Membrane potential in charged porous membranes

For charged porous membranes, the separation efficiency to charged particles and ions is affected by the electrical properties of the membrane surface. Such properties are most commonly quantified in terms of zeta-potential. In this paper, it is shown that the zeta-potential can be calculated numerically from the membrane potential. The membrane potential expression for charged capillary membranes in contact with electrolyte solutions at different concentrations is established by applying the theory of non-equilibrium thermodynamic to the membrane process and considering the space-charge model. This model uses the Nernst–Planck and Navier–Stokes equations for transport through pores, and the non-linear Poisson–Boltzmann equation, which is numerically solved, for the electrostatic condition of the fluid inside pores. The integral expressions of the phenomenological coefficients coupling the differential flow (solute relative to solvent) and the electrical current with the osmotic pressure and the electrical potential gradients are established and calculated numerically. The mobilities of anions and cations are individually specified. The variations of the membrane potential (or the apparent transport number of ions in the membrane pores) are studied as a function of different parameters: zeta-potential, pore radius, mean concentration in the membrane, ratio of external concentrations and type of ions.     

Preparation and characterization of porous conducting poly(dl-lactide) composite membranes

Solid conducting biodegradable composite membranes have shown to enhance nerve regeneration. However, few efforts have been directed toward porous conducting biodegradable composite membranes for the same purpose. In this study, we have fabricated some porous conducting poly(dl-lactide) composite membranes which can be used for the biodegradable nerve conduits. The porous poly(dl-lactide) membranes were first prepared through a phase separation method, and then they were incorporated with polypyrrole to produce porous conducting composite membranes by polymerizing pyrrole monomer in gas phase using FeCl₃ as oxidant. The preparation conditions were optimized to obtain membranes with controlled pore size and porosity. The direct current conductivity of composite membrane was investigated using standard four-point technique. The effects of polymerization time and the concentration of oxidant on the conductivity of the composite membrane were examined. Under optimized polymerization conditions, some composite membranes showed a conductivity close to 10⁻³ S cm⁻¹ with a lower polypyrrole loading between 2 and 3 wt.%. A consecutive degradation in Ringer's solution at 37 °C indicated that the conductivity of composite membrane did not exhibit significant changes until 9 weeks although a noticeable weight loss of the composite membrane could be seen since the end of the second week.     

Membrane characterization by solute transport and atomic force microscopy

Various ultrafiltration and nanofiltration membranes were characterized by solute transport and also by atomic force microscope (AFM). The molecular weight cut-off (MWCO) of the membranes studied were found to be between 3500 and 98,000 Daltons. The mean pore size (μ_p) and the geometric standard deviation (σ_p) around mean ranged from 0.7 to 11.12 nm and 1.68 to 3.31, respectively, when calculated from the solute transport data. Mean pore sizes measured by AFM were about 3.5 times larger than calculated from the solute transport. Pore sizes measured by AFM were remarkably fitted to the log-normal probability distribution curve. Pore sizes of the membranes with low MWCO (20,000 Daltons and lower) could not be measured by AFM because of indistinct pores. In most cases, the pore density ranged from 38 to 1291 pores/μm². In general, the pore density was higher for the membrane having lower MWCO. Surface porosity was around 0.5–1.0% as measured from the solute transport and was 9.5–12.9% as obtained from AFM images. When membranes were coated with a thin layer of sulfonated polyphenylene oxide, mean pore sizes were reduced for all the membranes. Surface roughness was also reduced on coating.     

Cellular porous polyvinylidene fluoride composite membranes for lithium-ion batteries

Macroporous polyvinylidene fluoride (PVdF) membranes were prepared by a phase inversion method and evaluated as battery separators. Two totally different morphologies (cellular and finger-like) were obtained by coagulating PVdF solutions with two different solvents. The cellular membranes were formed immediately by precipitating the PVdF solution with a latent solvent (acetone) in water, while the finger-like membranes were precipitated from the PVdF solution with a true solvent (N-methyl-2-pyrrolidone). The incorporation of a silica filler decreased the ionic resistance of the PVdF membranes of both morphologies. However, the cellular membranes showed better mechanical properties and enabled higher ionic conductivities than the finger-like ones, especially when the silica loading was low. Compared with a conventional untreated polyolefin separator, the porous PVdF membranes showed good wettability by a liquid electrolyte. After being activated with a commercial LiPF₆–ethylene carbonate–dimethyl carbonate electrolyte, the PVdF membranes were tested for their applications in lithium-ion batteries. Coin cells with these PVdF membranes exhibited stable cycling performance and good rate capability at room temperature. However, the cellular membranes are preferred over the finger-like ones because they offer higher mechanical performance, and can be processed into flat membranes more easily.     

Development and characterization of PPO composite membranes for gas separation

Poly(phenylene oxide) (PPO) composite membranes have been prepared on a polysulfone (PSf) ultrafiltration support, which was previously coated with highly permeable polydimethylsiloxane (PDMS). The PDMS gutter layer was used in order to: Plug the pores of the support; minimise the thickness of the separating PPO deposit; and reduce the tortuosity of the path of the gas molecules to the pores of the support. Composite membranes with high fluxes and good selectivities for gas separations have been obtained with an amorphous and cross-linkable phenylene oxide co-polymer.     

Effects of adsorbed polyelectrolytes on convective flow and diffusion in porous membranes

Poly(acrylic acid) and poly(styrene sulfonate) were adsorbed from aqueous solutions to track-etched mica membranes with pores of radius 290 to 1400 Å. Effects of the adsorbed polymers on momentum and mass transport within the pores were studied by measuring the decrease in both the hydraulic and diffusional permeabilities caused by the presence of the polymers. The diffusional permeability was determined by measuring the flux of a small, uncharged solute molecule (thiourea). Polymer-free, aqueous solutions of potassium chloride (KCl) were used in all transport experiments. The reduction in hydraulic permeability increased with a decrease in KCl concentration in the range 10^-2 to 10^-1 molarity (M), but was independent of electrolyte concentration below 10^-2 M, presumably because the small pores constrained expansion of the adsorbed polymer chains. Shear thickening effects, that is, a decrease in hydraulic permeability with increasing solvent velocity through the pores, was observed with both polymers at 10^-1 M KCl in pores of 600 Å or smaller. Effects of the polymer on diffusional permeability of thiourea, on the other hand, were relatively insensitive to electrolyte concentration. Perhaps the most significant result is that the reduction in diffusional permeability was substantially less than the reduction in hydraulic permeability at each pore size and electrolyte concentration, indicating that the blockage of momentum transport by these adsorbed polymers is greater than the blockage of diffusion of a small solute. Measurements of thiourea transport by simultaneous diffusion and convection over a range in Peclet numbers from -2 to +2 showed that thiourea was filtered by the polymer. This filtration was probably not due to steric limitations on the thiourea, rather it is likely that thiourea was excluded from the water which solvated densely packed regions of the polymer chains.     

Preparation and characterization of silica—polyimide composite membranes coated on porous tubes for CO2 separation

Silica-polyimide microcomposite membranes were prepared on γ-alumina-coated α-alumina support tubes, and their gas permeation properties were evaluated with He, N₂ and CO₂. Smoothing of the substrate surface and hybridization of silica and polyamic acid were both effective to form defect-free thin composite membranes. The CO₂ permeance of a membrane with a silica content of 68 wt% was one order of magnitude higher than that of a polyimide membrane having the same thickness. The permselectivity of CO₂ to N₂ was 30 at 30°C and 13 at 100°C. Contributions of the silica and polyimide phases to permeance of the composite membrane were analyzed with a two-phase permeation model. The effective thickness of the rate-controlling polyimide phase was less than one-tenth of the total thickness of the silica-polyimide membrane.     

Facile preparation and characterization of anatase TiO2/nanocellulose composite for photocatalytic degradation of methyl orange

Anatase TiO₂/nanocellulose composite was prepared for the first time via a one-step method at a relatively low temperature by using cellulose nanofibers as carrier and tetrabutyl titanate as titanium precursor. The morphology, structure and element composition of the composite were characterized by SEM, EDS, TEM, XRD, XPS and UV–vis DRS. The specific surface area and thermal stability of the composite were investigated by N₂ adsorption–desorption and thermogravimetric analysis, respectively, and the band gaps of the prepared photocatalysts were calculated based on the UV–vis DRS results. In addition, the prepared composite was used for the photocatalytic degradation of methyl orange (aqueous solution, 40 mg L⁻¹). It was found that the composite had a good morphology and anatase crystal structure, and Ti-O-C bond was formed between TiO₂ and nanocellulose. The specific surface area of composite was increased and the thermal stability was decreased compared with the cellulose nanofiber. Moreover, the degradation rate of methyl orange was achieved as 99.72% within 30 min, and no obvious activity loss was observed after five cycles. This work might give some insights into the design of efficient photocatalysts for the treatment of organic dye wastewater.     

Surface characterization of hemodialysis membranes based on electrokinetic measurements

Hemodialysis membranes were characterized by means of streaming potential measurements. By variation of the concentrations of different ionic species in the measuring solutions surface potential determining processes can be distinguished: The investigated materials (cellulose derivates) yield surface charges mainly from preferred adsorption of ions. A thermodynamic model of the electrochemical double layer according to STERN (1) was applied to quantify that processes; the resulting set of parameters provide a conjunction between chemical surface properties and the observed interfacial charging processes. Streaming potential measurements can be used for the in situ characterization of the adsorption of biologically relevant molecules like proteins and polysaccharides onto membrane materials. The results given here show the alteration of interfacial properties of different cellulosic membranes through adsorption of human serum albumin and fibrinogen in single, sequential and competitive adsorption.     

One-step-process composite colloidal monolayers and further processing aiming at porous membranes

Composite materials consisting of a monolayer of polystyrene spheres (diameters of 430 and 520 nm) and porous silica, filling in the interstices, have been fabricated and characterized. The proposed growth method introduces some novelties as far as the fabrication of this kind of monolayers is concerned, as it probes the compatibility of coassembly (in which a silica precursor, tetraethyl orthosilicate (TEOS), is added to the base colloid) with confined growth in a wedge-shaped cell, while profiting from the advantages of both techniques. Using this method, it is possible to fabricate the composite monolayer in a single growth step. A systematic study of the influence of TEOS concentration in the initial colloid was performed in order to improve the quality of the two-dimensional crystals produced. Thus, it was demonstrated that the two methods are compatible. Furthermore, the composites were then subjected to thermal treatment so that the polymer is removed to reveal the inverse structure. After the calcination the membranes still present very good quality and so the proposed approach is effective for the fabrication of porous membranes. A comparison of reflectance spectra, between composite monolayers fabricated using this method and composites achieved by infiltrating polystyrene bare opals with silica chemical vapor deposition, is also established. The procedure presented is expected to establish the route for an easier and quicker fabrication of inverse monolayers of high refractive index materials with applications in light control.     

Novel composite membranes embedded with molecularly imprinted porous polymeric nanospheres for targeted phenol

In the present research, novel hybrid molecularly imprinted polymer (HMIP) membranes were synthesized for selective adsorption and separation of phenol toxic molecules from aqueous solutions. Molecularly imprinted polymer (MIP) nanospheres for targeted phenol were successfully prepared using precipitation polymerization of methacrylic acid, trimethylolpropane trimethacrylate, and ethylene glycol dimethacrylate, followed by integrating into polysulfone matrix to create the HMIP membranes via a phase inversion method. The fabricated materials were characterized from the viewpoints of spectroscopic analysis, structural and surface morphological properties, porosimetry, and batch rebinding assays. The imprinted polymeric nanospheres with mean diameter value ranging from 210 to 250 nm and average pore diameter of 8 nm were obtained according to the morphological and Brunauer–Emmett–Teller analysis, respectively. Scanning electron microscopy pictures demonstrated that the MIP spheres were uniformly distributed on the surface and in the bulk polymer phase of the hybrid membrane. The surface roughness, porosity, and permeate flux of membrane were significantly augmented by addition of the imprinted polymer particles in the dope solution. HMIP‐2 membrane containing 10 wt% of MIP showed the highest binding capacity and an excellent molecular recognition for phenol with respect to the correlative blank membrane. The selective recognition of phenol on the HMIP‐2 membrane was 3.5 times larger than the analogous compound (i.e. catechol). Moreover, the maximum separation factor of phenol was obtained as 2.19 relative to catechol through selective permeation studies, which was also observed for HMIP‐2 membrane. Copyright © 2015 John Wiley & Sons, Ltd.     

Antimicrobial porous hybrids consisting of bacterial nanocellulose and silver nanoparticles

The increasing resistance of pathogens and bacteria is a serious problem in the medical treatment of wounds and injuries. Therefore, new therapeutic agents are not solely based on antibiotics, but also on the use of antimicrobial metal nanoparticles. In this paper we present an innovative method to prepare porous hybrids consisting of bacterial nanocellulose (BNC) and silver nanoparticles (AgNPs). The stepwise modification is based on fairly simple chemical reactions already described for two-dimensional cellulose films. We transferred this method to the three-dimensional, porous network of BNC leading to an antimicrobial activation of its surface. Compared to former approaches, the ultrafine network structure of BNC is less damaged by using mild chemicals. The amount and distribution of the AgNPs on the modified BNC was investigated using scanning electron microscopy. The AgNPs are firmly immobilized on the top and bottom surface of the BNC by chemical interactions. Their size and quantity increase with an increasing concentration of AgNO₃ and extended reaction time in the AgNO₃ solution. A strong antimicrobial activity of the BNC-AgNP hybrids against Escherichia coli was detected. Furthermore, agar diffusion tests confirmed that this activity is restricted to the modified dressing itself, avoiding a release of NPs into the wound. Therefore, the produced hybrids could be potentially suited as novel antimicrobial wound dressings.     

Transport of monomer surfactant molecules and hindered diffusion of micelles through porous membranes

Diffusion of Triton X-100 through Celgard 2500 membranes was examined. The pore permeability for monomers was 5.0 × 10⁻⁶ cm²/sec and it was measured for upstream concentrations below the CMC value of 2.29 × 10⁻⁴M at 30°C. This value is close to the monomer diffusion coefficient in bulk suggesting that the monomers do not experience significant hindrance due to the pore walls. The permeability of the surfactant drops abruptly within a narrow range of reservoir solution concentrations in the vicinity of the CMC. At concentrations 10 × CMC, the permeability coefficient becomes constant and equal to 3.9 × 10⁻⁷ cm²/sec which is the pore permeability for the Triton X-100 micelles. Compared to the diffusion coefficient of micelles in bulk water, the transport of micelles is hindered by the pore walls. In a 10-fold concentration range the micellar pore permeability is practically constant indicating no large change in micelle size. The chemical equilibrium model applied to surfactant diffusion in pores shows reasonable agreement over the entire range of the experimental data for reservoir concentrations from one-fifth times the CMC to 100 times the CMC.     

Comparative characterization of phosphorylated wood holocelluloses and celluloses for nanocellulose production

Cellulose - Raw material selection for cellulose nanofiber (CNF) production is a crucial step for tailoring CNF properties for its intended applications. Thus, understanding the dependency of the...     

Hydrophilicity/porous structure-tuned, SiO2/polyetherimide-coated polyimide nonwoven porous substrates for reinforced composite proton exchange membranes

Porous substrate-reinforced composite proton exchange membranes have drawn considerable attention due to their promising application to polymer electrolyte membrane fuel cells (PEMFCs). In the present study, we develop silica (SiO(2)) nanoparticles/polyetherimide (PEI) binders-coated polyimide (PI) nonwoven porous substrates (referred to as "S-PI substrates") for reinforced composite membranes. The properties of S-PI substrates, which crucially affect the performance of resulting reinforced composite membranes, are significantly improved by controlling the hygroscopic SiO(2) particle size. The 40 nm S-PI substrate (herein, 40 nm SiO(2) particles are employed) shows the stronger hydrophilicity and highly porous structure than the 530 nm S-PI substrate due to the larger specific surface area of 40 nm SiO(2) particles. Based on the comprehensive understanding of the S-PI substrates, the structures and performances of the S-PI substrates-reinforced composite membranes are elucidated. In comparison with the 530 nm S-PI substrate, the hydrophilicity/porous structure-tuned 40 nm S-PI substrate enables the impregnation of a large amount of a perfluorosulfonic acid ionomer (Nafion), which thus contributes to the improved proton conductivity of the reinforced Nafion composite membrane. Meanwhile, the reinforced Nafion composite membranes effectively mitigate the steep decline of proton conductivity with time at low humidity conditions, as compared to the pristine Nafion membrane. This intriguing finding is further discussed by considering the unusual features of the S-PI substrates and the state of water in the reinforced Nafion composite membranes.     

Low temperature diffusion bonding of Pd-based composite membranes with metallic module for hydrogen separation

A diffusion-bonding procedure at a low temperature, i.e. 500 °C, based on the high mobility of silver atoms was developed with a newly designed plate-and-frame type hydrogen purification membrane module consisting of a unit cell and a housing. Two membranes made of palladium and copper sputtered on polished porous nickel supports (PNS) followed by Cu-reflow at 750 °C, respectively, were assembled in a unit cell to verify that the low temperature diffusion-bonding method could be applied to gas-tight membranes. Ring-shaped silver foils with a thickness of 50 μm were placed between the membranes and the unit cell body made of nickel plate. A pair of membranes, a pair of silver foils and the unit cell body were compressed with a pair of covers and eight screws by a 17 cm long torque wrench at 12 N m. The diffusion-bonded unit cell was welded in a module housing comprised of a feed port and a retentate port by a laser-operated welder. After the module was constructed, gas-tightness tests were carried out using helium and the measured helium leakage was 8 × 10⁻⁵ mol m⁻² s⁻¹ at 0.7 MPa, which is the same as the value detected before diffusion bonding with a Viton O-ring. The hydrogen permeation test and durability test consisting of three cycles of alternately changing the temperature and transmembrane pressure difference were carried out using a single gas, hydrogen, and it was found that the hydrogen permeation flux remained constant during the durability test and that the helium leakage did not increase after the durability test.     

Preparation and characterization of N-methylene phosphonic and quaternized chitosan composite membranes for electrolyte separations

Chitosan was functionalized either by introducing a phosphonic acid group or by quaternization of existing primary ammonium groups in order to make it a water-soluble material. Functionalized chitosans and poly(vinyl alcohol) (PVA)-based nanoporous charged membranes were prepared in aqueous media and gelated in methanol at 10 degrees C to tailor their pore structure. These membranes were extensively characterized for their physicochemical, electrochemical, and permeation characteristics using FTIR, TGA, DSC, water content, ion-exchange capacity, ionic transport properties, and membrane permeability studies. N-Methylene phosphonic chitosan (NMPC)/PVA-based membranes exhibited mild cation selectivity and quaternized chitosan (QC)/PVA composite membranes had mild anion selectivity, while a blend of NMPC-QC/PVA membranes exhibited weak cation selectivity because of formation of zwitterionic structure. Viscosity measurements and interaction studies for individual and mixed solutions of NMPC and QC were carried out for the prediction of charge interactions between -PO3H2 and -N+(CH3)3 groups and effect on molecular weight due to functionalization. Elaborate electrochemical and permeation experiments were conducted in order to predict suitability of these membranes for the separation of mono- and bivalent electrolytes based on their hydrated ionic radius, and it was found that among all the synthesized membranes, PC/QC-30 had the highest relative permeability, which may extend its suitability for electrolyte separations. Observations were correlated with equivalent pore radius of the different membranes as estimated by membrane permeability measurements.