Novel selective ceramic-supported thin polyimide films produced in a single dip coating step are proposed for membrane applications at elevated temperatures. Layers of the polyimides P84^®, Matrimid 5218^®, and 6FDA-6FpDA were successfully deposited onto porous alumina supports. In order to tackle the poor compatibility between ceramic support and polymer, and to get defect-free thin films, the effect of the viscosity of the polymer solution was studied, giving the entanglement concentration (C*) for each polymer. The C* values were 3.09 wt. % for the 6FDA-6FpDA, 3.52 wt. % for Matrimid^®, and 4.30 wt. % for P84^®. A minimum polymer solution concentration necessary for defect-free film formation was found for each polymer, with the inverse order to the intrinsic viscosities (P84^® ≥ Matrimid^® >> 6FDA-6FpDA). The effect of the temperature on the permeance of prepared membranes was studied for H₂, CH₄, N₂, O₂, and CO₂. As expected, activation energy of permeance for hydrogen was higher than for CO₂, resulting in H₂/CO₂ selectivity increase with temperature. More densely packed polymers lead to materials that are more selective at elevated temperatures.

Novel selective polymeric thin-film composite membranes (TFCMs) for applications at elevated temperatures were developed. Thin selective layers of the polyimides Matrimid 5218^® and 6FDA-6FpDA were cast on a developed polybenzimidazole (PBI) porous support prepared by a phase inversion process. The TFCM properties were investigated with different gases in a wide temperature range, including temperatures up to 270 °C. The membranes showed very high thermal stability and performed well at the elevated temperatures. The development of highly thermally resistant polymeric membranes such as these TFCMs opens opportunities for application in high-temperature integrated processes, such as catalytic membrane reactors for the water-gas shift reaction in order to maximize H₂ yield.

Three polyimides and six inorganic fillers in a form of nanometer-sized particles were studied as thick film solution cast mixed matrix membranes (MMMs) for the transport of CO₂, CH₄, and H₂O. Gas transport properties and electron microscopy images indicate good polymer-filler compatibility for all membranes. The only filler type thatdemonstrated good distribution throughout the membrane thickness at 10 wt.% loading was BaCe_0.2Zr_0.7Y_0.1O₃ (BCZY). The influence of this filler on MMM gas transport properties was studied in detail for 6FDA-6FpDA in a filler content range from one to 20 wt.% and for Matrimid^® and P84^® at 10 wt.% loading. The most promising result was obtained for Matrimid^®—10 wt.% BCZY MMM, which showed improvement in CO₂ and H₂O permeabilities accompanied by increased CO₂/CH₄ selectivity and high water selective membrane at elevated temperatures without H₂O/permanent gas selectivity loss.

Three polyimides and six inorganic fillers in a form of nanometer-sized particles were studied as thick film solution cast mixed matrix membranes (MMMs) for transport of CO2, CH4 and H2O. Gas transport properties and electron microscopy images indicate good polymer-filler compatibility for all membranes. The only filler type which demonstrated good distribution throughout the membrane thickness at 10 wt. % loading was BaCe0.2Zr0.7Y0.1O3 (BCZY). The influence of this filler on MMM gas transport properties was studied in detail for 6FDA-6FpDA in a filler content range from 1 to 20 wt.% and for Matrimid® and P84® at 10 wt. % loading. The most promising result was obtained for Matrimid® - 10wt% BCZY MMM, which showed improvement in CO2 and H2O permeabilities accompanied by increased CO2/CH4 selectivity and high water selective membrane at elevated temperatures without H2O/permanent gas selectivity loss.