A highly efficient nanofibrous air filter membrane fabricated using electrospun amphiphilic PVDF-g-POEM double comb copolymer.

Current global emergencies, such as the COVID-19 pandemic and particulate matter (PM) pollution, require urgent protective measures. Nanofibrous air filter membranes that can capture PM0.3 and simultaneously help in preventing the spread of COVID-19 are essential. Therefore, a highly efficient nanofibrous air filter membrane based on amphiphilic poly(vinylidene fluoride)-graft-poly(oxyethylene methacrylate) (PVDF-g-POEM) double comb copolymer was fabricated using atomic transfer radical polymerization (ATRP) and electrospinning. Fourier transform infrared spectroscopy, X-ray diffraction, proton nuclear magnetic resonance, transmission electron microscopy, differential scanning calorimetry, and thermogravimetric analysis were employed to successfully characterize the molecular structure of the fabricated amphiphilic PVDF-g-POEM double comb copolymer. The nanofibrous air filter membrane based on amphiphilic PVDF-g-POEM double comb copolymer achieved a low air resistance of 4.69 mm H2O and a high filtration efficiency of 93.56 % due to enhanced chemical and physical adsorption properties.

Polymer-Infiltrated Metal-Organic Frameworks for Thin-Film Composite Mixed-Matrix Membranes with High Gas Separation Properties.

Thin-film composite mixed-matrix membranes (TFC-MMMs) have potential applications in practical gas separation processes because of their high permeance (gas flux) and gas selectivity. In this study, we fabricated a high-performance TFC-MMM based on a rubbery comb copolymer, i.e., poly(2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl] ethyl methacrylate)-co-poly(oxyethylene methacrylate) (PBE), and metal-organic framework MOF-808 nanoparticles. The rubbery copolymer penetrates through the pores of MOF-808, thereby tuning the pore size. In addition, the rubbery copolymer forms a defect-free interfacial morphology with polymer-infiltrated MOF-808 nanoparticles. Consequently, TFC-MMMs (thickness = 350 nm) can be successfully prepared even with a high loading of MOF-808. As polymer-infiltrated MOF is incorporated into the polymer matrix, the PBE/MOF-808 membrane exhibits a significantly higher CO2 permeance (1069 GPU) and CO2/N2 selectivity (52.7) than that of the pristine PBE membrane (CO2 permeance = 431 GPU and CO2/N2 selectivity = 36.2). Therefore, the approach considered in this study is suitable for fabricating high-performance thin-film composite membranes via polymer infiltration into MOF pores.

Synthesis, Characterization, and CO2/N2 Separation Performance of POEM-g-PAcAm Comb Copolymer Membranes.

Alcohol-soluble comb copolymers were synthesized from rubbery poly(oxyethylene methacrylate) (POEM) and glassy polyacrylamide (PAcAm) via economical and facile free-radical polymerization. The synthesis of comb copolymers was confirmed by Fourier-transform infrared and proton nuclear magnetic resonance spectroscopic studies. The bicontinuous microphase-separated morphology and amorphous structure of comb copolymers were confirmed by wide-angle X-ray scattering, differential scanning calorimetry, and transmission electron microscopy. With increasing POEM content in the comb copolymer, both CO2 permeability and CO2/N2 selectivity gradually increased. A mechanically strong free-standing membrane was obtained at a POEM:PAcAm ratio of 70:30 wt%, in which the CO2 permeability and CO2/N2 selectivity reached 261.7 Barrer (1 Barrer = 10-10 cm3 (STP) cm cm-2 s-1 cmHg-1) and 44, respectively. These values are greater than those of commercially available Pebax and among the highest separation performances reported previously for alcohol-soluble, all-polymeric membranes without porous additives. The high performances were attributed to an effective CO2-philic pathway for the ethylene oxide group in the rubbery POEM segments and prevention of the N2 permeability by glassy PAcAm chains.

Synergy, competition, and the "hanging" polymer layer: Interactions between a neutral amphiphilic 'tardigrade' comb co-polymer with an anionic surfactant at the air-water interface.

Understanding the structure of polymer/surfactant mixtures at the air-water interface is of fundamental importance and also of relevance to a variety of practical applications. Here, the complexation between a neutral 'tardigrade' comb co-polymer (consisting of a hydrophilic polyethylene glycol backbone with hydrophobic polyvinyl acetate grafts, PEG-g-PVAc) with an anionic surfactant (sodium dodecyl sulfate, SDS) at the air-water interface has been studied. Contrast-matched neutron reflectivity (NR) complemented by surface tension measurements allowed elucidation of the interfacial composition and structure of these mixed systems, as well as providing physical insights into the polymer/surfactant interactions at the air-water interface. For both polymer concentrations studied, below and above its critical aggregation concentration, cac, (0.2 cac and 2 cac, corresponding to 0.0002 wt% or 0.013 mM and 0.002 wt% or 0.13 mM respectively), we observed a synergistic cooperative behaviour at low surfactant concentrations with a 1-2 nm mixed interfacial layer; a competitive adsorption behaviour at higher surfactant concentrations was observed where the polymer was depleted from the air-water interface, with an overall interfacial layer thickness ~1.6 nm independent of the polymer concentration. The weakly associated polymer layer "hanging" proximally to the interface, however, played a role in enhancing foam stability, thus was relevant to the detergency efficacy in such polymer/surfactant mixtures in industrial formulations.

Self-Cleaning Membranes from Comb-Shaped Copolymers with Photoresponsive Side Groups.

In this study, we present a novel self-cleaning, photoresponsive membrane that is capable of removing predeposited foulant layers upon changes in surface morphology in response to UV or visible light irradiation while maintaining stable pore size and water permeance. These membranes were prepared by creating thin film composite (TFC) membranes by coating a porous support membrane with a thin layer of novel comb-shaped graft copolymers at two side-chain lengths featuring polyacrylonitrile (PAN) backbones and photoreactive side chains, synthesized by atom transfer radical polymerization (ATRP). Photoregulated control over membrane properties is attained through a light-induced transition, where the side chains switch between a hydrophobic spiropyran (SP) state and a zwitterionic, hydrophilic merocyanine (MC) state. The light-induced switch between the SP and MC forms changes surface hydrophilicity and causes morphological changes on the membrane surface as evidenced by atomic force microscopy (AFM). Before any phototreatment, the as-coated membrane surface comprises mostly hydrophobic SP groups that allow the adsorption of organic solutes such as proteins the membrane surface, reducing flow rate. Once exposed to UV light, conversion of the SP groups to hydrophilic MC groups leads to the release of adsorbed molecules and the full recovery of the initial water flux. A fouled membrane in the more hydrophilic MC form is also capable of self-cleaning upon conversion to the less hydrophilic SP form by visible light irradiation. The self-cleaning behavior observed for this system, where the surface became less hydrophilic but also experienced a morphological change, demonstrates a novel mechanism that has a mechanical component in addition to the changes in hydrophilicity. It is also the first report, to our knowledge, of self-cleaning performance accompanied by a decrease in hydrophilicity.

Well-organized meso-macroporous TiO2/SiO2 film derived from amphiphilic rubbery comb copolymer.

We report the facile synthesis of a well-organized meso-macroporous TiO2/SiO2 thin film with high porosity and good interconnectivity from a binary mixture (i.e., titania precursor and polymer template). Our process is based on self-assembly of the amphiphilic rubbery comb copolymer, poly(dimethylsiloxane)-g-poly(oxyethylene methacrylate) (PDMS-g-POEM) with titanium tetraisopropoxide (TTIP). SiO2 is self-provided by thermal oxidation of PDMS chains during calcination under air. The selective, preferential interaction between TTIP and the hydrophilic POEM chains was responsible for the formation of well-organized TiO2/SiO2 films, as supported by transmission electron microscopy, scanning electron microscopy, X-ray photospectroscopy, and X-ray diffraction analyses. We investigated in detail the effect of precursor content, solvent type, and polymer concentration on thin film morphology. Photodegradation of methyl orange by the well-organized meso-macroporous TiO2/SiO2 film was greater than that of a dense TiO2 film prepared without PDMS-g-POEM as well as a SiO2-etched TiO2 film. These results indicate that the well-organized structure and SiO2 doping of the TiO2 film play a pivotal role in enhancing its photocatalytic properties.