Study of the Thermochemical Effect on the Transport and Structural Characteristics of Heterogeneous Ion-Exchange Membranes by Combining the Cell Model and the Fine-Porous Membrane Model.

For the first time, based on the joint application of the fine-porous and cell models, a theoretical analysis of the changing transport and structural characteristics of heterogeneous polymeric ion-exchange membranes (IEMs) MK-40, MA-40, and MA-41 after exposure to elevated temperatures in water and aggressive media (H2SO4 and NaOH solutions), as well as after long-term processing in electrodialyzers of various types, was carried out. The studied membranes are composites of ion-exchange polymers with polyethylene and nylon reinforcing mesh. The external influences provoke the aging of IEMs and the deterioration of their characteristics. The transport properties of IEMs are quantitatively described using five physicochemical parameters: counterion diffusion and equilibrium distribution coefficients in the membrane, characteristic exchange capacity, which depends on the microporosity of ion-exchanger particles, and macroscopic porosity at a known exchange capacity of IEMs. Calculations of the physicochemical parameters of the membranes were performed according to a specially developed fitting technique using the experimental concentration dependences of integral diffusion permeability and specific electrical conductivity, and their model analogs. This made it possible to identify and evaluate changes in the membrane micro- and macrostructure and examine the process of artificial aging of the IEM polymer material due to the abovementioned external impacts.

Theoretical and Experimental Study of Joint Osmotic and Electroosmotic Water Transfer through a Cation-Exchange Membrane.

Using the previously developed cell model of a charged membrane and the principles of linear thermodynamics of irreversible processes (the Onsager approach), exact and approximate (in the case of an ideally selective membrane) analytical formulae for calculating the osmotic and electroosmotic permeability of the membrane in aqueous solutions of 1:1 electrolyte at constant electric current density and concentration gradient were suggested. The formulae have been successfully verified by our own experimental data for the extrusion cation-exchange membrane MF-4SC p.29 in NaCl solution up to concentrations of 3 M. The contribution of electroosmotic and osmotic water fluxes to the total water transport through the mentioned individual perfluorinated ion-exchange membrane under conditions close to the process of electrodialysis concentrating was experimentally estimated. The cases of co- and counter-directed osmotic and electroosmotic water fluxes are studied. A good correspondence between theoretical and experimental results was obtained, which made it possible to determine the physicochemical parameters of the electromembrane system (the diffusion coefficients of individual ions and the coefficient of equilibrium distribution of electrolyte molecules in the membrane matrix, the characteristic exchange capacity of the cell model). The achieved results make it possible to fully characterize existing and promising types of ion-exchange membranes based on the developed cell model of a charged membrane.

Influence of Surface Forces on Membrane Separations.

This Special Issue of Membranes, entitled "Influence of Surface Forces on Membrane Separation", is published in honour of Professor Victor Mikhailovich Starov, Doctor of Science in Chemistry, Fellow of the Royal Society of Chemistry [...].

Modeling Asymmetry of a Current-Voltage Curve of a Novel MF-4SC/PTMSP Bilayer Membrane.

A novel bilayer cation-exchange membrane-consisting of a thick layer of a pristine perfluorinated membrane MF-4SC (Russian equivalent of Nafion®-117) and a thinner layer (1 µm) of the membrane, on a base of glassy polymer of internal microporosity poly(1-trimethylsilyl-1-propyne) (PTMSP)-was prepared and characterized. Using the physicochemical characteristics of one-layer membranes MF-4SC and PTMSP in 0.05 M HCl and NaCl solutions, the asymmetric current-voltage curves (CVC) of the bilayer composite were described with good accuracy up to the overlimiting regime, based on the "fine-porous membrane" model. The MF-4SC/PTMSP bilayer composite has a significant asymmetry of CVC that is promising for using it in electromembrane devices, such as membrane detectors, sensors, and diodes.

Asymmetry of diffusion permeability of bi-layer membranes.

To reveal the reason of asymmetry of the diffusion permeability of bi-layer electrodialysis membranes the following problems have been solved using the model of "homogeneous porous membrane": - diffusion of non-electrolyte solutions across a bi-layer membrane; - diffusion of electrolyte solutions across a non-charged bi-layer membrane; - diffusion of electrolyte solutions across a charged single layer membrane; - diffusion of electrolyte solutions across a charged bi-layer membrane. It is shown that the main factor responsible for the asymmetry is the difference between absolute values of densities of fixed charges (or so called "exchange capacities") of different layers of a membrane under investigation. Only in this case the ratio of the thickness of the membrane layers as well as the ratio of ion diffusivities contributes also to the asymmetry of the diffusion permeability. In the present review we survey and generalize our previous investigations and propose a new theory of asymmetry of diffusion permeability of bi-layer membranes. We have deduced explicit algebraic formulas for the degree of asymmetry of diffusion permeability of bi-layer membranes under consideration.