Title: Ground state investigations of Ce and U intermetallic compounds Author: Attila Bartha Department: Department of Condensed Matter Physics Supervisor: RNDr. Jan Prokleška, Ph.D., Department of Condensed Matter Physics Abstract: Rare earth and actinide intermetallic compounds offer a plethora of interesting physical properties due to the varied behavior of f -electrons together with numerous interactions these electrons are exposed to. In this thesis we address a broad spectrum of ground state investigations on CePd2X3 (X=Zn, Ga) and (Ce,U)nTIn3n+2 (T=Rh, Ir) compounds. Single crystals of CePd2Zn3 and CePd2Ga3 compounds were synthesized for the first time using Bridgman method. CePd2Ga3 revealed a ferromagnetic transition with TC = 6.7 K with a strong magnetocrystalline anisotropy. CePd2Zn3 orders antiferromagnetically below TN = 1.9 K. Results of magnetization measurements on Ce2IrIn8 revealed effective magnetic moment µeff = 2.45µB/Ce3+ and a paramagnetic Curie temperature θP = −31 K. Decomposition of Hall resistivity ρxy(B) into NHE and AHE revealed a predom- inance of AHE in the temperature range from 60 K up to 100 K. Ce2RhIn8 was studied by means of magnetic field and angle dependent magnetization and heat capacity measurements. The resulting phase diagram reveals a complete unfold- ing and...

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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.:Einleitung 1 Grundlagen 2 YbPt2Sn und YbPt2In 3 Adiabatische Entmagnetisierung von YbPt2Sn 4 Struktureller quantenkritischer Punkt in Lu(Pt1-xPdx)2In 5 Zusammenfassung und Ausblick

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.

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No presente trabalho quatro ligas Al-Si hipereutéticas, três das quais foram produzidas por conformação por \"spray\" e a outra por fundição, foram caracterizadas quanto a textura, dureza, microestrutura e resistência à corrosão em meio de condensado sintético automotivo (CSA). Duas das ligas conformadas por \"spray\" foram retiradas de camisas de cilindro e a outra de um pré-formado obtido em laboratório. A conformação por \"spray\" envolve a atomização de uma liga e a deposição de gotículas em um substrato, antes mesmo que todas se encontrem no estado sólido. Este processo permite a obtenção de materiais que se caracterizam por uma microestrutura livre de macrossegregações e bastante refinada, implicando melhor trabalhabilidade a quente. A caracterização da microestrutura das quatro ligas hipereutéticas revelou a presença de porosidades na liga obtida em laboratório, e microestrutura com distribuição homogênea de precipitados primários nas três ligas conformadas por \"spray\". A microestrutura de uma das ligas apresentou-se muito diferenciada, com a presença de eutético, sugerindo que esta foi fabricada por fundição. Nas camisas de cilindro foram feitas medidas de rugosidade, e em todas as ligas foram realizados ensaios de microdureza. A liga conformada por \"spray\" e obtida em laboratório foi laminada a quente e a frio. Foram realizados também estudos de textura, para tentar estabelecer uma correlação entre todas as ligas quanto ao processo de fabricação. A avaliação da textura indicou que a presença de fases de silício primário, finamente distribuídas impedem o aparecimento de texturas típicas de deformação de ligas de alumínio, mesmo após severas deformações, como as necessárias para a transformação de pré-formados em tubos que originam as camisas de cilindro. As medidas de rugosidade indicaram características próprias do acabamento superficial usado para a produção das camisas, por brunimento ou por ataque químico. Os ensaios de microdureza apresentaram variações de acordo com as rotas de fabricação sendo que a liga eutética apresentou os maiores valores de microdureza em comparação às ligas conformadas por \"spray\". Todas as ligas foram avaliadas quanto a resistência à corrosão por ensaios de espectroscopia de impedância eletroquímica em dois meios, CSA com pH 3,3 e CSA com pH 11. As quatro ligas hipereutéticas estudadas apresentaram mecanismo de corrosão similar em condensado sintético automotivo (CSA) pH 3,3. Em todas ocorreu o ataque intenso da matriz de alumínio e as partículas de silício primário atuaram como regiões catódicas. A liga 2 apresentou maior resistência à corrosão entre todas as ligas ensaiadas, tanto em CSA pH 3,3 como em pH 11. Neste último meio, uma camada de produtos de corrosão formou-se sobre todas as ligas, e os resultados indicaram mecanismos diferentes para o ataque da matriz de Al e para o crescimento da camada depositada na superfície das ligas estudadas. O ataque da matriz da liga 2 neste meio foi aparentemente mais lento do que sobre as demais ligas, com a formação de uma camada mais compacta de produtos de corrosão, estabelecendo um controle por difusão dos processos interfaciais para maiores períodos de ensaio. A camada formada sobre as demais ligas neste meio apresentou-se mais defeituosa, e nestas ocorreu também menor controle da velocidade das reações interfaciais por processos difusionais. / In the present study four hypereutectic Al-Si alloys, three produced by spray forming and one by casting, were characterized for microhardness, roughness, microstructure, texture and corrosion resistance in a synthetic automotive condensed solution (SACS). Two of the spray formed alloys tested were obtained from cylinder liners and the other was laboratory made. Spray forming involves alloy atomization and droplets deposition on a substrate, previous to the solidification of all of the droplets. This process favours the production of materials with a fine microstructure free of macrosegregation that is related to improved hot workability. The microstructure characterization of the four alloys revealed the presence of porosities in the laboratory made alloy. All the three alloys produced by spray forming showed a homogeneous distribution of primary precipitates. The microstructure of one of the alloys showed eutectic microstructure, indicating that this alloy was fabricated by casting. In the cylinder liners, the surface roughness was measured and the microhardness of all the alloys was also evaluated. Furthermore, the laboratory made alloy was hot and cold rolled. Texture determinations were carried out to investigate the correlation between the alloy type and their fabrication process. The texture investigation indicated that the fine distribution of primary silicon phase in the alloy hindered the development of texture typical of aluminium alloys deformation, even after severe mechanical work, such as those used in the conversion of pre-formed in cylinder liners. The surface roughness results indicated typical characteristics of the surface finishing used, honing or chemical etching. The microhardness results were dependent on the fabrication process used, with higher microhardness associated to the eutectic alloy comparatively to the spray formed ones. All hypereutectic alloys were tested for corrosion resistance using electrochemical impedance spectroscopy in two electrolytes, SACS with pH 3.3 and SACS with pH 11. The four tested alloys showed similar corrosion mechanisms in the acid electrolyte (SACS pH 3.3). The intense attack of the aluminium matrix occurred in ali tested alloys and the primary silicon phase was unattacked and appeared as emerging from the surface after corrosion immersion test. The primary silicon particles acted as cathodic sites. The alloy 2 showed the highest corrosion resistance among the tested alloys in both electrolytes, SACS pH 3.3 and SACS pH 11. In this last medium, a layer of corrosion products formed on all the alloys, and the results indicated different mechanisms for the aluminium matrix corrosive attack and growth of the deposited layer on the alloys surface. The kinetics of aluminium matrix attack was apparently slower in the alloy 2 than for the other alloys, resulting in the formation of a more compact layer of corrosion products, leading to diffusion controlled interfacial processes for longer test periods. The layer of corrosion products on the other three alloys (1, 3, and 4) had more defects and for these alloys diffusional controlled interfacial processes were not as significant as for alloy 2.

Obwohl ultrahohe Magnetfelder jenseits von 100 T mittels spezieller Methoden experimentell nutzbar wurden, sind Magnetisierungsmessungen in diesen Feldern noch immer sehr kompliziert. Magnetfelder im Megagauß-Bereich lassen sich heute allein durch die semidestruktive Single-Turn-Coil (STC)-Methode und durch die vollständig destruktive Flußkompression erzeugen. In beiden Fällen sind die gepulsten Felder auf eine Dauer von wenigen Mikrosekunden und ein nutzbares Feldvolumen von wenigen Kubikzentimetern beschränkt. Dadurch bedingt sind nur solche Methoden für Magnetisierungsmessungen anwendbar, die sich an diese ungünstigen Randbedingungen anpassen lassen. Die Faraday-Rotation kann für optisch transparente Proben sinnvoll sein, jedoch ist die induktive Messung mittels kompensierter Pick-up-Spulen die einzige direkte Methode. Die vorliegende Arbeit beschreibt die Entwicklung und Anwendung eines solchen Meßsystems in einem STC-Feldgenerator. Im Hinblick auf das Meßsystem hat sich die sehr gute geometrische Kompensation der Pick-up-Spulen als wesentlich herausgestellt. Wichtig sind daneben aber auch eine hohe Bandbreite bzw. eine unverzerrte Sprungantwort. Als äußerst effektiv hat sich insbesondere die umfassende elektromagnetische Abschirmung des Meßsystems erwiesen, so daß die vom STC-Generator ausgehenden Störungen weitgehend unterdrückt werden. Besondere, für Magnetisierungsmessungen ungünstige Eigenschaften des STC-Systems, werden dargestellt und diskutiert. Magnetisierungsmessungen bei tiefen Temperaturen an den van Vleck-Paramagneten TmPO4 und TmPO4 ergaben Anomalien bei rund 30 T bzw. 50 T für ein Feld parallel zur tetragonalen Achse. Dieser Effekt resultiert aus einer Überkreuzung der beiden niedrigsten Energieniveaus in starken Magnetfeldern und führt zu einem scharfen Sprung in der Magnetisierung. Temperaturabhängige Messungen belegen den wesentlichen Einfluß des magnetokalorischen Effekts in kurzen gepulsten Feldern. Pulverproben der intermetallischen Verbindungen RMn2Ge2 (R = Gd, Tb, Dy, Ho, Er, Y) wurden bei Helium-Temperaturen in Feldern bis zu 150 T untersucht. Abhängig vom Selten-Erd-Ion wurden in allen Verbindungen ein oder mehrere feldinduzierte metamagnetische Phasenübergänge beobachtet. Sie können auf eine Änderung der magnetischen Struktur des Mn-Untersystems zurückgeführt werden. Die kritischen Felder für den Übergang zur ferromagnetischen Phase betragen zwischen 90 T und 118 T (YMn2Ge2: 55 T). Detaillierte Rechnungen werden im Rahmen eines erweiterten Molekularfeld-Modells durchgeführt. / Although ultrahigh magnetic fields in excess of 100 T have become available by specialized techniques, magnetization measurements in these fields are still a challenging task. Nowadays, magnetic fields in the megagauss range can be produced only by the semidestructive single-turn coil (STC) technique and by the fully destructive flux compression. In both cases these pulsed fields are limited to microsecond pulse duration and a usable field volume of not more than a few cubic centimeters. As a result, only those methods can be used for magnetization measurements, which can be adapted to these difficult boundary conditions. The Faraday rotation can be suitable for optically transparent samples, but the only direct technique is the induction method based on compensated pick-up coils. The present work deals with the development of such a measurement system and its application to various materials in fields up to 150 T produced by the STC. Regarding the measurement system, geometrically very well compensated pick-up coils turned out to be absolutely necessary as well as a large bandwidth and an appropriate transient response. In particular a comprehensive electromagnetic shielding, which makes use of a wire metal, proved to be very effective in suppressing disturbances produced by the STC system. Besides, some inherent characteristics and limitations of the STC generator with respect to magnetization measurements are revealed and discussed. Magnetization measurements were performed on the van Vleck paramagnets TmPO4 and PrVO4, and anomalies were found at about 30 T and 50 T, respectively, at low temperatures for a field along the tetragonal axis. This effect is due to a crossing of the lowest energy levels in high magnetic fields and results in a sharp jump in magnetization. Temperature dependent measurements provide evidence that the magnetocaloric effect plays an essential role in short pulse fields produced by the STC. Powder samples of the intermetallic compounds RMn2Ge2 (R = Gd, Tb, Dy, Ho, Er, Y) have been investigated at liquid helium temperature up to 150 T. Depending on the rare-earth ion one or more field-induced metamagnetic phase transitions have been observed in all compounds, and they are found to be associated with a change in the magnetic structure of the Mn subsystem. The phase transitions to the ferromagnetic phase occur between 90 T and 118 T (YMn2Ge2: 55 T). Detailed calculations are performed using an extended molecular field model.

The corrosion behaviour of cast Al-Mg alloy A535 and its composites containing 10 wt.% and 15 wt.% fly ash, and 10 wt.% hybrid reinforcement (5 wt.% fly ash + 5 wt.% SiC) was investigated using weight-loss and electrochemical corrosion tests, optical microscopy, Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDS). The tests were conducted in fresh water collected from the South Saskatchewan River and 3.5 wt.% NaCl solution at room temperature. The pH of the salt solution varied from 3 to 9. For comparison, two other aluminum alloys, AA2618 and AA5083-H116, were tested in the same electrolytes. The results of the weight-loss corrosion test showed that unreinforced A535 alloy had a lower corrosion rate in fresh water and seawater environments than the composites at all the tested pH values. The corrosion rate of the composites increased with increasing fly ash content. As expected, the corrosion rates of A535 alloy and the composites tested in fresh water were lower than those in salt solution. The results of the potentiodynamic and cyclic polarization electrochemical tests showed that the corrosion potential (Ecorr) and pitting potential (Epit) of the alloy were more positive than those of the composites. The corrosion and pitting potentials of the composites became more negative (active) with increasing fly ash content. The composites showed more positive (noble) repassivation or protection potential (Erp) than the matrix alloy, with the positivity increasing with fly ash content. Analysis of the electrochemical noise data showed that pitting corrosion was the dominant mode of corrosion for the alloy in 3.5 wt.% NaCl solution. Optical microscopy and SEM revealed that Mg2Si phase and Al-Mg intermetallics corroded preferentially to the matrix. The EDS data indicated that the protective oxide film formed on A535 contained Al2O3 and MgO.

Sc(AlxNi1-x)2 is a pseudobinary C14 Laves phase and a potential interstitial hydrogen storage material or anode in a Ni-MH battery. A previous study showed that Sc1Al1Ni1 can store hydrogen reversibly; both interstitially and trough decomposition into ScH2 and AlNi. It is also known that the exact composition is very important for the hydrogen storage properties of pseudobinary Laves phases. This thesis work is aimed at synthesising Sc(AlxNi1-x)2 and study the effect of the Ni/Al ratio on the hydrogen absorption/desorption process as well as the interstitial storage capacity. Compositions with high nickel content had the highest capacity (at least 0.67wt% for ScAl0.66Ni1.34) and ones with high aluminium content had the lowest total storage capacity (0wt% for ScAl1.28Ni0.62). The former composition was also shown to absorb and desorb hydrogen during multiple cycles. Desorption of interstitial hydrogen from ScAl0.66Ni1.34 requires 4.6kJ/mol in activation energy.

The corrosion behaviour of cast Al-Mg alloy A535 and its composites containing 10 wt.% and 15 wt.% fly ash, and 10 wt.% hybrid reinforcement (5 wt.% fly ash + 5 wt.% SiC) was investigated using weight-loss and electrochemical corrosion tests, optical microscopy, Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDS). The tests were conducted in fresh water collected from the South Saskatchewan River and 3.5 wt.% NaCl solution at room temperature. The pH of the salt solution varied from 3 to 9. For comparison, two other aluminum alloys, AA2618 and AA5083-H116, were tested in the same electrolytes. The results of the weight-loss corrosion test showed that unreinforced A535 alloy had a lower corrosion rate in fresh water and seawater environments than the composites at all the tested pH values. The corrosion rate of the composites increased with increasing fly ash content. As expected, the corrosion rates of A535 alloy and the composites tested in fresh water were lower than those in salt solution. The results of the potentiodynamic and cyclic polarization electrochemical tests showed that the corrosion potential (Ecorr) and pitting potential (Epit) of the alloy were more positive than those of the composites. The corrosion and pitting potentials of the composites became more negative (active) with increasing fly ash content. The composites showed more positive (noble) repassivation or protection potential (Erp) than the matrix alloy, with the positivity increasing with fly ash content. Analysis of the electrochemical noise data showed that pitting corrosion was the dominant mode of corrosion for the alloy in 3.5 wt.% NaCl solution. Optical microscopy and SEM revealed that Mg2Si phase and Al-Mg intermetallics corroded preferentially to the matrix. The EDS data indicated that the protective oxide film formed on A535 contained Al2O3 and MgO.