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1.
Stimuli-responsive membranes may act as “on–off switches” or “permeability valves”, producing patterns of pulsatile release, where the period and rate of mass transfer can be controlled by external or environmental triggers (e.g. pH, temperature, electric field). In this work, composite-heterogeneous polyelectrolyte gel (composite-HPG) membranes consisting of polymethacrylic acid (PMAA) gel particles dispersed within a polydimethylsiloxane (PDMS) network were developed and evaluated as pH-responsive membranes.The mechanism of permeability control for caffeine and vitamin B12 through composite-HPG membranes was determined to be a synergistic function of membrane hydration and the percolating volume fraction of PMAA gel. Larger changes in permeation as a function of pH were achieved when both hydration and percolation effects occurred together than when either of these effects occurred on their own. Vitamin B12 permeation was observed when the hydrated gel volume fraction was above approximately 0.38, but not below. Furthermore, the percolating fraction of composite-HPG membranes containing 28% (dry basis) PMAA gel particles was manipulated via pH to fall above (pH 7) or below (pH 3) this transition in permeability, resulting in membranes that delivered solutes of high molecular weight (vitamin B12) with large on/off delivery ratios (160).  相似文献   

2.
In this work the effect of pH on membrane structure, its permeability and retention was studied. In addition, we studied whether the possible changes in the membrane properties due to the pH change are reversible. This is important for understanding the performance of nanofiltration membranes at different conditions and for the selection of cleaning processes. Moreover, the results facilitate the choice of membrane for specific applications.

Several commercial NF membranes were studied at different pH values. Their retention and flux were explained by the charge and the hydrophilic characteristics of the membranes. The filtrations were made with uncharged sugar and salt solutions.

The lower the membrane contact angle (i.e., a more hydrophilic membrane) the higher was the change in apparent zeta potential when pH was increased from 4 to 7. As a result, the retention of ions with more hydrophilic membranes changed more than hydrophobic ones when the pH was increased in the feed solution. However, some membranes retained ions well at high pH although their apparent zeta potential or hydrophilicity was relatively low. These membranes had charge inside the pores and it was not detected by streaming potential measurement along the surface or by measuring the contact angle of the surface. Thus, the apparent zeta potential of the exterior membrane surface did not sufficiently describe the ionic transport through the membrane. In addition, some membranes became significantly more open at high pH (i.e., flux increased). This was explained by the chemical nature of the polymer chains in the membrane skin layer, i.e., dissociating groups in the polymer made the surface more hydrophilic and looser when charges of the polymer chains started to repel each other at elevated pH. Generally, the retention of uncharged glucose decreased more at high pH than the salt retention. The changes in permeabilities and retentions were found to be mostly reversible in the pH range studied (very slowly in some cases, however).  相似文献   


3.
In this paper the effect of zeolite particles incorporated in rubbery polymers on the pervaporation properties of membranes made from these polymers is discussed. Pervaporation of methanol/toluene mixtures was carried out with membranes prepared from the toluene selective polymer EPDM and the methanol selective polymers Viton and Estane 5707. From the results of the pervaporation experiments it could be concluded that the addition of the hydrophilic zeolite NaX as well as the hydrophobic zeolite silicalite-1 leads to an increase in methanol flux and a decrease in toluene flux through the membranes. Pervaporation experiments with bi-layer membranes consisting of an unfilled polymer layer filled with zeolite particles demonstrated that the effect of addition of particles depends on their position in the membrane. Furthermore, the component flux through the membranes as a function of the volume fraction of zeolite is modelled with existing theories describing the permeability of heterogeneous materials. The results show that the apparent permeability of the dispersed phase is lower than the intrinsic permeability of the dispersed phase when the flux through the particle is restricted by the polymer phase. This phenomenon was confirmed by numerical simulation of the transport in the membrane through a plane parallel to the transport direction. The simulations are carried out for an unfilled membrane, a membrane filled with an impermeable particle, a rubber particle and with a particle which shows Langmuir sorption behaviour. The reason for the discrepancy between the apparent permeability and the intrinsic permeability is that the apparent permeability of the zeolite phase is calculated by dividing the flux with the driving force over the entire membrane which is larger than that over the particle. In case of numerical simulation the concentration in every position in the plane is known and therefore the intrinsic permeability of the filler can be calculated on basis of the actual driving force. This treatment results in a permeability which is correct over several orders of magnitude.  相似文献   

4.
Group transfer polymerization was used to prepare hydrophilic, cationic large‐core star polymers (LCSPs) and networks of 2‐(dimethylamino)ethyl methacrylate (DMAEMA) and ethylene glycol dimethacrylate (EGDMA) in a two‐step procedure involving the synthesis of linear DMAEMA arms, followed by their crosslinking using a mixture of DMAEMA monomer and EGDMA crosslinker. The degree of polymerization of the linear chains prepared in the first step was kept constant, while the composition of the crosslinking mixture was varied systematically at a constant amount of crosslinker. The monomer/crosslinker molar ratio determined whether LCSPs or polymer networks would be produced. In particular, a high monomer/crosslinker molar ratio led to the formation of networks, whereas LCSPs were formed when a low monomer/crosslinker molar ratio was used. The absolute weight‐average molecular weight of the LCSPs was determined using static light scattering, whereas their hydrodynamic radii and radii of gyration were determined using dynamic light scattering and small‐angle neutron scattering, respectively. The sol fraction extracted from the networks decreased as the monomer/crosslinker molar ratio increased. The degrees of swelling of all of the networks were measured as a function of pH and were found to increase below pH 7. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3958–3969, 2008  相似文献   

5.
The mobility of hydration water and the dissolved oxygen permeability through different cation forms of the Nafion® membranes were determined. Two alkali metals (Na and K) and two amino sugars (an equivalent molar mixture of d-glucopyranosyl-α(1′  6)-2-amino-2-deoxy-d-mannitol and its sorbitol (GPA)and d-glucosamine (GLU)) were used as counterions. Based on the two-state model, the content and mobility of hydration water were determined using DSC and 17O NMR. The dissolved oxygen permeability through the Nafion® membrane containing GPA was the lowest value in this study because, for the membrane, the fraction of hydration water was the greatest and the mobility of hydration water was the lowest. The amount and location of the hydrophilic group contained in substances as well as the kind of hydrophilic group affected the fraction and mobility of hydration water and dissolved oxygen permeability through the membranes.  相似文献   

6.
This work deals with water-swollen hydrogel membranes for potential CO2 separation applications, with an emphasis on elucidating the role of water in the membrane for gas permeation. A series of hydrogel membranes with a wide range of water contents (0.9–10 g water/g polymer) were prepared from poly(vinyl alcohol), chitosan, carboxyl methyl cellulose, alginic acid and poly(vinylamine), and the permeation of CO2, H2, He and N2 through the membranes at different pressures (200–800 kPa) was studied. The gas permeabilities through the dry dense membranes were measured as well to evaluate the resistance of the polymer matrix in the hydrogel membranes. It was shown that the gas permeability in water-swollen membrane is lower than the gas permeability in water, and the selectivity of the water-swollen membranes to a pair of gases is close to the ratios of their permeabilities in water. The permeability of the water-swollen membranes increases with an increase in the swelling degree of the membrane, and the membrane permeability tends to level off when the water content is sufficiently high. A resistance model was proposed to describe gas permeation through the hydrogel membranes, where the immobilized water retained in the polymer matrix was considered to form transport passageways for gas permeation through the membrane. It was shown that the permeability of hydrogel membranes was primarily determined by the water content in the membrane. The model predictions were consistent with the experimental data for various hydrogel membranes with a wide range of water contents (0.4–10 g water/g polymer).  相似文献   

7.
Poly(methyl methacrylate) membranes of different fractional free volume (FFV) were prepared by dry casting from different solvents. Free volume data were determined by means of Bondi method and positron annihilation lifetime spectroscopy (PALS). It was found that both the boiling point and the solubility parameter of casting solvent affect the membrane’s free volume. It was believed that the difference in free volume was arisen from the difference in polymer packing.The gas permeability is higher when membranes are cast from higher molecular weight PMMA. But the plasticizing effect of CO2 is less serious compared with the low molecular weight one. The high molecular weight PMMA membrane also has an extremely high O2/N2 selectivity, indicating its high structure uniformity. These results indicate that membranes made from polymer of higher molecular weight have the advantages of high permeability, gas selectivity and are less sensitive to CO2 plasticization. The intrinsic gas transport properties such as the permeability, solubility and diffusivity of O2, N2, and CO2 are measured or calculated. The effects of fractional free volume on membrane gas separation properties were investigated. It was found that the fractional free volume had no definite effects on gas solubility, but the gas permeability and diffusivity increased accordingly to the measured free volume.  相似文献   

8.
The results of a structural study of conducting polymer coatings deposited onto poly(ethylene terephthalate) (PET) track membranes by template synthesis are reported. The following aspects of the quality of polymer coatings were studied: the ratio between film and granular polymers, the polymer distribution over the surface of track membranes, and the thickness of polymer layers on the opposite sides of track membranes. The fraction of granular polypyrrole (PPy) on the surface and in the pores of a film increased with pore diameter. A decrease in the polymerization temperature decreased the amount of granular PPy on the surface of membranes, whereas the effect of granular PPy on the water permeability of track membranes remained unchanged. A more homogeneous distribution of PPy over the surface of track membranes can be obtained by density equalization of reacting solutions; however, the fraction of granular PPy on the membrane surface increased in this case. It was found that polymer coatings on the two sides of the surface of a membrane template had different thicknesses. Poly(N-methylpyrrole) completely covered only one side of a track membrane facing a monomer solution.  相似文献   

9.
PPO (poly(2,6-dimethyl-1,4-phenylene oxide)) is a well-known membrane material showing good gas separation properties. The incorporation of nanoparticles can enhance or deteriorate the performance of composite membranes, sometimes depending only on the way of the composite preparation. We have modified the PPO polymer with C60 fullerenes up to a content of 2 wt %. Previous investigations showed a strong dependence of permeability on whether the C60 is simply dispersed in the polymer or chemically bonded to the polymer chains. Free volume effects were suggested as an explanation but not experimentally confirmed. Here, we present free volume studies by positron annihilation lifetime spectroscopy. An additional long positron lifetime shows the increased free volume of composite samples, while the high electron affinity of C60 helps to indicate the homogeneity of the samples. Combining the presented results with permeability measurements refines the understanding of this promising membrane material.  相似文献   

10.
This research aims to fabricate and characterize chemically crosslinked CMC/PVP-co-poly (AMPS) based hydrogel for the sustained release of model drug metoprolol tartrate through the free radical polymerization technique. Box-Behnken Design was used to optimize CMC/PVP-co-poly (AMPS) hydrogel by varying the content of reactants such as; polymers (CMC and PVP), monomer (AMPS), and crosslinker (EGDMA). Carboxymethyl cellulose (CMC) was crosslinked chemically with AMPS with a constant ratio of PVP by the ethylene glycol dimethacrylate as the crosslinker in the presence of sodium hydrogen sulfite (SHS)/ammonium peroxodisulfate (APS) as initiators. After developing CMC-based hydrogels using different polymers, monomer, and crosslinker concentrations, this study encompassed dynamic swelling, sol–gel fraction, drug release and chemical characterizations such as FTIR, XRD, TGA, DSC, and SEM. In vitro drug release and swelling were performed at 1.2 and 6.8 pH to determine the sustained release pattern and pH-responsive behavior. These parameters depended on the crosslinker, polymer, and monomer ratios used in the formulation development. XRD, SEM, and FTIR showed the successful grafting of constituents resulting in the formation of a stable hydrogel. DSC and TGA confirmed the thermodynamic stability of the hydrogel. Hydrogel swelling was increased with an increase in the ratio of monomer; however, an increase in the ratio of polymer and crosslinker decreased the hydrogel swelling. In vitro gel fraction and drug release also depended on polymer, monomer, and crosslinker ratios. The fabricated CMC/PVP-co-poly (AMPS) hydrogels constituted a potential system for sustained drug delivery.  相似文献   

11.
The present paper deals with the transport properties of membranes made of hydrophilic gels containing ionogenic groups. Introduction of ionogenic groups into a gel based on 2-hydroxyethyl methacrylate will affect the permeability of the investigated membranes for sodium chloride by an order or more. Dependences of the permeability on the content of ionogenic groups, three-dimensional network density, and pH were established. The permeability for NaCl was compared for that for bivalent salt (MgSO4). It is shown, on the basis of independently determined distribution coefficients, that an increase in the permeability of ampholytic membranes in comparison with the neutral ones is primarily due to an increase in the diffusivity of the salt in the membranes with modified structure. It can also be concluded that an approximation of the free volume from the volume of the solvent in the membrane cannot be applied to the poly(2-hydroxyethyl methacrylate) gel.  相似文献   

12.
Poly(4-methyl-2-pentyne) (PMP) has been crosslinked using 4,4′-(hexafluoroisopropylidene) diphenyl azide (HFBAA) to improve its chemical and physical stability over time. Crosslinking PMP renders it insoluble in good solvents for the uncrosslinked polymer. Gas permeability and fractional free volume (FFV) decreased as crosslinker content increased, while gas sorption was unaffected by crosslinking. Therefore, the reduction in permeability upon crosslinking PMP was due to decrease in diffusion coefficient. Compared to the pure PMP membrane, the permeability of the crosslinked membrane is initially reduced for all gases tested due to the crosslinking. By adding nanoparticles (FS, TiO2), the permeability is again increased; permeability reductions due to crosslinking could be offset by adding nanoparticles to the membranes. Increased selectivity is documented for the gas pairs O2/N2, H2/N2, CO2/N2, CO2/CH4 and H2/CH4 using crosslinking and addition of nanoparticles. Crosslinking is successful in maintaining the permeability and selectivity of PMP membranes and PMP/filler nanocomposites over time.  相似文献   

13.
Polymer of Intrinsic Microporosity (i.e. PIM-1) has been crosslinked thermally via nitrene reaction using polyethylene glycol biazide (PEG-biazide) as a crosslinker. The crosslinking temperature was optimized using TGA coupled with FT-IR spectroscopy. The dense membranes containing different ratios of PIM-1 to PEG-biazide were cast from chloroform solution. Crosslinking of PIM-1 renders it insoluble even in excellent solvents for the uncrosslinked polymer. The resulting crosslinked membranes were characterized by FT-IR spectroscopy, TGA and gel content analysis. The influence of crosslinker content on the gas transport properties of PIM-1, its density and fractional free volume (FFV) were investigated. Compared to the pure PIM-1 membrane, the crosslinked PIM-1 membranes showed better gas separation performance especially for CO2/N2, CO2/CH4 and propylene/propane (C3H6/C3H8) gas pairs and as well as suppressed penetrant-induced plasticization under high CO2 pressure.  相似文献   

14.
A method is developed for obtaining anisotropic composites based on the sulfonated cation-exchange MF-4SK and MK-40 membranes and the electroactive polymer polyaniline (PANI). The kinetics of aniline polymerization by successive diffusion in these membranes is investigated, and differences in the transport characteristics of the resulting MF-4SK/PANI and MK-40/PANI composites are identified. It is established from results of electroosmotic and diffusion experiments that the composite MF-4SK/PANI-1 membrane (after 1 h of aniline polymerization) suppresses electrolyte and water flow the most. Diffusion permeability drops by an order of magnitude, and water transport numbers are reduced by 50–70%. In the process of sodium chloride concentration by electrodialysis, the salt content of the concentrate increases by 50–70% with the composite MF-4SK/PANI-1 membrane compared to the base MF-4SK membrane and by 15–20% compared to the electrodialysis MK-40 membrane. Transport characteristics of the membrane pairs under investigation are calculated from the model of limiting concentration by electrodialysis: current efficiency, water transport numbers, osmotic and diffusion permeability. The dominant influence of the electroosmotic mechanism of water transport on the effect of salt solution concentration is established.  相似文献   

15.
新型含钴硅橡胶离聚体膜的富氧性能   总被引:3,自引:0,他引:3  
硅橡胶 ( PDMS)是最早使用的气体分离膜材料 ,其氧透过系数较高 ( PO2 =6 0 0 Barrer) ,但氧氮分离系数低 ( αO2 /N2 =2 .0 ) ,成膜性及膜强度差 ,因而限制了其应用 .PDMS改性一直是气体分离膜研究的重要课题[1] ,提高氧氮分离性 ,改善成膜性 ,而不影响其透气性 ,成为人们追求  相似文献   

16.
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   

17.
The gas (oxygen and nitrogen) transport characteristics of the interpenetrating polymer network (IPN) membranes of polyurethane/polystyrene were studied. The effect of synthesis temperature, composition, molecular weight of the polyol and aromatic content (of MDI, TDI and HDI) on the gas permeability were analyzed. In the IPN synthesis, first polyurethane was polymerized thermally, and then polystyrene was polymerized by photolytic methods at different temperatures. The permeability coefficient decreased and the separation factor increased with decreasing synthesis temperature due to the miscibility increase. The permeability coefficient showed a minimum value and the separation factor showed a maximum value at ca.25 wt.% polyurethane composition. The permeability coefficient decreased and the separation factor increased with increasing aromatic content in polyurethane component. The morphology and density behavior of the IPN's agreed well with the permeability data. The tensile strength of the membrane increased with decreasing synthesis temperature and with increasing crosslink density and polystyrene content.  相似文献   

18.
采用溶液浇铸法,制备了厚度为50~202 μm的聚(1-三甲基硅基-1-丙炔)(PTMSP)膜,研究了膜厚度、储存温度以及储存气氛对其气体渗透性能的影响。 在室温下储存时,PTMSP膜发生物理老化,气体渗透系数先是迅速下降,然后缓慢降低并趋向平稳。 在空气气氛中的下降速率要略大于在N2气气氛中。 气体渗透系数的下降速率随膜厚度的减小而增大。 在高温(100 ℃)空气气氛中,受物理及化学老化的共同作用,PTMSP膜气体渗透系数的下降速率进一步增大,IR谱图表明,聚合物氧化生成了C=O等极性基团。 随储存时间的延长,溶解度系数基本不变,扩散系数的下降是导致气体渗透系数下降的主要原因,这与聚合物体积松弛和(或)致密化及极性基团的形成所造成的自由体积的减小紧密相关。  相似文献   

19.
Poly(amide-6-b-ethylene oxide)(Pebax1657)/1-butyl-3-methylimidazo-lium bis[trifluoromethyl)sulfonyl]-imide([Bmim][Tf_2N]) blend membranes with different [Bmim][Tf_2N] contents were prepared via solution casting and solvent evaporation method. The permeation properties of the blend membranes for CO_2, N_2,CH_4 and H_2 were studied, and the physical properties were characterized by differential scanning calorimeter(DSC) and X-ray diffraction(XRD). Results showed that [Bmim][Tf_2N] was dispersed as amorphous phase in the blend membranes, which caused the decrease of Tg(PE) and crystallinity(PA). With the addition of [Bmim][Tf_2N], the CO_2 permeability increased and reached up to approximately 286 Barrer at 40 wt%[Bmim][Tf_2N], which was nearly double that of pristine Pebax1657 membrane. The increase of CO_2 permeability may be attributed to high intrinsic permeability of [Bmim][Tf_2N], the increase of fractional free of volume(FFV) and plasticization effect. However, the CO_2 permeability reduced firstly when the [Bmim][Tf_2N]content was below 10 wt%, which may be due to that the small ions of [Bmim][Tf_2N] in the gap of polymer chain inhibited the flexibility of polymer chain; the interaction between Pebax1657 and [Bmim][Tf_2N]decreased the content of EO units available for CO_2 transport and led to a more compact structure. For Pebax1657/[Bmim][Tf_2N] blend membranes, the permeabilities of N_2, H2 and CH4decreased with the increase of feed pressure due to the hydrostatic pressure effect, while CO_2 permeability increased with the increase of feed pressure for that the CO_2-induced plasticization effect was stronger than hydrostatic pressure effect.  相似文献   

20.
将聚氨酯(PU)与聚N-异丙基丙烯酰胺(PNIPAM)半互穿网络聚合物(semi-IPN)通过浸入沉淀相转化方法制备成微孔膜,并从亲水性、吸水溶胀性以及透湿性等方面对其温度响应性进行了讨论.PNIPAM的引入使膜的亲水性、吸水性和透湿性大为改善,并显著提高了膜的温度响应能力;但与此同时也使得膜的韧性降低.当PU/PNIPAM为3/1时,可获得最好的综合性能.同传统无孔致密膜相比,PU/PNIPAM semi-IPN微孔膜的透湿机理是基于微孔的开闭,在维持显著的温敏透湿性的同时可实现较高的高温透湿量.  相似文献   

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