In this thesis, a synthesis concept has been developed, which uses nitrogen-rich liquid phases for sintering of Ca-α-sialon ceramics. First, keeping the Si/Al ratios constant, the effects of N/O ratio on the properties and microstructure were investigated through a liquid phase sintering process. Second, nitrogen-rich Ca-α-sialon ceramics, with nominal compositions: CaxSi12-2xAl2xN16, x < 2.0, was synthesized and characterized. Third, mechanical and thermal properties of nitrogen-rich Ca-α-sialons were investigated in terms of high temperature deformation resistance,reaction mechanism, phase stability and oxidation resistance, and further correlated to their phase assemblage and microstructure observation. It has been found that increasing the N/O and Ca/Al ratio simultaneously in the materials could result in development of a microstructure with well shaped, high-aspect-ratio Ca-α-sialon grains, and an improvement in both toughness and hardness. For the nitrogen-rich Ca-α-sialon, mono-phasic α-sialon ceramics were obtained for 0.51 ≤ x ≤ 1.32. The obtained Ca-α-sialon ceramics with elongated-grain microstructures show a combination of high hardness and high fracture toughness. Compared with the oxygen-rich Ca-α-sialons, the nitrogen-rich Ca-α-sialons exhibited approximately 150 oC higher deformation onset temperatures and decent properties even after the deformation. The α-sialon phase was first observed at 1400 oC, however the phase pure Ca-α-sialon ceramics couldn’t be obtained until 1800 oC. The nitrogen-rich Ca-α-sialons were thermal stable, no phase transformation observed in the temperatures range1400-1600 oC. In general, mixed α/β-sialon showed better oxidation resistance than pure α-sialon in the low temperature range (1250-1325 oC), while α-sialons with compositions located at α/β-sialon border-line showed significant weight gains over the entire temperature range (1250-1400 oC).

La tenue au fluage des aubes de turbine haute pression est une problématique de premier ordre vis-à-visde la certification d'un turbomoteur d'hélicoptère. Les excellentes propriétés mécaniques à hautes températuresdes superalliages monocristallins base nickel en font les matériaux les plus utilisés pour la fabrication de cesaubes. Pour ces composants, les exigences réglementaires de certification imposent la réalisation d'essaisanisothermes, plus sévères que les conditions de fonctionnement en service, basés sur le mixage de différentsrégimes de fonctionnement d'un hélicoptère.L'enjeu de cette thèse est de mieux prédire le comportement mécanique et la durée de vie de cesmatériaux lors d'essais de certification des moteurs d'hélicoptères présentant des endommagementsprépondérants de type fluage grâce à l'établissement d'un modèle de comportement et d'endommagement. Cemodèle doit intégrer les effets transitoires de comportement mécanique et les effets d'anisotropie ; il doit êtreprédictif en termes de durée de vie et doit être apte à modéliser de manière satisfaisante les allongementsrencontrés lors de chargements complexes.Le premier objectif a été d'étudier l'impact de l'anisotropie cristalline sur les propriétés en fluageisotherme, puis son impact en conditions de fluage anisotherme à haute température.Le second objectif fut la formulation d'une modélisation mécanique du comportement en fluage sous trajets dechargements complexes à l'aide du modèle POLYSTAR, modèle de plasticité cristalline couplécomportement/endommagement et enrichi de nouvelles variables internes représentant explicitement lesévolutions rapides de microstructure.

The overall goals of this project were to develop microstructurally based constitutive models to characterize the mechanical behavior of arteries and to investigate the effects of HIV proteins and antiretroviral drugs on the microstructure and mechanical behavior. To this end we created several constitutive models in aim 1 using a rule of mixtures approach, investigated the role of viral proteins in aim 2 through the use a transgenic mouse model, and studied the effects of the antiretroviral drug AZT administered to mice in aim 3. It is well known that the local mechanical environment which cells experience mediates growth and remodeling and that subsequent growth and remodeling can change that mechanical environment. This remodeling includes changes in the content and organization of the constituents of arteries (collagen, elastin, and smooth muscle cells). The first aim thus created models that incorporated the content and organization of these constituents using a rule-of-mixtures approach. The models we developed were able to capture the mechanical behavior of the arteries as well as previously developed phenomenological models while providing more physical meaning to the parameters, some which can be measured experimentally for incorporation into future models. Aims 2 and 3 investigated the mechanical and microstructural changes to murine arteries in response to HIV proteins or the drug AZT. While the development of antiretroviral therapy has greatly increased the life expectancy of patients with HIV, a number of other complications and co-morbidities including cardiovascular disease have become apparent. While clinical data has implicated both the virus and the antiretroviral drugs as playing roles, this work addressed the need of investigating these effects in a controlled manner. Specifically we used mouse models and focused on the two subclinical markers of increased intima-media thickness and arterial stiffening. Aim 2 used a transgenic mouse that expressed most of the human HIV proteins. We observed both intima-media thickening and arterial stiffening in alignment with clinical data. Other changes that also support a proatherogenic phenotype included decreased elastin content and changes in cathepsin activity. Aim 3 administered the antiretroviral drug AZT to healthy mice and we also observed the same subclinical markers of atherosclerosis including intima-media thickening and arterial stiffening as well as the other proatherogenic changes of decreased elastin and changes in cathepsin activity. Several other parameters including axial behavior, opening angles, collagen content, and collagen fiber angles were also quantified. These were important to fully characterize the vessel and may also be incorporated in the future into the constitutive models developed in aim1. In conclusion, in aim 1 we developed a microstructurally based constitutive model of arteries that effectively captures the mechanical behavior and includes parameters that have more physical meaning and some of which are experimentally tractable. Aims 2 and 3 both observed several subclinical markers of atherosclerosis in mice that express HIV proteins or were given AZT, providing a good model for future work and suggesting that both the HIV virus and antiretroviral drugs may play roles in the development of atherosclerosis in HIV.

As individuals or families hold a substantial share of a firm at the cost of less diversified portfolio, they specialize their portfolio and have better inside information. Does the market marker react to this fact and maintain higher level of asymmetric information cost for such family-controlled firms? We analyze the bid-ask spread and the probability of informed trading (PIN) of Canadian-based publicly traded firms cross-listed with NYSE/AMEX to test this notion. We find that although the market maker maintains higher average spread, he does not form higher PIN for family-controlled firms when the entire day is considered as an event period. <p>The assumption of constant arrival rates of informed and uninformed traders during the day in Easley et al (1996b) is rejected in the two periods per day analysis. In addition, the notion of information event occurrence prior to the day in Easley et al (1996b) is consistently rejected as higher (non-statistically) probability of information events is found in the afternoon (second session) in the two (three) periods per day analyses, respectively. Based on these findings, we have serious doubts about any existing findings (including ours) of PIN based on one period per day. As such, we consider the possibility of several periods per day.<p>Though it remains an empirical question to choose how many periods should be considered, we find our results using two and three periods per day to be very interesting. We consistently reject the hypothesis that the PIN is higher for family-controlled firms. Since the market maker does not need to maintain high spread for firms with very high number of uninformed traders and very low number of informed traders, we do not perceive our findings to be either surprising or contradictory to the present literature. By developing a different formulation of PIN, we also show that this is empirically less than that developed by Easley et al (1996b).

Nano-grained nickel produced by electroforming technique was investigated for its microstructure evolution and mechanical properties upon annealing. It was found that during low temperature annealing (T<250 oC), electroformed nano-grained nickel showed scattered and isolated abnormal grain growth, followed by a major abnormal grain growth at 320 oC. A secondary abnormal grain growth, featuring faceted grain boundaries, was observed at a higher annealing temperature (T=528 oC). A semi-in-situ observation using optical microscopy was conducted to track the movement of the faceted grain boundaries, and it was found that these boundaries were mostly immobile. The mechanical properties under various annealing conditions were studies using hardness and tensile testing. The hardness was observed to decrease with increasing annealing temperature. The material became very brittle after annealing at 320 oC or higher temperatures. Fractography investigation showed that the brittleness is caused by intergranular fracture.

Multilayered iron electrodeposits composed of alternating layers of coarse-grained iron (grain size: 1.87 μm; (110) texture; hardness: 177 VHN) and fine-grained iron (grain size: 132 nm; (211) texture; hardness: 502 VHN), with layer thicknesses ranging from ~0.2-7 μm were successfully synthesized. The average hardness of the multilayered electrodeposits increased from 234 VHN to 408 VHN with decreasing layer thickness, consistent with a Hall-Petch type behaviour. In three-point bending tests, they failed in a macroscopically brittle manner although local ductility was observed in certain layers. Fractography analysis has shown that strain incompatibility between alternating layers contributes to the brittle nature of these materials. This study has demonstrated the possibility of applying a multilayered structure design to tailor the microstructure and mechanical properties of electrodeposited iron.

Nano-grained nickel produced by electroforming technique was investigated for its microstructure evolution and mechanical properties upon annealing. It was found that during low temperature annealing (T<250 oC), electroformed nano-grained nickel showed scattered and isolated abnormal grain growth, followed by a major abnormal grain growth at 320 oC. A secondary abnormal grain growth, featuring faceted grain boundaries, was observed at a higher annealing temperature (T=528 oC). A semi-in-situ observation using optical microscopy was conducted to track the movement of the faceted grain boundaries, and it was found that these boundaries were mostly immobile. The mechanical properties under various annealing conditions were studies using hardness and tensile testing. The hardness was observed to decrease with increasing annealing temperature. The material became very brittle after annealing at 320 oC or higher temperatures. Fractography investigation showed that the brittleness is caused by intergranular fracture.

Multilayered iron electrodeposits composed of alternating layers of coarse-grained iron (grain size: 1.87 μm; (110) texture; hardness: 177 VHN) and fine-grained iron (grain size: 132 nm; (211) texture; hardness: 502 VHN), with layer thicknesses ranging from ~0.2-7 μm were successfully synthesized. The average hardness of the multilayered electrodeposits increased from 234 VHN to 408 VHN with decreasing layer thickness, consistent with a Hall-Petch type behaviour. In three-point bending tests, they failed in a macroscopically brittle manner although local ductility was observed in certain layers. Fractography analysis has shown that strain incompatibility between alternating layers contributes to the brittle nature of these materials. This study has demonstrated the possibility of applying a multilayered structure design to tailor the microstructure and mechanical properties of electrodeposited iron.

Heterogeneities at the meso-scale strongly influence the shock compression response of composite materials. These heterogeneities arise from both structural variations and differing physical/mechanical properties between constituents. In mixtures of reactive materials, such as Ni and Al, the meso-scale heterogeneities greatly affect component mixing and activation, which, in turn, can induce a chemical reaction. Cold-rolled multilayered composites of Ni and Al provide a unique system for studying the effects of material heterogeneities on a propagating shock wave, due to their full density, periodic layering, and intimate particle contacts. Computational analysis of the shock compression response of fully dense Ni/Al multilayered composites is performed with real, heterogeneous microstructures, obtained from optical microscopy, using the Eulerian hydrocode CTH. Changes in the orientation, density, structure, and strength of the material interfaces, as well as the strength of the constituents, are used to understand the influence microstructure plays on the multilayered composite response at high strain rates. The results show a marked difference in the dissipation and dispersion of the shock wave as the underlying microstructure varies. These variations can be attributed to the development of two-dimensional effects and the nature of the wave reflections and interactions. Validation of the computational results is then obtained through time-resolved measurements (VISAR, PDV, and PVDF stress gauges) performed during uniaxial strain plate-on-plate impact experiments. The experimental results prove that the computational method accurately represents the multilayered composites, thereby justifying the conclusions and trends extracted from the simulations. The reaction response of cold-rolled multilayer composites is also investigated and characterized using uniaxial stress rod-on-anvil impact experiments through post-mortem microscopy and x-ray diffraction. This extensive understanding of the shock compression response of the multilayers systems is contrasted with other composites of Ni and Al, including shock consolidated and pressed (porous) powder compacts. A comprehensive design space is then developed to assist in the understanding and design of Ni/Al composites under conditions of high pressure shock compression. Research funded by ONR/MURI grant No. N00014-07-1-0740.

The objective of this thesis project was to compare the stress behaviour in thermal barrier coatings (TBCs) with FE analyses in both 2D and 3D. The main focus was to analyse the vertical stresses in the topcoat (TC) and how they varied in relation to different thicknesses of the thermally grown oxide (TGO), spraying methods of the bondcoat (BC) and the topography of the BC. For the 2D simulations six samples were used; three with BCs sprayed with high-velocity oxy-fuel spraying and three sprayed with atmospheric plasma spraying. The samples had been exposed to isothermal heat treatment at 1150 °C for 0, 100 and 200 hours. Five images of each sample were taken with a scanning electron microscope, resulting in a total of 30 images. FE simulations based on these 30 images were done simulating a cooling from 1100 °C to 100 °C. The 3D simulations were based on surfaces created from coordinates measured with stripe projection technique on three samples consisting of only substrate and BC. Three domains of each sample had been measured and three CAD models based on randomly selected surfaces of each domain were made, resulting in 27 CAD models. The CAD models were used in the 3D FE simulations also simulating a cooling from 1100 °C to 100 °C. The results showed that the 2D simulations corresponds to published assertions about a stress inversion after TGO growth and that cracking will propagate from one peak to another, presuming the roughness of the TGO can be expressed as a wave. No conclusions of differences between spraying methods of the BC could be drawn. The stress inversion phenomenon was also found in the 3D simulations. By inspecting the TGO/TC-interface profile in different sections of a 3D model, difficulties in predicting the stress behaviour in a TBC with 2D were explained. No differences in stresses in relation to the BC roughness could be stated.