Hemihedrite from the Florence Lead-Silver mine in Pinal County, Arizona, USA was first described and assigned the ideal chemical formula Pb10Zn(CrO4)(6)(SiO4)(2)F-2, based upon a variety of chemical and crystal-structure analyses. The primary methods used to determine the fluorine content for hemihedrite were colorimetry, which resulted in values of F that were too high and inconsistent with the structural data, and infrared (IR) spectroscopic analysis that failed to detect OH or H2O. Our reinvestigation using electron microprobe analysis of the type material, and additional samples from the type locality, the Rat Tail claim, Arizona, and Nevada, reveals the absence of fluorine, while the presence of OH is confirmed by Raman spectroscopy. These findings suggest that the colorimetric determination of fluorine in the original description of hemihedrite probably misidentified F due to the interferences from PO4 and SO4, both found in our chemical analyses. As a consequence of these results, the study presented here proposes a redefinition of the chemical composition of hemihedrite to the ideal chemical formula Pb10Zn(CrO4)(6)(SiO4)(2)(OH)(2). Hemihedrite is isotypic with iranite with substitution of Zn for Cu, and raygrantite with substitution of Cr for S. Structural data from a sample from the Rat Tail claim, Arizona, indicate that hemihedrite is triclinic in space group P (1) over bar, a = 9.4891(7), b = 11.4242(8), c = 10.8155(7) angstrom, alpha = 120.368(2)degrees, ss = 92.017(3)degrees, gamma = 55.857(2)degrees, V = 784.88(9) angstrom(3), Z = 1, consistent with previous investigations. The structure was refined from single-crystal X-ray diffraction data to R-1 = 0.022 for 5705 unique observed reflections, and the ideal chemical formula Pb10Zn(CrO4)(6)(SiO4)(2)(OH)(2) was assumed during the refinement. Electron microprobe analyses of this sample yielded the empirical chemical formula Pb-10.05(Zn0.91Mg0.02)(Sigma) (= 0.93) (Cr5.98S0.01P0.01)(Sigma = 6.00) Si1.97O34 H-2.16 based on 34 O atoms and six (Cr + S + P) per unit cell.

Ce travail de thèse s'inscrit dans le cadre de la description de la rupture ductile des métaux. L'influence couplée de la plasticité cristalline et de la porosité est abordée à l'aide d'approches micromécaniques. A partir des travaux existants en rupture ductile, notamment pour les matériaux isotropes poreux, et en nous appuyant sur les études traitant des monocristaux poreux, nous proposons une approche originale de la prédiction du comportement de divers matériaux cristallins poreux.Une approche numérique de cette question a tout d'abord était menée. Des outils d'homogénéisation numérique ont été développés et mis en œuvre pour prédire la résistance de monocristaux présentant une répartition périodique de cavités. Une étude de l'influence de l'orientation cristalline sur la surface de plasticité, sur l'écrouissage et l'évolution de la porosité a été effectuée pour différentes structures cristallines. Ces résultats numériques ont servi de référence pour évaluer la pertinence d'un modèle analytique approché que nous avons proposé. Celui-ci se fonde sur une approche par analyse limite intégrant l'anisotropie plastique cristalline. Notre critère a pu être ainsi validé pour différentes situations d'anisotropie du monocristal. Une extension permettant de décrire l'influence de l'écrouissage, en tenant compte de l'hétérogénéité de la déformation plastique, a été proposée. Notre critère a ensuite été utilisé dans un contexte polycristallin afin de décrire la plasticité de métaux présentant de la porosité intragranulaire.Enfin, le cas particulier de monocristaux n'obéissant pas à la loi de Schmid (plasticité cristalline non associée) est considéré. Celle-ci n'entrant pas dans le cadre classique de l'analyse limite, une approche basée sur le bipotentiel proposée par de Saxcé a été choisie. Un bipotentiel spécifique au modèle de plasticité cristalline non associée de Qin et Bassani pour le cristal cubique à faces centrées a été développé. Celui-ci est utilisé dans le cadre de l'homogénéisation par bipotentiel afin d'obtenir un critère de plasticité et une loi d'écoulement. Les outils numériques développés pour la plasticité associée ont été adaptés à la plasticité non associée, et des simulations numériques ont été réalisées pour confronter la loi de comportement obtenue. / This work is a part of the description of ductile rupture of metals. The coupled influences of the crystalline plasticity and the porosity growth is studied by micromecanichal approach. Following existing works in ductile rupture, especially for isotropic porous materials, and using works on porous single crystals, we propose an original approach to predict the behaviour of several crystalline porous materials.First, a numerical approach has been performed. Numerical homogenization tools has been developped and used to study the resistance of single crystals with periodic microstructures. The influence of the crystalline orientation on the plastic yield limit, the hardening and the evolution of the porosity has been evaluated for different crystalline structures.These numerical results has been used to assess an approximate yield criterion we proposed. This one is derived from a limit analysis process taking into consideration the plastic crystalline anisotropy. Thus, this criterion has been assessed for different plastic crystalline anisotropies. An extension to take into account the hardening has been proposed using an evaluation of the heterogeneity of the strain field. An exemple of use of this criterion for numerical computation of polycrystal with intragranular porosity is also proposed. Finally, the particular case of single crystals obeying non Schmid plasticity (non associated plasticity) is considered. As it does not fall in the classical scope of limit analysis, an approach based on the bipotential proposed by de Saxcé has been used. A specific bipotential for the non associated crystalline plasticity proposed by Qin and Bassani has been derived. Then, a macroscopic yield criterion and a macroscopic flow rule is derived by homogenization by bipotential. Numerical tools developped for the associated plasticity have been adaptated for the non associated one. Numerical simulations are performed to assess the behaviour law obtained.

In this thesis, results of the investigation of a new low-dimensional cobaltates Ba2-xSrxCoO4 are presented. The synthesis of both polycrystalline and single crystalline compounds using the methods of conventional solid state chemical reaction and floating-zone optical furnace is first introduced. Besides making polycrystalline powders, we successfully, for the first time, synthesized large single crystals of Ba2CoO4. Single crystals were also obtained for Sr doped Ba2-xSrxCoO4. Powder and single crystal x-ray diffraction results indicate that pure Ba2CoO4 has a monoclinic structure at room temperature. With Sr doping, the lattice structure changes to orthorhombic when x ≥ 0.5 and to tetragonal when x = 2.0. In addition, Ba2CoO4 and Sr2CoO4, have completely different basic building blocks in the structure. One is CoO4 tetrahedron and the later is CoO6 octahedron, respectively. Electronic and magnetic properties were characterized and discussed. The magnetic susceptibility, specific heat and thermal conductivity show that Ba2CoO4 has an antiferromagnetic (AF) ground state with an AF ordering temperature TN = 25 K. However, the magnitude of the Néel temperature TN is significantly lower than the Curie-Weiss temperature (|θ| ~ 110 K), suggesting either reduced-dimensional magnetic interactions and/or the existence of magnetic frustration. The AF interaction persists in all the samples with different doping concentrations. The Néel temperature doesn’t vary much in the monoclinic structure regime but decreases when the system enters orthorhombic. Magnetically, Ba2CoO4 has an AF insulating ground state while Sr2CoO4 has a ferromagnetic (FM) metallic ground state. Neutron powder refinement results indicate a magnetic structure with the spin mostly aligned along the a-axis. The result from a μ-spin rotation/relaxation (μ+SR) experiment agrees with our refinement. It confirms the AF order in the ab-plane. We also studied the spin dynamics and its anisotropy in the AF phase. The results from inelastic neutron scattering show that spin waves have a clear dispersion along a-axis but not along c-axis, indicating spin anisotropy. This work finds the strong spin-lattice coupling in this novel complex material. The interplay between the two degrees of freedom results an interesting phase diagram. Further research is needed when large single crystal samples are available.

No description available.

No description available.

LnBaCo2O5+δ (Ln-112) where Ln = lanthanide element; 0 ≤ δ ≤1 and LnBaCo4O7+δ (Ln-114) are highly correlated cobalt oxides. Synchrotron photoemission spectroscopy of LnBaCo2O5+δ (Ln = Gd, Dy, Dy1-xTbx) and LnBaCo4O7 (Ln = Yb) has been undertaken at the UK Synchrotron Radiation Source (Daresbury Laboratory).During the photoemission experiments, the samples were observed to be contaminated due to residual gases inside the main vacuum chamber. The surface degradation of the samples is studied using the difference spectra generated from the valence band spectra of freshly scraped and contaminated samples and the nature of contaminated species on these samples is identified in the light of the reviewed literature. High-resolution photoemission is carried out to study the metal-insulator (MI) transition in double perovskites LnBaCo2O5+δ (Ln = Gd, Dy, Dy1-xTbx - Ln-112; 0 ≤ δ ≤ 1) as a function of temperature. The high-resolution photoemission results of single crystal samples of GdBaCo2O5.5, DyBaCo2O5.5 and Dy1-xTbxBaCo2O5+δ show that the temperature-based MI transitions in these compounds occur in the 300-400 K temperature range. A post-growth oxygen annealing treatment for as-grown single crystals of Ln-112 is necessary, achieving oxygen contents close to 5.50, to observe a marked nonmetal-to-metal transition. Resonant photoemission is used to identify the atomic parentage of the valence band states. A comparison of the electronic structure of LnBaCo2O5+δ (Ln = Gd, Dy, Dy1-xTbx - Ln-112; 0 ≤ δ ≤ 1) and LnBaCo4O7 (Ln = Yb - Ln-114) single-crystal surfaces is made using synchrotron photoemission spectroscopy. In both cases, the states close to the Fermi energy are found to be of mixed Co 3d/O 2p character, and the comparison allows identification of states due to low spin Co³⁺ in octahedral environments. The contributions from Ln elements to the valence band are found at higher binding energies.

Intermetallic clathrates have long been of interest for materials science research. The promise these materials hold for useful applications ranges from thermoelectrics to photovoltaics and optoelectronics to potentially ultra-hard materials and magnetic cooling applications. Their unique physical properties are intimately related to their intriguing structural properties. Thus a fundamental understanding of the chemistry and physics of inorganic clathrates offers the possibility to assess their potential for use in the various applications mentioned above. The purpose of the current work is to expand the current knowledge of the synthetic routes for obtaining clathrate materials, their structural, chemical, and physical properties, particularly those that from in the type I, II and VIII crystal structures. New synthesis routes are presented and used for preparation of single crystals of Na8Si46 and Na24Si136. Single-crystal X-ray analysis, and resistivity, Seebeck coefficient and thermal conductivity measurements are presented. In addition, two "inverse" clathrates with compositions Sn24P19.3Br8 and Sn17Zn7P22Br8 have been characterized in terms of their transport properties. Since the magnetic refrigeration based on the magnetocaloric effect is a topic of great interest, type VIII Eu8Ga16Ge30 clathrates are also explored in terms of their application for magnetic cooling.

The solid-state interaction of palladium (Pd) with single crystal silicon carbide (6H- SiC) before and after annealing has been investigated using Rutherford backscattering spectrometry (RBS) in conjunction with RUMP simulation package, time-of-flight elastic recoil detector analysis (ToF-ERDA), glancing incident X-ray diffraction (GIXRD) and scanning electron microscopy (SEM). A thin layer of Pd (500 A) was deposited onto a clean 6H-SiC substrate at room temper- ature. The prepared difusion couples were then annealed in vacuum at different annealing temperatures for a maximum period of 1 h. The annealing temperature ranged from 2000C to 8000C. The composition of the as-deposited and the annealed samples was measured by using a He+ beam with an energy of 1.6 MeV. The ToF-ERDA measurements were per- formed on the as-deposited sample by using a high energy copper beam (about 30 MeV) for elemental depth distribution. The GIXRD measurements performed on the samples were able to identify the phases that form before and after annealing. The SEM micrograph obtained during this study gave some insight on the surface morphology of the samples before and after annealing. Our results obtained during this study showed that Pd reacts with SiC after annealing at 4000C resulting in the formation of metal-rich silicides and some unreacted Pd. Annealing at higher temperatures (5000C and 6000C) produced metal-rich silicides, which continued to grow until all the Pd has been consumed. Annealing at even higher temperatures (7000C and 8000C), the metal-rich silicides disappear and the silicon rich silicides start appearing. These appear by simply consuming the metal-rich silicides, resulting in the formation of two or more phases. The behaviour of the interaction between Pd with 6H-SiC is different than the Pd-Si system. The reaction temperature of the Pd/SiC are much more higher than those of the Pd/Si system. That is, Pd reacts with Si at temperatures as low as 2500C, while it starts to react with SiC at an annealing temperature of 4000C. In addition to this silicides such as Pd9Si2, Pd4Si form at the initial reaction temperature followed by the formation of the Pd2Si phase at the temperatures above 6000C for the Pd/SiC system. Meanwhile in the Pd/Si system the Pd2Si phase remains stable even after annealing at 8000C. No carbon compounds were observed in the temperature range used in this study and the formation of silicides were found to be accompanied by the formation of free carbon which remained immobile in the system. / Dissertation (MSc)--University of Pretoria, 2012. / Physics / unrestricted

Les lasers à impulsions ultra-courtes (< 10 ps) ont largement démontré leur intérêt pour de nombreuses applications scientifiques, industrielles ou encore médicales. Le domaine du micro-usinage par impulsions laser est l'un des domaines les plus actifs du moment. Les dernières avancées en la matière privilégient deux axes de recherche, l'augmentation du taux de répétition associé à de fortes puissances moyennes et une montée en énergie. Nos travaux s'inscrivent dans ce contexte et visent à développer des amplificateurs d'impulsions ultracourtes innovants à base de fibres cristallines Yb:YAG délivrant de fortes puissances moyennes et de fortes énergies en régime de polarisation cylindrique. Les sources développées sont destinées à être intégrées au sein de systèmes de micro-usinage laser aux performances inédites développés dans le cadre du projet européen Razipol. Celles-ci joueront le rôle de préamplificateur fort gain au sein d'une architecture MOPA composé d'un oscillateur ultra-rapide à base de cristal d'Yb:KYW et d'un amplificateur final à base de disque mince Yb:YAG. Pour répondre à la problématique des dégradations spatiales liées à la montée en puissance moyenne dans les architectures à laser solide pompé par diode, une architecture en cascade composée de trois étages d'amplification permettant de réduire la charge thermique a d'abord été réalisée. Grâce à une fine optimisation de l’ensemble des paramètres spectroscopiques (taux de dopage des cristaux, longueur d'onde de pompe...) et géométriques (longueur des cristaux, tailles de faisceaux...) a permis d'amplifier des impulsions femtosecondes (750 fs) jusqu'à des puissances moyennes de 100 et 85 W, respectivement obtenues en polarisation linéaire et cylindrique, à la cadence de 20 MHz. Un amplificateur picoseconde de forte énergie à également été réalisé. Intégrant un dispositif de combinaison cohérente à division temporelle à 4 ou 8 répliques visant à réduire les effets non-linéaires, la source développée délivre des énergies remarquablement élevées pour ce type de système à amplification directe. Il délivre des énergies de 1 et 2 mJ à des cadences inférieures à 20 kHz. Ces résultats ont fait l'objet de 2 publications dans des revues internationales à comité de lecture. Par ailleurs les deux amplificateurs développés ont été intégrés sous la forme de systèmes compactes et robustes, utilisables par les membres du projet européen Razipol. Ces travaux ont également inspirée une nouvelle ligne de produits désormais commercialisés la société Fibercryst. / In the last decade ultra-short pulse laser (< 10 ps) have sparked increasing interest for many industrial and scientific applications. Among the geometries used so far for high-power Yb-doped diode-pumped solid-state lasers as slabs, rods and thin disks, the single crystal fiber (SCF) technology was recently shown to have a high potential for the amplification of ultrashort pulses thanks to a very efficient thermal management and high optical efficiencies. This technology combined with the cubic crystal structure of Yb:YAG offers a cylindrical symmetry of the optical and thermo-mechanical properties. Yb:YAG SCFs are therefore well suited for the amplification of cylindrically polarized beams. In the context of a European Project called RAZIPOL, we have developed new laser amplifier architectures using SCF to directly amplify femtosecond pulses to achieve high energy and high average power pulses with radial and azimuthal polarizations without any stretching and recompression of the pulses.We first demonstrate a three-stage diode-pumped Yb:YAG single-crystal-fiber amplifier to generate femtosecond pulses at high average powers with linear or cylindrical (i.e., radial or azimuthal) polarization. At a repetition rate of 20 MHz, 750 fs pulses were obtained at an average power of 85 W in cylindrical polarization and at 100 W in linear polarization. Investigations on the use of Yb:YAG single-crystal fibers with different length/doping ratios and the zero-phonon pumping at a wavelength of 969 nm were conducted in order to optimize the performances of the amplifiers.The second part of the project is focused on pulse energy scaling. In this sense, we demonstrate a two-stage Yb:YAG single-crystal-fiber amplifier designed for high peak power to significantly increase the pulse energy of a low power picosecond laser. The first amplifier stage has been designed for high gain. Using a gain medium optimized in terms of doping concentration and length an optical gain of 32dB has been demonstrated. The second amplifier stage designed for high energy using divided pulse technique allows to generate recombined output pulse energy of 2mJ at 12.5 kHz with a pulse duration of 6 ps corresponding to a peak power 320MW. Average powers ranging from 25W to 55W with repetition rates varying from 12.5 kHz to 500 kHz have been demonstrated.This results has led to the publication of 2 articles in international peer-reviewed journals and have been presented in 7 conferences. Finally this work has inspired the launch of a new line of industrial products by Fibercryst.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19184号 / 工博第4061号 / 新制||工||1626(附属図書館) / 32176 / 京都大学大学院工学研究科マイクロエンジニアリング専攻 / (主査)教授 田畑 修, 教授 琵琶 志朗, 准教授 土屋 智由, 教授 松原 厚 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM