Radiation-Induced Asymmetric Grafting of Different Monomers into Base Films to Prepare Novel Bipolar Membranes

We prepared novel bipolar membranes (BPMs) consisting of cation and anion exchange layers (CEL and AEL) using radiation-induced asymmetric graft polymerization (RIAGP). In this technique, graft polymers containing cation and anion exchange groups were introduced into a base film from each side. To create a clear CEL/AEL boundary, grafting reactions were performed from each surface side using two graft monomer solutions, which are immiscible in each other. Sodium p-styrenesulfonate (SSS) and acrylic acid (AA) in water were co-grafted from one side of the base ethylene-co-tetrafluoroethylene film, and chloromethyl styrene (CMS) in xylene was simultaneously grafted from the other side, and then the CMS units were quaternized to afford a BPM. The distinct SSS + AA- and CMS-grafted layers were formed owing to the immiscibility of hydrophilic SSS + AA and hydrophobic CMS monomer solutions. This is the first BPM with a clear CEL/AEL boundary prepared by RIAGP. However, in this BPM, the CEL was considerably thinner than the AEL, which may be a problem in practical applications. Then, by using different starting times of the first SSS+AA and second CMS grafting reactions, the CEL and AEL thicknesses was found to be controlled in RIAGP.     

PEG-catalytic water splitting in the interface of a bipolar membrane

This paper investigates the effect of polyethylene glycol (PEG) on the water dissociation of bipolar membranes. To do this, bipolar membranes were prepared by immersing anion exchange membranes in different-concentration solutions of different-molecular-weight PEGs and then casting the solutions of sulfonated polyphenylene oxide (SPPO) on the anion exchange membranes. All the bipolar membranes with PEG in the interface are evaluated by current-voltage curves. The experimental results prove that PEG has excellent catalytic function for water dissociation. Furthermore, this function is enhanced by both PEG amount (PEG concentration) and PEG molecular weight in the interface of a bipolar membrane.     

Fundamental studies on the intermediate layer of a bipolar membrane V. Effect of silver halide and its dope in gelatin on water dissociation at the interface of a bipolar membrane

The effect of silver ions on the water dissociation of bipolar membranes was first investigated in this paper. To do this, the bipolar membranes were prepared by immersing the anion exchange layers in an AgNO3 solution and then coating a solution of sulfonated polyphenylene oxide (SPPO) on the anion exchange layers. XPS and AES observations indicated that silver at the intermediate layer was in the form of AgCl. The experimental results proved that AgCl has an excellent catalytic function for water dissociation in terms of I-V curves, and the quantity of AgCl played an important role in the behavior of a bipolar membrane. The bipolar membranes with gelatin and the gelatin doped with silver as a catalytic layer were also prepared in the same way, and their I-V behavior and the water dissociation pilot tests were also investigated. The experimental results showed that in the case of gelatin alone, the voltage drop increased slightly at high gelatin concentrations, due mainly to the steric effect and electrostatic interaction, but decreased at low gelatin concentrations due to the hydrophilicity. However, when gelatin was doped with AgCl, the bipolar membranes have an appreciable improvement in both stability and catalytic function, in comparison with those prepared from silver or gelatin.     

多羧基酞菁铜、乙酰基二茂铁改性CMC/CS双极膜的制备及表征

柔性链高分子聚乙二醇(PEG)分别与阳离子交换膜层羧甲基纤维素钠(CMC)、阴离子交换膜层壳聚糖(CS)共混以增强界面的相容性和膜的机械性能.以金属有机高分子多羧基酞菁铜(CuPc)改性CMC、乙酰基二茂铁改性CS,采用流延法制备了CuPc-mCMC/mCS双极膜.双极膜溶胀性和热重分析结果表明膜改性后稳定性能得到提高.膜交流阻抗、I-V工作曲线的测定结果表明该双极膜阻抗及工作电压均较小.双极膜经改性具有较高的离子渗透性能。     

Ionic rectification properties of a bipolar interface consisting of a cationic surfactant and cation-exchange membrane

A novel bipolar interface that consists of cationic surfactant and cation-exchange membrane was successfully prepared in an aqueous electrolyte system. This bipolar interface shows a ionic rectification behavior similar to that observed in bipolar membranes. However, different from bipolar membranes, this system has a total rectification behavior, where we cannot observe the occurrence of a water-splitting phenomenon, which always occurs in the bipolar membrane process under reverse bias conditions.     

Catalytic water dissociation using hyperbranched aliphatic polyester (Boltorn series) as the interface of a bipolar membrane

The effect of hyperbranched aliphatic polyester (Boltorn series) on the water dissociation in bipolar membranes was firstly investigated in this paper. The bipolar membranes were prepared by immersing the anion exchange layer in a hyperbranched aliphatic polyester solution and then coating on the layer a polyphenylene oxide (SPPO) solution. The SEM observations proved the existence of hyperbranched aliphatic polyester at the membrane intermediate layer. The adsorption amount was evaluated by the oxygen content via XPS. The junction thickness of the prepared bipolar membrane was determined by electrochemical impedance spectroscopy (EIS), and the membrane performances were evaluated by current-voltage curves. The results showed that the amount and generation of Boltorn series, and temperature all affected I-V behaviors of the fabricated bipolar membranes, and the former two played the critical role. These effects were explained on the basis of the water dissociation theory and the characteristics of hyperbranched aliphatic polyester.     

Tailoring A Poly(ether sulfone) Bipolar Membrane: Osmotic-Energy Generator with High Power Density

Osmotic energy, obtained through different concentrations of salt solutions, is recognized as a form of a sustainable energy source. In the past years, membranes derived from asymmetric aromatic compounds have attracted attention because of their low cost and high performance in osmotic energy conversion. The membrane formation process, charging state, functional groups, membrane thickness, and the ion-exchange capacity of the membrane could affect the power generation performance. Among asymmetric membranes, a bipolar membrane could largely promote the ion transport. Here, two polymers with the same poly(ether sulfone) main chain but opposite charges were synthesized to prepare bipolar membranes by a nonsolvent-induced phase separation (NIPS) and spin-coating (SC) method. The maximum power density of the bipolar membrane reaches about 6.2 W m⁻² under a 50-fold salinity gradient, and this result can serve as a reference for the design of bipolar membranes for osmotic energy conversion systems.     

Bipolar reverse osmosis membrane for separating mono-and divalent ions

Bipolar reverse osmosis membranes that have both negatively and positively charged layers have been prepared to enhance the selectivity towards mono- and divalent ions in respect of both cations and anions. Positively charged layers are formed on low pressure reverse osmosis membranes having negative charge (NTR-7410 and 7450) by an adsorption method using polyethyleneimine (PEI) or a quaternary ammonium polyelectrolyte (QAP). These layers attach to the membrane's dense layer, which is made of sulfonated polyether sulfone. The selectivity of mono- and divalent ions is proven by experimental results for single electrolytes (NaCl, Na₂SO₄ and MgCl₂). Although negatively charged membranes repulse divalent anions more strongly than cations and monovalent anions, bipolar reverse osmosis membranes reject both divalent cations and divalent anions better than monovalent ions. An optimal preparation method for bipolar membranes showing selectivity towards mono- and divalent ions were developed. The bipolar membranes showed good ion selectivity for artificial sea water.     

Deacidification of citric acid solutions by electrodialysis

Electrodialysis is a useful process to deacidify citrus juices. Besides the known allanion exchange membrane process, two alternative electrodialysis processes were investigated: a three-stream process using cation and anion exchange membranes and a twostream process with alternately arranged bipolar and anion exchange membranes. The results taken from a laboratory electrodialysis cell show, that according to current efficiency, consumption of sodium hydroxide and by-production of sodium citrate or citric acid the alternative processes are favourable, especially the process using bipolar membranes.     

Tailoring A Poly(ether sulfone) Bipolar Membrane: Osmotic‐Energy Generator with High Power Density

Osmotic energy, obtained through different concentrations of salt solutions, is recognized as a form of a sustainable energy source. In the past years, membranes derived from asymmetric aromatic compounds have attracted attention because of their low cost and high performance in osmotic energy conversion. The membrane formation process, charging state, functional groups, membrane thickness, and the ion‐exchange capacity of the membrane could affect the power generation performance. Among asymmetric membranes, a bipolar membrane could largely promote the ion transport. Here, two polymers with the same poly(ether sulfone) main chain but opposite charges were synthesized to prepare bipolar membranes by a nonsolvent‐induced phase separation (NIPS) and spin‐coating (SC) method. The maximum power density of the bipolar membrane reaches about 6.2 W m^?2 under a 50‐fold salinity gradient, and this result can serve as a reference for the design of bipolar membranes for osmotic energy conversion systems.     

Salicylic acid production by electrodialysis with bipolar membranes

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

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

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

Preparation of PVA-GA-CS/PVA-Fe-SA bipolar membrane and its application in electro-generation of 2,2-dimethyl-3-hydroxypropionic acid

PVA-GA-CS/PVA-Fe-SA bipolar membrane was prepared by a paste method. PVA-sodium alginate (SA) and PVA-chitosan (CS) were cross-linked by FeCl₃ and glutaraldehyde (GA), respectively. The charge densities of PVA-CS and PVA-SA solutions were determined by the colloid titration. The swelling level of bipolar membrane was in the range of 25–85%, meanwhile the permeability and the ion-exchange capacity as well as co-ion transport properties was investigated. FTIR was applied to analyze the functional groups of the bipolar membrane. Furthermore, SEM photographs of the BPM cross-section illustrated a structure that consists of an anion layer (PVA-GA-CS) and a cation layer (PVA-Fe-SA). TG analysis of PVA-GA-CS/PVA-Fe-SA bipolar membranes exhibited a good thermal stability. PVA-GA-CS/PVA-Fe-SA bipolar membranes were used as the separator in the electrolysis cell for electro-generation of 2,2-dimethyl-3-hydroxypropionic acid. The average current efficiency was 52.2%, and the highest current efficiency reached 68.9%.     

Microscopic approach for the identification of cationic membrane fouling during cheddar cheese whey electroacidification

This is the first time that fouling of cation-exchange membranes during cheddar cheese whey electroacidification with bipolar membranes is reported. A mineral fouling was observed only on the cationic membrane side in contact with the base. The deposit was identified as magnesium hydroxide and this fouling was more important on the cation-exchange membrane situated close to the cathode. Little deposit was formed after six electroacidification runs, but on long time, the buildup of fouling film would lead after many electroacidifications to an important decrease of the system efficiency. Since, fouling of permselective membranes represents one of the major issues in electrodialytic processes, this result will be the basis for the determination of cleaning conditions allowing the prevention of such a fouling.     

Dielectric relaxation on the intermediate layer in a bipolar membrane under the water splitting phenomenon. I. Shift of the dielectric properties by means of time-dependent impedance measurements

In this study, we examined the dielectric properties of an intermediate layer in a bipolar membrane, which is composed of a negatively charged layer and a positively charged layer joined in series. As a result of the time-dependent impedance measurements of charged membranes, the negative increment in electric conductivity and the positive increment in electric capacity were observed only in the case of a bipolar membrane under the application of reverse-biased voltages, which were quite different from the behavior of both monopolar membranes and of a bipolar membrane under forward-biased voltages. Further, the observed shifts showed a nearly constant value against the reverse-biased voltage. It is concluded that these characteristics coincide with the process of ion exclusion in the intermediate layer and are attributed to the water splitting mechanism.     

Three-compartment bipolar membrane electrodialysis for splitting of sodium formate into formic acid and sodium hydroxide: Role of diffusion of molecular acid

Bipolar membrane electrodialysis is used in a three-compartment configuration to regenerate formic acid and sodium hydroxide from sodium formate. A previous study showed that the diffusion of molecular formic acid induces the loss of acid current efficiency. The present study shows the following results: the diffusion of molecular formic acid through the bipolar membrane explains quantitatively the presence of sodium formate in the sodium hydroxide solution. The loss of acid current efficiency is only due to diffusion of molecular acid through both anion-exchange and bipolar membranes. The sodium hydroxide current efficiency is determined by acid diffusion through the bipolar membrane and OH⁻ leakage through the cation-exchange membrane. The flux of acid diffusion through the membranes is proportional to acid concentration and depends on sodium hydroxide concentration for bipolar membrane and on sodium formate concentration for anion-exchange membrane. The flux rates vary with temperature.     

Application of charged membranes in water softening: modeling and experiments in the presence of polyelectrolytes

In this paper theoretical and experimental results for water softening by bipolar membranes in the presence of polyelectrolytes have been presented. A modified capillary model is introduced for flow of a multiion solution through the membrane. The most important modifications are: an integral boundary condition in Poisson equation and a coupling coefficient in the convective molar flux by using the modified Faxen equation. In addition, electrical permittivity of solution has not been considered as a constant. The predictions of the model were compared well with the experimental data obtained by using bipolar membranes in a recirculating test system in the presence of polyelectrolytes.     

mCMC-PEG/mCS-PEG双极膜的制备与表征

以Fe3+改性羧甲基纤维素(mCMC)和聚乙二醇(PEG)共混为阳膜;以戊二醛改性壳聚糖(mCS)和聚乙二醇共混为阴膜,制备了mCMC-PEG/mCS-PEG双极膜.以FTIR测定了膜红外光谱,以扫描电镜观察了膜表面和界面层的形态,以TG进行膜的热重分析.测定了mCMC-PEG和mCS-PEG不同比例共混膜的含水率、离子交换容量、溶胀度,及mCMC-PEG/mCS-PEG双极膜的电性能.研究结果表明,在双极膜材料中引入亲水性的聚乙二醇后,因分子间的相容性增大,故而提高了双极膜的离子交换容量,并减小了膜的溶胀性.当CMC∶PEG质量比等于10∶1和CS∶PEG质量比等于2∶1时所制得的双极膜具有良好的电化学性能,在酸碱溶液中机械强度高、溶胀小.     

Fundamental studies on the intermediate layer of a bipolar membrane: Part III. Effect of starburst dendrimer PAMAM on water dissociation at the interface of a bipolar membrane

Starburst dendrimer polyamidoamine (PAMAM) with ellipsoidal or spheroidal shape is structure-regular and has much more amino groups than conventional polymers. This paper investigates the possibility of these amino groups on water dissociation in a bipolar membrane interface. To do this, a bipolar membrane is prepared by casting the solution of sulfonated poly(phenylene oxide) (SPPO) in dimethyl formamide (DMF) on a commercial anion exchange membrane that is immersed in PAMAM aqueous solution in advance. The existence of PAMAM adsorbed on the membrane is proved by X-ray photoelectron spectroscopy (XPS), and the adsorption amount is evaluated by weighting method. The junction thickness of the prepared bipolar membrane is determined by electrochemical impedance spectroscopy (EIS), and the performance is evaluated by current–voltage curves. The experiments show that both the generation and concentration of PAMAM would strongly affect the characteristics of the bipolar membranes. There exists a transitional concentration for various generations PAMAMs to catalyze effectively the water dissociation, and above or below the transitional concentration the performance of bipolar membranes is decreasing. The higher the generation, the lower the concentration. Moreover, at a fixed solution concentration, there is not the simple relation of monotone decreasing or increasing between the performance of bipolar membranes and the generations of PAMAMs. All these can be explained according to the characteristics of PAMAMs combined with available water dissociation theory.     

Application of bipolar membrane technology: A novel process for control of sulfur dioxide from flue gases

We have demonstrated that the phenomenon of electrodialytic water splitting by bipolar membranes can be developed to a practical engineering unit process for the removal and recovery of SO₂ from stack gas. The SO₂ is first removed from the stack gas by means of an alkaline scrubbing solution. The spent solution is then regenerated in an electrodialysis cell containing only cation and bipolar membranes by the process known as two compartment electrodialytic water splitting. Concentrated SO₂ is liberated and recovered for further processing. p]Experimental results on our regeneration system show that an excellent current efficiency of 85% is obtained and that since the potential drop is only about 1.6 volts per cell unit, the system consumes less than half of the energy required for a conventional electrolysis acid base generation process. Tests have also shown that the bipolar membranes can satisfactorily be operated in the present system for long periods of time. This new process appears to be an attractive means of SO₂ abatement and could lead to the first commercial application of the new engineering principle of electrodialytie water splitting.