Ion-exchange membranes (IEMs) find more and more applications; the success of an application depends on the properties of the membranes selected for its realization. For the first time, the results of a comprehensive characterization of the transport properties of IEMs from three manufactures (Astom, Japan; Shchekinoazot, Russia; and Fujifilm, The Netherlands) are reported. Our own and literature data are presented and analyzed using the microheterogeneous model. Homogeneous Neosepta AMX and CMX (Astom), heterogeneous MA-41 and MK-40 (Shchekinoazot), and AEM Type-I, AEM Type-II, AEM Type-X, as well as CEM Type-I, CEM Type-II, and CEM Type-X produced by the electrospinning method (Fujifim) were studied. The concentration dependencies of the conductivity, diffusion permeability, as well as the real and apparent ion transport numbers in these membranes were measured. The counterion transport number characterizing the membrane permselectivity increases in the following order: CEM Type-I MA-41 < AEM Type-I < MK-40<CMX CEM Type-II CEM Type-X AEM Type-II < AMX < AEM Type-X. It is shown that the properties of the AEM Type-I and CEM Type-I membranes are close to those of the heterogeneous MA-41 and MK-40 membranes, while the properties of Fujifilm Type-II and Type-X membranes are close to those of the homogeneous AMX and CMX membranes. This difference is related to the fact that the Type-I membranes have a relatively high parameter f2, the volume fraction of the electroneutral solution filling the intergel spaces. This high value is apparently due to the open-ended pores, formed by the reinforcing fabric filaments of the Type-I membranes, which protrude above the surface of these membranes.

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The interplay between the ion exchange capacity, water content and concentration dependences of conductivity, diffusion permeability, and counterion transport numbers (counterion permselectivity) of CJMA-3, CJMA-6 and CJMA-7 (Hefei Chemjoy Polymer Materials Co. Ltd., China) anion-exchange membranes (AEMs) is analyzed using the application of the microheterogeneous model to experimental data. The structure–properties relationship for these membranes is examined when they are bathed by NaCl and Na2SO4 solutions. These results are compared with the characteristics of the well-studied homogenous Neosepta AMX (ASTOM Corporation, Japan) and heterogeneous AMH-PES (Mega a.s., Czech Republic) anion-exchange membranes. It is found that the CJMA-6 membrane has the highest counterion permselectivity (chlorides, sulfates) among the CJMAED series membranes, very close to that of the AMX membrane. The CJMA-3 membrane has the transport characteristics close to the AMH-PES membrane. The CJMA-7 membrane has the lowest exchange capacity and the highest volume fraction of the intergel spaces filled with an equilibrium electroneutral solution. These properties predetermine the lowest counterion transport number in CJMA-7 among other investigated AEMs, which nevertheless does not fall below 0.87 even in 1.0 eq L−1 solutions of NaCl or Na2SO4. One of the reasons for the decrease in the permselectivity of CJMAED membranes is the extended macropores, which are localized at the ion-exchange material/reinforcing cloth boundaries. In relatively concentrated solutions, the electric current prefers to pass through these well-conductive but nonselective macropores rather than the highly selective but low-conductive elements of the gel phase. It is shown that the counterion permselectivity of the CJMA-7 membrane can be significantly improved by coating its surface with a dense homogeneous ion-exchange film.

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This study examines the mechanisms of adsorption of anthocyanins from model aqueous solutions at pH values of 3, 6, and 9 by ion-exchange resins making the main component of heterogeneous ion-exchange membranes. This is the first report demonstrating that the pH of the internal solution of a KU-2-8 aromatic cation-exchange resin is 2-3 units lower than the pH of the external bathing anthocyanin-containing solution, and the pH of the internal solution of some anion-exchange resins with an aromatic (AV-17-8, AV-17-2P) or aliphatic (EDE-10P) matrix is 2–4 units higher than the pH of the external solution. This pH shift is caused by the Donnan exclusion of hydroxyl ions (in the KU-2-8 resin) or protons (in the AV-17-8, AV-17-2P, and EDE-10P resins). The most significant pH shift is observed for the EDE-10P resin, which has the highest ion-exchange capacity causing the highest Donnan exclusion. Due to the pH shift, the electric charge of anthocyanin inside an ion-exchange resin differs from its charge in the external solution. At pH 6, the external solution contains uncharged anthocyanin molecules. However, in the AV-17-8 and AV-17-2P resins, the anthocyanins are present as singly charged anions, while in the EDE-10P resin, they are in the form of doubly charged anions. Due to the electrostatic interactions of these anions with the positively charged fixed groups of anion-exchange resins, the adsorption capacities of AV-17-8, AV-17-2P, and EDE-10P were higher than expected. It was established that the electrostatic interactions of anthocyanins with the charged fixed groups increase the adsorption capacity of the aromatic resin by a factor of 1.8–2.5 compared to the adsorption caused by the π–π (stacking) interactions. These results provide new insights into the fouling mechanism of ion-exchange materials by polyphenols; they can help develop strategies for membrane cleaning and for extracting anthocyanins from juices and wine using ion-exchange resins and membranes.

The presence of membrane fouling is the main drawback in membrane processes, and it is related to the premature use and high cost for the replacement of membranes. Polyphenols in cranberry juice are associated with ion-exchange membrane fouling, and it results in a loss of these beneficial compounds in the juice when treated by membrane processes such as electrodialysis. In the present work, four heterogeneous or pseudohomogeneous cation-exchange membranes (CSE-fg, MK-40, CEM Type-ll, and CJMC-5), different in terms of the polymer matrix (aromatic, aliphatic), exchange capacity, size, and location of meso and macropores, were studied to understand the impact of the membrane structure and physico-chemical properties on adsorption and desorption of phenolic compounds (anthocyanins and proanthocyanidins) from cranberry juice. It appeared from these results that MK-40, CEM Type-ll, and CSE-fg were more prone to fouling due to their high ion-exchange capacity, their thickness, and the presence of meso and macropores in their structure. Indeed, electrostatic interactions occurred between fixed groups of membranes and polyphenolic ions. Desorption of the entire membrane and cryogenic grinding with pH adjusted to 10 allowed a better recovery of anthocyanins and proanthocyanidins (PACs), respectively, since hydroxide ions competed with polyphenols and membrane that induced desorption of polyphenols. In the future, this new knowledge will become the basis for a more sensible choice of membranes and for the development of protocols for extending their lifetime.

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