Defects in polyethylene film are often caused by contaminant particles in the polymer melt. In this research, particle properties obtainable from in-line melt monitoring, combined with processing information, are used to predict film defect properties. “Model” particles (solid and hollow glass microspheres, aluminum powder, ceramic microspheres, glass fibers, wood particles, and cross-linked polyethylene) were injected into low-density polyethylene extruder feed. Defects resulted when the polyethylene containing particles was extruded through a film die and stretched by a take-up roller as it cooled to form films 57 to 241mm in thickness. Two off-line analysis methods were further developed and applied to the defects: polarized light imaging and interferometric imaging. Polarized light showed residual stresses in the film caused by the particle as well as properties of the embedded particle. Interferometry enabled measures of the film distortion, notably defect volume. From the images, only three attributes were required for mathematical modeling: particle area, defect area, and defect volume. These attributes yielded two ”primary defect properties”: average defect height and magnification (of particle area). For all spherical particles, empirical correlations of these properties were obtained for each of the two major types of defects that emerged: high average height and low average height defects. Analysis of data for non-spherical particles was limited to showing how, in some cases, their data differed from the spherical particle correlations. To help explain empirical correlations of the primary defect properties with film thickness, a simple model was proposed and found to be supported by the high average height defect data: the “constant defect volume per unit particle area” model. It assumes that the product of average defect height and magnification is a constant for all film thicknesses. A numerical example illustrates how the methodology developed in this work can be used as a starting point for predicting film defect properties in industrial systems. A limitation is that each prediction yields two pairs of primary defect property values, one pair for each defect type. If it is necessary to identify the dominant type, then measurement of a length dimension of sufficient defects in the film is required.

The purpose of this work was to develop a practical method for constitutive modelling of polyethylene, based on a phenomenological approach, which can be applied for structural analysis. Polyethylene (PE) is increasingly used as a structural material, for example in pipes installed by trenchless methods where relatively low stiffness of PE reduces the required installation forces, chemical inertness makes it applicable for corrosive environments, and adequate strength allows to use it for sewer, gas and water lines. Polyethylene exhibits time-dependent constitutive behaviour, which is also dependent on the applied stress level resulting in nonlinear stress-strain relationships. Nonlinear viscoelastic theory has been well established and a variety of modelling approaches have been derived from it. In order to be able to realistically utilize the nonlinear modelling approaches in design, a simple method is needed for finding the constitutive formulation for a specific polyethylene type. In this study, time-dependent constitutive relationships for polymers are investigated for polyethylene materials. Creep tests on seven polyethylene materials were conducted and the experimental results indicate strong nonlinear viscoelasticity in the material responses. Creep tests on seven materials were conducted for 24 hours for modelling purposes. However, creep tests up to fourteen days were performed on one material to study long-term creep behaviour. Multiple-stepped creep tests were also investigated. Constant rate (load and strain rate) tensile tests were conducted on two of the seven polyethylene materials. A practical approach to nonlinear viscoelastic modelling utilizing both multi-Kelvin element theory and power law functions to model creep compliance is presented. Creep tests are used to determine material parameters and models are generated for four different polyethylene materials. The corroboration of the models is achieved by comparisons with the results of different tensile creep tests, with one dimensional step loading test results and with test results from load and displacement rate loading.

The purpose of this work was to develop a practical method for constitutive modelling of polyethylene, based on a phenomenological approach, which can be applied for structural analysis. Polyethylene (PE) is increasingly used as a structural material, for example in pipes installed by trenchless methods where relatively low stiffness of PE reduces the required installation forces, chemical inertness makes it applicable for corrosive environments, and adequate strength allows to use it for sewer, gas and water lines. Polyethylene exhibits time-dependent constitutive behaviour, which is also dependent on the applied stress level resulting in nonlinear stress-strain relationships. Nonlinear viscoelastic theory has been well established and a variety of modelling approaches have been derived from it. In order to be able to realistically utilize the nonlinear modelling approaches in design, a simple method is needed for finding the constitutive formulation for a specific polyethylene type. In this study, time-dependent constitutive relationships for polymers are investigated for polyethylene materials. Creep tests on seven polyethylene materials were conducted and the experimental results indicate strong nonlinear viscoelasticity in the material responses. Creep tests on seven materials were conducted for 24 hours for modelling purposes. However, creep tests up to fourteen days were performed on one material to study long-term creep behaviour. Multiple-stepped creep tests were also investigated. Constant rate (load and strain rate) tensile tests were conducted on two of the seven polyethylene materials. A practical approach to nonlinear viscoelastic modelling utilizing both multi-Kelvin element theory and power law functions to model creep compliance is presented. Creep tests are used to determine material parameters and models are generated for four different polyethylene materials. The corroboration of the models is achieved by comparisons with the results of different tensile creep tests, with one dimensional step loading test results and with test results from load and displacement rate loading.

Aluminum complexes, specifically those employing bulky ligand frameworks such as sal (sal = 2-[CH═N(2,6-iPr2-C6H3)]-4,6-tBu2-phenoxide) and alpha-diimine (alpha-diimine = [(2,6-iPr2-C6H3)N═C(Me)]2) derivatives are studied in various contexts. During ethylene polymerization with LCu(II) catalysts in the presence of methylaluminoxane (MAO), ligand (L) transfer is observed from the copper centre to the aluminum centre present in MAO. In the alpha-diimine case, an (imino-amido)AlMe2 complex is formed by alpha-diimine ligand transfer to aluminum followed by alkylation of one imino moiety in the ligand backbone. These ligand transfer products are then shown to be active as ethylene polymerization catalysts, bringing into question the role of the copper species. The (sal)AlMe2, (sal)AlMeCl and (imino-amido)AlMe2 complexes were also used as initiators in the ring-opening polymerization of epsilon-caprolactone. Polymerization was studied with and without addition of tert-butanol as a co-initiator to determine its role and necessity in the catalytic cycle. Finally, the (imino-amido)AlMe2 complex was also used as the starting complex in attempts at forming a mononuclear aluminum(I) target species. Reaction of (imino-amido)AlMe2 with excess I2 proved successful in forming the isolable precursor, (imino-amido)AlI2. Attempts at reducing (imino-amido)AlI2 with excess potassium were carried out in hopes of forming a very rare example of a mononuclear aluminum(I) species.

In recent years, biodegradable polymeric systems have gained importance for design of surgical devices, artificial organs, drug delivery systems with different routes of administration, carriers of immobilized enzymes and cells, biosensors, ocular inserts, and materials for orthopedic applications. Polysaccharide-based polymers represent a major class of biomaterials, which includes agarose, alginate, dextran, and chitosan. Chitosan has found many biomedical applications, including tissue engineering, owing to its biocompatibility, low toxicity, and degradation in the body, which has opened up avenues for modulating drug release in vivo in the treatment of various diseases. These chitosan-based delivery systems range from microparticles to nanoparticles and from gels to films. In this study, chitosan (CH) and chitosan-polyethylene glycol (CH-PEG) microspheres with different compositions were prepared by oil/water emulsion method and crosslinked with gluteraldehyde. Some microspheres were loaded with a model chemotherapeutic drug, methotrexate (MTX). SEM, particle size and in vitro release analysis were performed. In vitro drug release studies showed that the release of MTX from CH-PEG microspheres was faster compared to CH microspheres. In the second part, CH-PEG microspheres were conjugated with a monoclonal antibody which is immunoglobulin G (IgG). The cytotoxicity efficiencies of entrapped drug were determined by using MCF-7 and MCF-7/MDA-MB breast cancer cell lines. In the third part, CHF-PEG films with the same compositions as in microspheres were prepared by solvent casting method. IR, DSC, mechanical and surface analysis were performed. The mechanical properties of films were improved by the presence of proper amount of PEG but higher amounts of PEG caused the deteriotion in the properties.

Abstract The polymer electrolytes (ion conducting polymers) consist of macromolecules (usually in the form of polyethereal units) that are doped with alkali mental salts. The polymer electrolytes are being used in Li-polymer buttery. It is suggested that conductivity in these systems takes place through two distinct events. The first is associated with the charge migration of ions between coordination sites in the host material, and the second is that the conductivity is generally observed to rise with increasing flexibility of the polymer chains. Rayleigh-Brillouin scattering spectra of molecular liquids will provide mechanical relaxation information in the frequency range from 10^8 to 10^11 Hz. We have carried out the Brillouin scattering study of PEG400/LiCl mixtures to probe its elastic properties. The change in the flexibility of polymer chains at different temperatures, the fraction of free ion, and their interactions with polymer all effect the Brillouin spectrum and the present work suggests the usefulness of this technique as an useful tool to probe the various interactions in polymer electrolytes.

In this thesis, molecular dynamics and dissipative particle dynamics simulation methods are adopted to investigate the effects of volume fraction (1:1; 1:4; 1:6; 1:14; 1:20), repulsive interaction parameter (aij) and chain length on the microstructure of (5,5) carbon-nanotube (CNT)/polyethylene (PE) mixture. In order to obtain the information of microstructure for different simulation conditions, we used the radius of gyration and orientational order parameter to explore the polymer conformation. It is found that micro-structures will be very different when different repulsive interaction parameters and volume fractions are used.

Zugl.: Berlin, Techn. Universiẗat, Diss., 2009.

Thesis (Ph. D.)--University of Washington, 2003. / Vita. Includes bibliographical references (leaves 157-172).

Thermal degradation of linear thermoplastics is modeled at several scales. High-density polyethylene (HDPE) is chosen as an example material. The relevant experimental data is surveyed. At the molecular scale, pyrolysis chemistry is studied with reactive molecular dynamics. Optimization is used to calibrate several pyrolysis mechanisms with thermogravimetric analysis (TGA) data. It is shown that molecular scale physics may be coupled to continuum scale transport equations through a population balance equation (PBE). A PBE solution method is presented and tested. This method has the advantage of preserving detailed information for the small species in the molecular weight distribution with minimal computational expense. The mass transport of these small species is modeled at the continuum scale with a bubble loss mechanism. This mechanism includes bubble nucleation, growth, and migration to the surface of the condensed phase. The bubble loss mechanism is combined with a random scission model of pyrolysis to predict TGA data for HDPE. The modeling techniques developed at these three scales are used to model two applications of engineering interest with a combined pyrolysis and devolatilization PBE. The model assumes a chemically consistent form of the random scission pyrolysis mechanism and an average, parameterized form of the bubble loss mechanism. This model is used to predict the piloted ignition of HDPE. Predictions of the ignition times are reasonable but the model over predicts the ignition temperature. This discrepancy between model and data is attributed to surface oxidation reactions. The second application is the prediction of differential scanning calorimetry (DSC) data for HDPE. The model provides detailed information on the energy absorption of the thermally degrading sample, but the literature data is too variable to validate the model. / text