahezu kein Einfluss auf die Reduktion der Metallionen gefunden, während die HER-Reaktion signifikant erhöht wird. Die Ursache ist in einer beschleunigten Desorption der Wasserstoffblasen von der Elektrodenoberfläche zu sehen, die durch lokale Konvektion in Blasennähe hervorgerufen und als mikro-MHD Effekt bezeichnet wird. Darüber hinaus bewirkt die magnetfeldinduzierte Konvektion unabhängig von der Magnetfeldorientierung einen geringeren Anstieg des oberflächennahen pH-Wertes. Das wiederum führt zu einer verbesserten Schichtqualität, da die spontane Bildung von Hydroxiden inhibiert wird. 2. Die Keimbildung und der Beginn des Schichtwachstums sind von besonderer Bedeutung für die Elektrokristallisation dünner Schichten, da die Schichteigenschaften wesentlich durch diese Prozesse bestimmt werden. Die Initialschritte der Elektrokristallisation wurden im Detail untersucht und dargestellt. Die Analyse erfolgt auf der Grundlage von Stromdichte-Zeit-Transienten. Es konnte gezeigt werden, dass das Keimbildungsverhalten durch ein überlagertes Magnetfeld beeinflusst wird. Unabhängig von der Zusammensetzung des Elektrolyten, der magnetischen Flussdichte und der Orientierung zur Elektrodenoberfläche wurden vergleichbare Stromdichte-Zeit-Verläufe beobachtet. Keimbildung und Wachstum können durch einen Layer-by-Layer Modus charakterisiert werden. Der erste Keimbildungs- und Wachstumsschritt, der unmittelbar nach dem Anlegen des Abscheidepotentials stattfindet, ist durch eine 2D Schichtbildung (wahrscheinlich epitaktisch) gekennzeichnet, die zur Ausbildung von einigen Monolagen führt. Dieser Schritt wird durch ein äußeres Magnetfeld nicht beeinflusst. Dem 2D-Schritt folgen weitere Keimbildungs- und Wachstumsschritte, die durch ein Maximum im Stromdichte-Zeit-Transienten gekennzeichnet sind. Das Verhalten ist auf Keimbildung und 3D diffusionskontrollierte Wachstumsprozesse zurückzuführen und wird durch ein Magnetfeld parallel zur Elektrodenoberfläche beeinflusst. Die experimentellen Ergebnisse wurden mit Hilfe bekannter theoretischer Modelle analysiert. Es wurde gezeigt, dass die Überlagerung eines parallel zur Oberfläche angeordneten Magnetdfeldes zu einer Verringerung der stationären Keimbildungsrate (AN0) führt, was ebenfalls auf die Wirkung des MHD-Effektes zurückzuführen ist. In der Arbeit wird ein qualitatives Modell für die Legierungsabscheidung in einem überlagerten homogenen Magnetfeld vorgeschlagen, das die beobachteten Phänomene erklärt. Im Gegensatz dazu wurde in einem senkrecht zur Elektrodenoberfläche ausgerichteten Magnetfeld kein Einfluss auf den Keimbildungs- und Wachstumsmechanismus anhand der Stromdichte-Zeit-Transienten festgestellt. Trotzdem wird eine stark veränderte Schichtmorphologie, die ein kolumnares Kornwachstum zeigt, beobachtet. 3. Der Einfluss eines äußeren Magnetfeldes auf die elektrochemischen Abscheideraten, auf die Desorption von Wasserstoff von der Elektrodenoberfläche und auf das Keimbildungsverhalten hat Konsequenzen auf die Schichteigenschaften. Diese können wie folgt zusammengefasst werden: • Der Einfluss eines äußeren Magnetfeldes auf die Schichtmorphologie ist auffallend. Die Qualität der Schichten, die in einem Magnetfeld abgeschieden wurden, wird unabhängig von der Orientierung des Magnetfeldes zur Elektrodenoberfläche deutlich verbessert. Als Ursache ist die beschleunigte Desorption der Wassersoffblasen von der Elektrodenoberfläche anzusehen. Ohne äußeres Magnetfeld verbleiben große Defekte in Form von Löchern auf der Oberfläche, die durch anhaftende Wasserstoffblasen verursacht werden, die in einem überlagerten Magnetfeld nicht beobachtet werden. Schichten, die in einem Magnetfeld parallel zur Elektrodenoberfläche erhalten werden, sind dichter und homogener. Im Gegensatz dazu haben Schichten in einem senkrecht zur Oberfläche abgeschiedenen Magnetfeld eine mannigfaltige Morphologie. Schichten aus Fe und CoFe Legierungen mit einem hohen Eisenanteil wachsen in Form von separaten Körnern und Säulen in Richtung des senkrecht ausgerichteten Magnetfeldes. Mittels Scaling-Analyse wurden Rauhigkeitsexponeten ermittelt, die den glättenden Effekt eines parallel zur Elektrode ausgerichteten Magnetfeldes auf die Schichtmorphologie bestätigen im Vergleich zu Schichten, die ohne Magnetfeld abgeschieden wurden. Die Rauhigkeitsexponenten für Schichten, die in einem senkrecht ausgerichteten Magnetfeld abgeschieden wurden, sind hingegen deutlich erhöht. • Weder auf die kristallographische Struktur noch auf die Textur der Schichten konnte ein Einfluss des überlagerten Magnetfeldes nachgewiesen werden. Alle Schichten unabhängig von den Abscheidebedingungen weisen eine Fasertextur auf. Trotzdem konnte ein signifikanter Einfluss des Magnetfeldes auf die innere Spannung der Schichten bestätigt werden. Insbesondere vermindert sich die innere Spannung von Schichten unabhängig von der Orientierung des angelegten Magnetfeldes, die aus einem gepufferten Elektrolyten abgeschieden wurden. Die Ursache ist auch hier auf die verbesserte Desorption von Wasserstoff zurückzuführen. • Die chemische Zusammensetzung der Schicht wird für die untersuchten Systeme durch ein Magnetfeld nicht verändert. • Die magnetischen Eigenschaften der Schichten werden beeinflußt, wenn während der Elektrokristallisation ein Magnetfeld überlagert wird. Diese Effekte werden durch die mikrostrukturellen Veränderungen, die durch ein überlagertes Magnetfeld induziert werden verursacht, d.h. durch die Rauhigkeit der Schicht, die innere Schichtspannung und die chemische Zusammensetzung. Es wird eine gute Korrelation zwischen der Koerzitivfeldstärke und Rauhigkeit der Schichten gefunden. Darüber hinaus wurde eine in-plane Anisotropie beobachtet, wenn während der Elektrokristallisation ein Magnetfeld parallel zur Elektrodenoberfläche angelegt wurde, obwohl aus röntgenographischen Untersuchungen isotrope Eigenschaften erwartet wurden. Als Ursache für dieses Phänomen wird eine bevorzugten Ausbildung und Ausrichtung von gleichatomigen Paaren im Magnetfeld angenommen.

The aim of this work was to investigate the effects that a magnetic field can induce during the electrodeposition of Ni and Ni-Fe alloys. Special regard was given to mass transport controlled effects. Magnetic field effects on the nucleation and growth of ferromagnetic layers and on the properties of electrodeposited layers (like grain size, texture, morphology or roughness) were investigated. The influence of a magnetic field on the magnetic properties of Ni layers and on the composition of Ni-Fe alloys was also studied. Nucleation and growth of thin Ni layers on gold electrodes under a superimposed magnetic field were analysed in-situ with the Electrochemical Quartz Crystal Microbalance technique. Three theoretical models were chosen for characterizing the Ni nucleation: Scharifker-Hills (SH), Scharifker-Mostany (SM) and Heerman-Tarallo (HT). The AFM images proved that more nuclei appear in a magnetic field in the case that the Lorentz force and the natural convection act in the same direction. From all the models, the HT model gave the best agreement with the AFM results. When the Lorentz force and the natural convection act in the same direction, an increase of the Ni partial current with the magnetic field was obtained. When they act in opposite directions, the Ni current was influenced just at the beginning of deposition (first 10 seconds). At longer times, the magnetic field has no effect on the Ni current. However, the total current (jNi+jHER) decreases with the magnetic field. In the absence of a macroscopic MHD convection, the Ni current decreases with the magnetic field the first 10-15 seconds of deposition. On longer time scales no influence of the magnetic field could be noticed for this configuration. When the magnetic field was applied perpendicular to the electric current, an increase of the hydrogen evolution reaction (HER) with the magnetic flux density was noticed. Hydrogen reduction is mass transport controlled. Therefore, the magnetic field will increase the limiting current of the HER. Optical microscopy images showed that the hydrogen bubbles were circular in the absence of the MHD convection and that they presented a tail when a Lorentz force was present. The direction of the tail depends on the net force induced by the natural and MHD convections. The interplay between the natural and MHD convections proved to be important during Ni-Fe alloy deposition, too. When the Lorentz force and the natural convection act in the same direction, an increase of the Fe content of the alloys with the magnetic field was observed. When the Lorentz force was perpendicular to the natural convection, no significant changes were observed in the composition of the layers. The alloy composition did not change with the magnetic field when the electric current was parallel to the magnetic field lines. Two surfactants were used in the case that Ni was electrodeposited from a sulfamate bath: SDS and sulfirol 8. The Ni layers obtained from a sulfamate bath with sulfirol 8 presented larger grains compared to the layers deposited from a bath free of surfactants. This increase of the grain size was attributed to the incorporation of the surfactant in the deposit. Coarser layers were obtained in a magnetic field (applied perpendicular to the electric current) when the electrodeposition was done from an electrolyte with surfactants. The number of grains increased with the magnetic field for the Ni layers electrodeposited from a bath free of surfactants and for a bath with SDS. As a consequence, the grain size decreased. In the case of the electrolyte with sulfirol 8, the number of grains decreased with the magnetic field, and their size increased. For the Ni-Fe alloys, which contained less than 10 at% Fe, the preferred crystalline orientation changes from (220), in the absence of a magnetic field, to (111), (when the magnetic field was applied perpendicular to the electric current). When the magnetic field lines were parallel to the electric current, both the (111) and (220) textures were preferred in almost the same proportion. As a general conclusion of this work it can be said that by choosing the right experimental condition, one can improve the morphology and the properties of the deposited layers by applying a magnetic field. At the same time, the mass transport processes can be influenced by a magnetic field.

Giant magnetostrictive RFe2 type (R represents rare earths) intermetallics form an important class of magnetic materials keeping in view of their potential applications as sensors and/ or actuators. In this thesis, one such mixed rare earth compound (Tb,Dy)Fe2 has been chosen for investigations. Being a technologically important material system, several investigations concerning physical and magnetic properties of the material and effect of processing parameters on magnetic properties have been reported in the available literature. However, existing literature does not provide a clear insight into some important aspects such as phase equilibria, evolution of texture and microstructure of directionally solidified Tb-Dy-Fe alloys. Therefore, the present work was undertaken to bring out tangible process-structure-property correlations with an emphasis to clarify the grey areas in the available literature. The investigation on the nature of ternary phase equilibria of Tb-Dy-Fe was taken up with an aim to understand the effect of Tb/Dy ratio on phase equilibria and magnetic properties of TbxDy1-xFe1.95 (x=0-1) alloys. Microstructural and micro-chemical analysis along with study of lattice parameter has been used to predict the nature of phase equilibria and the deviation from the assumed pseudo-binary behaviour. Further, from the microstructural investigations and study of lattice parameter and Curie temperature, a schematic sketch of a section of the ternary diagram, where (Tb,Dy) / Fe =1.95, was formulated and presented. Directional solidification technique is the most widely adopted method for processing the (Tb,Dy)Fe2, to impart grain orientation for practical applications. Therefore, it was aimed in the present study to understand the evolution of texture and microstructure in directionally solidified Tb0.3Dy0.7Fe1.95 alloy by modified Bridgman and zone melting techniques. The alloy was directionally solidified by modified Bridgman technique with a series of growth rates 5 - 100 cm/h, at a constant temperature gradient of 150oC/ cm. Microstructural investigation revealed formation of island banding at lower growth rate and peritectic coupled growth at higher growth rates. The texture study indicated a transition of growth texture from <113> to <110> and finally to <112> with increase of growth rate. A mechanism based on atomic attachment kinetics is proposed to explain the orientation selection with growth rate. The texture and microstructure have been correlated with magnetostriction and static strain co-efficient (dλ/dH) of the Bridgman solidified alloys. The solidification morphology observed in Bridgman solidified samples was found to be mostly plane front. Therefore, in order to understand the microstructure and texture evolution in cellular/ dendritic regime, directional solidification of Tb0.3Dy0.7Fe1.95 was attempted by zone melting technique with a lesser temperature gradient of 100oC/cm. A detailed texture study indicated a transition in preferred growth direction from <110> to <112> with increase of growth rate. In this case of cellular/ dendritic growth regime, a mechanism based on atomic attachment kinetics has been proposed and the preferred morphologies of the solid-liquid interface for <110> and <112> growth have been modelled. The modelled interfaces have been correlated to the shape of cell/ dendrite cross-section observed for the growth rates adopted in this study. Apart from the investigation carried out on the (Tb,Dy)Fe2 alloys, attempts have been made to understand the role of microstructure, especially the ordered phases on the magnetostriction of an emerging magnetostrictive material Fe-Ga. A series of alloy compositions of Fe-x at % Ga (x=17, 20, 23 and 25) were prepared and subjected to different thermal treatments and characterized for microstructural features and magnetostriction. Microstructure investigation of slow cooled, quenched and quenched + aged alloys reveals formation of ordered DO3 phase from disordered A2 phase by first order transformation in 17 and 20 at% Ga alloys, whereas for 23 and 25 at% alloys, the transformation takes place by continuous ordering. It could be observed that large magnetostriction arises owing to the presence of disordered A2 phase or ordered DO3 phase alone. The magnetostriction however decreases substantially when these two phases are co-existing.

Iron platinum (FePt) has attracted growing interest because of its high Curie temperature, magneto-crystalline anisotropy and chemical stability. Nanoparticles (NPs) made of this alloy are promising candidates for a wide range of biomedical applications including magnetic separation, magnetic targeted drug delivery, hyperthermia for cancer therapy and also as magnetic resonance imaging (MRI) contrast agents. This thesis presents the synthesis, functionalization and characterization of FePt NPs along with a toxicity study and an investigation into their application as MRI contrast agents. Regarding their synthesis, different approaches have been explored including the co-reduction of Fe and Pt precursors in an aqueous media, the thermal decomposition in a conventional high-boiling solvent such as benzyl ether, and in low-melting organic salts (ionic liquids). The data revealed an inhomogeneous composition distribution of Fe and Pt between particles obtained in aqueous media, due to the iron salts hydrolysis, and a mismatch in the co-reduction kinetic of the two metal precursors. While the iron content in the NPs could be increased by using more hydrolytically stable iron precursors or stronger reducing agents, there are remaining limiting parameters which prevent further Fe content increase in NPs. In contrast, by excluding the water from the reaction system and using a Fe²⁻ iron precursor, homogenous 1:1 Fe to Pt ratio NPs can be obtained through a modified thermal decomposition pathway in benzyl ether. Based on the study of synthesis in this conventional chemical, the potential of ionic liquids (ILs) to be used as novel solvents for FePt NPs synthesis was further explored. It was then demonstrated that ionic liquids (ILs) can not only be used as a solvent for synthesis of FePt NPs, but also can provide an exciting alternative pathway to direct synthesis fct-FePt NPs. In the context of the bioapplication of FePt NPs, a family of FePt NPs was specifically designed to enhance their MRI contrast agents properties. In contrast with previous reports, this thesis demonstrates that FePt NPs can be made non-toxic and provides the first data on their cellular uptake mechanisms. A six times increase in the FePt based T₂ contrast properties compared to clinical iron oxide NPs is reported. The relationship between the MRI contrast properties and the NPs architecture is explored and rationalised as the basis for the design of NPs as enhanced MRI contrast agents. Finally, the first observations of cellular and in vivo MR imaging with FePt NPs is also reported. This study opens the way for several applications of FePt NPs such as regenerative medicine and stem cell therapy, thus providing a bio-platform to develop novel diagnostic and therapeutic agents.

As the major electricity consumer, electrical machines play a key role for global energy savings. Machine manufacturers put considerable efforts into the development of more efficient electrical machines for loss reduction and higher power density achievements. A consolidated knowledge of the occurring losses in electrical machines is a basic requirement for efficiency improvements. This thesis deals with iron losses in electrical machines. The major focus is on the influences of the stator core magnetic material due to the machine manufacturing process, temperature influences, and the impact of inverter operation. The first part of the thesis gives an overview of typical losses in electrical machines, with focus put on iron losses. Typical models for predicting iron losses in magnetic materials are presented in a comprehensive literature study. A broad comparison of magnetic materials and the introduction of a new material selection tool conclude this part. Next to the typically used silicon-iron lamination alloys for electrical machines, this thesis investigates also cobalt-iron and nickel-iron lamination sheets. These materials have superior magnetic properties in terms of saturation magnetization and hysteresis losses compared to silicon-iron alloys. The second and major part of the thesis introduces the developed measurement system of this project and presents experimental iron loss investigations. Influences due to machine manufacturing changes are studied, including punching, stacking and welding effects. Furthermore, the effect of pulse-width modulation schemes on the iron losses and machine performance is examined experimentally and with finite-element method simulations. For nickel-iron lamination sheets, a special focus is put on the temperature dependency, since the magnetic characteristics and iron losses change considerably with increasing temperature. Furthermore, thermal stress-relief processes (annealing) are examined for cobalt-iron and nickel-iron alloys by magnetic measurements and microscopic analysis. A thermal method for local iron loss measurements is presented in the last part of the thesis, together with experimental validation on an outer-rotor permanent magnet synchronous machine. / <p>QC 20140516</p>