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1.
In this study, we focused on effect of the molecular weight of polyimide on the gas selectivity of the asymmetric membrane with an oriented surface skin layer prepared at different shear stresses. Asymmetric polyimide membranes, which have a defect‐free surface skin layer supported by a porous substructure, were prepared by a dry/wet phase inversion process. The structures of the asymmetric polyimides consisted of a thin skin layer and a porous substructure characterized by the presence of finger‐voids. The gas selectivities of the asymmetric polyimide membranes increased with an increase in the shear rate or a decrease in the molecular weight, indicating that the oriented polyimide structure in the surface skin layer provided a high size and shape discrimination between the gas molecules. The selectivity values of (O2/N2) and (CO2/CH4) in the asymmetric polyimide membrane prepared from the 7.2 × 104 molecular weight material at 1000 sec?1 shear rate were 12 and 143, respectively. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   

2.
Ion beam irradiation has been widely used to modify the structure and properties of membrane surface layers. In this study, the gas permeability and selectivity of an asymmetric polyimide membrane modified by He ion irradiation were investigated using a high vacuum apparatus equipped with a Baratron absolute pressure gauge at 76 cmHg and 35 °C. Specifically, we estimated the effects of the gas diffusion and solubility on the gas permeation properties of the asymmetric membranes with the carbonized skin layer prepared by ion irradiation. The asymmetric polyimide membranes were prepared by a dry–wet phase inversion process, and the surface skin layer on the membrane was irradiated by He ions at fluences of 1 × 1015 to 5 × 1015 ions/cm2 at 50 keV. The increase in the gas permeability of the He+‐irradiated asymmetric polyimide membrane is entirely due to an increase in the gas diffusion, and the gas selectivity increases of the membranes were responsible for the high gas diffusion selectivities. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 262–269, 2007.  相似文献   

3.
In this study, we report the gas permeance and selectivity of the asymmetric polyimide membrane prepared by plasma‐based ion implantation (PBII). The asymmetric polyimide membranes were prepared using a dry–wet phase inversion process, and the surface skin layer on the membrane was implantated by He ions at 2.5 keV. The asymmetric membranes treated by PBII were measured using a high vacuum apparatus with a Baratron absolute pressure gauge at 76 cmHg and 35°C. The (O2/N2) and (CO2/CH4) selectivities in the He+‐implanted asymmetric membrane at 60 sec resulted in 1.5 and 1.8 time increases, respectively, when compared to those of the asymmetric membrane before PBII. On the other hand, the O2 and CO2 permeances in the asymmetric membrane after PBII decreased with an increase in the He+ treatment time. In this paper, we addressed, for the first time, the gas permeation behavior of the asymmetric polyimide membranes prepared by PBII. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

4.
3‐Hydroxy‐N,N‐diethylaniline (HDEA) as a tertiary aromatic amine was introduced onto the surface of chloromethylated polysulfone (CMPSF) microfiltration membrane through modification reaction, resulting in the modified membrane PSF‐DEA. A redox surface‐initiating system (DEA/APS) was constituted by the bonded tertiary aromatic amine group DEA and ammonium persulfate (APS) in aqueous solution, and so, the free radicals formed on the membrane initiated sodium p‐styrenesulfonate (SSS) as an anionic monomer to produce graft polymerization, getting the grafting‐type composite microfiltration membrane, PSF‐g‐PSSS membrane. Subsequently, the adsorption property of PSF‐g‐PSSS membrane for three heavy metal ions, Pb2+, Zn2+, and Hg2+ ions, was fully examined, and the rejection performance of PSF‐g‐PSSS membrane towards the three heavy metal ions was emphatically evaluated via permeation experiments. The experimental results show that by the initiating of the surface‐initiating system of DEA/APS, the graft polymerization can smoothly be carried out under mild conditions. PSF‐g‐PSSS membrane as a functional microfiltration membrane has strong adsorption ability for heavy metal ions by right of strong electrostatic interaction (or ion exchange action) between the anionic sulfonate ions on the membrane and heavy metal ions. The order of adsorption capacity is Pb2+ > Zn2+ > Hg2+, and the adsorption capacity of Pb2+ ion gets up to 2.18 μmol/cm2. As the volume of permeation solutions, in which the concentrations of the three metal ions are 0.2 mmol/L, are in a range of 50 to 70 mL, the rejection rate of PSF‐g‐PSSS membrane for the three heavy metal ions can reach a level of 95%, displaying a fine rejection and removing performance towards heavy metal ions.  相似文献   

5.
Nanofiltration (NF) membranes have been widely used for the treatment of electroplating, aerospace, textile, pharmaceutical, and other chemical industries. In this work, halloysite nanotubes (HNTs) were directly anchored on the surface of commercial nanofiltration (NF) membrane by dopamine modification following advantageous bio‐inspired methods. SEM and AFM images were used to characterize the HNTs decorated membrane surface in terms of surface morphology and roughness. Water contact angle (WCA) was employed in evidencing the incorporation of HNTs and dopamine in terms of hydrophilicity or hydrophobicity. Augmentation of HNTs was found to obviously enhance the hydrophilicity and surface roughness resulting in improved water permeability of membrane. More importantly, the rejection ratios of membrane also increased during the removal of heavy metal ions from wastewater. The permeability and Cu2+ rejection ratio of modified NF membrane were as high as 13.9 L·m?2·h?1·bar?1 and 74.3%, respectively. Incorporation of HNTs was also found to enhance the anti‐fouling property and stability of membrane as evident from long‐term performance tests. The relative concentration of HNTs and dopamine on membrane surface was optimized by investigating the trade‐off between water permeability and rejection ratio.  相似文献   

6.
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.  相似文献   

7.
We synthesized the isomeric polyimides, 6FDA-m-DDS and 6FDA-p-DDS, and investigated the gas selectivity of the asymmetric polyimide membranes with an oriented surface skin layer. Particularly, we focused on the effect of the chemical structure of the polyimide on the molecular orientation. The asymmetric membranes with the oriented skin layer were prepared by a dry–wet phase inversion process at different shear stresses. The gas permeances of the asymmetric polyimide membranes were measured using a high vacuum apparatus with a Baratron absolute pressure gauge at 76 cmHg. The molecular orientation in the asymmetric polyimide membranes was measured using polarized ATR–FTIR spectroscopy. The gas selectivity of the asymmetric 6FDA-m-DDS membrane increased with an increased in the shear stress and were greater than that of the dense membrane. In contrast, the gas selectivities of the asymmetric 6FDA-p-DDS membrane did not depend on the shear stress and were similar to those of the dense membrane. We clarified that a parallel oriented surface formed on the asymmetric 6FDA-m-DDS membrane caused the enhanced gas selectivity of the membrane.  相似文献   

8.
In this article, we have reported the influence of alcohol as a casting solution on the structure and the gas permeability of asymmetric polyimide membranes made by dry–wet phase inversion. The apparent skin layer thickness of the asymmetric membrane decreased with an increase in molecular weight of the alcohol, and the thicknesses of the membranes made from methanol, ethanol, propanol, and butanol were 250, 120, 61, and 31 nm, respectively. We found that χ12 as an interaction parameter of solvent–nonsolvent had a significant influence on the phase inversion occurring in the coagulant medium. On the other hand, the gas permeance and the gas selectivity in the asymmetric membranes increased with the increasing molecular weight of the alcohol. We believe that a more packed structure formed in the asymmetric polyimide membrane with a thinner surface skin layer is also responsible for the thickness‐dependence of the gas selectivity obtained in this study. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2739–2746, 2007  相似文献   

9.
The effects of surface water pretreatment on membrane fouling and the influence of these different fouling types on the rejection of 21 neutral, positively and negatively charged pharmaceuticals were investigated for two nanofiltration membranes. Untreated surface water was compared with surface water, pretreated with a fluidized anionic ion exchange and surface water, pretreated with ultrafiltration. Fouling the nanofiltration membranes with anionic ion exchange resin effluent, resulted in the deposition of a mainly colloidal fouling layer, with a rough morphology. Fouling the nanofiltration membranes with ultrafiltration permeate, resulted in the deposition of a smooth fouling layer, containing mainly natural organic matter. The fouling layer on the nanofiltration membranes, caused by the filtration of untreated surface water, was a combination of both colloids and natural organic matter.Rejection of pharmaceuticals varied the most for the membranes, fouled with the anionic ion exchange effluent, and variations in rejection were caused by a combination of cake-enhanced concentration polarisation and electrostatic (charge) effects. For the membranes, fouled with the other two water types, variations in rejection were smaller and were caused by a combination of steric and electrostatic effects.Changes in membrane surface hydrophobicity due to fouling, changed the extent of partitioning and thus the rejection of hydrophobic, as well as hydrophilic pharmaceuticals.  相似文献   

10.
The influence of a transition layer between the skin porous sublayer in asymmetric membranes was investigated, using a numerical integration of the Spiegler—Kedem equation. It is shown that the transition layer will only interfere if the resistance to solute diffusion within this layer is of the same order of magnitude as in the skin layer.Experiments with multi-layer membranes were performed by placing a highly selective asymmetric membrane on top of a membrane of lower selectivity, and vice versa. The resulting retention-flux curves can be simulated by a three-layer model: σ Px for the two skin layers were determined from reverse osmosis data on the individual membranes whereas the values for the interjacent porous layer were correlated with the porosity and thickness of that layer.  相似文献   

11.
In recent years, Transparent exopolymer particles(TEPs) have been identified as significant contributors to membrane surface biofouling. Reported research on the effect of TEPs on membrane fouling has mainly focused on algae-derived TEPs in the ocean, and very limited investigations have been conducted on those in freshwater systems. In this study, we investigated the characteristics of TEPs derived from Microcystis aeruginosa and their influence on membrane fouling in an ultrafiltration (UF) system. The results indicated that bound TEPs could lead to more serious membrane fouling while free TEPs caused more serious irreversible membrane fouling. Further studies showed that in free TEP solutions, small-sized colloidal TEPs (c-TEPs) rather than large-sized particle TEPs (p-TEPs) showed a significantly positive correlation with irreversible membrane fouling. The presence of Ca2+ ions in influent water can reduce membrane fouling to some extent since a low concentration of Ca2+ ions (1 mM) can lead to the transformation of most free TEPs from the colloidal to particulate state. Both acidic and alkaline environments of free TEP solutions result in more serious membrane fouling compared to a neutral environment of free TEP solution. The negative impact of the acidic environment on membrane fouling was more significant than that of the alkaline environment. The abovementioned results show that when using a UF system to filter water with high algal content, greater attention should be paid to free TEPs, especially those in the colloidal state, because they can cause serious, irreversible membrane fouling.  相似文献   

12.
We have recently proposed a new method for generating uniformly sized microbubbles from Shirasu porous glass (SPG) membranes with a narrow pore size distribution. In this study, to obtain a high gas permeation rate through SPG membranes in microbubble formation process, asymmetric SPG membranes were used. At the transmembrane/bubble point pressure ratio of less than 1.50, uniformly sized microbubbles with a bubble/pore diameter ratio of approximately 9 were generated from an asymmetric SPG membrane with a mean pore diameter of 1.58 μm and a skin-layer thickness of 12 ± 2 μm at a gaseous-phase flux of 2.1–24.6 m3 m−2 h−1, which was much higher than that through a symmetric SPG membrane with the same pore diameter. This is mainly due to the much smaller membrane resistance of the asymmetric SPG membrane. Only 0.27–0.43% of the pores of the asymmetric SPG membrane was active under the same conditions. The proportion of active pores increased with a decrease in the thickness of skin layer. In contrast to the microbubble formation from asymmetric SPG membranes, polydispersed larger bubbles were generated from asymmetric porous ceramic membranes used in this study, due to the surface defects on the skin layer. The surface defects were observed by the scanning electron microscopy and detected by the bubble point method.  相似文献   

13.
Hydrous manganese dioxide (HMO) nanoparticles incorporated cellulose acetate (CA) composite ultrafiltration (UF) membranes are prepared with the aim of improving the water permeation and BSA contaminant removal. The HMO nanoparticles are synthesized from manganese ion and characterized by FT‐IR, XRD, and FESEM. The effect of variation of HMO on CA membranes is probed using FT‐IR, EDAX, contact angle, SEM, and AFM analysis to demonstrate their chemical functionality, hydrophilicity, and morphology. CA/HMO membranes are showing the enhancement in pure water flux (PWF), water uptake, porosity, hydrophilicity, fouling resistance, BSA rejection, and flux recovery ratio (FRR). CA‐1 membrane displayed higher PWF (143.6 Lm2h?1), BSA rejection (95.9%), irreversible fouling (93.3%), and FRR (93.3%). Overall results confirmed that the CA/HMO nanocomposite UF membranes overcome the bottlenecks and shows potential for water treatment applications.  相似文献   

14.
Flat sheet asymmetric reverse osmosis membranes were successfully prepared from N,N-dimethylacetamide (DMAc) solutions of a series of novel wholly aromatic polyamide-hydrazides that contained different amounts of para- and meta-phenylene rings. These polyamide-hydrazides were synthesized by a low temperature solution polycondensation reactions of either 4-amino-3-hydroxybenzhydrazide or 3-amino-4-hydroxybenzhydrazide with an equimolar amount of either terephthaloyl dichloride [TCl], isophthaloyl dichloride [ICl] or mixtures of various molar ratios of TCl and ICl in anhydrous DMAc as a solvent. All the polymers have the same structural formula except of the way of linking phenylene units inside the polymer chains. The content of para- to meta-phenylene moieties was varied within these polymers so that the changes in the latter were 10 mol% from polymer to polymer, starting from an overall content of 0-100 mol%. All the membranes were characterized for their salt rejection (%) and water permeability (cm3 cm−2 day−1) of 0.5 N aqueous sodium chloride feed solution at 3924 kPa operating pressure. The effects of polymers structural variations together with several processing parameters to achieve the best combination of high selectivity and permeability were studied. Effects of various processing parameters of the membranes on their transport properties were investigated by varying the temperature and period of the solvent evaporation of the cast membranes, coagulation temperature of the thermally treated membranes, annealing of the coagulated membranes, casting solution composition, membrane thickness and the operating pressure. During the thermal treatment step, the asymmetric structure of the membranes with a thin dense skin surface layer supported on a more porous layer was established. The former layer seems to be responsible for the separation performance. The results obtained showed that membrane performance was very much influenced by all of the examined processing variables and that membranes with considerably different properties could be obtained from the same polymer sample by using different processing parameters. Thus, the use of higher temperatures and longer exposure times in the protomembrane forming thermal treatment step would result in a membrane of lower solvent content and with a thicker skin layer and consequently led to higher salt rejection at lower water permeability. Most significantly, the membrane properties clearly depended on the polymer structure. Under identical processing condition, substitution para-phenylene rings for meta-phenylene ones within the polymer series resulted in an increase in salt rejection capability of the membranes. This may be attributed to an increase in their chain symmetry associated with increased molecular packing and rigidity through enhanced intermolecular hydrogen bonding. This produces a barrier with much smaller pores that would efficiently prevent the solute particles from penetration. Coagulation temperature controls the structure (porosity) of the membrane particularly its supported layer and consequently its water permeability. Moreover, annealing of the prepared membranes in deionized water at 100 °C was found essential for useful properties in the single-stage separation applications, which required optimum membrane selectivity. Upon annealing, the membrane shrinks resulting in reducing its pore size particularly in the skin layer and consequently improving the salt rejection. Addition of lithium chloride to the casting solution produced a membrane with increased porosity and improved water permeability. Salt rejection capability of the membranes is clearly affected by the applied pressure, reaching its maximum at nearly 4000 kPa. Furthermore, the water permeability is inversely proportional to the membrane thickness, while the salt rejection is not substantially influenced.  相似文献   

15.
Various polyimide layers [2.2–2.6 μm of hexafluoroisopropylidene bis(phthalic anhydride‐oxydianiline), pyromellitic dianhydride‐oxydianiline, and 3,3′‐4,4′‐biphenyltetracarboxylic dianhydride‐p‐phenylenediamine] spin‐coated on silicon substrates were studied with a variable‐energy positron beam in combination with a Doppler‐broadened annihilation radiation technique. From the experiments, the thickness of the layers was estimated with the VEPFIT routine. These values corresponded well to the values determined from interferometry and ellipsometry. Irradiation of the polyimides with 1 × 1015 boron ions/cm2 at an energy of 180 keV led to a strong chemical modification of the irradiated top layer. This caused the inhibition of positronium formation in the irradiated layer, which was observed as a lowering of the annihilation line S parameter. The thickness of the modified layer was estimated to be 700–800 nm. This value did not agree with the ellipsometric measurements but corresponded to the maximum implantation depth of boron ions calculated with TRIM (Transport of Ions in Matter) code. The positron results appeared somewhat larger than the TRIM estimates. Reasons for these relations are discussed. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3062–3069, 2000  相似文献   

16.
In some biomedical applications, hollow fiber membranes are highly demanded with desirably asymmetric structures, characterized by a dense selective inner skin with which the blood is in contact and supported by porous outer-layer. In this work, such membranes have been successfully prepared by appropriately adjusting membrane manufacturing parameters. Different molecular weights of polyvinylpyrrolidones (PVPs) were used as the hydrophilizing additives for membrane spinning in order to examine their underlying effects on membrane physicochemical properties, morphological structure, solute rejection behavior and hemofiltration performance. Numerous state-of-the-art characterizations on the resultant membranes showed that the hollow fiber membranes spun with the PVP having a molecular weight of 360K as the additive have the most hydrophilic, smooth and highly net negative charged inner surfaces. These membranes also exhibit the best hemofiltration performance in terms of the characteristically least fouling behavior with a normalized flux above 90%, the highest retention of serum albumin for more than 90%, and the best clearance for the simulated β2-microglobulin toxin in blood waste.  相似文献   

17.
Salinity gradient energy, as a type of blue energy, is a promising sustainable energy source. Its energy conversion efficiency is significantly determined by the selective membranes. Recently, nanofluidic membrane made by two-dimensional (2D) nanomaterials (e.g., graphene) with densely packed nanochannels has been considered as a high-efficient membrane in the osmotic power generation research field. Herein, the graphene oxide-cellulose acetate (GO–CA) heterogeneous membrane was assembled by combining a porous CA membrane and a layered GO membrane; the combination of 2D nanochannels and 3D porous structures make it show high surface-charge-governed property and excellent ion transport stability, resulting in an efficient osmotic power harvesting. A power density of about 0.13 W/m2 is achieved for the sea–river mimicking system and up to 0.55 W/m2 at a 500-fold salinity gradient. With different functions, the CA and GO membranes served as ion storage layer and ion selection layer, respectively. The GO–CA heterogeneous membrane open a promising avenue for fabrication of porous and layered platform for wide potential applications, such as sustainable power generation, water purification, and seawater desalination.  相似文献   

18.
Oil/water emulsion separation in harsh environments remains a big challenge. Herein, a double layered nanofibrous composite membrane was developed by assembly of polydopamine‐modified hexagonal boron nitride (h‐BN‐PDA) onto a poly(arylene ether nitrile) (PEN) nanofibrous mat. Owing to the synergistic effect of a h‐BN‐PDA skin layer and a PEN nanofibrous mat supporting layer, as‐prepared composite membrane exhibited high thermal stability, corrosion resistance, and superhydrophilic/underwater superoleophobic property. Consequently, the PEN composite membrane showed good antifouling performance and a high rejection ratio (>99.0%) for various oil/water emulsions. After 10 cycles, the separation flux of PEN composite membrane still reached 588.1 L/m2 h under the operating pressure of 0.04 MPa. Furthermore, the PEN composite membrane could still achieve high separation efficiency and high flux in high‐temperature (65 °C) and strongly corrosive conditions (pH = 1‐13). Therefore, the stable and efficient h‐BN‐PDA/PEN composite membrane showed potential application for treating oily wastewater in harsh environments.  相似文献   

19.
In this paper, we describe the investigation of membranes to concentrate aqueous low molecular weight (<500 Da) organics streams, while removing electrolytes including divalent salts such as sodium sulfate. Such membranes would be useful in many industrial applications as currently used pressure driven process such as nanofiltration (NF) or electrical processes such as electric dialysis (ED) cannot achieve such separations and concentrations. An analysis of ion/water transport in different membranes and, selectivity and flux requirements indicated that ion exchange mosaics in the form of integrally skinned asymmetric structures could achieve the required performance. The relationship between the internal structure of the mosaic membrane elements and the required separation properties was further analyzed as a development guide. It was found that such membranes could be made by casting a homogenous solution of two mutually incompatible polymers in a common solvent, containing non-solvents and additives, followed by a chemical modification. The process of forming such membranes involves phase separation between the two polymers and the phase inversion of each polymer. In this study the membrane consists of a cation exchange asymmetric membrane with a uniform distribution of anion exchange particles in the dense integrally skin layer. The choice of polymeric materials, their molecular weights, solvent combinations and surfactants determined the membranes’ surface morphology, mosaic dimensions and particle density. In this way membranes were formed with ∼1 μm sized anion exchange particles uniformly dispersed in a thin (∼1.0 μm) cation exchange selective layer of an asymmetric membrane. The best performance to date: Fluxes of 500+LMD, 10% rejection to sodium sulfate, 90% to sucrose and >98% rejection to 400 molecular weight organic ions. The membranes also show a mosaic effect of decreasing sulfate rejection with decreasing sulfate concentration. The membranes also show a musaic effect of decreasing sulfate rejection with decreasing sulfate concentration, which is desired to perform effectively the removal of mono and bivalent ions during diafiltration.  相似文献   

20.
Micropatterns of cells on a poly(vinyl chloride) (PVC) film surface were created by using ion irradiation. A PVC film was irradiated with H+ ions through a pattern mask in order to create patterns of the hydrophilic/hydrophobic regions on the PVC surface. The effect of ion irradiation on the surface properties of the PVC film was characterized by using Fourier transform‐infrared spectroscopy (FT‐IR), water contact angle measurement, and X‐ray photoelectron spectroscopy (XPS). The results revealed that the chemical environment of the PVC film surface was effectively changed by ion irradiation due to dehydrochlorination and oxidation. The in vitro cell culture on the patterned PVC film surface showed selective adhesion and proliferation of the cells on the ion‐irradiated regions. Well‐defined 50 µm patterns of the cells were obtained on the PVC film surface irradiated to 1 × 1015 ions/cm2. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

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