Mechanically Strong, Thermally Stable Gas Barrier Polyimide Membranes Derived from Carbon Nanotube-Based Nanofluids

Gas barrier membranes with impressive moisture permeability are highly demanded in air or nature gas dehumidification. We report a novel approach using polyetheramine oligomers covalently grafted on the carbon nanotubes (CNTs) to engineer liquid-like CNT nanofluids (CNT NFs), which are incorporated into a polyimide matrix to enhance the gas barrier and moisture permeation properties. Benefiting from the featured liquid-like characteristic of CNT NFs, a strong interfacial compatibility between CNTs and the polyimide matrix is achieved, and thus, the resulting membranes exhibit high heat resistance and desirable mechanical strength as well as remarkable fracture toughness, beneficially to withstanding creep, impact, and stress fatigue in separation applications. Positron annihilation lifetime spectroscopy measurements indicate a significant decrease in fractional free volume within the resulting membranes, leading to greatly enhanced gas barrier properties while almost showing full retention of moisture permeability compared to that of the pristine membrane. For membranes with 10 wt % CNT NFs, the gas transmission rates, respectively, decrease 99.9% for CH₄, 94.4% for CO₂, 99.2% for N₂, and 97.9% for O₂ compared with that of the pristine membrane. Most importantly, with the increasing amount of CNT NFs, the hybrid membranes demonstrate a simultaneous increase of barrier performance and permselectivity for H₂O/CH₄, H₂O/N₂, H₂O/CO₂, and H₂O/O₂. All these results make these membranes potential candidates for high-pressure natural gas or hyperthermal air dehydration.