Free volume defects and transport properties of mechanically stable polyhedral oligomeric silsesquioxane embedded poly(vinyl alcohol)‐poly(ethylene oxide) blend membranes

Abstract Polymer membrane based gas transport and pervaporation processes are fast growing areas in separation technology and have received wide attention as areas of ‘clean technology’. Mechanically stable novel polyhedral oligomeric silsesquioxane (POSS) embedded poly(vinyl alcohol) (PVA)/poly(ethylene oxide) (PEO) blend membranes were prepared by solution blending followed by casting. The addition of carboxymethyl cellulose enhanced the interfacial activities of the PVA and PEO blends. The peripheral organic substituent on POSS plays a key role in achieving compatibility with polymers whereas the rigid Si–O–Si core of POSS imparts high mechanical strength. Compared to PVA membrane, poly(ethylene glycol) and octa(tetramethylammonium) functionalized POSS embedded PVA/PEO membranes exhibit 680% and 580% enhancement in Young's modulus as well as 130% and 140% improvement in tensile strength respectively. The Einstein, Kerner and Frankel–Acrivos models were applied to compare the experimental and theoretical Young's modulus of PVA‐PEO/POSS membranes. The presence of an ethylene oxide tail on POSS as well as PEO in the blend membrane enhances the CO 2 affinity of the membrane. The presence of a hydrophilic functional group on the POSS improves the hydrophilicity of the membrane and produces more binding sites for water molecules in the membrane during the pervaporation separation of a tetrahydrofuran–water azeotropic mixture. The transport properties of the membrane are further elucidated by means of free volume defect analysis carried out by positron annihilation lifetime spectroscopy and coincidence Doppler broadening spectroscopy. © 2019 Society of Chemical Industry