The present work reports the effect of various organically functionalized polyhedral oligomeric silsesquioxane (POSS) particles on the gas transport properties (N 2 , O 2 , and CO 2 molecules) in poly(vinyl alcohol) (PVA) membranes. The incorporation of polyethylene glycol-POSS (PEG-POSS), octa-tetramethylammonium-POSS (Octa-TMA-POSS) and m-POSS (Octa-TMA-POSS molecule was modified using cetyltrimethyl ammonium bromide) led to the enhancement in CO 2 separation performance of PVA, among which, PEG-POSS exhibited highest CO 2 separation due to the dipole-quadrupolar interaction of CO 2 with ethylene oxide group in POSS. Octa-TMA-POSS and m-POSS reduced the O 2 and N 2 permeability of the PVA membrane due to the reduction in the number of permeating pathways as compared to pure PVA. Free volume of the membranes was evaluated by positron annihilation lifetime spectroscopic (PALS) and coincidence Doppler broadening measurements. PALS confirms the increase in polymer free volume in PVA/POSS system due to the presence of rigid and spherical POSS molecule, which could enter in the polymer chain and provide viable pathway for molecular transport. Maxwel-Wagner-Sillar and Higuchi models were applied for the theoretical prediction of permeability of the fabricated membranes.
In this work, the thermal degradation of functionalized cage structured polyhedral oligomeric silsesquioxane (POSS) incorporated poly(vinyl alcohol) (PVA) and poly(vinyl alcohol)-poly (ethylene oxide) (PEO) blend membranes were discussed. PVA-PEO/POSS and cross-linked PVA/POSS systems exhibited excellent improvement in thermal stability at lower loading of POSS as compared to pure PVA and uncross-linked PVA/POSS system. Uncrosslinked PVA and PVA/POSS systems exhibited mainly two degradation steps. However, cross-linked PVA/POSS systems showed more degradation steps due to the formation of 3-dimentional network structure in the polymer. The mechanical stability of PVA/POSS and PVA-PEO/POSS systems at hydrated state were analyzed and observed a remarkable stability even in the wet condition.
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