A series of cermet powders of composition NixCo(1-x)O-YSZ were synthesized for testing as cermet anode materials for SOFCs. The Co is found by powder XRD to become incorporated into the crystal lattice of the NiO, thus forming a true alloyed material. SEM and EDS results show two types of particles upon sintering to 1380oC: small, amorphous particles of YSZ and large, crystalline particles of nickel. The electrochemical oxidation of hydrogen on a cermet anode composed of Ni0.7Co0.3O-YSZ was investigated using a series of many button cells. Through EIS data, cyclic voltammetry data, the exchange current densities for these button cells were determined. Although a relatively large variation was found (expected to be due to microstructural variation) the average values for both methods of measurement is in good agreement in hydrogen. Following reduction in pure hydrogen, the fuel was changed to a mixture with high concentration of H2S. It was found that a concentration of 10 % H2S/H2 produced a sudden change in anode microstructure and resulted in loss of exchange current density. Lowering the amount of H2S in the initial fuel feed, which allowed for a more gradual microstructural change, allowed the cell to eventually function at concentrations in excess of 10 % H2S/H2. It was determined by OCV values in various concentrations of H2S/H2 that hydrogen is the predominant fuel of choice, even if H2S is available. Following electrochemical testing, slow cooling in a 10 % H2S/H2 mixture following produced metal sulfide spheres, as determined by SEM and EDS. Investigation in hydrocarbon, alcohol and biodiesel fuels was then undertaken to test the fuel variability of the given cermet anode material. Methane containing 10 % H2S was found to have increased exchange current density relative to poisoned hydrogen. Ethane and biodiesel experienced no increase in exchange current density, but a lengthening of the functional lifetime of the cell was observed, indicating reduced carbon poisoning. Methanol is a promising oxygen-containing SOFC fuel since it produced exchange current density values larger than hydrogen, and showed no evidence of coke formation by post-mortem SEM. Since oxygen-containing fuels are known to decompose in the gas phase at typical SOFC operating temperatures, the performance in a mixture of various CO/H2 fuels was then investigated. The Ni0.7Co0.3O-YSZ cermet anode gave higher exchange current density values for low ratio of CO/H2 fuels in the range 20/80 and 30/70 compared to pure H2. This is the first example of a Ni-based anode providing higher performance with a CO/H2 mixed fuel than for a pure H2 fuel. Finally, continuous running of a cell with fuel ratio 25/75 CO/H2 for 7 days produced exchange current density values, which were observed to increase significantly above the values for pure H2 during days 1-4 followed by deterioration below the value for hydrogen on subsequent days.

The mechanical response of geomaterials is highly influenced by geometrical and material heterogeneity. To date, most modelling practices consider heterogeneity qualitatively and the choice of input parameters can be subjective. In this study, a novel approach to combine detailed micro-scale characterization with modelling of heterogeneous geomaterials is presented. The influence of micro-scale heterogeneity and microcracks on the mechanical response and brittle fracture of a crystalline rock was studied using numerical and experimental tools. An existing Combined Finite-Discrete element (FEM/DEM) code was extended to suit heterogeneous, discontinuous, brittle rocks. By conducting grid micro-indentation and micro-scratch tests, the Young's modulus and fracture toughness of the constituent phases of the rock were obtained and used as accurate input parameters for the numerical models. The models incorporated the exact phase mapping obtained from a MicroCT-scanned specimen and the existing microcrack density obtained from thin section analysis. The results illustrated that by incorporating accurate micromechanical input parameters and the intrinsic rock geometric features, the numerical simulations could more accurately predict the mechanical response of the specimen, including the fracture patterns and tensile strength. The numerical simulations illustrated that microstructural flaws such as microcracks should be included in the models to more accurately reproduce the rock strength. In addition, the differential elastic deformations caused by rock heterogeneity altered the stress distribution in the specimen, creating zones of local tensile stresses, in particular, on the boundaries between different mineral phases. As a result, heterogeneous models exhibited rougher fracture surfaces. MicroCT observations emphasized the influence of heterogeneity and, in particular, biotite grains on the fracture trajectories in the specimens. Favourably oriented biotite flakes and cleavage splitting significantly deviated the cracks. The interaction of the main crack with perpendicular cleavage planes of biotite caused strong crack deviation and termination. Considering heterogeneity and the strength degradation caused by microcracks, the simulations captured reasonably accurate mechanical responses and failure mechanisms for the rock, namely, the nonlinear stress-strain relationships. The insights presented in this study improve the understanding of the role of heterogeneity and microstructure on damage and mechanical behaviour of brittle rock.

Experiments were conducted to investigate the potential of using a quench and self-tempering heat treatment process with AISI 1117 steel to satisfy the mechanical properties of ASTM A 706 rebar. A series of quenching tests were performed and the resulting microstructure and mechanical properties studied using optical microscopy, microhardness measurement, and tensile tests. The presence of martensite throughout the samples contributed to the enhanced strength and strain-hardening ratio (tensile to yield strength) of the material. The experimental results showed that AISI 1117 is capable of meeting the ASTM standard. In addition to the experiments, a computer model using the finite difference method and incorporating heat transfer and microstructure evolution was developed to assist in future optimization of the heat treatment process.

Experiments were conducted to investigate the potential of using a quench and self-tempering heat treatment process with AISI 1117 steel to satisfy the mechanical properties of ASTM A 706 rebar. A series of quenching tests were performed and the resulting microstructure and mechanical properties studied using optical microscopy, microhardness measurement, and tensile tests. The presence of martensite throughout the samples contributed to the enhanced strength and strain-hardening ratio (tensile to yield strength) of the material. The experimental results showed that AISI 1117 is capable of meeting the ASTM standard. In addition to the experiments, a computer model using the finite difference method and incorporating heat transfer and microstructure evolution was developed to assist in future optimization of the heat treatment process.

The mechanical response of geomaterials is highly influenced by geometrical and material heterogeneity. To date, most modelling practices consider heterogeneity qualitatively and the choice of input parameters can be subjective. In this study, a novel approach to combine detailed micro-scale characterization with modelling of heterogeneous geomaterials is presented. The influence of micro-scale heterogeneity and microcracks on the mechanical response and brittle fracture of a crystalline rock was studied using numerical and experimental tools. An existing Combined Finite-Discrete element (FEM/DEM) code was extended to suit heterogeneous, discontinuous, brittle rocks. By conducting grid micro-indentation and micro-scratch tests, the Young's modulus and fracture toughness of the constituent phases of the rock were obtained and used as accurate input parameters for the numerical models. The models incorporated the exact phase mapping obtained from a MicroCT-scanned specimen and the existing microcrack density obtained from thin section analysis. The results illustrated that by incorporating accurate micromechanical input parameters and the intrinsic rock geometric features, the numerical simulations could more accurately predict the mechanical response of the specimen, including the fracture patterns and tensile strength. The numerical simulations illustrated that microstructural flaws such as microcracks should be included in the models to more accurately reproduce the rock strength. In addition, the differential elastic deformations caused by rock heterogeneity altered the stress distribution in the specimen, creating zones of local tensile stresses, in particular, on the boundaries between different mineral phases. As a result, heterogeneous models exhibited rougher fracture surfaces. MicroCT observations emphasized the influence of heterogeneity and, in particular, biotite grains on the fracture trajectories in the specimens. Favourably oriented biotite flakes and cleavage splitting significantly deviated the cracks. The interaction of the main crack with perpendicular cleavage planes of biotite caused strong crack deviation and termination. Considering heterogeneity and the strength degradation caused by microcracks, the simulations captured reasonably accurate mechanical responses and failure mechanisms for the rock, namely, the nonlinear stress-strain relationships. The insights presented in this study improve the understanding of the role of heterogeneity and microstructure on damage and mechanical behaviour of brittle rock.

This thesis aims to improve the performance of latex-based pressure-sensitive adhesives (PSAs). PSA performance is usually evaluated by tack, peel strength and shear strength. Tack and peel strength characterize a PSA’s bonding strength to a substrate while shear strength reflects a PSA’s capability to resist shear deformation. In general, increasing shear strength leads to a decrease in tack and peel strength. While there are several commercial PSA synthesis methods, the two most important methods consist of either solvent-based or latex-based techniques. While latex-based PSAs are more environmentally compliant than solvent-based PSAs, they tend to have much lower shear strength, at similar tack and peel strength levels. Therefore, the goal in this thesis was to greatly improve the shear strength of latex-based PSAs at little to no sacrifice to tack and peel strength. In this study, controlling the polymer microstructure of latexes or their corresponding PSA films was used as the main method for improving the PSA performance. The research was sub-divided into four parts. First, the influence of chain transfer agent (CTA) and cross-linker on latex polymer microstructure was studied via seeded semi-batch emulsion polymerization of butyl acrylate (BA) and methyl methacrylate (MMA). Three techniques were used to produce the latexes: (1) adding CTA only, (2) adding cross-linker only, and (3) adding both CTA and cross-linker. It was found that using CTA and cross-linker simultaneously allows one to expand the range of latex microstructural possibilities. For example, latexes with similar gel contents but different Mc (molecular weight between cross-links) and Mw (molecular weight of sol polymers) could be produced if CTA and cross-linker concentration are both increased. However, for the corresponding PSAs with similar gel contents, the relationship between their polymer microstructure and performance was difficult to establish as almost all of the medium and high gel content PSAs showed very low tack and peel strength as well as extremely large shear strength readings. In the second part of this thesis, in order to improve the tack and peel strength of medium and high gel content PSAs, the monomer composition and emulsifier concentration were varied. It was found that changing the monomer mixture from BA/MMA to BA/acrylic acid (AA)/2-hydroxyethyl methacrylate (HEMA) while simultaneously decreasing emulsifier concentration dramatically improved the corresponding PSAs’ shear strength as well as tack and peel strength. The addition of polar groups to the PSA increased its cohesive strength due to the presence of strong hydrogen bonding; meanwhile, PSA films’ surface tension increased. In the third part, two series of BA/AA/HEMA latexes were generated by varying the amounts of CTA either in the absence or presence of cross-linker. The latexes produced in the absence of cross-linker exhibited significantly larger Mc and Mw compared to their counterparts with similar gel contents prepared with cross-linker. The PSAs with the larger Mc and Mw showed much larger shear strengths due to improved entanglements between the polymer chains. In the final part of the thesis, the performance of the BA/AA/HEMA PSAs was further improved by post-heating. Compared with original latex-based PSAs with similar gel contents, heat-treated PSAs showed not only significantly improved shear strengths, but also much larger tack and peel strengths. The different shear strengths were related to the PSAs’ gel structures, which were discrete in the original PSAs but continuous in the heat-treated PSAs. The improved tack and peel strengths were related to the PSA films’ surface smoothness. During the post-heating process, the PSA polymer flowed, resulting in much smoother surfaces than the original PSA films. In addition, the effect of post-heating was related to the polymer microstructure of the untreated PSAs. Decreasing the amount of very small or very big polymers or simultaneously increasing Mc and Mw could lead to post-treated PSAs with significantly better performance. Moreover, it was found that by optimizing the polymer microstructure of the original latex-based PSAs, it was possible to obtain a treated PSA with similar or even better performance than a solvent-based PSA with similar polymer microstructure. Our original objective was surpassed: in two cases, not only was shear strength greatly improved, but so were tack and peel strength due to the simultaneous modification of PSA bulk and surface properties.

A series of cermet powders of composition NixCo(1-x)O-YSZ were synthesized for testing as cermet anode materials for SOFCs. The Co is found by powder XRD to become incorporated into the crystal lattice of the NiO, thus forming a true alloyed material. SEM and EDS results show two types of particles upon sintering to 1380oC: small, amorphous particles of YSZ and large, crystalline particles of nickel. The electrochemical oxidation of hydrogen on a cermet anode composed of Ni0.7Co0.3O-YSZ was investigated using a series of many button cells. Through EIS data, cyclic voltammetry data, the exchange current densities for these button cells were determined. Although a relatively large variation was found (expected to be due to microstructural variation) the average values for both methods of measurement is in good agreement in hydrogen. Following reduction in pure hydrogen, the fuel was changed to a mixture with high concentration of H2S. It was found that a concentration of 10 % H2S/H2 produced a sudden change in anode microstructure and resulted in loss of exchange current density. Lowering the amount of H2S in the initial fuel feed, which allowed for a more gradual microstructural change, allowed the cell to eventually function at concentrations in excess of 10 % H2S/H2. It was determined by OCV values in various concentrations of H2S/H2 that hydrogen is the predominant fuel of choice, even if H2S is available. Following electrochemical testing, slow cooling in a 10 % H2S/H2 mixture following produced metal sulfide spheres, as determined by SEM and EDS. Investigation in hydrocarbon, alcohol and biodiesel fuels was then undertaken to test the fuel variability of the given cermet anode material. Methane containing 10 % H2S was found to have increased exchange current density relative to poisoned hydrogen. Ethane and biodiesel experienced no increase in exchange current density, but a lengthening of the functional lifetime of the cell was observed, indicating reduced carbon poisoning. Methanol is a promising oxygen-containing SOFC fuel since it produced exchange current density values larger than hydrogen, and showed no evidence of coke formation by post-mortem SEM. Since oxygen-containing fuels are known to decompose in the gas phase at typical SOFC operating temperatures, the performance in a mixture of various CO/H2 fuels was then investigated. The Ni0.7Co0.3O-YSZ cermet anode gave higher exchange current density values for low ratio of CO/H2 fuels in the range 20/80 and 30/70 compared to pure H2. This is the first example of a Ni-based anode providing higher performance with a CO/H2 mixed fuel than for a pure H2 fuel. Finally, continuous running of a cell with fuel ratio 25/75 CO/H2 for 7 days produced exchange current density values, which were observed to increase significantly above the values for pure H2 during days 1-4 followed by deterioration below the value for hydrogen on subsequent days.

The main goal of this research is to construct hierarchical microstructures from polymer nanocomposites. Specifically, the research focused on constructing tensegrity-inspired microstructure where the nanoparticles are the compression members and the polymer matrix is tensile web. In order to achieve the tensegrity-inpired microstruture, the research was conducted with the following objectives. 1. Synthesis of Hydroxyapatite (HAp) nanoparticles of controlled shapes using block copolymer templates. 2. Investigation of the effects of particle loadings and shapes on isotropic nanocomposite properties. 3. Construction of HAp building blocks into the tensegrity-inspired microstructures First, in order to use the nanoparticles for this structure, needle-shaped HAp nanoparticles were synthesized using block copolymer templates. The results indicated that significant amount of polymer remained on particle surface. Since these particles were coated with polymer blocks, the decorated polymer blocks were considered as the interphase material which would be used to prestress the HAp nanoparticles, and the particles would be acted as the building blocks for constructing tensegrity-inspired microstructure. For nanocomposites, polymer coating on HAp nanoparticles promoted particle dispersion. The effect of particle shapes on thermomechanical properties did not show significant differences between the two particle systems due to their low aspect ratios and chemical similarity. However, the polymer crystallinity and crystallization showed different trend as a function of particle loadings in two particle systems, and the behavior was unified through a common particle spacing of approximately 120 nm. In order to investigate the effect of particle arrangement in the polymer matrix, needle-shaped HAp nanoparticles synthesized with two different block copolymers were mixed with different morphology of polymer matrices and manipulated particle arrangement using the drawing process. Nanocomposites prepared with different matrix morphologies showed the similar dispersion characteristics and reinforcement behavior. The experimental results showed the drawing process influenced the particle arrangement in the polymer matrix, and the particle arrangement and reinforcement behavior were influenced by polymer matrix morphology. The thermomechanical properties of both matrix systems enhanced through the drawing process in the glassy region, but the effect of degree of particle orientation was difficult to distinguish due to low aspect ratios of HAp particles which was not enough to impact on overall microstructure.

Ce travail vise à mettre en relation les caractéristiques de la zone d'interphase " granulat-pâte de ciment " avec les caractéristiques de porosité, d'absorption d'eau, de dureté et de rugosité de calcaires poreux.La première partie de ce travail a consisté à étudier l'influence de la teneur en eau et de la dureté des granulats sur la résistance mécanique de mortiers. Les résultats montrent que, pour des calcaires poreux et absorbants, les mortiers fabriqués à partir de granulats à l'état sec sont plus résistants que ceux fabriqués à partir de granulats à l'état sursaturé. La deuxième partie de ce travail a consisté à étudier l'adhésion " roche-pâte de ciment ". Il a été constaté que la rugosité et l'état de saturation de la roche affectent significativement les résistances en traction et au cisaillement des composites.La dernière partie est consacrée à l'étude de la microstructure de la zone d'interphase par la technique d'analyse d'images. L'évolution de la porosité moyenne de la zone d'interphase est liée aux propriétés mécaniques des mortiers par la relation de Féret démontrant ainsi que la résistance à la compression dépend principalement de la mésoporosité de l'interphase. Le gradient de porosité est mis en relation avec le gradient de degré d'hydratation et le gradient de rapport E/C. Ces deux derniers sont calculés en appliquant le modèle de Powers. Les résultats obtenus montrent que pour des calcaires poreux et absorbants, la pâte de ciment et la zone d'interphase des mortiers de granulats secs et de granulats sursaturés ne sont pas équivalentes alors qu'initialement on visait le même rapport E/C.

The effects of Ca and Ce on the precipitation behaviour and microstructural characteristics of Mg-Zn based alloys are investigated by comprehensive multi-scale characterization and analysis. The elements Ca and Ce are chosen for their potential to enhance (a) precipitation hardening and (b) alloy texture and ductility, and are examined at both alloying and microalloying (< 0.5 wt%) levels. When added individually to Mg-Zn, Ca is found to enhance precipitation, but Ce produces a generally adverse effect on the hardening response. A pre-ageing strategy is proposed to alleviate this negative effect of Ce. The highlight of this work is the double microalloying addition of Ce-Ca to Mg-Zn, as this combination and quantity proves to be the most effective at increasing the age-hardening response, and enhancing microstructural characteristics for improved ductility. Transmission electron microscopy analysis reveals the hardening increase to originate from a refined precipitate microstructure, and the formation of fine-scale basal plate precipitates. These fine precipitates form during early ageing as monolayer GP zones consisting of Ca and Zn. The formation of these GP zones is facilitated by the atomic size difference between those two solutes, and their observed tendency to co-cluster. The monolayer GP zones evolve to multi-layered forms in the peak-aged condition. These precipitates are observed to be uniformly distributed, even where apparent precipitate-free zones are observed for the Mg-Zn type phases in the grain boundary regions. Notably, the size of these precipitate-free zones for the Mg-Zn phases is also reduced in the Ce-Ca microalloyed samples, compared to the binary alloy. The Ce-Ca microalloying additions also promote grain refinement and a weakening of the basal textures, typical of conventional Mg-based alloys, compared to both Mg-Zn and Mg-Zn-Ce. As a result, the tensile behaviour of the alloys with Ce-Ca is similarly enhanced. Considering both the precipitation hardening capability and microstructural characteristics, it is concluded that the double microalloying additions of Ce-Ca can be considered as a new alloy design strategy to successfully achieve improvement in both the strength and ductility of Mg-Zn alloys.