Suppressed crystallization and enhanced gas permeability in thin films of cellulose acetate blends

Abstract Film thickness and blending can affect crystallization and chain dynamics of semi-crystalline polymers, particularly for submicron films. Herein we apply these insights to elucidate a long-standing puzzle for industrial asymmetric membranes for CO2 removal from natural gas, which are based on blends of cellulose diacetate (CDA with a degree of acetylation or DS of 2.45) and cellulose triacetate (CTA with a DS of 2.87). The asymmetric membranes comprise thin selective layers (∼100 nm) and have been reported to exhibit gas permeability much higher than the bulk blends. We hypothesize that the film thickness and blending confine crystallization and decrease the crystallinity, increasing gas permeability while retaining high selectivity. Specifically, we systematically determined crystallinity for CTA and two blends with various thicknesses ranging from ≈500 nm to ≈20 μm. Adding 75 mass% CTA in CDA (CDA-CTA75) decreases the crystallinity from 34 vol% to 23 vol% at ≈ 20 μm (accompanied by CO2 permeability increase from 3.9 Barrer to 7.1 Barrer), while decreasing the film thickness of CDA-CTA75 from ≈20 μm to ≈ 1.0 μm decreases the crystallinity from 23 vol% to 13 vol% and increases CO2 permeability from 7.1 Barrer to 14 Barrer. Understanding polymer chain dynamics and crystallization in thin films can be instrumental in designing high-performance membranes for industrial gas separations.