Solid phase microextraction (SPME) has gained much popularity for in vivo applications recently. Thus far, there are two types of pre-equilibrium kinetic calibration that have been applied to in vivo SPME: on-fibre standardization and dominant pre-equilibrium desorption. Both of these techniques have their own advantages and disadvantages. To address the limitations presented by these two techniques, a third pre-equilibrium kinetic calibration method, the diffusion-based interface model, was investigated. The diffusion-based interface model had been successfully applied to air and water samples but was never utilized for in vivo SPME studies. For the first part of the research, on-fibre standardization, dominant pre-equilibrium desorption, and diffusion-based interface model were compared in terms of accuracy, precision, and experimental procedures, by using a flow-through system. These three kinetic calibrations were further validated by equilibrium SPME extraction and protein-plasma precipitation, a current state-of-the-art sampling method. The potential of diffusion-based interface model was yet again demonstrated in the second part of the research project. This calibration method was applied to comparative pharmacokinetic studies of two drugs, fenoterol and methoxyfenoterol, on 5 rats. To provide a constant sampling rate as required for diffusion-based interface model, a SPME animal sampling autosampler, AccuSampler®, was utilized. It custom-written program allowed the entire SPME sampling procedure excluding insertion and removal of SPME probes to be automated. Furthermore, to validate the results obtained by SPME, the AccuSampler® was programmed to withdraw blood after each SPME sampling time point for conventional method analysis using protein-plasma precipitation. The well correlated data obtained by SPME sampling and the conventional method illustrated the potential of diffusion-based interface model as an excellent choice for future in vivo SPME applications.

Abnormal pressures have been measured in the deep boreholes at the Bruce site, southern Ontario, where a deep geologic repository for low and intermediate level radioactive waste disposal has been proposed. The pressure regime in the stratigraphic units exhibits either higher than hydrostatic pressure (over-pressured) or lower than hydrostatic pressure (under-pressured) are considered to be abnormal. At the Bruce site, the Ordovician sediments are under-pressured while the underlying Cambrian sandstone and the overlying Guelph carbonate are over-pressured. Hypotheses have been documented in literature to explain the phenomenon of abnormal pressures. These hypotheses include osmosis, glacial loading and deglaciation unloading, exhumation of overlying sediments, crustal flexure and the presence of an immiscible gas phase. Previous work on the Bruce site has shown that the under-pressures in the Ordovician limestone and shales could not be explained by glaciation and deglaciation or by saturated analyses. The presence of a gas phase in the Ordovician formations has been determined to be a reasonable cause of the under-pressure developed in the Ordovician shales and limestones at the Bruce site. Support for the presence of a gas phase includes solution concentrations of methane, concentrations of environmental isotopes related to methane and estimates of water and gas saturations from laboratory core analyses. The primary contribution of this thesis is the sensitivity analyses performed on the hydrogeologic parameters with respect to a one dimensional two-phase flow model. First, a one dimensional two-phase air and water flow model was adopted and reconstructed to simulate the long-term evolution of the groundwater regimes at the DGR site. Then the hydrogeologic parameters which impact the presence of under-pressure in the groundwater are investigated. Data required to quantify the properties of geologic media and groundwater are adopted directly from borehole testing and laboratory testing results. The permeable boundaries of the domain are assumed to be water saturated and pressure specified (using hydrostatic conditions in the Guelph Formation and hydrostatic with 120 m over-pressure condition in the Cambrian and Precambrian). Isothermal conditions were assumed, thus constant water density and viscosity values are estimated for the average total dissolved solids (TDS) concentration of the modelled stratigraphic column. A constant diffusion coefficient (a diffusivity of $0.25\times10^{-8}$ m$^2$/s) of air in water is assumed with a saturation-dependent tortuosity. The air generation rate is assumed to simulate the gas phase generated in the Ordovician formations. The numerical simulation of up to 4 million years provides a means to explore the behaviour of gas phase dissipation due to partitioning into the water phase and diffusive transport in the solute phase. Results confirmed that the presence of a gas phase would result in the under-pressure in water.

A cooling system for high heat flux applications is examined using microchannel evaporators with water as the working fluid and boiling as the heat transfer mechanism. Experimental studies are performed using single channel microevaporators allowing for better control of the flow mechanics unlike other investigations where multiple, parallel, flow channels can result in a non-uniform distribution of the working fluid. High-speed flow visualizations are performed in conjunction with heat transfer and pressure drop measurements to support the quantitative experimental data. Flow patterns associated with a range of boundary conditions are characterized and then presented in the form of novel flow regime maps that intrinsically reflect the physical mechanisms controlling two-phase pressure distributions and heat transfer behavior. Given the complexity associated with modeling of boiling heat transfer and the lack of a universal model that provides accurate predictions across a broad spectrum of flow conditions, flow regime maps serve as a valuable modeling aid to assist in targeted modeling over specific flow regimes. This work represents a novel and original contribution to the understanding of boiling mechanisms for water in microchannels. The flow patterns in this work are found to be closely coupled with mass flux, heat flux, and channel size; where re-wetting and pressure oscillations play a crucial role, and are likely responsible for its development and evolution. Reversed flow, typically attributed to a non-uniform fluid distribution in multiple channel microevaporators by other researchers, is shown to be a result of the upstream expansion of confined bubbles. During flow boiling, the pressure drop in the microchannel increases with the heat flux for a constant flow rate due to the significant acceleration effects associated with smaller channels, unlike in single-phase flow where the pressure drop is constant. Water flow boiling in rectangular microchannels, although not extensively explored in the published literature, provides an extremely high cooling capacity, with dissipation rates approaching 440 W/cm², making this an ideal candidate for cooling of next generation electronic systems. Single-phase flow studies revealed that pressure and heat transfer coefficient macroscale models are transferable to microchannels with hydraulic diameters down to 200 µm, when the entrance effects and minor losses are properly considered. These studies include laminar developing flow conditions not commonly considered in the literature and fully developed flow. Since the applicability of macroscale theories to microchannels is often questioned, this investigation helps clarify this issue for microchannels within the range of experimental conditions explored in this work. Finally, new correlations for the hydrodynamic entrance length are proposed for rectangular microchannels and good agreement is found when compared with published experimental data over a wide range of Reynolds number. These correlations are more accurate, and original in the sense that they incorporate the effects of channel aspect ratio, and include creeping flow conditions which are currently unavailable for rectangular microchannels. This work represents a major advance in the development of new cooling systems for high heat flux applications requiring dissipation rates in excess of 100 W/cm².

In this work, we describe our recent efforts aimed at determining the mechanism of signal change for a diffraction-based sensor (DBS) system. The DBS detects analyte-binding events by monitoring the change in diffraction efficiency that takes place when analyte molecules adsorb to target molecules that have been patterned onto a surface. The exact parameters that affect the intensity of the diffraction intensity are currently not well understood.<p>In this work, the formalism used to describe the behaviour of volume-phase holography is used to understand the parameters that effect the diffraction intensity. It is hypothesized that the major factors that effect the diffraction intensity are the differences in optical path length between the wave trains that reflect off the diffraction grating and those that reffect off the substrate surface. Also key is the difference in refractive index between the two media. Two approaches were developed to investigate this hypothesis; the first was to develop a series of gratings of varying thickness using polyelectrolyte multilayers. The indices of refraction of these gratings were adjusted by the incorporation of charged gold nanoparticles. Since DBS systems operate by monitoring the binding of analyte molecules, a second series of experiments were developed to investigate the changes in diffraction intensity as micometer sized carboxylated beads were loaded onto an avidin grating. The first aspect that was investigated was the effect of adding more particles onto the grating surface on diffraction intensity. Second, the extent to which the particles reduced the periodicity of the diffraction grating, and the effect on the observed intensity of the diffraction signal were also investigated. Finally, this work shows the first use of a DBS system to extract the rate of and the maximum surface coverage of a specific binding reaction.

Solid-liquid equilibrium in isomorphous amino acid systems has been investigated as a model for systems that form solid solutions. Solid- and liquid-phase compositions in L-valine + L-leucine, L-valine + L-isoleucine, and L-isoleucine + L-valine in water were measured over the entire range of solid composition, and it was shown (from mass balance and phase rule considerations) that these systems form solid solutions. The solid- phases resulting from isothermal and cooling crystallization experiments were also investigated using powder x-ray diffractometry which showed that homogeneous solid solutions could only be obtained in cooling crystallization experiments, whereas isothermal experiments generally produced inhomogeneous solids. This suggests that data reported in the literature from isothermal experiments may not represent true equilibrium values. Solid-phase activity coefficients were estimated using binary and ternary equilibrium data and the UNIFAC-Kuramochi model for liquid-phase nonidealities. The solid phases in the three systems investigated exhibited significant nonidealities that were correlated using the Margules model. The model parameters exhibited a linear relationship with the ratio of binary solubilities of the two solutes. Such simple relationship may be advantageous when solid-liquid equilibrium of thermally unstable solutes or components with unknown physical properties are crystallized.

¡§Blue phase¡¨ LCD panels features the advantages of superior response times¡Bwide viewing angle and no requirement for alignment by rubbing greater than conventional LCD modes. Thus, recently several groups have been developed both scientific and technological interests in the blue phases. However, the blue phases only exist in the narrow temperature range, typically a few Kelvin below the phase transition temperature of materials, which has been a problem for practical applications such as fast light modulators or display. In this paper, we proposed polymer-stabilized liquid crystalline blue phase by photopolymerizing the monomers in the isotropic phase and discussed the theoretical model to describe the stability of the blue phases. The polymer networks play an important role in stabilizing a liquid crystal blue phase. The morphology of polymer network was determined by the process of polymerization condition, like exposure intensity and temperature. Moreover, scanning electron microscopy (SEM) images were used to understand directly the network structures and to find the regularity of temperature intervals. In the meantime, we successfully extended the temperature range of blue phase over 140oC under suitable conditions. Based on this research results, the different temperature interval properties of cholesteric blue phases will apply on various photoelectric elements in the future.

This study presents an optically switchable band gap of a 3D photonic crystal that is based on an azobenzene-doped liquid crystal blue phase. The trans-cis photoisomerization of azobenzene was induced by irradiation using 473nm light, and caused the deformation of the cubic unit cell of the blue phase and a shift in the photonic band gap. The fast back-isomerization of azobenzene was induced by irradiation with 532nm light. The crystalline structure was verified using a Kossel diffraction diagram. An optically addressable blue phase display, based on Bragg reflection from the photonic band gap, is also demonstrated. It can be written, erased, and rewritten repeatedly and exhibits a bright saturated color.

none

The C54 TiSi2 thin films are widely applied in semiconductor devices due to the low electric resistance and high thermal stability. Through the annealing processing in this study, the metastable C49 TiSi2 with an electric resistivity of 219.3 £g£[-cm transforms to the stable C54 TiSi2 phase at a higher annealing temperature, with a resistivity of 30.5 £g£[-cm. Hence the transformation temperature of C49 ¡÷ C54 is of great concern in metallization of gates and local interconnections. In this thesis, it is found that the oxygen content and Ag addition impose significant influence on the transformation temperature of C49 ¡÷ C54. The as-sputtered TiSi2 thin films are confirmed to be amorphous. After annealing at 600oC or 900oC, the silicides would transform to the metastable C49 TiSi2 or C54 TiSi2 phase, respectively. The current transformation temperatures are much higher than 200oC and 600oC for the normal TiSi2 system, due to high oxygen content in the current films (up to 15-20 at% as a result of our old sputtering system). Nevertheless, the co-sputtered TiSi2 thin films with 5 and 20 at% Ag can decrease the formation temperature of C54 TiSi2 phase to 800oC. Compare with the as-sputtered TiSi2 thin films, the desirable electric resistivity of the C54 phase in the 20 at% Ag thin films is also further reduced to 22.9 £g£[-cm. The time-dependent mechanical responses of the amorphous, crystalline C49, and C54 TiSi2 thin films are investigated by room-temperature nanoindentation at the different loading rates ranging from 0.0125 to 5 mN/s. The anelasticity response plays an important role in the current TiSi2 thin films and is found to be sensitive to the loading rate. The displacement of time-dependent anelasticity recorded during the period of hold time increases with increasing loading rate. The anelasticity behavior can be analyzed by the Kelvin model. The as-deposited amorphous phase, with a lower atomic packing density and higher degree of defects and free volumes, exhibits the higher anelasticity deformation and longer relaxation time.

Blue-Phase liquid crystal display possesses potential to become next generation display technology because of its submillisecond response time, alignment-layer-free process and wide view angle. Intrinsically, BP only operates across a narrow temperature range due to the influence of intrinsic structural defects. Recently, the temperature range of BP has been successfully extended beyond 60K through the polymer-stabilized effect. Unfortunately, the structure of the polymer networks poses a number of problems, for instance, hysteresis effect, which degrades the accuracy of grayscale control, and residual birefringence, which decreases the contrast ratio of LCDs. This paper investigates the voltage-induced hysteresis and residual birefringence in the polymer-stabilized blue phase I and II, under various phase separation conditions and material ratio. Based on experiment result, the polymer network morphology, distribution and pure BP temperature can result in a variety of PSBP electro-optical properties. Hysteresis and residual transmittance free PSBP display could be achieved by choosing appropriated phase separation condition and material ratio. Key word¡Gblue phase¡Bmonomer¡Bhysteresis¡Bresidual transmittance