Breathable properties of m‐Aramid nanofibrous membrane with high thermal resistance

Electrospinning of m‐aramid in dimethyl acetamide/LiCl solution was investigated to develop thermo‐resistant nanofibrous membranes for breathable waterproof materials. The m‐aramid nanofibers were continuously generated and densely mounted to the membrane without the blockage of the spinning tip during electrospinning. In order to obtain the electrospun m‐aramid nanofibers with different fiber diameters, the polymer concentration in the solution and the spinning distance were varied. Electrospun m‐aramid nanofibrous membranes of various fiber diameters and thicknesses were prepared, and then compared with two commercial expanded polytetrafluoroethylene (ePTFE) membranes with respect to water vapor permeability and pore size. The m‐aramid nanofibrous membrane showed a good water vapor permeability that satisfied the criterion of a breathable membrane, higher than those of the ePTFE porous membranes. Therefore, m‐aramid nanofibrous membrane with thermal and mechanical resistance has great potential for breathable waterproof materials and filters. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41515.     

A highly selective polybenzimidazole‐4,4′‐(hexafluoroisopropylidene)bis(benzoic acid) membrane for high‐temperature hydrogen separation

A polymeric gas separation membrane utilizing polybenzimidazole based on 4,4′‐(hexafluoroisopropylidene)bis(benzoic acid) was prepared. The synthesized membrane has an effective permeating area of 8.3 cm² and a thickness of 30 ± 2 µm. Gas permeation properties of the membrane were determined using H₂, CO₂, CO, and N₂ at temperatures ranging from 24°C to 200°C. The PBI‐HFA membranes not only exhibited excellent H₂ permeability, but it also displayed superior gas separation performance particularly for H₂/N₂ and H₂/CO₂. The permeation parameters for both permeability and selectivity [ and α(H₂/N₂); and α(H₂/CO₂)] obtained for the new material were found to be dependent on trans‐membrane pressure difference as well as temperature, and were found to surpass those reported by Robeson in 2008. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42371.     

A solvent-resistance OTS/PDA/O-PASS composite membrane for water-in-oil emulsions separation

Water-in-oil emulsions separation plays a critical role in industrial wastewater treatment. Membrane technology has attracted much interest in water-in-oil emulsions separation field for its excellent separation performance and facile processing method. However, versatile membrane with better solvent-resistance is still absent in chemical industry. In this work, oxidized polyarylene sulfide sulfone (O-PASS) membrane was severed as substrate, on which a hydrophobicity surface was built via coating of octadecyltrichlorosilane (OTS). And polydopamine (PDA) layer was employed and acted as connector between OTS and O-PASS membrane due to its abundant active hydroxyl group. The maximum water contact angle was 132.6° indicating good hydrophobicity of the membrane. Finally, the OTS/PDA/O-PASS composite membranes showed good separation performance for corrosive emulsions: the rejection and flux were 93.0% and 10.0 L/m²h for water-in-dichloromethane emulsions, and the rejection and flux were 92.3% and 34.6 L/m²h for water-in-n-hexane emulsions. The OTS/PDA/O-PASS composite membrane is a new candidate membrane for water-in-oil emulsions separation. In addition, the superior performance of the composite membrane under harsh environment conditions ensures its usefulness in resistance aggressive solvent.     

Properties of modified polyacrylonitrile membranes prepared by copolymerization with hydrophilic monomers for water–ethanol mixture separation

A new kind of terpolymer membrane was employed to separate a permselective water–alcohol mixture. This membrane was prepared via the copolymerization of acrylonitrile, sodium salt styrene sulfonic acid (SStSA), and hydroxyethyl methacrylate in dimethylsulfoxide with azobisisobutyronitrile as an initiator. The reaction mechanism, resultant structure, and polymer composition were confirmed by IR and elemental analysis. The effects of the feed composition on the polymer composition, mechanical properties, thermal properties, and degree of swelling were investigated. It was found that water permeated through the membrane preferentially in a water/alcohol system. The flux increased with the increase of SStSA, but the separation factor decreased drastically with higher SStSA. For a 50 wt % water–ethanol mixture, a flux of 0.65 kg/m² h and a separation factor of 212 were obtained at 30°C when the membrane containing the highest SStSA content was used. The capacities of the metal ions absorbed by the membranes were investigated in the study. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 244–250, 2003     

Pervaporation separation of water–acetic acid mixtures through NaY zeolite‐incorporated sodium alginate membranes

The pervaporation (PV) separation and swelling behavior of water–acetic acid mixtures were investigated at 30, 40, and 50°C using pure sodium alginate and its zeolite‐incorporated membranes. The effects of zeolite loading and feed composition on the pervaporation performance of the membranes were analyzed. Both the permeation flux and selectivity increased simultaneously with increasing zeolite content in the polymer matrix. This was discussed on the basis of a significant enhancement of hydrophilicity, selective adsorption, and molecular sieving action, including a reduction of pore size of the membrane matrix. The membrane containing 30 mass % of zeolite showed the highest separation selectivity of 42.29 with a flux of 3.80 × 10^?2 kg m^?2 h^?1 at 30°C for 5 mass % of water in the feed. From the temperature dependency of diffusion and permeation data, the Arrhenius activation parameters were estimated. The E_p and E_D values ranged between 72.28 and 78.16, and 70.95 and 77.38 kJ/mol, respectively. The almost equal magnitude obtained in E_p and E_D values signified that both permeation and diffusion contribute equally to the PV process. All the membranes exhibited positive ΔH_s values, suggesting that the heat of sorption is dominated by Henry's mode of sorption. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2101–2109, 2004     

Fabrication of a novel cellulose acetate imprinted membrane assisted with chitosan‐wrapped multi‐walled carbon nanotubes for selective separation of salicylic acid from industrial wastewater

Highly selective cellulose acetate (CA) blend imprinted membranes for salicylic acid (SA) removal were synthesized by phase inversion technique with chitosan as a functional polymer and chitosan‐wrapped multi‐walled carbon nanotubes (CHI‐wrapped MWCNTs) as the additives. The surface and cross‐sectional morphology of membranes were strongly affected by the amount of CHI‐wrapped MWCNTs. As compared to M₁‐MIM, M₂‐MIM, and M₄‐MIM, the M₃‐MIM with 2.0 wt % CHI‐wrapped MWCNTs showed higher membrane flux, faster kinetic, binding capacity and better selectivity for SA. The experimental data of adsorption kinetic were well fitted to the pseudo‐second‐order kinetic model by multiple regression analysis. The M₃‐MIM had the maximum adsorption capacity for SA. The selectivity coefficients of SA to p‐hydroxybenzoic acid (p‐HB) and acetylsalicylic acid (ASA) over M₃‐MIM were 6.3090 and 6.0019, respectively, showing that M₃‐MIM had excellent binding affinity and selectivity for separation of SA from SA‐contained aqueous solution. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42654.     

Fabrication of basalt embedded composite fiber membrane using electrospinning method and response surface methodology

In this study, a novel basalt embedded fiber membranes was prepared by the electrospinning method. The effects of the feed rate, voltage, tip to collector distance, and the basalt content on the prepared composite fiber membranes were investigated and optimized using the response surface method. Four models were built to compare the fibers in terms of deionized water flux (DWF), activated sludge flux, chemical oxygen demand (COD) removal, and porosity of fiber membranes. All the developed models were significant and adequately precise. The maximum flux of DWF was obtained when the voltage was 17.25 kV, the tip to collector distance of 19 cm, and a basalt content in polymer of 1.25%. COD removal decreased at higher voltage values as the feed rate increased. The porosity, pore size, and the contact angle values decreased for basalt embedded fiber membrane. The increases in the basalt percentage in polymer increased the hydrophilicity of the fiber. The flux decline for the basalt embedded fiber membrane was compared with the pristine fiber membrane. The permeate fluxes of pristine and basalt embedded fiber membranes were 42.3 and 59.6 L/m²/h, respectively. The biofouling performances of pristine and basalt embedded fiber membranes were also examined. Irreversible fouling decreased from 42.9% to 8.0%, and reversible fouling increased from 56.5% to 91.1% after modification of the membrane with basalt powder. Scanning electron microscopy with energy dispersive X-ray analysis (SEM–EDX) analysis showed that basalt powder was successfully embedded into polyether sulfone polymer.     

ZIF‐11/Polybenzimidazole composite membrane with improved hydrogen separation performance

Zeolitic imidazolate framework (ZIF)‐11 crystals were prepared by the toluene‐assisted method, and they were incorporated into polysulfone, polyethersulfone, and polybenzimidazole (PBI) matrix to investigate the compatibility. ZIF‐11 had a good connection with PBI matrix as they had the same benzimidazole groups. The evaporation temperature of the membrane formation was studied with two different solvents: N‐methyl‐2‐pyrrolidone (NMP) and N,N‐dimethylacetamide (DMAc). Then, the ZIF‐11/PBI composite membranes prepared using NMP or DMAc as the solvent were characterized and tested by gas separation. Improved H₂ and CO₂ permeabilities with a H₂/CO₂ ideal selectivity of 5.6 were obtained on the 16.1 wt % ZIF‐11/PBI composite membrane prepared with DMAc as the solvent. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41056.     

Synthesis and characterization of fluorene‐based polybenzimidazole copolymer for gas separation

The purpose of this study is to develop new cardo‐polybenzimidazole (CPBI) copolymers containing cardo fluorene, with improved gas permeability, specifically oxygen permeability. The characteristics of these copolymers are investigated by Fourier transform infrared spectroscopy, nuclear magnetic resonance, ¹H and ¹³C), thermo‐gravimetric analysis, and wide‐angle X‐ray diffraction. These membranes fabricated from copolymers have relatively high oxygen diffusion coefficients, determined using gas permeation. In particular, the CPBI‐co91 (synthesized by using the monomers ratio containing dibenzoic acid = 9 : 1) membrane have oxygen permeability coefficient (P_O2) of 10.69 Barrer, theoretical selectivity of 5.4 for oxygen to nitrogen, and O₂ diffusion coefficient of 9.64 × 10^?8 cm²/s. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40521.     

Optimization of coating solution viscosity of hollow fiber‐supported polydimethylsiloxane membrane for CO2/H2 separation

To optimize the CO₂ permeation and CO₂/H₂ separation performance of hollow fiber‐supported polydimethylsiloxane (PDMS) membranes, the effect of the viscosity of the PDMS coating solution on surface morphologies, thickness of PDMS layer, and solution intrusion into surface pores of hollow fiber supports was investigated. Increases in both stirring time and standing time could increase the viscosity of the PDMS solution. The PDMS layer thickness increased when the coating solution viscosity increased, whereas the surface roughness of the PDMS layer markedly decreased and then slightly changed. Moreover, when the stirring time of the PDMS coating solution was 9 min and the standing time was increased from 2 min to 25 min, the CO₂ permeance first decreased, then increased to ～2250 GPU probably due to the decreased intrusion depth, and finally decreased because of the substantially increased thickness of the PDMS layer. However, the CO₂/H₂ selectivity increased to 3.4 with an increase in coating solution viscosity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45765.     

Super-hydrophilic electrospun PVDF/PVA-blended nanofiber membrane for microfiltration with ultrahigh water flux

This work provides a novel approach to improve not only water flux but also fouling resistance of Polyvinylidene fluoride (PVDF) membranes. PVDF/Poly(vinyl alcohol) (PVA)-blended nanofiber membranes were prepared via electrospinning method. The structure and performance of blended nanofiber membranes were characterized by scanning electron microscopy (SEM), atomic force microscope (AFM), attenuated total reflection-Fourier-transform infrared (ATR-FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), contact angle measurement, tensile mechanical measurement, and filtration experiments. These results indicate that PVA was uniformly blend in the PVDF matrix. This blended nanofiber membranes with the ridge-and-valley structure and bicontinuous phase exhibited the hydrophilic performance and super-wettability, which is reflected in a drop of water fully spread within 1.44 s. Filtration experiments showed that the blended nanofiber membranes have ultrahigh flux and low irreversible fouling ratio. In general, this work enhances the possibility of hydrophilic modification of hydrophobic PVDF membranes. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48416.     

Similarly sized protein separation of charge‐selective ethylene‐vinyl alcohol copolymer membrane by grafting dimethylaminoethyl methacrylate

Similarly sized protein separation was investigated using a charge‐selective membrane, which prepared by grafting dimethylaminoethyl methacrylate (DMAEMA) onto ethylene vinyl alcohol copolymer (EVAL) membrane. Bovine serum albumin (BSA) and bovine hemoglobin (BHb) was used as model proteins. P(DMAEMA), the weak cationic polyelectrolyte with ionizable tertiary amine groups, contributed to the charge‐selective separation for BSA and BHb. At pH 6.0, the grafted EVAL membrane surface was positively charged and BSA was negatively charged, while BHb was positively charged. The BSA was adsorbed onto the membrane surface due to electrostatic interaction and the BHb passed through the membrane into the permeate. The charge‐selective behavior resulted in the separation of the similarly sized protein. The maximum separation factors of static adsorption separation for model protein and binary mixture were 32.4 and 37.2, respectively. In the dynamic separation process, the maximum separation factor value was 6.2. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46374.     

Recent advances in membrane hydrophilic modification with plant polyphenol-inspired coatings for enhanced oily emulsion separation

Oily wastewater, especially the emulsified one, causes serious environment pollution and poses threats to the ecosystem and resource recycling. Among various filtration media, porous polymeric membranes have gained tremendous attention in dealing with oily emulsions due to their energy-saving, cost-effective, and highly efficient features. However, to alleviate membrane fouling by oil droplets and ensure high separation efficiency, endowing membrane with superhydrophilicity and underwater superoleophobicity via facile strategy is highly desired. Taking advantages of the mild forming conditions, universality and cost-efficiency, more and more efforts have been devoted to membrane hydrophilic modification by plant polyphenol-inspired coatings in recent years. In this review, we focus on recent advances in constructing plant polyphenol-involved coatings on membrane surface for oil-in-water emulsion separation. The interactions between plant polyphenol and functional materials including amino-functionalized materials, transition metal ions and oxidants via covalent chemistry, coordination chemistry, and rapid oxidation are highlighted. In addition, the impacts of the resultant coating on the wettability, oily emulsion separation performance, and anti-oil fouling performance of the modified membrane are systematically summarized. Finally, future outlooks in membrane surface engineering with plant polyphenol-involved coatings are discussed to further broaden the research related to high-efficiency oil/water separation based on membrane technology.     

Pebax–polydopamine microsphere mixed‐matrix membranes for efficient CO2 separation

Novel facilitated‐transport mixed‐matrix membrane (MMM) were prepared through the incorporation of polydopamine (PDA) microspheres into a poly(amide‐b‐ethylene oxide) (Pebax MH 1657) matrix to separate CO₂–CH₄ gas mixtures. The Pebax–PDA microsphere MMMs were characterized by Fourier transform infrared spectroscopy, scanning electron microcopy, X‐ray diffraction, differential scanning calorimetry, and thermogravimetric analysis. The PDA microspheres acted as an adhesive filler and generated strong interfacial interactions with the polymer matrix; this generated a polymer chain rigidification region near the polymer–filler interface. Polymer chain rigidification usually results in a larger resistance to the transport of gas with a larger molecular diameter and a higher CO₂–CH₄ selectivity. In addition, the surface of PDA microspheres contained larger numbers of amine, imine, and catechol groups; these were beneficial to the improvement of the CO₂ separation performance. Compared with the pristine Pebax membrane, the MMM with a 5 wt % PDA microsphere loading displayed a higher gas permeability and selectivity; their CO₂ permeability and CO₂–CH₄ selectivity were increased by 61 and 60%, respectively, and surpassed the 2008 Robeson upper bound line. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44564.     

Blending PPO‐based molecules with Pebax MH 1657 in membranes for gas separation

This work explores the possibilities to blend block copolymers, i.e., Pebax MH 1657, with a variety of cheap poly(propylene oxide)‐rich molecules which could potentially play a double role in the resulting membranes as dispersing/stabilizing agents in multi‐component casting solutions and as a gas transport medium in the final membrane. These membranes were prepared by solution casting and were characterized by differential scanning calorimetry, scanning electron microscopy, atomic force microscopy, X‐ray diffraction, density measurements, and Fourier transform infrared‐attenuated total reflection, while additive incorporation was also studied with theoretical calculations. Gas permeation measurements showed that this approach resulted in increased permeabilities at the expense of mixed‐gas selectivity. An interpretation of the blend structure was finally made using gas transport models. The compatibility of these additives with the synthesis of selective gas separation membranes may enable a potential double role in membrane synthesis, i.e., as stabilizing agents in membrane synthesis and as a gas transport medium in the final membrane. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46433.     

Preparation of porous polymer materials using water‐in‐oil gel emulsions as templates

Water‐in‐oil gel emulsions consisting of water and n‐butyl acrylate were successfully prepared using N‐3‐hydroxybutylcarbonyl‐l ‐isoleucylaminooctadecane and sorbitan monooleate (Span 80) as gelator and surfactant, respectively. Stable gel emulsions were formed using aqueous phase fractions (APFs) ranging from 10 to 90 vol%. Creaming, flocculation and coalescence were not observed. Low‐temperature polymerization of the gel emulsions with a redox initiator gave the corresponding low‐density, highly porous poly(n‐butyl acrylate)s (PBAs). The microstructures of the PBAs were observed using scanning electron microscopy. All the porous PBAs comprised numerous spherical structures whose sizes could be controlled by adjusting the gel emulsion APF. The densities and porosities of the porous PBAs decreased and increased, respectively, with increasing APF. The absorption capacities of the porous PBAs in organic solvents were studied. The porous PBAs selectively absorbed kerosene from water instantly and the kerosene could then be recovered by physical compression of the PBAs. Further porous polymers were prepared from gel emulsions containing styrene, methyl methacrylate (MMA) or 2‐ethylhexyl acrylate (EHA) as continuous oil phases. The order of absorption capacity and swelling ratio in kerosene was poly(EHA) > PBA ? poly(MMA). Porous copolymers were also prepared from gel emulsions containing a mixture of EHA and MMA as the oil phase. Their absorption and swelling in liquids could be controlled by changing the ratio of EHA and MMA in the gel emulsions. poly(EHA‐co‐MMA) (6:4) was the best polymer when absorption capacity, swelling ratio and durability were simultaneously considered. © 2018 Society of Chemical Industry     

Preparation of bi‐continuous poly(acrylonitrile‐co‐methyl acrylate) microporous membranes by a thermally induced phase separation method

Poly(acrylonitrile‐co‐methyl acrylate) [P(AN‐MA)] flat microfiltration membranes were successfully prepared via the thermally induced phase separation (TIPS) method, by using low polar caprolactam (CPL) and methoxypolyethylene glycol 550 (MPEG 550) as the mixed diluent. In this work, P(AN‐MA) membranes exhibit bi‐continuous networks, porous surfaces, high porosity, and big pore size, when membrane fabricated from a high MPEG 550 content, low P(AN‐MA) concentration, and small cooling rate, it can be dry state preservation and do not need to be impregnated by any solvent. When the ternary system was composed of 15 wt % P(AN‐MA), 12.5 wt % CPL, and 87.5 wt % MPEG 550, formed at 25 °C air bath, membrane has the highest water flux of 4420 L m^?2 h^?1. The obtained P(AN‐AN) membrane displays a high carbonic black ink rejection ranging from 83.7 to 98.5 wt %. Moreover, P(AN‐MA) polymer not only retains the advantages of PAN but also reduces the polar component from 16.2 to 10.77 MPa^0.5. It can be used membrane matrix to obtain pore structure and excellent mechanical property membrane via TIPS. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46173.     

Metastable boundary conditions of water‐in‐oil emulsions in the hydrate formation region

A stepwise pressurization method was proposed for determining the metastable boundary conditions of water‐in‐oil emulsions in the hydrate formation region. The metastable boundary pressures of four water‐in‐n‐octane emulsions in the presence of methane gas were determined at four specified temperatures. The experimental results show that the metastable boundary pressures increase with decreasing water droplet sizes. A thermodynamic model was developed for calculating the metastable boundary conditions of a water‐in‐oil emulsion in which assuming that the collapse of a metastable emulsion requires the formation of a stable hydrate film with a critical thickness on the surfaces of water droplets. The model was used to correlate the experimental data and determine the critical thickness of the hydrate film. It was demonstrated that the calculated results were in good agreement with the experimental data. The determined critical thickness is at nanoscale, ranging from 14 to 40 nm, which decreases with decreasing water droplet sizes. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Chitosan/polyvinylpyrrolidone‐silica hybrid membranes for pervaporation separation of methanol/ethylene glycol azeotrope

Chitosan (CS)/polyvinylpyrrolidone (PVP)‐silica hybrid membranes are prepared to separate the methanol/ethylene glycol (EG) azeotrope. These hybrid membranes are formed in semi‐interpenetrating network structure at the molecular scale via sol‐gel reactions between CS and tetraethoxysilane (TEOS). The physico‐chemical property and morphology of the as‐prepared membranes are investigated in detail. They have lower crystallinity, higher thermal stability, and denser structure than the pristine CS membrane and its blending counterpart. The as‐prepared hybrid membranes demonstrate excellent performances and a great potential in pervaporation separation of methanol/EG. Silica‐hybridization depressed the swelling degree of membranes in the azeotrope, and remarkably enhanced methanol sorption selectivity. The membrane containing 7.77 wt % PVP and 14.52 wt % TEOS has a permeation flux of 0.119 kg m^?2 h^?1 and separation factor of 1899. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013