Modification of polysulfone membranes with polyethylene glycol and lignosulfate: electrical characterization by impedance spectroscopy measurements

Two sets of composite membranes having an asymmetric sulfonated polysulfone membrane as support layer have been obtained and electrically characterized (membranes SPS-PEG and PA-LIGS). The skin layer of the membrane SPS-PEG contains different percentages of polyethylene glycol in the casting solution (5, 25, 40, and 60 wt%), while lignosulfonate was used for manufacturing PA-LIGS membranes (5, 10, 20, and 40 wt%). Membrane electrical characterization was done by means of impedance spectroscopy (IS) measurements, which were carried out with the membranes in contact with NaCl solutions at different concentrations (10(-3) < or = c(M) < or = 5x10(-2)). Electrical resistance and equivalent capacitance of the different membrane samples were determined from IS plots by using equivalent circuits as models. Results show a clear decrease in the membrane electrical resistance as a result of both polysulfone sulfonation and the increase of the concentration of modifying substances, although a kind of limit concentration was obtained for both polyethylene glycol and lignosulfonate (40 and 20%, respectively). Results also show a decrease of around 90% in electrical resistance due to polysulfone sulfonation, while the value of the dielectric constant (hydrated state) clearly increases.     

Modification of active and porous sublayers of aged polyamide/polysulfone composite membranes due to HNO3 treatment: effect of treatment time

Changes in electrical and transport parameters for aged composite polyamide/polysulfone membrane samples (PAC) and their porous support layers (PSU) as a result of chemical treatment (immersion in 1 M HNO3 solution) at four different times (12 h < or = t < or = 72 h) have been obtained. Salt permeability, ion transport number, and membrane electrical resistance for the treated samples were determined from salt diffusion, membrane potential, and impedance spectroscopy measurements, which were carried out with the membranes in contact with NaCl solutions at different concentrations and compared with those determined for fresh and aged nontreated samples. Results show the strong effect of aging on membrane parameters, particularly the decrease in salt permeability (P(s)) and the increase in membrane electrical resistance (R(m)), while ion transport number is hardly affected by aging, chemical treatment, or treatment time. Results show how the compaction of the porous structure causes by aging (dried membrane matrix structure) can be partially reduced by HNO3 treatment, and they also allow the estimation of 24-h treatment as the optimum time (higher salt permeability and lower membrane electrical resistance), mainly for the polysulfone support layer. The use of equivalent circuits in the analysis of impedance spectroscopy data allows separate estimation of the electrical resistance associated with each sublayer of the composite PAC membrane samples. On the other hand, chemical changes in the active top layer of the PAC membrane (polyamide active layer) were obtained from XPS analysis, which show some modifications in the atomic concentration percentages of the polyamide characteristic elements as a result of acidic treatment time, which are more significant after 72-h acidic immersion.     

Electrochemical characterization of an asymmetric nanofiltration membrane with NaCl and KCl solutions: influence of membrane asymmetry on transport parameters

Electrochemical characterization of a nanofiltration asymmetric membrane was carried out by measuring membrane potential, salt diffusion, and electrical parameters (membrane electrical resistance and capacitance) with the membrane in contact with NaCl and KCl solutions at different concentrations (10(-3)< or =c(M)< or =5 x 10(-2)). From these experiments characteristic parameters such as the effective concentration of charge in the membrane, ionic transport numbers, and salt and ionic permeabilities across the membrane were determined. Membrane electrical resistance and capacitance were obtained from impedance spectroscopy (IS) measurements by using equivalent circuits as models. This technique allows the determination of the electrical contribution associated with each sublayer; then, assuming that the dense sublayer behaves as a plane capacitor, its thickness can be estimated from the capacitance value. The influence of membrane asymmetry on transport parameters have been studied by carrying out measurements for the two opposite external conditions. Results show that membrane asymmetry strongly affects membrane potential, which is attributed to the Donnan exclusion when the solutions in contact with the dense layer have concentrations lower than the membrane fixed charge (X(ef) approximately -0.004 M), but for the reversal experimental condition (high concentration in contact with the membrane dense sublayer) the membrane potential is practically similar to the solution diffusion potential. The comparison of results obtained for both electrolytes agrees with the higher conductivity of KCl solutions. On the other hand, the influence of diffusion layers at the membrane/solution interfaces in salt permeation was also studied by measuring salt diffusion at a given NaCl concentration gradient but at five different solutions stirring rates.     

Effect of age and chemical treatments on characteristic parameters for active and porous sublayers of polymeric composite membranes

Changes in the transport parameters and the chemical nature of the surface of composite polyamide/polysulfone membranes due to both aging and treatment with chemical products (HCl, H(3)NO, and NaOH) have been considered. Hydraulic and salt permeability were obtained from water flow and salt diffusion measurements, respectively, and their values seem to indicate a modification in the structural parameters (porosity/thickness) of aging samples, while HCl and HNO(3) treatments will act in the opposite way. Chemical modifications in the membrane surfaces were studied by X-ray photoelectron spectroscopy (XPS), which mainly show the effect of H(3)NO and HCl on the polyamide active layer of the membranes (polyamide oxidation), but no chemical damage for that sublayer. Electrical characterization of both sublayers of the composite membranes were determined from impedance spectroscopy (IS) measurements using equivalent circuits as models, and these results indicate: (i) a strong increase of the membrane electrical resistance as a consequence of aging, mainly that associated with the active sublayer (30 times higher for an old sample than for a fresh one) and treatment with NaOH; (ii) the reduction of this effect when the samples were treated with HCl and HNO(3) solutions. Changes in the values of the electrical resistance of the composite membranes are in agreement with those obtained for permeabilities, but the electrical parameter also allows the determination of the contribution of each sublayer.     

Electrokinetic parameters of ion transport across isolated pepper cuticular membranes

The transport of NaCl and CaCl₂ solutions across isolated pepper cuticular membranes was studied by means of conductivity, membrane potential and diffusion experiments. Some characteristic membrane parameters such as the electrical resistance, ionic and salt permeabilities were obtained as a function of the electrolyte concentrations. Cuticle morphological asymmetry accounts for differences in membrane potential values under external reverse gradients. The influence of temperature on the membrane structure was also considered, but only small changes in the electrokinetic parameters were obtained. From the NaCl diffusion experiments two activation energies were determined (54.8 kJ/mol for temperature ranging between 15 and 35°C, and 20.6 kJ/mol for the interval of temperature between 40 and 60°C), which could be associated to thermal transitions in the molecular structure of the cuticle for the interval 30–40°C.     

Relaxation spectra of the electrode impedance

A new analytical form is proposed enabling one to calculate the impedance of systems that contain no inductances. The method is based on breaking the overall impedance into a sum of isolated contours corresponding to a set of intrinsic frequencies of the system. Intrinsic frequencies, which exist in any real system, can be uniquely determined from the frequency characteristics. In this, they advantageously differ from speculative elements of equivalent circuits. For inductionless circuits, sets of intrinsic frequencies are replaced by intrinsic sets of reciprocal relaxation times. This allows one to construct a relaxation spectrum for the system, which describes quantitative contributions made by each relaxation contour to the overall impedance. As a result, one can estimate quantitatively conditions under which the system’s individual parameters may be observed, evaluate the resolving power of the experimental setup, and determine the full information capacity of an experiment (the maximum number of system’s parameters that can be determined).     

Chemical surface, diffusional, electrical and elastic characterizations of two different dense regenerated cellulose membranes

A comparison of NaCl transport across two dense cellulosic membranes from different suppliers is presented. Hydraulic and diffusional permeabilities were determined from volume flow-applied pressure and concentration-time relationships, while cation transport number and membrane conductivity were determined from electromotrice force and impedance spectroscopy measurements, respectively. Chemical surface differences between both membranes are correlated to transport parameters and morphology, but differences in elastic properties of both membranes might also be considered in order to get a more complete picture of membrane behaviors and to obtain structural-transport parameters correlations.     

Preparation of MF-4SC composite membranes with the anisotropic distribution of polyaniline and ion-transport asymmetry

A method of preparing MF-4SK membranes with the anisotropic distribution of aniline over the thickness is developed. The processes of aniline polymerization in the matrix of the MF-4SC sulfocationite membrane are investigated via electronic-absorption and IR spectroscopy. The processes of ion transport in the obtained composite membranes are studied via impedance spectroscopy, voltammetry, and potentiometry.     

An electrical impedance spectroscopic (EIS) study on transport characteristics of ion-exchange membrane systems

This study aimed at investigating ion-exchange membrane systems using impedance spectroscopy. Nyquist plots showed that the impedance obtained in this study described the ion-exchange membrane system well, as consisting of (i) an ion-exchange membrane immersed in solution, (ii) electrical double layers at the membrane surface, and (iii) diffusion boundary layers arising from the interface between the ion-exchange membrane and the electrolyte solutions. Taking into account the physical and electrochemical understanding of the ion-exchange membrane system, an equivalent circuit was suggested to quantitatively analyze each component of the ion-exchange membrane system. To confirm the reliability of the proposed equivalent circuit, the resistance and capacitance were estimated from the impedance data and the values were compared with other experimental results (e.g., I-V curves). The comparison showed good agreement and validated the equivalent circuit. Moreover, the impedance measurements made it possible to confirm the electroconvective effects in the over LCD region.     

Impact of Charge Transfer Complex on the Dielectric Relaxation Processes in Poly(methyl methacrylate) Polymer

The impact of the charge transfer complex on the dielectric relaxation processes in free poly(methyl methacrylate) (PMMA) polymer sheets was investigated. The frequency dependence of dielectric properties was obtained over the frequency range 0.1 Hz–1 MHz at temperatures ranging between 303 K and 373 K for perylene dye and acceptors (picric acid (PA) and chloranilic acid (CLA)) in an in situ PMMA polymer. The TG/dTG technique was used to investigate the thermal degradation of the synthesized polymeric sheets. Additionally, the kinetic parameters have been assessed using the Coats–Redfern relation. The dielectric relaxation spectroscopy of the synthesized polymeric sheets was analyzed in terms of complex dielectric constant, dielectric loss, electrical modulus, electrical conductivity, and Cole–Cole impedance spectroscopy. α- and β-relaxation processes were detected and discussed. The σ(ω) dispersion curves of the synthesized polymeric sheets show two distinct regions with increasing frequency. The impedance data of the synthesized polymeric sheets can be represented by the equivalent circuit (parallel RC).     

Analysis of fouling potential in the electrodialysis process in the presence of an anionic surfactant foulant

Fouling of ion exchange membranes in an electrodialysis process is highly sensitive to the concentration of a surfactant. To investigate the influence of the fouling on the process performance, an anion exchange membrane was characterized by electrochemical properties as well as physical and chemical properties. The fouling potential was then quantitatively analyzed using the membrane fouling index as a function of the surfactant concentration. It was observed that the fouling mechanism is initiated by the micelle formation. That is, most of SDBS molecules form a fouling layer on the membrane surface at a higher concentration than the critical micelle concentration. Also the SDBS fouling mechanisms caused by the fouling layer were examined by the electrochemical impedance spectroscopy. The equivalent circuits show that the fouling potential of the system was increased by an additional layer, simultaneously increasing the electrical resistance to permeation of ions through the membrane. However, the SDBS fouling on the membrane was a reversible process.     

Electrical impedance spectroscopy characterisation of conducting membranes: II. Experimental

An electrical impedance spectroscopy (EIS) method and apparatus that eliminates the need for electrodes in the feed and permeate solutions was evaluated as a means of characterising physical and performance properties of polysulphone ultrafiltration membranes in situ. The membranes were sputter-coated on one side with platinum before assembly in the apparatus. Alternating electrical current used for impedance measurements was injected directly into the coat via dry electrical contacts with the edges of the membrane. As the frequency of the EIS measurement was increased the current increasingly dispersed into the solution via the interfacial region (double layer) and/or fouling layers that the coat formed with the solution. These spatial dispersions manifested as characteristic dispersions with frequency of the impedance of the system. Water flux measurements, field emission scanning electron microscopy and atomic force microscopy were also used to quantify the important membrane performance parameters of porosity and surface roughness. These estimates were in good agreement with the impedance model for the in situ membrane system that was fitted to the measured impedance dispersions. The study shows that EIS measurements potentially can quantify membrane performance parameters in situ better than those techniques that require disruption of the membrane separation process. The method also has the potential for monitoring the deposition of particulate that can lead to fouling.     

Electrochemical impedance spectroscopy of tethered bilayer membranes

The electrochemical impedance spectra (EIS) of tethered bilayer membranes (tBLMs) were analyzed, and the analytical solution for the spectral response of membranes containing natural or artificially introduced defects was derived. The analysis carried out in this work shows that the EIS features of an individual membrane defect cannot be modeled by conventional electrical elements. The primary reason for this is the complex nature of impedance of the submembrane ionic reservoir separating the phospholipid layer and the solid support. We demonstrate that its EIS response, in the case of radially symmetric defects, is described by the Hankel functions of a complex variable. Therefore, neither the impedance of the submembrane reservoir nor the total impedance of tBLMs can be modeled using the conventional elements of the equivalent electrical circuits of interfaces. There are, however, some limiting cases in which the complexity of the EIS response of the submembrane space reduces. In the high frequency limit, the EIS response of a submembrane space that surrounds the defect transforms into a response of a constant phase element (CPE) with the exponent (α) value of 0.5. The onset of this transformation is, beside other parameters, dependent on the defect size. Large-sized defects push the frequency limit lower, therefore, the EIS spectra exhibiting CPE behavior with α ≈ 0.5, can serve as a diagnostic criterion for the presence of such defects. In the low frequency limit, the response is dependent on the density of the defects, and it transforms into the capacitive impedance if the area occupied by a defect is finite. The higher the defect density, the higher the frequency edge at which the onset of the capacitive behavior is observed. Consequently, the presented analysis provides practical tools to evaluate the defect density in tBLMs, which could be utilized in tBLM-based biosensor applications. Alternatively, if the parameters of the defects, e.g., ion channels, such as the diameter and the conductance are known, the EIS data analysis provides a possibility to estimate other physical parameters of the system, such as thickness of the submembrane reservoir and its conductance. Finally, current analysis demonstrates a possibility to discriminate between the situations, in which the membrane defects are evenly distributed or clustered on the surface of tBLMs. Such sensitivity of EIS could be used for elucidation of the mechanisms of interaction between the proteins and the membranes.     

Evaluation of electrical characteristics of biological tissue with electrical impedance spectroscopy

The electrical characteristics of biological tissue is evaluated by establishing an electrical equivalent circuit with electrical impedance spectroscopy. The least squares method is used to realize electrical equivalent circuit fitting by using the developed portable electrical impedance spectroscopy system. The EIS system is used to obtain the impedance spectrum data of the measured biological tissue. In the experiment, the impedance spectrum data of eggs under different heating time were measured, and the established equivalent circuit model of eggs was fitted by nonlinear least squares fitting algorithm. Moreover, the electrical characteristics of the biological tissue are also revealed by numerical simulation with HANAI model. The experimental and simulation results show that the extracted equivalent electrical parameters can clearly characterize the variation of the internal change of components of biological tissues.     

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.     

Transport limitations in ion exchange membranes at low salt concentrations

In this work we show that the electrical resistance of ion exchange membranes strongly depends on the solution concentration: especially at low solution concentrations (<0.1 M NaCl) we observe a very strong increase in electrical resistance of the membrane with decreasing concentration. To understand and clarify this behavior we systematically investigate the influence of the solution concentration on ion transport phenomena in two anion exchange membranes (Neosepta AMX and Fumasep FAD) and two cation exchange membranes (Neosepta CMX and Fumasep FKD) in the concentration range from 0.017 M to 0.5 M NaCl and for different hydrodynamic conditions. The results are highly valuable for processes that operate in the low concentration range (<0.5 M) such as reverse electrodialysis, electrodialysis, microbial fuel cells and capacitive deionization, where the standard membrane characterization values as usually determined in 0.5 M NaCl solutions do not represent the practical application.     

Proton transport in radiation-grafted membranes for fuel cells as detected by SECM

Scanning electrochemical microscopy (SECM) has been applied to investigate counter ion transport through four different proton conducting membranes with poly(styrene sulfonic acid) side chains. These membranes, intended for the polymer electrolyte fuel cell, are based on PVDF and PVDF-co-HFP matrix materials and have been prepared by an irradiation grafting method. SECM is found to be suitable for mapping variations in proton diffusion coefficient and concentration in these inhomogeneous membranes. It was found that the variations in these parameters are most considerable in a membrane with a high degree of grafting. Ionic conductivities measured with impedance spectroscopy were in agreement with calculated values obtained on the basis of the SECM measurements.     

Membrane impedance of internodal cells of Chara corallina obtained by analysis of low level transients

The relaxation of the membrane operational impedance of Chara cells has been investigated using a transient technique. This relaxation changes with the amplitude the sign of the electrical stimulation. A model which accounts for the time- and voltage-dependent channels conductance of the membrane is proposed. It describes both the time course of the transient electrical response and the relaxation of the operational impedance of the membrane of these plant cells.     

Impedance modelling of two-phase solid-state ionic conductors. Part I—theoretical model and computer simulations

An equivalent circuit model is introduced to account for the impedance properties of solid state ionic conductors, composed of two distinct phases. The model is developed on the basis of physical arguments, regarding the micrometer-scale structure of the two-phase material system and the comparison of different possible equivalent circuit representations. The final equivalent circuit reduces to two simpler circuits, suitable for fitting experimental impedance spectra. Computer simulations are provided to demonstrate the non-Arrhenius behaviour, which is observed in the temperature dependence of the ohmic elements of the equivalent circuits used for data analysis. This complex dual-slope behaviour of the Arrhenius plot is in agreement with the predictions of the model. Finally, with the aid of mathematical calculations and illustrated by computer simulations, a modified Arrhenius plot evaluation procedure was developed to derive correctly the electrical properties of the individual constituent phases from impedance measurements.     

交流阻抗法研究铝合金表面脉冲氧化膜

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