Synthesis,characterization and electrochemical properties of cation selective ion exchange composite membranes

In this work polystyrene based strontium phosphate membranes (SPMs) were prepared by applying different pressures. The membrane potential is measured with uni-univalent electrolytes (KCl, NaCl, and LiCl) solutions using saturated calomel electrodes (SCEs). The effective fixed charge density of these membranes is determined by the Torell, Meyer and Sievers method and it showed the dependence of membrane potential on the porosity, the charge on the membrane matrix, charge and size of permeating ions. The membranes are characterized by X-ray diffraction, scanning electron microscopy and IR spectroscopy. The order of surface charge density for electrolytes is KCl > NaCl > LiCl. Other parameters such as transport number, distribution coefficient, charge effectiveness and related parameters are calculated. The membrane was found to be mechanically stable, and can be operated over a wide pH range.     

Experimental analysis, modeling, and theoretical design of McMaster pore-filled nanofiltration membranes

A side-by-side comparison of the performance of McMaster pore-filled (MacPF) and commercial nanofiltration (NF) membranes is presented here. The single-salt and multi-component performance of these membranes is studied using experimental data and using a mathematical model. The pseudo two-dimensional model is based on the extended Nernst–Planck equation, a modified Poisson–Boltzmann equation, and hydrodynamic calculations. The model includes four structural properties of the membrane: pore radius, pure water permeability, surface charge density and the ratio of effective membrane thickness to water content. The analysis demonstrates that the rejection and transport mechanisms are the same in the commercial and MacPF membranes with different contributions from each type of mechanism (convection, diffusion and electromigration). Solute rejection in NF membranes is determined primarily by a combination of steric and electrostatic effects. The selectivity of MacPF membranes is primarily determined by electrostatic effects with a significantly smaller contribution of steric effects compared to commercial membranes. Hence, these membranes have the ability to reject ions while remaining highly permeable to low molecular weight organics. Additionally, a new theoretical membrane design approach is presented. This design procedure potentially offers the optimization of NF membrane performance by tailoring the membrane structure and operating variables to the specific process, simultaneously. The procedure is validated at the laboratory scale.     

Preparation and evaluation of effective fixed charge density of titanium phosphate membranes for uni-univalent electrolytes in aqueous solutions

The preparation of polystyrene-based titanium phosphate membranes at different pressures with varying amounts of material has been explained. The membrane potentials of inorganic membranes were measured with uni-univalent electrolytes (KCl, NaCl and LiCl) solution using saturated calomel electrodes (SCEs). The TMS method was used for the evaluation of the effective fixed charge density of these membranes with increasing pressure, and the surface charge density of membrane appeared to be increased due to gradually diminution in surface opening channels. The order of surface charge density for electrolytes used is found to be KCl > NaCl > LiCl. In addition to the effective fixed charge density, distribution coefficient, transport numbers, charge effectiveness and other related parameters were calculated for characterizing the ion exchange membranes by utilizing the TMS method. The theoretical prediction is consistent well with the experimental data. The SEM of these membranes at various pressures has been presented.     

The electrostatic and steric-hindrance model for the transport of charged solutes through nanofiltration membranes

Nanofiltration (NF) membranes possess the intermediate molecular weight cut-off between reverse osmosis membranes and ultrafiltration membranes, and also have rejection to inorganic salts. So one can assume that NF membranes have charged pore structure. We have developed the electrostatic and steric-hindrance (ES) model from the steric-hindrance pore (SHP) model and the Teorell-Meyer-Sievers (TMS) model (Wang et al., J. Chem. Eng. Japan, 28 (1995) 372) to predict the transport performance of charged solutes through NF membranes based on their charged pore structure. In this article, by doing the permeation experiments of aqueous solutions of neutral solutes and sodium chloride, the structural parameters (the pore radius and the ratio of membrane porosity to membrane thickness) and the charge density of NF membranes (Desal-S, NF-40, NTR7450 and G-20) were estimated on the basis of SHP model and the TMS model, respectively. Then, we selected an aqueous solution of different tracer charged solutes (sodium benzenesulfonate, sodium naphthalenesulfonate and sodium tetraphenyl-borate) and a supporting salt (sodium chloride) to verify the ES model. The prediction based on the ES model was in good agreement with the experimental results.     

The study of sorption and transport properties of membranes containing polyaniline

The transport properties of membranes based on polyimide-polyaniline composites are studied in the pervaporation separation of a methanol-toluene binary azeotropic mixture. The morphology of the membranes is investigated by electronic microscopy, and the wettability of their surface is analyzed by contact-angle measurements. Special attention is given to the study of sorption and diffusion characteristics of membranes affecting the selectivity and rate of membrane separation. It is found that the incorporation of polyaniline into the matrix of the aromatic polyimide facilitates a reduction in the density of the composites relative to that of the nonmodified polyimide. It is shown that the membranes based on the polyimide-polyaniline composites are more selective with respect to methanol and show lower permeability during pervaporation of the methanol-toluene mixture than polyimide membranes.     

A study of the transport of ions against their concentration gradient across ion-exchange membranes using the network method

The network method has been used to analyze the conditions that favour the uphill transport across ion-exchange membranes. A model for the Nernst-Planck-Poisson equations describing the ionic transport in such system is proposed, including the Donnan equilibrium relations at the membrane/solution interfaces. With this model and the electric circuit simulation program PSPICE, the transient response of the system under open circuit conditions (I=0) and the response of the system subject to an applied potential difference are simulated. The ionic concentrations and electric potential profiles, as well as the electric current density, the ionic fluxes and the charge density, have been obtained as a function of time.     

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.     

Assessing the selectivity of composite ion-exchange membranes within the framework of the extended three-wire model of conduction

The possibility of assessing the selectivity of composite perfluorated membranes MF-4SK modified with polyaniline (PANI), based on the concentration dependence of their specific conductivity in terms of the extended three-wire model of conduction of ion-exchange materials is investigated. To check the reliability of results obtained, the transport numbers of ions are calculated based on the electrodiffusion coefficients of counter ions and coions determined from concentration dependences of conductivity and diffusion permeability of ion-exchange membranes. The transport numbers of hydrogen ions found by these two methods are shown to coincide with high accuracy throughout the whole range of concentrations of HCl solutions for the original MF-4SK membrane and membranes with the fixed thickness of the modified polyaniline layer on their one side. For the MF-4SK sample the with gradient distribution of polyaniline, which exhibits asymmetrical transport characteristics, the deviation between the transport numbers of ions calculated with the use of electrodiffusion coefficients of counter ions and coions and those determined in terms of the extended three-wire model of conduction is shown to increase with the increase in solution concentration but not exceed 4%.     

Synthesis and diffusion permeability of MF-4SK/polyaniline composite membranes with controlled thickness of the modified layer

A new method is proposed for the synthesis of anisotropic membranes based on F-4SF films, which ensures their modification with polyaniline in a layer with a fixed thickness. The concentration dependences of conductivity and diffusion permeability of the composite membranes are studied. These parameters decrease with increasing thickness of the polyaniline-modified layer. The quantitative correlation is revealed between the regularities of variations in both transport characteristics and the thickness of the modified layer. The absence of the asymmetry of the diffusion permeability of the examined composite membranes is explained in terms of the model of a charged bilayer membrane.     

Theory of pressure-driven transport of neutral solutes and ions in porous ceramic nanofiltration membranes

Hindered transport theory and homogeneous electro-transport theory are used to calculate the limiting, high volume flux, rejection of, respectively, neutral solutes and binary electrolytes by granular porous nanofiltration membranes. For ceramic membranes prepared from metal oxides it is proposed that the membrane structural and charge parameters entering into the theory, namely the effective pore size and membrane charge density, can be estimated from independent measurements: the pore radius from the measured hydraulic radius using a model of sintered granular membranes and the effective membrane charge density from the hydraulic radius and the electrophoretic mobility measurements on the ceramic powder used to prepare the membrane. The electro-transport theory adopted here is valid when the membrane surface charge density is low enough and the pore radius is small enough for there to be strong electrical double layer overlap in the pores. Within this approximation the filtration streaming potential is also derived for binary electrolytes.     

Ion transport modelling through nanofiltration membranes

The aim of this work is to study the transport mechanism of ions through nanofiltration membranes. A model based on extended Nernst–Planck and film theory equations is reported. This model can be characterized by three transport parameters: the water permeability L_p, the salt transmittance Φ and the effective salt transfer coefficient K_eff. The knowledge of the feed and permeate concentration and of the permeate volumetric flux enable us to calculate these transport parameters. The model is used to estimate cadmium salts rejection by a NANOMAX 50 membrane. Experimental and calculated results are shown to be in good agreement. The model is then successfully extended to experimental data reported in the literature.     

Synthesis of Fullerene-Polyphenylene Oxide Membranes for Separating Aqueous-Organic Mixtures

Homogeneous fullerene-polyphenylene oxide membranes containing up to 2 wt % C₆₀ are synthesized and characterized by the density, electrical resistivity, and contact angle with water and ethanol. The effect of fullerene additive on the transport characteristics of the membranes in pervaporation of water mixtures with ethanol and ethyl acetate is studied.     

Investigation of gas transport through porous membranes based on nonlinear frequency response analysis

Theoretical development of a new experimental method for investigation of mass transport in porous membranes, based on the principle of the modified Wicke-Kallenbach diffusion cell and the nonlinear frequency response analysis is presented. The method is developed to analyze the transport of a binary gas mixture in a porous membrane. The mixture is assumed to consist of one adsorbable and one inert component. Complex mass transfer mechanism in the membrane, where bulk or transition diffusion in the pore volume and surface diffusion take place in parallel, is assumed. Starting from the basic mathematical model equations and following a rather standardized procedure, the frequency response functions (FRFs) up to the second order are derived. Based on the derived FRFs, correlations between some characteristic features of these functions on one side, and the whole set of equilibrium and transport parameters of the system, on the other, are established. As the FRFs can be estimated directly from different harmonics of the measured outputs, these correlations give a complete theoretical basis for the proposed experimental method. The method is illustrated by quantifying the transport of helium (inert gas) and C₃H₈ and CO₂ (adsorbable gases) through a porous Vycor glass membrane.     

Permeability of membranes containing ionogenic groups

The present paper deals with the transport properties of membranes made of hydrophilic gels containing ionogenic groups. Introduction of ionogenic groups into a gel based on 2-hydroxyethyl methacrylate will affect the permeability of the investigated membranes for sodium chloride by an order or more. Dependences of the permeability on the content of ionogenic groups, three-dimensional network density, and pH were established. The permeability for NaCl was compared for that for bivalent salt (MgSO₄). It is shown, on the basis of independently determined distribution coefficients, that an increase in the permeability of ampholytic membranes in comparison with the neutral ones is primarily due to an increase in the diffusivity of the salt in the membranes with modified structure. It can also be concluded that an approximation of the free volume from the volume of the solvent in the membrane cannot be applied to the poly(2-hydroxyethyl methacrylate) gel.     

Model verification of limiting concentration by electrodialysis of an electrolyte solution

The concentration of LiCl in brine and brine volume are obtained as functions of current density by the method of limiting concentration by electrodialysis. These relationships are used for model calculations of current efficiency, the diffusion, osmotic, and electroosmotic permeability of an MK-40/MA-40 membrane pair, and also salt hydration numbers. These theoretical values of water transport numbers and LiCl hydration numbers are compared with corresponding experimental and literature data. It is shown that the model adequately describes the phenomena of the mass electrotransport occurring in electrodialyzers with noncirculating concentration compartments, and it can be successfully applied in calculating the technological parameters of the process, finding the transport properties of ion-exchange membranes, and determining salt hydration numbers in aqueous electrolyte solutions.     

平板双分子层脂膜的制备及锌离子跨该膜的输运过程

制备了氧化胆固醇 卵磷脂(脑磷脂)平板双分子层脂膜,研究了膜配方对双分子层脂膜的稳定性和离子通透性的影响,得到了最佳制膜工艺,建立了锌离子跨卵 (脑 )磷脂膜的吸附 -扩散模型,其计算值与实验值基本吻合.     

Transport properties of highly ordered heterogeneous ion-exchange membranes

Model "ordered" heterogeneous ion exchange membranes are made with ion exchange particles heaving ion exchange capacity in the range 3 to 2.5 meq/gr (dry basis) and diameters ranging from 37 to 7 microm and 2 component room-temperature vulcanizing silicon rubber as a polymeric matrix, by applying an electric field normal to the membrane surface during preparation. These membranes were shown to have an improved ionic conductivity compared with "nonordered" membranes based on the same ion exchange content (for instance, at 10% resin content "nonordered" membranes show <10(-5) mS/cm while "ordered" membranes have conductivity of 1 mS/cm). The transport properties of ordered membranes were compared with those of nonordered membranes, through the current-voltage characteristics. Limiting currents measured for the ordered membranes were significantly higher than those of the nonordered membranes with the same resin concentration. In addition, higher limiting currents were observed in ordered membranes as the resin particles became smaller. Energy dispersion spectrometry analyses revealed that the concentration of cation exchange groups on the membrane surface was higher for ordered membrane as compared to that of nonordered membranes. This implies that the local current density for the conducting domains at the surface of the nonordered membranes is higher, leading to higher concentration polarization and, eventually, to lower average limiting current densities. The effect of ordering the particles on the membrane conductivity and transport properties was studied, and the advantages of the ordered membranes are discussed.     

A Comparative Study of the Electric Transport of Ions and Water in Sulfonated Cation-Exchange Polymeric Membranes of the New Generation

This work presents the results of the studies concerning the electric transport of ions and water through sulfonated cation-exchange membranes synthesized on the basis of polysulfone (PS) and poly(ether–ether–ketone) (PEEK). The concentration dependences of the water absorption capacity, specific conductance, and diffusion and electroosmotic permeabilities measured in sodium chloride solutions are compared to the analogous characteristics of some commercial membranes (MK-40, MF-4SK, CL-25T) under the same experimental conditions. The model concepts concerning the permeability of ion-conducting membranes as disperse systems are found to be applicable for interpreting the set of the electric transport properties of the membrane samples studied. A cluster–channel type of the membrane structure is identified. The polymeric films based on PS and PEEK are shown to possess characteristics comparable to those of commercial ion-exchange membrane samples and can be recommended for producing polymer compositions with an optimum set of electric transport properties.     

Membrane characterization by solute transport and atomic force microscopy

Various ultrafiltration and nanofiltration membranes were characterized by solute transport and also by atomic force microscope (AFM). The molecular weight cut-off (MWCO) of the membranes studied were found to be between 3500 and 98,000 Daltons. The mean pore size (μ_p) and the geometric standard deviation (σ_p) around mean ranged from 0.7 to 11.12 nm and 1.68 to 3.31, respectively, when calculated from the solute transport data. Mean pore sizes measured by AFM were about 3.5 times larger than calculated from the solute transport. Pore sizes measured by AFM were remarkably fitted to the log-normal probability distribution curve. Pore sizes of the membranes with low MWCO (20,000 Daltons and lower) could not be measured by AFM because of indistinct pores. In most cases, the pore density ranged from 38 to 1291 pores/μm². In general, the pore density was higher for the membrane having lower MWCO. Surface porosity was around 0.5–1.0% as measured from the solute transport and was 9.5–12.9% as obtained from AFM images. When membranes were coated with a thin layer of sulfonated polyphenylene oxide, mean pore sizes were reduced for all the membranes. Surface roughness was also reduced on coating.     

Experimental and theoretical studies of asymmetry of transport properties of modified ultrafiltration membranes

Ultrafiltration membranes based on polyamide and polysulfone modified by polyelectrolytes are produced. The effect of the nature of a polymer matrix and modifier on the rejection ability and diffusion permeability of membranes is studied. The effect of the asymmetry of transport properties, which is manifested at different orientations of membrane with respect to the flow of electrolyte, is quantitatively evaluated. It was demonstrated that the asymmetry of substance transport is more pronounced in the ultrafiltration regime than in the diffusion of sodium chloride solutions. A mathematical model that describes the filtration of binary electrolyte solutions on partially charged two-layer membranes is proposed and the corresponding boundary-value problem is solved analytically. The qualitative correspondence between theoretical calculations and experimental data on the asymmetry effect of the rejection ability of two-layer system is revealed.