Includes vita. / Title from PDF of title page. / Document formatted into pages; contains 172 pages. / Thesis (PH.D.)--University of South Florida, 2003. / Includes bibliographical references. / Text (Electronic thesis) in PDF format. / ABSTRACT: Modeling methods are required for predicting the chemical stability of macromolecular materials used in critical spacecraft components of satellites orbiting in the high-energy radiation environment of near earth and deep space planetary magnetic belts. Methods for establishing degradation mechanisms and predicting and simulating the total absorbed dose and ionization for long term space missions are presented herein. This investigation evaluates cross-linking, main-chain scission and elimination products in a linear series of narrowly dispersed poly(methyl methacrylate) (PMMA) and polystyrene (PS) polymers. A comparison is made of the scission radiation yield (Gs) and crosslinking (Gx) predicted for the simulated ionization data to the results of degradation in a ground-based simulation of the space radiation environment using a 60Co source. / ABSTRACT: The influence of molecular weight on the stability of post-irradiated polymer is evident in the degree of change observed for each molecular weight series with respect to the degradation products produced by exposure to gamma radiation. The analysis of the specific polymer degradation products and changes in the average molecular weight (Mw) were performed using chemical analysis (FTIR and GPC) and thermal analysis (DSC). The analytical results for PMMA and polystyrene radiation-induced degradation products demonstrate that, depending on Mw, the amount and types of degradation products will vary with respect to crosslinking, chain scission and other oxidative pathways. The results support the preference for end group loss with free volume properties driving the observed differences in the G(s) and (Gx) values. / ABSTRACT: The cross-linking observed for polystyrene is controlled by molecular weight as well wherein the lowest molecular weight molecules display greater resistance to cross-linking. This research investigation employs proven tools of analysis (NASA AP8 and AE8) that accurately predict the amount of energy applied to spacecraft materials during a typical near-earth, aggressive mission environment . Another model (SPENVIS) is applied to determine the amount of total energy absorbed by the spacecraft materials from proton, electron and Brehmsstralung radiation throughout the mission life. Another set of models (SRIM and CASINO) are used to asses the range of penetration of particles into the materials and the extent of ionization caused by the particle spectrum and fluence. The absorption coefficients for the PS and PMMA structure are determined to ensure good correlation between ground simulation and the true space environment. / ABSTRACT: The total dose values are used to establish the total dose that is to be deposited during the ground simulation experiments. A 60Co irradiator was used as the ground simulation source. Dosimetry was used to determine the exposure time needed to deposit an equivalent amount of dose accumulation needed to simulate the total dose modeled for the space mission. Using gel permeation chromatography, previous studies have demonstrated that the characteristic Gaussian distribution of narrowly-dispersed PS and PMMA is perturbed by the accumulation of degradation products following irradiation. The change in distribution provides insight into the preferred path of degradation. The role of free volume in the glass transition temperature are reported with respect to Tg variation with molecular weight. Using differential scanning calorimetry. / ABSTRACT: The role of free volume in the determination of the mechanism of radiation-induced degradation is a primary focus of this investigation when considering the ability of the main chain to recombine or undergo abstraction as opposed to crosslinking or scission where motion is restricted in the solid state. The subtle distinction of structural changes brought about by the loss of side groups, double bond formation and crosslinking have been characterized by infrared spectroscopy. The resultant spectra of irradiated polymers offer considerable information on verifying the extent of competing reactions that involve structural features of the molecule. These instrumental methods are the tools of research that will assess the affect of molecular structure on polymer radiation resistance, and will support the rationale explaining the preference for one degradation mechanism over another. / ABSTRACT: This research investigation has yielded information on the affect of polymer molecular structure on radiation resistance. The work goes beyond previous studies that define empirical observations for a change in radiation resistance by virtue of a change in side group. The effect of free volume, stabilized intermediates and reactive intermediates are related to molecular weight and side group functionality. The understanding of the mechanistic rationale behind the effect of structural features on polymer radiation resistance are essential to the development of modeling systems for predicting polymer stability in space mission environments. / System requirements: World Wide Web browser and PDF reader. / Mode of access: World Wide Web.

Ultra-high molecular weight polyethylene (UHMWPE) is used worldwide as a bearing material in total joint replacement prostheses. Despite its excellent biocompatibility and high wear resistance, wear of UHMWPE components continues to be a major problem limiting the clinical lifespan of UHMWPE-containing orthopaedic implant devices. Multi-directional motion or cross-path motion is known to affect wear rates of UHMWPE in total knee and hip replacement prostheses. The purpose of this study was to quantify the effect of counterface roughness on the cross-path wear of UHMWPE and to determine if the previously established unified theory of wear model could accurately predict wear rates in an abrasive wear environment. UHMWPE pins were articulated against both smooth (centerline roughness, Ra, of 0.015 µm) and rough (Ra = 0.450µm) cobalt-chromium counterfaces in a series of six rectangular wear paths (width = A, length = B) with systematically increasing aspect ratios (B/A) and linear tracking (A = 0), all with identical path lengths (20mm) per cycle. Gravimetric weight loss was converted into volumetric wear rates and wear factors, k. The results showed that for both smooth and rough-counterface tests, wear reached a maximum when a 3mmx7mm wear path was employed. The unified theory of wear was generally accurate in predicting wear rates; however, for rough-counterface tests there was a larger increase in the wear factor for higher aspect ratio rectangular wear paths. The ratio [k rough/ k smooth] decreased monotonically as a function of increasing width of rectangles, normalized by total path length, or A/(A +B). This study showed that wear of UHMWPE articulating in a rectangular motion path likely occurs via a two-step mechanism beginning with molecular orientation followed by material fracture from the UHMWPE surface. The models inability to accurately predict UHMWPE wear for rectangular paths with lower aspect ratios suggests that there may be other operative wear mechanisms including significant re-orientation in the perpendicular sliding direction. In conclusion, it is possible to predict the wear behavior of UHMWPE using mathematical models. A robust model would have an important role in characterizing and predicting performance of currently used and potential future orthopaedic implant materials.

The objective of this work is to develop mathematical models to predict molecular weight distributions (MWDs) of ethylene copolymers produced in an industrial gas-phase reactor using a Ziegler-Natta (Z-N) catalyst. Because of the multi-site nature of Z-N catalysts, models of Z-N catalyzed copolymerization tend to be very large and have many parameters that need to be estimated. It is important that the data that are available for parameter estimation be used effectively, and that a suitable balance is achieved between modeling rigour and simplification. In the thesis, deconvolution analysis is used to gain an understanding of how the polymer produced by various types of active sites on the Z-N catalyst responds to changes in the reactor operating conditions. This analysis reveals which reactions are important in determining the MWD and also shows that some types of active sites share similar behavior and can therefore share some kinetic parameters. With this knowledge, a simplified model is developed to predict MWDs of ethylene/hexene copolymers produced at 90 °C. Estimates of the parameters in this isothermal model provide good initial guesses for parameter estimation in a subsequent more complex model. The isothermal model is extended to account for the effects of butene and temperature. Estimability analysis and cross-validation are used to determine which parameters should be estimated from the available industrial data set. Twenty model parameters are estimated so that the model provides good predictions of MWD and comonomer incorporation. Finally, D-, A-,and V-optimal experimental designs for improving the quality of the model predictions are determined. Difficulties with local minima are addressed and a comparison of the optimality criteria is presented. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2009-05-28 20:43:58.37

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Fibroblast growth factor 2 (FGF2) is a multifunctional protein translated as CUG-initiated, high molecular weight (hi FGF2) or AUG-initiated, low molecular weight (lo FGF2) isoforms with potentially distinct functions. Previous work showed that overexpression of hi- but not lo FGF2 elicited chromatin compaction resulting in cell death, by an intracrine route. A series of studies were undertaken aimed at extending our understanding of the intracrine action of Hi FGF2. Major findings are as follows: a. Hi FGF2 overexpression induces apoptotic cell death, as indicated by increased TUNEL staining, and mitochondrial participation (cytochrome c release to cytosol, rescue of the hi FGF2 phenotype by the anti-apoptotic protein Bcl-2. b. Increased expression of pro-survival signals/proteins that are known to upregulate Bcl-2, such as nuclear Akt; the PIM-1 kinase; and the heat shock protein hsp70, also rescued the hi FGF2-induced phenotype. c. The hi-FGF2 effect was associated with sustained, intracrine, activation of ERK, and was blocked by ERK inhibitors. d. FGF2 isoform specific affinity chromatography followed by mass spectroscopy identified several proteins as potentially interacting with hi FGF2; of these, the p68 RNA helicase and the hsp70 were further confirmed as interacting partners, by co-immunoprecipitation. e. Increased nuclear co-localization, and possibly interaction, between hi FGF2 and overexpressed hsp70 correlated with rescue from hi FGF2 induced cell death. f. Factors associated with cardiac pathology (isoproterenol, angiotensin II, endothelin I) also upregulated endogenous hi FGF2 in cardiac cells in culture. Adriamycin-induced cardiotoxicity in the rat, known to be linked to increased incidence of apoptosis, was also associated with increased endogenous hi FGF2. g. Hi FGF2 is expressed in the human heart (atria) and localizes in both cytosol and nuclei, suggesting a participation in human heart physiology and pathophysiology. Work presented here is consistent with the notion that endogenous hi FGF2 up-regulation may play a role in promoting cell death during prolonged tissue stress and dysfunction. It follows that processes related to hi FGF2 upregulation, hi FGF2-nuclear protein interactions and mechanisms of hi FGF2 induced cell death, represent potential therapeutic targets for modulating cell death.

The UK Health & Safety Executive are responsible for advising on ways to ensure the safety of employees within the workplace. One of the main areas of concern is the potential problem of unwanted fire, and it has been identified that within the area of large-scale storage in warehouses, there is an uncertainty posed by large quantities of thermoplastic. Some forms of thermoplastic exhibit melt-flow behaviour when heated, and a large vertical array exposed to a fire may melt and ignite forming a pool fire in addition to a wall fire. This project is largely experimental, and aimed at quantifying the effect of a growing pool fire fuelled by a melting wall on overall fire growth rate. The pool fire has been found to increase melting and burning rates, producing a much faster growing fire. It has also been found that - 80% of flowing and burning material will enter a potential pool fire, with only 20 - 25% of total mass loss actually burning from the original array. During the project 400+ small-scale tests and several medium-scale experiments have been undertaken at both Edinburgh University and the HSE's Fire & Explosion Laboratory, Buxton. The experiments have confirmed the main parameters governing pool fire development are molecular weight degradation rate and mechanism, which control flow viscosity. There have also been investigations into other influences, the most significant of which was found to be flooring substrate. These parameters then form the basis of a simple 1-D model. A semi-infinite heat transfer approximation is used to determine temperature profile through a thermoplastic exposed to its own flame flux, with extrapolated temperature dependant material properties. The derived profile is then inserted into a gravity driven flow model, to produce estimates of flow rate and quantity for plastics undergoing either random or end chain scission thermal degradation processes. The model identifies property data which are required to permit its use as a hazard assessment tool.

In this study, membranes were made from three polyvinylidene fluoride (PVDF) polymers individually and the blend systems of high (H) and low (L) molecular weight PVDF by phase inversion process. After investigating membrane casting solutions’ viscous and thermodynamic properties, the membranes so fabricated were characterized by scanning electron microscopy, gas permeation tests, porosity measurement, contact angle (CA) and liquid entry pressure of water (LEPw) measurement, and further subjected to vacuum membrane distillation (VMD) in a scenario that was applicable for cooling processes, where the feed water temperature was maintained at 27℃. It was found that PVDF solutions’ viscosities and thermodynamic instabilities were determined by the types of PVDF employed in single polymer systems and the mixing ratios of two PVDF polymers in blend systems. Thus the membrane properties and performances were influenced by the aforesaid factors as well. In single polymer systems, it was found that the membrane surface roughness and porosity increased with an increase in molecular weight. Among all the membranes casted in this study, the water vapor flux of VMD was found to be the highest at the intermediate range of H:L ratio, i.e., 4:6, at which the thickness of the sponge-like layer showed a minimum, the finger-like macro-voids formed a more orderly single-layer structure, and the LEPw showed a minimum. A conclusion can be made that blend systems of high molecular weight PVDF polymers and low molecular weight PVDF polymers could be used to optimize membrane performance in vacuum membrane distillation.

Fibroblast growth factor 2 (FGF2) is a multifunctional protein translated as CUG-initiated, high molecular weight (hi FGF2) or AUG-initiated, low molecular weight (lo FGF2) isoforms with potentially distinct functions. Previous work showed that overexpression of hi- but not lo FGF2 elicited chromatin compaction resulting in cell death, by an intracrine route. A series of studies were undertaken aimed at extending our understanding of the intracrine action of Hi FGF2. Major findings are as follows: a. Hi FGF2 overexpression induces apoptotic cell death, as indicated by increased TUNEL staining, and mitochondrial participation (cytochrome c release to cytosol, rescue of the hi FGF2 phenotype by the anti-apoptotic protein Bcl-2. b. Increased expression of pro-survival signals/proteins that are known to upregulate Bcl-2, such as nuclear Akt; the PIM-1 kinase; and the heat shock protein hsp70, also rescued the hi FGF2-induced phenotype. c. The hi-FGF2 effect was associated with sustained, intracrine, activation of ERK, and was blocked by ERK inhibitors. d. FGF2 isoform specific affinity chromatography followed by mass spectroscopy identified several proteins as potentially interacting with hi FGF2; of these, the p68 RNA helicase and the hsp70 were further confirmed as interacting partners, by co-immunoprecipitation. e. Increased nuclear co-localization, and possibly interaction, between hi FGF2 and overexpressed hsp70 correlated with rescue from hi FGF2 induced cell death. f. Factors associated with cardiac pathology (isoproterenol, angiotensin II, endothelin I) also upregulated endogenous hi FGF2 in cardiac cells in culture. Adriamycin-induced cardiotoxicity in the rat, known to be linked to increased incidence of apoptosis, was also associated with increased endogenous hi FGF2. g. Hi FGF2 is expressed in the human heart (atria) and localizes in both cytosol and nuclei, suggesting a participation in human heart physiology and pathophysiology. Work presented here is consistent with the notion that endogenous hi FGF2 up-regulation may play a role in promoting cell death during prolonged tissue stress and dysfunction. It follows that processes related to hi FGF2 upregulation, hi FGF2-nuclear protein interactions and mechanisms of hi FGF2 induced cell death, represent potential therapeutic targets for modulating cell death.

A distribuição de massa molar (DMM) e seus parâmetros são de fundamental importância na caracterização dos polímeros. Por este motivo, o desenvolvimento de técnicas que permitam a determinação da DMM de forma mais rápida e a menor custo é de grande importância prática. Os principais objetivos deste trabalho foram a implementação de alguns dos modelos baseados da teoria da reptação dupla propostos na literatura para descrever o mecanismo de relaxação das cadeias poliméricas, a avaliação dessas implementações e a análise de dois passos fundamentais na obtenção da DMM a partir de dados reológicos que são a metodologia de cálculo do espectro de relaxação baseado no modelo de Maxwell e a estratégia para a avaliação numérica das integrais que aparecem nos modelos de relaxação. Foi resolvido o problema denominado problema inverso, ou seja, a determinação da DMM a partir de dados reológicos usando um modelo de relaxação especificado e uma função de distribuição imposta. Foi usada a função Exponencial Generalizada (GEX) para representar a probabilidade de distribuição, sendo consideradas duas abordagens: i) cálculo explícito do espectro de relaxação e ii) aproximações paramétricas de Schwarzl, que evitam a necessidade do cálculo explícito do espectro de relaxação. A metodologia de determinação da DMM foi aplicada para amostras de polietileno e foram estimadas distribuições com boa representação dos dados experimentais do GPC, ao considerarem-se amostras com polidispersões inferiores a 10. Com relação a metodologia de cálculo do espectro de relaxação, foi realizado um estudo comparativo da aplicação de espectros de relaxação discreto e contínuo, com o objetivo de estabelecer critérios para especificação do número ótimo de modos de Maxwell a serem considerados. Ao efetuar-se a comparação entre as técnicas, verificou-se o espectro discreto apresenta como um sistema melhor condicionado, permitindo assim obter maior confiabilidade dos parâmetros estimados. Também é proposta uma modificação da metodologia de determinação da DMM, em que é aplicada a quadratura de Gauss-Hermite para a resolução numérica da integral dos modelos de relaxação. / The molecular weight distribution (MWD) and its parameters are of the fundamental importance in the characterization of polymers. Therefore, the development of techniques for faster and less time consuming determination of the MWD is of great practical relevance. The goals of this work were the implementation of some of the relaxation models from double reptation theory proposed in the literature, the evaluation of these implementations and the analysis of two key points in the recovery of the MWD from rheological data which are the methodology for calculation of the relaxation spectrum based on the Maxwell model and the numeric strategy for the evaluation of the integrals appearing in the relaxation models. The inverse problem, i.e., the determination of the MWD from rheological data using a specified relaxation model and an imposed distribution function, was solved. In the analysis of the inverse problem, the Generalized Exponential (GEX) was used as distribution function and two approaches were considered: i) explicit calculation of the relaxation spectrum and ii) use of the parametric method proposed by Schwarzl to avoid the explicit calculation of the relaxation spectrum. In the test of commercial samples of polyethylene with polidispersity less than 10, the application of this methodology led to MWD curves which provided good fit of the experimental SEC data. Regarding the methodology for calculation of the relaxation spectrum, a comparison between the performance of discrete and continuous relaxation spectrum was performed and some possible a criteria to determine the appropriate number of relaxation modes of Maxwell to be used were evaluated. It was found that the technique of discrete spectrum leads to better conditioned systems and, consequently, greater reliability of the estimated parameters. With relation to the numeric strategy for the evaluation of the integrals appearing in the relaxation models, the use of Gauss-Hermite quadrature using a new change of variables was proposed.

A distribuição de massa molar (DMM) e seus parâmetros são de fundamental importância na caracterização dos polímeros. Por este motivo, o desenvolvimento de técnicas que permitam a determinação da DMM de forma mais rápida e a menor custo é de grande importância prática. Os principais objetivos deste trabalho foram a implementação de alguns dos modelos baseados da teoria da reptação dupla propostos na literatura para descrever o mecanismo de relaxação das cadeias poliméricas, a avaliação dessas implementações e a análise de dois passos fundamentais na obtenção da DMM a partir de dados reológicos que são a metodologia de cálculo do espectro de relaxação baseado no modelo de Maxwell e a estratégia para a avaliação numérica das integrais que aparecem nos modelos de relaxação. Foi resolvido o problema denominado problema inverso, ou seja, a determinação da DMM a partir de dados reológicos usando um modelo de relaxação especificado e uma função de distribuição imposta. Foi usada a função Exponencial Generalizada (GEX) para representar a probabilidade de distribuição, sendo consideradas duas abordagens: i) cálculo explícito do espectro de relaxação e ii) aproximações paramétricas de Schwarzl, que evitam a necessidade do cálculo explícito do espectro de relaxação. A metodologia de determinação da DMM foi aplicada para amostras de polietileno e foram estimadas distribuições com boa representação dos dados experimentais do GPC, ao considerarem-se amostras com polidispersões inferiores a 10. Com relação a metodologia de cálculo do espectro de relaxação, foi realizado um estudo comparativo da aplicação de espectros de relaxação discreto e contínuo, com o objetivo de estabelecer critérios para especificação do número ótimo de modos de Maxwell a serem considerados. Ao efetuar-se a comparação entre as técnicas, verificou-se o espectro discreto apresenta como um sistema melhor condicionado, permitindo assim obter maior confiabilidade dos parâmetros estimados. Também é proposta uma modificação da metodologia de determinação da DMM, em que é aplicada a quadratura de Gauss-Hermite para a resolução numérica da integral dos modelos de relaxação. / The molecular weight distribution (MWD) and its parameters are of the fundamental importance in the characterization of polymers. Therefore, the development of techniques for faster and less time consuming determination of the MWD is of great practical relevance. The goals of this work were the implementation of some of the relaxation models from double reptation theory proposed in the literature, the evaluation of these implementations and the analysis of two key points in the recovery of the MWD from rheological data which are the methodology for calculation of the relaxation spectrum based on the Maxwell model and the numeric strategy for the evaluation of the integrals appearing in the relaxation models. The inverse problem, i.e., the determination of the MWD from rheological data using a specified relaxation model and an imposed distribution function, was solved. In the analysis of the inverse problem, the Generalized Exponential (GEX) was used as distribution function and two approaches were considered: i) explicit calculation of the relaxation spectrum and ii) use of the parametric method proposed by Schwarzl to avoid the explicit calculation of the relaxation spectrum. In the test of commercial samples of polyethylene with polidispersity less than 10, the application of this methodology led to MWD curves which provided good fit of the experimental SEC data. Regarding the methodology for calculation of the relaxation spectrum, a comparison between the performance of discrete and continuous relaxation spectrum was performed and some possible a criteria to determine the appropriate number of relaxation modes of Maxwell to be used were evaluated. It was found that the technique of discrete spectrum leads to better conditioned systems and, consequently, greater reliability of the estimated parameters. With relation to the numeric strategy for the evaluation of the integrals appearing in the relaxation models, the use of Gauss-Hermite quadrature using a new change of variables was proposed.