Chelate membrane from poly(vinyl alcohol)/poly(N-salicylidene allyl amine) blend. III. Effect of Mn(II) and Co(II) on oxygen/nitrogen separation

Facilitated transport of oxygen through Co(II) and Mn(II) chelate membranes from poly(vinyl alcohol)/poly(N-salicylidene allyl amine) was investigated. As the membranes became chelated, oxygen diffusivity decreased and the solubility toward oxygen was enhanced. The oxygen permeability of the base poly(vinyl alcohol)/poly(N-salicylidene allyl amine) membrane was 2.6 × 10⁻³ cm³(STP)cm/cm² cm Hg sec (barrer), and the selectivity toward oxygen was 2.2. As Co(II) was introduced into this membrane, oxygen permeability and oxygen selectivity increased to 2.82 × 10⁻² barrer and 8.5, respectively. The permeability and selectivity of Mn(II) chelate membrane were 3.28 × 10⁻² and 5, respectively. A major reason for the increased selectivity was the enhanced solubility of oxygen in chelate membrane upon chelation. The transport behavior of chelate membranes followed a dual-mode transport, and the parameters were estimated and compared between Co(II) and Mn(II) membranes. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 483–490, 1997     

Preparation and characterization of sulfonated block‐graft copolyimide/sulfonated polybenzimidazole blend membranes for fuel cell application

Polymer electrolyte blend membranes composed of sulfonated block‐graft polyimide (S‐bg‐PI) and sulfonated polybenzimidazole (sPBI) were prepared and characterized. The proton conductivity and oxygen permeability coefficient of the novel blend membrane S‐bg‐PI/sPBI (7 wt%) were 0.38 S cm^?1 at 90 °C and 98% relative humidity and 7.2 × 10^?13 cm³(STP) cm (cm² s cmHg)^?1 at 35 °C and 76 cmHg, respectively, while those of Nafion^® were 0.15 S cm^?1 and 1.1 × 10^?10 cm³(STP) cm (cm² s cmHg)^?1 under the same conditions. The apparent (proton/oxygen transport) selectivity calculated from the proton conductivity and the oxygen permeability coefficient in the S‐bg‐PI/sPBI (7 wt%) membrane was 300 times larger than that determined in the Nafion membrane. Besides, the excellent gas barrier properties based on an acid ? base interaction in the blend membranes are expected to suppress the generation of hydrogen peroxide and reactive oxygen species, which will degrade fuel cells during operation. The excellent proton conductivity and gas barrier properties of the novel membranes promise their application for future fuel cell membranes. © 2015 Society of Chemical Industry     

Preparation of vinylpyridine irradiation-grafted poly(4-methyl-pentene-1) membrane for oxygen enrichment

By adjusting the casting conditions, the oxygen permeabilities of poly(4-methyl-pentene-1) (TPX) membranes prepared in this study are in the range of 2.91–7.14 × 10^?9 cm³(STP) cm/cm² s cm Hg and permeability ratio of O₂/N₂ between 2.7 and 4.4. To increase O₂? N₂ selectivity, the vinylpyridine is γ-ray irradiation-grafted onto the substrate–TPX membrane. The factors that affect the structure and performance of the grafted membrane considered are: tightness of substrate, kind of solvent for grafting monomers, irradiation conditions, total irradiation dose, and operating temperature and pressure. The O₂/N₂ selectivities of grafted TPX membranes are significantly improved comparing to that of nongrafted TPX membranes. For example, an O₂ permeability of 35.6 × 10^?10 cm³(STP) cm/cm² s cm Hg and an O₂/N₂ permeability ratio of 7.5 for the grafted membrane can be obtained.     

Preparation of composite membranes with polyimides and poly (amide-imide)s skin via interfacial condensation for air separation

Composite membranes were prepared by the interfacial condensation of water-soluble diamines with an organic solvent (dichloromethane)-soluble dicarbo-methoxy terephthaloyl chloride or carbomethoxy terephthaloyl chloride on top of a porous aluminum oxide support. The morphology of skin on the composite membranes is different in the two different procedures. The polyimide composite membranes with 40-times coatings provide a high gas permeation rate of oxygen and good permselectivity [α(O₂/N₂)]. The composite membrane with the polyimides skin at 40-times coatings had a gas permeation rate of oxygen range from 83 × 10⁻⁵ to 130 × 10⁻⁵ cm³(STP) s⁻¹ cm⁻² cmHg⁻¹, and a permselectivity [α(O₂/N₂)] range of 3.57 to 5.60. The composite membrane with poly (amide-imide)s skin at 40-times coatings had a gas permeation rate of oxygen range from 102 × 10⁻⁵ to 146 × 10⁻⁵ cm³(STP) s⁻¹ cm⁻² cmHg⁻¹, and the permselectivity (α(O₂/N₂)) range from 3.20 to 4.96.     

Gas transport in poly(alkoxyphosphazenes)

The permeability of four structurally related poly(alkoxyphosphazenes), three isomers of poly(dibutoxyphosphazenes) (PBuP), and poly(di-neopentyloxyphosphazene) (Pneo-PeP), to 13 gases has been determined by the time-lag method. Systematic variations in chemical structure have shown a large effect of side chains on permeabilities and permselectivities. The permeability of poly(di-n-butoxyphosphazene) (Pn-BuP) is of the order of 10^?8 cm³ (STP) cm/(cm² s cmHg) for many gases, and the value for a large gas is higher than that for a smaller one. For small gases such as He and H₂, poly(di-sec-butoxyphosphazene) (Ps-BuP) is as permeable as Pn-BuP, but its diffusivities for larger gases such as Xe and C₃H₈ are about one order lower than those of Pn-BuP. While the permselectivity of Pn-BuP is determined by the solubility, that of Ps-BuP depends on both the diffusivity and solubility factors. The property of poly(diisobutoxyphosphazene) (Pi-BuP) is intermediate between them. These polymers are constitutionally identical, and the only difference is the arrangements of carbons in the side groups. As the side chains become bulky, the permeability decreases, whereas the permselectivity increases. Further decreases of diffusivity and then permeability are observed for Pneo-PeP, whose side groups have one more methyl group than does Pi-BuP. But the solubility data are not much different from other three polymers and the diffusivity factor becomes more significant in permselectivity. The diffusivity depends on the polymer structure much more than does the solubility. The relationships between chemical structure and gas diffusivity and solubility are discussed.     

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     

Selective Permeation of Ammonia and Carbon Dioxide by Novel Membranes

Abstract

Experimental results are presented on membranes of novel composition which selectively permeate ammonia and carbon dioxide from mixtures containing hydrogen. The CO₂-selective membrane, which consists of a thin liquid film of the salt hydrate tetramethylammonium fluoride tetrahydrate, exhibits a CO₂ permeance of 4-1 × 10^?5 cm³/cm²·s·cmHg with selectivity, α(CO₂/H₂), ranging from 360-30. The NH₃-selective membrane, poly(vinylammonium thiocyanate), displays a high NH₃ permeance, 5?20 × 10^?5 cm³/cm²·s·cmHg, with α(NH₃/N₂) as high as 3600 and α(NH₃/H₂) as high as 6000. Such membranes, which retain H₂ at pressure in the feed stream, may offer new opportunities in the design of separation processes.     

Actual air separation through poly(aniline‐co‐toluidine)/ethylcellulose blend thin‐film composite membranes

Several multilayer thin‐film composite membranes were fabricated of ethylcellulose (EC) and poly(aniline‐co‐ortho‐toluidine) or poly(ortho‐toluidine) blend as selective thin films and three ultrafiltration membranes with a 10‐ to 45‐nm pore size and 100‐ to 200‐μm thickness as porous supports. The relationships between the actual air‐separation performance through the composite membranes and layer number, composition, casting solution concentration of the thin selective film are discussed. The oxygen‐enriched air (OEA) flux through the composite membranes increases steadily with increasing operational temperature and pressure. The oxygen concentration enriched by the composite membranes appears to decrease with operating temperature, but increases with operating pressure. The actual air‐separation property through the composite membranes seems to remain nearly constant for at least 320 days. The respective highest OEA flux, oxygen flux, and oxygen concentration, respectively, were found to be 4.78 × 10⁻⁵ cm³ (STP)/s · cm², 2.2 × 10⁻⁵ cm³ (STP)/s · cm², and 46% across EC/poly(o‐toluidine) (80/20) blend monolayer thin‐film composite membranes in a single step at 20°C and 650 kPa operating pressure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 458–463, 2000     

Effects of supercritical carbon dioxide treatment conditions on the gas separation properties of polydimethylsiloxane hybrid membrane materials for air purification

A siloxane/polydimethylsiloxane (PDMS) hybrid membrane containing fluorinated side chains was prepared by a convenient and mild sol–gel process and a crosslinking reaction. The effects of the supercritical carbon dioxide (scCO₂) conditions (i.e., treatment temperature, treatment time, and treatment pressure) on the permeation properties of fluorinated PDMS containing hybrid membrane were investigated. The chemical structure, microstructure, and physical performance of the membranes treated before and after were also discussed. The chemical structure of the PDMS membranes did not change with the scCO₂ treatment conditions. The membranes still retained better membrane‐forming abilities, higher permeability, and selectivity than normal PDMS membranes. Compared to those of the membrane with membrane formation after scCO₂ treatment, the oxygen permeability coefficient and oxygen/nitrogen separation factor of the membrane with scCO₂ treatment before membrane formation were higher and were up to 7.11 × 10^?8 cm³ (STP) cm/(cm² s cmHg) and 3.27, respectively. The permeation properties of the hybrid membrane were obviously higher than those of Robeson's upper bound. The high air‐purification performance of the hybrid membrane may have been due to the introduction of fluorine atoms into PDMS membrane, and the increase in free volume resulted from the plasticizing function of the scCO₂ treatment. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Gas permeation properties of a composite membrane filled with poly(ethylene oxide) into a porous membrane

The permeability coefficients of O₂, N₂, and CO₂ gases at 25°C were examined for composite membranes that were prepared by filling poly(ethylene oxide)(PEO) with different molecular weights into a porous membrane. The permeability coefficients of O₂, N₂, and CO₂ were 2 × 10⁻¹⁰ – 4 × 10⁻¹⁰, 5 × 10⁻¹¹ – 9.5 × 10⁻¹¹, and 6 × 10⁻¹⁰ – 1 × 10⁻⁹ (cm³ STPcm/cm² s cmHg), respectively. The higher permeability coefficients of CO₂ are explained in terms of high solubility of CO₂ in filled PEO. The permeability coefficient of CO₂ was affected by the degree of crystallinity of PEO in the composite. On the other hand, there was little effect of crystallinity on O₂ and N₂ permeability coefficients. Some probable relationships between selectivities of O₂ to N₂ and CO₂ to N₂ and the degree of crystallinity of PEO were observed. The CO₂ gas permeability coefficients of the composite membrane for PEO50000 (M_w = 5 × 10⁴) showed a marked change due to melting or crystallization of PEO. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2733–2738, 1999     

Gas permeation properties of new type asymmetric membranes

We have developed a new type of asymmetric membranes having a homogeneous hyperthin skin layer, which was used as a polyimide synthesized by 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 2,2-bis(4-amino phenyl) hexafluoro-propane (BAAF). The skin layer thicknesses of the 6FDA-BAAF polyimide asymmetric membranes were 40–60 nm, and the porosity was 10^-6% when a defect size was assumed as 5 nm. The permselectivity of 6FDA-BAAF polyimide asymmetric membranes after silicone coating had α of 40 for CO₂/CH₄ and a flux of 1.0 [Nm³/m²-h-atm] (=3.7 × 10⁻⁴ [cm³(STP)/cm² s cmHg]) for CO₂, α of 4.3 for O₂/N₂ and a flux of 2.0 × 10⁻¹ [Nm³/m²/h/atm] (=7.1 × 10⁻⁵ [cm³(STP)/cm²s cmHg]) for O₂. These values were constant for large-scale manufacturing. © 1996 John Wiley & Sons, Inc.     

Novel membranes based on poly(5‐(methacrylamido)tetrazole) and sulfonated polysulfone for proton exchange membrane fuel cells

Proton‐exchange membrane fuel cells (PEMFC)s are increasingly regarded as promising environmentally benign power sources. Heterocyclic molecules are commonly used in the proton conducting membranes as dopant or polymer side group due to their high proton transfer ability. In this study, 5‐(methacrylamido)tetrazole monomer, prepared by the reaction of methacryloyl chloride with 5‐aminotetrazole, was polymerized via conventional free radical mechanism to achieve poly(5‐(methacrylamido)tetrazole) homopolymer. Novel composite membranes, SPSU‐PMTetX, were successfully produced by incorporating sulfonated polysulfone (SPSU) into poly(5‐(methacrylamido)tetrazole) (PMTet). The sulfonation of polysulfone was performed with trimethylsilyl chlorosulfonate and high degree of sulfonation (140%) was obtained. The homopolymers and composite membranes have been characterized by NMR, FTIR, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). ¹H‐NMR and FTIR confirmed the sulfonation of PSU and the ionic interaction between sulfonic acid and poly(5‐(methacrylamido)tetrazole) units. TGA showed that the polymer electrolyte membranes are thermally stable up to ～190°C. Scanning electron microscopy analysis indicated the homogeneity of the membranes. This result was also supported by the appearance of a single T_g in the DSC curves of the blends. Water uptake and proton conductivity measurements were, as well, carried out. Methanol permeability measurements showed that the composite membranes have similar methanol permeability values with Nafion 112. The maximum proton conductivity of anhydrous SPSU‐PMTet0.5 at 150°C was determined as 2.2 × 10^?6 S cm^?1 while in humidified conditions at 20°C a value of 6 × 10^?3 S cm^?1 was found for SPSU‐PMTet2. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40107.     

Alkaline polymer electrolyte membranes from quaternized poly(phthalazinone ether ketone) for direct methanol fuel cell

Quaternized poly(phthalazinone ether ketone)s (QPPEK)s were synthesized by the chloromethylation and quaternization of poly(phthalazinone ether ketone) (PPEK) with chloromethyl methyl ether in 98% concentrated sulfuric acid and following trimethylamine. The presence of ? CH₂Cl groups in chloromethylated PPEK was confirmed by ¹H‐NMR. An alkaline QPPEK membrane was prepared and its thermal and mechanical properties were tested. The alkaline QPPEK membrane had a methanol permeability 6.57 × 10^?7 cm²/s and the highest anion conductivity 1.14 × 10^?2 S/cm. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Gas permeation through water‐swollen polysaccharide/poly(vinyl alcohol) membranes

The effect of Na‐alginate content on the gas permeation properties of water‐swollen membranes prepared by varying Na‐alginate and poly(vinyl alcohol) (PVA) content in membranes was investigated. The influences of water content and crystallinity of the membranes on the gas permeation performance of the water‐swollen membranes were studied. The gas permeation rate and selectivity of Na‐alginate/PVA water‐swollen membranes were compared with those of the dry membranes. The permeation rates of nitrogen and carbon dioxide through water‐swollen membranes were in the range of 0.4–7.6 × 10^?7 to 3.7–8.5 × 10^?6 cm³ (STP)/cm² s^?1 cmHg^?1, which were 10,000 times higher than those of dry‐state membranes. The permeation rates of mixture gases through water‐swollen Na‐alginate/PVA membranes were found to increase exponentially with the increase of Na‐alginate content, whereas carbon dioxide concentration in permeates was decreased linearly. It was found that the gas permeance of the water‐swollen membranes increased with increasing the Na‐alginate content in the membrane. Gas permeation rates of the water‐swollen Na‐alginate/PVA membranes increased with increasing the water content in the membrane and decreasing the crystallinity of the membrane. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3225–3232, 2004     

Solute diffusion in swollen membranes. Part V: Solute diffusion in poly(2-hydroxyethyl methacrylate)

Studies with phenylalanine diffusing in well-characterized poly(2-hydroxyethyl methacrylate) (PHEMA) membranes swollen in water at 37°C were conducted. Films were prepared by reaction of HEMA monomer with the cross-linking agent ethylene glycol dimethacrylate (EGDMA) at cross-linking ratios, X, of 0.005, 0.01, 0.0128, 0.025, and 0.050 mole EGDMA/mole HEMA in the presence of 40 weight percent water at 60°C for 12 hours. These membranes were subsequently swollen in water at 37°C and their structure analyzed using a modified Gaussian distribution equation of swelling. The calculated values of M?_c varied between 1,700 and 3,425 daltons, which corresponded to a correlation length of the mesh size, egr, of 24 to 35 A. The phenylalanine solute diffusion coefficient varied from 0.17 × 10^?6 to 0.97 × 10^?6 cm²/s, and depended on the aforementioned structural parameters of the membranes.     

Suppression of radiation‐induced oxidation of polymers by sputtered silicon oxide coating

Oxygen barrier coating on polymers was attempted to obtain polymeric composite materials with improved radiation resistance. Silicon oxide (SiO_1.6) films ranging from 120 to 240 nm thick were formed on polypropylene (PP) and polyethylene (PE) by radio frequency (RF) magnetron sputtering. Oxygen permeability after SiO_1.6 deposition was reduced significantly in all samples studied, indicating that silicon oxide is a useful gas barrier. The oxygen permeability coefficient of deposited films for PP was 1.7–2.2 × 10^?14 cm³‐cm/cm²/s/cmHg and that for PE was 2.8–4.8 × 10^?13 cm³‐cm/cm²/s/cmHg. We studied the effect of such films on the radiation resistance of polymers in the presence of oxygen by microscopic infrared (IR) absorption spectroscopy. Silicon oxide films 180 nm thick were deposited on the surfaces of PP and PE, and the formation of carbonyl groups after irradiation in air was measured as a function of depth from the surface. Results compared with those for uncoated PE and PP showed that the radiation‐induced polymer oxidation is dramatically suppressed by silicon oxide coating. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 186–190, 2002     

Characterization of pressure-sensitive adhesives. II. Water vapor permeation studies

The permeability of water vapor in a composite film [a Mylar (trademark of DuPont, Inc.) film coated with a pressure sensitive adhesive on both sides] and a Mylar film (type D) have been determined at 23°C. The water vapor permeability in the pressure sensitive adhesive, Flexbond 150 (a trademark of Air Products and Chemicals), and the Mylar film have been found to be 3.23 × 10^?7 and 2.30 × 10^?8 cm³ (STP) cm · cm^?2 · s^?1 · (cm Hg)^?1, respectively, at 23°C.     

TPX/siloxane blend membrane for oxygen enrichment

The effects of composition, molecular weight, and milling temperature on homogeneity, gas permeability, selectivity of oxygen/nitrogen, and mechanical strength of the TPX/siloxane blend membranes were studied. By adjusting the blending conditions and hence controlling the homogeneity, the gas permeability of TPX membrane was significantly improved without loss of oxygen/nitrogen selectivity. The oxygen permeability of 1.57 × 10^?8 cm³ (STP) cm/cm² s cm Hg and the oxygen/nitrogen permeation ratio of 6.92 can be obtained under the condition of TPX (MX-001)/siloxane (75,000 MW) = 9/1 at 65°C milling temperature. This membrane possesses 133 kg/cm² tensile strength and 92% elongation. The morphology of the blend membranes was studied.     

A quaternized poly(vinyl alcohol)/chitosan composite alkaline polymer electrolyte: preparation and characterization of the membrane

Quaternized poly(vinyl alcohol)/chitosan (QPVA/CS) composite membranes were prepared by solution casting method with AlCl₃·6H₂O aqueous solution as solvent for CS and glutaraldehyde as a crosslinker. The crystalline, thermal and mechanical properties of the QPVA/CS composite membranes were studied by Fourier transform infrared spectroscopy, X-ray diffractometry, differential scanning calorimetry, thermogravimetry and tensile test measurements, respectively. The composite membranes were immersed in potassium hydroxide aqueous solution to form polymer electrolyte membranes. The alkaline uptake, swelling ratio, ion conductivity and methanol permeability of the electrolyte membranes were studied. The experimental results indicated that aluminum chloride hexahydrate (AlCl₃·6H₂O) had a positive effect on the mechanical properties of the QPVA/CS composite membrane. The elongation-at-break of this membrane reached the maximum of 401.0%. The alkaline uptake and swelling ratio of the composite membranes decreased. With the addition of 30 wt% AlCl₃·6H₂O, the composite membrane showed the ion conductivity and methanol permeability of 1.82 × 10^?2 S cm^?1 and 2.17 × 10^?6 cm² s^?1, respectively. These values were higher than those of the membrane with acetic acid as the solvent for CS. The selectivity of the QPVA/CS membrane could reach 8.39 × 10³ S s cm^?3. This study showed that with AlCl₃·6H₂O as the solution for CS, the high performance QPVA/CS composite alkaline polymer electrolyte membrane could be prepared.