Morphological, mechanical and gas-transport characteristics of crosslinked poly(propylene glycol): homopolymers, nanocomposites and blends

Linear polyethers possess unusually high CO₂ solubility and, hence, selectivity due to the presence of accessible ether linkages that can interact with the quadrupolar moment of CO₂ molecules. In this work, membranes derived from crosslinked poly(propylene glycol) diacrylate (PPGda) oligomers differing in molecular weight (M), as well as PPGda nanocomposites containing either an organically-modified montmorillonite clay or a methacrylate-terminated fumed silica are investigated and compared with highly CO₂-selective poly(ethylene glycol) diacrylate (PEGda) homopolymer and nanocomposite membranes previously reported. The rheological and permeation properties of PPGda depend sensitively on M, with the elastic modulus decreasing, but CO₂ permeability and CO₂/H₂ selectivity increasing, with increasing M. Incorporation of either nanofiller into PPGda enhances the elastic modulus and reduces the gas permeability in the resultant nanocomposites without strongly affecting CO₂/H₂ selectivity. Blending PPGda and PEGda prior to chemical crosslinking yields binary membranes that exhibit intermediate gas-transport properties accurately described by a linear rule of mixtures.     

Enhancing hydrogen gas separation performance of thin film composite membrane through facilely blended polyvinyl alcohol and PEBAX

Polymeric membranes offer economic separation processes but are less explored for H₂ separation application. This work aims to unveil the H₂ separation potential of polymeric membrane by developing PVA-based reverse selective composite membrane. CO₂-selective PEBAX was blended at different PVA:PEBAX ratio. The effect of PEBAX blending on membrane morphology, crystallinity and gas separation behavior was studied. Incorporation of PEBAX at <50 wt% resulted in composite with improved CO₂ permeability but selectivity loss. Blending of >60 wt% PEBAX enhanced both permeance and selectivity of the resulted composite as the host matrix was dominated by this PEO containing material thus greatly enhancing polymer chain mobility and promoting CO₂-solubility. The best composite which contains 60 wt% PEBAX exhibited CO₂ permeability of 20.0 Barrer and CO₂/H₂ selectivity of 7.6. This performance surpasses the Robeson's boundary and unleashes the potential of tailoring the properties of polymeric nanocomposite membrane for H₂ separation application through facile PVA/PEBAX blending.     

In situ fabrication of cross-linked PEO/silica reverse-selective membranes for hydrogen purification

Targeting at hydrogen purification, cross-linked organic–inorganic reverse-selective membranes containing poly(ethylene oxide) (PEO) are fabricated in situ by using functional oligomers (O,O′-bis(2-aminopropyl) polypropylene glycol-block-polyethylene glycol-block-polypropylene glycol: Jeffamine^® ED-2003) with a high content of PEO and epoxy-functional silanes (3-glycidyloxypropyltrimethoxysilane: GOTMS). Changes in physicochemical properties due to varying silica content have been characterized; including a great decline in melting temperature; an improvement in glassy and degradation temperature, and the suppression of PEO crystallinity. The strong affinity between quadrupolar CO₂ and polar ethylene oxide (EO) groups enhances the CO₂/H₂ separation performance of hybrid membranes, which can be further tuned by controlling the organic/inorganic ratio. The organic–inorganic hybrid membrane with 90 wt% of ED-2003 demonstrates an appealing CO₂ permeability of 367 Barrer with an attractive CO₂/H₂ selectivity of 8.95 at 3.5 atm and 35 °C. The transport performance trend with composition variations is explained by analyzing the calculated solubility and diffusivity based on the solution-diffusion mechanism. Moreover, CO₂ permeability increases with applied pressure in pure gas tests because of CO₂ plasticization phenomena, which is beneficial for CO₂/H₂ separation. Attributing to CO₂ plasticization and CO₂ dominant sorption, the mixed gas test results of the membrane containing only 25 wt% ED-2003 show greatly improved CO₂/H₂ selectivity of 13.2 with CO₂ permeability of 148 Barrer at 35 °C compared to pure gas results. Interestingly, at a stipulated CO₂ pressure, the inherent tension in cross-linked networks maintains the CO₂ permeability stable with the time. The cross-linked organic–inorganic membranes with enhancements in mechanical and thermal properties are promising for industrial-scale hydrogen purification.