Evidence of ion transport through surface conduction in alkylsilane-functionalized nanoporous ceramic membranes

Alkylsilane-modified nanoporous ceramic membranes exclude water from their pores yet exhibit transmembrane electrical conductivity in aqueous electrolyte solutions. That effect was studied using impedance spectroscopy and (29)Si NMR. Anodic aluminum oxide membranes with alkylsilane-functionalized pores exhibited a transmembrane electrical resistance that increased with the length of the hydrocarbon chain. Microstructural studies revealed that the conduction was due primarily to a small number of "hydrophilically defective" pores in membranes modified by long-chain alkylsilanes and both hydrophilic defects and surface conduction in pores modified by short-chain alkylsilanes. Hydroxyl groups in short-chain alkylsilane layers act as "water wires" to enable surface ion transport. The local concentration of hydroxyl groups decreased with alkylsilane chain length, explaining the resistance trend. This constitutes the first direct evidence that alkylsilane functionalization affects electrical as well as wetting properties.     

Self‐Assembled Asymmetric Block Copolymer Membranes: Bridging the Gap from Ultra‐ to Nanofiltration

The self‐assembly of block copolymers is an emerging strategy to produce isoporous ultrafiltration membranes. However, thus far, it has not been possible to bridge the gap from ultra‐ to nanofiltration and decrease the pore size of self‐assembled block copolymer membranes to below 5 nm without post‐treatment. It is now reported that the self‐assembly of blends of two chemically interacting copolymers can lead to highly porous membranes with pore diameters as small as 1.5 nm. The membrane containing an ultraporous, 60 nm thin separation layer can fully reject solutes with molecular weights of 600 g mol^?1 in aqueous solutions with a water flux that is more than one order of magnitude higher than the permeance of commercial nanofiltration membranes. Simulations of the membrane formation process by dissipative particle dynamics (DPD) were used to explain the dramatic observed pore size reduction combined with an increase in water flux.     

High-flux,porous and homogeneous PVDF/cellulose microfiltration membranes

Low hydrophilicity of membranes is probably the biggest concern in membrane filtration since it increases the costs for water treatment. Conversely, application of hydrophilic biopolymers (such as cellulose) is limited because of its complex and crystalline structure. Enabling the wide use of the most common biopolymer in nature is crucial to improve the performance of water treatment, especially in terms of membrane sustainability. Here, we study the effect of cellulose dissolution in the synthesis of homogeneous PVDF/cellulose membranes. Although only partial dissolution was achieved for studied samples, adding cellulose to the membranes greatly improved their water flux. Besides, the porous structure obtained after partial solvent removal indicates the water flux (and consequently the pore size) may be tailored according to the membrane production method. Therefore, the homogeneous cellulose microfiltration membranes studied here may have potential for water treatment considering their high-water flux and low complexity to produce.

     

Chain-length dependence of the antifouling characteristics of the glycopolymer-modified polypropylene membrane in an SMBR

Membrane-bioreactor processes have increased considerably in recent years. However, the natural disadvantages of common membrane materials, such as hydrophobic surface, cause membrane fouling and cumber further extensive applications. In this work, hydrophilic surface modification of polypropylene microporous membranes was carried out by the sequential photoinduced graft polymerization of d-gluconamidoethyl methacrylate (GAMA) to meet the requirements of wastewater treatment and water reclamation applications. The grafting density and grafting chain length were controlled independently in the first and second step, respectively. Attenuated total reflection–Fourier transform infrared spectroscopy (FT-IR/ATR) and X-ray photoelectron spectroscopy (XPS) were employed to confirm the surface modification on the membranes. Water contact angle was measured by the sessile drop method. Results of FT-IR/ATR and XPS clearly indicated that GAMA was grafted on the membrane surface. It was found that the grafting chain length increased reasonably with the increase of the UV irradiation time. Water contact angle on the modified membrane decreased with the increase of the grafting chain length, and showed a minimum value of 43.2°, approximately 51.8° lower than that of the unmodified membrane. The pure water fluxes for the modified membranes increased systematically with the increase of the grafting chain length. The effect of the grafting chain length on the antifouling characteristics in a submerged membrane-bioreactor for synthetic wastewater treatment was investigated. After continuous operation in the submerged membrane-bioreactor for about 70 h, reduction from pure water flux was 90.7% for the virgin PPHFMM, and ranged from 80.8 to 87.2% for the modified membranes, increasing with increasing chain length. The flux of the virgin PPHFMM membrane after fouling and subsequent washing was 31.5% of the pure water flux through the unfouled membrane; for the modified membranes this ranged from 27.8 to 16.3%, decreasing with increasing chain length. These results demonstrated that the antifouling characteristics for the glucopolymer-modified membranes were improved with an increase in GAMA chain length.     

Temperature-sensitive membranes prepared from blends of poly(vinylidene fluoride) and poly(N-isopropylacrylamides) microgels

In this study, temperature-sensitive membranes were prepared by phase transition of the mixture of the temperature-sensitive poly(N-isopropylacrylamides) (PNIPAAM) microgels and poly(vinylidene fluoride). The results of Fourier transformed infrared spectrometer, X-ray photoelectron spectroscopy, elemental analysis, and scanning electron microscope photographs indicate that the PNIPAAM microgels are distributed more in the inner membrane than on the surface. The scanning electron microscope photographs reveal the blend membranes having porous surfaces with nanometer sizes and porous cross-sections with micrometer sizes. The addition of the PNIPAAM microgels is found to improve the porosity, the pore size, water flux, as well as to enhance the hydrophilicity and anti-fouling property of the blend membranes. The blend membrane shows temperature-sensitive permeability and protein rejection with the most dramatic change at around 32 °C which is the lower critical solution temperature of PNIPAAM, when water or bovine serum albumin solution flow through. Specifically, below 32 °C, the blend membrane shows a high protein rejection ratio which decreases with increasing temperature and a low water flux which increases with increasing temperature; above 32 °C, the blend membrane shows a low protein rejection ratio which decreases with increasing temperature and a high water flux which increases with increasing temperature.     

A versatile coating approach to fabricate superwetting membranes for separation of water-in-oil emulsions

Separation of oil/water mixtures, especially for the emulsified oil/water mixtures, is important because of the frequent occurrence of oil spill accidents. Utilizing superwetting porous membrane has become a promising approach to separate either surfactant-free or surfactant-stabilized emulsions. Herein we report a facile and versatile strategy for preparing hydrophobic/under-oil superhydrophobic membranes by coating the skeletons of the membranes with the poly[(3,3,3-trifluoropropyl)methylsiloxane] (PTFPMS) nanoparticles. The obtained membranes could be used to separate various waterin- oil emulsions with high flux and separation efficiency. In addition, owning to the outstanding resistance of PTFPMS to the most organic solvents or oils, the modified membranes exhibited the excellent reusability and the antifouling properties that were critical in the practical applications. Many commercially available membranes can be modified by such a simple method.     

ANTIFOULING PROPERTIES OF POLYVINYL CHLORIDE) MEMBRANES MODIFIED BY AMPHIPHILIC COPOLYMERS P(MMA-A-MAA)

Three well-defined diblock copolymers of poly(methyl methacrylate-b-methacrylic acid)(P(MMA-b-MAA))were synthesized using atom transfer radical polymerization method and varying poly(methacrylic acid)(PMAA)chain lengths. These copolymers were blended with PVC to fabricate porous membranes via phase inversion process.Membrane morphologies were observed by scanning electron microscopy(SEM),and chemical composition changes of the membrane surfaces were measured by X-ray photoelectron spectroscopy(XPS).Static and dynamic protein adsorption experiments were used to evaluate antifouling properties of the blend membranes.It was found that,the blend membranes containing longer PMAA arm length showed lower static protein adsorption,higher water permeation flux and better protein solution flux recovery.     

In vitro stability study of organosilane self-assemble monolayers and multilayers

The stability of self-assembled monolayers (SAMs) and multilayers formed on silicon surface by amino-terminated silanes and SAMs formed by alkyl and glycidyl terminated silanes were investigated in vitro with saline solution at 37 degrees C for up to 10 days. FTIR and XPS results indicated that amino-terminated SAMs and multilayers are very unstable if the alkyl chain is short ((CH2)3), while stable if the alkyl chain is long ((CH2)11). On the other hand, alkyl-terminated SAMs are very stable regardless of the alkyl chain length, and glycidyl terminated SAM retained approximately 77% of the organosilane molecules after 10 days. Hydrogen bonding between the organosilane monomer and silicon surface and among the organosilane monomers is believed to contribute to the instability of the SAM and multilayer formed by amino-terminated silane with a short alkyl chain ((CH2)3). Therefore, the widely used (3-aminopropyl) trimethoxysilane (APTMS) SAM and multilayer may not be suitable for implantable biomedical applications.     

Sodium ion internalized within phospholipid membranes

Seven phospholipids, modified with ester groups in their hydrophobic chains, were synthesized and examined for their ability to promote sodium ion flux across vesicular membranes. It was found by 23Na NMR that only the phospholipids having short chain segments beyond their terminal ester groups catalyze sodium ion transfer by up to 2 orders of magnitude relative to a conventional phospholipid, POPC. The rates increase with the concentration of the ester-phospholipid admixed with POPC in the bilayer. More surprisingly, the rates increase with the time allowed for the vesicles to age. This was attributed to ester-phospholipid migrating in the bilayers to form domains that solubilize the sodium ion within the hydrocarbon interior of the membrane. Such membrane domains explain why shift reagent-modified NMR spectra display three 23Na signals representing sodium outside the vesicles, sodium within the vesicular water pools, and sodium within the membranes themselves.     

Membrane formation mechanism and permeation properties of a novel porous polyimide membrane

The transport properties of a novel porous fluorinated polyimide membrane fabricated by a wet phase inversion process were studied with a stirred dead‐end filtration cell. The porous membrane‐forming solvents were tetrahydrofuran (THF), acetone, N,N‐dimethylacetamide (DMAc), N‐methylpyrrolidone (NMP), N,N‐dimethylformamide (DMF), and dimethylsulfoxide (DMSO). The phase separation phenomena in a ternary system of polyimide/solvent/water were investigated from cloud point curves by a titration method and binary interaction parameters. Solvent–water demixing in the system has been found to play very important roles in determining the structure and surface morphology of the polyimide membrane. The porous fluorinated polyimide membranes showed pore sizes from 4 to 500 nm and permeation properties from ultrafiltration to a microfiltration range. In this study, we particularly focused on fouling of the polyimide membranes, because fouling decreases the flux and increases the resistance. Interestingly, the porous polyimide membrane showed excellent water flux recovery after water cleaning compared with that of the polyethersulfone (PSf) membrane, which suggest that for a 6FDA‐6FAP membrane, the protein–membrane and protein–protein interaction was not so strong compared with those in a PSf membrane. Copyright © 2002 John Wiley & Sons, Ltd.     

Tribological properties of alkylsilane self-assembled monolayers

In this study, we perform molecular dynamics simulations of adhesive contact and friction between alkylsilane Si(OH)(3)(CX(2))(10)CX(3) and alkoxylsilane Si(OH)(2)(CX(2))(10)CX(3) (where X = H or F) self-assembled monolayers (SAMs) on an amorphous silica substrate. The alkylsilane SAMs are primarily hydrogen-bonded or physisorbed to the surface. The alkoxylsilane SAMs are covalently bonded or chemisorbed to the surface. Previously, we studied the chemisorbed systems. In this work, we study the physisorbed systems and compare the tribological properties with the chemisorbed systems. Furthermore, we examine how water at the interface of the SAMs and substrate affects the tribological properties of the physisorbed systems. When less than a third of a monolayer is present, very little difference in the microscopic friction coefficient mu or shear stresses is observed. For increasing amounts of water, the values of mu and the shear stresses decrease; this effect is somewhat more pronounced for fluorocarbon alkylsilane SAMs than for the hydrocarbon SAMs. The observed decrease in friction is a consequence of a slip plane that occurs in the water as the amount of water is increased. We studied the frictional behavior using relative shear velocities ranging from v = 2 cm/s to 2 m/s. Similar to previously reported results for alkoxylsilane SAMs, the values of the measured stress and mu for the alkylsilane SAM systems decrease monotonically with v.     

Modified Silica Sol Coatings for Water-Repellent Textiles

The preparation of water repellent textiles by coating with different modified silica sols has been investigated. For this, pure and with 3-glycidoxypropyl triethoxysilane co-condensed silica sols were modified by three types of additives: alkyltrialkoxysilanes, polysiloxane derivatives and a fluorine containing silane. Hydrophobic properties of the coated fabrics of polyamide and of polyester mixed with cotton were determined using contact angle measurements. The hydrophobicity increases with increasing concentration of the alkylsilane additive in the silica sol and the length of the alkyl chain but with high additive concentrations plateau values in hydrophobicity were reached. Analogously textile coatings with high hydrophobicity were gained using hydrophobic polysiloxane or fluorine containing silicon compounds. The comparison of the different variants reveals that high wash-out stabilities were reached only by silica sols containing fluorine compoundsand hexadecylsilane additives. Therefore long-chain alkyltrialkoxysilane compounds could be used as substitutes for fluorine compounds for the surface modification of textiles in some practical applications.     

亲水膜的表面改性及在膜蒸馏中的应用

膜的微孔性和疏水性是水溶液膜蒸馏的两个基本条件,迄今人们均采用疏水性高分子材料制成疏水微孔膜用于膜蒸馏研究。本文采用辐照接枝聚合和等离子体表面聚合的方法,将亲水的醋酸纤维素微孔膜和硝酸纤维素微孔膜表面疏水化改性,成功地用于膜蒸馏研究,大大扩展了疏水微孔膜的材料来源。实验结果表明,亲水膜表面改性得到的疏水膜,其膜蒸馏性能不低于疏水材料制成的膜,尤其是等离子体聚合法可以实现多种特殊单体在多孔的材料表面聚合,成为制备高性能疏水微孔膜的有效手段,为膜蒸馏的深入发展和实用化创造了有利条件。     

Effect of epoxidation of natural rubber on the pervaporation separation of acetone–chlorinated hydrocarbon mixtures

The pervaporation separation and the swelling behavior of chlorinated hydrocarbon/acetone mixtures were investigated using natural rubber (NR) and epoxidized natural rubber (ENR) membrane with 25 and 50 mol% epoxidation, respectively. The swelling degree increases with increase in the epoxidation level. The flux and separation factor of the membranes were determined both as a function of mole percent epoxidation and of the feed mixture composition. The membranes were found to be permselective to chlorinated hydrocarbons from acetone–chlorinated hydrocarbon mixtures. The flux decreases with increase in epoxidation level, whereas the separation factor increases. The permeation decreases and separation factor increases with increase in the acetone feed concentration. The availability of raw materials, low cost of implementation and easy processability of the system makes this method of separation highly applicable and recommendable.     

Surface‐initiated atom transfer radical polymerization from porous poly(tetrafluoroethylene) membranes using the C?F groups as initiators

This work reports the surface‐initiated atom transfer radical polymerization (ATRP) from hydrogen plasma‐treated porous poly(tetrafluoroethylene) (PTFE) membranes using the C? F groups as initiators. Hydrogen plasma treatment on PTFE membrane surfaces changes their chemical environment through defluorination and hydrogenation reactions. With the hydrogen plasma treatment, the C? F groups of the modified PTFE membrane surface become effective initiators of ATRP. Surface‐initiated ATRP of poly(ethylene glycol) methacrylate (PEGMA) is carried out to graft PPEGMA chains to PTFE membrane surfaces. The chain lengths of poly(PEGMA) (PPEGMA) grafted on PTFE surfaces increase with increasing the reaction time of ATRP. Furthermore, the chain ends of PPEGMA grown on PTFE membrane surfaces then serve as macroinitiators for the ATRP of N‐isopropylacrylamide (NIPAAm) to build up the PPEGMA‐b‐PNIPAAm block copolymer chains on the PTFE membrane surfaces. The chemical structures of the modified PTFE membranes are characterized using X‐ray photoelectron spectroscopy. The modification increases the surface hydrophilicity of the PTFE membranes with reductions in their water‐contact angles from 120° to 60°. The modified PTFE membranes also show temperature‐responsive properties and protein repulsion features owing to the presence of PNIPAAM and PPEGMA chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2076–2083, 2010     

Surface modification of polysulfone ultrafiltration membranes and fouling by BSA solutions

Five different chemically modified versions of polysulfone were prepared via two different homogeneous chemical reaction pathways. They, together with the base polymer, were cast as membranes by a phase-inversion process. The surface energies of these membranes, as measured by contact angles, were used to characterize the different membranes. Streaming-potential measurements were obtained to probe the surface charge of the membranes. The surface roughness of each membrane was also determined by atomic-force microscopy. Each membrane was then exposed to deionized water, 0.08 g/l bovine serum albumin solution and deionized water using a standard filtration procedure to simulate protein fouling and cleaning potential.Both the chemistry and the size of the grafted molecules were correlated with respect to volumetric flux during ultrafiltration of protein solutions. Surface roughness seemed to be important for filtering pure water. Hysteresis between advancing and receding contact angles increased with hydrophilicity of the membrane surfaces. One possible explanation could be that surface reorientation was more likely with hydrophilic than with hydrophobic membranes. The membrane modified by direct sulfonation had the lowest surface energy and the shortest grafted chain length and exhibited the highest volumetric flux with BSA solution. It was also the easiest to clean and exhibited the highest initial flux recovery by stirring (91%) and backflush (99%) methods with deionized water. In most cases, backflushing rather than stirring was more effective in recovering the water flux.     

Glass-liquid transition of vapor-deposited hexane studied using TOF-SIMS

Thermodynamic connection between liquid and glass is not obvious for poor glass formers. In this study, microscopic molecular diffusivity and macroscopic fluidity of vapor-deposited thin films of n-hexane were investigated using TOF-SIMS to elucidate the mechanism of the glass-liquid transition. The C 6H 14 film deposited at 15 K is characterized by a porous structure, as inferred from the intermixing with adsorbed C 6D 14 and D 2O molecules, as well as the formation of D 2O nanoclusters on the surface. The hexane molecules are reoriented at temperatures higher than 60-70 K, resulting in smoothing of the surface and densification of the film. Self-diffusion of the hexane molecules commences at 110 K; then, the film dewets the Ni(111) substrate after some aging time. Results indicate that ultraviscous liquid formed at the glass transition temperature of 110 K transforms into fluidized liquid immediately before crystallization. The D 2O molecules adsorbed onto the surface play a role as a surfactant, as evidenced by quenching the film dewetting. The ultraviscous liquid is likely to be a distinct phase, which might explain the absence of calorimetric glass transition for poor glass formers like hexane.     

Water concentration profiles in membranes measured by ESEEM of spin-labeled lipids

Electron spin-echo envelope modulation (ESEEM) spectroscopy of phospholipids spin-labeled systematically down the sn-2 chain was used to detect the penetration of water (D2O) into bilayer membranes of dipalmitoyl phosphatidylcholine with and without 50 mol % cholesterol. Three-pulse stimulated echoes allow the resolution of two superimposed 2H-ESEEM spectral components of different widths, for spin labels located in the upper part of the lipid chains. Quantum chemical calculations (DFT) and ESEEM simulations assign the broad spectral component to one or two D2O molecules that are directly hydrogen bonded to the N-O group of the spin label. Classical ESEEM simulations establish that the narrow spectral component arises from nonbonded water (D2O) molecules that are free in the hydrocarbon chain region of the bilayer membrane. The amplitudes of the broad 2H-ESEEM spectral component correlate directly with those of the narrow component for spin labels at different positions down the lipid chain, reflecting the local H-bonding equilibria. The D2O-ESEEM amplitudes decrease with position down the chain toward the bilayer center, displaying a sigmoidal dependence on position that is characteristic of transmembrane polarity profiles established by other less direct spin-labeling methods. The midpoint of the sigmoidal profile is shifted toward the membrane center for membranes without cholesterol, relative to those with cholesterol, and the D2O-ESEEM amplitude in the outer regions of the chain is greater in the presence of cholesterol than in its absence. For both membrane types, the D2O amplitude is almost vanishingly small at the bilayer center. The water-penetration profiles reverse correlate with the lipid-chain packing density, as reflected by 1H-ESEEM intensities from protons of the membrane matrix. An analysis of the H-bonding equilibria provides essential information on the binding of water molecules to H-bond acceptors within the hydrophobic interior of membranes. For membranes containing cholesterol, approximately 40% of the nitroxides in the region adjacent to the lipid headgroups are H bonded to water, of which ca. 15% are doubly H bonded. Corresponding H-bonded populations in membranes without cholesterol are ca. 20%, of which ca. 6% are doubly bonded.     

Construction by molecular dynamics modeling and simulations of the porous structures formed by dextran polymer chains attached on the surface of the pores of a base matrix: characterization of porous structures

Significant increases in the separation of bioactive molecules by using ion-exchange chromatography are realized by utilizing porous adsorbent particles in which the affinity group/ligand is linked to the base matrix of the porous particle via a polymeric extender. To study and understand the behavior of such systems, the M3B model is modified and used in molecular dynamics (MD) simulation studies to construct porous dextran layers on the surface of a base matrix, where the dextran polymer chains and the surface are covered by water. Two different porous polymer layers having 25 and 40 monomers per main polymer chain of dextran, respectively, are constructed, and their three-dimensional (3D) porous structures are characterized with respect to porosity, pore size distribution, and number of conducting pathways along the direction of net transport. It is found that the more desirable practical implications with respect to structural properties exhibited by the porous polymer layer having 40 monomers per main polymer chain, are mainly due to the higher flexibility of the polymer chains of this system, especially in the upper region of the porous structure. The characterization and analysis of the porous structures have suggested a useful definition for the physical meaning and implications of the pore connectivity of a real porous medium that is significantly different than the artificial physical meaning associated with the pore connectivity parameter employed in pore network models and whose physical limitations are discussed; furthermore, the methodology developed for the characterization of the three-dimensional structures of real porous media could be used to analyze the experimental data obtained from high-resolution noninvasive three-dimensional methods like high-resolution optical microscopy. The MD modeling and simulations methodology presented here could be used, considering that the type and size of affinity group/ligand as well as the size of the biomolecule to be adsorbed onto the affinity group/ligand are known, to construct different porous dextran layers by varying the length of the polymeric chain of dextran, the number of attachment points to the base matrix, the degree of side branching, and the number of main polymeric chains immobilized per unit surface area of base matrix. After the characterization of the porous structures of the different porous dextran layers is performed, then only a few promising structures would be selected for studying the immobilization of adsorption sites on the pore surfaces and the subsequent adsorption of the bioactive molecules onto the immobilized affinity groups/ligands.     

Highly increased breakdown potential of anodic films on aluminum using a sealed porous layer

The growth of a uniform barrier-type anodic film on aluminum is usually terminated by electric breakdown, which is controlled by the resistance of electrolyte or anion concentration. In this study, highly resistive porous layers have been introduced by anodizing aluminum in sulfuric acid electrolyte followed by boiling water treatment to examine their influence on the electric breakdown potential. The pores of the porous alumina film are sealed by forming hydrated alumina (pseudo-boehmite) after the boiling water treatment. The breakdown potential increases to over 1500 V for the pore-sealed aluminum specimens on anodizing in sodium tungstate electrolyte. The electrochemical impedance spectroscopy measurements revealed an increased resistance of the porous layer after the pore-sealing treatment. GDOES depth profile analysis disclosed that the sealed porous layer impedes the incorporation of tungsten species into the barrier layer. The introduction of a highly resistive layer that also suppresses the anion incorporation on aluminum is effective in increasing the breakdown potential of anodic films.