A new family of poly(ethylene glycol) (PEG) based membranes for CO2 separation was developed using thiol–ene photopolymerization. Compared to photopolymerized PEG-containing acrylate membranes, these new thiol–ene based membranes offer improved mechanical properties and processing advantages. The starting material, a combination of a trithiol cross-linker and a PEG diene, was gradually modified with a PEG dithiol while maintaining 1:1 thiol:ene stoichiometry. This approach made it possible to decrease the network cross-link density, resulting in simultaneous increases in free volume and PEG content. Materials with high concentrations of dithiol were very stretchable, with largely, up to 500%, improved elongation at break, yet they exhibited commendable CO2/N2, O2, H2, and CH4 permeability-selectivity performance. The average molecular weight of polymer chains between cross-links, M c, was determined experimentally by fitting the classic network affine model to stress–strain data obtained via tensile testing. M c was also calculated assuming an ideal, lattice-like, network structure based on monomer stoichiometry. The effect of M c on glass transition temperature and gas permeation behavior was studied. A free volume based model was employed to describe experimental gas permeability (diffusivity) trends as a function of M c.

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Large-scale industrial applications of barrier films and coatings that prevent permeation of degradative gases and moisture call for the development of cost-efficient and ecofriendly polymer nanocomposites. Herein, we report the facile fabrication of latex nanocomposites (LNCs) by incorporating surface-modified graphene oxide (mGO) at various loadings (0.025-1.2 wt %) into a styrene-acrylic latex using water as the processing solvent. LNCs fabricated with mGO exhibited significant reductions (up to 67%) in water vapor sorption, resulting in greater environmental stability when compared to LNCs fabricated with equivalent loading of hydrophilic, unmodified GO. The assembly and coalescence of the exfoliated latex/mGO dispersions during the film formation process produced highly dispersed and well-ordered mGO domains with high aspect ratios, where alignment and overlap of the mGO domains improved with increasing mGO content. The addition of only 0.7 vol % (1.2 wt %) mGO led to an 84% decrease (relative to the neat polymer latex film) in oxygen permeability of the LNC films, an excellent barrier performance attributed to the observed LNC film morphologies. This work enables ecofriendly development of mechanically flexible mGO/LNC films with superior barrier properties for many industrial applications including protective coatings, food packaging, and biomedical products.

A self-healable gas barrier nanocoating, which is fabricated by alternate deposition of polyethyleneimine (PEI) and polyacrylic acid (PAA) polyelectrolytes, is demonstrated in this study. This multilayer film, with high elastic modulus, high glass transition temperature, and small free volume, has been shown to be a super oxygen gas barrier. An 8-bilayer PEI/PAA multilayer assembly (≈700 nm thick) exhibits an oxygen transmission rate (OTR) undetectable to commercial instrumentation (<0.005 cc (m d atm )). The barrier property of PEI/PAA nanocoating is lost after a moderate amount of stretching due to its rigidity, which is then completely restored after high humidity exposure, therefore achieving a healing efficiency of 100%. The OTR of the multilayer nanocoating remains below the detection limit after ten stretching-healing cycles, which proves this healing process to be highly robust. The high oxygen barrier and self-healing behavior of this polymer multilayer nanocoating makes it ideal for packaging (food, electronics, and pharmaceutical) and gas separation applications.

Front Cover: A polyelectrolyte‐based nanocoating exhibits super oxygen barrier and humidity‐responsive self‐healing behavior. An 8‐bilayer polyethylenimine/poly(acrylic acid) thin film improves the oxygen barrier of a thick poly(ethylene terephthalate) substrate by more than 1000×. High humidity (symbolized by the thread in this schematic) completely restores the super oxygen barrier of the damaged/cracked coating in just 10 minutes. This fast and high‐efficiency self‐healing is repeatable for at least 10 damaging–healing cycles. Further details can be found in article number https://doi.org/10.1002/marc.201700064 by Y. Song, K. P. Meyers, J. Gerringer, R. K. Ramakrishnan, M. Humood, S. Qin, A. A. Polycarpou, S. Nazarenko* and J. C. Grunlan*.