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

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

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

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

Studies with nickel phosphate membranes: evaluation of charge density and test of recently developed theory of membrane potential

The preparation of polystyrene-based nickel phosphate membrane at different pressures with varying amounts of material has been described. In order to understand the mechanism of transport of ions, membrane potential measurements were carried out using different concentrations of 1:1 electrolyte (KCl, NaCl and LiCl) solutions and also to evaluate various membrane parameters controlling the transport phenomena. Teorell, Meyer and Sievers (TMS) method was used for the estimation of the thermodynamically effective fixed charge density of membranes. The data were then utilized to calculate membrane potential using the extended TMS theory. It was interesting to note that the theoretical predictions were borne out quite satisfactorily with experimental results. scanning electron microscope (SEM) micrographs of the membranes have also been presented.     

静电位阻模型在纳滤膜跨膜电位解析中的应用

采用静电位阻模型对纳滤膜的跨膜电位进行了理论解析, 考察了溶液体积通量密度、原料液浓度、阴阳离子扩散系数比、膜孔半径和膜体积电荷密度对KCl(1-1型电解质)和MgCl2(2-1型电解质)中的纳滤膜跨膜电位的影响. 研究结果表明, 随着通量密度的增大, KCl和MgCl₂的跨膜电位线性程度增强; 两种电解质的跨膜电位均随着原料液浓度和膜孔半径的增大而下降; 在不同的考察范围内, 阴阳离子扩散系数比对1-1型和2-1型电解质的跨膜电位的影响差别较大; KCl的跨膜电位随着膜体积电荷密度的变化关于零点呈现出对称性, 而MgCl₂的跨膜电位零点则出现在膜体积电荷密度为负的条件下.     

Electrokinetic studies on testosterone/aqueous electrolyte interface : Part 1. Electro-osmosis,electrophoresis, streaming potential and streaming current

The electrical properties of testosterone interfaces were investigated. For this purpose, measurements of electro-osmosis, hydrodynamic permeation, streaming potential and streaming currents of metabolically important solutions of the electrolytes NaCl, KCl and MgCl₂ (in the concentration range 10^?4?10^?3 mol/l) across a testosterone plug were carried out. Electrophoretic mobility of testosterone particles suspended in these electrolyte solutions was also studied. The data were analysed from the viewpoint of nonequilibrium thermodynamics. Phenomenological coefficients were evaluated from the linear transport equations and Saxen's relationship was verified. Dependence of phenomenological coefficients on electrolyte concentration was examined. Electro-osmotic and electrophoretic transport coefficients were found to vary linearly with concentration, whereas hydrodynamic permeation and membrane conductance coefficients show non-linear variation. The results are explained on the basis of structural modifications occurring during the passage of the permeating species through the membrane. The nature of the electrical double layer formed at the testosterone/solution interface was ascertained on the basis of the direction of electro-osmotic permeation and electrophoretic migration of testosterone particles.Zeta potentials were estimated in order to obtain a plausible picture of the electrical double layer at the testosterone/solution interfaces. Dependence of zeta potentials on concentration was examined and membrane parameters calculated. The double layer thickness was estimated, which reveals that the diffuse double layer is more compact in the case of MgCl₂ than in that of KCl.     

The Micellization and Clouding of Nonionic Surfactant,Poly(Ethylene Glycol) t-Octylphenyl Ether (Triton X-100): Effect of Halide Ions of (Sodium Salt) Electrolytes

In this investigation, the micellization and the clouding phenomena of a nonionic surfactant, poly(ethylene glycol) t-octylphenyl ether (Triton X-100) in the absence and presence of halide ions (sodium salt) electrolytes has been reported. The critical micelle concentration (CMC) of Triton X-100 (in the absence and presence of electrolytes) was measured by surface tension measurements. A decreasing trend of CMC was found with increasing the temperature as well as the concentration of electrolyte. The effectiveness of the halide ions was found in the order: F^? > Cl^? > Br^? > I^?. The surface properties of Triton X-100 were evaluated. The thermodynamic parameters of the micellar systems of Triton X-100 were evaluated and from these thermodynamics data, it was found that in the presence of electrolyte the stability of the micellar system is more. The cloud points (CPs) of Triton X-100 were also measured in the absence and presence of halide ions of electrolytes. With the addition of halide ions of sodium salt (electrolyte), a decrease in CP values was observed and the order was found to be: F^? > Cl^? > Br^? > I^?.     

The Micellization and Clouding Phenomena of a Nonionic Surfactant,Poly(ethylene glycol) t-octylphenyl ether (Triton X-100): Effect of (Chloride Salt) Electrolytes

Herein, we report the micellization and the clouding of a nonionic surfactant, poly(ethylene glycol) t-octylphenyl ether (Triton X-100), in aqueous solutions in the absence and presence of (chloride salt) electrolytes. In the absence and presence of electrolytes, the critical micelle concentration (CMC) of Triton X-100 was measured by surface tension measurements. Upon increasing the temperature as well as the concentration of electrolytes, the CMCs decreased. The surface properties and the thermodynamic parameters of the micellar systems were evaluated. From these evaluated thermodynamic parameters, it was found that in the presence of an electrolyte, the stability of the micellar system is high. The cloud points (CPs) of Triton X-100 were also measured in the absence and presence of metallic ions of electrolytes. Upon the addition of metallic ions of chloride salts (electrolytes), the decrease in CP values was observed and the order was found to be: K⁺ > Na⁺ > Li⁺ > NH⁺₄.     

Dye-sensitised solar cells with iodine-free discotic electrolytes

Discotic mesogenic molecules viz., hexahexylthiotriphenylene (HHTT) and hexahexyloxytriphenylene were applied, for the first time, as iodine-free redox electrolyte in dye-sensitised solar cells (DSSCs). The cell shows open circuit voltage (V_oc) of 0.95 V, short circuit current density (J_sc) of 0.534 mA/cm², fill factor 88.24% and overall power conversion efficiency (η) 0.45% in a typical fluorine doped tin oxide/TiO₂/N719/HHTT/Pt DSSC configuration. Scanning electron microscopy was used to study surface profile of electrolytes while electrochemical impedance spectroscopy was used to understand the electrochemical behaviour of electrolytes. The photovoltaic parameters were measured under standard conditions using Oriel solar simulator class AAA. These first results demonstrate the potential of the discotic molecules as charge transporter and mediator and show promise to be used in iodine-free DSSCs.     

Studies on the fixed charge density and permselectivity of parchment supported manganese ferrocyanide membrane

Summary Membrane potentials across parchment supported manganese ferrocyanide membrane for various electrolytes over a wide concentration range have been studied. It was found that the membrane potential increases with dilution of the external electrolyte solutions. The fixed charge density of the membrane has been evaluated byAltug andHair's method and comes out to be −0.06 N. The variation of the transport number of the counterions in the membrane phase and perm-selectivity of the membrane with dilution have also been studied.

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Zusammenfassung Es wurden Membranpotentiale von Manganferrocyanid-Membranen auf Pergamenttr?gern in L?sungen verschiedener Elektrolyte über weite Konzentrationsbereiche untersucht. Das Membranpotential nahm mit der zunehmenden Verdünnung zu. Die fixierte Ladungsdichte wurde nachAltug undHair ermittelt und betrug −0.06 N. Die ?nderung der überführungszahl der Gegenionen in die Membranphase und die Permselektivit?t der Membran wurden ebenfalls bestimmt.

     

Lithium garnet based free-standing solid polymer composite membrane for rechargeable lithium battery

Electrolytes with high lithium-ion conductivity, better mechanical strength and large electrochemical window are essential for the realization of high-energy density lithium batteries. Polymer electrolytes are gaining interest due to their inherent flexibility and nonflammability over conventional liquid electrolytes. In this work, lithium garnet composite polymer electrolyte membrane (GCPEM) consisting of large molecular weight (W_avg ~?5?×?10⁶) polyethylene oxide (PEO) complexed with lithium perchlorate (LiClO₄) and lithium garnet oxide Li_6.28Al_0.24La₃Zr₂O₁₂ (Al-LLZO) is prepared by solution-casting method. Significant improvement in Li⁺ conductivity for Al-LLZO containing GCPEM is observed compared with the Al-LLZO free polymer membrane. Maximized room temperature (30 °C) Li⁺ conductivity of 4.40?×?10^?4 S cm^?1 and wide electrochemical window (4.5 V) is observed for PEO₈/LiClO₄?+?20 wt% Al-LLZO (GCPEM-20) membrane. The fabricated cell with LiCoO₂ as cathode, metallic lithium as anode and GCPEM-20 as electrolyte membrane delivers an initial charge/discharge capacity of 146 mAh g^?1/142 mAh g^?1 at 25 °C with 0.06 C-rate.     

A Study of Concentration Polarization on Ion Exchange Membrane Electrodialysis

The concentration polarization phenomena in ion exchange membrane electrodialysis have been studied with single exchange membrane cell. The limiting current densities of Asahi ion-permselective membranes CK-1 and CK-2, Selemion ion-exchange membranes CMV, AMV, DMV and ASV have been measured with Ag-AgCl reversible electrode in various electrolyte solutions under 25°C and constant flow rate. In sodium chloride solution, the cation exchange membrane is easier to occur concentration polarization than the anion exchange membrane. The limiting current density increases as the concentration of solution increases for the same kind of ion exchange membrane. The experimental limiting current densities of Selemion CMV and AMV in NaCl, KCl, MgCl₂, CaCl₂, BaCl₂, Na₂SO₄, NaOH and HCl aqueous solutions are measured. The results show that the limiting current density increases as the ion mobility and diffusivity increase, and is affected by the transference number of ion. For the mixture of electrolyte solution, there are linear relationship between limiting current density and equivalent fraction of electrolytes.     

1-1型单组分盐溶液中荷电膜膜电位的研究

根据固定电荷模型和非线性最小二乘法, 研究膜体积电荷密度为定值和其大小随电解质主体溶液浓度呈指数变化的两种初始条件下, 五种纳滤膜(NTR 7450, ESNA 1, ESNA 1-LF, LES 90和UTC 60)在不同浓度的氯化钠和氯化钾溶液中的膜电位, 获得膜体积电荷密度与电解质主体溶液浓度的关系. 结果表明, 当体积电荷密度随浓度呈指数变化时, 拟合的膜电位与实验结果更接近, 得到的固定电荷密度更精确. 膜电位的大小与膜两侧电解质溶液浓度的比值相关. 在较高浓度时, 膜电位的值还与扩散系数相关; 其中阴阳离子的扩散系数之比大于1.0是膜电位反号的标志. 在中间浓度时, 膜电位随电解质主体溶液浓度近似呈线性变化.     

Separation of carrier-free 90Y from 90Sr using flat sheet supported liquid membranes containing multiple diglycolamide-functionalized calix[4]arenes

Abstract

Five diglycolamide-appended calix[4]arene (C4DGA) ligands, viz. C4DGA with no substituent (L-I), n-propyl (L-II), 3-pentyl (L-III), n-octyl (L-IV) and both side (L-V) substituents were evaluated for the separation of carrier free ⁹⁰Y from a ⁹⁰Y–⁹⁰Sr mixture using the flat sheet supported liquid membrane technique. Based on the results of earlier batch studies, the transport properties of the C4DGA ligands towards Y(III) and Sr(II) were monitored at two different feed acidities. The transport rates were significantly lower for 6 M HNO₃ as compared to 3 M HNO₃ as the feed. After 6 h, the observed trend of Y(III) transport with the C4DGA ligands using a feed of 3 M HNO₃ was: L-I ~ L-III > L-V > L-IV > L-II which changed to L-III > L-I > L-IV > L-V > L-II for 6 M HNO₃ as the feed. With 3 M HNO₃ as feed, >97% Y(III) transport was obtained with L-I and L-III in 6 h. Comparative Sr(II) transport was negligible resulting in high decontamination factors. In a one-step separation process, using L-I as the carrier ligand, pure ⁹⁰Y was obtained as the respective complex with either EDTA or DOTA. The highlights of this liquid membrane-based separation method comprise: its easiness, one-step separation, low ligand inventory, relatively pure product and continuous method.     

Behaviour of a cobalt spinel ultrafiltration membrane during salt filtration with different ionic strengths

The characterisation of the surface charge of a cobalt spinel ultrafiltration membrane was investigated in the presence of electrolyte solutions by means of streaming potential measurements. The selectivity of a membrane towards different salts depends on the electrostatic interactions between the species in solution and the charge of the membrane surface. Firstly, the values of the streaming potential coefficient were measured during the filtration of NaCl, CaCl₂, Na₂SO₄ and CaSO₄ as a function of pH and ionic strength. The iso-electric point was determined for each electrolyte. Secondly, the rejection rates of the electrolytes were measured by ionic chromatography. The rejection was explained by a correlation with the surface charge of the membrane.     

Electrochromic performance of Zn-Ti-O composite thin film with electrolyte dependence

Zn-Ti-O composite thin film prepared on FTO by sol-gel technique is discovered presenting electrochromic behavior in electrolytes with Li⁺ ion (LiClO₄) and K⁺ (KCl) as well. The observed EC colored/bleached switching is electrolyte dependent which is blue-green/transparent in LiClO₄ and gray-blue/transparent in KCl, respectively. Accordantly, the respective most optical modulation (ΔT) between colored and bleached states is ~?32% (710 nm) in LiClO₄ and ~?37% (600 nm) in KCl. The finding of appreciable steady EC durability with appealing visual optical contrast (ΔT) in conventionally fabricated Zn-Ti-O thin film using with bigger/heavier K⁺ electrolyte helps expanding the applicable components in EC device.     

Strong deformations induced by a DC electric field in homeotropic flexo-electric nematic layers

Elastic deformations of homeotropic nematic liquid crystal layers subjected to a DC electric field were studied numerically in order to determine their development under increasing voltage. Both signs of the dielectric anisotropy, Δ?, and of the sum of flexo-electric coefficients, e ₁₁ + e ₃₃, were considered, as were also low, moderate and high ion concentrations. The electrical properties of the layer are described in terms of a weak electrolyte model. Quasi-blocking electrode contacts and a finite surface anchoring strength were adopted. Director orientation, the electric potential and the ion concentrations were each calculated as a function of the coordinate normal to the layer. The director distributions turned out to depend not only on the sign of Δ? but also on the sign of e ₁₁ + e ₃₃, due to the difference in the mobility of anions and cations. The importance of ion content was also confirmed.     

Electrophoretic mobility of latex spheres in the presence of divalent ions: experiments and modeling

Electrophoretic mobilities (EPM) of negatively charged latex spheres were measured as a function of salt type and salt concentration. The measured values of EPM were analyzed using a standard electrokinetic model that includes double layer relaxation and the Poisson–Boltzmann model of diffuse double layer. Calculated values of EPM were in good agreement with experimental data taken in simple 1:1 (KCl) and 1:2 (Na₂SO₄) electrolyte solutions without using any fit parameters. For 2:1 electrolytes (CaCl₂ and MgCl₂), however, the magnitude of EPM calculated by the model was higher than the measured values of EPM at higher electrolyte concentrations. The difference between measured and calculated EPM was reduced by assuming the distance of slipping plane x _s?=?0.25 nm or by assuming the decrease of the magnitude of surface charge density from ?0.07 to ?0.025 C/m². These are probably due to the accumulation of divalent counterions in the vicinity of a particle’s surface.     

Irreversible adsorption of latex particles on fibrinogen covered mica

Physicochemical properties of bovine plasma fibrinogen (Fb) in electrolyte solutions were characterized. These comprised the diffusion coefficient (hydrodynamic radius), determined by the DLS method, electrophoretic mobility and the isoelectric point. The hydrodynamic radius of Fb was 12 nm for pH<5. The number of uncompensated (electrokinetic) charges on the protein N _c was calculated from the electrophoretic mobility data. It was found that for pH<5.8 the electrokinetic charge was positive, independently of the ionic strength and negative for pH>5.8. For pH=3.5 the value of N _c , was 26 for 10^?3 M. Similar electrokinetic measurements were performed for the mica substrate using the streaming potential cell. It was shown that for pH=3.5 and 10^?3 M, the zeta potential of mica remained negative (?50 mV). This promoted an irreversible, electrostatically driven adsorption of Fb, which was confirmed in experiments carried out under diffusion-controlled transport. The surface concentration of Fb on mica was determined directly by AFM counting. By adjusting the time of adsorption, Fb monolayers of desired coverage were produced. Independently, the presence of Fb on mica was determined quantitatively by the colloid enhancement method, in which negatively charged latex particles were used, having the diameter of 800 nm. It was found that for Fb coverage below 0.05 the method was more sensitive than other indirect methods. The experimental data obtained in latex deposition experiments were adequately interpreted in terms of the random site model used previously for polyelectrolytes. It was shown that adsorption sites consisted of a cluster of two Fb molecules. It was concluded that the colloid enhancement method can be successfully used for detecting the presence of proteins at solid substrates and to determine the uniformity of monolayers in the nanoscale.     

Effect of alkaline and alkaline–earth cations on the supercapacitor performance of MnO2 with various crystallographic structures

The electrochemical performances of the α-, γ-, and δ-MnO₂ with different crystallographic structures were systematically investigated in 0.5 mol/L Li₂SO₄, 0.5 mol/L Na₂SO₄, 1 mol/L Ca(NO₃)₂, and 1 mol/L?Mg(NO₃)₂ electrolytes. The results showed that the electrochemical performances of the manganese dioxides depended strongly on the crystallographic structures of MnO₂ as well as the cation in the electrolytes. Because the δ-MnO₂ consists with layers of structure and the interlayer separation is 7 Å, which is suitable for insertion/extraction of some alkaline and alkaline–earth cations, the δ-MnO₂ electrode showed the higher specific capacitance than that of α-MnO₂ and γ-MnO₂. We also found that the α-, γ-, and δ-MnO₂ electrodes in the Mg(NO₃)₂ electrolyte showed a higher specific capacitance, while all the α-, γ-, and δ-MnO₂ electrodes in the Li₂SO₄ electrolyte exhibited a better cycle life. The reason for the different behavior of Li⁺ and Mg²⁺ during the charge/discharge process can be ascribed to the charge effect of the cations in the electrolytes. The ex situ X-ray diffraction (XRD) and long-time cyclic voltammogram measurements were used to systematically study the energy storage mechanism of MnO₂-based electrodes. A progressive crystallinity loss of the materials is also observed upon potential cycling at the oxidized states. A reasonable charge/discharge mechanism is proposed in this work.     

Investigation of the Ionic Conduction Mechanism in Carboxymethyl Cellulose/Chitosan Biopolymer Blend Electrolyte Impregnated with Ammonium Nitrate

In the present work, an attempt has been made to prepare a new natural biopolymer blend electrolyte of carboxymethyl cellulose/chitosan impregnated with NH₄NO₃ by the solution casting technique. The conductivity for the system was measured by impedance spectroscopy. The incorporation of 40 wt.% NH₄NO₃ optimized the ambient temperature conductivity of the electrolyte up to 1.03 × 10^?5 S cm^?1. All electrolytes were found to follow the Arrhenius relationship. Dielectric studies confirmed that the electrolytes obey non-Debye behavior. The temperature dependence of the power law exponent s for the highest conducting film can be represented by the correlated barrier hopping model.