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.     

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.     

Preparation and characterization of nanocomposite heterogeneous cation exchange membranes modified by silver nanoparticles

We prepared polyvinylchloride based nanocomposite heterogeneous cation exchange membranes by solution casting technique using cation exchange resin powder as functional groups agent and tetrahydrofuran as solvent. Silver nanoparticles were also used as fillers in membrane fabrication. The effect of silver nanoparticles concentration in casting solution on membrane physico/chemical and antibacterial characteristics was studied. The SEM images showed compact structure for the modified membranes. X-ray diffraction results also revealed that membrane crystallinity was clearly changed by increase of nanoparticle concentration. Membrane selectivity and transport number were enhanced initially by increase in nanoparticle content up to 4%wt in prepared membrane, and then showed decreasing trend by more increase in additive concentration from 4 to 8%wt. Selectivity and transport number were enhanced another time by further increase in nanoparticle loading ratio from 8 to 16%wt. Opposite trend was found for the membranes’ average grain size by variation in additive content. Ionic flux was also clearly enhanced by using Ag nanoparticles in membrane matrix. Moreover, modified membranes showed good ability in decrease of Escherichia coli growth rate.     

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     

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 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.     

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.     

Preparation and characterization of monovalent ion‐selective poly(vinyl chloride)‐blend‐poly(styrene‐co‐butadiene) heterogeneous anion‐exchange membranes

New types of composite anion‐exchange membranes were prepared by blending of suspension‐produced poly(vinyl chloride) (S‐PVC) and poly(styrene‐co‐butadiene), otherwise known as styrene–butadiene rubber (SBR), as binder, along with anion‐exchange resin powder to provide functional groups and activated carbon as inorganic filler additive. Also, an ultrasonic method was used to obtain better homogeneity. In solutions with mono‐ and divalent anions, the effect of activated carbon and sonication on the morphology, electrochemical properties and selectivity of these membranes was elucidated. For all solutions, ion‐exchange capacity, membrane potential, permselectivity, transport number, ionic permeability, flux and current efficiency of the prepared membranes initially increased on increasing the activated carbon concentration to 2 wt% in the casting solution and then began to decrease. Moreover, the electrical resistance and energy consumption of the membranes initially decreased on increasing the activated carbon loading to 2 wt% and then increased. S‐PVC‐blend‐SBR membranes with additive showed a decrease in water content and a slight decrease in oxidative stability. Also, these membranes showed good monovalent ion selectivity. Structural images of the prepared membranes obtained using scanning optical microscopy showed that sonication increased polymer‐particle interactions and promoted the compatibility of particles with binder. Copyright © 2010 Society of Chemical Industry     

Influence of casting conditions on the properties of sulfonated poly(ether ether ketone ketone)/phosphotungstic acid composite proton exchange membranes

The sulfonated poly(ether ether ketone ketone)/phosphotungstic acid (SPEEKK/PWA) composite membranes were researched for proton exchange membranes. The effect of casting condition on the properties of membranes was studied in detail. The study showed that the casting condition has great influence on the membrane properties because of the hydrogen bond between the SPEEK and PWA and the interaction between the SPEEKK and dimethylformamide (DMF). The PWA particles are well crystallized on the surface when the velocity of the solvent volatilization is very slow under the SEM. The study will favor further research on excellent composite membranes for proton exchange membrane fuel cells. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 4020–4026, 2007     

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.     

Preparation of polyvinylchloride membranes from solvent mixture by immersion precipitation

In this study, polyvinylchloride (PVC) membranes were prepared through the immersion precipitation method using a mixture of two solvents (tetrahydrofuran (THF) and dimethyl formamide (DMF)), which had different affinities with the nonsolvent (water). Membranes prepared from PVC/THF/water system showed a sponge‐like structure with isolated pores, which were impermeable to water even at a feed pressure of 20 bars, whereas those prepared from PVC/DMF/water exhibited a porous macrovoid containing morphology with a high water flux. The precipitation time and polymer concentration profiles were calculated by using a simple mathematical model and were in good agreement with the experimental findings on PVC/THF/water and PVC/DMF/water systems. By using a mixture of DMF and THF as solvent and changing the mixed solvent composition, membranes with different morphologies from sponge‐like to macrovoid containing were obtained. The membranes showed no water flux below a DMF concentration of 50 wt % and then became increasingly permeable with increasing DMF content in the casting solution. Measurement of the system cloud points showed a linear change of system thermodynamics with variation of the mixed solvent composition. The obtained results showed that although the system thermodynamics could explain the overall behavior of the system, but the local changes such as change of membrane performance from impermeable to permeable at a certain mixed solvent composition could not be explained by the thermodynamics alone. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40206.     

Sulfonated Polyethersulfone (SPES) – Charged Surface Modifying Macromolecules (cSMMs) Blends as a Cation Selective Membrane for Fuel Cells

Polyethersulfone (PES) was sulfonated by chlorosulfonic acid and concentrated sulfuric acid. The pure sulfonated PES (SPES) and modified SPES membranes were prepared by blending with different charged surface modifying macromolecules (cSMMs) namely, SPES/DEG‐HBS, SPES/PEG‐HBS, and SPES/PPG‐HBS. Membranes were characterized for their morphology, physical properties, and electrochemical properties in order to evaluate these membranes as cation exchange membranes. The blended membranes showed an increase in hydrophilicity, water uptake, and proton conductivity compared to the pure SPES membranes. The highest values of water uptake and proton conductivity were obtained for the SPES/PPG‐HBS blended membrane. Morphological studies revealed that the nodule size and surface roughness also influenced the water uptake, apart from the additional –SO₃H group. Among the modified membranes, the SPES/DEG‐HBS blended membrane exhibited a lower methanol permeability value of 8.895 × 10⁻⁸ cm² s⁻¹ than the corresponding SPES membrane. The other two cSMM blended membranes showed higher methanol permeability values than SPES but still a smaller value than Nafion 117. The highest selectivity ratio (i.e., ratio of proton conductivity to methanol permeability) was obtained with the SPES/DEG‐HBS cSMM blended membrane. These results showed that the SPES/cSMM blended membranes have promise for possible use as a cation exchange membrane in fuel cells and electrolyzer applications.     

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.     

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 of bipolar membranes (I)

The bipolar membranes were prepared by charged material of polysulfone as a base. The bipolar membranes were composed of a solvent‐resistant anion exchange layer with a crosslinking matrix prepared by the reaction of chloromethylated polysulfone in DMF with diamine, an interfacial layer made from chloromethylated polysulfone solution in DMF containing cation exchange resin and amine, and a cation exchange layer made from sulfonated polysulfone dispersing cation resin powder. The prepared bipolar membrane can exhibit lower voltage drop over 100 mA/cm². The critical requirement for producing bipolar membranes of low potential drop is the creation of a thin interfacial region with a low electrical resistance and a suitable chemical structure, which act to catalyze water splitting. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1658–1663, 2001     

Composite Proton Exchange Membranes of Sulfonated Poly(ether ketone ether sulfone) (S-PEKES) and Molecular Sieve With High Mechanical Strength for Direct Methanol Fuel Cell

Composite proton exchange membranes are prepared by solvent casting via the incorporation of molecular sieves 3A, 4A, and 5A into the sulfonated poly(ether ketone ether sulfone) (S-PEKES) at the sulfonation degree of 0.66, with varying the ratio at of 3%, 6%, 9%, and 12% v/v. The influences of type and amount of the molecular sieves on the proton conductivity, methanol permeability, structural, thermal, and mechanical stabilities of the membranes are investigated. The composite membranes are characterized by FTIR, TGA, LCR meter, and GC techniques. All properties of the composite membrane are compared with the pristine S-PEKES and Nafion 117 membrane.     

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.     

Chemical modification of poly(substituted-acetylene). IV. Pervaporation of organic liquid/water mixture through poly(1-phenyl-1-propyne)/polydimethylsiloxane graft copolymer membrane

Poly(1-phenyl-1-propyne)/polydimethysiloxane (PPP/PDMS) graft copolymer membranes having various PDMS content were prepared by solvent casting method, and the permeation characteristics at pervaporation were examined upon the aqueous solutions containing organic liquids such as alcohols, acetone, dioxane, acetonitrile, pyridine, and DMF. At pervaporation of ethanol/water mixture, preferential permeation of ethanol was observed for all the copolymer membranes, although PPP membrane showed water permselectivity. The permselectivity of the copolymer membrane also depended on operation temperature, but was independent on the thickness of the membrane. Furthermore, an excellent permselectivity of organic liquids was observed at the pervaporation of several organic liquid/water mixtures except in the case of DMF/water mixture. Observed high selectivity is thought to be due to the depression of the membrane swelling and the high solubility of the liquids into the membrane.     

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