ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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.
