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The rheological properties of polymer melts and polymer/blowing agent (BA) solutions are determined experimentally and the influences of material rheological properties and crystallization on low-density foaming behaviour of polylactic acid (PLA) are investigated. Understanding the rheological properties of foaming polymers allows the optimization of polymer chemical structure and the development of technologies that produce desired cell morphologies. Although the technology for producing CO2-blown polystyrene (PS) foams is well established, the rheological properties of a PS/CO2 solution, especially its extensional property, are not well understood. In this study, these properties are determined with an in-house developed, online technique, and the measured data are compared with those from commercial rheometers. The online measurement system consists of a tandem foam extrusion system and a die for measuring pressure drops. Shear viscosity is determined from the pressure drop over a straight rectangular channel, while planar extensional viscosity from the pressure drop over a thin hyperbolic channel, taking into account the pressure drop due to shearing. Measured viscosities of the polystyrene without CO2 compare well with those from commercial rheometers. With the presence of dissolved CO2, both the shear and extensional viscosities of the polystyrene are significantly reduced. The influence of CO2 on the two viscosities is found to be similar to an increase of temperature. Polylactic acid is the first mass-produced biodegradable polymer, and has potential to replace petroleum-based polymers in foaming applications. In this study, the influences of material rheological properties and crystallization on the low-density, microcellular extrusion foaming behaviour of polylactic acids (PLAs) are investigated. Comparisons are made between linear and branched PLAs and between amorphous and crystalline PLAs. The branched PLAs are found to produce foams with higher expansion ratios and reduced open-cell content compared to the linear PLA. The foaming behaviour of the linear PLA, then, is significantly improved by adding a small amount of long-chain-branched PLA. The improved cell structure with branched PLAs is attributed to their relatively high melt strength and strain to break. For the first time, it is shown that crystallization, induced by cooling and macroscopic flow during processing, increases melt strength, which aids the production of low-density foams.

This thesis looks at the study of nanocomposites of Poly(ethylene terephthalate) and organoclays. Two methods of materials blending are investigated for the production of the nanocomposites: solvent blending and melt blending. The main objectives were the investigation of the influence of organoclays and processing conditions on morphological, rheological, mechanical properties, crystal structure and isothermal crystallization kinetics of the nanocomposite and a comparison with unfilled PET. In solvent blending, the use of long sonication time and epoxy led to the formation of a two-dimensional network structure of long, thin particles in a solvent blended PET nanocomposite at low clay loading. The clay network structure seemed not to affect the tensile properties. The long, thin particles were able to be separated and dispersed further by high shear in a twin screw extruder, resulting in a high level of separation and dispersion. The crystallization of the solvent blended nanocomposite was not only influenced by the nanoclay but also by the residual solvent. The extent of clay dispersion did not affect the crystallization of the solvent blended sample. Both solvent blended and melt blended nanocomposites showed that increasing the amount of surfactant improved the degree of nanoclay dispersion in the PET that led to an enhancement in the tensile properties of the nanocomposite compared to the unfilled polymer. The degradation of the organoclay during melt blending did not limit the nanoclay dispersion in the PET. The low thermal stability of the organoclay reduced the strength of the crystalline nanocomposite but it did not affect the strength of the amorphous nanocomposite. In contrast to the solvent blended sample, the extent of clay dispersion influenced the crystallization of the melt blended sample. The poorly dispersed particles were more efficient in nucleating PET crystallization than the well dispersed particles. The crystallization rate of PET increased as the surfactant concentration decreased.

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by Chung Yiu Cho. / Parallel title in Chinese characters. / Thesis (M.Ph.)--Chinese University of Hong Kong, 1988. / Bibliography: leaves 124-131.

Inertial granular flows lie in a region of parameter space between quasi-static and collisional regimes. In each of these phases the mechanisms of energy dissipation are often taken to be the defining features. Frictional contacts between grains and the transmission of energy through co-operative force chains dominate slowly sheared flows. In the opposite extreme infrequent high-energy collisions are responsible for dissipation in so-called gaseous granular flows. Borrowing from each of these extremes, it is postulated that during liquid-like flow, grain energy is transferred through frequent frictional interactions as the particles rearrange. This thesis focuses on the μ(I)-rheology which generalises the simple Coulomb picture, where greater normal forces lead to greater tangential friction, by including dependence on the inertial number I, which reflects the frequency of grain rearrangements. The equations resulting from this rheology, assuming that the material is incompressible, are first examined with a maximal-order linear stability analysis. It is found that the equations are linearly well-posed when the inertial number is not too high or too low. For inertial numbers in which the equations are instead ill-posed numerical solutions are found to be grid-dependent with perturbations growing unboundedly as their wavelength is decreased. Interestingly, experimental results also diverge away from the original μ(I) curve in the ill-posed regions. A generalised well-posedness analysis is used alongside the experimental findings to suggest a new functional form for the curve. This is shown to regularise numerical computations for a selection of inclined plane flows. As the incompressibility assumption is known to break down more drastically in the high-I and low-I limits, compressible μ(I) equations are also considered. When the closure of these equations takes the form suggested by critical state soil mechanics, it is found that the resultant system is well-posed regardless of the details of the deformation. Well-posed equations can also be formed by depth-averaging the μ(I)-rheology. For three-dimensional chute flows experimental measurements are captured well by the depth-averaged model when the flows are shallow. Furthermore, numerical computations are much less expensive than those with the full μ(I) system.