Thesis (Ph. D.)--Oregon State University, 2008. / Printout. Includes bibliographical references. Also available on the World Wide Web.

Thesis (M.Phil.) - University of Queensland, 2006. / Includes bibliography.

When operating microsystems in harsh environments, many conventionally used techniques are limiting. Further, depending on if the demands arise from the environment or the conditions inside the system, different approaches have to be used. This thesis deals with the challenges encountered when microsystems are used at high pressures and high temperatures. For microsystems operating at harsh conditions, many parameters will vary extensively with both temperature and pressure, and to maintain control, these variations needs to be well understood. Covered within this thesis is the to-date strongest membrane micropump, demonstrated to pump against back-pressures up to 13 MPa, and a gas-tight high pressure valve that manages pressures beyond 20 MPa. With the ability to manipulate fluids at high pressures in microsystems at elevated temperatures, opportunities are created to use green solvents like supercritical fluids like CO2. To allow for a reliable and predictable operation in systems using more than one fluid, the behavior of the multiphase flow needs to be controlled. Therefore, the effect of varying temperature and pressure, as well as flow conditions were investigated for multiphase flows of CO2 and H2O around and above the critical point of CO2. Also, the influence of channel surface and geometry was investigated. Although supercritical CO2 only requires moderate temperatures, other supercritical fluids or reactions require much higher temperatures. The study how increasing temperature affects a system, a high-temperature testbed inside an electron microscope was created. One of the challenges for high-temperature systems is the interface towards room temperature components. To circumvent the need of wires, high temperature wireless systems were studied together with a wireless pressure sensing system operating at temperatures up to 1,000 °C for pressures up to 0.3 MPa. To further extend the capabilities of microsystems and combine high temperatures and high pressures, it is necessary to consider that the requirements differs fundamentally. Therefore, combining high pressures and high temperatures in microsystems results in great challenges, which requires trade-offs and compromises. Here, steel and HTCC based microsystems may prove interesting alternatives for future high performance microsystems.

Thesis (Ph. D.)--Drexel University, 2004. / Includes abstract and vita. Includes bibliographical references (leaves 178-191).

Thesis (Ph. D.)--Ohio State University, 2007. / Full text release at OhioLINK's ETD Center delayed at author's request

Les nitrures binaires des métaux de transition synthétisés à hautes pressions et hautes températures sont de nouveaux matériaux dont le principal intéret réside dans leur multifonctionalité. Dans cette thèse, nous avons synthétisé de nouveaux nitrures de zirconium et d’hafnium, à une pression inférieure à celle de formation des composés cubiques c-M₃N₄ (M=Zr, Hf), mais supérieure à la pression de formation des mononitrures δ-MN. Les mesures par diffraction de rayons X, ont montré que la structure cristalline de ces composés est monoclinique de type Ca₃Tl₄O₉. La composition chimique M₇N₉ (avec une substitution mineure de l’azote par l’oxygène) vérifiée par une analyse quantitative par microsonde électronique suggère la présence de cations métalliques dans des états d’oxydation +3 et +4. Cette observation indique, pour les autres métaux de transition, la possibilité de former à hautes pressions divers nitrures thermodynamiquement stable avec un large éventail de valeur pour le rapport N:M. Les valeurs des modules élastiques pour les échantillons poreux de Zr₇ N₉ et Hf₇N₉ ont été obtenus par mesures laser ultrasonique (LU) et par nanoindentation. Les résultats pour les matériaux denses ont été dérivés en appliquant l’approche d’Hashin- Shtrickman précédemment développée. Nous obtenons ainsi G₀ = 95(9) GPa et B₀ = 130(10) GPa pour Zr₇N₉ et G₀ = 105(10) GPa et B₀ = 161(10) GPa pour Hf₇N₉. La mesure de la nanodureté donne Hn = 8.0(8) GPa et Hn = 9.1(7) GPa pour Zr₇N₉ et Hf₇N₉ respectivement. Finalement, pour Zr₇N₉ , la dureté de Vickers a été déterminée, Hv = 6.5 GPa et est en accord avec la mesure par nanoindentation. Nous avons dérivé la ténacité soit KIc-if = 3.7(4) MPa.m½ pour Zr₇N₉ . La propriété de self-healing a été partiellement observée pour le nouveau nitrure de zirconium. Pour Hf₇N₉, nous obtenons une valeur moyenne Hv = 6.4(1.0) GPa et une ténacité de 2.3-2.9 MPa.m½. Denses, ces matériaux sont supposés avoir une dureté de l’ordre de 10 GPa et la ténacité de Zr₇N₉ similaire à celle de c-Zr₃N₄, matériau poreux. Pour vérifier la méthode de nanoindentation appliquée dans cette thèse, nous avons réalisé une série de tests sur l’échantillon c-Zr₃N₄ précédemment étudié par LU et nanoindentations mais à de plus faibles profondeurs. Nous avons mesuré le module d’Young réduit, Er, pour le matériau poreux c-Zr₃N₄ et en utilisant la valeur du module d’élasticité isostatique B₀ (mesurée indépendamment par LU ou par l’équation d’état) nous avons déterminé les autres modules élastiques d’un matériau polycristallin, qui sont en accord avec les études LU précédemment présentées. La raison pour laquelle nous avons une moins bonne concordance avec les précédentes données de nanoindenation a été découverte. Pour vérifier d’avantage l’application des mesures par nanoindentation, étendre notre connaissance des propriétés de η-Ta₂N₃ et comparer ce matériaux avec M₇N₉, nous avons examiné un échantillon poreux de η-Ta₂N₃ plus en détail : Er et Hn ont été obtenus à la fois pour l’échantillon poli mécaniquement et pour l’échantillon non modifié et ont montré une différence de comportement sur les 400 premiers nanomètres de la mesure, ce qui a confirmé l’effet de “self-healing”, soit une densification de la surface d’une épaisseur similaire à la taille des grains de polissage. A partir des mesures aux plus grandes profondeurs, nous obtenons E₀= 329-369 GPa et n₀ 0.28-0.33, après calcul à partir de la valeur de la porosité (14%), de B₀ précédemment mesuré et en utilisant l’approche d’Hashin-Shtrickman. La valeur mesurée de la nanodureté s’est révélée être Hn = 18.3 GPa. Enfin, la mesure par dureté de Vickers, Hv, a confirmé les mesures par nanoindentation et montré l’existence d’un effet de la taille de l’indentation pour ce matériau. Pour le matériau dense, nous estimons que Hv > 24 GPa [...] / ₀ ₁ ₂ ₃ ₄ ₅ ₆ ₇ ₈ ₉ ₀
 Binary nitrides of transition metals synthetized at high pressures and high temperatures are new materials which are of interest due to their multifunctionality : They can have combinations of advanced properties, among them elevated elastic moduli, high hardness, high fracture toughness, chemical stability and some of them were found to be suitable for optoelectronic applications. Since the first synthesis of c-Zr₃N₄ in 2003 the studies on such materials extended. For example, c-Zr₃N₄ was found to have a high hardness and an exceptional wear resistance by milling of ferric alloys. ƞ-Ta₂N₃ having orthorhombic structure has a higher B₀ than c-Zr₃N₄ and a similar shear modulus G₀. Moreover, a self-healing effect upon mechanical polishing of a porous ƞ-Ta₂N₃ sample was recognised. There are also reports about synthesis of noble metal nitrides at high pressures and temperatures but these compounds are not recoverable to ambient conditions. In this work we synthetized new nitrides of zirconium and hafnium at pressures below those where c-M₃N₄ (M=Zr, Hf) form but above the pressures of formation of mononitrides δ-MN. X-ray diffraction measurements showed that their crystal structure is monoclinic of the type Ca₃Tl₄O₉. The chemical composition M₇N₉ (with a minor substitution of nitrogen by oxygen), verified by quantitative microprobe analysis, suggests presence of metal cations in the oxidation states +3 and + 4. This observation suggests for other transition metals the possibility to form at high pressures thermodynamically stable nitrides with the N:M ratio varying in a broad range. Elastic moduli of the porous samples of Zr₇N₉ and Hf₇N₉ were measured using laser ultrasonics (LU) and nanoindentation. Values for the dense samples were derived by applying the earlier developed Hashin-Shtrickman approach. We obtained G₀ = 95(9) GPa and B₀ = 130(10) GPa for Zr₇N₉ and G₀ = 105(10) GPa and B₀ = 161(10) GPa for Hf₇N₉. The nanohardness was measured to be Hn = 8.0(8) GPa and Hn = 9.1(7) GPa for Zr₇N₉ and Hf₇N₉, respectively. Vickers hardness of Zr₇N₉ was determined to be Hv = 6.5 GPa which is in agreement with our nanoindentation measurements. We derived its fracture toughness to be KIc-if = 3.7(4) MPa.m½, similar to that of c-Zr₃N₄, and recognised a weak self-healing behaviour. For Hf₇N₉, we obtained an average value of Hv = 6.4(1.0) GPa and KIc-if = 2.3-2.9 MPa.m½. Hardness of dense samples of Zr₇N₉ and Hf₇N₉ was estimated to be ~10 GPa. In order to verify the nanoindentation method we applied in this work, we performed tests on the c-Zr₃N₄ sample studied previously by LU and nanoindentation but at much shallower depths. We measured the reduced Young's modulus, Er, for the porous sample, and, applying the known B₀ (form laser ultrasonic- or equation of state measurements), we determined other elastic moduli for the porous and dense polycrystalline sample, which were in agreement with the earlier LU studies. Reasons for a less good agreement with the earlier nanoindentation data were disclosed. In order to further verify the applied nanoindentation method and extend our knowledge about properties of ƞ-Ta₂N₃ and compare this material with M₇N₉, we examined a porous sample of ƞ-Ta₂N₃ in more detail : Er and Hn obtained for the mechanically polished sample and for the non modified sample showed a distinct behaviour in the first 400 nm of indentation thus confirming the "self-healing" effect at the thickness similar to the size of the polishing grains. From Er measured at larger depths we derived E₀= 329-369 GPa and v₀= 0.28-0.33 using the porosity value (14%), the earlier measured B₀ and applying the Hashin-Shtrickman approach. The nanohardness was measured to be Hn = 18.3 GPa. Measurements of Vickers hardness confirmed our nanoindentation results and revealed the indentation size. For the dense ƞ-Ta₂N₃ we estimate Hv > 24 GPa.

A new approach is developed for evaluating the mixing properties of binary solutions at high pressure. This involves solving Poisson's equation throughout three-dimensional cubic lattices, consistent with Thomas-Fermi-Dirac (TFD) theory. Zero temperature calculations are carried out for a variety of compositions and crystal structures in 3 pressure groups relevant to Jovian planetary interiors. Pseudopotentials based on the two-component-plasma model (with a uniform electron background) are fitted to the solid-state results, and are then used in liquid-state calculations using hard-sphere perturbation theory. TFD results for H-He solutions find critical temperatures (above which all compositions are soluble) to be ∿ 0, 500, and 1500°K at pressures of 10, 100, and 1000 Mbar, respectively. These temperatures are much lower than those obtained using free electron perturbation theory, where T(crit) ∿ 10,000°K at 10 Mbar. Thus, unlike the perturbation theory results, the TFD results predict that helium should be soluble in metallic hydrogen in the deep interiors of both Jupiter and Saturn, and our calculations give an indication of the degree of model-dependence in computing high pressure mixing properties. In addition, TFD calculations for H-C and H-O solutions find phase separation temperatures to be≲ 10⁴ °K for pressures ≲ 10³ Mbar. These temperatures are considerably lower than those found assuming a uniform electron distribution (where T(crit) ≳ 10⁵ °K), and suggest that H-C and H-O solutions should also be miscible in the metallic zones of Jupiter and Saturn.

Pontos quânticos de carbono (C-dots) luminescentes na região do azul-verde aprisionados em matriz de sílica foram produzidos por um processo novo, baseado na pirólise de grupos contendo carbono dispersos nas bordas dos grãos de dimensões nanométricas de sílica (AEROSIL) previamente sinterizados a frio sob alta pressão, onde nenhuma técnica de passivação foi exigida. A análise de difração de elétrons de área selecionada (SAED – Selected Area Electron Diffraction) e espectroscopia de perda de energia de elétrons (EELS – Electron Energy Loss Spectroscopy) confirmaram a formação de C-dots contendo átomos de carbono com ligações do tipo sp2. Foram investigados diferentes valores de pressão (2,5, 4 e 7,7 GPa) para sinterização a frio e diferentes temperaturas de pirólise, a partir de 500 até 900°C. Resultados de análise térmica revelaram pequena perda de massa durante a pirólise das amostras, praticamente independente da pressão utilizada na sinterização. Espectroscopia na faixa do infravermelho revelou alterações nas bandas de aborção na faixa correspondente aos modos de vibração de CH2 e CH3, dependentes da temperatura e da pressão utilizadas. Os espectros de fotoluminescência (FL) foram fortemente dependentes do comprimento de onda de excitação e observou-se uma intensidade de emissão mais elevada no intervalo entre 500-550 nm para a amostra sinterizada a frio em 7,7 GPa e tratada termicamente a 800°C para excitação em 460 nm. Também foi investigado a contribuição da matriz de silica após a sinterização. / Quantum dots in the blue-green region embedded in a silica matrix were produced by a new process based on the pyrolysis of groups containing carbon dispersed on the edges of the grain of nanosized silica (AEROSIL) previously sintered under high pressure, where no passivation technique was required. The Selected Area Electron Diffraction (SAED) and Electron Energy Loss Spectroscopy (EELS) confirmed the formation of Cdots containing carbon atoms with sp2 bonds. Different pressure values (2,5, 4 and 7,7 GPa) were investigated for cold sintering and the pyrolsys was in the temperature range from 500 to 900°C. Results of thermal analysis revealed a small loss of mass during the pyrolysis of the samples, practically independent of the sintering pressure. Infrared spectroscopy revealed changes in the absorption bands in the range corresponding to the CH2 and CH3 vibration modes, depending on the temperature and pressure conditions. Photoluminescence (PL) spectra were strongly dependent on the excitation wavelength and a higher emission intensity was observed in the range 500-550 nm for the sample sintered at 7.7 GPa and pyrolysed at 800°C for excitation at 460 nm. The contribution of the silica matrix after sintering was also investigated.

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In the development of explosively formed projectiles (EFPs), researchers are faced with the problem of testing prospective metals at high strain rates. So far it has been assumed that, relative to the cooling time, the deformation time is practically instantaneous indicating that the test is adiabatc: none of the heat generated within the metal is lost to conduction. In this paper we construct a model that subtracts out the effects of kinetic energy and uses specific heat as a function of temperature. In this way we can focus on the energy change in the specimen that can be attributed to temperature and determine just how adiabatic the high strain rate test is. / vi, 74 leaves : ill. ; 28 cm.