Thesis (Ph.D.)--State University of New York at Buffalo, 2006. / Includes bibliographical references. Also available online from ProQuest (http://proquest.umi.com/).

Glass is a common material in each person’s life, e.g. drinking vessels, windows, displays, insulation and optical fibres. By modifying the glass surface it is possible to change the performance of the entire glass object, generally known as Surface Engineering. Ion exchange is a convenient technique to modify the glass surface composition and its properties, e.g. optical, mechanical, electrical and chemical properties, without ruining the surface finish of the glass.   This thesis reports the findings of two different research tasks; characterisation of the single-side ion exchange process and the novel properties induced. The characterisation of the ion exchange process was mainly performed by utilising a novel analytical equipment: the Surface Ablation Cell (SAC), allowing continuous removal of the flat glass surface by controlled isotropic dissolution. SAC-AAS has provided concentration vs. depth profiles of float glass ion exchanged with K+, Cu+, Rb+ and Cs+. In addition, SEM-EDX has provided concentration vs. depth profiles of Ag+ ion exchanged samples and validation of a copper concentration vs. depth profile. From the concentration vs. depth profiles, the effective diffusion coefficients and activation energies of the ion exchange processes have been calculated. Depending on the treatment time and treatment temperature, penetration depths in the range of 5-10 μm (Rb+, Cs+), 20-30 μm (K+, Cu+) and 80-100 μm (Ag+) can be readily obtained. The effective diffusion coefficients followed the order Ag+>K+>Cu+>Rb+>Cs+. This is in accordance with the ionic radii for the alkali ions (K+<Rb+<Cs+) but reverse for the noble metal ions (Cu+<Ag+).   The glass properties modified by single-side ion exchange have mainly been characterised by UV-VIS spectroscopy and flexural strength measurements. Cu+ and Ag+ ion exchange give rise to surface colouration, Cu+ copper-ruby and Ag+ yellow/amber. The surface-ruby colouration was found to depend on the residual tin ions in the tin-side of the float glass. The flexural strength was studied using the coaxial double ring-test method which also was suitable for holed specimens. The flexural strength of K+ ion exchanged float glass samples was found to substantially increase compared to untreated.

Transparent glass-ceramics have been of industrial interest because of their multifarious applications. These are becoming increasingly important because of the flexibility that is associated with this route of fabricating intricate sizes and shapes as per the requirement. A number of glass-ceramics, based on well known ferroelectric crystalline phases (LiNbO3, LaBGeO5, SrBi2Nb2O9, Bi2WO6 etc.) were fabricated and their polar and electro-optic properties were reported. Keeping the potential applications of transparent glass-nano/microcrystal composites in view, attempts were made to fabricate SrBi2B2O7 and CaBi2B2O7 glasses and glass-nano/microcrystal composites. An attempt has been made to employ strontium bismuth borate SrBi2B2O7 (SBBO) as a reactive host glass matrix for growing the nanocrystals of ferroelectric oxides belonging to the Aurivillius family. The in situ nucleation and growth of SrBi2Nb2O9 (SBN) nanocrystals in a reactive SrBi2B2O7-Nb2O5 system and its influence on various physical (dielectric, pyroelectric and optical) properties were investigated. The strategy has been to visualize the formation of nanocrystalline SrBi2Nb2O9 as a result of the simple chemical reaction between glassy SrBi2B2O7 and Nb2O5. Indeed at lower concentrations of Nb2O5 transparent glasses were obtained which upon heat-treatment at appropriate temperatures yielded nanocrystalline SrBi2Nb2O9 phase in a transparent glass matrix. Textured SrBi2Nb2O9 ceramics were obtained by quenching the melts of SrBi2B2O7-Nb2O5 in equimolar ratio and their physical properties were studied. A strong anisotropy in physical properties (which are akin to single crystals) were demonstrated in the textured ceramics.

Composite materials have become viable alternatives to traditional engineering materials for many different product categories. Liquid transfer moulding (LTM) processes, specifically resin transfer moulding (RTM), is a cost-effective manufacturing technique for creating high performance composite parts. These parts can be tailor-made to their specific application by optimizing the properties of the textile preform. Preforms which require little or no further assembly work and are close to the shape of the final part are critical to obtaining high quality parts while simultaneously reducing labour and costs associated with other composite manufacturing techniques. One type of fabric which is well suited for near-net- shape preforms is stitched non-crimp fabrics. These fabrics offer very high in-plane strength and stiffness while also having increased resistance to delamination. Manufacturing parts from these dry preforms typically involves long-scale fluid flow through both open channels and porous fibre bundles. This thesis documents and analyzes the flow of fluid through preforms manufactured from non-crimp fabrics featuring through-thickness stitches. The objective of this research is to determine the effect of this type of stitch on the RTM injection process. All of the tests used preforms with fibre volume fractions representative of primary and secondary structural parts. A series of trials was conducted using different fibre materials, flow rates, fibre volumes fractions, and degrees of fibre consolidation. All of the trials were conducted for cases similar to RTM. Consolidation of the fibres showed improvements to both the thoroughness of the filling and to the fibre volume fraction. Experimentally determined permeability data was shown to trend well with simple models and precision of the permeability data was comparable to values presented by other authors who studied fabrics which did not feature the through-thickness stitches.

The benefits of observing a model when acquiring a new motor skill are well known, however, there is little research on the influence of viewing angle of the model. The purpose of the present experiment was to assess whether a looking-glass (face on) or subjective (facing away) viewing angle would result in different acquisition and retention levels when learning a complex Zumba dance sequence. Greater cognitive effort was expected during the looking-glass condition, consequently resulting in slower acquisition but greater physical performance scores and error recognition/identification. Thirty females were evenly divided into the looking-glass or subjective group and began with the pre-test phase to assess degrees of motivation, self-efficacy, and physical performance. Participants were then lead through six acquisition dances, within which they performed the to-be-learned sequence 18 times. An assessment of cognitive effort followed, then post-test performances and error recognition/identification scores were obtained to conclude the study. While both the looking-glass and subjective conditions demonstrated equal rates of acquisition (p>.05), the looking-glass group performed significantly fewer errors during the post-test (p<.05) and were significantly better at identifying errors when a video of the dance sequence was shown from the same viewing angle as the acquisition phase (p<.05). No differences were reported between the two conditions with respect to cognitive effort (p>.05). Based on the results of this study, the looking-glass viewing angle appears to result in better learning of a dance sequence, but cannot be explained by cognitive effort.

For high-resolution X-ray imaging scintillator applications, we have prepared and optically characterized divalent samarium doped fluorochlorozirconate (FCZ:Sm2+) glasses and glass-ceramics. Sm2+ doped FCZ glasses were obtained by adding a reducing agent, NaBH4 into the initial melt to convert some of the Sm3+ to Sm2+. However, the Sm2+ concentration at most was estimated to be only approximately 0.003 %. The as-prepared glass samples were further heat treated to obtain glass-ceramics; the nucleation and growth of BaCl2 nanocrystals were confirmed by powdered X-ray diffraction (XRD) experiments. Depending on the heat treatment conditions (temperature and time), the average nanocrystal size varies from 8 to 170 nm, and the sample contains BaCl2 nanocrystals with the orthorhombic and/or hexagonal structure. The optical absorption spectra for our glass-ceramic samples suggested the substitution of Sm2+ ions into the BaCl2 lattice site. The FCZ:Sm2+ glass-ceramics samples showed strong fluorescence in the red region of spectrum (approximately 8 times that of an as-prepared glass), and the transparency can be very high (transmittance > 80 % for samples with thickness about 0.5 mm) and can be equivalent to that of an as-prepared glass . These two results promise potential as a high-resolution X-ray scintillator due to the emission wavelength range and high transparency. Extensive studies of photoluminescence (PL) spectra at low temperatures (12 -- 200 K) for FCZ:Sm2+ glass-ceramics suggested useful indicators of the crystal structure and average size of embedded BaCl2 nanocrystals. A detailed analysis of the optical spectra has lead to the identification of the origin of the emission peaks and the location of Sm ions at specific crystallographic sites. X-ray induced luminescence (XL) studies have suggested a strong dependence of the fluorescence intensity on the concentration of Sm2+ ions. In addition, for more efficient fluorescence, a sample should be heat treated in a hydrogen containing atmosphere (e.g. H2 + Ar gas), and the heat treatment conditions should be such that the nanocrystals grow in the hexagonal structure.

This essay claims that the novels Alice's Adventures in Wonderland and Through the Looking-Glass trigger nostalgia in the contemporary reader. Nostalgia is a powerful and complex feeling which, in contemporary times, is triggered by a longing for the lost childhood. This essay connects that longing with the novels about Alice. I argue that the nostalgic experience in the Alice in Wonderland books combines utopia and Bakhtin's concept of carnival and brings it into the lost childhood. The utopian part strives for something better while the carnivalesque part is an upheaval of daily life. This essay illustrates how utopia and carnival are related to a childhood free of adulthood anxieties and that they are a part of Alice in Wonderland, which triggers nostalgia in the adult reader.

Optical amplifiers are highly sought-after in optical communications to power boost light signals carrying information. Rare Earth doped glasses have been the medium of choice for optical amplification. It is, therefore, essential to understand the interaction of light with potential host glasses for rare-earths before they could be proposed as suitable candidates. In this research, we have optically characterized three different rare earth doped bulk glasses. The glass samples investigated were Neodymium doped Gallium Lanthanum Sulfide (GLS:Nd), Erbium doped Germanium Gallium Sulfide (GeGaS:Er) and Erbium doped Fluorochlorozirconate (FCZ:Er). The transmission spectra, T(λ), was used in identifying the absorption transitions of rare earth ions from the ground level to the various excited levels and in obtaining the optical absorption coefficient, α(λ). This in turn was used in determining the Judd-Ofelt parameters, which were then used in obtaining radiative lifetimes of the energy levels of interest. Photoluminescence emission bands were also identified and their shapes were investigated. Finally, a comparison of the Judd-Ofelt lifetime with the experimental decay time was also done. From which, the major decay mechanism of the rare earth ions from the energy level under investigation was concluded.

Random Glass Mat Thermoplastic (GMT) composites are increasingly being used by the automotive industry for manufacturing semi-structural components. The polypropylene based materials are characterized by superior strength, impact resistance and toughness. Since polymers and their composites are inherently viscoelastic, i.e. their mechanical properties are dependent on time and temperature. They creep under constant mechanical loading and the creep rate is accelerated at elevated temperatures. In typical automotive operating conditions, the temperature of the polymer composite part can reach as high as 80°C. Currently, the only known report in the open literature on the creep response of commercially available GMT materials offers data for up to 24 MPa at room temperature. In order to design and use these materials confidently, it is necessary to quantify the creep behaviour of GMT for the range of stresses and temperatures expected in service. The primary objective of this proposed research is to characterize and model the creep behaviour of the GMT composites under thermo-mechanical loads. In addition, tensile testing has been performed to study the variability in mechanical properties. The thermo-physical properties of the polypropylene matrix including crystallinity level, transitions and the variation of the stiffness with temperature have also been determined. In this work, the creep of a long fibre GMT composite has been investigated for a relatively wide range of stresses from 5 to 80 MPa and temperatures from 25 to 90°C. The higher limit for stress is approximately 90% of the nominal tensile strength of the material. A Design of Experiments (ANOVA) statistical method was applied to determine the effects of stress and temperature in the random mat material which is known for wild experimental scatter. Two sets of creep tests were conducted. First, preliminary short-term creep tests consisting of 30 minutes creep followed by recovery were carried out over a wide range of stresses and temperatures. These tests were carried out to determine the linear viscoelastic region of the material. From these tests, the material was found to be linear viscoelastic up-to 20 MPa at room temperature and considerable non-linearities were observed with both stress and temperature. Using Time-Temperature superposition (TTS) a long term master curve for creep compliance for up-to 185 years at room temperature has been obtained. Further, viscoplastic strains were developed in these tests indicating the need for a non-linear viscoelastic viscoplastic constitutive model. The second set of creep tests was performed to develop a general non-linear viscoelastic viscoplastic constitutive model. Long term creep-recovery tests consisting of 1 day creep followed by recovery has been conducted over the stress range between 20 and 70 MPa at four temperatures: 25°C, 40°C, 60°C and 80°C. Findley’s model, which is the reduced form of the Schapery non-linear viscoelastic model, was found to be sufficient to model the viscoelastic behaviour. The viscoplastic strains were modeled using the Zapas and Crissman viscoplastic model. A parameter estimation method which isolates the viscoelastic component from the viscoplastic part of the non-linear model has been developed. The non-linear parameters in the Findley’s non-linear viscoelastic model have been found to be dependent on both stress and temperature and have been modeled as a product of functions of stress and temperature. The viscoplastic behaviour for temperatures up to 40°C was similar indicating similar damage mechanisms. Moreover, the development of viscoplastic strains at 20 and 30 MPa were similar over all the entire temperature range considered implying similar damage mechanisms. It is further recommended that the material should not be used at temperature greater than 60°C at stresses over 50 MPa. To further study the viscoplastic behaviour of continuous fibre glass mat thermoplastic composite at room temperature, multiple creep-recovery experiments of increasing durations between 1 and 24 hours have been conducted on a single specimen. The purpose of these tests was to experimentally and numerically decouple the viscoplastic strains from total creep response. This enabled the characterization of the evolution of viscoplastic strains as a function of time, stress and loading cycles and also to co-relate the development of viscoplastic strains with progression of failure mechanisms such as interfacial debonding and matrix cracking which were captured in-situ. A viscoplastic model developed from partial data analysis, as proposed by Nordin, had excellent agreement with experimental results for all stresses and times considered. Furthermore, the viscoplastic strain development is accelerated with increasing number of cycles at higher stress levels. These tests further validate the technique proposed for numerical separation of viscoplastic strains employed in obtaining the non-linear viscoelastic viscoplastic model parameters. These tests also indicate that the viscoelastic strains during creep are affected by the previous viscoplastic strain history. Finally, the developed comprehensive model has been verified with three test cases. In all cases, the model predictions agreed very well with experimental results.

Microbeam Radiation Therapy (MRT) is an experimental form of radiation treatment which has the potential to improve the treatment of many types of cancer. In MRT, the radiation is applied as a grid by passing the collimated X-ray beam from a synchrotron through a microplane collimator, which is a stack of parallel plates of two materials with dramatically different X-ray transparencies. The peak-to-valley dose ratio (PVDR) is the difference between the dose in the microbeams and the dose delivered between the beams. It is the PVDR that is of biological importance in MRT. Therefore a dosimeter for MRT requires a combination of a large dynamic range for dose response into the kilo-Gray regime, and high spatial resolution on the micron scale. This project characterizes fluorophosphate glasses doped with trivalent samarium ions as a potential valency conversion dosimeter for MRT using the conversion of Sm3+→Sm2+ to measure the delivered dose. Samples irradiated at the Canadian Light Source synchrotron showed X-ray induced conversion that could be optically characterized by changes in the photoluminescence emission spectra to obtain irradiation dose. The conversion efficiency depends almost linearly on the irradiation dose up to 150 Gy and saturates at doses exceeding 1500 Gy. The conversion shows a strong correlation with an observed increase in absorbance of the glass in the range of 200-750 nm. The absorbance increases with X-ray dose and is related to the formation of phosphorous-oxygen hole centers (POHC) and POn electron centers. The presence of these defects within the irradiated glass was determined by examination of the induced optical absorbance and electron paramagnetic resonance (EPR) spectra. The formation of these hole centers along with the conversion of Sm3+→Sm2+ under X-ray irradiation suggests that the X-rays cause the formation of electron-hole pairs in the glass. The electrons are then primarily captured by the Sm3+ ions, becoming Sm2+ ions, with some of the electrons being captured by POn electron centers. The holes are captured by the POHCs. This process can be represented chemically as Sm3+ + e-→ Sm2+ and PO + h+→POHC. The stability of the Sm conversion under illumination was examined using photoluminescence spectra and the stability of the X-ray induced defects was examined via the induced optical absorbance and EPR spectra.