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     

Analytical model of laminar flow electrodialysis with ion-exchange membranes

A boundary-value problem for electrodialysis with ion-exchange membranes is posed and its analytical solution obtained. The solution allows one to calculate concentration fields in desalination and brine compartments, the current-density distribution along the flow coordinate and the thickness of diffusion boundary layers. It also makes it possible to estimate the value of local limiting current-density and to obtain the dependence of the process on physico-chemical characteristics of ion-exchange membranes (transport numbers and conductivity). The mathematical model was verified by a local distributive analysis made by means of laser interferometry.     

Demineralization of alkaline soil extracts by electrodialysis with inert and ion-exchange membranes

Mass-transfer in electrodialysis of alkaline soil extracts containing pyrophosphate ions with cellophane and MA-40 and MA-41 ion-exchange membranes was studied. The transport numbers of hydroxide- and phosphorus-containing ions and the degree of demineralization of the alkaline soil extracts were determined under the conditions under study.     

Mathematical model of electrodialysis with ion-exchange membranes and inert spacers

A mathematical model describing the two-dimensional concentration field of an electrodialysis device with inert spacers is proposed. The boundary-value problem includes the Navier-Stokes, continuity, and steady-state convective diffusion equations and well-defined conditions and is solved by the control-volume numerical method. Results are expressed in the form of functional relationships of generalized variables. It is shown that when channels of the electrodialysis device are filled with spacers that do not conduct electric current, mass transport increases by several times in comparison to devices with open channels. The possibility is discussed for replacing the inert spacers with ones that conduct ion, not only in the complete demineralization of natural waters, but also in the desalination of brackish ground waters.     

Auto-organisation of hybrid organic-inorganic materials prepared by sol-gel process

Silica-based hybrid organic-inorganic materials prepared by sol-gel chemistry exhibit chemical and physical properties revealing their anisotropic organisation. Besides the opportunities that this phenomenon opens for the preparation of new materials, it also provides arguments to the chemist looking for a better comprehension and control of the organisation of solids.     

Effects of circulation and facilitated electromigration of amino acids in electrodialysis with ion-exchange membranes

Dependences of fluxes of the mass of amino acids and mineral ions on the density of a direct electrical current in an electrodialysis process are obtained experimentally. Mutual influence of components on transport at low strengths of the electric field in membranes is discussed. Effects of circulation and facilitated electromigration of amino acids are considered. At a small excess of the limiting current density, the effects lead to a decrease in fluxes of amino acids through membranes. At a large excess of the limiting current, the effects result in an intensive conjugated transport of bipolar ions with the medium ions through membranes.     

An organic-inorganic hybrid thermochromic ferroelastic with multi-channel switches

Multifunctional switchable materials are attracting tremendous interest because of their great application potential in signal processing, information encryption, and smart devices. Here, we reported an organic-inorganic hybrid thermochromic ferroelastic crystal, [TMIm][CuCl₄] (TMIm = 1,1,3,3-tetramethylimidazolidinium), which undergoes two reversible phase transitions at 333 K and 419 K, respectively. Intriguingly, these three phases experience a remarkable ferroelastic-paraelastic-ferroelastic (2/m-mmm-2/m) transition, which remains relatively unexplored in ferroelastics. Moreover, the ferroelastic domains can be simultaneously switched under temperature and stress stimuli. Meanwhile, [TMIm][CuCl₄] exhibits thermochromic phenomenon, endowing it with extra spectral encryption possibilities during information processing. Combined with dielectric switching behavior, [TMIm][CuCl₄] are promising for practical applications in memory devices, next-generation sensors, and encryption technology.     

Study of pH correction process of chloride-bicarbonate dilute solutions by electrodialysis with bipolar membranes

The pH of a dilute chloride-hydrocarbonate solution and the concentrations of chloride ions and carbonic acid anions at the outlet of the alkaline and acid chambers of the electrodialysis cell formed by bipolar and anion-exchange membranes were determined. The decrease in the concentration of hydrocarbonate ions in the alkaline chamber with growth of current density was not equal to its increase in the acid chamber. This disbalance was caused by two concurrent processes: the electromigration ion transport through the anion-exchange membrane and the chemical reactions of hydrocarbonate ions with the water dissociation products formed on the bipolar and anion-exchange membranes. A mathematical model was suggested to describe the electrodialysis correction of the pH of a dilute chloride-hydrocarbonate solution. The experimental data on the correction of pH of the chloride-hydrocarbonate solution were well approximated by both the model that takes into account water dissociation on the anion-exchange membrane and the simplified model that neglects water dissociation. The experimental data agreed well with the results of calculations by the model in which the effective anion transport numbers were calculated only from ion concentrations and diffusion coefficients in solution. This reflects the outer diffusion character of the kinetics of ion transport through the anion-exchange membrane, with pH of dilute solutions corrected by electrodialysis.     

sol-gel 法在有机-无机杂化体系中制备二氧化硅微粒

利用sol-gel法,通过正硅酸乙酯（tetraethyl orthosilicate（TEOS））在聚氧化乙烯／二甲基甲酰胺溶液中水解、缩聚,制备了粒径分布均匀的微米级二氧化硅粒子;利用扫描电子显微镜观测了制备条件对二氧化硅粒子的粒度和形貌的影响;研究了这一方法在制备无机粒子过程中的原理．     

Composite sulfonated cation-exchange membranes modified with polyaniline and applied to salt solution concentration by electrodialysis

A method is developed for obtaining anisotropic composites based on the sulfonated cation-exchange MF-4SK and MK-40 membranes and the electroactive polymer polyaniline (PANI). The kinetics of aniline polymerization by successive diffusion in these membranes is investigated, and differences in the transport characteristics of the resulting MF-4SK/PANI and MK-40/PANI composites are identified. It is established from results of electroosmotic and diffusion experiments that the composite MF-4SK/PANI-1 membrane (after 1 h of aniline polymerization) suppresses electrolyte and water flow the most. Diffusion permeability drops by an order of magnitude, and water transport numbers are reduced by 50–70%. In the process of sodium chloride concentration by electrodialysis, the salt content of the concentrate increases by 50–70% with the composite MF-4SK/PANI-1 membrane compared to the base MF-4SK membrane and by 15–20% compared to the electrodialysis MK-40 membrane. Transport characteristics of the membrane pairs under investigation are calculated from the model of limiting concentration by electrodialysis: current efficiency, water transport numbers, osmotic and diffusion permeability. The dominant influence of the electroosmotic mechanism of water transport on the effect of salt solution concentration is established.     

Salicylic acid production by electrodialysis with bipolar membranes

Production of salicylic acid from sodium salicylate was carried out by electrodialysis (ED) using bipolar membranes (BPM). The process feasibility was tested using a laboratory ED-cell with a membrane area of 40 cm². The performances of two commercial bipolar membranes (Tokuyama Soda and Stantech membranes) are compared. Current efficiencies for salicylic acid and caustic soda production are close for both bioolar membranes (80–90%), but differences are observed with respect to energy consumption which are related to the electrical characteristics of the membranes.     

Ion and water transport during lithium chloride concentration from aqueous organic solutions by electrodialysis

The concentration of lithium chloride from aqueous organic solutions with different volume concentrations of N,N-dimethylacetamide (DMAA) was studied experimentally. An extended model of the limiting electrodialysis concentration of electrolytes from mixed media was developed. The model takes into account the osmotic and electroosmotic mechanisms of the transfer of water and organic solvent, as well as the electromigration and diffusion mechanisms of the salt transfer. Using the experimental data and the extended model, we evaluated the transport parameters of the MK-40/MA-40 membrane pair in aprotic solutions of variable compositions and studied how they changed with an increase in the volume fraction of DMAA in a mixed solution. The contribution of each of these mechanisms of ion and water transport to the electrodialysis concentration of electrolyte from aqueous and organic aqueous solutions was determined. Electroosmotic transfer was found to be the main mechanism of the solvent transfer that limits the stage of the electrodialysis concentration of the electrolyte from aqueous and organic aqueous solutions.     

Design and properties of functional hybrid organic-inorganic membranes for fuel cells

This critical review presents a discussion on the major advances in the field of organic-inorganic hybrid membranes for fuel cells application. The hybrid organic-inorganic approach, when the organic part is not conductive, reproduces to some extent the behavior of Nafion where discrete hydrophilic and hydrophilic domains are homogeneously distributed. A large variety of proton conducting or non conducting polymers can be combined with various functionalized, inorganic mesostructured particles or an inorganic network in order to achieve high proton conductivity, and good mechanical and chemical properties. The tuning of the interface between these two components and the control over chemical and processing conditions are the key parameters in fabricating these hybrid organic-inorganic membranes with a high degree of reproducibility. This dynamic coupling between chemistry and processing requires the extensive use and development of complementary ex situ measurements with in situ characterization techniques, following in real time the molecular precursor solutions to the formation of the final hybrid organic-inorganic membranes. These membranes combine the intrinsic physical and chemical properties of both the inorganic and organic components. The development of the sol-gel chemistry allows a fine tuning of the inorganic network, which exhibits acid-based functionalized pores (-SO(3)H, -PO(3)H(2), -COOH), tunable pore size and connectivity, high surface area and accessibility. As such, these hybrid membranes containing inorganic materials are a promising family for controlling conductivity, mechanical and chemical properties (349 references).     

Effect of polyether diamine on gas permeation properties of organic-inorganic hybrid membranes

The quantitative incorporation and high dispersion of platinum nanoparticles into MCM-41 has been carried out by the coordination between Pt(IV) ion and APTMS-anchored MCM-41. Before and after calcination of Pt/APTMS/MCM41 samples, the Pt content in samples was evaluated from home-made photoacoustic spectrometer (PAS). The PAS bands at 350 nm and 450 nm can be assigned to d–d transition bands of Pt complexes. By increasing the concentration of Pt solution, the PAS intensity of Pt/APTMS/MCM41 was increased proportionally up to 1.0×10⁻² M, and remained constant above 1.0×10⁻² M. It can be attributed to the saturation of Pt content within Pt/APTMS/MCM41. The Pt content in the saturated Pt/APTMS/MCM41 was 8.5 wt% (the theoretical value), 9.7 wt% (measured by EDX) and 9.2 wt% (measured by ESCA), respectively. This indicates that the content of Pt precursor within MCM-41 could be controlled by the concentration of Pt precursor solution. The PAS intensity of calcined Pt/APTMS/MCM41's in H₂ flow was increased up to 1.0×10⁻² M and remained nearly constant above 1.0×10⁻² M. Therefore, we suggest that the formation of Pt complexes with APTMS-anchored MCM-41 made it possible to incorporate quantitatively Pt nanoparticles in the range of 0.5–9.2 wt% within MCM-41 channels.     

Perspectives of aerosol-photopolymerization: organic-inorganic hybrid nanoparticles

The technique of aerosol-photopolymerization is employed for the generation of organic-inorganic spherical polymer-matrix nanocomposites (PMNCs). The loading amount of well-distributed ZnO nanoparticles in polymer networks is varied in a broad range up to 40 wt.%. Similar hybrid particles are produced without the addition of a conventional photoinitiator by making use of the UV absorptivity of ZnO nanoparticles only. Highlights of the process are the continuous, aerosol-based setup with a flow-through photoreactor operated at ambient temperature and atmospheric pressure. Aerosol-photopolymerization possesses great potential of incorporating various materials in situ into a polymer matrix, resulting in hybrid materials for diverse applications. Furthermore, the process can be integrated with further unit operations for the design of smart materials.     

Diffusion dialysis aided electrodialysis process for concentration of radionuclides in acid medium

A study on the separation of the long-lived heat generating fission products¹³⁷Cs and⁹⁰Sr from acidic solutions has been carried out using a specially fabricated electrodialytic cell equipped with a pair of cation and anion exchange membranes forming a catholyte and anolyte, respectively, and a radioactive feed chamber. The studies were done with feed solutions containing different concentrations of Na⁺, Cs⁺ and Sr²⁺ individually and with a mixture of these cations in 0.3 M HNO₃. In all the cases, the transfer of Cs and Sr was found to be greater than 90%. To facilitate the separation of the above radionuclides from higher acidity (∼3.0M HNO₃), diffusion dialysis was taken as a possible pretreatment step using a two compartment diffusion cell with an anion exchange membrane in between. All the experiments were done under non-stirring mode.     

Correction of pH of diluted solutions of electrolytes by electrodialysis with bipolar membranes

The current efficiencies of the water dissociation water and the voltage-current characteristics of the bipolar (asymmetric bipolar) membranes were measured in a two-chamber electrochemical cell. The cell was formed of an MB-3 bipolar membrane or an asymmetric bipolar membrane, which is an MA-40 heterogeneous membrane with a thin surface layer in the form of a cation-selective homogeneous film and MA-40 and MA-41 heterogeneous monopolar membranes. The dissociation of water on MA-40 in 0.01 M sodium chloride decreased the current efficiency of the acid and alkali both in the channel with a bipolar membrane and in the channel with an asymmetric bipolar membrane. The effective ion transport numbers across MA-40 and MA-41 at different pH values were determined. The water dissociation rate on MA-40 decreased at pH > 9.5. A kinetic model of the electrodialysis of a dilute solution of sodium chloride in a two-chamber unit cell with a bipolar and anionite membranes was suggested.     

Regeneration of mixed solvent by electrodialysis: selective removal of chloride and sulfate

The applicability of electrodialysis for the selective removal of sulfate and chloride ions from a mixed solvent solution of sodium carbonate is investigated. The mixed solvent consists of 70 wt.% ethylene glycol and 30 wt.% water. Six different ion exchange membranes, the homogeneous membranes Neosepta CM-2, AM-3, AMX and ACM as well as the heterogeneous FuMA Tech CM-A and AM-A, are tested for their chemical and physical resistance to the mixed solvent carbonate solution, their ethylene glycol retention, their electrical resistance in the mixed solvent and their selectivity for sulfate and chloride over carbonate transport.     

Features of the sorption of phenylalanine by profiled ion-exchange membranes

Features of the equilibrium sorption of phenylalanine from neutral media by profiled ion-exchange membranes in a wide range of concentrations is studied under static conditions. The mechanism of phenylalanine sorption by ion-exchange membranes with profiled and smooth surfaces is discussed. It is shown that phenylalanine sorption is accompanied by the formation of spatial associative structures of the aminoacid in an external equilibrium solution, and in a solution of the membrane’s pore spaces or on its surface. The increased sorption capacity of the profiled membranes is explained by features of the microstructure of their surface and volume.     

Effect of an ion-exchange filler on the deionized water quality in electrodialysis

Desalination channels, containing an inert separator and a monolayer of ionites AV-17 and KU-2 taken in various volume ratios, are studied while maintaining concentrations of all solution components invariant. It is shown that the composition of the ion-exchange filler of the desalination channel affects the rate of transport of salt ions through relevant membranes, pH, and specific resistance of desalinated solution. The behavior of membrane systems in an overlimiting state is explained by using notions about different mechanisms governing the so-called overlimiting current through anion-exchange and cation-exchange membranes