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The time dependence of the physical properties of ethylene/1-octene (EO)-copolymers after primary crystallization is investigated by calorimetry, density, and creep measurements. The temporal evolution of the multiple melting of EO-copolymers is monitored by differential scanning calorimetry. The low temperature endotherm displays an evolution similar to that observed for the enthalpy recovery in glasses after physical aging. Using this analogy, a calorimetry-aging rate is defined, which quantifies the change in the low endotherm temperature with time. Similarly a density-aging rate is defined from the evolution of density with time. A non-classical creep behavior is observed for short aging times, consistent with crystallization-induced shrinkage. The change in crystallinity during aging leads to a change in the shape of the relaxation spectrum. Hence, analysis of creep data cannot be carried out using Struik's superposition method. For both short and long aging times, the creep rate exhibits a dependence on copolymer composition similar to those associated with the calorimetry- and the density-aging rates, suggesting a common origin for the evolution of the low endotherm, the creep behavior and the bulk density. The calorimetry, density, and creep data are reexamined based on the following assumptions: First, a single population of small crystals is formed during crystallization at low temperature; Second, these small crystals increase in stability under isothermal conditions, easily melt and recrystallize during heating and serve as efficient thermo-reversible cross-links to increase the conformational constraints in the residual amorphous fraction. These assumptions appear to be consistent with all observations made to date. / Master of Science

The performance of some polymeric materials is profoundly affected by long-term exposure to moisture during service. This poses problems for high precision and/or load bearing components in engineering applications where moisture-induced changes in mechanical properties and dimensional stability could compromise the reliability of the device or structure. In addition to external factors such as moisture, the material properties are also evolving due to inherent structural relaxation within the polymeric material through a process known as physical aging. Based on the current knowledge of both mechanisms, they have opposite effects on material properties. The common approach to studying the effects of moisture is to expose the polymeric material to combined moisture and heat, also referred to as hygrothermal conditions. The application of heat not only increases the rate of moisture diffusion but also accelerates physical aging processes which would otherwise be very slow. In spite of this coupled response, nearly all hygrothermal studies ignore physical aging in their investigations due to the complexity of the coupled problem. The goal of this work is to develop a numerical model for simulating the interactive effects of moisture diffusion and physical aging in a glassy polymer. The intent is to develop a capability that would also allow one to model these effects under various mechanical loading and heat transfer conditions. The study has chosen to model the response of polycarbonate/acrylonitrile-butadiene-styrene (PC/ABS), which is a glassy polymer blend that has very similar behaviour to polycarbonate. In this study, a comprehensive approach which considers four physical mechanisms – structural mechanics, moisture diffusion, heat conduction, and physical aging – has been applied. The most current analytical models in the literature usually attempt to model two or three coupled physical phenomena. To develop the four coupled phenomena model, the current work has undertaken an extensive scope of work involving experimental characterization and finite element modeling. In the experimental part of this work, seven sets of different tests were conducted to characterize the behaviour of PC/ABS exposed to moisture diffusion and accelerated physical aging. These experiments provided a comparative study between the effects of physical aging and moisture diffusion on the material’s behaviour; and at the same time, provided data for the numerical modeling. The dual glass transition temperatures (Tg) of the material were determined using two techniques: dynamic mechanical analysis (DMA) and thermo-mechanical analysis (TMA). The DMA tests provided data for studying the effects of hygrothermal aging on the Tg’s of the material and were also useful for mechanical tests such as creep and stress relaxation performed using the DMA. The Tg’s obtained using the TMA were also required for physical aging experiments using the dilatometry mode of TMA. Structural relaxation of the blend was studied by aging the material at 80 °C for 7 aging times in the TMA. These experiments gave an insight into the volume relaxation behaviour of the blend at a constant temperature. Specific heat capacity of the PC/ABS blend was also measured using another thermal analysis technique; i.e., differential scanning calorimeter (DSC), before and after test specimens were exposed to hygrothermal aging for 168 hours. The interactive effects of physical aging and moisture diffusion on the moisture uptake of the material were studied using gravimetric experiments performed at 5 different hygrothermal conditions. The experimental results were used to determine the coefficient of diffusion as well as the equilibrium moisture uptake of the samples. Furthermore, the effects of both moisture diffusion and physical aging on the mechanical behaviour of the polymer blend were investigated using stress relaxation tests. The comparison of the results of the tests performed on un-aged specimens with those of thermally and hygrothermally aged samples showed how physical aging effects competed with moisture diffusion. Also, the coefficient of hygroscopic expansion of the PC/ABS blend was determined using a so-called TMA/TGA technique. The numerical modeling of the four-coupled physics was achieved using the governing equations in the form of partial differential equations. Modeling was performed using the commercial finite element software package, COMSOL Multiphysics®. First, the uncoupled physical mechanisms of structural mechanics, moisture diffusion, and heat conduction were modeled separately to investigate the validity of the PDEs for each individual phenomenon. The modeling of the coupled physics was undertaken in two parts. The three coupled physics of structural mechanics, moisture diffusion, and heat conduction was first simulated for a gas pipe having a linear elastic behaviour. The comparison of the results with similar analysis available in the literature showed the capability of the developed model for the analysis of the triple coupled mechanisms. The second part modeled the four coupled phenomena by incorporating the experimentally determined coupling coefficients. In the developed numerical model, the material behaviour was considered to be linear viscoelastic, which complicated the model further but provided more realistic results for the behaviour of the polymer blend. Moreover, an approximation method was proposed for estimating the coupling coefficients that exist between different coupled physics in this study. It was also suggested that the anomalous moisture diffusion in the material can be modeled using a time varying boundary condition. Finally, the model was successfully verified and demonstrated using test case studies with thin thermoplastic plates. The proposed four-coupled physics model was able to predict with good accuracy the deflection of thin thermoplastic plates under bending for a set of hygorthermal test condition.

Both novel membrane materials with better separation characteristics and a better fundamental understanding of membrane transport stability are needed to improve the competitiveness of commercial membrane separations. In this work, the effect of a novel moiety, hexafluoroalcohol, on the gas transport properties of an aromatic polyimide membrane are evaluated. The hexafluoroalcohol group increases the membrane’s fractional free volume, which increases the membrane’s permeability to all gases. Additionally, the HFA-containing polyimide shows resistance to plasticization by carbon dioxide. However, ideal selectivity for several gas pairs is unchanged by the inclusion of hexafluoroalcohol and the increase in the polymer’s fractional free volume. This lack of selectivity loss with increasing free volume is attributed to hydrogen bonding between the hexafluoroalcohol and imide groups, which reduces chain mobility. The ethanol dehydration characteristics of a so-called “TR” polymer are also evaluated in this work. TR polymers are heterocyclic, aromatic polymers synthesized by a solid-state, high temperature condensation from ortho-functional polyimides. Pervaporation studies on a representative TR polymer film demonstrate that the material has separation properties that exceed those of a commercial ethanol dehydration membrane. The transport properties of the TR film, combined with high thermal and chemical stability characteristic of these materials, make TR polymers promising materials for high-temperature, high-water content ethanol dehydration. Finally, the physical aging and plasticization of cellulose triacetate, the dominant natural gas purification membrane, is presented. Although this material has been used industrially for over 30 years, the physical aging and plasticization of the material, particularly in sub-micron films, has never been studied. Although cellulose triacetate does show physical aging behavior, as observed by permeability decreases over time, cellulose triacetate thin films do not show accelerated aging. Furthermore, the plasticization of thin cellulose triacetate films is reduced, rather than increased as seen in other polymers. The unusual transport stability of thin cellulose triacetate films may be due to their complex, semi-crystalline morphology, which, due to the thermal instability of the material, may not be thermally controlled. / text

Thermal and fatigue cracking are pavement distresses that deteriorate asphalt pavements in Canada. However, the current AASHTO M320 standard specification protocol does not give satisfactory correlation between the properties measured in the laboratory to thermal and fatigue cracking performance of the asphalt in service. This thesis is aimed at validating the newly developed MTO LS-299 and LS-308 specification test methods for predicting pavement distress. A secondary objective is to determine how well laboratory-aged and field-aged binders correlate with each other in terms of their chemical and physical properties. Chemical testing using infrared (IR) spectroscopy and X-ray fluorescence (XRF), as well as physical and mechanical testing using the regular bending beam rheometer (BBR), extended BBR (eBBR), dynamic shear rheometer (DSR), and double edge notched tension (DENT) tests were performed on laboratory-aged and recovered binders from Highway 417. Asphalt cements with significant amounts of waste engine oil residues as determined by XRF data were found to have cracked severely due to their high tendency for chemical aging. Western Canadian binders modified with styrene-butadiene-styrene polymer showed low affinity for both chemical and physical aging as determined from their carbonyl indices. Asphalt binders with smaller paraffinic structures exhibited insignificant pavement deterioration while the opposite occurred to those with low aromatic indices according to their IR data. The DSR data show that chemical aging occurs much faster in the laboratory-aged binders than the field-aged binders. The DENT test is able to separate superior performing binders from inferior ones with 86% accuracy according to their CTOD data. The regular BBR gave poor correlation between the laboratory test methods and the performance of the pavements. Good correlation exists between the laboratory test methods and the performance of the pavements in service according to the eBBR data. Pavements without any cracks showed lower grade losses, while pavements with severe thermal cracking recorded higher grade losses after three days of conditioning prior to testing. The study has shown that the eBBR and DENT tests are better tools for predicting pavement performance and provide good specification tests for the control of thermal and fatigue cracking in modern pavements. / Thesis (Master, Chemistry) -- Queen's University, 2012-02-28 13:16:02.222

The performance of some polymeric materials is profoundly affected by long-term exposure to moisture during service. This poses problems for high precision and/or load bearing components in engineering applications where moisture-induced changes in mechanical properties and dimensional stability could compromise the reliability of the device or structure. In addition to external factors such as moisture, the material properties are also evolving due to inherent structural relaxation within the polymeric material through a process known as physical aging. Based on the current knowledge of both mechanisms, they have opposite effects on material properties. The common approach to studying the effects of moisture is to expose the polymeric material to combined moisture and heat, also referred to as hygrothermal conditions. The application of heat not only increases the rate of moisture diffusion but also accelerates physical aging processes which would otherwise be very slow. In spite of this coupled response, nearly all hygrothermal studies ignore physical aging in their investigations due to the complexity of the coupled problem. The goal of this work is to develop a numerical model for simulating the interactive effects of moisture diffusion and physical aging in a glassy polymer. The intent is to develop a capability that would also allow one to model these effects under various mechanical loading and heat transfer conditions. The study has chosen to model the response of polycarbonate/acrylonitrile-butadiene-styrene (PC/ABS), which is a glassy polymer blend that has very similar behaviour to polycarbonate. In this study, a comprehensive approach which considers four physical mechanisms – structural mechanics, moisture diffusion, heat conduction, and physical aging – has been applied. The most current analytical models in the literature usually attempt to model two or three coupled physical phenomena. To develop the four coupled phenomena model, the current work has undertaken an extensive scope of work involving experimental characterization and finite element modeling. In the experimental part of this work, seven sets of different tests were conducted to characterize the behaviour of PC/ABS exposed to moisture diffusion and accelerated physical aging. These experiments provided a comparative study between the effects of physical aging and moisture diffusion on the material’s behaviour; and at the same time, provided data for the numerical modeling. The dual glass transition temperatures (Tg) of the material were determined using two techniques: dynamic mechanical analysis (DMA) and thermo-mechanical analysis (TMA). The DMA tests provided data for studying the effects of hygrothermal aging on the Tg’s of the material and were also useful for mechanical tests such as creep and stress relaxation performed using the DMA. The Tg’s obtained using the TMA were also required for physical aging experiments using the dilatometry mode of TMA. Structural relaxation of the blend was studied by aging the material at 80 °C for 7 aging times in the TMA. These experiments gave an insight into the volume relaxation behaviour of the blend at a constant temperature. Specific heat capacity of the PC/ABS blend was also measured using another thermal analysis technique; i.e., differential scanning calorimeter (DSC), before and after test specimens were exposed to hygrothermal aging for 168 hours. The interactive effects of physical aging and moisture diffusion on the moisture uptake of the material were studied using gravimetric experiments performed at 5 different hygrothermal conditions. The experimental results were used to determine the coefficient of diffusion as well as the equilibrium moisture uptake of the samples. Furthermore, the effects of both moisture diffusion and physical aging on the mechanical behaviour of the polymer blend were investigated using stress relaxation tests. The comparison of the results of the tests performed on un-aged specimens with those of thermally and hygrothermally aged samples showed how physical aging effects competed with moisture diffusion. Also, the coefficient of hygroscopic expansion of the PC/ABS blend was determined using a so-called TMA/TGA technique. The numerical modeling of the four-coupled physics was achieved using the governing equations in the form of partial differential equations. Modeling was performed using the commercial finite element software package, COMSOL Multiphysics®. First, the uncoupled physical mechanisms of structural mechanics, moisture diffusion, and heat conduction were modeled separately to investigate the validity of the PDEs for each individual phenomenon. The modeling of the coupled physics was undertaken in two parts. The three coupled physics of structural mechanics, moisture diffusion, and heat conduction was first simulated for a gas pipe having a linear elastic behaviour. The comparison of the results with similar analysis available in the literature showed the capability of the developed model for the analysis of the triple coupled mechanisms. The second part modeled the four coupled phenomena by incorporating the experimentally determined coupling coefficients. In the developed numerical model, the material behaviour was considered to be linear viscoelastic, which complicated the model further but provided more realistic results for the behaviour of the polymer blend. Moreover, an approximation method was proposed for estimating the coupling coefficients that exist between different coupled physics in this study. It was also suggested that the anomalous moisture diffusion in the material can be modeled using a time varying boundary condition. Finally, the model was successfully verified and demonstrated using test case studies with thin thermoplastic plates. The proposed four-coupled physics model was able to predict with good accuracy the deflection of thin thermoplastic plates under bending for a set of hygorthermal test condition.

Gas separation membranes are proving to be a sustainable method to mitigate climate change given the rising energy demand. Polymers of intrinsic microporosity (PIMs) have emerged as a novel material class for such application. Physical aging is a major concern for the growth and commercialization of these glassy polymers. Several factors play an important role in determining the effects of physical aging for a PIM film; one important parameter is its thickness. Gas transport properties of PIM-Trip-TB films of thicknesses between 20-150 µm were monitored over 150 days for physical aging and its dependence on film thickness. Over this period, thicker films had generally higher permeability, and thinner films aged faster. Although fresh films showed higher selectivity during the initial tests, no correlation was found between film thickness and selectivity after aging. In addition, physical aging was more severe and independent of film thickness for larger-sized gases. Film storing environment affected the physical aging of multiply tested samples significantly, whereas films which were not tested periodically showed very minimal aging. A more systematic approach is required to fully analyze and comprehend factors yielding this phenomenon.

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