Crosslinking and stabilization of nanoparticle filled poly(1‐trimethylsilyl‐1‐propyne) nanocomposite membranes for gas separations

Poly(1‐trimethylsilyl‐1‐propyne) (PTMSP) has been crosslinked using 4,4′‐diazidobenzophenone bisazide to improve its chemical and physical stability over time. Crosslinking PTMSP renders it insoluble in good solvents for the uncrosslinked polymer. Gas permeability and fractional free volume decreased as crosslinker content increased, while gas sorption was unaffected by crosslinking. Therefore, the reduction in permeability upon crosslinking PTMSP was due to decrease in diffusion coefficient. Compared with the pure PTMSP membrane, the permeability of the crosslinked membrane is initially reduced for all gases tested due to the crosslinking. By adding nanoparticles (fumed silica, titanium dioxide), the permeability is again increased; permeability reductions due to crosslinking could be offset by adding nanoparticles to the membranes. Increased selectivity is documented for the gas pairs O₂/N₂, H₂/N₂, CO₂/N₂, CO₂/CH and H₂/CH₄ using crosslinking and addition of nanoparticles. Crosslinking is successful in maintaining the permeability and selectivity of PTMSP membranes and PTMSP/filler nanocomposites over time. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and pervaporation performances of fumed‐silica‐filled polydimethylsiloxane–polyamide (PA) composite membranes

Fumed‐silica‐filled polydimethylsiloxane (PDMS)–polyamide (PA) composite membranes were prepared by the introduction of hydrophobic fumed silica into a PDMS skin layer. The cross‐sectional morphology of these filled composite membranes was observed with scanning electron microscopy. Their pervaporation performances were tested with aqueous ethanol solutions at 30, 35, and 40°C. Increasing the amount of the fumed silica resulted in significantly enhanced ethanol permeability of the membranes. When the content of the fumed silica in the PDMS skin layer was 20 wt %, the ethanol permeability increased to nearly twice that of the unfilled PDMS–PA composite membrane. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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     

Synthesis and gas transport properties of novel hyperbranched polyimide–silica hybrid membranes

Physical and gas transport properties of hyperbranched polyimide (HBPI)—silica hybrid membranes prepared with a dianhydride monomer, 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA), and triamine monomers, 1,3,5‐tris(4‐aminophenoxy)triazine (TAPOTZ), and 1,3,5‐tris(4‐aminophenyl)benzene (TAPB), were investigated and compared with those of 6FDA‐TAPOB HBPI system synthesized from 6FDA and 1,3,5‐tris(4‐aminophenoxy)benzene (TAPOB). Glass transition and 5% weight‐loss temperatures of the 6FDA‐based HBPI–silica hybrid membranes were increased with increasing silica content. 6FDA‐TAPOTZ HBPI system, however, showed relatively low 5% weight‐loss temperatures, suggesting thermal instability of triazine‐ring in the TAPOTZ moiety. CO₂/CH₄ permselectivity of the HBPI–silica hybrid membranes were increased with increasing silica content, tending to exceed the upper bound for CO₂/CH₄ separation. This result indicated that free volume elements effective for CO₂/CH₄ separation were created by the incorporation of silica for the HBPI–silica hybrid systems. Especially, 6FDA‐TAPB HBPI system had high gas permeabilities and CO₂/CH₄ separation ability, arising from high fractional free volume and characteristic size and distribution of free volume elements. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Perfluorosulfonic acid—Tetraethoxysilane/polyacrylonitrile (PFSA‐TEOS/PAN) hollow fiber composite membranes prepared for pervaporation dehydration of ethyl acetate–water solutions

Preparation of organic‐inorganic composite membranes and their pervaporation (PV) permeation and separation characteristics for the aqueous solution of ethyl acetate were described. Polyacrylonitrile (PAN) hollow fiber ultrafiltration membrane as support membrane, the mixtures of perfluorosulfonic acid (PFSA) and tetraethoxysilane (TEOS) by the sol‐gel reaction as the coating solution, the PFSA‐TEOS/PAN hollow fiber composite membranes by the different annealing conditions were prepared. The swelling of PFSA in ethyl acetate aqueous solutions was inhibited with addition of TEOS. The PFSA‐TEOS/PAN composite membranes containing up to 30 wt % TEOS in coating solution exhibited high selectivity towards water, then the selectivity decreased and permeation flux increased with increasing the TEOS concentration more than 30 wt %. When the PFSA‐TEOS/PAN composite membranes were annealed, the separation factor increased with increasing annealing temperature and time. Higher annealing temperature and longer annealing time promoted the crosslinking reaction between PFSA and TEOS in PFSA‐TEOS/PAN composite membranes, leading to the enhanced selectivity towards water. For the PFSA/PAN and PFSA‐TEOS/PAN composite membrane with 5 and 30 wt % TEOS annealed at 90°C for 12 h, their PV performance of aqueous solution 98 wt % ethyl acetate were as follows: the separation factors were 30.8, 254 and 496, while their permeation flux were 1430, 513 and 205 g/m² h at 40°C, respectively. In addition, the PV performance of PFSA‐TEOS/PAN composite membranes was investigated at different feed solution temperature and concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Evaluation and fabrication of pore‐size‐tuned silica membranes with tetraethoxydimethyl disiloxane for gas separation

Organic/inorganic hybrid silica membranes were prepared from 1,1,3,3‐tetraethoxy‐1,3‐dimethyl disiloxane (TEDMDS) by the sol‐gel technique with firing at 300–550°C in N₂. TEDMDS‐derived silica membranes showed high H₂ permeance (0.3–1.1 × 10^?6 mol m^?2 s^?1 Pa^?1) with low H₂/N₂ (～10) and high H₂/SF₆ (～1200) perm‐selectivity, confirming successful tuning of micropore sizes larger than TEOS‐derived silica membranes. TEDMDS‐derived silica membranes prepared at 550°C in N₂ increased gas permeances as well as pore sizes after air exposure at 450°C. TEDMDS had an advantage in tuning pore size by the “template” and “spacer” techniques, due to the pyrolysis of methyl groups in air and Si? O? Si bonding, respectively. For pore size evaluation of microporous membranes, normalized Knudsen‐based permeance, which was proposed based on the gas translation model and verified with permeance of zeolite membranes, reveals that pore sizes of TEDMDS membranes were successfully tuned in the range of 0.6–1.0 nm. © 2011 American Institute of Chemical Engineers AIChE J, 2011     

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     

Sulfonated poly(ether sulfone)/silica composite membranes for direct methanol fuel cells

A series of sulfonated poly(ether sulfone) (SPES)/silica composite membranes were prepared by sol–gel method using tetraethylorthosilicate (TEOS) hydrolysis. Physico–chemical properties of the composite membranes were characterized by thermogravimetric analysis (TGA), X‐ray diffraction (XRD), scanning electron microscope–energy dispersive X‐ray (SEM–EDX), and water uptake. Compared to a pure SPES membrane, SiO₂ doping in the membranes led to a higher thermal stability and water uptake. SEM–EDX indicated that SiO₂ particles were uniformly embedded throughout the SPES matrix. Proper silica loadings (below 5 wt %) in the composite membranes helped to inhibit methanol permeation. The permeability coefficient of the composite membrane with 5 wt % SiO₂ was 1.06 × 10^?7 cm²/s, which was lower than that of the SPES and just one tenth of that of Nafion® 112. Although proton conductivity of the composite membranes decreased with increasing silica content, the selectivity (the ratio of proton conductivity and methanol permeability) of the composite membrane with 5 wt % silica loading was higher than that of the SPES and Nafion® 112 membrane. This excellent selectivity of SPES/SiO₂ composite membranes could indicate a potential feasibility as a promising electrolyte for direct methanol fuel cell. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Gas permeation properties of silica membranes with uniform pore sizes derived from polyhedral oligomeric silsesquioxane

The sol‐gel method was applied in the fabrication of homogenous polyhedral oligomeric silsesquioxane (HOMO‐POSS)‐derived silica membranes. Single gas permeation characteristics in a temperature range of 100–500^°C were examined to discuss the effect of silica precursor on amorphous silica networks. HOMO‐POSS‐derived membranes showed a CO₂ permeance of 1.1 × 10^?7 mol m^?2 s^?1 Pa^?1 with a CO₂/CH₄ permeance ratio of 131 at 100^°C, which is a superior CO₂/CH₄ separation performance by comparison with tetraethoxysilane (TEOS)‐derived silica membranes. Normalized Knudsen‐based permeance (NKP) was applied for quantitative evaluation of pore size. HOMO‐POSS‐derived membranes had loose amorphous silica structures compared to TEOS‐derived membranes and pore size was successfully tuned by changing the calcination temperatures. The activation energy for a HOMO‐POSS‐derived membrane fired at 550^°C with a uniform pore size of ～ 0.42 nm increased linearly with the ratio of the kinetic diameter of the gas molecule to the pore diameter, λ (=d_k/d_p), and showed a trend similar to that of DDR‐type zeolite membranes. © 2011 American Institute of Chemical Engineers AIChE J, 58: 1733–1743, 2012     

Organic‐acid‐catalyzed sol–gel route for preparing poly(methyl methacrylate)–silica hybrid materials

In this study, a series of organic–inorganic hybrid sol–gel materials consisting of a poly(methyl methacrylate) (PMMA) matrix and dispersed silica (SiO₂) particles were successfully prepared through an organic‐acid‐catalyzed sol–gel route with N‐methyl‐2‐pyrrolidone as the mixing solvent. The as‐synthesized PMMA–SiO₂ nanocomposites were subsequently characterized with Fourier transform infrared spectroscopy and transmission electron microscopy. The solid phase of organic camphor sulfonic acid was employed to catalyze the hydrolysis and condensation (i.e., sol–gel reactions) of tetraethyl orthosilicate in the PMMA matrix. The formation of the hybrid membranes was beneficial for the physical properties at low SiO₂ loadings, especially for enhanced mechanical strength and gas barrier properties, in comparison with the neat PMMA. The effects of material composition on the thermal stability, thermal conductivity, mechanical strength, molecular permeability, optical clarity, and surface morphology of the as‐prepared hybrid PMMA–SiO₂ nanocomposites in the form of membranes were investigated with thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, gas permeability analysis, ultraviolet–visible transmission spectroscopy, and atomic force microscopy, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

New organic–inorganic hybrid membranes based on sulfonated polyimide/aminopropyltriethoxysilane doping with sulfonated mesoporous silica for direct methanol fuel cells

A series of novel composite methanol‐blocking polymer electrolyte membranes based on sulfonated polyimide (SPI) and aminopropyltriethoxysilane (APTES) doping with sulfonated mesoporous silica (S‐mSiO₂) were prepared by the casting procedure. The microstructure and properties of the resulting hybrid membranes were extensively characterized. The crosslinking networks of amino silica phase together with sulfonated mesoporous silica improved the thermal stability of the hybrid membranes to a certain extent in the second decomposition temperature (250–400°C). The composite membranes doping with sulfonated mesoporous silica (SPI/APTES/S‐mSiO₂) displayed superior comprehensive performance to the SPI and SPI/APTES membranes, in which the homogeneously embedded S‐mSiO₂ provided new pathways for proton conduction, rendered more tortuous pathways as well as greater resistance for methanol crossover. The hybrid membrane with 3 wt % S‐mSiO₂ into SPI/APTES‐4 (SPI/A‐4) exhibited the methanol permeability of 4.68 × 10^?6 cm² s^?1at 25°C and proton conductivity of 0.184 S cm^?1 at 80°C and 100%RH, while SPI/A‐4 membrane had the methanol permeability of 5.16 × 10^?6 cm² s^?1 at 25°C and proton conductivity of 0.172 S cm^?1 at 80°C and 100%RH and Nafion 117 exhibited the values of 8.80 × 10^?6 cm² s^?1 and 0.176 S cm^?1 in the same test conditions, respectively. The hybrid membranes were stable up to about 80°C and demonstrated a higher ratio of proton conductivity to methanol permeability than that of Nafion117. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of inorganic fillers on the structural and transport properties of mixed matrix membranes

In this study, three types of inorganic fillers—fumed nano‐SiO₂, synthesized mesoporous MCM‐41, and zeolite 4A—were incorporated into P84 matrix to prepare mixed matrix membranes. The structural characteristics and transport properties of the resulting composite membranes were investigated. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to observe the dispersion of the filler particles in the composite membranes. TEM micrographs verified that there were no nonselective pores at the particle–polymer interfaces of the composite membranes. Differential scanning calorimetry tests were conducted to investigate the structure of the composite membranes. The glass transition temperatures (T_g) of the P84/MCM‐41 and P84/4A composite membranes were 11 and 30°C, respectively, above that of pure P84 membrane. But, the T_g value for the P84/SiO₂ composite membrane decreased by 22°C when compared with that of the P84 membrane. The density of the composite membrane was also measured to calculate its fractional free volume. Gas permeation tests showed that, among the three synthesized composite membranes, the P84/SiO₂ membrane had the best performance in terms of gas separation. P84/SiO₂ membrane exhibited 20, 63, 59, and 45% increases in the permeabilities of He, O₂, N₂, and CO₂, respectively, above those for the P84 membrane whilst maintaining comparable good selectivities. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Pervaporation dehydration of ethyl acetate aqueous solution using the doubly modified polyvinyl alcohol (PVA) composite membrane

Polyvinyl alcohol–tetraethoxysilane–perfluorosulfonic acid (PVA–TEOS–PFSA) hybrid membrane was prepared by sol–gel method through PVA being modified doubly by PFSA and TEOS. With polyacrylonitrile (PAN) ultrafiltration membrane as a substrate membrane, PVA–TEOS–PFSA/PAN composite membrane was fabricated by dip-coating method for pervaporation (PV) dehydration of ethyl acetate (EAc) aqueous solution. The hybrid membrane was characterized by swelling degree, static contact angle, Fourier transform infrared spectra and scanning electron microscope. Effects of PFSA and TEOS contents in coating solution on PV performance of composite membrane were investigated, respectively. With increasing PFSA content, the permeation flux of composite membrane increased, while the separation factor decreased. Just the opposite, the increase of TEOS content resulted in the decrease in permeation flux and the increase in separation factor. In addition, the PV performances of composite membranes were also investigated at different feed temperatures and water concentrations in feed, respectively. The PVA–TEOS–PFSA/PAN composite membrane, which was prepared from coating with PVA/PFSA mass ratio of 80/20 and TEOS content of 20 wt%, exhibited the permeation flux of 347.9 g m^?2 h^?1 and the separation factor of 2218 for PV dehydration of 2 wt% water of EAc solution at 40 °C.     

CO2‐facilitated transport through poly(N‐vinyl‐γ‐sodium aminobutyrate‐co‐sodium acrylate)/polysulfone composite membranes

Poly(N‐vinyl‐γ‐sodium aminobutyrate‐co‐sodium acrylate) (VSA–SA)/polysulfone (PS) composite membranes were prepared for the separation of CO₂. VSA–SA contained secondary amines and carboxylate ions that could act as carriers for CO₂. At 20°C and 1.06 atm of feed pressure, a VSA–SA/PS composite membrane displayed a pure CO₂ permeation rate of 6.12 × 10^?6 cm³(STP)/cm² s cmHg and a CO₂/CH₄ ideal selectivity of 524.5. In experiments with a mixed gas of 50 vol % CO₂ and 50 vol % CH₄, at 20°C and 1.04 atm of feed pressure, the CO₂ permeation rate was 9.2 × 10^?6 cm³ (STP)/cm² s cmHg, and the selectivity of CO₂/CH₄ was 46.8. Crosslinkages with metal ions were effective for increasing the selectivity. Both the selectivity of CO₂ over CH₄ and the CO₂ permeation rate had a maximum against the carrier concentration. The high CO₂ permeation rate originated from the facilitated transport mechanism, which was confirmed by Fourier transform infrared with attenuated total reflectance techniques. The performance of the membranes prepared in this work had good stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 275–282, 2006     

The morphology and gas‐separation performance of membranes comprising multiwalled carbon nanotubes/polysulfone–Kapton

The development of desirable chemical structures and properties in nanocomposite membranes involve steps that need to be carefully designed and controlled. This study investigates the effect of adding multiwalled nanotubes (MWNT) on a Kapton–polysulfone composite membrane on the separation of various gas pairs. Data from Fourier transform infrared spectroscopy and scanning electron microscopy confirm that some studies on the Kapton–polysulfone blends are miscible on the molecular level. In fact, the results indicate that the chemical structure of the blend components, the Kapton–polysulfone blend compositions, and the carbon nanotubes play important roles in the transport properties of the resulting membranes. The results of gas permeability tests for the synthesized membranes specify that using a higher percentage of polysulfone (PSF) in blends resulted in membranes with higher ideal selectivity and permeability. Although the addition of nanotubes can increase the permeability of gases, it decreases gas pair selectivity. Furthermore, these outcomes suggest that Kapton–PSF membranes with higher PSF are special candidates for CO₂/CH₄ separation compared to CO₂/N₂ and O₂/N₂ separation. High CH₄, CO₂, N₂, and O₂ permeabilities of 0.35, 6.2, 0.34, and 1.15 bar, respectively, are obtained for the developed Kapton–PSF membranes (25/75%) with the highest percentage of carbon nanotubes (8%), whose values are the highest among all the resultant membranes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43839.     

6FDA-TAPOB hyperbranched polyimide-silica hybrids for gas separation membranes

Physical and gas transport properties of hyperbranched polyimide-silica hybrid membranes were investigated. Hyperbranched polyamic acid as a precursor was prepared by polycondensation of a triamine, 1,3,5-tris(4-aminophenoxy) benzene (TAPOB), and a dianhydride, 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), and subsequently modified a part of end groups by 3-aminopropyltrimethoxysilane (APTrMOS). The hyperbranched polyimide-silica hybrid membranes were prepared by sol–gel reaction using the polyamic acid, water, and alkoxysilanes. 5% weight-loss temperature of the hybrid membranes increased with increasing silica content, indicating effective crosslinking at polymer-silica interface mediated by APTrMOS moiety. On the other hand, glass transition temperature of the hybrid membranes prepared with methyltrimethoxysilane (MTMS) showed a minimum value at low silica content region, suggesting insufficient formation of three-dimensional Si O Si network compared to the hybrid membranes prepared with tetramethoxysilane (TMOS). CO₂, O₂, N₂, and CH₄ permeability coefficients of the hybrid membranes increased with increasing silica content. Especially for TMOS/MTMS combined system, the hybrid membranes showed simultaneous enhancements of gas permeability and CO₂/CH₄ separation ability. It was concluded that the 6FDA-TAPOB hyperbranched polyimide-silica hybrid membranes have high thermal stability and excellent CO₂/CH₄ selectivity and are expected to apply to high-performance gas separation membranes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of crosslinking modification on the O2/N2 separation characteristics of poly(phenyl sulfone)/poly(bisphenol A‐co‐4‐nitrophthalic anhydride‐co‐1,3‐phenylenediamine) blend membranes

A series of blend membranes of poly(phenyl sulfone) (PPSU) with poly(bisphenol A‐co‐4‐nitrophthalic anhydride‐co‐1,3‐phenylenediamine) (PBNPI) were prepared through a solution casting method. This was done to examine the permeation characteristics of oxygen and nitrogen. The effect of the PPSU/PBNPI ratio on the membrane structure and O₂/N₂ separation performance were investigated. The results show that the permeability increased remarkably with the content of PPSU, whereas the selectivity decreased slightly. To enhance the selectivity of O₂/N₂, the blend membranes were further crosslinked with a p‐xylylenediamine agent via the immersion method. According to the Fourier transform infrared analysis, the N? H group was formed on the imide group of PBNPI. Therefore, we suggest that during the crosslinking modification, the PBNPI served as a crosslinkable polymer; this resulted in increased crosslinking efficiency with PBNPI content. The high‐resolution X‐ray diffraction and melting point method results show that crosslinking modification improved the selectivity with an acceptable loss in permeability along with increased crystallinity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Hybrid H2-Selective Silica Membranes Prepared by Chemical Vapor Deposition

Hybrid organic-inorganic H₂-selective membranes consisting of single-layer or dual-layers of silica incorporating aromatic groups are deposited on a porous alumina support by chemical vapor deposition (CVD) in an inert atmosphere at high temperature. The single-layer silica membranes, which are made by the simultaneous decomposition of phenyltriethoxysilane (PTES) and tetraethylorthosilicate (TEOS), have good hydrothermal stability at high temperature and a high permeance for hydrogen in the order of 10^?7 mol m^?2 s^?1 Pa^?1 at 873 K, while preventing the passage of other larger molecular gases such as CH₄ and CO₂. The dual-layer silica membranes, which are obtained from the sequential decomposition of PTES and TEOS, exhibit an extremely high permeance for hydrogen of 3.6 × 10^?6 mol m^?2 s^?1 Pa^?1 at 873 K with a permselectivity of hydrogen over methane of 30. A normalized Knudsen based permeance method is applied to measure the pore size of PTES-derived silica membrane on the dual-layer silica membrane before treatment with TEOS. The method indicates that the pore size of the silica network is approximately in the range of 0.50–0.85 nm, which is higher than the characteristic length of pure silica membranes of 0.3 nm, accounting for the high permeance of the hybrid membranes.     

Organic base‐catalyzed sol–gel route to prepare PMMA–silica hybrid materials

A series of sol–gel‐derived organic–inorganic hybrid materials that comprise organic poly(methyl methacrylate) (PMMA) and inorganic silica (SiO₂) was successfully prepared using aniline as an organic base catalyst to catalyze the sol–gel reactions of tetraethylorthosilicate (TEOS). Aniline was adopted not only as a catalyst but also as a dispersing agent during the preparation of the hybrid materials. The as‐prepared hybrid materials were then characterized using transmission electron microscopy, SEM/energy dispersive X‐ray spectroscopy and Fourier transform infrared spectroscopy. The characteristic temperatures (including T_d and T_g) of the hybrid materials slightly exceeded those of neat PMMA, as revealed from thermogravimetric analysis and differential scanning calorimetry evaluations. Studies of the protection against corrosion demonstrated that the hybrid coatings all improved the protection performance on cold‐rolled steel coupons relative to that of neat PMMA coatings, according to measurements of electrochemical corrosion parameters. Additionally, incorporating silica particles into the polymer may effectively reduce the gas permeability of the polymer membrane. Reducing the size of silica particles (at the same silica feeding) further improved the gas barrier property. Optical clarity studies indicated that introducing silica particles into the PMMA matrix may slightly reduce the optical clarity of the films/membranes, as determined by UV‐visible transmission spectroscopy. The contact angle of H₂O of the hybrid films increased with the amount of aniline. Copyright © 2006 Society of Chemical Industry Society of Chemical Industry     

Gas‐sorption properties of 6FDA–durene/1,4‐phenylenediamine (pPDA) and 6FDA–durene/1,3‐phenylenediamine (mPDA) copolyimides

We investigated the sorption isotherms of O₂, N₂, CH₄, and CO₂ gases in 6FDA–durene, 6FDA–1,4‐phenylenediamine (6FDA–pPDA), and 6FDA–1,3‐phenylenediamine (6FDA–mPDA) homopolymers and 6FDA–durene/pPDA and 6FDA–durene/mPDA copolyimides. The solubilities decrease in the order of the inherent condensabilities of the penetrant gases, namely, CO₂, CH₄, O₂, and N₂. The chemical structures of the polymer, as well as the chain packing, determine the sorption properties of these homopolymers and copolymers. The FDA–durene homopolymer has the highest solubility for all gases because of its high specific free volume and fractional free volume. The solubilities of the copolymers increase with an increasing 6FDA–durene content, while the solubility selectivities of the copolymers only vary slightly. The values of K_D (Henry's law constant) and C_H′ (Langmuir site capacity) of these copolyimides decrease with a decreasing 6FDA–durene content. To our surprise, contradictory to the previous known fact that the meta‐connected materials tend to have denser molecular packing than that of the para‐linked materials for homopolymers, the 6FDA–durene/mPDA 80/20 copolymer has higher gas solubilities than those of the 6FDA–durene/pPDA 80/20 copolymer. The random moiety sequence within the copolymer may be the main cause for the abnormal phenomenon. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2187–2193, 2003