ABSTRACT
A bilayer membrane based on a heterogenous cation exchange membrane with a homogeneous cation exchange layer and a polyaniline on its surface is prepared. The intercalation of polyaniline into the membrane with a homogeneous cation exchange layer is performed by oxidative polymerization of aniline. The influence of the homogeneous cation exchange layer and the polyaniline on the structure, conductivity, diffusion permeability, selectivity, and current-voltage curve of the heterogeneous cation exchange membrane is established. Membrane properties are studied in the HCl, NaCl, and CaCl2 solutions. The homogeneous cation exchange layer has a negligible effect on the transport properties of the initial heterogeneous membrane. The polyaniline synthesis leads to a decrease in the macropore volume in the membrane structure, conductivity, and diffusion permeability. The counterion transport number in the bilayer membrane is significantly reduced in a solution of calcium chloride and practically does not change in sodium chloride and hydrochloric acid. In addition, the asymmetry of the diffusion permeability and shape of current-voltage curve depending on the orientation of the membrane surface to the flux of electrolyte or counterion are found.
ABSTRACT
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.
Subject(s)
Electrolytes , Water , Water/chemistry , Osmosis , Electrolytes/chemistry , Cations , MembranesABSTRACT
A correlation between changes in structural and electrotransport properties of membranes after modification by silica and zirconium hydrophosphate was established. The total water volume, volume fraction of the free water in the membrane and the volume fraction of the water having high binding energy were considered as structural characteristics, which were found from the curves of water distribution on the water binding energy and the effective pore radii. The conductivity, diffusion and electroosmotic permeabilities were investigated as electrotransport properties. The influence of the modifier type on the current flow paths in the membrane was analyzed within the framework of the extended three-wire model. It has been established that the treatment of membranes with alcohol before the intercalation of a modifier leads to the appearance of cavities with an effective size of more than 100 nm filled with free water with the binding energy less than 10 J/mol. It is accompanied with an increase in the diffusion permeability of hybrid membranes by approximately 3-6 times in NaCl and HCl solutions, which limits the application of such materials in proton exchange membrane fuel cells. The different conditions of modification of perfluorinated membranes with similar properties by the dopant with same type allow for the preparation of the hybrid materials for various applications such as electrodialysis concentration or electric current generation devices.
