Chelate membrane from poly(vinyl alcohol)/poly(n-salicylidene allyl amine) blend. II. Effect of co(II) content on oxygen/nitrogen separation

Facilitated transport of oxygen was performed through chelate membranes containing cobalt with selective oxygen binding ability as a fixed oxygen carrier. Chelate membranes were obtained from Schiff base membranes after treating a poly(allyl amine) (PAAm) and poly(vinyl alcohol) (PVA) blend with salicylaldehyde. It is confirmed that the O? O stretching peak through a frequency change in FTIR could be seen at 1150 cm^?1 between cobalt in the membrane and incoming oxygen. The permeability of oxygen through Schiff base membranes was 2.01?2.98 × 10^?13 [cm³ (STP) cm²/cm s cmHg] and oxygen permselectivity was in the range of 1.83?3.27. For chelate membranes, both the permeability of oxygen and oxygen selectivity increased to 2.15?2.82 × 10^?12 [cm³ (STP) cm²/cm s cmHg] and around 8, respectively. Permselectivity of chelate increased as a result of facilitation of O₂ and inhibition of N₂ transport. Detailed results and the mechanism of facilitation of oxygen are discussed on the basis of molecular interactions. © 1995 John Wiley & Sons, Inc.     

Preparation of poly(acrylic acid)/poly(vinyl alcohol) membrane for the facilitated transport of CO2

Poly(acrylic acid) (PAA)/poly(vinyl alcohol) (PVA) membrane was prepared for the facilitated transport of CO₂. The carrier of CO₂ was monoprotonated ethylenediamine and was introduced in the membrane by ion exchange. The ion‐exchange capacity of the membrane was 4.5 meq/g, which was much higher than that of the Nafion 117 membrane. The membrane was highly swollen by the aqueous solution. Much higher selectivity of CO₂ over N₂ and higher CO₂ permeability were obtained in the PAA/PVA membrane than in the Nafion membrane because of the higher ion‐exchange capacity and solvent content. The highest selectivity was more than 1900 when the CO₂ partial pressure in the feed gas was 0.061 atm. Effects of ion‐exchange capacity, membrane thickness, and annealing temperature in conditions of membrane preparation on membrane performance were investigated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 936–942, 2001     

Separation of benzene/cyclohexane by pervaporation through chelate poly(vinyl alcohol)/poly(allyl amine) blend membrane

Summary Chelate poly(vinyl alcohol)/poly(allyl amine) blend membrane was prepared and used for the separation of benzene/cyclohexane mixture by pervaporation processes. The coordination of benzene in the feed with cobalt in the membrane plays a major role in the separation of the mixture. Chelate poly(vinyl alcohol)/poly(allyl amine) blend membrane showed a preferential sorption toward benzene and was found to be more effective for permeating benzene in the benzene/cyclohexane mixture than an original Schiff base poly(vinyl alcohol)/poly(allyl amine) membrane.     

Phase separation in poly(vinyl alcohol)/gelatin blend systems

Blends of a commercial poly(vinyl alcohol) (a-PVA) derived from vinyl acetate and gelatin obtained from collagen were prepared by mixing aqueous solutions of both samples under various conditions. For the blend hydrogels, the depression of melting temperatures was observed at high PVA content. Similarly to the a-PVA/silk fibroin (SF) system, when the degrees of polymerization of PVA increased, the microphase separation region in a phase diagram of the blend films increased for the a-PVA/gelatin system. In the IR spectra of the blend films, no absorption bands corresponding to a conformational change of gelatin appeared. Comparison of the mechanical properties of the a-PVA/gelatin and a-PVA/SF systems, showed the interaction between PVA and gelatin molecules to be smaller than that between PVA and SF molecules. © 1999 Society of Chemical Industry     

Phase separation structure in poly(vinyl alcohol)/silk fibroin blend films

Blend films of a commercial poly(vinyl alcohol) (a-PVA) derived from vinyl acetate and silk fibroin (SF) obtained from degummed silk were prepared by mixing the aqueous solutions of both samples. A plain weave structure was recognized only in the blend films, whereas no structure was found for the superimposed films of both samples. The phase separation structure of the blend films was examined by microscopic observations elongation, tensile tests, and IR measurements. The microphase separation region increased with increase in the degree of polymerization of the PVA. In the IR spectra of the blend films with high PVA contents cast under certain conditions, the absorption peak attributed to the cross-β-form conformation of SF appeared strongly. Gelatin, a water-soluble and natural polymer, was also used for comparison with SF. The ternary phase diagram in an a-PVA/gelatin/H₂O system was obtained experimentally and the critical point was used to estimate the interaction parameter between PVA and gelatin molecules. The phase separation structure and the interaction between PVA and SF molecules were also discussed taking into consideration the results of the a-PVA/gelatin system. © 1998 SCI.     

Poly(vinyl alcohol) and poly(vinyl amine) blend membranes for isopropanol dehydration

Blended membranes of hydrophilic polymers poly(vinyl alcohol) (PVA) and poly(vinyl amine) (PVAm) were prepared and crosslinked with glutaraldehyde. The prepared membranes were characterized using infrared (attenuated total reflection mode) spectroscopy, differential scanning calorimetry, X‐ray diffractometry, and scanning electron microscopy measurements. Pervaporation performances of the membranes were evaluated for the separation of water‐isopropanol (IPA) mixtures. As the PVAm content increased from PVAm0 to PVAm1.5, the flux through a 70 μm film increased from 0.023 to 0.10 kg/m² h at an IPA/water feed ratio of 85/15 at 30 °C. The driving force for permeation of water increased due to the temperature but it has no effect on IPA permeation. Activation energies for the permeation of IPA and water were calculated to be 17.11 and 12.46 kJ/mol, respectively. Controlling the thickness of the blend membrane could improve the permeation flux with only a marginal reduction in the separation factor. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45572.     

Fullerene membrane transport mediated by γ‐cyclodextrin immobilised in poly(vinyl alcohol) films

This paper reports on fullerene C₆₀ and C₇₀ transport across hydrophilic membrane materials consisting of a poly(vinyl alcohol) matrix on which γ‐cyclodextrin moieties were attached as molecular recognition sites. The rate‐limiting step of the membrane transport was demonstrated to be dissociation of the inclusion complex at the stripping interface. Copyright © 2003 Society of Chemical Industry     

Preparation and characterization of blend anion-exchange membrane from quarternized hydroxyethylcellulose/quaternized poly(vinyl alcohol)

阴离子交换膜是碱性直接甲醇燃料电池（ADMFC）的核心。本文将季铵化羟乙基纤维素（QHEC）和季铵化聚乙烯醇（QPVA）共混制备了一系列不同配比的QPVA/QHEC阴离子交换膜并对其进行热交联,对膜进行测试和分析,结果表明：膜表面均匀致密,低于300 ℃膜基本稳定;QPVA/QHEC共混膜的导电率随着QPVA量的增大而增大,在（2.0～7.8）×10－2 s/cm范围内,随着使用温度的升高逐渐升高;QHEC膜对甲醇有很好的阻隔效果,在20 ℃时,甲醇渗透率最低为2.49×10－6 cm2/s;随QPVA量的增加,共混膜的甲醇渗透率会略有增加。     

Facilitated oxygen transport in a novel silicone polymer membrane containing carboxylic cobalt groups

A novel silicone polymer membrane with facilitated oxygen transport properties was prepared by using 11‐alkene acid cobalt, a silicone rubber containing vinyl groups of 5 mol %, a hydrogen‐containing silicon oil, and chlorine platinum acid. The solution casting and the vulcanization were carried out simultaneously at room temperature. Investigation showed that PO ₂ increased and PN ₂ did not change with decreasing gas pressure difference. This facilitated oxygen transport behavior was contributed by a polymeric cobalt complex formed from carboxylic groups and cobaltous ions in the membrane to result in the simultaneous increase of both PO ₂ and αO ₂/N ₂ under lower gas pressure difference. For example, the PO ₂ and αO _2/N ₂ of the membrane containing 11‐alkene acid cobalt of 2.5 wt% were 750 Barrer and 3.09 under a gas pressure difference of 0.05 mPa. As much as 5 wt% 11‐alkene acid cobalt could be added to the membranes; PO ₂ and αO _2/N ₂ increased to 802 Barrer and 3.34 respectively when the membrane contained 11‐alkene acid cobalt of 5 wt %. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1038–1044, 2003     

Selective separation of some heavy metals by poly(vinyl alcohol)‐grafted membranes

A poly(vinyl alcohol) membrane (PVA) was modified by radiation graft copolymerization of acrylic acid/styrene (AAc/Sty) comonomers. The Cu and Fe ion‐transport properties of these membranes were investigated using a diaphragm dialysis cell. In the feed solution containing CuCl₂ or a mixture of CuCl₂ and FeCl₃, the PVA‐g‐P(AAc/Sty) membranes showed high degrees of permselectivity toward Cu²⁺ rather than toward Fe³⁺. The permeation of Cu²⁺ ions through the membranes was found to increase with decrease in the grafting yield. However, as the content of Cu²⁺ ions in the Cu/Fe binary mixture feed solutions decreased, the rate and the amount of transported Cu²⁺ through the grafted membrane decreased, with no appreciable permselectivity toward Fe³⁺. When Fe²⁺ ions were used instead of Fe³⁺ ions in the feed solution containing Cu²⁺, the transport of both Cu²⁺ and Fe²⁺ through the membrane was observed. The rate of transport of Fe²⁺ was higher than that of Cu²⁺. In addition, it was found that the selective transport of ions was significantly influenced by the pH difference between both sides of the membranes. As the pH of the feed or the received solution decreased, both Cu²⁺ and Fe³⁺ passed through the membrane and were transported to the received solution. The role of carboxylic acid and the hydroxyl groups of the grafted membranes in the transportation process of ions is discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 125–132, 2000     

Preparation and membrane performance of poly(ethylene-co-vinyl alcohol) hollow fiber membrane via thermally induced phase separation

Poly(ethylene-co-vinyl alcohol) (EVOH) hollow fiber membranes with ultrafiltration performance were prepared from EVOH/glycerol systems via thermally induced phase separation (TIPS). The diluent glycerol was used as bore liquid to make a lumen of the hollow fiber for the purpose of prevention of the diluent evaporation and the larger pores formation at the inner surface of the hollow fiber. The obtained hollow fiber membranes showed asymmetric structures with skin layer near the outer surface, the larger pores just below the skin layer and the smaller pores near the inner surface. The formation of the larger pores near the outer surface was due to the enhanced pore growth by the water penetration. Some primary factors affecting the structure and performance of the membranes such as ethylene content (EC) in EVOH, cooling water bath temperature and take-up speed were studied extensively. The water permeability can be improved by increasing the water bath temperature and the take-up speed and by decreasing the EC. Both the pore size at the outer surface and the connectivity between the pores have to be considered together to understand the experimental result of the water permeability and the solute rejection.     

Formation of porous poly(ethylene‐co‐vinyl alcohol) membrane via thermally induced phase separation

Crystalline poly(ethylene‐co‐vinyl alcohol) (EVOH) membranes were prepared by a thermally induced phase separation (TIPS) process. The diluents used were 1,3‐propanediol and 1,3‐butanediol. The dynamic crystallization temperature was determined by DSC measurement. No structure was detected by an optical microscope in the temperature region higher than the crystallization temperature. This means that porous membrane structures were formed by solid–liquid phase separation (polymer crystallization) rather than by liquid–liquid phase separation. The EVOH/butanediol system showed a higher dynamic crystallization temperature and equilibrium melting temperature than those of the EVOH/propanediol system. SEM observation showed that the sizes of the crystalline particles in the membranes depended on the polymer concentration, cooling rate, and kinds of diluents. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2449–2455, 2001     

Effect of graphene loading on thermomechanical properties of poly(vinyl alcohol)/starch blend

Polymer nanocomposites based on poly(vinyl alcohol) (PVA)/starch blend and graphene were prepared by solution mixing and casting. Glycerol was used as a plasticizer and added in the starch dispersion. The uniform dispersion of graphene in water was achieved by using an Ultrasonicator Probe. The composites were characterized by FTIR, tensile properties, X‐ray diffraction (XRD), thermal analysis, and FE‐SEM studies. FTIR studies indicated probable hydrogen bonding interaction between the oxygen containing groups on graphene surface and the –OH groups in PVA and starch. Mechanical properties results showed that the optimum loading of graphene was 0.5 wt % in the blend. XRD studies indicated uniform dispersion of graphene in PVA/starch matrix upto 0.5 wt % loadings and further increase caused agglomeration. Thermal studies showed that the thermal stability of PVA increased and the crystallinity decreased in the presence of starch and graphene. FE‐SEM studies showed that incorporation of graphene increased the ductility of the composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41827.     

Thermal and spectroscopic studies of poly(N‐vinyl pyrrolidone)/poly(vinyl alcohol) blend films

Poly(N‐vinyl pyrrolidone) (PVP) and poly (vinyl alcohol) (PVA) homopolymers and their blended samples with different compositions were prepared using cast technique and subjected to X‐ray diffraction (XRD) measurements, infrared (IR) spectroscopy, ultraviolet/visible spectroscopy, and thermogravimetric analysis (TGA). XRD patterns of homopolymers and their blended samples indicated that blending amorphous materials, such as PVP, with semicrystalline polymer, such as PVA, gives rise to an amorphous structure with two halo peaks at positions identical to those found in pure PVP. Identification of structure and assignments of the most evident IR ‐ absorption bands of PVP and PVA as well as their blends in the range 400–2000 cm^?1 were studied. UV–vis spectra were used to study absorption spectra and estimate the values of absorption edge, E_g, and band tail, E_e, for all samples. Making use of Coats‐Redfern relation, thermogravimetric (TG) data allowed the calculation of the values of some thermodynamic parameters, such as activation energy E, entropy ΔS^#, enthalpy ΔH, and free energy of activation ΔG^# for different decomposition steps in the samples under investigation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

聚乙烯醇/二氧化硅杂化膜的制备及渗透蒸发分离环己醇（酮）/环己烷

以聚乙烯醇（PVA）和正硅酸乙酯（TEOS）为原料,经溶胶-凝胶（sol-gel）法制备了不同二氧化硅（SiO2）含量的 PVA/SiO2杂化膜。傅里叶变换红外光谱（FT-IR）表明,随着SiO2含量增大,1060cm?1和970cm?1处Si—O—Si特征吸收峰的相对强度逐渐加强,说明TEOS与PVA发生了交联反应;同时膜的分解温度从248℃升高到342℃。杂化膜的SiO2含量从10 %增大到40 %,其玻璃态温度从115℃升高到124℃。以水为溶剂,测定了杂化膜的耐溶剂性能,与PVA膜相比,杂化膜的耐溶剂性能显著提高。以质量比为0.950/0.025/0.025的环己烷/环己醇/环己酮为原料,测定杂化膜的分离性能,结果表明SiO2含量从10 %增大到40 %,通量从15.94 g/(m2?h)升高到75.69 g/(m2?h),环己醇的分离因子从1.8升高到2.65。     

Plasma polymer membranes from hexafluoroethane/hydrogen mixtures for separation of oxygen and nitrogen

Thin plasma polymer layers were produced employing feed mixtures of hexafluoroethane and hydrogen in an rf parallel-plate reactor. The layers are intended for use in membrane-based separation of oxygen and nitrogen. The hexafluoroethane-to-hydrogen mixture ratio was varied over a wide range, whereas all other process parameters (power, pressure, substrate temperature, and total gas flow) were held constant. The plasma polymers were examined by scanning electron microscopy, X-ray analysis, quantitative elemental analysis, and X-ray photoelectron spectroscopy. Permeability coefficients of oxygen and nitrogen and selectivities of the pure gases were determined. Pinhole-free plasma polymer films containing different amounts of fluorine, carbon, and hydrogen were formed. The distributions of fluorine and hydrogen in the products reflect their distributions in the feed gas. Traces of oxygen in some of the polymers are explained by the reaction of trapped radicals with atmospheric oxygen on the samples' exposure to air. Fluorine-containing carbon moieties such as CF₃, CF₂, and CF, and carbon moieties with fluorine atoms exclusively in secondary positions are present. A method of calculating crosslink density using the analytical data is described. The oxygen permeability coefficient and the selectivity of the plasma polymers increase as the hexafluoroethane content of the feed gas is raised. This behavior is attributed to growing solubility selectivity as a result of the rising fluorine content of the polymers. Maximum selectivity amounts to 3.4 at an oxygen permeability coefficient of 21 Barrer. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1517–1526, 1997     

CO2 separation performance by chitosan/tetraethylenepentamine/poly(ether sulfone) composite membrane

CO₂ separation from CO₂/N₂ (20:80) gas mixture has been demonstrated by tetraethylenepentamine blended with chitosan (CS‐TEPA) membrane. Optimization of CS and TEPA weight ratio were carried out based on characterization details involving thermogravimetric analysis, Fourier transform infrared spectroscopy, X‐ray diffraction, atomic force microscope, and field emission scanning electron microscope. Effects of water flow rate, pressure, and temperature were concurrently studied on CS‐TEPA membranes through gas permeation. Almost twofold increase in CO₂ permeance (24.7 GPU) was detected in CS blend with 30% (w/w) of TEPA (CS70) as compared to pure CS membrane (12.5 GPU). CS70 yielded CO₂/N₂ selectivity of 80 whereas CS demonstrated a maximum of 54 at 90 °C. The membrane also exhibited improved stability at temperatures less than 120 °C which was evident from TGA isotherm trace. The proposed composite membrane can be a promising candidate for flue gas separation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45206.     

Dialdehyde polyethylene glycol cross-linked poly(vinyl alcohol) membranes with enhanced CO2/N2 separation performance

The development of carbon dioxide (CO₂) separation technology is crucial for mitigating global climate change and promoting sustainable development. In this study, we successfully synthesized an array of cross-linked poly(vinyl alcohol) (PVA) membranes, xALD-PEG-ALD-c-PVA, with enhanced CO₂/N₂ separation performance by employing dialdehyde polyethylene glycol (ALD-PEG-ALD) as a cross-linker. The formation of the cross-linked network structure not only inhibits the crystallization of PVA but also disrupts hydrogen bonding and thus increases fractional free volume of PVA chains. Under the synergistic effect of these multiple factors, the cross-linked PVA membranes exhibit a significantly improved CO₂ permeability. Moreover, they maintain high CO₂/N₂ selectivity, attributing to the CO₂-philic characteristic of ethylene oxide groups in the cross-linked structure. At the ALD-PEG-ALD content of 1.6 mmol g⁻¹, the xALD-PEG-ALD-c-PVA membrane demonstrates a CO₂ permeability of 41.4 barrer and a CO₂/N₂ selectivity of 57.4 at 2 bar and 25°C. Furthermore, compared with the pristine PVA membrane, xALD-PEG-ALD-c-PVA membranes manifest superior mechanical properties and outstanding separation performance for a CO₂/N₂ (15/85, vol%) gas mixture. The excellent combination of permeability and selectivity makes xALD-PEG-ALD-c-PVA membranes highly promising for various CO₂ separation applications.     

Characterization of sodium alginate and poly(vinyl alcohol) blend membranes in pervaporation separation

By blending a rigid polymer, sodium alginate (SA), and a flexible polymer, poly(vinyl alcohol) (PVA), SA/PVA blend membranes were prepared for the pervaporation separation of ethanol–water mixtures. The rigid SA membrane showed a serious decline in flux and a increase in separation factor due to the relaxation of polymeric chains, whereas the flexible PVA membrane kept consistent membrane performance during pervaporation. Compared with the nascent SA membrane, all of the blend membranes prepared could have an enhanced membrane mobility by which the relaxation during pervaporation operation could be reduced. From the pervaporation separation of the ethanol–water mixtures along with the temperature range of 50–80°C, the effects of operating temperature and PVA content in membrane were investigated on membrane performance, as well as the extent of the relaxation. The morphology of the blend membrane was observed with PVA content by a scanning electron microscopy. The relaxational phenomena during pervaporation were also elucidated through an analysis on experimental data of membrane performance measured by repeating the operation in the given temperature range. SA/PVA blend membrane with 10 wt % of PVA content was crosslinked with glutaraldehyde to enhance membrane stability in water, and the result of pervaporation separation of an ethanol–water mixture through the membrane was discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:949–959, 1998     

pH‐controlled uphill transport of boric acid through a poly(vinyl alcohol) (PVA) membrane

The uphill transport of boric acid in aqueous solutions through a thermal‐crosslinked poly(vinyl alcohol) (PVA) membrane was investigated. A normal permeation caused by the concentration difference of the boron along the PVA membrane was observed for equal pH conditions at both sides of the membrane, and higher flux was observed under an acidic condition at pH = 5.0 than under a basic condition at pH = 10.0. When the pH of one side is kept pH = 5.0 (acid side) and the other side was kept at pH = 10.0 (base side), uphill transport of boric acid from the acid side to the base side was observed under an equal initial concentration of both sides. Such an uphill transport was also observed against the concentration difference under the condition in which the initial concentration of the base side was higher than that of the acid side. The uphill transport could be explained by the difference in the permeation rates through the PVA membrane between B(OH)₃, the dominant form under lower pH, and B(OH)₄^?, the dominant form under higher pH, which makes a complex with diols in PVA. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1451–1455, 2007