A comparative analysis is performed on the effect thermochemical treatment in aqueous, alkali, and acid media has on the surface morphology and hydrophobicity of swelling heterogeneous ion-exchanged...

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.

The desalination of dilute NaCl solutions with heterogeneous Russian commercial and modified ion-exchange membranes was studied in a laboratory cell imitating desalination channels of large-scale electrodialysers. The modification was made by casting a thin film of a Nafion-type material on the surface of cation-exchange membrane, and by processing with a strong polyelectrolyte the surface of anion-exchange membrane. It was shown that the modifications resulted in an increase of mass transfer coefficient and in a decrease in water splitting rate, both by up to 2 times. The effect of mass transfer growth is explained by higher surface hydrophobicity of the modified membrane that enhances electroconvection. The decrease in water splitting rate in the case of cation-exchange membrane is due to homogenization of its surface layer. In the case of anion-exchange membrane the effect is due to grafting of quaternary ammonium bases onto the original membrane surface layer. The suppression of water splitting favors development of electroconvection. In turn, intensive electroconvection contributes to deliver salt ions to membrane surface and thus reduces water splitting.

Coating ion exchange membranes with polyelectrolyte has been proven to be a cheap way to reduce concentration polarization and increase limiting current (for polyelectrolytes carrying fixed groups of the same sign of charge with respect to the membrane bulk), to create high monovalent selectivity, and to add the function of H⁺/OH⁻ ions generation (for polyelectrolytes bearing fixed groups of the opposite sign of charge with respect to the membrane bulk). In the latter case, the balance between the counterion transport and the H⁺/OH⁻ ions generation is affected by parameters of the substrate and the modifying layer. In this study we investigated the electrochemical characteristics of homogeneous Neosepta AMX-Sb and heterogeneous MA-41P membranes coated with one, two, or three layers of oppositely charged polyelectrolyte (the maximum thickness of each layer was 5 µm). It was found that the limiting current decreased earlier and the generation of H⁺/OH⁻ ions was stronger in the case of the heterogeneous membrane. The shift in the pH of the solution depended more on the generation of H⁺/OH⁻ ions at the modifying layer/solution interface than on the generation at the membrane/modifying layer interface, and in all cases water splitting started in the same range of potential drops over the membrane.

Coating of ion exchange membranes used in electrodialysis with layers of polyelectrolytes is a proven approach that allows for the increasing of the limiting current, the suppressing of sedimentation, the controlling of the intensity of generation of H⁺ and OH⁻ ions, and also the improving of monovalent selectivity. However, in the case when two materials with the opposite sign of the charge of fixed groups come in contact, a bipolar boundary is created that can cause undesirable changes in the membrane properties. In this work, we used a MK-40 heterogeneous membrane on the surface of which a layer of polyethyleneimine was applied by adsorption from a solution as a model of heterogeneous membranes modified with oppositely charged polyelectrolyte. It was found that, on one hand, the properties of modified membrane were beneficial for electrodialysis, its limiting current did not decrease and the membrane even acquired a barrier to non-selective electrolyte transport. At the same time, the generation of H⁺ and OH⁻ ions of low intensity arose, even in underlimiting current modes. It was also shown that despite the presence of a layer of polyethyleneimine, the surface charge of the modified membrane remained negative, which we associate with low protonation of polyethyleneimine at neutral pH.