Innovative ion exchange membranes have become commercially available in recent years. However, information about their structural and transport characteristics is often extremely insufficient. To address this issue, homogeneous anion exchange membranes with the trade names ASE, CJMA-3 and CJMA-6 have been investigated in NaxH(3−x)PO4 solutions with pH 4.4 ± 0.1, 6.6 and 10.0 ± 0.2, as well as NaCl solutions with pH 5.5 ± 0.1. Using IR spectroscopy and processing the concentration dependences of the electrical conductivity of these membranes in NaCl solutions, it was shown that ASE has a highly cross-linked aromatic matrix and mainly contains quaternary ammonium groups. Other membranes have a less cross-linked aliphatic matrix based on polyvinylidene fluoride (CJMA-3) or polyolefin (CJMA-6) and contain quaternary amines (CJMA-3) or a mixture of strongly basic (quaternary) and weakly basic (secondary) amines (CJMA-6). As expected, in dilute solutions of NaCl, the conductivity of membranes increases with an increase in their ion-exchange capacity: CJMA-6 < CJMA-3 << ASE. Weakly basic amines appear to form bound species with proton-containing phosphoric acid anions. This phenomenon causes a decrease in the electrical conductivity of CJMA-6 membranes compared to other studied membranes in phosphate-containing solutions. In addition, the formation of the neutral and negatively charged bound species suppresses the generation of protons by the “acid dissociation” mechanism. Moreover, when the membrane is operated in overlimiting current modes and/or in alkaline solutions, a bipolar junction is formed at the CJMA- 6/depleted solution interface. The CJMA-6 current-voltage curve becomes similar to the well-known curves for bipolar membranes, and water splitting intensifies in underlimiting and overlimiting modes. As a result, energy consumption for electrodialysis recovery of phosphates from aqueous solutions almost doubles when using the CJMA-6 membrane compared to the CJMA-3 membrane.

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Electrodialysis with layer-by-layer coated membranes is a promising method for the separation of monovalent and polyvalent ions. Since the separation selectivity is significantly reduced in the presence of defects in the multilayer system, the stability of the modifiers becomes an important issue. This article reports the i-V curves of layer-by-layer coated membranes based on the heterogeneous MK-40 membrane before and after 50 h long electrodialysis of a solution containing sodium and calcium ions at an underlimiting current density, and the values of concentrations of cations in the desalination chamber during electrodialysis. It is shown that the transport of bivalent ions through the modified membranes is reduced throughout the electrodialysis by about 50%, but the operation results in decreased resistance of the membrane modified with polyethylenimine, which may suggest damage to the modifying layer. Even after electrodialysis, the modified membrane demonstrated experimental limiting current densities higher than that of the substrate, and in case of the membrane modified with polyallylamine, the limiting current density 10% higher than that of the substrate membrane.

During electrodialysis the ion exchange membranes are affected by such factors as passage of electric current, heating, tangential flow of solution and exposure to chemical agents. It can potentially cause the degradation of ion exchange groups and of polymeric backbone, worsening the performance of the process and necessitating the replacement of the membranes. This article aims to review how the composition and the structure of ion exchange membranes change during the electrodialysis or the studies imitating it.

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