Semi-solid deformation mechanisms are important in a range of manufacturing and natural phenomena, which range from squeeze casting to magma flows. In this thesis, using high speed synchrotron X-ray tomography and a bespoke precision thermo-mechanical rig, a four dimensional (3D plus time) quantitative investigation was performed to study the mechanical / rheological behavior of semi-solid Al-Cu alloys. Various deformation techniques, namely, isothermal semi-solid compression, extrusion and indentation were used. The time-resolved dynamic 3D images were analyzed with the help of novel image quantification techniques including digital volume correlation and image-based simulations of fluid flow. The quantified dynamics at a microstructural scale was then linked with macroscopic mechanical properties. The qualitative and quantitative analyses revealed a range of important semi-solid micromechanical mechanisms including the occurrence and effects of dilatancy, associated liquid flow through the equiaxed microstructure, intra-dendritic deformation, and strain localization during semi-solid deformation, not only shedding new insights into the mechanisms of deformation-induced solidification defect formation (solute segregation, porosity and hot tearing) of semi-solid alloys at both a macroscopic and microscopic level, but also providing benchmark cases for semi-solid deformation models and theories. The experimental methodology, techniques and analysis procedures developed in this thesis are generic in nature and can be applied to a wide range of research fields.

Research to design and synthesise new porous materials is a rapidly growing field with thousands of new systems proposed every year due to their potential use in a multitude of application in a wide range of fields. Pressure is a powerful tool for the characterisation of structure-property relationships in these materials, the understanding of which is key to unlocking their full potential. In this thesis we investigate a range of porous materials at a range of pressures. Over time the chemical architecture and complexity of porous materials has increased. Although some systems display remarkable stability to high-pressures, which we generally think of as being above 1 GPa (10,000 bar), in general, the compressibility of porous materials have increased substantially over the last 10 years, rendering most unstable at GPa pressures. Here we present new methods for investigating porous materials at much more moderate pressures (100's of bar), alongside more traditional high-pressure methods (diamond anvil cell techniques), finishing with gas sorption studies in a molecular based porous material. Here, the design and development of a new moderate pressure sapphire capillary cell for the small molecule beamline I19 at the Diamond Light Source is described. This cell allowed access to pressures of more than 1000 bar regularly with a maximum operating pressure of 1500 bar with very precise pressure control (< 10 bar) on both increasing and decreasing pressure. This cell closes the gap between ambient pressure and the lowest pressures attainable using a diamond anvil cell (DAC), which is generally above 0.2 GPa (2000 bar). Along with the development of the sapphire capillary pressure cell, the compression to 1000 bar of the small organic sample molecule Hexamethylenetetramine (hexamine, C6H12N4) and its deuterated form (C6D12N4) was determined, demonstrating the precision possible using this cell. Solvent uptake into porous materials can induce large structural changes at 100's of bar. In the case of the Sc-based Metal-organic framework (MOF), Sc2BDC3 (BDC = 1,4-benzenedicarboxylate), we used the sapphire capillary pressure cell to study changes in the framework structure on the uptake of n-pentane and isopentane. This work shows how the shape and smaller size of n-pentane facilitated the swelling of the framework that could be used to explain the increase in stability of the MOF to applied pressure. The effect of pressure on the previously unreported Cu-framework bis[1-(4- pyridyl)butane-1,3-dione]copper(II) (CuPyr-I) was investigated using high-pressure single-crystal diffraction techniques (DAC). CuPyr-I was found to exhibit high-pressure and low-temperature phase transitions, a pressure induced Jahn- Teller switch (which was hydrostatic medium dependent), piezochromism, and negative linear compressibility. Although each of these phenomena has been reported numerous times in a range of materials, this is to the best of our knowledge the first example to have been observed within the same material. The final two chapters investigate the exceptional thermal, chemical, and mechanical stability of a porous molecular crystal system (PMC) prepared by the co-crystallisation of a cobalt phthalocyanine derivative and a fullerene (C 60 or C70). The stabilising fullerene is captured in the cavity between two phthalocyanines in a ball and socket arrangement. These PMCs retain their porous structure: on the evacuation of solvent of crystalisation; on heating to over 500 K; on prolonged immersion in boiling aqueous acid, base, and water; and at extreme pressures of up to 5.85 GPa, the first reported high-pressure study of a PMC. the reactive cobalt cation is accessible via the massive interconnected voids, (8 nm3), as demonstrated by the adsorption and binding of CO and O2 to the empty metal site using in situ crystallographic methods available at beamline I19, Diamond Light Source.

Successful management of hydrocarbon reservoirs, geothermal energy extraction sites, radioactive waste and CO2 storage sites depends on a detailed knowledge of fluid transport properties, porosity and permeability. Amongst deformation processes, fluid-rock interaction plays an important role in controlling the petrophysical properties of a rock. The presence of fluids in the rocks induce chemical and physical changes in compositions and texture, affecting porosity and permeability, hence influencing dynamic transport properties and fluid flow. Fluid-rock interaction processes have been deeply investigated in nature and in numerous experimental and numerical modelling studies. However, these studies lack a spatio-temporal characterization of the dynamic evolution of porosity and reaction microfabrics. There is no clear understanding of the spatio-temporal evolution of these properties in three dimensions, and how this evolution affects fluid percolation in the rock. Computed X-ray micro-Tomography (μCT) was applied to investigate these processes in three dimensions and observe their evolution in time (4DμCT). The combination of μCT with 2D analytical techniques (e.g. scanning electron microscope, SEM, electron microcrobe, EMPA, electron backscatter diffraction, EBSD) furthermore enables the extrapolation of the information gained from 2D analyses to the 3rd an 4th dimension (4D μCT). The thesis investigates two different categories of fluid-rock interaction processes, by using 4DμCT to monitor the evolution of mineral reactions (in the first case) and porosity (second case) in relation to strain and time. In the first case study, natural rock samples were analysed. The samples show a compositional change along a strain gradient from olivinic metagabbros to omphacite-garnet bearing eclogites in a ductile shear zone. Synchroton-based x-ray microtomography (sμCT) was applied to document the 3D evolution of garnets along the strain gradient (which represent the 4th dimension). The 3D spatial arrangement of garnet microfabrics can help determine the deformation history and the extent of fluid-rock interaction active during deformation. Results from the sμCT show that in the low strain domain, garnets form a large and well interconnected cluster that develops throughout the entire sample and garnet coronas never completely encapsulate olivine grains. In the most highly deformed eclogites, the oblate shapes of garnets reflect a deformational origin of the microfabrics. EBSD analyses reveal that garnets do not show evidence for crystal plasticity, but rather they highlight evidence for minor fracturing, neo-nucleation and overgrowth, which points to a mechanical disintegration of the garnet coronas during strain localisation. In the second case study, pressure-solution processes were investigated using NaCl as rock-analogue, to monitor the evolution of porosity and pore connectivity in four dimensions, providing a time-resolved characterization of the processes. NaCl samples were uniaxially compacted and μCT scans were taken at regular interval times to characterize the evolution of grain morphologies, pore space and macro-connectivity of the samples. Different uniaxial loads, as well as different bulk sample compositions (phyllosilicates and/or glass beads) were used to investigate their effect on the process. Greater uniaxial loads, and the presence of phyllosilicates within the deforming NaCl columns were found to enhance pressure-solution processes. The pore space becomes highly disconnected in the presence of phyllosilicates, with important implications for fluid percolation and dynamic transport properties. Mean strain rates, calculated from volumetric Digital Image Correlation (3D-DIC) analyses, were found to be higher where phyllosilicates were located. The combination of μCT with volumetric DIC and SEM imaging proved to be an efficient analytical method for investigating the dynamic behaviour of porosity and permeability during ongoing pressure-solution processes. The results showed that fluid-rock interaction critically modifies the rocks at the pore/grain scale, with important consequences on dynamic fluid transport properties. The combination of μCT with classical 2D techniques provided a better understanding on the dynamic evolution of transport properties and fluid percolation during fluid-rock interaction processes, allowing the characterization in three dimensions of reaction microfabrics and porosity.

No description available.

Nanotechnology offers a great potential do design fertilizers with unique properties capable to boost the plant productivity. However, the nanoparticles environmental fate and their toxic responses still need to be deeply investigated to their safe use. This study aims to investigate the effect of copper oxide (nCuO) and magnetite nanoparticles (nFe3O4) on the germination and seedling development of Phaseolus vulgaris L. Seeds were treated in nanoparticles dispersions in a wide range of concentrations (1, 10, 100 and 1 000 mg L-1) and incubated in a germination chamber during 5 days. Different sized nCuO (25, 40 and <80 nm) and polyethylene glycol (PEG) coated nFe3O4 were evaluated. Although both nCuO and nFe3O4 treatments did not affected the germination rate, seedling weight gain was promoted by 40 nm CuO at 100 mg Cu L-1 and inhibited by 1 000 mg Cu L-1 of 25 nm CuO and positive control (CuSO4). Among the tested nCuO, the higher chemical reactivity was found for the 25 nm CuO, and this may partially explain the observed deleterious effects. Seeds treated in nFe3O4-PEG at 1 000 mg Fe L-1 increased radicle elongation compared to the negative control (water), while Fe2+/Fe3+ (aq) (positive control) and bare nFe3O4 at 1 000 mg Fe L-1 treatments reduced the radicle of the seedlings. The growth promoted by the PEG-coated nanoparticles can be justified by the higher water uptake induced by the PEG, and also by its lower chemical reactivity compared to the bare nanoparticles. This was reinforced by enzymatic assays since nFe3O4-PEG treatment was also the least harmful to the alpha-amylase activity. X-ray fluorescence spectroscopy (XRF) showed that most of the Cu and Fe incorporated by the seeds remained in the seed coat, specially in the hilum region, and X-ray tomography indicated that Fe3O4-PEG penetrated in this structure. X-ray absorption spectroscopy (XAS) unraveled that the Cu and Fe chemical environment of the nCuO and nFe3O4-PEG treated seeds persisted mostly in its primitive form. These results contribute to the understanding of how nCuO, nFe3O4 and nFe3O4-PEG interact with common bean seeds and seedlings and highlights its potential use in seed priming / A nanotecnologia oferece um grande potencial para o desenvolvimento de fertilizantes com propriedades únicas, capazes de impulsionar a produtividade das plantas. Contudo, o destino ambiental e os efeitos tóxicos das nanopartículas ainda necessitam ser profundamente investigados para o seu uso seguro. Este estudo visa investigar o efeito das nanopartículas de óxido de cobre (nCuO) e magnetita (nFe3O4) na germinação e desenvolvimento das plântulas de Phaseolus vulgaris L. As sementes foram tratadas em dispersões de nanopartículas em diversas concentrações (1, 10, 100 and 1 000 mg L-1) e incubadas em uma câmara de germinação durante 5 dias. Diferentes tamanhos de nCuO (25, 40 e <80 nm) e nFe3O4 recoberta com polietileno glicol (PEG) e foram avaliados. Embora ambos tratamentos de nCuO e nFe3O4 não afetaram a taxa de germinação, o ganho de massa das plântulas foi promovido pela nCuO de 40 nm à 100 mg Cu L-1 e inibido pelos tratamentos de nCuO de 25 nm e controle positivo (CuSO4) à 1 000 mg Cu L-1. Dentre as nCuO testadas, a maior reatividade química foi encontrada para a nCuO de 25 nm, e isso pode explicar parcialmente os efeitos deletérios desta nanopartícula. Sementes tratadas com nFe3O4-PEG à 1 000 mg Fe L-1 aumentaram o alongamento das radículas em comparação ao controle negativo (água), enquanto que os tratamentos Fe2+/Fe3+ (aq) (controle positivo) e nFe3O4 sem recobrimento à 1 000 mg Fe L-1 reduziram as radículas das plântulas. O crescimento promovido pelas nanopartículas recobertas com PEG pode ser justificado pela maior absorção de água induzido pelo PEG, e também pela sua baixa reatividade química comparada às nanopartículas sem recobrimento. Isso foi reforçado por ensaios enzimáticos uma vez que o tratamento de nFe3O4-PEG foi também o menos prejudicial à atividade da alfa-amilase. A espectroscopia de fluorescência de raios-X (XRF) mostrou que a maior parte do Cu e do Fe incorporados pelas sementes permaneceu no tegumento, especialmente na região do hilo, e a tomografia de raios-X indicou que nFe3O4-PEG penetrou nesta estrutura. A espectroscopia de absorção de raios-X (XAS) revelou que o ambiente químico do Cu e do Fe das sementes tratadas com nCuO e nFe3O4-PEG persistiram majoritariamente em sua forma primitiva. Estes resultados contribuem para o entendimento de como nCuO, nFe3O4 e nFe3O4-PEG interagem com sementes de feijão e destaca seu potencial uso no tratamento de sementes

Foram realizadas medidas das seçõesde choque de produção de raios X L, L e L bem como medidas das seções de choque de ionização das subcamadas L1, L2 e L3 para os elementos Au e Ta com o Acelerador de elétrons Microtron de São Paulo, do Instituto de Física da Universidade de São Paulo. Os alvos foram produzidos no Laboratório de Alvos do Pelletron por evaporação desses elementos sobre substratos finos de carbono. Eles foram posicionados no centro da câmara de irradiação, de modo que o feixe incidia perpendicularmente à sua superfície. Os raios X decorrentes da ionização do alvo de tântalo foram observados com um detetor de Si(Li), enquanto que para o alvo de ouro usou-se um detetor HPGe, ambos posicionados a 120 graus em relação ao feixe. As curvas de eficiência de ambos os detetores foram levantadas usando as fontes de calibração e ajustando os pontos obtidos com um modelo analítico. Para cada energia de feixe, a seção de choque foi determinada a partir das áreas dos picos dos raios X característicos, da corrente incidente no alvo, da eficiência de deteção no pico e da espessura do alvo. As áreas dos picos foram determinadas pelo ajuste de uma forma gaussiana, a corrente incidente no alvo foi medida com um copo de Faraday e corrigida para a dispersão dos elétrons ao passarem pelo alvo, e as medidas de espessura dos alvos foram realizadas pelo método de retro-espalhamento de Rutherford (RBS). Os resultados experimentais obtidos ficaram acima do calculado com a aproximação de Born de ondas distorcidas para as medidas de seção de choque de produção de raios X L, L do Au e para os multipletos L e L do Ta. Para o grupo L do Au e do Ta as medidas foram consistentes com o modelo teórico. Os dados encontrados na literatura para ambos os elementos referem-se todos a energias próximas do limiar de ionização da camada L e nessa faixa são consistentes com o modelo teórico, embora em alguns casos afetados por incertezas superiores a 20%. Este trabalho traz as primeiras medidas para a seção de choque de produção de raios X L do Ta para energias superiores a 50 keV. / Measurements were made of the L, L and L x-rays production cross section and also of the ionization cross section of subshell L1 , L_2 and L3 for the elements Au and Ta in the electron accelerator Microtron of São Paulo, located at the Institute of Physics of the University of São Paulo. The targets used were produced in the Pelletron Targets Laboratory and consisted of fine targets evaporated on thin carbon substrates. These targets were positioned in the center of the Microtrons irradiation chamber, so that the focused beam perpendicular to the surface. The x-ray originated from the ionization of the Ta target were obtained with a Si(Li), for the Au target it was used a HPGe detector, both positioned at 120 degrees relative to the electrons beam. The efficiency curve for both detectors was made by using calibration sources and by adjusting the points with a analytical model. For every beam energy the x-rays production cross section were obtained by an accurate knowledge of the peak areas, of the current incident on the target, of the absolute efficiency, and of the thickness of the target. The peak areas were determined by fitting a Gaussian shape, the measurements of the current were made with a Faraday cup and it were corrected for the electrons\' dispersion when they pass through the target, and the measurements of the thickness were performed with the method of Rutherford Back Scattering (RBS). The experimental results were above the Born approximation of distorted waves for measurements of L and L x-rays production cross sections of Au and for the multiplets L and L and of Ta. The measurements of L group of Au and Ta were consistent with the theoretical model. The data founded in literature for both elements are all near to the region of the threshold ionization energy of the shell L, on that energy range they are consistent with the theoretical model, although in some instances they are affected by uncertainties greater than 20%. This work presents the first measurements of Ta L x-rays production cross section to energies above 50 keV.

The ability to diagnose the structure of a material at extreme conditions of high-pressure and high-temperature is fundamental to understanding its behaviour, especially since it was found that materials will adopt complex crystal structures at pressures in the Terapascal regime (1TPa). Static compression, using the diamond anvil cell coupled with synchrotron radiation has to date been the primary method for structural studies of materials at high pressure. However, dynamic compression is the only method capable of reaching pressures comparable to the conditions found in the interior of newly discovered exo-planets and gas giants where such exotic high-pressure behaviour is predicted to be commonplace among materials. While generating extreme conditions using shock compression has become a mature science, it has proved a considerable experimental challenge to directly observe and study such phase transformations that have been observed using static studies due to the lack of sufficiently bright X-ray sources. However, the commissioning of new 4th generation light sources known as free electron lasers now provide stable, ultrafast pulses of X-rays of unprecedented brightness allowing in situ structural studies of shock compressed materials and their phase transformation kinetics in unprecedented detail. Bismuth, with its highly complex phase diagram at modest pressures and temperatures, has been one of the most studied systems using both static and dynamic compression. Despite this, there has been no structural characterisation of the phases observed on shock compression and it is therefore the ideal candidate for the first structural studies using X-ray radiation from a free electron laser. Here, bismuth was shock compressed with an optical laser and probed in situ with X-ray radiation from a free electron laser. The evolution of the crystal structure (or lack there of) during compression and shock release are documented by taking snapshots of successive experiments, delayed in time. The melting of Bi on release from Bi-V was studied, with precise time scans showing the pressure releasing from high-pressure Bi-V phase until the melt curve is reached off-Hugoniot. Remarkable agreement with the equilibrium melt curve is found and the promise of this technique has for future off-Hugoniot melt curve studies at extreme conditions is discussed. In addition, shock melting studies of Bi were performed. The high-pressure Bi - V phase is observed to melt along the Hugoniot where melting is unambiguously identified with the emergence of a broad liquid-scattering signature. These measurements definitively pin down where the Hugoniot intersects the melt curve - a source of some disagreement in recent years. Evidence is also presented for a change in the local structure of the liquid on shock release. The impact of these results are discussed. Finally, a sequence of solid-solid phase transformations is observed on shock compression as well as shock release and is detected by distinct changes in the obtained diffraction patterns. The well established sequence of solid-solid phase transformations observed in previous static studies is not observed in our experiments. Rather, Bi is found to exist in some metastable structures instead of forming equilibrium phases. The implications these results have for observing reconstructive phase transformations in other materials on shock timescales are discussed.

Pressure and temperature are two environmental variables that are increasingly being exploited by solid-state researchers probing structure-property relationships in the crystalline state. Modern high-pressure apparatus is capable of generating many billions of Pascals in the laboratory, and therefore can produce significantly greater alterations to crystalline materials than changes in temperature, which can typically be varied by only a few thousand Kelvin. Many systems such as single-molecule magnets exhibit interesting properties under low-temperature regimes that can be substantially altered with pressure. The desire by investigators to perform analogous single-crystal X-ray diffraction studies has driven the development of new high-pressure apparatus and techniques designed to accommodate low-temperature environments. [Ni(en)3][NO3]2 undergoes a displacive phase transition from P6322 at ambient pressure to a lower symmetry P6122/P6522 structure between 0.82 and 0.87 GPa, which is characterized by a tripling of the unit cell c axis and the number of molecules per unit cell. The same transition has been previously observed at 108 K. The application of pressure leads to a general shortening of O···H hydrogen bonding interactions in the structure, with the greatest contraction (24%) occurring diagonally between stacks of Ni cation moieties and nitrate anions. A novel Turnbuckle Diamond Anvil Cell designed for high-pressure low-temperature single-crystal X-ray experiments on an open-flow cryostat has been calibrated using the previously reported phase transitions of five compounds: NH4H2PO4 (148 K), ferrocene (164 K), barbituric acid dihydrate (216 K), ammonium bromide (235 K), and potassium nitrite (264 K). From the observed thermal differentials between the reported and observed transition temperatures a linear calibration curve has been constructed that is applicable between ambient-temperature and 148 K. Low-temperature measurements using a thermocouple have been shown to vary significantly depending on the experimental setup for the insertion wire, whilst also adding undesirable thermal energy into the sample chamber which was largely independent of attachment configuration. High-pressure low-temperature single-crystal X-ray diffraction data of [Mn12O12(O2CMe)16(H2O)4] (known as Mn12OAc) reveals a pressure-induced expulsion of the crystallized acetic acid from the crystal structure and resolution of the Jahn-Teller axes disorder between ambient pressure and 0.87 GPa. These structural changes have been correlated with high-pressure magnetic data indicating the elimination of a slow-relaxing isomer over this pressure range. Further application of pressure to 2.02 GPa leads to the expansion of these Jahn-Teller axes, resulting in an enhancement of the slow-relaxing magnetic anisotropy as observed in the literature. Relaxation of pressure leads to a resolvation of the crystal structure and re-disordering of the Jahn-Teller axes, demonstrating that this structural-magnetic phenomenon is fully reversible with respect to pressure. The space group of the Prussian blue analogue Mn3[Cr(CN)6].15H2O has been re-evaluated as R-3m between ambient pressure and 2.07 GPa using high-pressure single-crystal X-ray and high-pressure neutron powder data. Reductions in metal-metal distances and gradual distortions of the Mn octahedral geometry have been correlated with previously reported increases in Tc and declines in ferrimagnetic moment in the same pressure range. Increasing the applied pressure to 2.97 GPa leads to partial amorphization and results in a loss of long-range magnetic order as shown by the literature. The application of pressure (1.8 GPa) to the structure of K2[Pt(CN)4]Br0.24.3.24H2O (KCP(Br)) causes a reduction in the Pt intra-chain and inter-chain distances, and results in an enhancement of the overall conductivity under these conditions as demonstrated in the literature. Almost no changes occur to the high-pressure crystal structure upon cooling to 4 K, except in the Pt-Pt intra-chain distances which converge and suppress the Peierls distortion known to occur at 4 K, resulting in a comparatively greater electrical conductivity under these conditions.

Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Electrical Engineering and Computer Science, 1982. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND ENGINEERING. / Includes bibliographical references. / by Andrew Michael Hawryluk. / Ph.D.

Three new tetrakis [Rh2(PhNCOCH3)4·xNCR] (R = {2-CH3}C6H4 (x=2), R = {3-CH3}C6H4 (x=1), R = (3-CN)C6H4∞ (x=1)) complexes have been synthesized and characterized. These complexes were characterized by IR and 1H NMR spectroscopies and X-ray crystallography which solved with R1<0.05. [Rh2(PhNCOCH3)4·2NC{2-CH3}C6H4] was triclinic (a=9.79Å, b=14.79Å, c=16.36Å, α=103.84⁰, β=99.17⁰, γ=99.77⁰, P-1(#2), μCN=2227.78cm-1, Rh-Rh=2.42Å, N-C=1.13Å, 1.14Å, Rh-N=2.34Å, 2.35Å, Rh-N-C=151.6⁰, 152.5⁰, Rh-Rh-N=173.0⁰, 174.6⁰). [Rh2(PhNCOCH3)4·NC{3-CH3}C6H4] was triclinic (a=11.71Å, b=13.02Å, c=13.40Å, α=72.34⁰, β=66.78⁰, γ=82.74⁰, P-1(#2), μCN=2241.28cm-1, Rh-Rh=2.40Å, N-C=1.14Å, Rh-N=2.16Å, Rh-N-C=166.3⁰, Rh-Rh-N=175.9⁰). [Rh2(PhNCOCH3)4·2NC{3-CN}C6H4]∞ was triclinic (a=11.88Å, b=13.30Å, c=14.88Å, α=77.98⁰, β=74.61⁰, γ=65.48⁰, P-1(#2), μCN=2233.57cm-1, Rh-Rh=2.41Å, N-C=1.13Å, 1.13Å, Rh-N=2.18Å, 2.38Å, Rh-N-C=166.8⁰, 127.7⁰, Rh-Rh-N=178.4⁰, 175.4⁰). The bond distances, bond angles and bonding interactions (σ and π) are similar to the metal-carbene bond formed during carbenoid transformations catalyzed by dirhodium(II) compounds.