Preparation of novel semihomogeneous cation‐permeable membranes from blends of sulfonated poly(phenylene sulfide) and sulfonated phenolphthalein poly(ether ether ketone)

A series of semihomogeneous cation‐exchange membranes were prepared with binary blend systems, such as sulfonated phenolphthalein poly(ether ether ketone) (SPEEK‐C)/sulfonated poly(phenylene sulfide) (SPPS), or ternary blend systems, such as phenolphthalein poly(ether ether ketone) (PEEK‐C)/SPEEK‐C/SPPS, by solution blending and phase inversion, in which PEEK‐C and SPEEK‐C acted as binders and SPPS powder acted as a polyelectrolyte. Compared with homogeneous and heterogeneous membranes, the prepared semihomogeneous membranes had good electrochemical properties and mechanical strength as well as good dimensional stability. The fundamental properties of the membranes, such as the ion‐exchange capacity, water content, electrical resistance, transport number, diffusion coefficient of the electrolytes, and streaming potential, were largely dependent on both the loading of the SPPS resin and the sulfonation degree of PEEK‐C. Through the adjustment of these two important parameters, a series of semihomogeneous membranes with the desired conductivity and selectivity and the proper water content for different industrial purposes, such as electrodialysis, diffusional dialysis, and proton exchange, were achieved. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1478–1485, 2004     

Effects of heat treatment on the properties of heterogeneous cation permeable membranes from blends of poly(ether sulfone)/sulfonated poly(phenylene sulfide) and phenolphthalein poly(ether ether ketone)/sulfonated poly(phenylene sulfide)

The effects of heat treatment on the properties of membranes prepared from blends of poly(ether sulfone)/sulfonated poly(phenylene sulfide) (SPPS) and phenolphthalein poly(ether ether ketone)/SPPS were studied in detail. The membranes' fundamental properties, including water content, transport number, diffusion coefficient of electrolytes, flux, and so on, changed with both treated temperature and time, whereas the ion‐exchange capacity and electrical resistance remained approximately unchanged. The trends may have been due to the possible structural change resulted from the shrinking of the polymers forming the membranes. Furthermore, the membranes also retained a good physical appearance at temperatures below 220°C. Therefore, a series of heterogeneous membranes with desired conductivities and selectivities as well as proper water contents, which could satisfy different industrial purposes, such as electrodialysis, diffusional dialysis, and proton exchange, were achieved by simple heat treatment for a proper time and at a proper temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 494–499, 2005     

Thermally crosslinkable poly(phenylene sulfide)/poly(ether sulfone)/polymerization of monomer reactant–polyimide blends

The effects of thermally crosslinkable polymerization of monomer reactant–polyimide (POI) on the miscibility, morphology, and crystallization of partially miscible poly(ether sulfone) (PES)/poly(phenylene sulfide) (PPS) blends were investigated with differential scanning calorimetry and scanning electron microscopy. The addition of POI led to a significant reduction in the size of PPS particles, and the interfacial tension between PPS and crosslinked POI was smaller than that between PES and crosslinked POI. During melt blending, crosslinking and grafting reactions of POI with PES and PPS homopolymers were detected; however, the reaction activity of POI with PPS was much higher than that with PES. The crosslinking and grafting reactions were developed further when blends were annealed at higher temperatures. Moreover, POI was an effective nucleation agent of the crystallization of PPS, but crosslinking and grafting hindered the crystallization of PPS. The final effect of POI on the crystallinity of the PPS phase was determined by competition between the two contradictory factors. The crosslinking and grafting reactions between the two components was controlled by the dosage of POI in the blends, the premixing sequence of POI with the two components, the annealing time, and the temperature. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2906–2914, 2002; DOI 10.1002/app.10287     

Sulfonated graphene oxide‐doped proton conductive membranes based on polymer blends of highly sulfonated poly(ether ether ketone) and sulfonated polybenzimidazole

Simultaneously improving the proton conductivity and mechanical properties of a polymer electrolyte membrane is a considerable challenge in commercializing proton exchange membrane fuel cells. In response, we prepared a new series of miscible polymer blends and thus the corresponding crosslinked membranes based on highly sulfonated poly(ether ether ketone) and sulfonated polybenzimidazole. The blended membranes showed more compact structures, due to the acid‐base interactions between the two constituents, and improved mechanical and morphological properties. Further efforts by doping sulfonated graphene oxide (s‐GO) forming composite membranes led to not only significantly elevated proton conductivity and electrochemical performance, but also better mechanical properties. Notably, the composite membrane with the filler content of 15 wt % exhibited a proton conductivity of 0.217 S cm^?1 at 80 °C, and its maximum power density tested by the H₂/air single PEMFC cell at room temperature reached 171 mW cm^?2, almost two and half folds compared with that of the native membrane. As a result, these polymeric membranes provided new options as proton exchange membranes for fuel‐cell applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46547.     

Solution blown sulfonated poly(ether sulfone)/poly(ether sulfone) nanofiber‐Nafion composite membranes for proton exchange membrane fuel cells

A composite membrane of sulfonated poly(ether sulfone) (SPES)/poly(ether sulfone) (PES) nanofiber (NF) mat impregnated with Nafion was prepared and evaluated for its potential use as a proton conductor for proton exchange membrane (PEM) fuel cells. The supporting composite nanofibrous mat was prepared by solution blowing of a mixture of SPES/PES solution. The characteristics of the SPES/PES NF and the composite membrane, such as morphology, thermal stability, and performance of membrane as PEMs, were investigated. The performance of composite membranes was compared with that of Nafion117. The introduction of solution blown NFs to composite membranes modestly improved proton conductivity, water swelling, and methanol permeability. Therefore, composite membrane containing SPES/PES NFs can be considered as a novel PEM for fuel cell applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42572.     

Protein‐grafted carboxylic poly(ether sulfone) membranes: Preparation and characterization

Carboxylic poly(ether sulfone) membranes were prepared by a controlled acetylating and surface‐oxidating reaction followed by the grafting of bovine serum albumin (BSA) and bovine serum fibrinogen (BFG) onto the surfaces. Attenuated total reflection–Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and Micro BCA Protein Assay Kits confirmed that the proteins were successfully grafted onto the surfaces of the membranes. The protein grafting degrees were measured at different time intervals and under different conditions. The modified membranes showed higher hydrophilicity, lower protein (BSA and BFG) adsorption, and suppressed platelet adhesion values. Because of the binding of calcium ions in blood, the modified membranes showed longer plasma recalcification times, activated partial thromboplastin times, prothrombin times, and whole blood clotting times. The results indicate that the blood compatibility of the poly (ether sulfone) membranes could be improved after surface carboxylic modification and protein immobilization and that the modified membranes could be used in the blood purification field. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

pH‐ and temperature‐sensitive microfiltration membranes from blends of poly(vinylidene fluoride)‐graft‐poly(4‐vinylpyridine) and poly(N‐isopropylacrylamide)

The copolymer poly(vinylidene fluoride)‐graft‐poly(4‐vinylpyridine) (PVDF‐g‐P4VP) was prepared through the graft copolymerization of poly(vinylidene fluoride) with 4‐vinylpyridine. Through the blending of the PVDF‐g‐P4VP copolymer with poly(N‐isopropylacrylamide) (PNIPAm) in an N‐methyl‐2‐pyrrolidone solution, PVDF‐g‐P4VP/PNIPAm membranes were fabricated by phase inversion in aqueous media. Elemental analyses indicated that the blend concentration of PNIPAm in the blend membranes increased with an increase in the blend ratio used in the casting solution. Scanning electron microscopy revealed that the membrane surface tended to corrugate at a low PNIPAm concentration and transformed into a smooth morphology at a high PNIPAm concentration. The surface morphology and pore size distribution of the microfiltration membranes could be regulated by the blend concentration of the casting solution, temperature, pH, and ionic strength of the coagulation bath. X‐ray photoelectron spectroscopy revealed a significant enrichment of PNIPAm on the membrane surface. The flux of aqueous solutions through the blend membranes exhibited a pH‐ and temperature‐dependent behavior. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4089–4097, 2006     

Highly selective sulfonated poly(vinylidene fluoride‐co‐hexafluoropropylene)/poly(ether sulfone) blend proton exchange membranes for direct methanol fuel cells

Proton exchange membranes (PEMs) based on blends of poly(ether sulfone) (PES) and sulfonated poly(vinylidene fluoride‐co‐hexafluoropropylene) (sPVdF‐co‐HFP) were prepared successfully. Fabricated blend membranes showed favorable PEM characteristics such as reduced methanol permeability, high selectivity, and improved mechanical integrity. Additionally, these membranes afford comparable proton conductivity, good oxidative stability, moderate ion exchange capacity, and reasonable water uptake. To appraise PEM performance, blend membranes were characterized using techniques such as Fourier transform infrared spectroscopy, AC impedance spectroscopy; atomic force microscopy, and thermogravimetry. Addition of hydrophobic PES confines the swelling of the PEM and increases the ultimate tensile strength of the membrane. Proton conductivities of the blend membranes are about 10^?3 S cm^?1. Methanol permeability of 1.22 × 10^?7cm² s^?1 exhibited by the sPVdF‐co‐HFP/PES10 blend membrane is much lower than that of Nafion‐117. AFM studies divulged that the sPVdF‐co‐HFP/PES blend membranes have nodule like structure, which confirms the presence of hydrophilic domain. The observed results demonstrated that the sPVdF‐co‐HFP/PES blend membranes have promise for possible usage as a PEM in direct methanol fuel cells. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43907.     

Methanol permeability and properties of DMFC membranes based on sulfonated PEEK/PVDF blends

Proton exchange membranes for a direct methanol fuel cell were prepared by blending poly(vinylidene fluoride) [PVDF] with sulfonated poly(etheretherketone) [SPEEK]. The effects of PVDF content on methanol permeability in the blend membranes were investigated by using a diffusion cell and gas chromatography technique. The thermal resistance and proton conductivity of the membranes were also determined by using a thermal gravimetric analysis (TGA) and an impedance analysis technique, respectively. It was found that methanol permeability in the blend membranes decreased with PVDF content at the expense of proton conductivity. The methanol permeability values of the blend membranes are much lower than that of Nafion 115, whereas proton conductivities of the membranes are comparable to that of Nafion. The thermal stability of these blend membranes are above 250°C which is sufficiently high for use in DMFC. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5941–5947, 2006     

Synthesis of a novel sulfonated poly(amide‐imide) and its application in preparation of ultrafiltration PES membranes as a modifier

Sulfonated poly(amide‐imide) (SPAI) copolymer was synthesized, characterized, and blended into poly(ether sulfone) (PES)/dimethylacetamide casting solutions to prepare ultrafiltration membranes. Different weight ratios of the copolymer (0–10 wt %) were mixed in the PES casting solution. The analyses of contact angle and attenuated total reflection‐Fourier transform infrared spectra were used to study hydrophilicity and physicochemical properties of the membrane surface, respectively. The membranes were further characterized by scanning electron microscopy images, ultrafiltration performance, and fouling analyses. The outcomes showed that addition of the SPAI in the PES matrix improved considerably the membranes hydrophilicity. Moreover, with increasing SPAI concentration, the porosity, flux recovery ratio, and pure water permeability of the modified membranes were improved. The pure water flux was increased from 3.6 to 12.4 kg/m² h by increasing 2 wt % SPAI. The antifouling property of the modified PES membranes against bovine serum albumin, tested by a dead‐end filtration setup revealed that bovine serum albumin rejection of the obtained membrane was also enhanced and the antifouling properties of the blending membranes were improved. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46477.     

Montmorillonite‐reinforced sulfonated poly(phthalazinone ether sulfone ketone) nanocomposite proton exchange membranes for direct methanol fuel cells

To produce a composite membrane with high conductivity and low permeability, SPPESK with a degree of sulfonation of 101% was carefully selected for the preparation of montmorillonite (MMT)‐reinforced SPPESK using solution intercalation. The fundamental characteristics such as water uptake, swelling ratio, proton conductivity, methanol permeability, and mechanical properties of the composite membranes were studied. Water uptake is improved when organic MMT (OMMT) loading increase. The composite membranes with CTAB‐MMT loading of 4–0.5% show 0.143–0.150 S cm^?1 proton conductivity at 80°C, which approaches the value of Nafion112. In addition, methanol permeability was decreased to 6.29 × 10^?8 cm² s^?1 by the addition of 6 wt % OMMT. As a result, the SPPESK‐MMT composite membrane is a good candidate for use in direct methanol fuel cells. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39852.     

Synthesis and properties of sulfonated biphenyl poly(ether sulfone) and its mixed‐matrix membranes containing carbon nanotubes for gas separation

We prepared mixed‐matrix membranes (MMMs) composed of carboxylated single‐walled carbon nanotubes (f‐SWCNTs) and a sulfonated biphenyl poly(ether sulfone) (S‐PPSU) polymer matrix. The thermal stability and properties of the pores of the S‐PPSU and f‐SWCNTs were characterized by thermogravimetric analysis and sorption isotherm curves, respectively; these showed that the surface and pore diameter decreased after the introduction of carboxyl groups to the single‐walled carbon nanotubes (SWCNTs), and the pore properties did not restore original values even when the f‐SWCNTs were preheated to 350 °C to remove carboxyl groups. The gas‐separation measurement showed that the MMMs comprised of the S‐PPSU and f‐SWCNTs possessed better gas‐separation properties than the ones composed of biphenyl poly(ether sulfone) and SWCNTs. The permeability for N₂, O₂, He, and CO₂ and the selectivity for O₂/N₂ and O₂/CO₂ were enhanced simultaneously because of the good dispersion of f‐SWCNTs and the improved interaction between the two phases. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44995.     

Crystallization and melting behavior of poly(p‐phenylene sulfide) in blends with poly(ether sulfone)

Crystallization and melting behaviors of poly(p‐phenylene sulfide) (PPS) in blends with poly(ether sulfone) (PES) prepared by melt‐mixing were investigated by differential scanning calorimetry (DSC). The blends showed two glass transition temperatures corresponding to PPS‐ and PES‐rich phases, which increased with increasing PES content, indicating that PPS and PES have some compatibility. The cold crystallization temperature of the blended PPS was a little higher than that of pure PPS. Also, the heats of crystallization and melting of the blended PPS decreased with increasing PES content, indicating that the degree of crystallinity decreased with an increase of PES content. The isothermal crystallization studies revealed that the crystallization of PPS is accelerated by blending PPS with 10 wt % PES and further addition results in the retardation. The Avrami exponent n was about 4 independent on blend composition. The activation energy of crystallization increased by blending with PES. The equilibrium melting point decreased linearly with increasing PES content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1686–1692, 1999     

Effect of thermal crosslinking on the properties of sulfonated poly(phenylene sulfone)s as proton conductive membranes

The synthesis and characterization of crosslinked aromatic polymer membranes with high ion exchange capacity (IEC) values are reported. Through aromatic nucleophilic substitution polycondensation and the subsequent sulfonation reaction, the highly sulfonated polymers SPPSU‐2S and SPPSU‐4S with high molecular weight (M_n = 138–145 kDa, M_w = 200–279 kDa) and well‐defined structures were synthesized. By solution casting and thermal annealing treatment, flexible crosslinked membranes with high solvent insolubility were obtained. The membranes exhibited mechanical and chemical stability as confirmed by dynamic mechanical analysis (DMA) and conductivity measurement. The crosslinked SPPSU‐4S membrane with IEC = 3.20 meq/g showed the highest proton conductivity of 0.163 S/cm at 120 °C, 90% RH, and improved thermal stability compared with its precursor (uncrosslinked) membrane. The results show that simple annealing method could improve significantly membranes properties of highly sulfonated aromatic polymers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44218.     

Proton conductivity and methanol permeability of sulfonated poly(vinyl alcohol) membranes modified by using sulfoacetic acid and poly(acrylic acid)

Sulfonated poly(vinyl alcohol) (PVA) for use as a proton conductive membrane in a direct methanol fuel cell (DMFC) was prepared by reacting the PVA with sulfoacetic acid and poly(acrylic acid). The effects of the amount of sulfoacetic acid and poly(acrylic acid) on proton conductivity, methanol permeability, water uptake, and ion exchange capacity (IEC) of the sulfonated PVA membranes were investigated by using impedance analysis, gas chromatography, gravimetric analysis, and titration techniques, respectively. The water uptake of the membranes decreased with the amount of the sulfoacetic acid and the amount of poly(acrylic acid) used. The proton conductivity and the IEC values of the membranes initially increased and then decreased with the amount of the sulfoacetic acid. The methanol permeability of the sulfonated PVA membranes decreased continuously with the amount of the sulfoacetic acid. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Ion‐exchange membranes prepared by blending sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide) with polybenzimidazole

New ion‐exchange acid/base‐blend (SPPO/PBI) membranes were prepared by mixing N,N‐dimethylacetamide (DMA) solutions of sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (SPPO) in the ammonium form and of polybenzimidazole (PBI), casting the solution as a thin film, evaporating the solvent, and treating the membrane with aqueous hydrochloric acid. The resulting membranes were found insoluble in DMA. The preliminary tests of the membranes were carried out in an H₂/O₂ fuel cell at room temperature. Their performance in the fuel cell increased with the increase in the concentration of SPPO sulfonic acid groups in the blend, but the membranes formed with the highly sulfonated SPPO alone or predominanting, which swelled excessively in water, did not give reproducible results, and their performance was usually inferior to that of the membranes having an optimum ratio of both components. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1118–1127, 2002     

Polysulfone/poly(ether sulfone) blended membranes for CO2 separation

Polymer blending as a modification technique is a useful approach for augmenting the gas‐separation and permeation properties of polymeric membranes. Polysulfone (PSF)/poly(ether sulfone) (PES) blend membranes with different blend ratios were synthesized by conventional solution casting and solvent evaporation technique. The synthesized membranes were characterized for miscibility, morphology, thermal stability, and spectral properties by differential scanning calorimetry (DSC), field emission scanning electron microscopy, thermogravimetric analysis, and Fourier transform infrared (FTIR) spectroscopy, respectively. The permeation of pure CO₂ and CH₄ gases was recorded at a feed pressure of 2–10 bar. The polymer blends were miscible in all of the compositions, as shown by DSC analysis, and molecular interaction between the two polymers was observed by FTIR analysis. The thermal stability of the blend membranes was found to be an additive property and a function of the blend composition. The morphology of the blend membranes was dense and homogeneous with no phase separation. Gas‐permeability studies revealed that the ideal selectivity was improved by 65% with the addition of the PES polymer in the PSF matrix. The synthesized PSF/PES blend membranes provided an optimized performance with a good combination of permeability, selectivity and thermal stability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42946.     

A simple postsulfonation of poly(arylene ether sulfone) Radel® R

Commercially available Radel® R, a poorly acid resistant biphenol‐based poly(arylene ether sulfone), was successfully sulfonated by a simple and rapid postsulfonation reaction using oleum as the sulfonating agent. Polymer degradation due to contact with acid could easily be minimized by adjusting reaction conditions. The suitable reaction conditions, when the 1 : 3 molar ratio of the polymer to the sulfonating agent was used, were: 10% of oleum in chloroform, 10% concentration of Radel® R in chloroform, and temperature between 0 and 50°C. Under these conditions, the reaction was complete within 45 min. Thermal properties, degradation characteristics and the viscosity of the postsulfonated polymer are reported. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Microporous carbon membranes from sulfonated poly(phthalazinone ether sulfone ketone): Preparation,characterization, and gas permeation

Microporous carbon membranes (MCM) were prepared from sulfonated poly(phthalazinone ether sulfone ketone) (SPPESK) through stabilization and pyrolysis processes. The effects of sulfonation degree (SD) of SPPESK and the stabilization temperature on the structure and gas permeation of MCM were investigated. The thermal decomposition behavior of SPPESK was studied by thermogravimetric analysis‐mass spectrometry. The evolution of functional groups on membrane surface was detected by Fourier transform infrared spectroscopy during heat treatment. The resultant MCM was characterized by X‐ray diffraction, Raman spectroscopy, nitrogen adsorption technique and pure gas permeation test (including the gases of H₂, CO₂, O₂, and N₂), respectively. The results have shown that the removal of sulfonic acid groups in SPPESK leads to a weight loss stage in the temperature range of 250–450°C. The surface area, maximum pore volume, and gas permeability of MCM increase with the SD increasing from 59 to 75%, together with the reduction of selectivity. Similarly, the gas permeability of MCM also increases with elevating the stabilization temperature from 350 to 400°C at the loss of selectivity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal studies of blends of poly(phenylene sulfide) (PPS) with poly(phenylene sulfide sulfone) (PPSS) and with poly(phenylene sulfide ether) (PPSE)

The miscibilities of poly(phenylene) sulfide/poly(phenylene sulfide sulfone) (PPS/PPSS) and poly(phenylene) sulfide/poly(phenylene sulfide ether) (PPS/PPSE) blends were invesigated in terms of shifts of glass transition temperatures T_g of pure PPS, PPSS, a dn PPSE. The crystallization kinetics of PPS/PPSS blends was also studied as a function of molar composition. The PPS/PPSS and PPS/PPSE blends are respectively partially and fully miscible. PPSE shows a plasticizing effect on PPS as does PPS on PPSS, which necessarily improves te processibility in the respective systems. We can control T_g and melting temperature T_m of PPS by varying amounts of PPSE in blends. The melt crystallization temperature T_mc of PPS/PPSE blends was higher than that of the PPSE homopolymer. Therefore, these blends require shorter cycle times in processing than pure PPSE. The overall rate of crystallization for PPS/PPSS blends follows the Avrami equation with an exponent ?2. The maximal rate of crystallization for PPS/PPSS blends occurs at a temperatre higher by 10°C than that for PPS, while the crystallization half time t_1/2 is 4 times shorter. In the cold crystallization range, crystal growth rates increase and Avrami exponents decrease significantly as the temperature increases.