Honeycomb structured porous films from different polymer architectures - preparation, mechanism, analysis and post-treatment

This dissertation studies and examines the process of formation of honeycomb structured porous films using various polymer architectures ranging from linear, comb, star polymers and a random copolymer. Four casting methods were designed and applied for the production of structured porous materials. The airflow casting technique, cold-stage casting technique, casting on water technique and emulsion casting technique all based in either direct water introduction to the system or indirect condensation from the environment showed to be viable options for casting of high quality porous materials. The control and study of the effect of environmental conditions towards the quality of the films has been examined through the design of a casting device and the use of the casting methods. Furthermore, the versatility of each of the architectures towards the production of honeycomb porous films has been studied. Highly regular honeycomb structured porous films were obtained from all the complex architectures namely comb polymers, star polymers and the random copolymer. However, the linear polymers did not result in regular films. Moreover the quality of the films has been assessed and mathematically quantified. In addition, some mechanistic aspects of the process of formation of honeycomb structured porous films have been addressed. Variables such as the viscosity and evaporation of polymer solutions were examined. Furthermore, the precipitation behaviour of various polymer architectures was inspected. Only the polymer architectures showing a lower viscosity and late precipitation deemed highly regular films. Finally, the modification of highly regular films from a comb polymer and a random copolymer was successfully performed for the first time by grafting a thermoresponsive polymer from the RAFT groups already present in the porous material. The non-treated films showed a typical hydrophobic behaviour for a porous membrane however after the grafting, the films exhibited hydrophilic behaviour