Tuning the microstructure of polycarbosilane-derived SiC(O) separation membranes via thermal-oxidative cross-linking

Abstract

In this study, the physicochemical properties and microstructural variations of polycarbosilane (PCS) were systematically investigated at curing temperatures of 150–350 °C and pyrolysis temperatures of 350–850 °C. Oxidative cross-linking remarkably enhanced the thermal stability of the PCS structure. Elemental composition and microstructure of the final ceramic material could be precisely tailored via the air curing process. Cross-linking by air curing that is either excessive or insufficient could cause the micropores of the resulting ceramic material to collapse or disappear. The most promising PCS-derived membranes, which were cured at 250 °C and then pyrolyzed at 750 °C, had high thermal stability and oxidation resistance at 500 °C in addition to excellent permeation properties: H2 permeance of 1–2 × 10−6 mol/(m2 s Pa) at 500 °C with H2/N2 selectivity of 31 and H2/C3H8 selectivity of 1,740; and, CO2 permeance of 1.8 × 10−6 mol/(m2 s Pa) at 27 °C with CO2/CH4 selectivity of 40. Moreover, permeance and selectivity in an equimolar H2/C3H8 mixture at 500 °C were approximately the same as those in single gases, suggesting the separation mechanism could be ascribed to molecular sieving. This is the first study to propose the concept of tailoring the microstructure of SiC-based membranes by controlling the curing process.