Material transport properties of polymer–gel composite‐charged mosaic membrane with and without reinforcement [II]

The charged mosaic membranes (CMM) without reinforcement and the composite charged mosaic membrane (CCMM) with reinforcement were investigated in terms of solute and solvent transport. The composite charged mosaic membrane (CCMM) with reinforcement showed an unique transport behavior such as preferential material transport L_p and ω. Filtration coefficient, L_p and salt permeability coefficient ω were estimated by taking account of active layer thickness of composite polymer gel. The L_p and ω values of CCMM with reinforcement were larger than those of charged mosaic membrane (CMM) without reinforcement. On the other hand, the reflection coefficient of CCMM σ showed negative value, which suggested the preferential material transport to solvent transport. This indicates that σ was independent of active layer thickness. Furthermore, the results of transport properties of CCMM with reinforcement were supported by the membrane potential measurements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3507–3513, 2006     

Transport Behavior of Electrolytes Through Charged Mosaic Composite Membranes

The first part of this article reviews the strong acid/strong base type charged mosaic composite membrane. A template pattern with alternating poly(4-vinylpvridine) (P4VP)/poly(vinyl alcohol) (PVA) lamellae was fabricated upon a microporous membrane by casting of poly[4-vinylpyridine (4VP)-g-vinyl alcohol (VA)] graft copolymer from a water/l-propanol mixture. After a treatment involving the binding of the microporous membrane with the graft copolymer and also domain fixing of the PVA phases, a dilute solution of poly[sodium p-styrenesulfonate (SSS)-g-VA] graft co-polymer/P4VP binary blend was cast on this template surface. After chemical treatments (introduction of a positive charge and domain fixing of ion-exchange regions), we examined the transport of KCl and selective transport of a KCl-sucrose mixture through the charged mosaic composite membrane. The second section reviews the weak acid strong base type charged mosaic composite membrane. In this type, the charged mosaic regions were composed of poly(acrylic acid) (PAA) and quaternized P4VP microdomains. The microstructure of binary blend was observed from scanning electron microscopy (SEM) by wet-etching of films after domain fixing of one component of the binary blend. We examined the transport of KCl and L-phenylalanine through the charged mosaic composite membranes.     

聚酰胺荷电镶嵌膜的制备及表征(英文)

A novel composite charged mosaic membrane(CCMM) was prepared via interfacial polymerization(IP) of polyamine[poly(epichlorohydrin amine) ]and trimesoyl chloride(TMC) on the polyethersulfone(PES) support. Fourier transform infrared spectroscopy(FT-IR) ,environmental scanning electron microscopy(ESEM) ,atomic force microscopy(AFM) and water contact angle analysis were applied to characterize the resulted CCMM.The FT-IR spectrum indicates that TMC reacts sufficiently with polyamine.ESEM and AFM pictures show that the IP process produces a dense selective layer on the support membrane.The water contact angle of the CCMM is smaller than that of the substrate membrane because of the cross-linked hydrophilic polyamine network.Several factors affecting the IP reaction and the performance of the CCMM,such as monomer concentration,reaction time,pH value of aqueous phase solution and post-treatment,were studied.The pure water flux of the optimized CCMM is 14.73 L·m -2 ·h -1 ·MPa -1 at the operating pressure of 0.4 MPa.The values of separation factorαfor NaCl/PEG1000/water and MgCl2/PEG1000/water are 11.89 and 9.96,respectively.These results demonstrate that CCMM is promising for the separation of low-molecular-weight organics from their salt aqueous solutions.     

Preparation of composite‐imprinted alumina membrane for effective separation of p‐hydroxybenzonic acid from its isomer using Box–Behnken design–based statistical modeling

Highly selective composite imprinted membrane for p‐hydroxybenzonic acid (p‐HB) was prepared by using semicovalent imprinting technique. A thermally reversible covalent bond was used to link p‐HB molecule to a functional alkoxysilane monomer to generate covalently bound imprint precursor. This precursor was incorporated into a cross‐linked functional silica sol with the tetraethoxysilane as cross‐linker via a typical acid‐catalyzed, sol‐gel synthesis. Then, the SCIM was prepared through dipping and grafting on the upper side and inner pores of the Al₂O₃ microporous membrane and then removing of the template molecule after thermal treatment. Compared with composite imprinted membrane via noncovalent imprinting approach as well as the black Al₂O₃ microporous membrane, the SCIM exhibited higher membrane flux and selective rebinding of p‐HB as well as showing excellent permeability for p‐HB. Response surface methodology was used to investigate the best combination of separation conditions in the dynamic separation process. The optimal conditions for the separation of p‐HB from salicylic acid were as follows: the p‐HB concentration of 5 mg L^?1, the temperature of 10°C, and the flow rate of 1 mL min^?1. Under these conditions, the experimental selective separation factor was 32.75 ± 0.91%, which was close to the predicted selectivity coefficient value. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40621.     

Bentonite-stabilized CDA/CTA membranes: II. Determination of the transport coefficients lep and lp

Improved integral-asymmetric CDA/CTA blend membranes developed at the GKSS Research Center Geesthacht were formulated with various bentonite dopes to investigate their influence on membrane properties. The characterization of the membrane transport behavior was determined by the hydrodynamic permeability, l_p, and the electromechanical coupling coefficient, l_ep, as functions of the external NaCl-concentrations, c_s. The membranes tested were prepressurized in reverse osmosis experiments for 1 hour and 200 hours, respectively, at the experimental conditions of 0.6 mol/l NaCl-solution, 25°C, 80 bar. The results obtained were as follows:The transport coefficients l_ep and l_p were considerably changed after the long-term RO test run. For all salt concentrations, the permeability l_p was lowered by about 20%. But at the highest salt concentration of c_s = 0.2 mol/l, the minimum permeability changes were observed for the membranes with 700 ppm and without bentonite addition. Moreover, both these membrane types showed the smallest reduction of thickness after the 200 hours test run.The alterations of the electro-mechanical coupling coefficient l_ep were interpreted — applying the finely porous membrane model to the two-layer membranes — as an increase of the diffusion potential and a decrease of the streaming potential. The salt diffusion coefficient was analysed to be diminished by about 10% for all membrane types. The lowest performance changes of the membranes with about 1000 ppm bentonite dope, support the experimental findings of flux stabilization of the bentonite-containing CDA/CTA membranes, published previously.     

正交实验法优化制备复合荷电镶嵌膜

以聚醚砜为基膜,以聚环氧氟丙烷胺及2,5-二胺基苯磺酸混合水溶液(无机相)与三酰氯的正己烷溶液(有机相)通过界面聚合反应,制备了一种新型的复合荷电镶嵌膜.采用正交设计实验方法,研究了界面聚合条件如界面聚合单体的浓度及界面聚合反应时间对膜性能的影响.结果表明:三酰氯的浓度对膜性能的影响最为显著,其次是界面聚合时间,而聚环氧氟丙烷胺的浓度对膜性能的影响最小.优化后所制备的复合膜对盐类的截留率较低(均低于40%).膜能截留低相对分子质量有机物而透过盐,说明该膜可用于盐类与有机物的分离.     

Gas holdup,bubble size distribution,and mass transfer in an airlift reactor with ceramic membrane and perforated plate distributor

The airlift reactor is one of the most commonly used gas–liquid two-phase reactors in chemical and biological processes. The objective of this study is to generate different-sized bubbles in an internal loop airlift reactor and characterize the behaviours of the bubbly flows. The bubble size, gas holdup, liquid circulation velocity, and the volumetric mass transfer coefficient of gas–liquid two-phase co-current flow in an internal loop airlift reactor equipped with a ceramic membrane module (CMM) and a perforated-plate distributor (PPD) are measured. Experimental results show that CMM can generate small bubbles with Sauter mean diameter d₃₂ less than 2.5 mm. As the liquid inlet velocity increases, the bubble size decreases and the gas holdup increases. In contrast, PPD can generate large bubbles with 4 mm < d₃₂ < 10 mm. The bubble size and liquid circulation velocity increase as the superficial gas velocity increases. Multiscale bubbles with 0.5 mm < d₃₂ < 10 mm can be generated by the CMM and PPD together. The volumetric mass transfer coefficient k_La of the multiscale bubbles is 0.033–0.062 s⁻¹, while that of small bubbles is 0.011–0.057 s⁻¹. Under the same flow rate of oxygen, the k_La of the multiscale bubbles increases by up to 160% in comparison to that of the small bubbles. Finally, empirical correlations for k_La are obtained.     

Ionic salt permeability through phase‐separated membranes composed of amphoteric polymers

Amphoteric copolymers composed of hydrophilic poly(dimethyl acrylamide) and hydrophobic poly(dimethyl siloxane) formed phase‐separated membranes. The hydrophilic and hydrophobic components formed continuous phase‐separated domains in the membranes. The hydrated poly(dimethyl acrylamide) domains formed membrane‐spanning pathways, which permitted an ionic salt to permeate the membranes. The permeability of the ionic salt through the amphoteric copolymer membranes was studied. On the basis of the results, the mechanism of salt transport could be explained by the free‐volume theory, which was used for the analysis of diffusive transport in the hydrated, homogeneous membranes. The diffusion coefficient of the ionic salt increased exponentially as the volume ratio of the hydrophilic polymer to water [(1 − H)/H, where H is the degree of hydration] decreased in the membrane. It was possible to postulate that the diffusion of the ionic salt through the membranes was dependent on the free‐volume fractions of water and hydrophilic poly(dimethyl acrylamide) domains in the membranes. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

界面聚合表面改性法制备高效抗污染油水分离复合膜

引　言油污染作为一种常见的污染 ,对环境保护和生态平衡危害极大 .膜分离法则是对含油污水进行深度处理的可行而有效的方法[1] .在使用膜分离法理含油污水时 ,膜污染是影响分离过程的最主要问题 .提高膜表面的亲水性能有效缓解膜分离含油污水过程中的膜污染情况[2 ,3] .目前处     

Enhancing water flux through semipermeable polybenzimidazole membranes by adding surfactant‐treated CNTs

In this study, surfactant‐treated carbon nanotubes (CNTs) were incorporated into polybenzimidazole (PBI) matrix to prepare the PBI/CNT composite membranes with CNT content in the range of 0 to 15 wt %. The composite membranes were fabricated by spin‐coating. The membrane morphology, mechanical property, and water and salt transport properties were investigated to characterize the additive effect of CNTs. The tensile strength of all the PBI/CNT composite membranes was lower than that of pristine PBI membrane, indicating the weak interaction between CNT and PBI. In addition, water flux increased without reducing the salt rejection when CNTs were homogeneously dispersed in the PBI matrix at a less than 7.5 wt % content. On the other hand, at 10 wt % and higher CNT content, submicro‐scaled cellular structure was formed, and both the water flux and salt rejection decreased. The well‐dispersed CNTs in the PBI matrix via weak interaction preferentially improve the water permeability by 1.7 times without depressing the salt rejection. The incorporation of well‐dispersed CNTs in polymer matrix provides a promising and facile option for improvement in the water transport properties through the polymeric semipermeable membranes with intrinsically low water permeability such as PBI. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45875.     

Pore size of microporous polymer membranes

Pore sizes of microporous polymer membranes were determined by the calculation based on the gas permeability of porous media. The gas permeability coefficient K (given by J = K Δp/l, where J is the steady-state gas flux, Δp is the pressure, difference, and l = the thickness of a membrane) for porous membrane can be given generally by where K₀ is the Knudsen permeability coefficient, η is the viscosity of the permeant gas, B₀ is the geometric factor of a membrane, and Δp? is the mean pressure of the gas on both sides of a membrane. From gas permeability measurements which yield the pressure dependence of gas permeability coefficient (expressed as above equation), the mean pore size of the porous membrane can be estimated as where M is the molecular weight of the permeant gas. The validity of this method was examined with various Millipore filters of which nominal pore sizes are known. It was confirmed that the method provided a simple and reliable means of estimating mean pore size of microporous membranes. The method was applied to investigate the influence of factors involved in preparation of microporous polysulfone membranes by coagulation procedure. It was found that the mean pore size of porous polysulfone membrane increases with (1) increasing with casting thickness, (2) increasing temperature of coagulation bath, and (3) decreasing concentration of polymer in casting solution (DMF as solvent). Water flux and water flux decline due to compaction are also examined as a faction of pore size, porosity, and the thickness of membranes.     

Characterization of a sulfonated pentablock copolymer for desalination applications

Water and salt transport properties were determined in a family of sulfonated pentablock copolymers to characterize their potential as chlorine-tolerant desalination membrane materials. The degree of sulfonation, block molecular weight, and casting conditions can be independently varied to tune the transport properties of these materials. Data for water uptake, water permeability, salt permeability, and apparent surface charge are presented. Apparent diffusion coefficients of water in these materials were calculated using the solution-diffusion theory. Generally speaking, water sorption, water diffusivity, water permeability, and salt permeability increase with increasing degree of sulfonation. As ion exchange capacity increases from 0.4 to 2.0 meq/g (dry polymer), water uptake values vary between 21% and 118%, and water permeability values, in units of cm² s⁻¹, vary over 4 orders of magnitude. Salt permeability depends on both the upstream sodium chloride concentration, between 0.01 and 1.0 mol L⁻¹, and the degree of sulfonation. Both water permeability and salt permeability are sensitive to the conditions used when casting the polymer films. Apparent surface charge, as characterized by zeta potential, has been shown to be related to the fouling tendency of several membrane materials. In these materials, zeta potential is most negative in samples with low levels of sulfonation and is near neutral in samples with the highest level of sulfonation.     

Evaluation of membrane fouling and flux decline related with mass transport in nanofiltration of tartrazine solution

BACKGROUND: This work was carried out to investigate and analyze the interrelated dynamics of mass transport, membrane fouling and flux decline during nanofiltration of tartrazine. A combined application including pore diffusion transport model and a material balance approach was used to model an experimental flux data obtained from different values of pH (3, 5, 7 and 10), feed‐dye concentration (25, 100 and 400 mg L^?1), and transmembrane pressure (1200, 1800 and 2400 kPa). RESULTS: Almost 100% dye solution removal and a permeate flux of 135 L m^?2 h^?1 were obtained for 25 mg L^?1 and 1200 kPa at pH 10. At pH 10, lower membrane fouling was obtained due to the increase of electrostatic repulsion between anionic dye molecules and the more negatively charged membrane surface. Flux decline and membrane fouling increased together with transmembrane pressure and dye concentration. Fouling was found to be directly related to proportional‐permeation coefficient (k_O′) of dye which was identified as the solute passing into the permeate with respect to the amount transported into the membrane from the feed. CONCLUSIONS: For a decrease of pH (10 to 3) and transmembrane pressure (2400 to 1200 kPa) or an increase of feed‐dye concentration (25 to 400 mg L^?1), fewer dye molecules passed into the permeate with respect to the amount transported into the membrane from the feed. This situation depended mainly on the combined influences of the gel layer and fouling in the membrane. Copyright © 2010 Society of Chemical Industry     

Pebax–polydopamine microsphere mixed‐matrix membranes for efficient CO2 separation

Novel facilitated‐transport mixed‐matrix membrane (MMM) were prepared through the incorporation of polydopamine (PDA) microspheres into a poly(amide‐b‐ethylene oxide) (Pebax MH 1657) matrix to separate CO₂–CH₄ gas mixtures. The Pebax–PDA microsphere MMMs were characterized by Fourier transform infrared spectroscopy, scanning electron microcopy, X‐ray diffraction, differential scanning calorimetry, and thermogravimetric analysis. The PDA microspheres acted as an adhesive filler and generated strong interfacial interactions with the polymer matrix; this generated a polymer chain rigidification region near the polymer–filler interface. Polymer chain rigidification usually results in a larger resistance to the transport of gas with a larger molecular diameter and a higher CO₂–CH₄ selectivity. In addition, the surface of PDA microspheres contained larger numbers of amine, imine, and catechol groups; these were beneficial to the improvement of the CO₂ separation performance. Compared with the pristine Pebax membrane, the MMM with a 5 wt % PDA microsphere loading displayed a higher gas permeability and selectivity; their CO₂ permeability and CO₂–CH₄ selectivity were increased by 61 and 60%, respectively, and surpassed the 2008 Robeson upper bound line. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44564.     

Effect of sub-Tg relaxations on the gas transport properties of polyesters

The relationship was determined between sub-T_g molecular motions and the transport of O₂ and CO₂ in amorphous polyesters and copolyesters based on poly(ethylene terephthalate) [PET] and poly(1,4-cyclohexylenedimethylene terephthalate) [PCDT], Modifications of the polyester with certain acid co-monomers restricted the molecular motions that occurred in the β-relaxation region and in turn decreased the O₂ diffusion coefficient. The solubility coefficient was unchanged by those modifications. Modification of PET with 1,4-cyclohex-anedimethanol increased the magnitude of the β-relaxation and both the diffusion and solubility coefficients of O₂. Similar relationships between the β-relaxation magnitude and CO₂ permeability were also found. The temperature dependence of O₂ permeability followed an Arrhenius relationship, with different activation energies (E_p) above and below the β-relaxation. The activation energy was smaller below the β-relaxation. Values of E_p above and below the β-relaxation did not depend on the chemical structure of the polymer.     

The shock and release behavior of an aerospace‐grade cured aromatic amine epoxy resin

Knowing the dynamic behavior of polymer materials that are used in the construction of fiber‐reinforced composite materials is particularly important for such materials that are subjected to impact. In this work, we have conducted a number of plate‐impact experiments on a commercially important aromatic amine epoxy resin that is used in the construction of carbon fiber composite materials. The measured Hugoniot in shock velocity–particle velocity space was U_s = 2.65 + 1.55 u_p (ρ₀ = 1.141 g/cc), and is similar to the measured Hugoniots of other resins presented by different researchers. We have also measured the longitudinal stress in the shocked material and shown, in common with other polymers, that above a threshold stress, an increase in shear strength with impact stress is observed. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Preparation and characterization of a novel positively charged nanofiltration membrane based on polysulfone

The goal of this study was to prepare positively charged nanofiltration (NF) membranes to remove cations from aqueous solutions. A composite NF membrane was fabricated by the modification of a polysulfone ultrafiltration support. The active top layer was formed by the interfacial crosslinking polymerization of poly(ethylene imine) (PEI) with p‐xylene dichloride (XDC). Then, it was quaternized by methyl iodide (MI) to form a perpetually positively charged layer. The chemical and morphological changes of the membrane surfaces were studied by Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), and atomic force microscopy. To optimize the membrane operation, the PEI solution concentration, PEI coating time, XDC concentration, crosslinking time, and MI concentration were optimized. Consequently, high water flux (5.4 L m^?2 h^?1 bar^?1) and CaCl₂ rejection (94%) values were obtained for the composite membranes at 4 bars and 30°C. The rejections of the NF membrane for different salt solutions, obtained from pH testing, followed the order Na₂SO₄ < MgSO₄ < NaCl < CaCl₂. The molecular weight cutoff was calculated by the retention of poly(ethylene glycol) solutions with different molecular weights, and finally, the stoke radius was calculated as 1.47 nm. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41988.     

Preparation of thermal‐responsive poly(propylene) membranes grafted with n‐isopropylacrylamide by plasma‐induced polymerization and their water permeation

Poly(propylene) (PP) membrane grafted with poly(N‐isopropylacrylamide) (PNIPAAm), which is known to have a lower critical solution temperature (LCST) at around 32°C, was prepared by the plasma‐induced graft polymerization technique. Graft polymerization of PNIPAAm onto a PP membrane was confirmed by microscopic attenuated total reflection/Fourier transform IR spectroscopy. The grafting yield of PNIPAAm increased with the concentration of N‐isopropylacrylamide monomer and the reaction time of graft polymerization. The average pore size of the PP membrane also affected the grafting yield. From the field emission scanning electron microscopy (FE‐SEM) measurement, we observed a morphological change in the PP‐g‐PNIPAAm membrane under wet conditions at 25°C below LCST. The permeability of water through the PP‐g‐PNIPAAm membrane was controlled by temperature. The PP‐g‐PNIPAAm membrane (PN05 and PN10) exhibited higher water permeability (L_p) than the original PP substrate membrane below LCST. As the temperature increased to above LCST, L_p gradually decreased. In addition, the graft yield of PNIPAAm and the average pore size of the PP substrate influenced water permeability. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1168–1177, 2002; DOI 10.1002/app.10410     

High oxygen permeable Zeolite-4A poly(dimethylsiloxane) membrane for air separation

High oxygen permeability with optimal selectivity of the membrane is required for advancement in air separation membrane technology. Zeolite 4A-PDMS composite membranes were prepared by incorporation of Zeolite 4A nanoscale crystals during the polymerization process of PDMS membrane using toluene and n-heptane solvents, and their oxygen gas permeability and selectivity were explored. Small angle neutron scattering (SANS) technique was further used to study the polymer chain conformation and structure of membranes influenced by Zeolite 4A loading. The intersegmental distance between polymer chains and polymer chain aggregation or clustering were found to be increased on increasing the Zeolite 4A content in the membranes. Increment in the O₂ permeability and O₂/N₂ selectivity were observed for both type of membranes (toluene and n-heptane) with 1 wt% Zeolite 4A loading. The best performance result with O₂/N₂ selectivity of 2.6, and O₂ permeability of 1052 Barrer was exhibited by PDMS/toluene membrane loaded with 1 wt% Zeolite 4A. The PDMS/toluene membranes with 10 wt% Zeolite 4A loading exhibited increased O₂ permeability of 1245 Barrer with a fair O₂/N₂selectivity of ~1.7, while the PDMS/n-heptane membrane with the same loading exhibited excellent O₂ permeability of 6773 Barrer but lesser O₂/N₂ selectivity of ~1.2. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48047.     

Effects of mechanical drawing on gas transport in an emulsion acrylic multipolymer

A study was conducted on the gas sorption and transport properties of a multiphase commercial acrylic polymer trade-named Korad ACV before and after subjecting the polymer to mechanical drawing operations. The Korad system is an emulsion-polymerized amorphous composite comprised of a glassy, predominantly PMMA matrix phase and a ply(butyl acrylate)-dispersed phase surrounded by a PMMA/PBA copolymer shell. Large increases (up to eightfold) in permeability P to several gases were observed upon drawing Korad. The observed changes in the permeability to He, Ar, N₂, and CH₄ on drawing were correlated with the draw ratio, drawing temperature, and molecular diameter of the gas penetrant. Most of the increase in permeability occurred at low draw ratios (1–2). The increases in P were most dramatic for drawing temperatures below or near the T_g of the matrix phase (about 90°C) and were quite small for drawing temperatures 30°C or more above the matrix T_g. The extent of the permeability increase also depended on the gas, being greatest for CH₄ and essentially imperceptible for He. The changes in permeability behavior were interpreted in terms of a morphological transformation in the phase of the drawn Korad, which causes the originally dispersed rubber particles to assume a more continuous character. The behavior of the composite was modeled by the Takayanagi and Nielson treatments of two-phase composite systems. Volumetric, thermal, mechanical, and viscoelastic properties were measured for the as-received and processed Korad films to elucidate physical changes in the drawn polymer.