Dans la recherche de nouveaux matériaux piézoélectriques pour capteurs haute température (T > 600°C), nous nous sommes intéressés au matériau α-GeO2 dont le domaine de stabilité structurale en température et l'activité piézoélectrique seraient les plus importants parmi les composés isotypes du quartz-α. La littérature rapporte quelques limitations de ces deux propriétés dans le cas de monocristaux de α-GeO2 provenant de synthèses sous pression en milieu aqueux dues notamment à la présence de groupements hydroxyles au sein de la structure. Afin de remédier à cette contamination, une autre voie de croissance a été appliquée à GeO2 ; la méthode du flux par nucléation spontanée et à partir d'un germe monocristallin. Pour faciliter la croissance de la phase quartz-α de GeO2, métastable dans les conditions ambiantes, nous avons envisagé de substituer une faible partie des cations Ge4+ par des cations Si4+ (environ 10 % atomique). Après optimisation des différents paramètres expérimentaux, les cristaux synthétisés lors de ce travail ont été analysés par plusieurs techniques de caractérisation complémentaires (spectroscopies infrarouge et Raman, analyse E.D.X., D.R.X sur monocristal et sur poudre et D.S.C.) qui ont démontré leur excellente qualité cristalline, l'absence de contamination chimique (dans la limite de détection des techniques de caractérisation) et l'absence de transition de phase de la structure quartz-α, de la température ambiante à la fusion de ces matériaux (proche de 1100°C). L'approche de l'activité piézoélectrique de α-GeO2 en fonction de la température a été réalisée via l'étude de ses propriétés électromécaniques par spectroscopie d'impédance et spectroscopie Brillouin. Nous avons ainsi démontré que le matériau de structure quartz-α de GeO2 résonnait à très haute température (≈ 900°C) avec cependant une intensité diminuée par rapport à celle enregistrée à température ambiante. / In the research of new piezoelectric materials for high temperature sensors (T > 600°C), we have been interested in α-GeO2 material which would exhibit the most important piezoelectric activity and structural stability domain with temperature among the α-quartz isotype compounds. Some limitations are described in the literature concerning those two properties in the case of hydrothermally-grown α-GeO2 single crystals mainly due to the presence of hydroxyl groups in their structure. To prevent this contamination, another growth approach was applied to GeO2: flux-growth method by spontaneous nucleation and from a crystalline seed. To facilitate the growth of the α-quartz phase of GeO2, metastable in ambient conditions, we have thought to substitute a part of Ge4+ cations by Si4+ cations (around 10 atomic per cent). After optimization of the different experimental parameters, flux-grown single-crystals were analyzed by several complementary characterization techniques (infrared and Raman spectroscopies, E.D.X. analyses, single-crystal and powder X-R.D. and D.S.C.) which have demonstrated their excellent crystalline quality, the absence of chemical contamination (inside the detection limit of characterization techniques) and the absence of phase transition of the α-quartz structure, from ambient temperature to the fusion of those materials (around 1100°C). The observation of piezoelectric activity of α-GeO2 as a function of temperature was realized from the study of its electromechanical properties by impedance spectroscopy and Brillouin spectroscopy. By these means, we have demonstrated that the α-quartz structure of GeO2 still resonate at very high temperature (≈ 900°C) with a weaker intensity compared to that recorded at ambient temperature.

La fragilisation par l’hydrogène est une des causes les plus évoquées lors de la rupture prématurée des pièces métalliques. Il est donc nécessaire de clarifier l’effet de ce soluté sur les propriétés mécaniques et les mécanismes de plasticité dans ces matériaux. L’étude proposée de cette thèse consiste à étudier l’effet de l’hydrogène sur la réponse mécanique du nickel monocristallin déformé par la fatigue de l’échelle macroscopique jusqu’à l’échelle atomique. A l’échelle macroscopique, des essais de fatigue ont été réalisés sur du nickel orienté en glissement multiple avec plusieurs teneurs en hydrogène pour évaluer ses conséquences sur l’écrouissage cyclique du métal. Ensuite, une caractérisation microstructurale des hétérogénéités développées par la fatigue a été conduite pour plusieurs amplitudes de déformation plastique sur le nickel avec et sans hydrogène. La déformation du métal induit une organisation de la microstructure sous forme de chenaux et de murs qui dépend en partie des interactions élastiques entre l’état de contrainte, l’hydrogène et les défauts cristallins. Par conséquent, l’impact de l’hydrogène sur les propriétés élastiques du métal a été étudié à l’aide de calculs à l’échelle atomique et complété par des expériences. D’autres calculs à cette échelle, associés à des modèles analytiques basés sur la théorie élastique des dislocations, ont été réalisés pour évaluer la stabilité des structures de dislocations induites par la fatigue en présence d’hydrogène, de lacunes et d’amas de lacunes. Les principales conclusions de cette étude proviennent d’une analyse multi-échelle des résultats obtenus par la combinaison d’approches numériques et expérimentales. Nous suggérons que l’incorporation de l’hydrogène induit un durcissement intrinsèque du nickel. Cependant, la formation de lacunes et d’amas de lacunes atténue l’effet du soluté et participe à la compétition entre adoucissement et durcissement du nickel à l’échelle macroscopique. / Hydrogen in metals can lead to irreversible damages on engineering structures. Consequently, the effects of the solute on the mechanical properties and the plasticity mechanisms of these materials have to be clarified. The proposed study consists to investigate the effects of hydrogen on the mechanical response of nickel single crystal strained by fatigue from macroscopic scale down to the atomic scale. At macroscopic scale, cyclic tests are conducted on multi-slip oriented nickel with several hydrogen concentrations to evaluate its consequences on the cyclic hardening of the metal. Then, a microstructural characterisation of the heterogeneities developed by fatigue is conducted for several plastic deformation amplitudes on nickel with and without hydrogen. The deformation of the metal induces a microstructure in form of wall and channel phases, which partially depend on the elastic interactions between the stress state, hydrogen and the induced crystalline defects. Therefore, the impact of hydrogen of the elastic properties of nickel single crystal is investigated using atomic scale calculations and experiments. Further calculations at this length scale associated with analytical elastic models are conducted to evaluate the stability of fatigue induced dislocation structures in presence of the solute, vacancies and vacancy clusters. The main conclusions of this study arise from the analysis of the results obtained from macroscopic scale down to the atomic scale and from the combination of both numerical and experimental techniques. In particular, the incorporation of hydrogen leads to a hardening of the nickel intrinsically. However, the formation of vacancies and vacancy clusters by the incorporation of hydrogen counteracts the effects of the solute and participates in the competition between the softening and the hardening of cyclically strained nickel single crystal observed at macroscopic scale.

Os radicais nitróxidos tem sido muito utilizados em estudos de sistemas biológicos através do método de marcagem de spin. Apesar do grande número de publicações sobre aplicações, o número de estudos das propriedades intrínsecas dos nitróxidos ê bem reduzido. A importância de tais estudos é grande uma vez que o estudo de um sistema simples permite avaliar e interpretar os resultados dos sistemas biológicos, geralmente mais complicados Assim no presente trabalho estudou-se o espectro do RPE do 4-hidroxi-2,2,6,6-tetrametil piperidina-1 oxil (I) introduzido como impureza na sua matriz diamagnética 4-hidroxi-2,2,6,6-tetrametilpiperidina (II). Este processo de dopagem muito utilizado em física do estado sólido permitiu a determinação dos tensores g e A. Os valores obtidos gxx = 2.0098, gyy = 2.0061, gzz = 2.0024, e A xx = 5.3 G, Ayy = 7.0 G, Azz = 35.0 G, encontram-se dentro do esperado sendo que o valor de go = 2.0061 e Ao = 15.8 G evidencia a interação do fragmento N-O com ponte de hidrogênio (de hidroxila na posição 4 de uma molécula vizinha). A existência de dois centros paramagnéticos inequivalentes é interpretada corno devido a presença de duas possíveis conformações do fragmento N-O. As larguras das linhas de RPE observadas são grandes e em certas orientações do campo magnético ocorre o desdobramento da transição eletrônica num dubleto devido a interação com o hidrogênio da hidroxiIa que faz ponte com o N-O. A temperatura de cerca de -140&#176C e observada uma mudança sensível nos espectros de RPE evidenciando a desaparição da estrutura hiperfina na região de Axx e Ayy. Esta mudança está relacionada com o congelamento da rotação dos grupos metila afetando assim a interação dos prótons destes grupos com o elétron do fragmento N-O. O sistema estudado parece ser extremamente interessante do ponto de vista do estudo de influência de prótons na relaxação eletrônica do radical nitroxido. É evidenciada a forte dependência das propriedades paramagnéticas do nitróxido em relação à estrutura da vizinhança do fragmento N-O. / Nitroxide radicals are being used in many studies of biological systems through the spin label method. Despite the great number of publications involving the application of nitroxides only a reduced number of work s about nitroxides themselves is known. These studies are important because the knowledge of the properties of simple systems could be used in the interpretation of results in biological systems, normally mare complicated. In the present work the EPR spectra of 4-hydraxy-2,2,6,6-tetramethyl piperidine-l oxyl (I) introduced as impurity in the diamagnetic matrix of 4-hidraxy-2,2,6,6-tetramethyl piperidine (II) were studied. This process commonly used in solid state physics made it possible the determination of the g and A tensors. The values obtained : gxx = 2.0098, gyy = 2.0061, gzz = 2.0024, and A xx = 5.3 G, Ayy = 7.0 G, Azz = 35.0 G are typical for nitroxides. The mean values go = 2.0061 and Ao 15.8G are consistent with the presence af hydrogen bond to the N-O fragment (this bond is made with the proton of a hydroxyl in position 4 of a neighbour molecule). The existence of two magnetically inequivalent centers is interpreted so that two different conformations for the N-O fragment are possible. The line widths of the EPR lines are quite great and for some orientations of the magnetic field a splitting of the electronic transition in to a dublet occur. This splitting is due to the interaction of the electron in the N-Q fragment with the hydroxyl hydrogen which is bonded to the nitroxide group. At a temperature around -140&#176C a change in the EPR spectra is observed, when the hyperfine nitrogen structure in the region of A and A disappear. This change x y is related to the freezing of the rotation of the methyl groups affecting the interaction of the protons of these groups with the electron in the N-O. The system studied in the present work seems to be very interesting from the point of view of the influence of the protons in the electronic relaxation in the nitroxide radical. ln this context the strong dependency of the properties of the nitroxide relative to the structure of the neighbouring of the N-O fragment become evident.

In dieser Arbeit wurden Segregationen, die bei der Z"uchtung einkristalliner Fasern von Oxidmischkristallsystemen mittels der Micro-Pulling-Down Methode auftreten, experimentell und theoretisch untersucht. Dazu wurden Fasern von hochschmelzenden Oxidmischkristallsystemen mit unterschiedlichen Gleichgewichtsverteilungskoeffizienten gezüchtet. Es wurde gezeigt, dass die Dotierstoffprofil von dem Gleichgewichtsverteilungskoeffizienten, der Ziehgeschwindigkeit, dem Sauerstoffpartialdruck der Züchtungsatmosphäre sowie der Meniskushöhe abhängt. Ein analytisches und ein numerisches Modell wurden erstellt um den Segregationsprozess zu beschreiben. Ein Modell basierend auf der irreversiblen Thermodynamik wurde zur Berechnung der Thermodiffusionskoeffizienten mittels Enthalpie und Entropie hergeleitet. Ausserdem wurden mechanische Spannungen, die durch die Segregationen erzeugt werden, untersucht. LiYF4 wurde erfolgreich gezüchtet. Für diesen Fall wurde die Notwendigkeit einer reinen Züchtungsatmosphäre sowie eines reinen Ausgangsmaterials in Bezug auf Wasser- und Sauerstoffverunreinigungen, gezeigt. / Within this study segregations, which occur during micro-pulling-down growth of single-crystal fibers of oxide solid solutions, have been analyzed in an experimental and theoretical manner. Single-crystal fibers of high melting point oxide solid solutions with different equilibrium distribution coefficient have been grown. It has been shown, that the dopant distribution depends on the equilibrium distribution coefficient of the dopant, the pulling speed, the oxygen partial pressure of the growth atmosphere and the meniscus height. An analytical and a numerical model have been established to describe the segregation process. A theoretical model based on irreversible thermodynamics to calculate the thermodiffusion factors using the enthalpy and entropy was derived. Also mechanical stresses induced by the segregation have been analyzed. LiYF4 has been grown successfully. In this case the necessity of a very high purity atmosphere and source material in terms of water and oxygen trace impurities has been shown.

Neste trabalho, foram realizadas sínteses dos tungstatos duplos NaLa(WO4)2 (NLW), NaGd(WO4)2 (NGW) e LiLa(WO4)2 (LLW) puros e simplesmente dopados com os íons Nd3+ e Yb3+; comparando-se dois métodos de obteção: o de reação no estado sólido e o sol-gel modificado (Pechini). Verificou-se que o envelhecimento do reagente La2O3 (adsorção de umidade ambiente) é um fator determinante na formação dos materiais desejados. Ambos os métodos testados são análogos para obtenção desses materiais se a proporção estequiométrica dos reagentes for a correta. Um estudo empírico foi realizado para crescimento, a partir da fusão, de fibras cristalinas, através do método de micro-pulling-down (µ-PD) (nos modos de aquecimento resistivo e indutivo), de NLW, NGW e LLW puros e simplesmente dopados com os íons Nd3+ e Yb3+. Neste estudo observou-se a evaporação do líquido durante o processo, o efeito da variação das taxas de puxamento e a interação do líquido com o material do cadinho e com a interface de cristalização. Foram obtidas fibras monocristalinas para todos os compostos. Amostras destas fibras foram caracterizadas por difratometria de raios-X (DRX) para verificação da fase formada, por microscopia ótica (MO) e eletrônica de varredura (MEV) para caracterização do diâmetro das fibras, espectrometria por dispersão em energia (EDS/EDX) para determinação da concentração dos dopantes; e também espectroscopia ótica de absorção no VIS-IR para determinação da incorporação do dopante na forma trivalente. / At the present work, the pure and Nd,Yb-doped alkali rare earth double tungstates NaLa(WO4)2 (NLW), NaGd(WO4)2 (NGW) and LiLa(WO4)2 (LLW) were synthesized. Two synthesis methods were evaluated: the solid state reaction method and the modified sol-gel method (Pechini). Both of them are similar for the synthesis of these materials if stoichiometric proportion of reagents is used. It was verified that the moisture adsorption from air by the reagent La2O3 is a problem in the formation of the studied compounds. An empirical study of growth from the melt of single-crystalline fibers was achieved through the micro-pulling-down (µ-PD) method (in the heating inductive and resistive modes) of pure and Nd,Yb-doped NLW, NGW and LLW. It was observed in this study the liquid evaporation during the process, the effect of different pulling rates, the liquid interaction with the crucible material and the crystallization interface. Single-crystalline fibers were achieved for all compounds studied. Samples were characterized through X-ray powder diffraction (XRD) for phases identification, optical (OM) and scanning electronic microscopy (SEM) for fiber diameter visualization, energy dispersion scattering (EDS/EDX) for determining dopants concentration and also optical absorption spectroscopy in the VIS-IR for determining dopants incorporation in the trivalent state.

Neste trabalho, foram realizadas sínteses dos tungstatos duplos NaLa(WO4)2 (NLW), NaGd(WO4)2 (NGW) e LiLa(WO4)2 (LLW) puros e simplesmente dopados com os íons Nd3+ e Yb3+; comparando-se dois métodos de obteção: o de reação no estado sólido e o sol-gel modificado (Pechini). Verificou-se que o envelhecimento do reagente La2O3 (adsorção de umidade ambiente) é um fator determinante na formação dos materiais desejados. Ambos os métodos testados são análogos para obtenção desses materiais se a proporção estequiométrica dos reagentes for a correta. Um estudo empírico foi realizado para crescimento, a partir da fusão, de fibras cristalinas, através do método de micro-pulling-down (µ-PD) (nos modos de aquecimento resistivo e indutivo), de NLW, NGW e LLW puros e simplesmente dopados com os íons Nd3+ e Yb3+. Neste estudo observou-se a evaporação do líquido durante o processo, o efeito da variação das taxas de puxamento e a interação do líquido com o material do cadinho e com a interface de cristalização. Foram obtidas fibras monocristalinas para todos os compostos. Amostras destas fibras foram caracterizadas por difratometria de raios-X (DRX) para verificação da fase formada, por microscopia ótica (MO) e eletrônica de varredura (MEV) para caracterização do diâmetro das fibras, espectrometria por dispersão em energia (EDS/EDX) para determinação da concentração dos dopantes; e também espectroscopia ótica de absorção no VIS-IR para determinação da incorporação do dopante na forma trivalente. / At the present work, the pure and Nd,Yb-doped alkali rare earth double tungstates NaLa(WO4)2 (NLW), NaGd(WO4)2 (NGW) and LiLa(WO4)2 (LLW) were synthesized. Two synthesis methods were evaluated: the solid state reaction method and the modified sol-gel method (Pechini). Both of them are similar for the synthesis of these materials if stoichiometric proportion of reagents is used. It was verified that the moisture adsorption from air by the reagent La2O3 is a problem in the formation of the studied compounds. An empirical study of growth from the melt of single-crystalline fibers was achieved through the micro-pulling-down (µ-PD) method (in the heating inductive and resistive modes) of pure and Nd,Yb-doped NLW, NGW and LLW. It was observed in this study the liquid evaporation during the process, the effect of different pulling rates, the liquid interaction with the crucible material and the crystallization interface. Single-crystalline fibers were achieved for all compounds studied. Samples were characterized through X-ray powder diffraction (XRD) for phases identification, optical (OM) and scanning electronic microscopy (SEM) for fiber diameter visualization, energy dispersion scattering (EDS/EDX) for determining dopants concentration and also optical absorption spectroscopy in the VIS-IR for determining dopants incorporation in the trivalent state.

Poly-aryl, also known as polyphenylene compounds are a class of dendrimer, which contain a large number of aromatic rings. They are of interest because they display restricted rotation of their stearically congested aromatic rings. These extended structures have the potential to act as precursors for even larger aromatic systems and have many applications including electronic devices, drug delivery and catalysis. A total of 23 novel poly-aryl compounds have been examined using single crystal X-ray diffraction and a number of structural patterns have emerged. Six of the compounds contain alkynes and it has been observed that their conformation is governed by a combination of conjugation between the alkyne and aryl groups and inter-molecular interactions. In the more extended poly-aryl compounds steric congestion rules out any possibility of conjugation between the rings and their conformation is governed by intra-molecular non-bonded interactions in the core of the molecules and by inter-molecular interactions in their periphery. Where possible, solution NMR measurements were carried out on the poly-aryl compounds and confirmed that the solution structures are in agreement with those obtained from individual crystal.

The spinel structure (general formula AB2O4) is widely occurring in natural and synthetic materials, and has a marked technological and scientific significance due to its magnetic, electric and multiferroic behaviours. The presence of transition metal cations with multiple oxidation state and the resulting charge, orbital and spin degrees of freedom of the partially occupied d-orbitals lead to uniquely ordered ground states. The coupling of all the three degrees of freedom can result in a structurally distorted ground state where the direct metal-metal interaction forms atomic clusters, or 'orbital molecules'. The Verwey phase of magnetite (Fe3O4), occurring below TV ~ 125 K, is driven by a cooperative bond distortion that forms linear Fe3+-Fe2+-Fe3+ arrangement (trimeron). The effect of non-stoichiometry and chemical modification on this complex structure has been investigated with a variety of samples through microcrystal synchrotron XRD. A mineral sample (Al, Si, Mg and Mn impurities, TV = 119 K) confirms the Verwey phase as the most complex long-range electronic order known to occur naturally; its relevance in space sciences is discussed. Moreover, the structural analysis of two synthetic magnetites (Fe3(1-δ)O4 with 3δ = 0.012 and TV = 102 K, Fe3-xZnxO4 with x = 0.03 and TV = 90 K) univocally confirmed the persistence of the transition, and its first order, at doping level > 1 %, contrary to previous reports. Moreover, the temperature evolution of the trimerons and their persistence above TV was probed through X-ray Pair Distribution Function analysis on pure Fe3O4: the data analysis between 90 K < T < 923 K show that the Verwey phase goes from long-range ordered (T < 125 K) to short-range ordered (T > 850 K). Magnetite can thus only be considered to have a regular cubic spinel structure above the Curie temperature (TC = 858 K). The pyrochlore lattice of B cations in a spinel gives the structure the potential for frustration upon antiferromagnetic ordering. Fe2GeO4 and γ-Fe2SiO4 were synthesised through conventional solid state routes, with the use of high-pressure synthesis for the latter. Magnetometry and heat capacity measurements highlighted two transitions (Tm1 = 8.6 K and Tm2 = 7.2 K, and Tm1 = 11.2 K and Tm2 = 7.5 K respectively). Powder neutron diffraction data between 2 K < T < 25 K showed that both materials stay undistorted below TN. Magnetic Rietveld refinement led to two highly unconventional magnetic structures, with incommensurate propagation vectors and modulation of the moment magnitude. γ-Fe2SiO4 also shows a spin-ice order below Tm2. The results are unique and unusual for transition metal oxides; the models are systematised by proposing a 'frustration wave' model, in which the degree of frustration is a spatial quantity that can be distributed through the structure in order to stabilise the ground state.

<p>In this licentiate thesis the work done in the project KME410 will be presented. The overall objective of this project is to evaluate and develop tools for designing against fatigue in single-crystal nickel-base superalloys in gas turbines. Experiments have been done on single-crystal nickel-base superalloy specimens in order to investigate the mechanical behaviour of the material. The constitutive behaviour has been modelled and verified by simulations of the experiments. Furthermore, the  microstructural degradation during long-time ageing has been investigated with  respect to the component’s yield limit. The effect has been included in the  constitutive model by lowering the resulting yield limit. Finally, the fatigue crack  initiation of a component has been analysed and modelled by using a critical plane approach.</p><p>This thesis is divided into three parts. In the first part the theoretical framework, based upon continuum mechanics, crystal plasticity and the critical plane approach, is derived. This framework is then used in the second part, which consists of three included papers. Finally, in the third part, details are presented of the used  numerical procedures.</p>

<p>Understanding lithium-ion insertion/extraction mechanisms in battery electrode materials is of crucial importance in developing new materials with better cycling performance. In this thesis, these mechanisms are probed for two different potential cathode materials by a combination of electrochemical and single-crystal X-ray diffraction studies. The materials investigated are V₆O₁₃and cubic LiMn₂O₄spinel.</p><p>Single-crystal X-ray diffraction studies of lithiated phases in the Li_xV₆O₁₃ system (x=2/3 and 1) exhibit superlattice phenomena and an underlying Li⁺ ion insertion mechanism which involves the stepwise addition of Li⁺ions into a two-dimensional array of chemically equivalent sites. Each successive stage in the insertion process is accompanied by a rearrangement of the Li⁺ ions together with an electron redistribution associated with the reduction of specific V-atoms in the structure. This results in the formation of electrochemically active sheets in the structure. A similar mechanism occurs in the LiMn₂O₄ delithiation process, whereby lithium is extracted in a layered arrangement, with the Mn atoms forming charge-ordered Mn³⁺/Mn⁴⁺ layers.</p><p>Lithium-ion insertion/extraction processes in transition-metal oxides would thus seem to occur through an ordered two-dimensional arrangement of lithium ions extending throughout the structure. The lithium ions and the host structure rearrange cooperatively to form superlattices through lithium and transition-metal ion charge-ordering. A picture begins to emerge of a universal two-dimensional lithium-ion insertion/extraction mechanism analogous to the familiar staging sequence in graphite.</p>