Zugl.: Berlin, Techn. Univ., Diss., 2004.

Hannover, Universiẗat, Diss., 2004.

Essen, Universiẗat, Diss., 2000.

Zugl.: Dresden, Techn. Univ., Diss., 2004.

Konstanz, Univ., Diss., 2000.

Universiẗat, Diss., 2001--Freiburg (Breisgau).

Due to the wide range of properties of plastics (e.g. low density), more and more conventional materials are substituted by polymer materials. Complex requirement profiles on technical parts increase the demand for joining processes that enable the reliable joining of otherwise incompatible thermoplastics. In this case, material bonded connections are approaching their limits. In the following study two incompatible thermoplastic polymers were welded by using polymer blends that are compatible to both components. Industrially relevant thermoplastics polyethylene (PE) and polyamide 12 (PA12) were chosen to demonstrate the potential of an innovative joining technology.

This thesis describes a fundamental study of the miscibility and the nature of the interface between components of core-shell polymer blends using the technique of Fluorescence Resonance Energy Transfer (FRET) coupled with data analysis that involves Monte-Carlo simulations. Our aim in this study was to develop a fundamental methodology to quantitatively determine the width of the interface between the two components in binary polymer blends. At the current state of the art, data analysis of FRET experiments requires translational symmetry. In the system under study, uniform core-shell structures satisfy this criterion. Thus, in this work our focus was directed toward the study of a blend system with a core-shell structure. For this FRET study, I have identified a number of potential donor and acceptor dye pairs that fluoresce in the visible range of the spectrum and can be chemically attached to polymers. Among them, I selected, as the donor and the acceptor, a pair of naphthalimide dyes that have not previously been used for FRET experiments. Model experiments showed that while the fluorescence decay profile of the donor chromophore was exponential in solution, it was not exponential in polystyrene (PS) or poly(methyl methacrylate) (PMMA) films. Thus, I carried out refinements to existing FRET theory to interpret the data generated by using these dyes. Also, I derived a new model to predict the fluorescence intensity of non-exponential decaying donor dyes in core-shell systems. I selected a model system composed of a PS core surrounded by a PMMA shell. The PS core particles were prepared by miniemulsion polymerization to obtain cross-linked PS particles with a narrow size distribution. Seeded emulsion polymerization under starved-fed condition was employed to synthesize monodisperse dye-labeled core-shell particles. The extent of miscibility and the nature of interface between the core and the shell polymers were retrieved from a combined study by Monte-Carlo simulations and analysis of the donor fluorescence intensity decays. Agreement between the retrieved interface thickness and the literature data on PS-PMMA validates the methodology developed here for the use of such donor dyes in FRET studies on polymer blends.

This thesis describes a fundamental study of the miscibility and the nature of the interface between components of core-shell polymer blends using the technique of Fluorescence Resonance Energy Transfer (FRET) coupled with data analysis that involves Monte-Carlo simulations. Our aim in this study was to develop a fundamental methodology to quantitatively determine the width of the interface between the two components in binary polymer blends. At the current state of the art, data analysis of FRET experiments requires translational symmetry. In the system under study, uniform core-shell structures satisfy this criterion. Thus, in this work our focus was directed toward the study of a blend system with a core-shell structure. For this FRET study, I have identified a number of potential donor and acceptor dye pairs that fluoresce in the visible range of the spectrum and can be chemically attached to polymers. Among them, I selected, as the donor and the acceptor, a pair of naphthalimide dyes that have not previously been used for FRET experiments. Model experiments showed that while the fluorescence decay profile of the donor chromophore was exponential in solution, it was not exponential in polystyrene (PS) or poly(methyl methacrylate) (PMMA) films. Thus, I carried out refinements to existing FRET theory to interpret the data generated by using these dyes. Also, I derived a new model to predict the fluorescence intensity of non-exponential decaying donor dyes in core-shell systems. I selected a model system composed of a PS core surrounded by a PMMA shell. The PS core particles were prepared by miniemulsion polymerization to obtain cross-linked PS particles with a narrow size distribution. Seeded emulsion polymerization under starved-fed condition was employed to synthesize monodisperse dye-labeled core-shell particles. The extent of miscibility and the nature of interface between the core and the shell polymers were retrieved from a combined study by Monte-Carlo simulations and analysis of the donor fluorescence intensity decays. Agreement between the retrieved interface thickness and the literature data on PS-PMMA validates the methodology developed here for the use of such donor dyes in FRET studies on polymer blends.

Polycarbonate (PC) is a glassy engineering thermoplastic that has been used for decades because of its superior mechanical properties such as high toughness and stiffness, and for its general thermal stability. However, the industrial demand for higher performance polymers with faster processing times has caused PC to be gradually replaced by different engineered polymer blends, such as polycarbonate/acyrlonitrile-butadiene-styrene (PC/ABS). Blends combine the advantages of the individual components but because they are a relatively new class of materials, their time-dependent behaviour is less well understood. The goal of the present work is to characterize two primary time-dependent processes in a commercial 75:25 PC:ABS blend that are known to affect the long-term mechanical properties of the individual components. The first is physical aging which is a result of non-equilibrium fast cooling of glassy or amorphous polymers. Physical aging is associated with structural relaxation due to enthalpic and volumetric recovery. The second process is hygrothermal conditioning which is the combined application of thermal aging and moisture absorption. Three sets of characterization tests were conducted using Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared spectroscopy (FTIR). The enthalpic relaxation results determined from DSC data for aging at nine different combinations of time and temperature showed that aging experiments are best conducted at temperatures between 80 and 90°C. This range is below the glass temperature of the ABS component. The activation energy for enthalpic relaxation for the unaged blend was found to fall between energies for PC and ABS relaxations, but not according to the rule-of-mixtures. The present study attempted to adopt the Tool–Narayanaswamy-Moynihan (TNM) phenomenological model to predict relaxation kinetics but was found to be complicated by multiple endothermic peaks. It was then concluded that the TNM model, although very useful for single polymer systems, is unsuitable for blends. A semi-empirical model was applied instead to fit the experimental data which provided a reasonable estimate of the relaxation behaviour. Aging at 80°C for the period investigated did not reach equilibrium and it is expected that aging times of upwards of 2 years will be necessary to minimize the errors associated with the data fitting to provide a better fit of the model. The FTIR studies revealed that thermal aging at 80°C in dry atmosphere results in oxidation of the butadiene component. However, the addition of moisture to the aging process appears to prevent, or at least impede, oxidation from occurring. The presence of moisture seems to trigger hydrogen bonding, which saturates regardless of the moisture content after approximately 80 days. The initial rate of moisture diffusion in PC/ABS appeared to depend predominantly on temperature while the ambient moisture concentration tends to only affect the final equilibrium content in the blend.