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.

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.

Research in local fracture processes and micro-machining of polymers and polymer-based composites has attracted increasing attention, in development of composite materials and miniaturisation of polymer components. In this thesis, sectioning (machining) of a glassy polymer and a carbon nanotube based composite at the nanoscale was performed by an instrumented ultramicrotome. The yield stresses and fracture toughness of these materials were determined by analysing the sectioning forces. Fractographic analysis by atomic force microscopy was conducted to characterise the topographies and elastic properties of the sectioned surfaces to explore the deformation and fracture behaviour of the polymer during nanosectioning. The study reveals that a transition from homogenous to shear localised deformation occurred as the uncut chip thickness (depth of cut) or sectioning speed increased to a critical value. Analytical and finite element methods were used to model the nanosectioning process. The shear localised deformation was caused by thermal softening due to plastic dissipation. Although not considering sectioning, the tensile properties of a polymer nanocomposite were additionally investigated, where the degree of nanofibrillation and polyethylene glycol (PEG) content had significant effects.

During high strain rate deformations of metals and metallic alloys, narrow regions of intense plastic deformations have been observed experimentally. The phenomenon is termed strain localization and is usually a precursor to catastrophic failure of a structure. Similar phenomenon has been observed in glassy polymers deformed both at slow and high strain rates. Whereas strain localization is attributed to material softening due to thermal heating in metallic alloys, it is believed to be due to the reorganization of the molecular structure in polymers. Here we numerically study the strain localization in Tungsten Heavy Alloys (WHAs), and glassy polymers. WHAs are heterogeneous materials and thus inhomogeneities in deformations occur simultaneously at several places. Thus strains may localize into narrow bands at one or more places depending upon the microstructure of the alloy. We analyze the strain localization phenomenon during explosion and implosion of WHA hollow cylinders. We have developed a procedure to generate three-dimensional microstructures from planar images so that the two have the same 2-point correlation function. The WHA considered here is comprised of W particulates in a Nickel-Iron (NiFe) matrix, and each constituent is modeled as a heat conducting, strain hardening, strain-rate hardening and thermally softening elastic-plastic material. Furthermore, the porosity is taken to evolve in each constituent and the degradation of material properties due to porosity is incorporated into the problem formulation. It is found that the strain localization initiation in WHA hollow cylinders does not significantly depend on microstructural details during either explosive or implosive loading. However, the number of disconnected regions of localized deformations is influenced by the microstructure. We have generalized constitutive equations for high strain rate deformations of two glassy polymers, namely, Polycarbonate (PC) and poly (methyl methacrylate) (PMMA). These have been validated by comparing computed results with test findings in uniaxial compression at different axial strain rates, and subsequently used to study strain localization in a plate with a through-the-thickness elliptic hole at the centroid and pulled axially at a nominal strain rate of 5,000 /s. For the problems studied, the intensely deformed narrow regions have very high shear strains in WHAs, but large axial strains in glassy polymers. / Ph. D.

The possibility to extract bio-SNG from the product gas obtained from gasification of biofuel with a pressurized, oxygen-blown CFB gasifier connected to a heat and power station using only membrane separation was theoretically investigated. Selling the methane, instead of feeding it to the plant’s turbine(s), might mean that overall profitability is increased. The considered product gas mainly consists of H2, CO, CO2, H2O and CH4. By doing a literature review different membrane types were studied and it was concluded that for now only polymers may be of interest, due to high production costs for other membranes or for the fact they are still at laboratory stage. It was further determined though that neither membranes made of glassy polymers (fixed polymer chains) nor rubbery polymers (mobile polymer chains) are probably capable of separating the methane from the other gas components on their own. Glassy membranes will most likely have trouble separating CO from CH4 due to similarity in size of the two molecules, while a separation using rubbery membranes will result in at least H2 accompanying the methane. The rubbery polymers’ incapability of separating H2 from CH4 despite greatly differing condensation temperatures between the two components can be explained by the fact that rubbery membranes, apart from condensation temperature, also separate according to molecular diffusivity. If a multistep process with recirculation that combines both glassy and rubbery polymers is applied, satisfying results may be obtained. This, however, builds on a higher separation of CH4 and CO with rubbery membranes than condensation data indicates and needs to be further investigated with help of real life experiments and more advanced computation programs than used in this study.

The application of polymers in robust engineering designs is on the rise due to their excellent mechanical properties such as high fracture toughness, specific strength, durability, as well as, thermal and chemical resistances. Implementation of some advanced polymeric solids is limited due to the lack of available mechanical properties. In order for these materials to endure strenuous engineering designs it is vital to investigate their response in multiple loading rates and conditions. In this thesis, the mechanical response of polyethermide (PEI) is characterized under quasi-static, high strain rate, and multiple impact conditions. Standard tension, torsion, and compression experiments are performed in order to distinguish the multi-regime response of PEI. The effects of physical ageing and rejuvenation on the quasi-static mechanical response are investigated. The strain softening regime resulting from strain localization is eliminated by thermal and mechanical rejuvenation, and the advantages of these processes are discussed. The dynamic fracture toughness of the material in response to notched impact via Charpy impact test is evaluated. The high strain-rate response of PEI to uniaxial compression is evaluated at rates exceeding 104/s via miniaturized Split Hopkinson Pressure Bar (MSHPB), and compared to the quasi-static case to determine strain-rate sensitivity. The elastic response of the aged material to multiple loading conditions are correlated using the Ramberg-Osgood equation, while the elastoplastic response of rejuvenated PEI is correlated using a both the Ramberg-Osgood equation and a novel model. The strain-rate sensitivity of the strength is found to be nominally bilinear and transition strains are modeled using the Ree-Erying formulation. Finally, multiple impact experiments are performed on PEI using the MSHPB and a model is proposed to quantify damage as a result of collision.