Enhancement of the monovalent cation perm-selectivity of Nafion by plasma-induced surface modification

In this paper, we focus on improvement of the monovalent cation perm-selectivity of a perfluorinated cation-exchange membrane, Nafion 117, by depositing an anion-exchange layer using a plasma surface modification process. The anion-exchange layer was deposited from 4-vinylpyridine monomer vapor followed by quaternization with 1-bromopropane. The transference number of divalent cation (Fe²⁺) through the membrane, t_Fe, decreased with increasing thickness of the plasma polymer layer at the expense of enhanced membrane resistance. A large interfacial resistance was observed between Nafion and the plasma polymer layer which was ascribed to the implantation of cationic species containing nitrogen. To avoid the formation of an interfacial layer, a novel method of plasma-induced surface modification was devised. After a Nafion 117 sheet was placed on an RF (radio-frequency) electrode and sputtered with an oxygen or argon plasma in order to produce active sites on the Nafion, 4-vinylpyridine or 3-(2-aminoethyl)aminopropyltrimethoxysilane vapor was introduced into the reactor to react with radical sites. t_Fe decreased with increasing RF power. t_Fe through Nafion modified with 3-(2-aminoethyl)aminopropyltrimethoxysilane was lower than that for Nafion modified with 4-vinylpyridine, probably due to its weak Si-C bond. Nafion treated by the plasma surface modification method exhibited a very high monovalent cation perm-selectivity compared with Nafion treated by the plasma polymerization method.     

Thorium (IV) phosphate‐polyaniline composite‐based hydrophilic membranes for bending actuator application

In the present study, ionic polymer metal composite (IPMC) membrane actuator based on triple‐layered thorium(IV) phosphate/polyaniline/Pt (ThP‐PANI‐Pt) was prepared via consecutive solution recasting and electroless plating methods. The triple‐layered membrane is composed of thorium(IV) phosphate (ThP) inorganic cation exchanger layer in the middle section, two layers of polyaniline deposited through in situ polymerization and finally Pt electrode layers on both the surfaces on the outer section. The water uptake capacity of the ThP‐PANI composite polymer membrane was found to be 95.40% at 45ºC for 10 h of immersion time. The ion exchange capacity and proton conductivity was found to be 1.6 meq g^?1of dry membrane and 1.12 × 10^?3 S cm^?1, respectively. Maximum water loss from IPMC was 38% at 4 V for a time period of 12 min. Scanning electron micrographs shows the smooth and uniform coating of Pt on both side of composite polymer membrane surfaces. Cyclic voltammetry, linear sweep voltammetry, transmission electron microscopy, Fourier transforms infrared spectroscopy, thermal gravimetric analysis, X‐ray diffraction, and tip displacement of ThP‐PANI‐Pt IPMC membrane actuator was also examined. POLYM. ENG. SCI., 57:258–267, 2017. © 2016 Society of Plastics Engineers     

Preparation of microporous membranes from cation exchange membranes prepared by the paste method

A microporous membrane is prepared by treating the cation exchange membrane (Fe⁺⁺⁺ form) with an H₂O₂ aqueous solution. The cation exchange membrane is prepared by the paste method: the base membrane is prepared beforehand and then sulfonated. The preparative conditions of the base membrane were studied in connection with the characteristics of the resultant microporous membrane. Furthermore, the availability of the microporous membrane for ultrafiltration was studied by using an aqueous solution of a bovine hemoglobin.     

阴离子交换膜改性及抗污染性能研究进展

电渗析技术应用于工业废水脱盐时,废水中有机物及其它杂质组分等会造成膜污染,进而影响脱盐性能。电渗析膜污染防治对促进电渗析在工业废水处理中的应用有重要意义。相比于阳离子交换膜,阴离子交换膜更易形成有机污染,且更严重。阴离子交换膜污染主要由腐殖酸、牛血清蛋白、阴离子表面活性剂等有机物造成,污染过程主要受静电作用、亲和作用和几何因素的影响。膜改性提高阴离子交换膜的抗污染性能是电渗析膜污染防治的有效方法,目前已有许多有关膜改性提高阴离子交换膜抗污染性能的报道。膜改性方法主要有化学改性法、等离子体改性法、表面涂覆改性法、电沉积改性法、自聚合改性法及改进基膜结构法等。本工作对阴离子交换膜改性及抗污染性能的研究进展进行了综述,对不同改性方法的优缺点进行了分析和评价。这些改性方法能提高阴膜表面的负电荷密度和亲水性、降低膜表面粗糙度和基膜含水率等,因此可以改善阴离子交换膜的抗污染性能。然而,目前研究获得的改性阴离子交换膜仍存在修饰层不稳定、抗污染性能不理想和性能测试不系统等缺点,需进一步优化改性方法、改性工艺、组分修饰及性能测试等,以获得抗污染性能稳定且效果良好的改性阴离子交换膜。     

Surface modification of composite ion exchange membranes by polyaniline

The aim of this work is to develop new selective cation exchange membranes (CEMs) from bivalent to monovalent selectivity by surface functional groups. So, a novel hybrid cation exchange membrane was prepared by polymerization of polyaniline on a composite membrane, made of polyvinylidene fluoride (PVDF) and sulfonated PVDF (S-PVDF). Polyaniline was doped with different doping agents and their effect on total salt extraction and selectivity of bivalent to monovalent cations was evaluated. The chemical and morphological properties of hybrid membranes were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). Ion exchange capacity (IEC), transport number, ion conductivity and water uptake decreased after surface polymerization. Composite membrane has a good selectivity (∼2) for bivalent and excellent removal of both cations. The hybrid membrane, doped with pTSA has a very high selectivity for monovalent ions (∼7.1) and a high removal of monovalent ions.     

Application of Psf–PPSS–TPA composite membrane in the all-vanadium redox flow battery

The Psf–PPSS–TPA composite cation exchange membrane consist of Psf(polysulfone)–PPSS (polyphenylenesulfidesulfone) block copolymer with TPA (tungstophosphoric acid) is prepared to apply for a separator in the all-vanadium redox flow battery. The membrane properties such as membrane resistance and ion exchange capacity, and thermal stability are investigated. The prepared Psf–PPSS–TPA composite cation exchange membrane showed higher thermal stability than Nafion117. The lowest membrane resistance of the prepared Psf–PPSS–TPA composite cation exchange membrane measured in 1 M (mol/dm³) H₂SO₄ aqueous solution was 0.94 Ω cm² at 0.5 g of TPA solution. The performance properties of the all-vanadium redox flow battery (V-RFB) using the prepared cation exchange membrane are measured. The electromotive force, open circuit voltage at state of charge (SOC) of 100%, was 1.4 V. This value meets a theoretical electromotive force value of the V-RFB. The measuring cell resistance in charge and discharge at SOC 100% were 0.26 Ω and 0.31 Ω, respectively. The results of the present study suggest that the prepared Psf–PPSS–TPA composite cation exchange membrane is well suited for use in V-RFB as a separator.     

PVC膜改性助剂PVDF/PS-SO3H/GMS的制备

将聚偏氟乙烯(PVDF)和阳离子交换树脂(PS-SO3H)、单甘酯(GMS)以适当的比例充分混合均匀,经造粒机挤出即得到新型PVC膜改性助剂。最佳工艺条件为:配比PVDF/PS-SO3H/GMS为82∶14∶4,用于PVC膜混合料,PVC树脂/PVC膜改性助剂的最佳配比为85∶15,加入膜改性助剂后,膜制品的透水率得到提高,力学性能也有所改善。     

Preparation and monovalent selective properties of multilayer polyelectrolyte modified cation‐exchange membranes

This study reports the modification of commercial cation‐exchange membrane by layer‐by‐layer adsorption of polyethyleneimine and poly(acrylic acid) (PAA) to endow them with monovalent ion selectivity. The chemical and morphological changes of the modified membrane surface were examined by ATR‐FTIR and SEM, respectively. The permselectivity for monovalent cations of the membranes was investigated by electrodialysis experiments. The effects of deposited bilayer number, the salt concentration, and pH of the dipping polyelectrolyte solutions on selectivity were investigated. Meanwhile, the resistance of membranes was measured taking energy consumption into consideration. The polyelectrolyte multilayer was crosslinked using epichlorohydrin to improve stability, and the durability of the composite membrane was studied. Separation mechanism of the composite membrane was also investigated. It is demonstrated that the bivalent cations are mainly rejected by electrostatic repulsion from the positive charge on the surface of the composite membranes. The sieving effect of the dense structure of skin layer becomes more pronounced with the number of deposited layers increased. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41488.     

A kinetic model for the adsorption of gold from I2/I− solutions onto a porous polymer membrane

A model for the adsorption of gold from I₂/I^? aqueous solutions onto a cellulose acetate (CA)‐polyaniline (PANI) porous membrane is presented. The adsorption of gold is represented by an ion‐exchange overall reaction in which AuI₂^? ions replace the Cl^? ions at the active sites of the polyaniline matrix. The model incorporates the external mass transfer of AuI₂^? from the bulk solution to the membrane surface, followed by the pore diffusion of AuI₂^? to reach the active sites in the membrane. The overall ion‐exchange reaction was assumed to achieve local instantaneous equilibrium. Verification of the kinetic model with the experimental data showed that the effective diffusivity of AuI₂^? within the membrane is about 8.3 × 10^?6 cm²/s. The potential applications of the present formulation are discussed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Electrochemical synthesis and anticorrosive properties of Nafion-poly(aniline-co-o-aminophenol) coatings on stainless steel

The objective of this work was to compare the electrochemical behavior and possible anticorrosive properties of composite with Nafion^®, poly(aniline-co-o-aminophenol) (P(An-co-OAP)) and polyaniline (PAn) films with those of corresponding simple films. The electrochemical synthesis of polymer films was carried out on stainless steel AISI 304 (SS) surfaces by using the cyclic potential sweep (CPS) deposition. Scanning electron microscopy (SEM) was used for the characterization of the structure and morphology of deposited films. Evaluation of anticorrosive properties of films in 0.5 M H₂SO₄ without and with chlorides was achieved by monitoring the open circuit potential (E_OC) of coated SS electrodes as well as by tracing the anodic current-potential polarization curves. These studies have shown that the SS remains in its passive state in the presence of polymer coatings. Composite with Nafion^®, P(An-co-OAP) and PAn films, keep their redox activity in chloride-containing acid solutions providing almost a complete protection of the SS substrate against pitting corrosion. These films prevent chloride exchange with solution because of the cation permselectivity of the Nafion^® membrane. The charge compensation during redox reactions occurs mainly by protons since sulfonate groups of Nafion^® act as dopants in composite films. The redox behavior of the Nafion^®-P(An-co-OAP) film is improved as compared with that of the Nafion^®-PAn film in both Cl⁻-free and Cl⁻-containing solutions. This behavior may be ascribed to the functional group -OH that facilitates charge compensation through proton during redox reactions.     

Perfluorinated nanocomposite membranes modified by polyaniline: Electrotransport phenomena and morphology

This work summarizes results on the modification of perfluorinated sulfocationic membranes MF-4SC by in situ chemical polymerization of aniline. The investigation of transport properties of polyaniline/MF-4SC composite membranes after bulk modification - conductivity, diffusion and electroosmotic permeability, proton permselectivity - as well as porosimetry and polarization behavior is carried out as functions of aniline polymerization parameters and acid concentration. The fibrous-cluster model of a composite membrane is proposed for the estimation of transport and structural parameters, taking into account different mechanism of charge transfer in structural fragments of the composite. The atomic force microscopy images and curves of water distribution on the effective pore radii in the composite membranes testify to a morphological transition from the nano- to the microsize of polyaniline inclusions with increasing the aniline polymerization time. This effect is confirmed by the analysis of two-phase model transport and structural parameters. High values of the “true” proton transport numbers of composites are obtained and discussed. The dynamic hydration numbers of protons and chloride co-ions are estimated using the “true” transport numbers of protons and the electroosmotic coefficients of composites. The current-voltage curves of composite membranes in the “free standing” state after bulk and surface modification by polyaniline are investigated. The effect of stabilization of limiting current density is observed for MF-4SC membrane after bulk modification. The effect of current-voltage curves asymmetry is observed for different orientation of the polyaniline layer towards the current direction for an anisotropic composite membrane after surface modification.     

Adsorption of CO2+ by stylene‐g‐polyethylene membrane bearing sulfonic acid groups modified by radiation‐induced graft copolymerization

Cation‐exchange hollow fiber membrane was prepared by radiation‐induced grafting polymerization of styrene onto polyethylene hollow fiber membrane and its sulfonation. Adsorption characteristics for the cation‐exchange membranes are examined when the solution of Co²⁺ permeates across the cation‐exchange fiber membrane. The maximum grafting peak was obtained from 70% styrene concentration at 50°C. The degree of grafting (%) was enhanced with additives such as H₂SO₄ and divinylbenzene. The content of  SO₃H groups ranged from 2 to 5 mmol g⁻¹ with chlorosulfonic acid (ClSO₃H) in dichloroethane, from 0.5 to 6 mmol g⁻¹ with ClSO₃H in H₂SO₄, respectively. The adsorption of Co²⁺ by the cation‐exchange membranes increased with increasing  SO₃H content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2227–2235, 1999     

Surface-functionalized cation exchange membrane by covalent immobilization of polyelectrolyte multilayer for effective separation of mono- and multivalent cations

The existence of numerous non-conductive regions retards the further functionalization of heterogeneous membrane surface. In this report, a modification scheme for covalent immobilization of polyethyleneimine (PEI) multilayer on heterogeneous cation exchange membrane (CEM) was developed by means of diazonium-induced carboxyl group grafting. Of particular note are the influences of some important modification conditions, including the molecular weight of PEI and its deposition times, which were explored and understood. Series of electrodialysis experiments confirmed the achievement of the monovalent cation permselectivity. Furthermore, the results also indicated that the PEI coating can also effectively improve surface homogeneity and then alleviate concentration polarization behaviour during the electrodialysis process.     

Surface modification of ion‐exchange membranes: Methods,characteristics, and performance

Considerable effort has been made to improve ion‐exchange membrane (IEM) properties in order to achieve better performance of IEM‐based processes in various applications. Surface modification is one of the effective ways to improve IEM properties. Various methods have been used to modify IEM surfaces, for example, plasma treatment, polymerization, solution casting, electrodeposition, and ion implantation. These methods are able to produce a thin and fine distributed layer and also to modify the chemical structure of the surface. The new layer can be adsorbed, deposited, or chemically bonded on a membrane surface. By using these methods, IEM properties are improved, and the desired or specific characteristics such as high monovalent ion permselectivity, low fuel crossover, and anti‐organic‐fouling property can be obtained. In this paper, methods for surface modification of IEMs are reviewed. Moreover, the effects of modification on IEM properties and performance are discussed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45540.     

Synthesis of Er2O3 Nanoparticles and Er2O3 Nanoparticle/Polyaniline Deposition on the Surface of Stainless Steel by Potentiostatic Deposition

Erbium oxide nanoparticles (Er₂O₃ NP) were synthesized with an efficient method in the presence and absence of sodium dodecylsulfate (SDS) as surfactant. The effect of SDS on the morphology of the synthesized Er₂O₃ NP is described. The NP were studied through scanning electron microscopy and X‐ray diffractometry. Then, polyaniline and a hybrid material of polyaniline/Er₂O₃ NP were deposited directly on a stainless steel wire by the potentiostatic process. The electrochemical data and scanning electron microscopic studies of polyaniline and its nanocomposite on the stainless steel wire demonstrate the influence of the synthesized Er₂O₃ NP on the electrodeposition of polyaniline. The presence of NP in the electrolyte solution during electrodeposition of polyaniline creates a nanocomposite with a more porous structure than pure polyaniline.     

Characterization of semi‐interpenetrating polymer network polystyrene cation‐exchange membranes

Polystyrene cation exchange membranes were prepared by a PVC‐based semi‐interpenetrating polymer network (IPN) method. The reaction behaviors during polymerization and sulfonation in the preparation method were investigated. The prepared membranes were characterized in terms of the physical and electrochemical properties. The membranes exhibited reasonable mechanical properties (tensile strength, 13 MPa, and elongation at break, 52%) for an ion‐exchange membrane with the ratio of polystyrene–divinylbenzene (DVB)/poly(vinyl chloride) (PVC) (R_St‐DVB/PVC) of below 0.9. Fourier transform infrared/attenuated total reflectance, differential scanning calorimetry, and scanning electron microscopy studies revealed the formation of a homogeneous membrane. The resulting membrane showed membrane electrical resistance of 2.0 Ω cm² and ion‐exchange capacity of 3.0 meq/g dry membrane. The current–voltage (I–V) curves of the membrane show that the semi‐IPN polystyrene membranes can be properly used at a high current density, and that the distribution of cation‐exchange sites in the membrane was more homogenous than that in commercial membranes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1488–1496, 2003     

Preparation and Electrochemical Characterization of Monovalent Ion Selective Poly (Vinyl Chloride)-Blend-Poly (Styrene-Co-Butadiene) Heterogeneous Cation Exchange Membrane Coated with Poly (Methyl Methacrylate)

In this research, polyvinylchloride/ styrene-butadiene-rubber blend heterogeneous cation exchange membranes were prepared by solution casting technique using tetrahydrofuran as solvent and cation exchange resin powder as functional groups agent. Poly methyl methacrylate (PMMA) was also employed as membrane surface modifier by emulsion polymerization technique to improve the membrane selectivity and anti-fouling property. The effect of used emulsion composition on properties of home-made membranes was studied. SOM images showed uniform particles distribution and relatively uniform surfaces for the membranes. Results revealed that surface modification of membrane led to decrease in water content, ion exchange capacity, and ionic permeability in composite membranes. Membrane potential, transport number, selectivity, ionic concentration, and membrane surface electrical resistance all were increased by the PMMA coating on membrane surface. Also, the results showed that decrease of (Methyl methacrylate (MMA): Sodium dodecyl benzene solfanate (SDBS)) ratio in used emulsion during the modification process led to decrease in water content, IEC and permeability in composite membranes. Conversely, opposite trends were found for membrane potential, transport number, selectivity, and electrical resistance by (MMA: SDBS) ratio decreasing in used emulsion. Composite membranes exhibited higher potential, selectivity, transport number, and permeability for monovalent ions compared to bivalent ones. Modified membranes showed good ability in (monovalent/ bivalent) ions separation.     

Adsorption and Diffusion of VO2+ and VO2 + across Cation Membrane for All‐Vanadium Redox Flow Battery

A method based on a selectivity coefficient and the Nernst‐Planck equation is proposed to determine diffusion coefficients of vanadium ions across a cation exchange membrane in VO²⁺/H⁺ and VO₂ ⁺/H⁺ systems. This simplified method can be applied to high concentrations of vanadium ions. Three cation exchange membranes were studied. The logarithmic value of the selectivity coefficient was linearly dependent on the molar fraction of vanadium ions in solution. The diffusion coefficient of vanadium ions decreased with decreasing water content. The membrane with the lowest diffusion coefficient was selected as a battery separator and showed the lowest capacity loss of the studied membranes.     

Gas permeability of wet cation exchange membranes

The permeation of CO₂ across a Nafion cation exchange membrane in different hydrated forms is studied. The water solvent linked to the ion exchanging sites of the charged membranes forms a liquid supported membrane in which the transport of the polar gas is enhanced. This effect is still higher when the dry membrane is swollen in a Li₂CO₃ solution which increases the carbonate/bicarbonate anion concentration in the wet membranes and reduced the effectiveness of the Donnan co-ion exclusion from the membrane phase.     

Interactions between large organic cations and cation exchange membranes

Interactions between cation exchange membranes and large organic cations have been studied; namely (1) adsorption and electrodialytic desorption of cationic surface active agents, and (2) change in transport properties of the membranes by adsorption.N-dodecyl pyridyl compounds, such as N-dodecyl pyridinium bromide (C₁₂-Py), N-dodecyl dipyridyl bromide (C₁₂-Dipy) and N-dodecyl tripyridyl bromide (C₁₂-Tripy) were used for the adsorption and electrodialytic desorption; and for the study on the change in transport properties of membranes, N-dodecyl pyridinium chloride, C₁₂-Py, C₁₂-Dipy, C₁₂-Tripy and hexadecyl trimethylammonium chloride were used. It was confirmed that the higher the molecular weight of the cation the longer the time required to reach adsorption equilibrium, and that the amount of adsorption exceeded the ion-exchange capacity of the membrane. After equilibrium was attained, electrodialytic desorption from the membranes was difficult.The adsorption or ion-exchange of large organic cations was effective to the permselectivity of the cation exchange membrane to the sodium ion in electrodialysis of a solution of sodium chloride and calcium chloride. The relationship between the permselectivity and the properties of the cations was examined.