Ion current rectification at nanopores in glass membranes

The origin of ion current rectification observed at conical-shaped nanopores in glass membranes immersed in KCl solutions has been investigated using finite-element simulations. The ion concentrations and fluxes (due to diffusion, migration, and electroosmotic convection) were determined by the simultaneous solution of the Nernst-Planck, Poisson, and Navier-Stokes equations for the two-ion (K+ and Cl-) system. Fixed surface charge on both the internal and external glass surfaces that define the pore structure was included to account for electric fields and nonuniform ion conductivity within the nanopores and electric fields in the external solution near the pore mouth. We demonstrate that previous observations of ion current rectification in conical-shaped glass nanopores are a consequence of the voltage-dependent solution conductivity in the vicinity of the pore mouth, both inside and outside of the pore. The simulations also demonstrate that current rectification is maximized at intermediate bulk ion concentrations, a combination of (i) the electrical screening of surface charge at high concentrations and (ii) a fixed number of charge-carrying ions in the pore at lower concentration, which are physical conditions where the voltage dependence of the conductivity disappears. In addition, we have quantitatively shown that electroosmotic flow gives rise to a significant but small contribution to current rectification.     

Preparation of ultra-and nanoporous glasses and study of their structural and electrokinetic characteristics in 1: 1 electrolyte solutions

Nano-and ultraporous glass membranes with pore radii of 4.5–150 nm are prepared from sodium borosilicate glasses of various compositions. Structural parameters (structure resistance coefficient, volume porosity, and filtration factor) and electrokinetic characteristics (conductivity, counterion transport numbers, and electrokinetic potential ζ _α ^* ) of membranes are determined at various KCl and NaCl solution concentrations (10^?4?10^?1 M) in a neutral pH region. The passage from nano-to ultraporous glasses is accompanied by an increase in |ζ _α ^* | values, which is apparently related to a decrease in the thickness of a gel layer due to the removal of ion-permeable secondary silica from pore channels. The comparison of electrokinetic characteristics of glass membranes (counterion transport numbers, efficiency coefficients, and electrokinetic potentials) measured in NaCl and KCl solutions indicates a higher specificity of K⁺ counterions as compared to Na⁺ ions.     

Colloido-chemical characteristics of nanoporous glasses with different compositions in solutions of simple and organic electrolytes. 2. Equilibrium electrochemical characteristics of membranes

The regularities of variations in the electrokinetic potential and surface charge of nanoporous glass membranes with different compositions have been studied as depending on the type of an electrolyte (sodium, potassium, ammonium, tetramethylammonium, and tetraethylammonium chlorides) and the structure of pore space. It has been shown that, in solutions containing specifically sorbed organic counterions, the range of positive values of electrokinetic potential arises due to the superequivalent absorption of counterions in the Stern layer. It has been found that the influence of the specific adsorption of counterions on the electrokinetic potential of porous glasses increases with the amount of secondary silica in the pore space. The effects of the counterion specificity, pore channel sizes, and composition of a porous glass on the value of the surface charge have been analyzed. The absolute value of the surface charge has been shown to significantly increase in the presence of organic counterions in comparison with inorganic ions throughout the examined range of background electrolyte concentrations.     

Electrokinetic characteristics of initial porous glasses and those modified with titanium- and aluminum-oxide particles

The structural (volume porosity, structural resistance coefficient, and average pore radius) and electrokinetic (specific electrical conductivity, ion-transport numbers, and electrokinetic potential) characteristics of macroporous glass membranes obtained from two-phase sodium-borosilicate glasses with different times of thermal treatment have been studied in solutions of hydrochloric acid and potassium chloride. The properties of the initial membranes have been compared with the characteristics of the same membranes modified by filtering through them suspensions of aluminum- and titanium-oxide nanoparticles with different weight concentrations. It has been shown that, at low degrees of pore channel surface coverage with nanoparticles (<0.1), the structural parameters of the membranes remain almost unchanged. In addition, it has been found that the presence of positively charged nanoparticles on the negatively charged surface increases the surface conductivity and the absolute value of the electrokinetic potential.     

Colloido-chemical characteristics of porous glasses with different compositions in KNO3 solutions. 1. Structural and electrokinetic characteristics of membranes

The structural (specific surface area, liquid-filtration coefficient, average pore radius, volume porosity, and structural-resistance coefficient) and electrokinetic (counterion transport numbers, specific electrical conductivity, and electrokinetic potential) characteristics of porous glasses with different compositions have been determined in potassium nitrate solutions with concentrations of 10^?3–10^?1 M. All the membranes under investigation have been shown to exhibit the dependences of efficiency coefficients and counterion transport numbers on electrolyte concentration and pore size that are predicted by the theory of an electrical double layer. It has been established that, at a constant electrolyte concentration, the absolute values of electrokinetic potential increase with the average pore radius because of variations in the slipping-plane position.     

Hydraulic and surface characteristics of membranes with parallel cylindrical pores

Pore size distributions and pore densities of track-etched polycarbonate ultrafiltration (UF) membranes with pore sizes ranging from 10 to 100 nm (0.01–0.10 μm) were characterized by image analysis of field emission scanning electron micrographs (FESEM) of membranes. Porosity data obtained from image analysis compared well with those derived from manufacturer's specifications, but this may have been coincidental, as pore size and pore density results differed by 20–40% and 25–70%, respectively. The experimentally determined flux through each membrane type varied by up to 30–45% within a batch, and were about 8–46 times higher than the theoretical over the range of membranes. The disparity between theoretical and experimental flux was beyond the bounds of physical variability of the membranes. The membranes with smaller pore size tended to show a greater disparity. Water flux of all membranes increased with increasing temperature, generally in accord with the decreasing viscosity of water. However, unlike the linear increase for the membranes with larger pores (> 50 nm), the membranes with smaller pores (10 and 30 nm) showed exponential increase with temperature. Water flux also increased with a pressure increase from 50 to 300 kPa. Raised pressure appear to enlarge pores resulting in exponential flux enhancement at higher pressure, particularly for membranes with smaller pores (PC10). The pores may have stretched open under pressure to deliver the higher than expected fluxes due to flexibility of polycarbonate films, although FESEM showed no visible evidence of fracturing or tearing of the membranes. The flux results from filtration of aqueous protein solution were a little lower and correlated well with water permeability of the membranes, but remained in discord with the pore size distribution results.     

Specific features of the diffusion of potassium dichromate aqueous solutions in porous glass membranes

The diffusion coefficients of 0.1 M aqueous solution of potassium dichromate (pH 2–8) in a series of glass membranes with the prevailing pore radii from 4.5 to 70 nm were determined. Characteristic features of variation of the diffusion coefficient were correlated with the calculated content of chromium(VI) anionic species over a wide interval of pH of the solution.     

Electric transport properties of ultra-and nanoporous glasses in electrolyte solutions

Electric transport characteristics (conductivity, specific surface conductance, and transport numbers of counterions) for nano-and ultraporous glass membranes with pore radii of 1.3–160 nm are studied and compared for chloride solutions containing single-, double-, and triple-charged cations.     

Pore‐filling electrolyte membranes based on microporous polyethylene matrices activated with plasma and sulfonated hydrogenated styrene butadiene block copolymer. Synthesis,microstructural and electrical characterization

In this research a series of pore‐filling electrolyte membranes were prepared, based on a sulfonated and hydrogenated styrene/butadiene block copolymer (SHSBS) and plasma‐treated microporous polyethylene (PE) membranes. The pore‐filling electrolyte membranes were characterized by means of scanning electronic microscopy (SEM), infrared spectroscopy (FTIR‐ATR), and dynamic mechanical analysis (DMA). In addition, the water uptake and methanol/water uptake capacities of these membranes were determined using several methanol in water solutions, as well as the permeability coefficients, for both water and methanol, using a 2 M methanol in water solution and pure methanol. Finally, electrical behavior was recorded by means of electrochemical impedance spectroscopy (EIS) and the four probe technique (FPT). The SEM images recorded show good coating of the pore‐filling electrolyte membranes on the plasma‐treated PE matrices, and DMA shows the proper relaxations of the two components: PE and SHSBS. Furthermore, the methanol/water absorption capacity was observed to diminish with plasma treatment of the matrix. Methanol permeability of the pore‐filling electrolyte membranes is notably lower than that of the Nafion® membrane, ion conductivity moving in the order of 10⁻² S cm⁻¹. Both of these characteristics qualify the experimental membranes as candidates to be applied as proton exchangers in fuel cells (FCs). © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1684–1695, 2008     

A review of: “Nineteenth Century Attitudes: Men of Science (Chemists and Chemistry Series,Vol. 13)”. Sydney Ross. Kluwer Academic Publishers; Dordrecht, 1991. pp. xi+235. $69.00.

Abstract

The potential of polytetrafluoroethylene (PTFE) membranes as water‐in‐oil (W/O) emulsification devices was investigated to obtain uniformly sized droplets and to convert them into microcapsules and polymer particles via subsequent treatments. Uniform W/O emulsion droplets have not been achieved using glass membranes unless the membrane was rendered hydrophobic by treatment with silanes. If a PTFE membrane is capable of providing uniform droplets for a W/O emulsion, a coordinated membrane emulsification system can be established since glass membranes have been so successful for O/W (oil‐in‐water) emulsification. In order to examine the feasibility of PTFE membrane emulsification, O/W and W/O emulsion characteristics prepared using PTFE membranes were compared with those prepared by the conventional SPG (Shirasu porous glass) membrane emulsification method. A 3 wt.% sodium chloride solution was dispersed in kerosene using a low HLB surfactant. Effects of the membrane pore size, permeation pressure, and the type of emulsifiers and concentration on the droplet size and on the size distribution (CV, coefficient of variation) were investigated. The CV of the droplets was fairly low, and the average droplet size was correlated with the critical permeation pressure of the dispersed phase, revealing that the PTFE membrane could be used as a one‐pass membrane emulsification device. Low CV values were maintained with a Span 85 (HLB = 1.8) concentration, 0.2–5.0 wt.% and a range of HLB from 1.8–5.0. For a brief demonstration of practical applications, nylon‐6,10 microcapsules prepared by interfacial polycondensation and poly(acrylamide) hydrogels from inverse suspension polymerization are illustrated.     

Copper ion-selective chalcogenide glass electrodes: Analytical characteristics and sensing mechanism

New copper ion-selective electrodes based on chalcogenide glasses, Cu_xAg_25?xAs_37.5Se_37.5, display high copper(II) ion sensitivity with Nernstian response in the range pCu 1–6, short response time, high selectivity, potential stability and reproducibility. These electrodes are 10–30 times more sensitive in strongly acidic media than crystalline copper ion-selective sensors and are superior to the copper(I) selenide electrode in selectivity and resistance to acids and oxidation. A model is proposed to explain the ion sensitivity of these chalcogenide glass sensors. The sensitivity depends on direct exchange of copper(II) ions between solution and the modified surface layer of the glass. The modified surface layer is formed as a result of partial destruction of the glass network on soaking in solution; its atomic density is 2.0–2.5 times less than that of the original glass. The structural defects and hollows make fast copper(II) ion migration within the modified surface layer possible. Exchange sites in this layer can be formed by both disproportionation and oxidation of copper(I) in the glass network, as well as by diffusion of copper(II) ion from solution in the case of glasses with low copper content. Experimental confirmation of this model is provided by x-ray, photo-electron and scanning Auger electron spectroscopy.     

Structural and electrokinetic characteristics of ultra-and nanoporous glasses in tetraethylammonium chloride solutions

The structural and electrokinetic characteristics of ultra-and nanoporous glasses produced from basic sodium borosilicate glass have been investigated in tetraethylammonium chloride solutions. Colloido-chemical characteristics of the membranes have been compared with those determined in sodium and potassium chloride solutions. It has been found that the regularities of variations in counterion transference numbers and efficiency coefficients are related to a decrease in tetraethylammonium cation mobility in the membranes.     

Poly(acrylonitrile) ultrafiltration membranes. II. Membrane morphology and permeation characteristics

The rheology and phase‐boundary characteristics of various solutions comprising three polyacrylonitrile (PAN) grades dissolved in solutions of N,N‐dimethylformamide + salt (LiCl, ZnCl₂, or AlCl₃) additives were correlated with the resulting membrane morphology as determined by microscopy and permeability measurements. The phase separation characteristics of the dope solution were not markedly affected by the PAN molecular weight (MW); however, they were affected by the salt additive. For higher MW grades, the effect of salt addition can also be masked by the increased self‐association tendency of the polymer chains. PAN‐B and ‐C membranes were clearly less asymmetric in structure than the lower MW PAN‐A–based membranes. This is attributed to the higher viscosity/lower diffusivity of the PAN‐B and ‐C solutions, which results in slower solvent–nonsolvent exchange during the phase inversion process. Two factors reduce the incidence of surface defects (increased bubble points): (a) higher solution viscosity dampens surface perturbations during phase inversion, and (b) phase inversion pathways resulting in more homogenous morphology lead to membranes with higher bubble points. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2074–2085, 2005     

Fabrication of highly ordered porous membranes of cellulose triacetate on ice substrates using breath figure method

Highly ordered porous membranes of cellulose triacetate (CTA) were prepared successfully on ice substrates using breath figure method. The pore size and structure of the membrane were modulated by changing CTA concentrations and substrate materials. As the CTA concentration in the casting solution increased, the pore size in the formed membrane decreased. The regularity of the membrane cast on the ice substrate was much better than that of the membrane cast on glass substrate, because the low temperature of ice substrate slowed down the evaporation rate of organic solvent, which offered enough time for condensed water droplets to self‐organize into an ordered array dispersed in the polymer solution before their coagulation. The ordered porous CTA membrane was not only used for microfiltration, but also used for fabrication of functional microstructures. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 552–558     

Preparation of water and alkali durable porous glass membrane coated on porous alumina tubing by sol-gel method

Composite porous glass membranes were prepared by the sol-gel method. A thin porous glass layer, about 2 μm thick, was coated on the surface of the porous ceramic tubing (Al₂O₃:99.9 wt.%, pore diameter: 200 nm). The composition of the porous glass layer of the composite membrane was SiO₂-ZrO₂. Considering from the fact that the desalination ratio of the feed aqueous NaCl solution (NaCl 0.5 wt.%) was about 90% by use of these membranes, they were defect-free. The best composition of the porous glass layer was 70 SiO₂-30 ZrO₂ from the standpoint of preparing membranes. These membranes had a large water and alkali durability. These membranes can be expected to apply to recovering dyes and paints from organic solvents and to be used as a gas separation membrane.     

Electrokinetic Characteristics of Porous Glasses in Solutions of Sodium and Iron(III) Chlorides

The structural (structural resistance coefficient, bulk porosity, average pore radius, and specific surface area) and electrokinetic (surface conductivity and electrokinetic potential) characteristics of high-silica micro- and macroporous glasses produced from two-phase sodium borosilicate glass have been compared in solutions of an indifferent electrolyte (sodium chloride) and iron(III) chloride containing iron ions, which have a high specificity to silica surfaces. It has been shown that, in the presence of iron ions, the electrokinetic behavior of porous glasses is governed by two factors. First, the superequivalent adsorption of these ions in the Stern layer leads to positive values of the electrokinetic potential, and, second, their mobility in the pore space decreases, thereby resulting in the appearance of equilibrium solution concentration ranges, in which the specific conductivity of a pore solution becomes lower than that of a free solution.     

Hybrid liquid membrane (HLM) system in separation technologies

A novel liquid membrane system, denoted hybrid liquid membrane (HLM), was developed for the separation of solutes (metal ions, acids, etc.). It utilizes a solution of an extracting reagent (carrier solution), flowing between membranes. The membranes, which separate the carrier solution from feed and receiving (strip) solutions, enable the transport of solutes, but block the transfer of the carrier to the feed or to the strip. Blocking the carrier is achieved through membranes hydrophilic/hydrophobic or ion exchange properties, or through their rentention abilities, due to pore size.     

Physico-chemical characterization of nanofiltration membranes.

This study presents a methodology for an in-depth characterization of six representative commercial nanofiltration membranes. Laboratory-made polyethersulfone membranes are included for reference. Besides the physical characterization [molecular weight cut-off (MWCO), surface charge, roughness and hydrophobicity], the membranes are also studied for their chemical composition [attenuated total reflectance Fourier spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS)] and porosity [positron annihilation spectroscopy (PAS)]. The chemical characterization indicates that all membranes are composed of at least two different layers. The presence of an additional third layer is proved and studied for membranes with a polyamide top layer. PAS experiments, in combination with FIB (focused ion beam) images, show that these membranes also have a thinner and a less porous skin layer (upper part of the top layer). In the skin layer, two different pore sizes are observed for all commercial membranes: a pore size of 1.25-1.55 angstroms as well as a pore size of 3.20-3.95 angstroms (both depending on the membrane type). Thus, the pore size distribution in nanofiltration membranes is bimodal, in contrast to the generally accepted log-normal distribution. Although the pore sizes are rather similar for all commercial membranes, their pore volume fraction and hence their porosity differ significantly.     

Structural and Electrosurface Properties of Porous Glasses of Various Composition in 1 : 1 Electrolyte Solutions

Complex studies of structural (the specific surface area, the volume porosity, the structural resistance coefficient, and the average pore radius), adsorption and electrokinetic (the electrical conductivity, the ion transport numbers, and the electrokinetic potential) characteristics as functions of pH and the concentration of KCl solution were carried out on porous glasses (PGs) with or without lead oxide and leached under various conditions. It was established that temperature of the leaching solution affects the colloidochemical parameters of PGs, while the addition of salt to the leaching solution exerts practically no influence on the PG behavior. It was shown that the addition of lead oxide results in the formation of membranes with thinner pores and higher surface charge.     

Characterization of ultrafiltration membranes. Part III. Role of solvent media and conformational changes in ultrafiltration of synthetic polymers

The influence of some solution properties of synthetic polymers on their transport through ultrafiltration membranes has been reported.The rejection of polyvinyipyrrolidone and polyethylene glycol by solvent resistant membranes (IRIS membranes) increases with the size of solvated molecule, i.e., when the polymer is dissolved in better solvents. The polyvinylpyrrolidone polymer was more retained when it was in alcoholic solvents than when it was in water, while the opposite behaviour has been observed for polyethyleneglycol; this is due to the difference in the solvation of the two polymers by these solvents.When a salt is added to a solution of polyhydroxycarboxylate, two opposite behaviour patterns can be obtained whichever of the IRIS 3042, IRIS 3038 of GR5 membranes is used. When sodium chloride is added to the solution of polyhydroxycarboxylate, there is a decrease in rejection due to the contraction of the polymer chains caused by the shielding effect on the fixed charges of the polyion. But if a cupric salt is used, the complexation of carboxylate groups of the macromolecule by this divalent ion would bring about an ionic cross-linking of chains and increase in rejection will result.The effect of the deformability on the characteristics of the solute transport through membranes has been shown with the ultrafiltration of poly(L-glutamic acid). The rejection of the organized helical form of this polypeptide (in acidic medium) was higher than that of the same macromolecule in random conformation (in basic medium).