Preparation and characterization of anion-exchange membranes with a semi-interpenetrating network structure of poly(vinyl alcohol) and poly(allyl amine)

doi:10.1016/j.desal.2007.09.038

Desalination

Volume 233, Issues 1–3, 15 December 2008, Pages 157-165

Presented at the Fourth Conference of Aseanian Membrane Society (AMS 4), 16–18 August 2007, Taipei, Taiwan

https://doi.org/10.1016/j.desal.2007.09.038 Get rights and content

Abstract

Anion-exchange membranes with a semi-interpenetrating network structure were prepared by blending poly-(vinyl alcohol) and a polycation, poly(allyl amine), in varying ratios. The membranes obtained were physically cross-linked by annealing them at various temperatures and/or chemically cross-linked by reaction with glutaraldehyde aqueous solutions. The water content of the membranes can be controlled easily by changing the annealing temperature and the concentration of the cross-linker. The charge density increases during the initial stage, and then decreases with increasing polycation content after reaching a maximum value. The membrane resistance is proportional to a function of water content, which means that the value of the resistance will be estimated from the water content. The membranes in this study are easily prepared and have high mechanical strength. Hence, the membranes will have potential application to the desalination of salt water at low salt concentration.

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AAEMs are OH− ion conductive solid polymer electrolyte membranes which mostly contain quaternary ammonium (QA) groups grafted into the polymer chains. Several quaternary ammonium functionalized polymers such as poly (arylene ether sulfone), poly (phenylene oxide), poly (ether sulfone ketone) and poly (vinyl alcohol) have been developed and used as AAEM materials [17–20]. A key challenge in developing AAEM is to enhance the stability of cationic groups attached to the polymeric backbone.
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The transport number of an IEM depends on the ratio of the charge density to the concentration of solution in contact with the membrane surface [31]. The charge density is defined as the division of the ion-exchange capacity by the water content of an AEM [32,33]. Table 2 shows that the transport number of both the aromatic and the aliphatic AEMs reacted with TMA increases with increasing CLC.
Anion-exchange membranes (AEMs) with various membrane structures were prepared by introducing various amines: trimethylamine (TMA), triethylamine (TEA), tri-n-propylamine (TPA) and tri-n-butylamine (TBA) into precursor membranes prepared from chloromethylstyrene (CMS)–divinylbenzene (DVB) and glycidyl methacrylate (GMA) – DVB. Their properties for ionic transport and anti-organic fouling were examined. Almost all of the prepared AEMs have excellent ionic transport properties: transport number of anions >0.94 and membrane resistance <4 Ωcm². The voltage change through the AEMs during electrodialysis operation using solutions containing sodium dodecylbenzene-sulfonate as a foulant indicated that there are three cases of fouling mechanism being related to membrane structure: (a) aliphatic AEMs show lower fouling than aromatic ones; (b) the lower the water content of an AEM, the more remarkable the fouling; (c) the longer the chain length of the alkyl groups of the anion-exchange groups of an AEM, the more remarkable the fouling.
Charge mosaic membranes with semi-interpenetrating network structures prepared from a polymer blend of poly(vinyl alcohol) and polyelectrolytes
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In order to examine the effect of charged groups on ionic transport through the membranes, a non-charged PVA membrane, PVA-1, was prepared by casting an aqueous solution of PVA on a plastic plate, drying the membrane obtained, and then annealing it under the same conditions as mentioned above. The membrane potential, Δϕ, of PBCM membranes was measured using an acrylic plastic cell comprising two parts separated by a sample membrane, as shown elsewhere [31]. One chamber of the cell was filled with 0.01 mol dm−3 KCl solution, while the other chamber was filled with 0.05 mol dm−3 KCl solution.
Charge mosaic (CM) membranes with semi-interpenetrating network structures were prepared by blending poly(vinyl alcohol) as a membrane matrix, poly(allyl amine) as a polycation and poly(vinyl alcohol-co-2-acrylamido-2-methyl propane sulfonic acid) as a polyanion with varying polyelectrolyte contents under different cross-linking conditions. Our method can prepare CM membranes of a large area easily at low manufacture cost. Although the flux of electrolytes through the membrane is less than that through a typical charge mosaic membrane such as Desalton^® (Tosoh Co., Ltd.), which was prepared using micro-phase separation, the permselectivity for electrolytes through the CM membrane was more than 4 times higher than Desalton^®. These CM membranes have enough mechanical strength to form thin layer on a porous support membrane, thereby increasing the flux of electrolytes.
Characterization of cation-exchange membranes prepared from poly(vinyl alcohol) and poly(vinyl alcohol-b-styrene sulfonic acid)
2012, International Journal of Hydrogen Energy
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Fig. 2 shows the chemical cross-linking mechanism of PVA and GA. The electrical resistance of the membranes was measured by using a hand-made acrylic plastic cell composed of two parts separated by a membrane, as described elsewhere [32], with an LCR meter operated at 10 KHz AC (A&D Corp. Ltd.
Block-type cation-exchange membranes (CEMs) have been prepared by blending poly(vinyl alcohol) (PVA) and the polyanion poly(vinyl alcohol-b-styrene sulfonic acid) at various molar percentages of cation-exchange groups to vinyl alcohol groups, C_pa, and by cross-linking the PVA chains with glutaraldehyde (GA) solution at various GA concentrations, C_GA. The characteristics of the block-type CEMs were compared with random-type CEMs prepared in a previous study from the random copolymer, poly(vinyl alcohol-co-2-acrylamido-2-methylpropane sulfonic acid). At equal molar percentages of the cation-exchange groups, the water content of the block-type CEMs was less than that of the random-type CEMs. The charge density of the block-type CEMs increased with increasing C_pa and reached a maximum value. Further, the maximum value of the charge density increased with increasing C_GA. The maximum charge density value of 1.3 mol/dm³ was obtained for the block-type CEM with C_pa = 3.1 mol% and C_GA = 0.10 vol.%, which is almost two thirds of the value of a commercially available CEM [CMX: ASTOM Corp. Japan]. A comparison of the block-type and random-type CEMs with almost the same membrane resistance showed that the block-type CEMs had higher dynamic transport numbers than the random-type ones. The dynamic transport number and membrane resistance of the block-type CEM with C_pa = 4.0 mol% and C_GA = 0.10 vol.% were 0.96 and 4.9 Ω cm², respectively.
Preparation of aliphatic-hydrocarbon-based anion-exchange membranes and their anti-organic-fouling properties
2011, Journal of Membrane Science
Novel aliphatic-hydrocarbon-based anion-exchange membranes (AEMs) were prepared from glycidyl methacrylate (GMA)/divinylbenzene (DVB) by changing their cross-linker content (CLC). Their ion-transport and anti-organic-fouling properties were compared with those of aromatic-hydrocarbon-based AEMs prepared from chloromethylstyrene (CMS)/DVB copolymers. Aliphatic AEMs with CLCs less than 11.5 have excellent ion-transport properties: anion transport numbers >0.95 and membrane resistances <3.5 Ω cm². In an electrodialysis (ED) system consisting of an AEM and an NaCl solution containing sodium dodecylbenzenesulfonate (DBS) as an aromatic foulant, the change in the voltage drop through the aliphatic AEMs during ED was lower than that with aromatic AEMs. This means that adsorption of DBS on the surface of the aliphatic AEMs is lower than that on aromatic AEMs. The aliphatic AEMs have much lower permeability coefficients for DBS in the ED system than the aromatic AEMs have. These results indicate that the anti-organic-fouling properties of aliphatic AEMs are better than those of aromatic AEMs.
Anion exchange membranes for alkaline fuel cells: A review
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The ion exchange capacity obtained was 1.1 × 10−3 eq g−1 [154]. Also, PVA was blended with poly(allyl amine) and cross-linked with glutaraldehyde [155]. Recently, AEMs based on cross-linked PVA-poly(acrylonitrile-co-2-dimethylamino ethylmethacrylate) were developed [156].
Recent years have seen extensive research on the preparation and properties of anion exchange membranes. Nevertheless, there is as yet no rigorous scientific classification of these membranes, and the methods of synthesis and characterization. The present review offers a practical classification based on the nature and the properties of anion exchange membranes for alkaline fuel cells, arrived at studying the relevant literature. This review also contains a description and assessment of all polymeric materials potentially suitable for use in alkaline fuel cells, and of their specific properties. Although there is ample literature on anion exchange membranes for various other applications, such as electrodialysis, the number of publications reporting alkaline fuel cell performance is still relatively low compared to their acidic homologues, the proton exchange membrane fuel cell. Two tables at the end of the manuscript offer the reader a comprehensive overview by listing all reviewed commercial and non-commercial anion exchange membranes. Suggestions for further research such as elucidation of the ionic transport mechanisms, AFC testing and important issues like the chemical stability and ionic conductivity are addressed as well.

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Preparation and characterization of anion-exchange membranes with a semi-interpenetrating network structure of poly(vinyl alcohol) and poly(allyl amine)

Abstract

Desalination

J. Membr. Sci.

J. Membr. Sci.

J. Membr. Sci.

J. Membr. Sci.

Solid State Ionics

Desalination

J. Membr. Sci.

J. Membr. Sci.

Electrochim. Acta