Nb3Sn Rutherford cables are used in CERN’s superconducting 11 T dipole and MQXF quadrupole magnets, which are proposed for the instantaneous luminosity (rate of particle collisions) upgrade of the Large Hadron Collider (LHC) by a factor of five to a High Luminosity-Large Hadron Collider (HL-LHC). Nb3Sn-based conductors are the key technology for the envisioned Future Circular Collider (FCC) with an operating magnetic dipole field of 16 T. The baseline superconductor of the LHC dipole magnets is Nb–Ti, whereas an operation above 10 T is not possible due to the current carrying performance limitations of this superconductor at higher magnetic fields. Therefore, a superconducting material such as Nb3Sn has to be used with proven performance capabilities of 10 T and above. The conductor choice towards Nb3Sn-based cables affects the magnet manufacturing process, as it requires a heat treatment up to 650°C, an epoxy resin impregnation and introduces mechanical diffculties as the superconducting filaments are brittle and strain sensitive. A mechanical over loading of the filaments lead to irreversible conductor damage. The designs of 11 and 16 T magnets are supposed to push the conductor towards its mechanical and electrical performance limitations. The magnetic field induced forces on the current carrying conductor are balanced by mechanical pre-loading of the magnet. Thereby the highest controlled mechanical pre-load for the 11 T dipole magnet is set at ambient temperature. The mechanical stress limits of Nb3Sn-based cables have been investigated at cryogenic temperatures. The material strength and stiffness of the cable insulation system, formed by glass-fibre-reinforced resin, is increased at low temperatures. The ultimate stress values, determined at cryogenic temperature, are therefore not conservative. The ultimate stress limitation of the insulated conductor is assumed to be lower at ambient temperature. The cable limitations at ambient temperature need to be known for the ongoing magnet manufacturing process and also for future design approaches. Furthermore, the compressive stress–strain behaviour of a coil conductor block at ambient temperature is the key material characteristic, in order to recalculate the stress level in the coil during the assembly process. Existing approaches using an indirect strain measurement method provide uncertainties in the low-strain regime, which is the essential strain range for a material compound consisting of major fractions composed of heat-annealed copper and epoxy resin. Compressive stress–strain data of an impregnated conductor block are required, based on a direct strain measurement system, as available data have been collected on samples based on a different strand type and insulation system. The elaborated direct strain measurements can be correlated to strain gauge data, measured directly on a coil. The stress distribution in a Nb3Sn Rutherford cable need to be understood and validated to understand strain-induced degradation effects in the insulated conductor. This knowledge can also help to optimise the stress distribution envisioned magnet designs. The stress–strain state in the copper and Nb3Sn phase of a loaded conductor block has to be determined experimentally. This dissertation describes a test protocol and first elaborated results on the investigated stress limitations of a Nb3Sn Rutherford cable under homogeneous load applied in transversal direction. The compressive stress–strain behaviour of impregnated Nb3Sn Rutherford cable stacks was investigated experimentally. This includes a detailed report on the sample manufacturing process, measurements performed and validation of results through a comparison with the elaborated data of cable stacks extracted from a coil. The presented results from neutron diffraction measurements of loaded cable stacks allow the determination of the stress–strain level of the copper and Nb3Sn phase in the impregnated conductor. The relevant measured results have been recalculated with numerical calculations based on the Finite Element Method (FEM).:1. Introduction 1 1.1. The LHC and the HL-LHC project 1.2. The FCC study 1.3. Superconducting materials for accelerator magnets 1.4. Multi-filamentary wires and Rutherford cables 1.5. Coil manufacturing process 1.6. Magnet coil assembly 1.7. Objectives of this thesis 2. Theory: fundamental principles 17 2.1. Analytical calculation: sector coil dipole 2.2. Mechanical behaviour of composite materials 2.3. Failure criteria and strength hypotheses for materials 2.4. Compressive tests 2.5. Fundamental principles of Neutron scattering 2.5.1. Test apparatus and measurement method 2.5.2. Lattice plane and Miller indices 2.5.3. Bragg diffraction and interference 2.5.4. Diffraction-based strain calculation 2.5.5. Diffraction-based stress calculation 2.6. Fundamental principles of FEM 3. Homogeneous transversal compression of Nb3Sn Rutherford cables 3.1. Superconducting cable test stations 3.2. The FRESCA test facility and specific sample holder 3.3. The sample description 3.4. Experimental procedure 3.5. Review of existing contact pressure measurement system 3.6. Compressive test station 3.7. Validation of the pressure-sensitive films 3.8. Press punch 3.9. Improvement of the contact stress distribution 3.9.1. First test: cable pressed between the bare tools 3.9.2. Second test: tool shimmed with a soft Sn96Ag4 3.9.3. Third test: tool shimmed with a soft Sn60Pb40 3.9.4. Fourth test: tool shimmed with a soft indium 3.9.5. Fifth test: tool shimmed with a polyimide film 3.10. Test results 3.11. Conclusion 4. Material characterisation by a compression test 4.1. Test set-ups for compressive tests and validation 4.2. Sample preparation 4.3. Compressive stress–strain measurement 4.4. Ten-stack sample stiffness estimation-based composite theories 4.5. Dye penetration test on loaded and unloaded samples 4.6. Conclusion 5. Neutron diffraction measurements 80 5.1. Test set-up for neutron diffraction measurement 5.2. The samples 5.3. Experiment: lattice stress–strain measurements 5.4. Conclusion 6. Simulation and modelling of Nb3Sn cables 6.1. The models 6.2. The 2D simulation results 6.3. The 3D simulation results 6.4. Conclusion 7. Comprehensive summary 7.1. Summary 7.2. Critical review 7.3. Next steps Appendix 113 A. Calculation of the magnetic field components in a sector coil without iron B. Approaches for the determination of diffraction elastic constants C. Manufacturing drawings D. FEM calculation results of the 2D model E. FEM calculation results of the 3D model F. Source Codes Bibliography

Ce travail est consacré à la synthèse et à la caractérisation de composés chalcogénures. Pour la plupart nouveaux, ces composés ont la particularité de présenter des structures complexes ou dont le désordre amène une certaine complexité. La première partie de ce manuscrit est consacré à l’étude du nouveau composé monocristallin Ba0,5Cr5Se8 et de la solution solide polycristalline BaxCr5Se8 (0,5 ≤ x ≤ 0,55). Ce composé fait partie de la famille des pseudo-hollandites. Sa structure cristalline a été déterminée par diffraction des rayons X sur monocristal, un abaissement de la symétrie est observé par rapport aux pseudo-hollandites usuelles. Ces composés sont antiferromagnétiques avec une température de transition unique à 58 K, la structure magnétique du composé a été déterminée par diffraction des neutrons sur échantillon polycristallin, et sa maille magnétique correspond à une maille cristalline doublée selon b et c. Les propriétés thermoélectriques des composés sont étudiées, Ba0.5Cr5Se8 présente une ZT de 0,12 à 800 K. La deuxième partie s’est d’abord focalisée sur une structure similaire à la précédente, TlIn5Se8. Toutefois trop résistif, les structures de deux nouveaux composés ont été étudiées : TlIn4,8Cr0,2Se8 et Tl0,98In13,12Se16,3Te2,7. Ce dernier présente sur certains sites un désordre considéré statique. Finalement, le dernier chapitre a permis de mettre en avant des composés de la famille de composé lamellaire MnPSe3, ayant la particularité de présenter une paire P2. La structure du nouveau composé In2Ge2Te6 est résolue et les propriétés thermoélectriques des composés InSiTe3, Cr2Si2Te6, Cr2Ge2Te6 et In2Ge2Te6 sont étudiées. Des défauts d’empilement ont été mis en lumière et expliquent l’impact sur le libre parcours moyen des phonons. L’ensemble des composés dont les propriétés thermoélectriques ont été étudiées présentent des conductivités thermiques faibles, bien en deçà du W.m-1.K-1 dans de nombreux cas. Des ZTs de 0,18 à 673 K et 0,43 à 773 K sont trouvées pour In2Ge2Te6 et Cr2Ge2Te6. / This work has been focused on synthetizing and characterising chalcogenide compounds. Most new, those compounds show complex structures or where disorder bring complexity. The first part of this manuscript is dedicated to the study of the new single-cristalline Ba0.5Cr5Se8 and of the related polycristalline solid-solution BaxCr5Se8 (0.5 ≤ x ≤ 0.55). This compound is part of the pseudo-hollandite family. Its cristalline structure has been resolved by means of single-crystal X-ray diffraction, a lowering of symetryis observed compared to usual pseudo-hollandites. All antiferromagnetic, the compounds exhibit a transition at 58 K, the magnetic structure has been resolved using neutron diffraction on polycrystal and is twice the cristalline one along b and c. Thermoelectric properties of the compounds have been studied and a maximum ZT of 0.12 is observed at 800 K for Ba0.5Cr5Se8. The second section has first focused on a similar structure to the previous one, TlIn5Se8. Although too resistive to be interesting, two new compounds have been studied: TlIn4.8Cr0.2Se8 and Tl0.98In13.12Se16.3Te2.7. The latter quaternary exhibits static disorder on specific crystallographic sites. The last chapter highlights compounds from the lamellar compound MnPSe3 family, with the particularity to possess P2 pairs. The structure of the new In2Ge2Te6 has been resolved and thermoelectric properties of the InSiTe3, Cr2Si2Te6, Cr2Ge2Te6 and In2Ge2Te6 have been studied. Stacking faults were observed in In2Ge2Te6 and explain the impact on the phonon mean free path. All the compounds whose thermoelectric properties have been studied exhibit low thermal conductivity, below 1 W.m-1.K-1 for most of them. ZTs of 0.18 at 673 K and 0.43 at 773 K were found for In2Ge2Te6 and Cr2Ge2Te6.

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...

Die Hydrierung von Zintl-Phasen führt zur Bildung von Einlagerungshydriden, die ausschließlich von Kationen koordiniert sind, zu polyanionischen Hydriden, bei denen Wasserstoff kovalent an das stärker elektronegative Element bindet, oder zu einer Kombination von beiden Motiven. Es wurde eine Reihe neuer Verbindungen dargestellt und mittels Laborröntgen-, Synchrotron- und Neutronenpulverbeugung strukturell charakterisiert. Die meisten Beispiele werden durch die Hydrierung von Zintl-Phasen im CrB- oder FeB-Strukturtyp erhalten. Die beiden Typen sind strukturell eng verwandt. Sie sind durch das Auftreten von polyanionischen Zickzackketten gekennzeichnet. Die Einlagerungshydride LnTtH (Ln = La, Nd, Tt = Si, Ge, Sn) sind Oxidationsprodukte der formal metallischen Zintl-Phasen LnTt = Ln3+ Tt2- e- . Wasserstoff besetzt dabei Ln-Tetraederlücken. Die Produkte treten als gefüllter FeB- (P -Phase, LaGeH-Strukturtyp) oder als gefüllter CrB-Strukturtyp (C -Phase, NiZrH-Strukturtyp) auf. Die Hydrierung der elektronenpräzisen Zintl-Phasen AeTt (Ae = Sr, Ba, Tt = Ge, Sn, CrB-Strukturtyp) führt zu wasserstoffarmen (AeTtHy , y < 1) und wasserstoffreichen (AeTtHy , 1 < y ≤ 2) Phasen. Erstere weisen partiell gefüllte Ae4-Lücken auf. In Phasen mit kleinem y (< 0.4) wird der Wasserstoff statistisch über die Lücken verteilt (α-Phasen). Etwas höhere Gehalte führen zu partieller (β-SrGeHy , 0.47 < y < 0.75) oder vollständiger (β-BaGeH0.5 ) Ordnung. Die wasserstoffreichen Phasen AeTtHy , 1 < y ≤ 2 (γ-Phasen), zeigen sowohl die Strukturmotive von Einlagerungs- als auch von polyanionischen Hydriden. SrSiH1.6 und BaSiH1.9 als literaturbekannte Verbindungen wurden das erste mal strukturell charakterisiert. Die homologe Reihe konnte um SrGeH1.2 , BaGeH1.6 und BaSnH1.3 erweitert werden. Die Ae4 -Tetraeder sind in diesen Phasen vollständig mit Hydridionen besetzt. Zusätzlicher Wasserstoff bindet kovalent an die Polyanionen. Außerdem verknüpfen sich die Zickzackketten z. T. senkrecht zur Kettenrichtung. Es wurden insgesamt drei Strukturtypen differenziert, die alle strukturell eng verwandt sind. Das führt zu Problemen bei der Strukturbestimmung aus Pulverdaten. Der kovalente Charakter der Bindung wurde durch Festkörperkernresonanzspektroskopie und Dichtefunktionaltheorierechnungen charakterisiert. Typische Tetrel-Wasserstoff-Bindungslängen sind 155(2) pm (Si-H), 163(2) pm (Ge-H) und 186(1) pm (Sn-H). In situ -Neutron, Röntgen- und Synchrotronpulverbeugung wurden angewandt um Reaktionsabläufe aufzuklären. Beim Heizen unter Wasserstoffdruck treten im AeTt-H2 -System (Ae = Sr, Ba, Tt = Ge, Sn) verschiedene reversible Reaktionen zwischen den γ-, β- und α-Phasen auf, bevor ein irreversibler Zersetzungsschritt in die binären Hydride AeH2 und die Tt-reichen Zintl-Phasen AeTt2 beobachtet wird. Ein In situ Beugungsexperiment der Reaktion von NdGa mit Wasserstoff zeigt direkt die Bildung von NdGaH1+x (isostrukturell zu γ-AeTtHy ), das eine Zusammensetzung von mindestens x = 0.17 bis 0.80 aufweist. Die Ga-H Abstände sind lang (ca. 200 pm) und darum keine klassischen 2-Elektronen-2-Zentrenbindungen. In situ Beugung an den Reaktionen von KSi und CsSi mit Wasserstoff konnte gezeigt werden, dass die Hydride KSiH3 und CsSiH3 in einem Schritt gebildet werden. Diese Phasen weisen SiH3--Anionien auf, die isoelektronisch zu PH3 sind. Weiteres Heizen unter Wasserstoffdruck führt zur Zersetzung in KH und K8Si46 oder zur Rückbildung von CsSi. Außerdem wurde eine Reihe weiterer Verbindungen auf die Reaktivität gegenüber Wasserstoff untersucht. Die Phasen AeTt2 , AGe und ASixGe1-x (A = K, Rb, Cs) bilden keine Hydride unter den untersuchten Bedingungen (mindestens 5 MPa H2, 700 K). Die Gallide CaGa, Sr8Ga7 und Ba8Ga7 weisen Reaktivität gegenüber Wasserstoff auf. Diese Beispiele zersetzen sich in binäres Hydrid und die galliumreichen Phasen Ca3Ga8, SrGa4 und BaGa4 . In situ Laborröntgenbeugung der Reaktion von CaGa mit Wasserstoff führt zur Bildung einer neuen, kristallinen Phase. Bildung und Zersetzung laufen in einem sehr schmalen Temperaturfenster ab. Die neue Phase konnte noch nicht charakterisiert werden. / The hydrogenation of Zintl phases leads to interstitial hydrides that are coordinated exclusively by cations, polyanionic hydrides that exhibit a covalent bond to the more electronegative element, or a combination of both motifs. A series of new compounds is prepared and structurally characterised by laboratory X-ray, synchrotron and neutron powder diffraction. Most examples can be derived via hydrogenation of CrB- or FeB-type Zintl phases. These structure types are closely related and characterised by polyanionic zigzag chains. The interstitial hydrides LnTtH (Ln = La, Nd, Tt = Si, Ge, Sn) are oxidation products of the formally metallic Zintl phases LnTt = Ln3+ Tt2- e- . Hydrogen occupies tetrahedral Ln4-voids. The products occur as a filled FeB-type phase (P-phase, LaGeH-structure type) or a filled CrB-type phase (C-phase, ZrNiH-structure type). The hydrogenation of electron-precise Zintl phases AeTt (Ae = Sr, Ba, Tt = Ge, Sn, CrB-structure type) leads to hydrogen-poor (AeTtHy , y < 1) and hydrogen-rich phases (AeTtHy , 1 < y ≤ 2). The first show partially hydrogen-filled Ae4-voids. For low contents y < 0.4, hydrogen is statistically distributed over the voids (α-phases). Slightly increased hydrogen contents lead to partial (β-SrGeHy , 0.47 ≤ y ≤ 0.75) or full ordering (β-BaGeH0.5 ). The hydrogen-rich phases AeTtHy, 1 < y ≤ 2 (γ-phases), combine interstitial and polyanionic hydride motifs. The literature-known phases SrSiH1.6 and BaSiH1.9 could be structurally characterised for the first time. The homologue series was extended to SrGeH1.2, BaGeH1.6 and BaSnH1.3 . Tetrahedral Ae4-voids are totally filled with hydride anions. The additional hydrogen binds to the polyanions. Furthermore, some of the zigzag chains are interconnected perpendicular to the chain direction. Three different structure types exhibiting a close structural relationship were identified. This leads to difficulties in structure determination from powder diffraction. The covalent character of the bond is characterised by solid-state nuclear magnetic resonance and density functional theory calculations. Typical tetrel-hydrogen bond lengths are 155(2) pm (Si-H), 163(2) pm (Ge-H) and 186(1) pm (Sn-H). In situ neutron, X-ray and synchrotron powder diffraction were used to elucidate reaction schemes. The AeTt-H2 systems (Ae = Sr, Ba, Tt = Ge, Sn) show several reversible reaction steps between γ-, β- and α-phases upon heating under hydrogen pressure. Finally, an irreversible decomposition into the binary hydrides AeH2 and Tt-rich Zintl phases AeTt2 occurs. In situ diffraction of the reaction of NdGa with hydrogen leads directly to NdGaH1+x (isostructural to γ-AeTtHy ) which shows a large compositional range from at least x = 0.17 to 0.80. Ga-H distances are long (about 200 pm) and, thus, not classical 2-electron-2-center bonds. In situ diffraction of the reactions of KSi and CsSi with hydrogen show a one step formation of the corresponding hydrides KSiH3 and CsSiH3 . They exhibit SiH3--anions which are isoelectronic to PH3 . Further heating under hydrogen pressure leads to decomposition into KH and K8Si46 or reformation of CsSi, respectively. Finally, further compounds were tested for reactivity towards hydrogen. The phases AeTt2 (Ae = Ca, Sr, Ba, Tt = Si, Ge), AGe and ASixGe1-x (A = K, Rb, Cs) do not form corresponding hydrides under the investigated conditions (at least 5 MPa H2, 700 K). The gallides CaGa, Sr8Ga7 and Ba8Ga7 show reactivity towards hydrogen. They decompose into binary hydride and the gallium-rich phases Ca3 Ga8 , SrGa4 or BaGa4. Furthermore, laboratory in situ diffraction of the reaction of CaGa with hydrogen indicates the formation of a new, crystalline phase. Formation and decomposition occur in a relative small temperature window. The new phase could not be characterised, yet.

1979 wurde mit CeCu2Si2 erstmalig ein Schwere-Fermionen-Supraleiter entdeckt. Diese Verbindung, entdeckt von Steglich und Mitarbeitern, befindet sich nahe an einem quantenkritischen Punkt, an dem die magnetische Ordnung gerade unterdrückt wird. Der Abstand zu diesem Punkt kann sowohl durch Druck als auch durch Germaniumsubstitution auf dem Siliziumplatz variiert werden. Dabei treten neben der Supraleitung in CeCu2Si2 auch verschiedene magnetische Phasen bei höherem Germaniumgehalt auf. CeCu2Si2 ordnet magnetisch unterhalb von TN = 0.8 K in einer Spindichtewelle, während das Schwere-Fermionen-System CeCu2Ge2 unterhalb von TN = 4.1 K antiferromagnetisch ordnet. In dieser Arbeit wurde die Substitutionsreihe CeCu2(Si1-xGex)2 mittels Neutronendiffraktion untersucht. Ausgehend von Proben mit hohem Germaniumgehalt von x = 0.45, deren magnetische Struktur detailliert untersucht wurde, wurden schrittweise die Eigenschaften von Proben mit kleinerem x erschlossen, um schließlich die (bis dato unbekannte) magnetische Struktur in CeCu2Si2 aufzuklären. Weiterhin wurden Untersuchungen zumWechselspiel zwischenMagnetismus und Supraleitung durchgeführt. Hierzu wurde mit einem selbstentwickelten Aufbau dieWechselfeldsuszeptibilität simultan zu den Diffraktionsexperimenten aufgezeichnet. Durch die direkte Korrelation konnte nachgewiesen werden, dass in CeCu2Si2 keine mikroskopische Koexistenz von Supraleitung und magnetischer Ordnung vorliegt, sondern mikroskopische Phasenseparation. - Die Arbeit ist auch über den Cuvillier-Verlag; Nonnenstieg 8; 37075 Göttingen mit der ISBN 978-3-86727-587-3 erhältlich. / In 1979 the first heavy-fermion superconductor CeCu2Si2 was discovered by Steglich et al. The system is near a quantum critical point (QCP), where the magnetic order is just suppressed. The distance to the QCP can be variied with hydrostatic pressure as well as by germanium substitution on the silicon site. Next to the superconductivity in CeCu2Si2 one finds distinct magnetic phases while increasing the germanium content. CeCu2Si2 shows a magnetic order of a spin-density-type below TN = 0.8 K, whereas the heavy fermion system CeCu2Ge2 orders below TN = 4.1 K as an antiferromagnet. The focus of this thesis is on neutron-diffraction in the system CeCu2(Si1-xGex)2. Starting with a sample with a high germanium content of x = 0.45, the magnetic structures are investigated in detail. Following a step-by-step approach, samples with reduced x are investigated subsequently to figure out the properties of pure CeCu2Si2, which were not accessible before. Furthermore, the complex interaction between magnetism and superconductivity is investigated in detail. Using a specially designed setup, the ac-susceptibility could be recorded simultaneously during the neutron diffraction experiments. Due to the direct correlation between antiferromagnetic signals and diamagnetic features, the microscopic coexistence of superconductivity and magnetic order can be ruled out. Instead, a phase separation on the microscopic scale is found. - The thesis is also available from the publisher Cuvillier-Verlag; Nonnenstieg 8; 37075 Göttingen under the ISBN 978-3-86727-587-3.

Von der Verbindungsklasse der heteroanionischen Hydride sind nur relativ wenige Vertreter bekannt, dabei zeigen sie großes Potential für Funktionsmaterialien. In dieser Arbeit werden verschiedene heteroanionische Hydride der seltenenen Erden in Kombination mit O2– -, F– - und N3– -Anionen untersucht. Die ternären Verbindungen REHO dienen dabei als Ausgangspunkt und der Fokus liegt auf der Kristallstrukturanalyse per Pulverneutronenbeugung. Verschiedene Synthesestrategien werden mit Unterstützung durch thermodynamische Rechnung auf Grundlage quantenchemischer Studien angewandt. Zwei neue REHO-Modifikationen werden identifiziert: der orthorhombische Anti-LiMgN-Typ mit Raumgruppe Pnma f¨ur RE =Y und Lu, sowie der kubische Halb-Heusler LiAlSi-Typ mit Raumgruppe F¯43m f¨ur RE =Dy–Er und vermutlich Lu. Der Anti-LiMgN-Typ zeigt ein für Seltenerdverbindungen untypisches Verhalten, da seine Ausbildung scheinbar nicht mit den Kationenradien korreliert ist. Die Berechnung von Zustandsdichten und Bader-Analysen unterstützen das Bild eines vornehmlich ionischen Bindungstyps. Eine Neutronenbeugungsuntersuchung an SmHO zeigt Überstrukturreflexe, die vermutlich aus einer langreichweitigen Ordnung von Anionen auf der Oktaederl¨ucke stammen. Ihre Stabilität an Luft wird durch in situ Pulverröntgenbeugung und Differentialthermoanalyse sowie ex situ Pulverröntgenbeugung untersucht. YHO ist bis 500 K, HoHO bis 540K stabil an Luft. Bei höheren Temperaturen zersetzt sich HoHO unter Bildung von Ho2O3 und HoH3 über ein Intermediat, das vermutlich Ho2O3–xH2x ist; YHO verhält sich scheinbar analog. An Luft werden sie langsam durch Luftfeuchtigkeit hydrolysiert, wobei der Grad mit dem Kationenradius im Vergleich verschiedener REHO abnimmt. Zwei Gestaltungskonzepte dienen der Entdeckung neuer heteroanionischer Hydride. Durch H/F-Metathese an SmOF wird die neue Verbindung SmHxOF1–x erhalten. Sie kristallisiert in einer Auff¨ullungsvariante des Bixbyit- bzw. im Anti-Li3ScN2-Typen mit Raumgruppe Ia¯3 und weist zwei Anionenlagen auf, von der auf einer H– , O2– und F– mischen. Durch eine formale aliovalente Anionensubstitution werden das erste Seltenerd-Nitridhydrid LiLa2N1.5H2.5 und das erste Seltenerd-Nitridhydridoxid LiLa2NH2O entdeckt. Gemeinsam mit dem Hydridionenleiter LiLa2HO3 stellen sie eine aliovalente Substitutionsreihe dar. Beide kristallisieren im tetragonalen K2NiF4-Typ mit gemischten N3–/H– - bzw. N3–/O2– -Lagen. / Heteroanionic hydrides are a compound class with relatively few members but simultaneous great potential for use in functional materials. In this work, several rare earth heteroanionic hydrides containing O2– -, F– -, or N3– -anions are studied starting from the ternary REHO compounds with focus on the crystal structure analysis by powder neutron diffraction. Different synthesis routes are examined and accompanied by thermodynamic calculations based on quantum chemical studies. Two new REHO polymorphs are identified: the orthorhombic anti-LiMgN-structure type with space group Pnma for RE =Y and Lu, and the cubic half-Heusler LiAlSi-type with space group F¯43m, that is adopted by RE =Dy–Er and probably also Lu. Density of states calculations and Bader charge analyses support the picture of a predominant ionic bonding type. The Anti-LiMgN-Type shows a rare-earth unusual behavior, as its adaption is apparently not correlated to the cationic radii. SmHO shows super structure reflections in the powder neutron diffraction experiments, which probably result from a long-range ordering of anions on the octahedral interstice. The air-resistivity is investigated by in situ powder X-ray diffraction and differential scanning calorimetry as well as ex situ powder X-ray diffraction. YHO is stable up to 500K and HoHO up to 540K in air. HoHO decomposes at higher temperatures to Ho2O3 and HoH3 via an intermediate, which is probably Ho2O3–xH2x ; YHO apparently behaves analogously. A degradation upon storage in air could be attributed to hydrolysis by air humidity and its degree declines along with the cationic radii among different REHO compounds. Two design concepts are employed to discover new heteroanionic hydrides: The H/Fmetathesis on SmOF lead to the discovery of SmHxOF1–x , samarium hydride oxide fluoride, which crystallizes in a filled bixbyite- or anti-Li3ScN2-type with space group Ia¯3 and exhibits two anion sites with one shared by H– , O2– , and F– . By a formal aliovalent anion substitution, the first rare earth nitride hydride LiLa2N1.5H2.5 and the first nitride hydride oxide LiLa2NH2O were discovered, which represent an aliovalent substitution series with the hydride ion conductor LiLa2HO3. Both crystallize in the tetragonal K2NiF4-type with mixed N3–/H– resp. N3–/O2– sites.

Dans le cadre d'un projet de transport automobile propre pour la mise en place de véhicules électriques décarbonés grand public, les aimants représentent un enjeu important au niveau des moteurs électriques. Il est alors nécessaire de se passer des aimants à base de terres rares, peu écologiques et dont un seul pays détient le monopole. Deux voies sont explorées ici : la nanostructuration des hexaferrites de type M par frittage flash de type SPS (Spark Plasma Sintering), et la synthèse d'alliages Mn-Al-C par la méthode de la trempe rapide sur roue. Concernant le premier matériau, l'optimisation du protocole de synthèse a permis d'augmenter le champ coercitif d'un facteur 2. Deux outils de caractérisation des aimants ont été mis en place : le premier évalue la texture du matériau (modèle de Stoner et Wohlfarth), le second étudie les processus d'aimantation (Preisach). Pour les alliages Mn-Al-C, nous avons pu démontrer la présence d'un couplage antiferromagnétique entre les atomes de Mn des sites 1a et 1d. La diffraction de neutrons à également pu montrer que le moment magnétique du Mn du site 1d est par ailleurs très supérieur à celui du site 1a. Un broyage cryogénique suivi d'un frittage SPS à haute pression (400 MPa) a permis d'augmenter la valeur du champ coercitif de 40 %. Les résultats obtenus sont très prometteurs quant à la faisabilité d'alternatives aux aimants à base de terres rares. / In the context of green car development for mass market, development of low cost rare-earth-free magnets is clearly a milestone, because the rare-earth are expensive and their production is not ecological and a monopoly of one country. Two routes are explored herein : nanostructuration of M-type hexaferrites by flash sintering (Spark Plasma Sintering), and the synthesis of Mn-Al-C alloys by melt spinning. Concerning the first material, the optimization of the synthesis protocol allowed to increase the coercive field by a factor of 2. Two characterization tools of the magnets were set-up : the first evaluates the texture of the material (Stoner and Wohlfarth model), the second, based on Preisach model, is used to infer the magnetization processes. For Mn-Al-C alloys, we have evidenced from Weiss plots the antiferromagnetic coupling between 1a and 1d-sites Mn atoms. Neutron diffraction confirmed this result and shown that the magnetic moment of the 1d-site Mn is also much larger than that of 1a-site. Cryogenic ball milling followed by high-pressure SPS (400 MPa) increased the coercive field by 40 %. The results obtained are very promising as to the feasibility of alternatives to rare-earth magnets.

Title: Investigation of titanium alloys using neutron diffraction Author: Gergely Németh Department / Institute: Department of Physics of Materials Supervisor of the master thesis: prof. RNDr. Kristián Mathis, Ph.D., DrSc., Department of Physics of Materials Abstract: Titanium grade 2 was treated by multiple passes of the continuous equal- channel angular pressing technique (CONFORM ECAP) and, after each pass, additionally by rotary swaging. The residual strain field in samples processed by only CONFORM ECAP was studied by neutron diffraction strain scanning. In order to elucidate the microscopic background and calculate the related residual stress field, the local microstructure was thoroughly investigated by various experimental techniques. The microstructure and the deformation behavior of the rotary swaged samples was studied by transmission electron microscopy and by in-situ neutron diffraction during compression. The results of the analyses indicated that microstructural gradients were present in the material as the result of the inhomogeneous deformation during the CONFORM ECAP treatment. These gradients were identified as the main reason of the presence of residual stress fields. The distributions of stress fields calculated based on microstructural parameters were in correlation with simulation...

Polycrystalline NiTi shape memory alloys have the ability to recover their original, pre-deformed shape in the presence of external loads when heated through a solid-solid phase transformation from a lower-symmetry B19' martensite phase to a higher-symmetry B2 austenite phase. The strain associated with a shape memory alloy in an actuator application typically has thermal, elastic and inelastic contributions. The objective of this work was to investigate the aforementioned strains by recourse to in situ neutron diffraction experiments during selected combinations of heating, cooling and/or mechanical loading. The primary studies were conducted on polycrystalline Ni49.9Ti50.1 specimens on the Spectrometer for MAterials Research at Temperature and Stress (SMARTS) at Los Alamos National Laboratory. Quantitative information on the phase-specific strain, texture and phase fraction evolution was obtained from the neutron data using Rietveld refinement and single-peak analyses, and compared with macroscopic data from extensometry. First, the lattice strain evolution during heating and cooling in an unloaded sample (i.e., free-recovery experiment) was studied. The lattice strain evolution remained linear with temperature and was not influenced by intergranular stresses, enabling the determination of a thermal expansion tensor that quantified the associated anisotropy due to the symmetry of B19' NiTi. The tensor thus determined was subsequently used to obtain an average coefficient of thermal expansion that was consistent with macroscopic dilatometric measurements and a 30,000 grain polycrystalline self-consistent model. The accommodative nature of B19' NiTi was found to account for macroscopic shape changes lagging (with temperature) the start and finish of the transformation. Second, the elastic response of B19' martensitic NiTi variants during monotonic loading was studied. Emphasis was placed on capturing and quantifying the strain anisotropy which arises from the symmetry of monoclinic martensite and internal stresses resulting from intergranular constraints between individual variants and load re-distribution among variants as the texture evolved during variant reorientation and detwinning. The methodology adopted took into account both tensile and compressive loading given the asymmetric response in the texture evolution. Plane specific elastic moduli were determined from neutron measurements and compared with those determined using a self-consistent polycrystalline deformation model and from recently reported elastic stiffness constants determined via ab initio calculations. The comparison among the three approaches further helped understand the influence of elastic anisotropy, intergranular constraint, and texture evolution on the deformation behavior of polycrystalline B19' NiTi. Connections were additionally made between the assessed elastic properties of martensitic NiTi single crystals (i.e., the single crystal stiffness tensor) and the overall macroscopic response in bulk polycrystalline form. Lastly, the role of upper-cycle temperature, i.e., the maximum temperature reached during thermal cycling, was investigated during load-biased thermal cycling of NiTi shape memory alloys at selected combinations of stress and temperature. Results showed that the upper-cycle temperature, under isobaric conditions, significantly affected the amount of transformation strain and thus the work output available for actuation. With the objective of investigating the underlying microstructural and micromechanical changes due to the influence of the upper-cycle temperature, the texture evolution was systematically analyzed. While the changes in transformation strain were closely related to the evolution in texture of the room temperature martensite, retained martensite in the austenite state could additionally affect the transformation strain. Additionally, multiple thermal cycles were performed under load-biased conditions in both NiTi and NiTiPd alloys, to further assess and understand the role of retained martensite. Dimensional and thermal stabilities of these alloys were correlated with the volume fraction and texture of retained martensite, and the internal strain evolution in these alloys. The role of symmetry, i.e., B19' monoclinic martensite vs. B19 orthorhombic martensite in these alloys was also assessed. This work not only established a methodology to study the thermal and elastic properties of the low symmetry B19' monoclinic martensite, but also provided valuable insight into quantitative micromechanical and microstructural changes responsible for the thermomechanical response of NiTi shape memory alloys. It has immediate implications for optimizing shape memory behavior in the alloys investigated, with extension to high temperature shape memory alloys with ternary and quaternary elemental additions, such as Pd, Pt and Hf. This work was supported by funding from NASAÂ s Fundamental Aeronautics Program, Supersonics Project (NNX08AB51A) and NSF (CAREER DMR-0239512). It benefited additionally from the use of the Lujan Neutron Scattering Center at Los Alamos National Laboratory, which is funded by the Office of Basic Energy Sciences (Department of Energy) and is operated by Los Alamos National Security LLC under DOE Contract DE-AC52-06NA25396.

Many Zintl phases exhibiting a CrB type structure form hydrides. Systematic studies of AeTtHx (Ae = Ca, Sr, Ba; Tt = Si, Ge, Sn), LnTtHx (Ln = La, Nd; Tt = Si, Ge, Sn), and LnGaHx (Ln = Nd, Gd) showed the vast structural diversity of these systems. Hydrogenation reactions on REGa (RE = Y, La, Tm) and RESi (RE = Y, Er, Tm) were performed in steel autoclaves under hydrogen pressure up to 5 MPa and temperatures up to 773 K. The products were analyzed by X-ray and neutron powder diffraction. RESi (RE = Y, Er, Tm) form hydrides in the C-LaGeD type. LaGaD1.66 is isostructural to NdGaD1.66 and shows similar electronic features. Ga-D distances (1.987(13) Å and 2.396(9) Å) are considerably longer than in polyanionic hydrides and not indicative of covalent bonding. In TmGaD0.93(2) with a distorted CrB type structure deuterium atoms exclusively occupy tetrahedral voids. Theoretical calculations on density functional theory (DFT) level confirm experimental results and suggest metallic properties for the hydrides.