Gas‐transport properties through cation‐exchanged sulfonated polysulfone membranes

Sulfonated polysulfone (SPS) membranes were prepared, and the gas‐transport properties of the resulting ionic polymers were examined. Gas‐transport measurements were made on dense films of these polymers with a continuous flow technique. The sulfonation of polysulfone and the metal‐cation exchange of SPS were confirmed with Fourier transform infrared spectroscopy and electron spectroscopy for chemical analysis. The SPS membranes exchanged with the monovalent metal ions showed higher permeability coefficients than the SPS membranes exchanged with the multivalent metal ions, whereas the selectivities of all the metal‐cation‐exchanged sulfonated polysulfone (MeSPS) membranes for O₂/N₂ and CO₂/N₂ gas pairs were higher than those of SPS membranes. When the MeSPS membranes with metal cations of similar ionic radii were compared, the ideal selectivities of O₂/N₂ and CO₂/N₂ through MeSPS with divalent cations were higher than those through MeSPS with monovalent cations. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2611–2617, 2002     

Mechanical and hydration properties of Nafion®/ceramic nanocomposite membranes produced by mechanical attrition

A solid state method of Nafion®/ceramic nanocomposite membrane preparation is described. A nanocomposite powder from Nafion pellets and a zirconium phosphate ceramic is formed by mechanical milling. The nanoparticles are then consolidated into membrane form by mechanical pressing. Cross‐sectional analysis by scanning electron microscopy indicates that the ceramic particles exist in agglomerates that are evenly dispersed across the membrane. Dynamic mechanical analysis and tensile testing found the membranes to be mechanically equivalent, and in some cases superior, to a commercial extruded membrane. Increasing ceramic content is accompanied by an increase in modulus and shift in the alpha peak to higher temperature. Maximum water uptake of the membranes, as measured by thermal gravimetric analysis, is double that of values reported for the commercial membrane, and complete dehydration is postponed to higher temperature. The proton conductivity of fully hydrated membranes, measured by the 4‐probe method at 60°C in water, is comparable with that of the extruded membrane. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Durability enhancement of Nafion® fuel cell membranes via in situ sol‐gel‐derived titanium dioxide reinforcement

To improve durability of Nafion® membranes, samples were modified via an in situ sol‐gel polymerization of titanium isopropoxide to generate titania quasi‐networks in the polar domains. The incorporated titania reduced water uptake but equivalent weight was essentially unchanged. Fuel cell performance of the modified membrane was inferior to that of the unfilled membrane although these were considered as model studies with focus on mechanical durability. Mechanical analysis of contractile stress buildup during drying from a swollen state in samples clamped at constant length demonstrated considerable reinforcement of Nafion® by the titania structures. Tensile studies showed that at 80°C and 100% relative humidity the dimensional change of the composite membrane is one half and the initial modulus is three times higher than that of the unmodified membrane. During an open circuit voltage decay test the voltage decay rate for the modified membrane is 3.5 times lower than that of control Nafion®. Fluoride emission for the composite is at least an order of magnitude lower than that of the control Nafion® membrane indicating reduced chemical degradation. These model studies indicate that this in situ inorganic modification offers a way to enhance fuel cell membrane durability by reducing both physical and chemical degradation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Hybrid sol–gel membranes of polyacrylonitrile–tetraethoxysilane composites for gas permselectivity

Sol–gel reaction of tetraethoxysilane (TEOS) with fumed silica–polyacrylonitrile (PAN) membrane was carried out to prepare hybrid gas permeable membranes for oxygen and nitrogen separation. Various amounts of fumed silica microparticles with a few μm diameters were compounded in PAN–dimethylsulfoxide (DMSO) solution. After casting of the viscous compound solution on a flat sheet with 100 μm thickness, DMSO was evacuated under vacuum at 80°C. Then, the silica–PAN composite membranes were treated with TEOS for 1 day at 40°C in methanol. Air permeation was examined and compared in silica–PAN composite membranes with and without TEOS treatment. The latter hybrid membranes showed selective oxygen permeability, which depended on amounts of fumed silica in the membrane. The TEOS hybrid PAN membranes have a high ability of oxygen permselectivity for O₂/N₂ gas mixture with α(O₂/N₂) = 13–17, when the silica content was in the range of 13–20 wt %. This is attributed to siloxane network formation in hybrid silica–PAN composite membranes. Favorable siloxane network formation resulted in high oxygen permeability of the hybrid composite membranes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1752–1759, 2003     

Enhanced mechanical flexibility and performance of sodium alginate polymer electrolyte bio‐membrane for application in direct methanol fuel cell

A new membrane was synthesized containing pure alginate, crosslinking agent (CaCl₂), and plasticizer (glycerol). Characterization studies of the membrane were applied to determine the characteristics and morphology using field emission scanning electron microscope, EDX, FTIR, XRD, and atomic force microscopy analysis. The half‐cell performance test of the membrane was verified by several tests, including proton conductivity and methanol permeability. The best membrane had high proton conductivity (10.1 × 10^?3 S cm^?1) and very low methanol permeability (1.984 × 10^?7 cm² s^?1), which consequently resulted in very high selectivity (5.0907 × 10⁴ Ss cm^?3). Glycerol had a positive modification and good influence on the alginate characteristics. Furthermore, the poor mechanical properties of the alginate biopolymer were enhanced by calcium chloride and glycerol inside the polymer. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46666.     

Degradation behaviors of perfluorosulfonic acid polymer electrolyte membranes for polymer electrolyte membrane fuel cells under varied acceleration conditions

The degradation of perfluorosulfonic acid (PFSA) membranes (e.g., Nafion membranes) in polymer electrolyte membrane fuel cells has caused wide widespread concern. However, their degradation behaviors, which lead to the damage of fuel cells, need to be investigated under alternative accelerating environments by the simulation of fuel‐cell operating conditions. Nafion membranes showed a homogeneous degradation behavior during hydrogen peroxide (H₂O₂) aging, whereas a nonhomogeneous (or crack‐type) degradation behavior occurs for Nafion membranes aged in an H₂O₂/Fe²⁺ system (Fenton's reagent), where plenty of the typical microcracks appeared. Interestingly, in the case of nonhomogeneous degradation, the membrane presented a lower fluoride emission rate than that with the homogeneous degradation; this indicates a possible selective attack model of free radicals to both CF₂ and the defect end groups in PFSA membranes. In addition, the effects of the different degradation behaviors on the thermal stability and water uptake of membranes were examined by thermogravimetric analyses. H₂ crossover and single‐fuel‐cell tests were carried out to evaluate the influence of the degradation behaviors on the fuel‐cell performance. These showed that the membrane with a nonhomogeneous degradation behavior had a higher hydrogen crossover and was more destructive than that with a homogeneous behavior. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Methanol permeability and proton conductivity of direct methanol fuel cell membranes based on sulfonated poly(vinyl alcohol)–layered silicate nanocomposites

Layered silicate nanocomposite membranes to be used as electrolyte polymeric membranes in a direct methanol fuel cell were prepared through the mixing of poly(vinyl alcohol) (PVA) with various amounts (2, 4, and 5% w/w) of sodium montmorillonite layered silicate nanoclay. The proton conductivity of the polymer was induced by the reaction of the polymer with sulfosuccinic acid. After that, a solution of the sulfonated PVA–layered silicate nanocomposite was cast into membranes. The proton conductivity and methanol permeability of the membranes were determined with a four-point probe technique and a gas chromatography technique, respectively. In addition, structures of the nanocomposite membranes were characterized with X-ray diffraction, differential scanning calorimetry, and Fourier transform infrared techniques. The mechanical properties of the nanocomposite membranes were also determined with a universal testing machine. From the results, it was found that the water uptake, proton conductivity, and methanol permeability of the membranes initially decreased after a 2% (w/w) concentration of the layered silicate was added. Above this nanoclay loading, the water uptake of the membranes increased again. The results were examined in the light of the interaction between the clay and sulfonated polymer, and the steric effect provided the exfoliation of the nanoclay. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Matrimid‐based carbon tubular membranes: The effect of the polymer composition

In this article, we present a development study of new membrane materials and enhancements of productive membranes to improve the current performance of polymeric membranes. Carbon membranes are a promising material for this matter as they offer an improvement in the gas‐separation performance and exhibit a good combination of permeability and selectivity. Carbon membranes produced from the carbonization of polymeric materials have been reported to be effective for gas separation because of their ability to separate gases with almost similar molecular sizes. In this study, a carbon support membrane was prepared with Matrimid 5218 as a polymeric precursor. The polymer solution was coated on the surface of a tubular support with the dip‐coating method. The polymer tubular membrane was then carbonized under a nitrogen atmosphere with different polymer compositions of 5–18 wt %. The carbonization process was performed at 850°C at a heating rate of 2°C/min. Matrimid‐based carbon tubular membranes were fabricated and characterized in terms of their structural morphology, thermal stability, and gas‐permeation properties with scanning electron microscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, and a pure‐gas‐permeation system, respectively. Pure‐gas‐permeation tests were performed with the pure gases carbon dioxide (CO₂) and N₂ at room temperature at a pressure of 8 bar. On the basis of the results, the highest CO₂/N₂ selectivity of 75.73 was obtained for the carbon membrane prepared with a 15 wt % polymer composition. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42394.     

Preparation and properties of chitosan/acidified attapulgite composite proton exchange membranes for fuel cell applications

A composite proton exchange membrane chitosan (CS)/attapulgite (ATP) was prepared with the organic–inorganic compounding of ATP and CS. The composite membranes were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), and fourier transform infrared spectroscopy (FTIR). The mechanical properties, thermal stability, water uptake, and proton conductivity of the composite membranes were fully investigated. The composite membranes exhibited an enhanced mechanical property, dimensional and thermal stability compared to CS membrane, owing to the interface interaction between ATP and CS. The maximum tensile strength of 53.1 MPa and decomposition temperature of 223.4°C was obtained, respectively. More importantly, the proton conductivity of the composite membrane is also enhanced, the composite membrane with 4 wt% ATP content (CS/ATP-4) exhibited the highest proton conductivity of 26.2 mS cm⁻¹ at 80°C with 100% relative humidity, which is 25.1% higher than pure CS membrane. These results may explore a simple and green strategy to prepare CS-based PEMs, which have a great potential in the application of proton exchange membrane fuel cells.     

Composite membranes of chitosan and titania‐coated carbon nanotubes as promising materials for new proton‐exchange membranes

Titania‐coated carbon nanotubes (TCNTs) were obtained by a simple sol–gel method. Then chitosan/TCNT (CS/TCNT) composite membranes were prepared by stirring chitosan/acetic acid and a TCNT/ethanol suspension. The morphology, thermal and oxidative stabilities, water uptake and proton conductivity, and mechanical properties of CS/TCNT composite membranes were investigated. The CNTs coated with an insulated and hydrophilic titania layer eliminated the risk of electronic short‐circuiting. Moreover, the titania layer enhanced the interaction between TCNTs and chitosan to ensure the homogenous dispersion of TCNTs in the chitosan matrix. The water uptake of CS/TCNT composite membranes was reduced owing to the decrease of the effective number of the ? NH₂ functional groups of chitosan. However, the CS/TCNT composite membranes exhibited better performance than a pure CS membrane in thermal and oxidative stability, proton conductivity, and mechanical properties. These results suggest that CS/TCNT composite membranes are promising materials for new proton‐exchange membranes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43365.     

Nanopaper membranes from chitin–protein composite nanofibers—structure and mechanical properties

Chitin nanofibers may be of interest as a component for nanocomposites. Composite nanofibers are therefore isolated from crab shells in order to characterize structure and analyze property potential. The mechanical properties of the porous nanopaper structures are much superior to regenerated chitin membranes. The nanofiber filtration‐processing route is much more environmentally friendly than for regenerated chitin. Minerals and extractives are removed using HCl and ethanol, respectively, followed by mild NaOH treatment and mechanical homogenization to maintain chitin–protein structure in the nanofibers produced. Atomic force microscope (AFM) and scanning transmission electron microscope (STEM) reveal the structure of chitin–protein composite nanofibers. The presence of protein is confirmed by colorimetric method. Porous nanopaper membranes are prepared by simple filtration in such a way that different nanofiber volume fractions are obtained: 43%, 52%, 68%, and 78%. Moisture sorption isotherms, structural properties, and mechanical properties of membranes are measured and analyzed. The current material is environmentally friendly, the techniques employed for both individualization and membrane preparation are simple and green, and the results are of interest for development of nanomaterials and biocomposites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40121.     

Gas permeability of NH3‐plasma‐treated poly(methyl methacrylate) membranes

The effect of NH₃ plasma treatment on glassy poly(methyl methacrylate) (PMMA) membranes on the diffusion process for penetrant gases (CO₂, O₂, and N₂) was investigated from mean permeability data. The mean permeability coefficient for CO₂ definitely depended on the upstream pressure, whereas those for O₂ and N₂ remained constant regardless of the upstream pressure. For O₂ transport, the permeability increased a little with increasing treatment power, and for N₂ transport, it was not affected by the treatment power. For CO₂ transport, NH₃ plasma treatment promoted the transport of Langmuir mode, presumably through an increased Langmuir capacity constant for CO₂. NH₃ plasma treatment for PMMA membranes resulted in an increase in the separation factor of CO₂ relative to N₂ and in the permeability to CO₂. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1068–1072, 2003     

Structure and gas permeation properties of asymmetric polyimide membranes made by dry–wet phase inversion: Influence of the polyimide molecular weight

In this article, we report the influence of the polyimide molecular weight (1.2 × 10⁵, 2.6 × 10⁵, and 4.1 × 10⁵) on the structure and the gas permeation properties of asymmetric polyimide membranes made by the dry–wet phase‐inversion process. The apparent skin layer thickness of the asymmetric membrane increased with increasing molecular weight, and the thicknesses of the membranes prepared from the three polyimides with a casting polymer solution containing 8.0 wt % butanol were 132, 350, and 739 nm, respectively. That is, the gas permeance in the asymmetric membranes increased with decreasing molecular weight. In contrast, the gas selectivity of the asymmetric membranes did not depend on the skin layer thickness. The solvent evaporation in the dry phase‐inversion process and the nonsolvent diffusion in the dry process were important factors that determined the formation of the asymmetric membrane. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Gas sorption in polymers,molecular sieves,and mixed matrix membranes

Gas sorption has been an underutilized technique for characterizing organic–inorganic hybrid (mixed matrix) membranes. Sorption in these membranes, which are composed of rigid inorganic domains, such as zeolites, dispersed in a polymer matrix, should be approximately additive. Sorption in the neat polymers and zeolites were first measured to demonstrate that sorption in mixed matrix membranes is approximately additive in the absence of other effects. Sorption in mixed matrix membranes was demonstrated to be additive. This extends to cases where sorption in one or both phases of the mixed matrix membrane is affected by an outside contaminant. For example, zeolite 4A is extremely hydrophilic and easily affected by contaminants from processing or from the test gases. Zeolite 4A encapsulated within a polymer matrix can still be affected by these same components, and this causes sorption lower than predicted based on that in unaffected polymers and sieves. This sorption analysis has proven to be very important in understanding the permeabilities and selectivities of mixed matrix membranes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4053–4059, 2007     

Effects of halloysite nanotubes on the morphology and CO2/CH4 separation performance of Pebax/polyetherimide thin-film composite membranes

Enhancing the performance of gas separation membranes is one of the major concerns of membrane researchers. Thus, in this study, poly(ether-block-amide) (Pebax)/polyetherimide (PEI) thin-film composite membranes were prepared and their CO₂/CH₄ gas separation performance was investigated by means of pure and mixed gases permeation tests. To improve the properties of these membranes, halloysite nanotubes (HNT) were added to Pebax layer at different loadings of 0.5, 1, 2, and 5 wt % to form Pebax-HNT/PEI membranes. Scanning electron microscopy, gas sorption, X-ray diffraction, Fourier-transform infrared, and differential scanning calorimetry tests were also performed to investigate the impact of HNT on structure and properties of prepared membranes. Results showed that both CO₂/CH₄ selectivity and CO₂ permeance increased by adding HNT to Pebax layer up to 2 wt %. By increasing HNT loading to 5 wt %, the CO₂/CH₄ selectivity decreased from 32 to 18, while CO₂ permeance increased from 3.25 to 4.2 GPU. Pebax/PEI and Pebax-HNT/PEI membranes containing 2 wt % of HNT were tested using CO₂/CH₄ gas mixtures at different feed CO₂ concentrations and feed pressure of 4 bar. The results showed that with increasing CO₂ concentration from 20 to 80 vol %, CO₂/CH₄ selectivity of Pebax/PEI composite membranes increased by 19%, while, in Pebax-HNT/PEI membrane, CO₂/CH₄ selectivity decreased by 40%. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48860.     

Poly(phenylene oxide)‐based polymer electrolyte membranes for fuel‐cell applications

Poly(phenylene oxide)s were synthesized by the oxidative polymerization of 2‐phenyl phenol (PP) and 2‐allyl phenol (AP). The copolymers were also synthesized with 80 mol % PP and 20 mol % AP and with equimolar monomers. The polymers were characterized. Blends of these polymers with poly(vinylidene fluoride) were prepared. These blend membranes were sulfonated, and their suitability for applications in fuel cells was evaluated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 307–311, 2003     

Facile preparation of ODPA‐ODA type polyetherimide‐based carbon membranes by chemical crosslinking

A chemical crosslinking protocol was developed to prepare carbon membranes from 3,3′,4,4′‐oxydiphthalic dianhydride‐4,4′‐oxydianiline (ODPA–ODA) type polyetherimide on the support of phenolic resin sheets. The effects of support pretreatment, membrane‐coating methods and crosslinking protocols on the resultant carbon membranes were investigated. The microstructure, functional group evolution, thermal stability, mechanics, morphology, and gas separation performance of samples were characterized by XRD, FTIR, TGA, mechanical testing technique, and gas permeation technique, respectively. Results have shown that the chemical crosslinking is more beneficial than the popular thermal crosslinking protocol to fabricate supported carbon membranes for the advantage of simple preparation process. In addition, spin‐coating is superior to drop‐coating in terms of good membrane formation on the support. Under the preferred preparation conditions of crosslinker ethylene glycol usage at 10 wt % and spin‐coating, supported carbon membranes can be obtained with good hydrogen separation performance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44889.     

Novel fixed‐carrier membranes for CO2 separation

A new membrane material having two kinds of CO₂ carriers was obtained. Composite membranes were prepared with the material and support membranes. The facilitated transport of CO₂ through these membranes was performed with pure CH₄ and CO₂ as well as CH₄/CO₂ mixtures containing 50 vol % CO₂. The results show that the membranes possess better CO₂ permeance than that of other fixed carrier membranes reported in the literature. In the measurements with pure gases, at 26°C, 0.013 atm of CO₂ pressure, the membrane with polysulfone support displays a CO₂ permeance of 7.93 × 10^?4 cm³ /cm² s cmHg and CO₂/CH₄ ideal selectivity of 212.1. In the measurements with mixed gases, at 26°C, 0.016 atm of CO₂ partial pressure, the membrane displays a CO₂ permeance of 1.69 × 10^?4 cm³ /cm² s cmHg and CO₂/CH₄ selectivity of 48.1. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2222–2226, 2002