Cette thèse décrit le travail accompli au cours des trois dernières années sur la nouvelle expérience d’Hélium métastable de l'Institut d'Optique à Palaiseau.Le premier chapitre décrit une étude visant à améliorer à la fois l'efficacité et la précision du système de détection par galettes à micro-canaux (MCP). Nous avons fait des mesures avec des galettes recouvertes d'une couche d'or sur la face avant, obtenant un accroissement de l'efficacité de détection mais également une réduction de la précision. L'ajout d'une tension intermédiaires entre les deux galettes empilées a au contraire améliorer à la fois l'efficacité et la précision des MCP, en l’absence d’une couche d’or.Le deuxième chapitre est consacré à la construction de l'appareil expérimental pour le refroidissement et le piégeage d’atomes. L’excitation de l'état fondamental de l’Hélium à l'état métastable est décrite, ainsi que la collimation et le refroidissement ultérieur par Zeeman lent du faisceau atomique chaud résultant. Le faisceau ralenti est alors capturé dans un piège magnéto-optique (PMO), dans lequel nous avons capturé 8x108 atomes.Dans le troisième chapitre une étude originale du refroidissement Doppler tridimensionnel dans un PMO et une mélasse désaccordée vers le rouge de la transition atomique est discutée. L’atome d’Hélium métastable est unique et ses propriétés ont permis une telle étude. En effet, les faibles densités atomiques impliquent qu’il n'y a pas de diffusion multiple de photons d’une part, et la faible masse et la faible largeur de la transition 23S1 -> 23P2 rend inefficace les processus de refroidissement sous la limite Doppler. Ces conditions nous ont permis d’observer pour la première fois à trois dimensions un gaz refroidit dans le régime Doppler.Le quatrième chapitre présente une étude sur les collisions dans un piège magnéto-optique d’Hélium métastable. Les collisions Penning induites par la lumière, en particulier à des intensités élevées et à des fréquences proches de la fréquence de transition, sont responsables de pertes élevées d’atomes piégés. Nous mesurons le coefficient de taux associé à ces pertes, Ksp = 2,8 ± 0,4 x 10-7cm3/ s. / This thesis describes the work done over the past three and a half years on the new metastable helium experiment at the Institut d'Optique in Palaiseau. In the first chapter it describes a study to improve both the efficiency and the accuracy of the Microchannel Plate (MCP) detection system. We have experimented with adding a gold layer on the top of the input plate, something that we have found increases the efficiency but also decreases the accuracy. The addition of a voltage between the two stacked plates has been shown to both raise the efficiency and improve the accuracy in non-coated MCPs.The second chapter is devoted to the construction of the experimental apparatus. Here the excitation of ground state helium to its metastable state is described, as well as the subsequent collimation and cooling by Zeeman slower of the resulting hot atomic beam. The slowed beam is then captured in a Magneto-Optical Trap, in which we have captured 8x108 atoms.In the third chapter an original study on three-dimensional Doppler cooling in a red-detuned molasses and in the Magneto-Optical trap is presented. The metastable helium system is unique as there is no multiple scattering of photons and there are no sub-Doppler effects. This allows for a never before seen experimental realisation of pure Doppler cooling theory. The fourth chapter describes a study on collisions in a magneto-optical trap of metastable helium. Light-induced Penning collisions are responsible for high trap losses at high intensities and at frequencies close to the transition frequency. We measure the constant rate coefficient to Ksp = 2.8 ± 0.4 x 10-7cm3/s.

A cavitação e a dinâmica de bolhas são tópicos bastante recorrentes na literatura, devido sobretudo a seus efeitos em diversos tipos de fenômenos, como transferência de calor e escoamento em tubos. Considerando fases líquidas, sabe-se que estas estruturas de cavidade estão normalmente associadas ao equilíbrio metaestável, alcançado devido a quedas locais de pressão ou ao superaquecimento de uma substância pura (ou quase). Nestes casos é necessária a inicialização da mudança de fase através de algum mecanismo adequado, o qual gera uma sequência rápida de fenômenos. Apesar de comumente associado a danos, recentemente vários estudos vêm mostrando aplicações práticas deste tema, além de um campo ainda pouco explorado, que é o das macro cavidades. Essas cavidades podem ser geradas através do aquecimento de água a baixa pressão, sob condições específicas, criando sequências explosivas e formando movimentos como pistão para a água no interior de um invólucro convenientemente dimensionado. Este fenômeno mostra-se semelhante em diversos aspectos às micro cavidades, mais especificamente às cavidades próximas a superfícies livres, embora, sem dúvida, em escala muito maior. Os aspectos mencionados foram filmados com câmeras de alta velocidade e as características observadas foram comparadas com aquelas observadas em micro escala. Vários testes foram desenvolvidos de forma a melhor entender a dinâmica da formação e colapso dessas estruturas, sobretudo levando em conta um comportamento mais unidimensional para a evolução da bolha. Através de várias aproximações e análise de diferentes hipóteses para a variação de pressão e para a força de resistência, soluções analíticas e numéricas foram obtidas para a força exercida no fundo do contêiner e para a expansão e colapso das bolhas ao longo do tempo. As soluções propostas, em comparação com os dados experimentais, mostraram boa concordância entre si, sugerindo que os aspectos fundamentais da dinâmica da cavidade foram devidamente considerados e quantificados. / Cavitation and bubble dynamics are fairly recurring topics in literature, mostly due to their effects in various types of phenomena such as heat transfer and flow in pipes. Considering liquid phases, it is known that these cavity structures are normally associated with the metastable equilibrium, reached due to local pressure drop or overheating of a pure substance (or nearly so). In these cases, the phase change require a startup via some appropriate mechanism, which generates a fast sequence of phenomena. Although commonly associated with damage, recently several studies shown practical applications of these topics, and a still little explored field emerged, which is the field of macro cavities. These cavities can be generated by heating water at a low pressure, under specific conditions, creating an explosive sequences and forming piston like movements for the water inside a properly scaled casing. This phenomenon appears to be similar in many aspects to micro cavities, more specifically for cavities near free surfaces, although, without doubt, on a much larger scale. The mentioned aspects were filmed with high-speed cameras and the main features were compared with those observed in micro scale. Several tests have been developed to better understand the dynamics of the formation and collapse of these structures, especially taking into account a more one-dimensional behavior to the evolution of the bubble. Through various approximations, and analysis of different assumptions for the variation of pressure and the resistance force, analytical and numerical solutions were obtained for the force exerted on the bottom of the container and the expansion and collapse of bubbles over time. The proposed solutions in comparison with experimental data showed good agreement between each other suggesting that the fundamental aspects of the dynamics of the cavity were properly considered and quantified.

<p>Black liquors are presently combusted in recovery boilers where the inorganic cooking chemicals are recovered and the energy in the organic material is converted to steam and electricity. A new technology, developed by Chemrec AB, is black liquor gasification (BLG). BLG has more to offer compared to the recovery boiler process, in terms of on-site generation of electric power, liquid fuel and process chemicals. A prerequisite for both optimization of existing processes and the commercialization of BLG is better understanding of the physical and chemical processes involved including interactions with the refractory lining. The chemistry in the BLG process is very complex and to minimize extensive and expensive time-consuming studies otherwise required accurate and reliable model descriptions are needed for a full understanding of most chemical and physical processes as well as for up-scaling of the new BLG processes. However, by using these calculated model results in practice, the errors in the state of the art thermochemical data have to be considered. An extensive literature review was therefore performed to update the data needed for unary, binary and higher order systems. The results from the review reviled that there is a significant range of uncertainty for several condensed phases and a few gas species. This resulted in experimental re-determinations of the binary phase diagrams sodium carbonate-sodium sulfide (Na2CO3-Na2S) and sodium sulfate-sodium sulfide (Na2SO4-Na2S) using High Temperature Microscopy (HTM), High Temperature X-ray Diffraction (HT-XRD) and Differential Thermal Analysis (DTA). For the Na2CO3-Na2S system, measurements were carried out in dry inert atmosphere at temperatures from 25 to 1200 °C. To examine the influence of pure CO2 atmosphere on the melting behavior, HTM experiments in the same temperature interval were made. The results include re-determination of liquidus curves, in the Na2CO3 rich area, melting points of the pure components as well as determination of the extent of the solid solution, Na2CO3(ss), area. The thermal stability of Na2SO3 was studied and the binary phase diagram Na2SO4-Na2S was re-determined. The results indicate that Na2SO3 can exist for a short time up to 750 °C, before it melts. It was also proved that a solid/solid transformation, not reported earlier, occurs at 675 ± 10 °C. At around 700 °C, Na2SO3 gradually breaks down within a few hours, to finally form the solid phases Na2SO4 and Na2S. From HTM measurements a metastable phase diagram including Na2SO3, as well as an equilibrium phase diagram have been constructed for the binary system Na2SO4-Na2S. Improved data on Na2S was experimentally obtained by using solid-state EMF measurements. The equilibrium constant for Na2S(s) was determined to be log Kf(Na2S(s)) (± 0.05) = 216.28 – 4750(T/K)–1 – 28.28878 ln (T/K). Gibbs energy of formation for Na2S(s) was obtained as ΔfG°(Na2S(s))/(kJ mol–1) (± 1.0) = 90.9 – 4.1407(T/K) + 0.5415849(T/K) ln (T/K). The standard enthalpy of formation of Na2S(s) was evaluated to be ΔfH°(Na2S(s), 298.15 K)/(kJ mol–1) (± 1.0) = – 369.0. The standard entropy was evaluated to be S°(Na2S(s), 298.15 K)/(J mol–1 K–1) (± 2.0) = 97.0. Analyses of used refractory material from the Chemrec gasifier were also performed in order to elucidate the stability of the refractory lining. Scanning electron microscopy (SEM) analysis revealed that the chemical attack was limited to 250-300 μm, of the surface directly exposed to the gasification atmosphere and the smelt. From XRD analysis it was found that the phases in this surface layer of the refractory were dominated by sodiumaluminosilicates, mainly Na1.55Al1.55Si0.45O4.</p>

Black liquors are presently combusted in recovery boilers where the inorganic cooking chemicals are recovered and the energy in the organic material is converted to steam and electricity. A new technology, developed by Chemrec AB, is black liquor gasification (BLG). BLG has more to offer compared to the recovery boiler process, in terms of on-site generation of electric power, liquid fuel and process chemicals. A prerequisite for both optimization of existing processes and the commercialization of BLG is better understanding of the physical and chemical processes involved including interactions with the refractory lining. The chemistry in the BLG process is very complex and to minimize extensive and expensive time-consuming studies otherwise required accurate and reliable model descriptions are needed for a full understanding of most chemical and physical processes as well as for up-scaling of the new BLG processes. However, by using these calculated model results in practice, the errors in the state of the art thermochemical data have to be considered. An extensive literature review was therefore performed to update the data needed for unary, binary and higher order systems. The results from the review reviled that there is a significant range of uncertainty for several condensed phases and a few gas species. This resulted in experimental re-determinations of the binary phase diagrams sodium carbonate-sodium sulfide (Na2CO3-Na2S) and sodium sulfate-sodium sulfide (Na2SO4-Na2S) using High Temperature Microscopy (HTM), High Temperature X-ray Diffraction (HT-XRD) and Differential Thermal Analysis (DTA). For the Na2CO3-Na2S system, measurements were carried out in dry inert atmosphere at temperatures from 25 to 1200 °C. To examine the influence of pure CO2 atmosphere on the melting behavior, HTM experiments in the same temperature interval were made. The results include re-determination of liquidus curves, in the Na2CO3 rich area, melting points of the pure components as well as determination of the extent of the solid solution, Na2CO3(ss), area. The thermal stability of Na2SO3 was studied and the binary phase diagram Na2SO4-Na2S was re-determined. The results indicate that Na2SO3 can exist for a short time up to 750 °C, before it melts. It was also proved that a solid/solid transformation, not reported earlier, occurs at 675 ± 10 °C. At around 700 °C, Na2SO3 gradually breaks down within a few hours, to finally form the solid phases Na2SO4 and Na2S. From HTM measurements a metastable phase diagram including Na2SO3, as well as an equilibrium phase diagram have been constructed for the binary system Na2SO4-Na2S. Improved data on Na2S was experimentally obtained by using solid-state EMF measurements. The equilibrium constant for Na2S(s) was determined to be log Kf(Na2S(s)) (± 0.05) = 216.28 – 4750(T/K)–1 – 28.28878 ln (T/K). Gibbs energy of formation for Na2S(s) was obtained as ΔfG°(Na2S(s))/(kJ mol–1) (± 1.0) = 90.9 – 4.1407(T/K) + 0.5415849(T/K) ln (T/K). The standard enthalpy of formation of Na2S(s) was evaluated to be ΔfH°(Na2S(s), 298.15 K)/(kJ mol–1) (± 1.0) = – 369.0. The standard entropy was evaluated to be S°(Na2S(s), 298.15 K)/(J mol–1 K–1) (± 2.0) = 97.0. Analyses of used refractory material from the Chemrec gasifier were also performed in order to elucidate the stability of the refractory lining. Scanning electron microscopy (SEM) analysis revealed that the chemical attack was limited to 250-300 μm, of the surface directly exposed to the gasification atmosphere and the smelt. From XRD analysis it was found that the phases in this surface layer of the refractory were dominated by sodiumaluminosilicates, mainly Na1.55Al1.55Si0.45O4.

Experiments on the production of porous metallic materials were performed on Fe-base and Al-base alloys. The method involves dissolution of gases in the liquid state and solidification at various cooling rates. The alloy compositions were selected to induce solidification of primary particles intended to control the pore distribution. For the Fe-base alloys, nitrogen was introduced into the melt by dissolution of chromium nitride powder. Fe-Cr-Mn-Si-C alloys featuring M7C3 carbide particles were selected. For the Al-base alloys, hydrogen gas was dissolved into the melt by decomposition of water vapor. Al-Ti and Al-Fe alloys featuring primary Al3Ti and Al3Fe intermetallic particles, respectively, were considered. In the Fe-base alloys, a homogeneous distribution of gas pores through the specimens’ volume was obtained at high cooling rate (water quenching) and after introduction of external nucleating agents. In the case of the Al-base alloys, a good pore distribution was observed at all cooling rates and without addition of nucleating agents. Calculations of the variation of nitrogen (respectively hydrogen) solubility based on Wagner interaction parameters suggest that pore nucleation and growth occur during precipitation of the primary particles (M7C3 carbides, Al3Ti or Al3Fe intermetallics), due to composition changes in the melt and resultant supersaturation with gas atoms. Microscopic analyses revealed that the primary particles control the pore growth in the melt and act as barriers between adjacent pores, thereby preventing pore coalescence and promoting a fine pore distribution. Uniaxial compression testing of the porous Al-Ti and Al-Fe materials showed the typical compressive behavior of cellular metals. Further work is needed to improve the quality and reproducibility of the porous structures which can possibly be used in energy absorption or load-bearing applications. As a corollary result of the quenching of hypereutectic Fe-Cr-Mn-Si-C alloys in the experiments of synthesis of porous metals, a homogeneous featureless structure was observed in some parts of the samples, instead of the equilibrium structure of M7C3 and eutectic phases. Subsequent investigations on rapid solidification of Fe-base alloys at various alloy compositions and cooling rates led to the formation of a single-phase structure for the composition Fe-8Cr-6Mn-5Mo-5Si-3.2C (wt.%), at relatively low cooling rates (≈103 K/s) and for large sample dimensions (2.85 mm). The single phase, which is likely to be the hcp ɛ-phase, was found to decompose into a finely distributed structure of bainite and carbides at ≈600 °C. The annealed structure showed very high hardness values (850 to 1200 HV), which could be exploited in the development of high-strength Fe-base materials. / QC 20100809

The aim of the present work is to characterize a metastable hard magnetic phase referred to as &amp;quot;A1&amp;quot; in Nd-Fe alloys, which forms as a part of the fine eutectic depending on the composition and cooling rate. In order to define the range of composition for the formation of A1, Nd100-xFex (x = 20, 25, 40) alloys are cooled at about 150 K/s. The results indicate that for a cooling rate of 150 K/s, the hypereutectic Nd100-xFex (x = 20) alloys solidify into hard magnetic A1 whilst the hypoeutectic alloys (x = 40) show the formation of Nd2Fe17 crystallites. However, no sample cooled at 150 K/s shows the peaks of Nd5Fe17 as expected from the equilibrium Nd-Fe phase diagram. The effect of cooling rate on the formation of hard magnetic A1 is studied by investigating the Nd80Fe20 alloys cooled at different rates. The microstructure of hard magnetic Nd80Fe20 alloys displays a fine eutectic-like matrix consisting of Nd-richer and Fe-richer regions. The Nd-richer regions are identified as dhcp Nd and fcc Nd-Fe solid solution. However, the Fe-richer regions also referred to as A1, are diffuse and give an average composition of Nd56Fe44. These regions yield complex electron diffraction patterns, which do not match with any known Nd-Fe phase. HRTEM images of the Fe-richer regions reveal the presence of 5-10 nm crystallites embedded in an amorphous phase. Thus the Fe-richer regions of the hard magnetic Nd80Fe20 specimens are not a single homogeneous phase rather they are mixture of finely dispersed nanocrystallites in an amorphous phase. The demagnetization curves the hard magnetic Nd80Fe20 measured at temperatures above 30 K are typical of a hard magnetic material. The coercivity increases from 0.48 to 4.4 T with the temperature decreasing from 300 to 55 K. The demagnetization curves change from single to two-phase type when the temperature approaches 29 K, ordering temperature of fcc Nd-Fe solid solution. The measurements of initial magnetization, field dependence of coercivity, and temperature dependence of coercivity suggest the Stoner-Wohlfarth type magnetization reversal process for the hard magnetic A1. The values of anisotropy constant are estimated by fitting the magnetization data to the law-of-approach to saturation. The temperature dependence of anisotropy constant and the coercivity indicate that the origin of coercivity is magnetic anisotropy. A cluster model with sperimagnetic arrangement of Nd and Fe spins is used to explain the hard magnetic behavior of the mold-cast Nd80Fe20. Structural and magnetic properties of multicomponent Nd60Co30-xFexAl10 (0 &amp;lt; x &amp;lt; 30) alloys are compared with the binary Nd-Fe alloys. Magnetic measurements of the multicomponent alloys show that the magnetic properties are controlled by the fraction of the Fe content. The coercivity of the Nd60Co30-xFexAl10 mold-cast rods does not vary much with the Fe-content for more than 10 at.% Fe but the remanence and the maximum magnetization increase linearly with the Fe content. The temperature dependence of coercivity, effective anisotropy constant, and anisotropy field are identical to those for the binary Nd80Fe20 mold-cast rod. These results clearly suggest that the binary Nd80Fe20 and the multicomponent Nd60Co30-xFexAl10 (x &amp;gt; 5) mold-cast rods are magnetically identical.

Digital in-line holographic microscopy (DIHM) has been incorporated as an additional simultaneous in situ optical technique with ellipsomicroscopy for surface imaging and microscopy to study metastable pitting corrosion on stainless steel 316LVM in simulated biological solutions. DIHM adds microscopic volume imaging, allows one to detect local changes of the index of refraction in the vicinity of a pitting event, and allows one to track tracer particles and/or material ejected from the pitting sites. To improve the pitting corrosion resistance of stainless steel 316LVM, a simple surface treatment was tested and the aforementioned imaging techniques were used to verify that pitting occurred only on the wire face. Treatments consisted of polishing the samples to remove the passive layer, then immersing the wires in 90 C nanopure water for several hours. Treated wires show a marked increase in pitting corrosion resistance over untreated wires: the pit initiation potential increases by a minimum of 200 mV. Additional testing with scanning electron microscopy and energy dispersive X-ray spectroscopy indicate that the removal of sulphide inclusions from the surface is the most probable cause of this enhancement. To increase holographic reconstruction performance, Graphics Processing Units (GPUs) have been used; 4 Mpixel holograms are reconstructed using the dot product approximation of the Kirchhoff-Fresnel integral in 60 ms on a Tesla c1060 GPU. Errors in sizes and positions can easily be as large as 5 to 10 % for regions where the dot product approximation is not valid, so algorithms with fewer or no approximations are also required. Reconstructions for arbitrary holographic geometries using the full Kirchhoff-Fresnel integral take approximately 1 hour (compared to 1 week on a quad-core CPU), and reconstructions using convolution methods, in which the results of 256 reconstructions at 4096 x 4096 pixels in one plane are combined, take 17 s. This method is almost exact, with approximations only in the obliquity factor.

In the course of this PhD thesis metastable Cu50Zr50-xTix (0≤ x ≤ 10) and (Cu0.5Zr0.5)100-xAlx (5 ≤ x ≤ 8) alloys were prepared and characterised in terms of phase formation, thermal behaviour, crystallisation kinetics and most importantly in terms of mechanical properties. The addition of Al clearly enhances the glass-forming ability although it does not affect the phase formation. This means that the Cu-Zr-Al system follows the characteristics of the binary Cu-Zr phase diagram, at least for Al additions up to 8 at.%. Conversely, the presence of at least 6 at.% Ti changes the crystallisation sequence of Cu50Zr50-xTix metallic glasses and a metastable C15 CuZrTi Laves phase (Fd-3m) precipitates prior to the equilibrium phases, Cu10Zr7 and CuZr2. A structurally related phase, i.e. the “big cube” phase (Cu4(Zr,Ti)2O, Fd-3m), crystallises in a first step when a significant amount of oxygen, on the order of several thousands of mass-ppm (parts per million), is added. Both phases, the C15 Laves as well as the big cube phase, contain pronounced icosahedral coordination and their formation might be related to an icosahedral-like short-range order of the as-cast glass. However, when the metallic glasses obey the phase formation as established in the binary Cu-Zr phase diagram, the short-range order seems to more closely resemble the coordination of the high-temperature equilibrium phase, B2 CuZr. During the tensile deformation of (Cu0.5Zr0.5)100-xAlx bulk metallic glasses where B2 CuZr nanocrystals precipitate polymorphically in the bulk and some of them undergo twinning, which is due to the shape memory effect inherent in B2 CuZr. Qualitatively, this unique deformation process can be understood in the framework of the potential energy landscape (PEL) model. The shear stress, applied by mechanically loading the material, softens the shear modulus, thus biasing structural rearrangements towards the more stable, crystalline state. One major prerequisite in this process is believed to be a B2-like short-range order of the glass in the as-cast state, which could account for the polymorphic precipitation of the B2 nanocrystals at a comparatively small amount of shear. Diffraction experiments using high-energy X-rays suggest that there might be a correlation between the B2 phase and the glass structure on a length-scale less than 4 Å. Additional corroboration for this finding comes from the fact that the interatomic distances of a Cu50Zr47.5Ti2.5 metallic glass are reduced by cold-rolling. Instead of experiencing shear-induced dilation, the atoms become more closely packed, indicating that the metallic glass is driven towards the more densely packed state associated with the more stable, crystalline state. It is noteworthy, that two Cu-Zr intermetallic compounds were identified to be plastically deformable. Cubic B2 CuZr undergoes a deformation-induced martensitic phase transformation to monoclinic B19’and B33 structures, resulting in transformation-induced plasticity (TRIP effect). On the other hand, tetragonal CuZr2 can also be deformed in compression up to a strain of 15%, yet, exhibiting a dislocation-borne deformation mechanism. The shear-induced nanocrystallisation and twinning seem to be competitive phenomena regarding shear band generation and propagation, which is why very few shear offsets, due to shear banding, can be observed at the surface of the bulk metallic glasses tested in quasistatic tension. The average distance between the crystalline precipitates is on the order of the typical shear band thickness (10 - 50 nm) meaning that an efficient interaction between nanocrystals and shear bands becomes feasible. Macroscopically, these microscopic processes reflect as an appreciable plastic strain combined with work hardening. When the same CuZr-based BMGs are tested in tension at room temperature and at high strain rate (10-2 s-1) there seems to be a “strain rate sensitivity”, which could be related to a crossover of the experimental time-scale and the time-scale of the intrinsic deformation processes (nanocrystallisation, twinning, shear band generation and propagation). However, further work is required to investigate the reasons for the varying slope in the elastic regime. As B2 CuZr is the phase, that competes with vitrification, it precipitates in a glassy matrix if the cooling rate is not sufficient to freeze the structure of the liquid completely. The pronounced work hardening and the plasticity of the B2 phase, which are a result of the deformation-induced martensitic transformation, leave their footprints in the stress-strain curves of these bulk metallic glass matrix composites. The behaviour of the yield strength as a function of the crystalline volume fraction can be captured by the rule of mixtures at low crystalline volume fractions and by the load bearing model at high crystalline volume fractions. In between both of these regions there is a transition caused by percolation (impingement) of the B2 crystals. Furthermore, the fracture strain can be modelled as a function of the crystalline volume fraction by a three-microstructural-element body and the results imply that the interface between B2 crystals and glassy matrix determines the plastic strain of the composites. The combination of shape memory crystals and a glassy matrix leads to a material with a markedly high yield strength and an enhanced plastic strain. In the CuZr-based metastable alloys investigated, there is an intimate relationship between the microstructure and the mechanical properties. The insights gained here should prove useful regarding the optimisation of the mechanical properties of bulk metallic glasses and bulk metallic glass composites.

xxiv, 265 p. : ill. (some col.) / Stabilizing mechanisms and design considerations for generating misfit layer compounds with a variety of different structural motifs were explored using designed precursors consisting of elemental layers. Layer order in the precursor film and the behavior of binary reaction couples was used to avoid undesirable reaction intermediates. Electron diffraction patterns of CuCr2 Se4 were inconsistent with prior reports that this compound has the spinel structure and were more consistent with a hexagonal R 3 ̄ structure. STEM imaging also suggests CuCr2 Se4 prepared using the compositionally modulated kinetic trapping approach is a new polymorph of the spinel structure. Electrical and magnetic properties were consistent with prior literature reports. Magnetic susceptibility measurements show pronounced hard and easy axes of magnetization not previously documented, which are consistent with a hexagonal crystal symmetry. The [{(PbSe)m }0.99 (WSe2 )n ] r and [{(PbSe)m }1.00 (MoSe2 )n ] r systems were investigated by STEM, XRD and density functional theory (DFT) modeling. No crystallographic registration between MSe and TSe 2 layers was observed and the diffraction observed in the hk 0 and hkl directions, where h = k = 0, can be described by diffraction from discrete layers of finite thickness. A distortion of the MX structure for m > 4 was documented. The distortion in MSe layers was largest for m = 2 and independent of TSe2 thickness. A novel family of compounds, [{(FeSe)m }1+y (NbSe 2 )n ]r , were synthesized inspired by a geological precedent. Single FeSe and NbSe2 layer thicknesses ((0.571 ± 0.005) nm and (0.653 ± 0.002) nm respectively) are consistent with literature values for the binary compounds. STEM-HAADF images of the [{(FeSe) 5 }1+y (NbSe2 )5 ]r revealed a multilayer structure with two distinct structural subunits. STEM-EELS analysis of the film showed no intermixing between the Nb and Fe regions within the limit of the measurement. Another family of misfit layer compounds, [{(NbSe2 )m }1+y (CuCr2Se4)n]r, designed to test requirements for a stable misfit layer compound, were successfully synthesized. STEM analysis of the [{(NbSe2 )5 }1+y (CuCr2 Se4 ) 1 ]r compound showed a well segregated film with two distinct subunit structures. Thicknesses for individual layers of NbSe2 or CuCr2 Se4 ((0.648 ± 0.004) nm and (1.76 ± 0.01) nm respectively) are consistent with prior literature reports of the individual binary compounds. This dissertation includes previously published and unpublished co-authored material. / Committee in charge: Dr. Mark C. Lonergan, Chair; Dr. David C. Johnson, Advisor; Dr. James Hutchison, Member; Dr. Catherine Page, Member; Dr. Stephen Gregory, Outside Member; Dr. Ian M. Anderson, Honorary Member

Made available in DSpace on 2014-10-09T12:41:56Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:04:33Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP