Tailoring the ionic transfer characteristics of polyvinyl chloride-based heterogeneous ion exchange membranes by embedding carboxy methyl cellulose in membrane channels

Polyvinyl chloride-based heterogeneous cation exchange membranes were modified by embedding carboxy methyl cellulose in ionic transfer channels of membrane. The effect of CMC to PVC blend ratios on properties of membranes was studied. SOM images showed uniform distribution and surfaces for prepared membranes relatively. The SEM images showed uniform and dense structure for the membranes. The XRD pattern also demonstrated amorphous structure for the membranes. Membrane water content was improved from 25 to 39 % by increase of CMC concentration up to 32 %wt. Similar trend was found for membrane surface hydrophilicity. The membrane ion exchange capacity, fixed ion concentration, membrane potential, charge density, transport number, permselectivity, and ionic flux were enhanced initially by increase of CMC ratio up to 16 %wt and then began to decrease by increase in CMC concentration from 16 to 32 %wt. The membrane oxidative stability and areal electrical resistance showed decreasing trends by utilizing of carboxy methyl cellulose in the membrane matrix. Membrane transport number and selectivity were also increased by increase of electrolyte concentration. Similar trend was found for the membrane electrical conductivity by increase of electrolyte concentration. Also prepared membranes showed higher transport number, selectivity, and areal electrical resistance at pH 7 compared to other pH values.     

Surface modification of heterogeneous cation exchange membrane through simultaneous using polymerization of PAA and multi walled carbon nano tubes

Polyvinylchloride based heterogeneous cation exchange membrane was modified by using in situ polymerization of polyacrylic acid and multi walled carbon nano tubes simultaneously. Spectra analysis confirmed graft polymerization decisively. SEM images illustrated that grafted-PAA/MWCNTs filled the cracks in membrane by simple gel network entanglement. Ion exchange capacity was improved by PAA/MWCNTs grafting in modified membranes. Membrane water content was decreased by PAA grafting and then showed increasing trend by using MWCNTs in modifier solution up to 0.1%wt. Water content was decreased again by more MWCNTs loading ratio. Grafted-PAA membranes showed lower membrane potential, transport number, selectivity and flux compared to pristine membrane in sodium chloride ionic solution. These parameters were decreased more by using MWCNTs up to 0.1%wt in modifier solution and then showed increasing trend by more MWCNTs concentration from 0.1 to 0.3%wt. All mentioned parameters were declined again by more increase in MWCNTs content from 0.3 to 1.0%wt. Results exhibited lower membrane selectivity for the modified membranes compared to pristine ones in bivalent ionic solution. The grafted-PAA/MWCNTs modified membranes also showed lower electrical resistance compared to unmodified ones. Obtained results showed different behavior for permeability in bivalent ionic solution compared to monovalent type.     

Fabrication of novel polyethersulfone based nanofiltration membrane by embedding polyaniline-co-graphene oxide nanoplates

Mixed matrix polyethersulfone (PES) based nanofiltration membrane was prepared through phase inversion method by using of polyvinylpyrrolidone (PVP) as pore former and N, N dimethylacetamide (DMAc) as solvent. Polyaniline-co-graphene oxide nanoplates (PANI/GO) were utilized as additive in membrane fabrication. The PANI/GO nanoplates were prepared by polymerization of aniline in the presence of graphene oxide nanoplates. FTIR analysis, scanning electron microscopy (SEM), scanning optical microscopy (SOM), 3D images surface analysis, water contact angle, water content tests, tensile strength tests, porosity tests, salt rejection and flux tests were used in membrane characterization. FT-IR results verified formation of PANI on graphene oxide nanoplates. SOM images showed uniform particles distribution for the mixed matrix membranes. SEM images also showed formation of wide pores for the modified membranes. Water flux showed constant trend nearly by use of PANI/GO in the casting solution. Opposite trend was found for the membrane surface hydrophilicity. Salt rejection was enhanced sharply by utilizing of PANI/GO. The membrane’s tensile strength was improved by increase of PANI/GO concentration. The water content was increased initially by use of PANI/GO nanoplates up to 0.05%wt into the casting solution and then decreased. Membrane porosity was also enhanced by using of PANI/GO nanoplates. Modified membrane containing 0.5%wt PANI/GO nanoplates showed more appropriate antifouling characteristic compared to others.     

Preparation and characterization of PVC based heterogeneous ion exchange membrane coated with Ag nanoparticles by (thermal-plasma) treatment assisted surface modification

PVC based heterogeneous cation exchange membranes were prepared by solution casting technique. Ag nanoparticles were also utilized as surface modifier by plasma treatment. Thermal treatment was used to improve the Ag nanoparticles stability on membrane surface. The effect of treating temperature on separation characteristics of coated membranes was studied. SEM images showed membrane rugosity increasing by the increase of treating temperature. Transport number, selectivity and permeability were enhanced initially by increase of treating temperature up to 80 °C and then showed decreasing trend. Conversely membrane resistance showed opposite trend. Modified membrane at 80 °C showed better performance compared to others.     

Preparation and characterization of poly (vinyl chloride)-blend-poly (carbonate) heterogeneous cation exchange membrane: Investigation of solvent type and ratio effects

In this research polyvinylchloride/polycarbonate blend heterogeneous cation exchange membranes were prepared by solution casting technique using cation exchange resin powder as functional groups agent. Tetrahydrofuran (THF) and dimethylformamide (DMF) were utilized as solvents. The effect of solvent type and ratio (THF/DMF mixture) on properties of prepared membranes was studied. SEM and SOM images showed relatively uniform particle distribution and also uniform surface for the membranes. Images showed that at high DMF ratio decrease of polymer conformation with particles surface reduces the compatibility of polymer-particle. The membrane ion exchange capacity and permeability were enhanced initially by increase of DMF ratio up to 5% (v/v) in casting solution and then they began to decrease with more DMF ratio. Results showed that membrane potential, transport number, selectivity and thermal stability all were decreased by DMF ratio increasing. Conversely, membrane water content, specific surface area and roughness showed opposite trends. Membrane electrical resistance initially declined by increase in DMF content up to 15% (v/v) and then it began to increase. The increase of electrolyte concentration also led to decrease in membrane transport number and selectivity. Membrane with (95:5) (v/v) solvent ratio (THF:DMF) exhibited more appropriate performance compared to others.     

Preparation and Characterization of Heterogeneous Cation Exchange Membranes Based on S-Poly Vinyl Chloride and Polycarbonate

This research deals with the preparation of heterogeneous cation exchange membranes by solution-casting techniques using S-polyvinylchloride (S-PVC) and polycarbonate (PC) as binders, cation exchange resin powder as functional groups agent, and tetrahydrofuran as solvent. The effects of polymer binder type and resin ratio loading on morphological, electrochemical, and mechanical properties of prepared membranes were studied and evaluated. Scanning electron microscopy and scanning optical microscopy were used for the membranes structure investigation. Images showed that increase of resin loading in casting solution resulted in a highly uniform phase forming. Moreover resin particles were distributed more uniformly in polycarbonate membranes compared to the polyvinylchloride ones. The water content, surface hydrophilicity, ion exchange capacity, ion concentration, permselectivity, membrane potential, surface charge density, transport number, ionic permeability, flux of ions, and current efficiency were enhanced for the prepared membranes by increase in resin ratio loading. Moreover, the increase of resin ratio in casting solution reduced the mechanical strength of the prepared membranes. The mechanical strength of S-PVC membrane was higher than the PC ones. Furthermore, the increment of resin content caused some decreases in areal electrical resistance and oxidative stability of the prepared membranes. Home-made membranes exhibited appropriate electrochemical properties in comparison with a tested commercial heterogeneous cation exchange membrane in the same experimental conditions. Swelling of the prepared membranes was also negligible compared to the commercial type.     

Heterogeneous Cation Exchange Membrane: Preparation,Characterization and Comparison of Transport Properties of Mono and Bivalent Cations

Polycarbonate heterogeneous cation exchange membranes were prepared by solution casting techniques using tetrahydrofuran as solvent and cation exchange resin powder as functional groups agent. The effect of resin ratio loading on properties of prepared membranes was studied. Also, transport properties of the prepared membranes for mono and bivalent cations were evaluated. Scanning electron microscopy and scanning optical microscopy were used for the membranes structure investigation. Images showed that increase of resin ratio in casting solution results in a highly uniform phase to form. Formation and propagation of voids, cavities, and cracks were facilitated through higher resin ratio loading. The water content, surface hydrophilicity, specific surface area, ion exchange capacity, ion concentration, ionic permeability, conductivity, flux, and current efficiency of the membranes were enhanced and their energy consumption, oxidative stability, and mechanical strength were declined by increase of resin ratio loading. Moreover, membranes showed higher ionic flux, current efficiency, and lower energy consumption for sodium ions in comparison with bariums. Furthermore, with the increase of resin loading, permselectivity, membrane potential and transport number of membranes were improved for monovalent ions and diminished for bivalent ones. Also, membranes exhibited lower membrane potential, selectivity, and transport number for bivalent ions in comparison with the monovalent type.     

Preparation and characterization of ABS/HIPS heterogeneous anion exchange membrane filled with activated carbon

Acrylonitrile‐butadiene‐styrene (ABS)/high impact polystyrene (HIPS) blend heterogeneous anion exchange membranes were prepared by phase inversion method using tetrahydrofuran as solvent and anion exchange resin powder as functional group agent. Activated carbon was selected as inorganic filler additive. The additive concentration effect on properties of the prepared membranes was studied. Ultrasonic method was used to help appropriate dispersion of particles in the membrane's matrix. Scanning optical microscopy showed that sonication has a significant influence on distribution of resin particles in the membrane matrix and makes it possible to form more uniform phase. Moreover, images showed a relatively uniform surface for membranes. The increase of activated carbon concentration in casting solution led to a decline in membrane water content. The ion exchange capacity, membrane potential, permselectivity, transport number, ion permeability, ionic flux, and current efficiency of prepared membranes all were increased initially by the increase in additive concentration up to 1% wt and then they showed decrease trend with higher increase in additive concentration from 1 to 4% wt. Conversely, the electrical resistance and energy consumption showed opposite trends. In addition, with more additive loading, the oxidative stability of membranes was slightly decreased and their thermal stability was increased. Membrane with 1% wt additive loading exhibited higher efficiency and electrochemical properties in comparison with other prepared membranes in this research. Furthermore, prepared membranes exhibited suitable electrochemical properties compared to a commercial heterogeneous anion exchange membrane with the same experimental conditions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fabrication and modification of polyvinylchloride based heterogeneous cation exchange membranes by simultaneously using Fe-Ni oxide nanoparticles and Ag nanolayer: Physico-chemical and antibacterial characteristics

Polyvinylchloride-blend-styrene butadiene rubber based nanocomposite cation exchange membranes were prepared by solution casting technique. Iron-oxide nanoparticles and Ag-nanolayer were simultaneously utilized as filler and surface modifier in membrane fabrication. The effects of Ag-nanolayer film thickness on membrane physicochemical and antibacterial characteristics of nanocomposite PVC-blend-SBR/Iron-oxide nanoparticles were studied. SEM images showed membrane roughness decreasing by Ag nanolayer thickness increasing. Membrane charge density and selectivity declined by Ag nanolayer coating up to 5 nm in membranes and then showed increasing trend by more nanolayer thickness. Ionic flux also showed increasing trend. Membranes showed good ability in E-Coli removal. 20 nm Ag-nanolayer coated membrane showed better performance compared to others.     

Cellulose acetate butyrate membrane containing TiO2 nanoparticle: Preparation, characterization and permeation study

Cellulose acetate butyrate/TiO₂ hybrid membranes were prepared via phase inversion by dispersing the TiO₂ nanoparticles in casting solutions. The influence of TiO₂ nanoparticles on the morphology and performance of membranes was investigated. The scanning electron microscope images and experiments of membrane performance showed that the membrane thickness and pure water flux were first increased by adding the TiO₂ nanoparticles to the casting solution up to 4 wt% and then decreased with the addition of further nanoparticles to it. The obtained results indicated that the addition of TiO₂ in the casting solution enhanced the rejection and permeate flux in filtration of bovine serum albumin solution. Furthermore, increasing the TiO₂ nanoparticle concentration in the casting solution increased the flux recovery and consequently decreased the fouling of membrane.     

Effect of silver loaded sodium zirconium phosphate (nanoAgZ) nanoparticles incorporation on PES membrane performance

Polyethersulfone (PES) based ultrafiltration membranes were fabricated via phase inversion by adding silver-loaded sodium zirconium phosphate nanoparticles (nanoAgZ) in PES casting solutions. The effect of nanoAgZ concentration on the membrane performance, i.e., morphology, hydrophilicity, thermal stability, permeation and antifouling properties was investigated. The results of thermal gravitational analysis (TGA) showed that the thermal stability of the hybrid membrane had been improved by the addition of nanoAgZ particles. Contact angle results indicated that the hydrophilicity of the modified membranes was enhanced. The contact angle of the membrane decreased from 71.5° to 52.6° with the increase of the nanoparticle content in the casting solution. Permeation experiment results showed that the modified PES membranes demonstrate better separation performance over the pure PES membrane. The pure water flux of PES membrane increased from 82.1 L/m² h to 100.6 L/m² h with the addition of the nanoparticles. Most importantly, the incorporation of the nanoAgZ particles enhanced the BSA fouling resistance and also the anti-biofouling performance of the membrane.     

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.     

Developing homogeneous ion exchange membranes derived from sulfonated polyethersulfone/N-phthaloyl-chitosan for improved hydrophilic and controllable porosity

Ion exchange membranes (IEMs) composed of sulfonated poly (ether sulfone) (SPES) and N-phthaloyl chitosan (NPHCs) were synthesized. NPHCs was employed in membrane fabrication to improve the porosity and hydrophilicity of membranes. The effect of blend ratio of sulfonation (DS) and NPHCs content on physico-chemical characteristics of home-made membranes was investigated. The morphology of prepared membranes was investigated by Fourier transform infrared spectroscopy (FTIR), X-ray diffractometer (XRD) and scanning electron microscopy (SEM). SEM images revealed the formation of a more porous membrane structure and smoother surface. The electrochemical and physical properties of CEMs were characterized comprising water content, contact angle, ion exchange capacity (IEC) and thermal stability. Membrane water content, surface hydrophilicity and IEC were enhanced with increase of DS and NPHCs blend ratios in casting solution. Furthermore, the diffusion coefficient was also improved slightly with increase of DS and NPHCs blend ratios in prepared membranes. Membrane potential, permselectivity, transport number and areal membrane resistance all showed decreasing trends by the increase in NPHCs blend ratio in casting solution. These results indicated that the prepared membrane has good prospective and great potential for desalination in electrodialysis applications.     

Effect of polymers blend ratio binder on electrochemical and morphological properties of PC/S‐PVC‐based heterogeneous cation‐exchange membranes

In this research, heterogeneous cation exchange membranes were prepared by the casting‐solution technique using polycarbonate (PC) and S‐polyvinylchloride (S‐PVC) as binders along with cation exchange resin as functional group agent. The effect of blend ratio (PC to S‐PVC) of polymer binder on structure and electrochemical properties of the prepared membranes were elucidated. The morphology of the prepared membranes was investigated by scanning electron microscopy (SEM) and scanning optical microscopy (SOM). The images show that the addition of PC ratio in the casting solution results in formation of a membrane with more inner cavities and micro voids. The electrochemical properties and mechanical strength tests were conducted. Water content, ion exchange capacity, ion permeability, flux, current efficiency, and oxidative stability of the prepared membranes initially were decreased by increasing the PC ratio in the casting solution and then it began to increase. The blending of S‐PVC and PC polymers results in membranes with lower mechanical strength. Membrane potential, surface charge density, perm‐selectivity, cationic transport number, electrical resistance, and energy consumption were initially improved by the increment of PC ratio in the casting solution and then it decreased. The membrane with 70% PC exhibited the highest flux, maximum current efficiency, and minimum energy consumption. However, the selectivity of this membrane was low compared with the other prepared membranes. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of hydrophilic additive and PVC polymerization degree on morphology and electrochemical properties of PVC‐based heterogeneous cation‐exchange membrane

Membrane solution composition is one of the important factors that determine properties of ion‐exchange membranes. In this study, PVC‐based heterogeneous cation‐exchange membranes were prepared by the solution casting method. Effects of a hydrophilic additive [poly(ethylene glycol), PEG400] and degree of polymerization of poly(vinyl chloride) (PVC) on the morphology and electrochemical properties of the cation‐exchange membranes were investigated. The results revealed that the hydrophilic additive can improve membrane properties, including water uptake (Wu), ion‐exchange capacity (IEC), conductivity, and permselectivity. The improvements might be associated with an increase in accessibility of functional sites in the membrane matrix due to a higher hydrophilicity, indicated by a reduction of water contact angle and the greater void fraction shown by scanning electron microscopy. However, the permselectivity slightly decreased when the additive concentration was increased further. Meanwhile, increasing the degree of polymerization and PVC concentration resulted in higher permselectivity and lower conductivity, which might be due to a better resin distribution and a lower void fraction. Overall, the prepared membranes had relatively good conductivities (up to ～2.5 mS/cm) and permselectivities (up to ～0.92). In general the conductivity increased with increasing Wu and IEC, while the permselectivity showed the opposite trends. This could be associated with the efficacy of Donnan exclusion indicated by the IEC/Wu ratio and the Donnan equilibrium constant of the cation (K⁺). © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46690.     

Electrodialytic transport properties of heterogeneous cation‐exchange membranes prepared by gelation and solvent evaporation methods

The heterogeneous cation‐exchange membranes were prepared by employing two different methods: immersing the cation‐exchange resin‐loaded membranes in gelation bath; evaporating the solvent upon casting a uniform solution of cation‐exchange resin on a glass plate. The effect of resin loading on the electrochemical properties of the membranes was evaluated. The permselectivity of these heterogeneous membranes and transport number of calcium ions relative to sodium ions was evaluated with respect to the extent of resin loading and the methods of preparation. It is found that the membrane potential, transport number, permselectivity, and relative transport number are prominently high in the solvent evaporation method compared with the gelation method. The transport number of calcium ions relative to sodium ions in the solvent evaporation method increased monotonously with increasing resin loading. However, the increase of resin loading did not influence much on the relative transport numbers in the gelation method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 198–207, 2006     

Electrochemical Properties of Chemically Treated Polyvinylchloride‐Based Heterogeneous Cation‐Exchange Membrane

Chemical treatment is a facile method for improving electrochemical properties of a heterogeneous ion‐exchange membrane. In this work, polyvinylchloride (PVC)‐based heterogeneous cation‐exchange membrane is prepared by a dry–wet phase inversion process. The membrane is treated with a sulfuric acid solution in a room and a high temperature (80 °C). Effects of the treatment procedure and hydrophilic additive on membrane electrochemical properties are investigated. Chemically treated PVC and PVC/additive heterogeneous cation‐exchange membranes show a change in membrane electrochemical properties in terms of water uptake (Wu), conductivity, ion‐exchange capacity (IEC), and permselectivity (Ps). In general, Wu and conductivity increase after the chemical treatment. Significant improvement is observed when a high temperature is used. Meanwhile, the conductivity is more pronounced for PVC/additive membranes. The improvement may be associated with an increase in hydrophilicity. A significant increase in IEC is also observed for modified PVC/additive membrane. This may be associated with the removal or leaching of the additive during the treatment which in turn increases the portion of ion‐exchange resins in the membrane. Most of the modified membranes show a decrease in Ps. It may be due to a decrease in the effectiveness of Donnan effect indicated by Donnan equilibrium constant (K+). POLYM. ENG. SCI., 59:E219–E226, 2019. © 2018 Society of Plastics Engineers     

Study on Preparation and Performance of Modified Polyvinyl Chloride-co-vinyl Acetate Microfiltration Membranes

In this paper, flat-sheet microfiltration membranes were prepared from modified polyvinyl chloride-vinyl acetate (VC-co-VAc) material with hydroxyl group, VC-co-VAc-OH, by phase inversion technique. The influences of casting solution composition (polymer concentration, additive types, and content) and preparation conditions (coagulation temperature, evaporation time of solvent, and the relative humidity in the environment) on pure water flux, retention, and pore size distribution were discussed. The results showed that casting solution composition and the membrane preparation conditions all have significant impacts on the performances of the membrane: on the one hand, in order to prepare membranes with high flux, either decrease the polymer concentration, or increase the PEG molecular weight or the coagulation temperature or the relative humidity can achieve it; on the other hand, with the increase of additive content, the pure water flux increased quickly, then decreased dramatically, while the effect of evaporation time were the opposite. And these results were confirmed by the SEM images. Furthermore, the microfiltration membranes, which were prepared under optimized conditions, were used to treat synthetic oilfield polymer-flooding wastewater, and good experimental results were obtained.     

Bipolar membranes in forward bias region for fuel cell reactors

Three bipolar membranes, two home-made composed of commercial cation (DuPont) and anion (FuMA-Tech) exchange membranes (called Nafion/FT-FAA and Nafion/FT-FAS) and a commercial one, BP-1 from FuMA-Tech, were investigated in order to characterize their suitability to use in a H₂/O₂ fuel cell intended to produce hydrogen peroxide on the cathode instead of water. The Nafion/FT-FAA and Nafion/FT-FAS membranes were prepared using a hot-pressing method. The optimal hot-pressing conditions were determined by measuring the ionic conductivity of the membranes. The latter was observed to depend on the relative humidity of the bipolar membrane. Of the studied bipolar membranes, Nafion/FT-FAA showed the best performance. The transport number of protons measured in a concentration cell was observed to depend on the direction of the proton diffusion flux through these membranes so that transport numbers of ca. unity were obtained when the cation exchange side faced the solution with higher proton concentration. In the opposite case, when the higher concentration faced anion exchange side, the transport number of proton was clearly lower, indicating the usefulness of the bipolar membranes for hydrogen peroxide production in the fuel cell.     

聚乙烯吡咯烷酮对聚醚砜膜结构和性能的影响

以聚醚砜为膜材料,聚乙烯吡咯烷酮（PVP）为添加剂,N,N-二甲基乙酰胺为溶剂,采用相转化法制备了聚醚砜超滤膜。通过制膜液粘度、膜的孔隙率、表面接触角、机械性能以及对牛血清蛋白分离性能的测试和扫描电镜（SEM）对膜孔结构的观察,研究了PVP的添加量对聚醚砜制膜液粘度及其膜结构和性能的影响。结果表明,PVP的添加提高了膜的亲水性和制膜液的粘度,但膜的抗拉强度有所降低;膜的水通量随着PVP含量的增加先升高后降低,在5%时最大水通量是508.33L/（m^2·h）,而此时牛蛋白截留率最小为66.27%;SEM观察的结果是膜的断面上部形成指状孔结构,下部形成海绵状孔结构,当PVP含量为5%时膜有斜指状孔结构,且指状孔也逐渐延伸到膜的底部,其壁为稀疏的海绵状孔结构。