V. I. Vasil’eva

The surface inhomogeneity of ion-exchange membranes by SEM and AFM data

The surface structure (morphology and roughness) of different types of ion-exchange membranes is investigated via scanning electron microscopy and atomic-force microscopy. It is established that the distribution of ion-exchange regions on the surface of heterogeneous membranes exhibits a complex stochastic character; the sizes of these regions are 5–30 μm. The sizes of irregularities on the surface of homogeneous membranes do not exceed 1 μm. After the samples are subjected to conditioning and the effect of current and temperature, the sizes and portions of the conducting regions of the surface thereof become larger than those of commercial samples by 10–20%. The dependence of the surface microrelief on the membrane type and external factors (chemical conditioning, current, and temperature) is revealed for the first time. The minimum roughness factor corresponds to the surfaces of artificially homogenized and commercial samples of heterogeneous membranes, and the maximum quantities fr are obtained for membranes with pronounced surface reliefs after current and temperature effects.

Effect of thermochemical treatment on the surface morphology and hydrophobicity of heterogeneous ion-exchange membranes

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 membranes. A correlation between changes in surface morphology and hydrophobicity is established. It is shown that under prolonged (50 h) membrane thermal treatment above room temperature, hydrophobicity is reduced due to substantial enlargement of cavities and cracks resulting from the partial destruction of inert binder (polyethylene) and reinforcing poly-ɛ-caproamide fabric (capron).

SEM diagnostics of the surface of MK-40 and MA-40 heterogeneous ion-exchange membranes in the swollen state after thermal treatment

The morphology of the surface of MK-40 and MA-40 ion-exchange membranes in the swollen state after chemical and thermal treatment is studied using scanning electron microscopy. The distribution of portions of the ion exchanger on the surface of heterogeneous membranes is found to be of a complex stochastic nature; their sizes for the MK-40 and MA-40 membranes are 5–30 and 8–40 μm, respectively, while the sizes typical for the secondary porous structure are 2–8 μm. An increase in the share of the ion-exchange component of the surface (by 20–40%), the sizes of the ion-exchange portions (by 20%), and the surface porosity (by two-three times) in the samples subjected to thermal treatment is revealed.

Diffusion boundary layers during electrodialysis

A laser interferometry method for direct measurements of thicknesses of diffusion boundary layers is described. The method is employed to explore electromembrane processes. Thicknesses of diffusion boundary layers at below and above limiting diffusion current densities are measured and compared with theoretical values. It is shown that the diffusion boundary layers in narrow channels of electrodialyzer sections overlap one another at high current densities. This radically alters traditional notions concerning the diffusion boundary layer. An interpretation for variations in the thickness of a diffusion boundary layer at current densities in excess of the limiting diffusion current density is given.

Effect of the chemical nature of the ionogenic groups of ion-exchange membranes on the size of the electroconvective instability region in high-current modes

The size of the electroconvective instability region on the membrane-solution boundary at currents exceeding the limiting diffusion current was measured by laser interferometry. The influence of the chemical nature of the ionogenic groups of ion-exchange membranes on the development of electroconvective instability was studied. The thickness of the electroconvection region decreased as the catalytic activity of the ionogenic groups of commercial and pilot membrane samples with respect to the heterolytic water dissociation increased. The maximum size of the electroconvective instability region and the minimum currents at which it was recorded for the anion-exchange membranes under study were determined for the highly basic modified anion-exchange membrane MA-41M with an almost completely suppressed water dissociation function. A correlation was found between the size of the convective instability region and the characteristic points on the current-voltage curves.

Thermoconvective instability during electrodialysis

A laser interferometry method is proposed for studying the instability of concentration fields during electrodialysis. It is shown that exceeding the limiting diffusion current density first gives rise to alternating oscillations and then to oscillations at the membrane whose ionogenic groups exhibit the lowest catalytic activity towards the water dissociation reaction. Thereafter, the auto-oscillation process extends over the whole solution volume in the compartments, and dissipative chaos is observed with a further increase in the current density. This instability is presumably a consequence of unevenly distributed heat sources, namely, the Joule heat and the heat of dissociation and recombination of water molecules.

Electrochemical properties and structure of ion-exchange membranes upon thermochemical treatment

The effect of temperature-induced morphological changes on the electrochemical and physicochemical properties of the heterogeneous sulfo cation-exchange membrane MK-40 in aqueous, alkaline, and acidic media is subjected to comparative analysis. The deviation between the surface and volume microstructure of swollen membrane samples after their chemical conditioning and thermochemical treatment are visualized by a scanning electron microscope. The porosity and the fraction of the ion-exchange component in membranes subjected to heating in water and aggressive media are observed to increase more noticeably in their surface layer as compared with their volume. The maximum effect thus modified structural characteristics on the transport (conductivity, diffusion permeability, selectivity) and physicochemical (exchange capacity, water content, density, linear sizes) properties is observed for MK-40 membrane samples when heated in a sulfuric acid solution. The effect of thermal destruction of inert polymers (divinylbenzene, caprone) involved in the membrane composition on the transport characteristics is revealed.

Concentration polarization of ion-exchange membranes in electrodialysis: An interferometric study

The three-frequency laser interferometry method is used for studying the concentration polarization of ion-exchange membranes in a wide range of current densities. The concentration and temperature fields of solutions involved in electrodialysis of sodium chloride are measured simultaneously. The proposed method makes it possible to measure absolute values of local concentrations of acids and bases that form during irreversible dissociation of water molecules at the solution-membrane interfaces following an increase in the current density above the limiting value. According to an analysis of the concentration and temperature distributions in an electrodialyzer channel, maximum variations in the measured quantities occur near the interface. Dependences of the near-membrane concentrations and temperatures on the current density are compared with the voltammogram. The comparison shows that reaching the limiting current density sharply accelerates the nonequilibrium dissociation of water molecules and increases the temperature

A mathematical model describing voltammograms and transport numbers under intensive electrodialysis modes

A three-layer mathematical model of overlimiting state is developed. A reactive layer with a thickness depending on the current density is introduced into the model. A decrease in the thickness of diffusion layer, which donates the counterions, with increasing current density as a result of electroconvection is also taken into account. A boundary-value problem is formulated within the Nernst-Planck and Poisson’s model in the three-layer region with the boundary conditions of constant concentrations in the bulk solution. It is shown that an increase in the reactive layer thickness with increasing current density determines the behavior of effective transport numbers in the overlimiting state of ion-exchange electromembrane system. In the current range under consideration (from 1 to 20 limiting currents), the reactive layer thickness is several tens nanometers and reaches 70 nm at a 100-fold excess over the limiting current. To calculate the voltammograms, the dependence of effective thickness δN of diffusion layer on the current density is required. This dependence can be obtained by solving an inverse problem, from the laser interferometry experiments, or calculated by the Navier-Stokes hydrodynamic model. The model enables one to calculate the distribution of electric field strength, potential, concentrations in the diffusion layers and membrane.

Selective separation of sodium ions from a mixture with phenylalanine by Donnan dialysis with a profiled sulfogroup cation exchange membrane

The possibility of separating ions of metal from a mixture with ampholyte (an amino acid) by Donnan dialysis with an MK-40 sulfogroup cation exchange membrane is demonstrated. Conditions ensuring the selectivity and intensity of the mass transfer of sodium ions from a mixture with bipolar phenylalanine ions into a diffusate containing hydrochloric acid through a cation exchange membrane are found.