The effect of supercritical fluid on polymer systems

Great interest has been directed toward the study of polymer thin films recently due to their emerging applications, and appreciable deviated properties and phenomena as compared with bulk polymers. Carbon dioxide (CO₂) has received attention as an environmentally benign alternative to hazardous industrial solvents. Unlike conventional liquid solvents, the density and hence the solvent strength of supercritical CO₂ can be tuned by small variations in pressure, temperature or both. The objective of this work is to study the interaction between high pressure CO₂ and polymer systems. We introduced the methodology used in this dissertation. The combination of gradient theory of inhomogeneous systems and Sanchez-Lacombe Equation of State is used to calculate the interfacial properties, such as interfacial density profile, interfacial tension and interfacial thickness. We first investigated the adsorption of supercritical fluid on polymer surfaces. We showed analytically that surface adsorption of high pressure fluid on an attractive surface is proportional to the compressibility of the fluid. We have also investigated numerically the sorption of supercritical CO₂ on poly(dimethylsiloxane) (PDMS) and polyisobutylene (PIB), and supercritical 1,1-difluorethane on PS. By calculating the Gibbs adsorption and adsorption layer thickness of the supercritical fluids, we found in all cases that maximum adsorption occurred when the supercritical fluid was near its compressibility maximum. We then examined the compatibilization effect of supercritical fluid on two incompatible polymers. We calculated the interfacial density profile, interfacial thickness and interfacial tension between the two polymers with and without the supercritical fluid. We found that the interfacial tension was decreased and the interfacial thickness was increased with high pressure super-critical fluid for the ternary systems we have investigated. No enhancement or deleterious effects on compatibilization were observed as the critical point was approached and the compressibility became large. We also examined the morphological structures of asymmetric poly(ethylene oxide)-b-poly(1,1'-dihydroperflurooctyl methacrylate) (PEO-b-PFOMA) thin films upon annealing in supercritical CO₂. The strong affinity between PFOMA and CO₂ was found to induce phase segregation when annealing PEO-b-PFOMA films as compared with vacuum at the same temperature.