ISSN 0018-1439, High Energy Chemistry, 2009, Vol. 43, No. 3, pp. 181–188. © Pleiades Publishing, Ltd., 2009. Original Russian Text © L.I. Kravets, S.N. Dmitriev, A.B. Gil’man, 2009, published in Khimiya Vysokikh Energii, 2009, Vol. 43, No. 3, pp. 227–234.
PLASMA CHEMISTRY PLENARY REPORTS FROM THE 5th INTERNATIONAL SYMPOSIUM ON THEORETICAL AND APPLIED PLASMA CHEMISTRY (September 3–8, 2008, Ivanovo, Russia)
Modification of Properties of Polymer Membranes by Low-Temperature Plasma Treatment L. I. Kravetsa, S. N. Dmitrieva, and A. B. Gil’manb a
Flerov Laboratory of Nuclear Reactions, Joint Institute for Nuclear Research, ul. Zholio-Kyuri 6, Dubna, Moscow oblast, 141980 Russia e-mail:
[email protected] b Enikolopov Institute of Synthetic Polymer Materials, Russian Academy of Sciences, ul. Profsoyuznaya 70, Moscow, 117393 Russia Received October 20, 2008
Abstract—The results of investigations into the use of low-temperature plasma for modification of porous polymer membranes are summarized. The basic lines of research in this area are considered. It is shown that plasma treatment is a quite effective tool for both improving the properties of existing polymer membranes and manufacturing new composite membranes with unique characteristics. DOI: 10.1134/S0018143909030059
Membrane processes have found wide application in many areas of science and technology, such as gas separation, desalination of water, pervaporation, separation and isolation of individual solutes, and purification and concentration of biologically active substances [1]. Prominent among the variety of the membranes used in these processes are polymer membranes. However, the properties of existing membranes are frequently inconsistent with the requirements of industrial processing technologies, since the range of polymers suitable for the manufacture of membranes is limited. To extend the application area of commercial membranes, research works on the modification of their properties are performed. The most popular technique used for this purpose is the treatment of membranes in low-temperature plasma [2]; an important advantage offered by this process is the possibility for modifying a thin surface layer, which alters membrane properties, namely, the adsorption, transport, and selectivity properties. This possibility substantially extends the application area of membranes. The bulk of the membrane matrix remains intact in this case, which is undoubtedly very important from the viewpoint of retention of its mechanical and physicochemical properties. The effect of low-temperature plasma on porous polymer membranes is of particular interest, as it gives rise to new advanced materials used in some modern membrane processes—membranes for bioreactors, fuel cells, catalytic reactions, etc.
In this paper, studies reported over the last decade in the Russian and foreign scientific literature on the lowtemperature plasma treatment with the aim of modifying the properties of porous polymer membranes are surveyed. The low-temperature plasma treatment entails a number of physicochemical process, depending of the discharge type (plasma frequency) and the nature of the plasma gas, which make it possible to control in the targeted mode the structure and the chemical composition of the surface of polymer membranes (Tables 1–3). A low-temperature plasma can be created by means of low-frequency (alternative-current), radiofrequency (RF), and microwave (MW) discharges, as well as a direct-current discharge. Chemical processes that occur during modification in the surface membrane layers are largely determined by the gas-phase composition of plasma. Two kinds of plasma are used, the plasmas of simple gases that do not result in the formation of polymers (nonpolymerizable gases ç2, He, Ar, O2, N2, air, halogens) and the plasma produced by discharge in a vapor of any organic or organoelement compound that leads to polymer formation. The central process characteristics of the membrane treatment in inert-gas ac discharge plasmas is the crosslinking of the polymer surface layer [3] or cyclization of macromolecules [4], which substantially increases the chemical resistance of the modified membranes. During the treatment of a polymer membrane in an RF discharge (including pulsed discharge) or a
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Table 1. Use of nonpolymerizable-gas plasma treatment for modification of membrane properties MemPlasma gas, discharge type brane PA PAN PAN
Ar, 20-kHz glow discharge He, He/H2O, 20-kHz glow discharge Ar, He, 13.56-MHz RF discharge Air, dc discharge
Effect of plasma treatment Crosslinking of surface layer Cyclization of PAN surface layer
Degradation of polymer macromolecules, etching of surface layer PVC Etching of surface layer, formation of COOH groups PAN, PS Air, 2.45-GHz microwave Etching of membrane surface layer discharge and pore surface, formation of oxygen-containing groups PAN, PS O2, air, 13.56-MHz RF dis- Etching of membrane surface layer PP, PU charge and pore surface, change in surface morphology, formation of oxygencontaining groups PET O2, air, N2, 13.56-MHz RF Etching of membrane surface layer discharge and pore surface, formation of oxygen-containing groups
Properties of modified membranes
Reference
Enhancement of chemical resistance [3] Enhancement of chemical resistance [4] An increase in surface wettability and water permeability An increase in surface wettability and water permeability An increase in surface wettability and water permeability
[5] [6] [7]
An increase in surface wettability [5, 8–11] and water permeability, a decrease in albumen adsorption
Change in pore geometry, enhance- [12–16] ment of surface wettability and water permeability, a decrease in the oligomer content in the polymer matrix PP, PS, N2, NH3, 13.56-MHz RF Etching of membrane surface layer An increase in surface wettability [17–20] PET discharge and pore surface, formation of ni- and water permeability, a decrease trogen-containing polar groups in in adsorption of proteins the surface layer PS N2, NH3, 2.45-GHz micro- Etching of membrane surface layer An increase in surface wettability [21, 22] wave discharge and pore surface, formation of ni- and water permeability, a decrease trogen-containing polar groups in in adsorption of proteins the surface layer PS NH3, Ar/NH3, O2/NH3, Etching of membrane surface layer An increase in surface wettability [23] 13.56-MHz RF discharge and pore surface, formation of po- and water permeability, a decrease lar groups in the surface layer in adsorption of proteins PVDF NH3, 13.56-MHz RF dis- Formation of polar NH2 groups in Fabrication of catalytic membranes [24, 25] charge the surface layer with surface immobilized tungsten PS, PES, H2O, 13.56-MHz RF dis- Alteration of the surface morpho- An increase in wettability and devel- [26, 27] PE charge logy and chemical structure of opment of surface roughness membrane PS CO2, 2.45-GHz microwave Alteration of the surface morphol- An increase in wettability and devel- [28] discharge ogy and chemical structure of opment of surface roughness, a demembrane crease in adsorption of proteins PS, PP CO2, 13.56-MHz RF dis- Formation of oxygen-containing An increase in wettability, a de[29, 30] charge polar groups in the surface layer crease in adsorption of proteins Note: PA is polyamide, PAN is polyacrylonitrile, PVC is poly(vinyl chloride), PS is polysulfone, PES is polyethersulfone, PP is polypropylene, PE is polyethylene, PU is polyurethane. PET is poly(ethylene terephthalate), PC is polycarbonate, PI is polyimide, PVD is poly(vinylidene fluoride), and PTFE is polytetrafluoroethylene.
microwave discharge in a nonpolymerizable gas, the etching (physical sputtering or oxidation) takes place [5–23], with the etching rate depending on the plasma gas composition. For example, the etching of the surface layer by physical sputtering is insignificant in the case of membrane treatment in an inert-gas or a hydrogen plasma [5], whereas the rate of (prevalently, oxidative) etching in a nitrogen, oxygen, or air plasma is sev-
eral times higher under identical conditions [6–16]. The etching rate depends on the discharge parameters (generally, it is proportional to the discharge power [7–9]), the nature of the polymer, and its crystallinity (the rate of etching of amorphous regions is somewhat higher because of their lower density and a higher rate of diffusion of reactive gases [8, 9]). Owing to the difference in the etching rate between the amorphous and crystalHIGH ENERGY CHEMISTRY
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Table 2. Examples of the use of plasma polymerization for modification of membrane properties Plasma gas, discharge type
Effect of plasma treatment
Cyclohexane, 13.56-MHz RF discharge Hexafluoroethane, 13.56MHz RF discharge Perfluorohexane, 13.56MHz RF discharge Acetylene/N2, 13.56MHz RF discharge Cyclohexane/N2, 13.56MHz RF discharge Acrylic acid, 2.45-GHz microwave discharge Acrylic acid, 13.56-MHz RF discharge Acrylic acid, allylamine, 13.56-MHz RF discharge
Deposition of hydrophobic hydrocarbon film Deposition of hydrophobic fluorocarbon film Deposition of hydrophobic fluorocarbon film Deposition of polymer film, nitrogen incorporation Deposition of polymer film, nitrogen incorporation Deposition of hydrophilic film containing COOH groups Deposition of hydrophilic film containing COOH groups Deposition of hydrophilic film containing COOH or NH2 groups
PET, PP, PS, PI
Allylamine, 13.56-MHz RF discharge
Deposition of hydrophilic film containing NH2 groups
PET, PS
Allylamine, butylamine, Deposition of hydrophilic film con2.45-GHz microwave dis- taining NH2 groups charge
PVDF
Diaminocyclohexane, 13.56-MHz RF discharge Acrylamide, 13.56-MHz RF discharge Dimethylaniline, 50-Hz ac discharge
Deposition of hydrophilic film containing NH2 groups Deposition of hydrophilic film
PVDF
Tetramethylsilan/NH3, 40 kHz
Deposition of hydrophilic film containing NH2 groups
PET
Allyl alcohol, 13.56-MHz RF discharge Allyl alcohol, 2.45-GHz microwave discharge
Deposition of hydrophilic film containing OH groups Deposition of hydrophilic film containing OH groups
Aniline, 50 Hz ac discharge Tiophene, 13.56-MHz RF discharge
Deposition of conducting polymer film Deposition of conducting polymer film
Membrane PET PP PC PTFE PET PET PET, PP, PS PP
PES PET
PS
PET PET
Deposition of hydrophilic film containing NH groups
line regions, the character of the surface relief changes: the surface becomes rougher. The roughness improves the adhesive properties of membranes [8–11]. As a result of etching the membrane surface layer, the pore diameter increases [7–11]. The plasma treatment of track membranes, in which pores are cylindrical channels, leads to the formation of asymmetric HIGH ENERGY CHEMISTRY
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Properties of composite membranes A decrease in wettability of the membrane surface A decrease in wettability of the membrane surface A decrease in permeability for O2 and CO2 An increase in wettability of the membrane surface Enhancement of membrane hydrodynamic properties Enhancement of membrane surface wettability An increase in surface wettability and permselectivity of membrane Controlling the membrane permeability for water by variation in pH of solution An increase in membrane surface wettability, enhancement of biocompatibility with blood Enhancement of membrane hydrodynamic properties in acidic media, a decrease in adsorption of proteins An increase in surface wettability and permselectivity A decrease in adsorption of proteins Controlling the membrane permeability for water by variation in pH of solution and pressure Fabrication of anion-exchange membrane with high permselectivity Enhancement of membrane hydrodynamic properties Enhancement of immobilization of enzymes on the membrane surface Fabrication of composite membrane with conduction asymmetry Fabrication of composite membrane with conduction asymmetry
Reference [31] [32] [33] [34] [35] [36] [37–41] [42]
[40–44]
[45–49]
[50] [51] [38, 52, 53] [54]
[55] [56]
[57] [58]
membranes owing to a change in the pore shape [12– 16]. The filtration performance considerably increases with the use of such membranes. The etching of the polymeric matrix also decreases the mass fraction of low-molecular-mass products (oligomers) in the membrane [16], as they occur on the polymer surface for the most part. Surface modification of membranes by this
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Table 3. Examples of the use of surface activation in nonpolymerizable-gas plasma followed by grafting by conventional chemical polymerization means for modification of membrane properties Membrane
Plasma gas, discharge type
PAN
Ar, 13.56-MHz RF discharge PES He, 13.56-MHz RF discharge PAN, PES Ar, 13.56-MHz RF discharge PET
Air, 13.56-MHz RF discharge PET Air, 13.56-MHz RF discharge PP, PE, PC, Ar, 13.56-MHz RF PVDF discharge PVDF, PA Ar, 13.56-MHz RF discharge
PE
Ar, 13.56-MHz RF discharge
PP, PE
Ar, 13.56-MHz RF discharge Ar, O2, 13.56-MHz RF discharge
PE
Monomer used for grafting
Properties of composite membranes
Reference
Styrene from vapor phase Hydrophobic composite membranes for purification of organic solvents N-vinyl-2-pyrrolidone Hydrophilic composite membranes with low protein adsorption Acrylic acid from vapor Hydrophilic composite membranes with imphase proved hydrodynamic properties and low protein adsorption Acrylic acid from vapor Chemical-valve chemomechanical membranes phase 2-Methyl-5-vinylpyridine Chemical-valve chemomechanical membranes from aqueous solution N-Isopropylacrylamide Temperature-responsive membranes from aqueous solution Copolymer of N-isopropy- Temperature-responsive membranes lacrylamide with butyl methacrylate from aqueous solution Glycidyl methacrylate Composite pervaporation membranes from acetone, methyl methacrylate from toluene Glycidyl methacrylate Cation-exchange membranes with high permfrom ethanol selectivity Polyelectrolytes, adsorp- Cation- and anion-exchange membranes with tion from aqueous solution high permselectivity
technique makes them applicable to filtration of organic solvents. The treatment of polymer membranes in nonpolymerizable-gas plasmas alters the chemical composition of the surface layer (Table 1). For example, the action of oxygen or air plasma leads to the formation on the surface of oxygen-containing functional groups, including carboxyl groups, which result from the oxidation of terminal groups appearing upon the rupture of chemical bonds [6–14]. The appearance of these functional groups leads to substantial hydrophilization of the membrane surface, thereby considerably improving the performance of the membranes in some applications. In the case of hydrogen or inert-gas plasma treatment, oxygen-containing groups appear largely at the sites of the formation of polymer radicals during degradation and are produced via the subsequent oxidation of the polymer after its exposure to air [5]. Treatment in nitrogen-containing plasma (N2, NH3) is accompanied by nitrogen incorporation into membrane surface layers to form nitrogen–carbon chemical bonds, along with etching and the generation of macroradicals [17–25]. Modification in water vapor [26, 27] or carbon dioxide plasma [28–30] changes both the surface morphology of the polymeric matrix and its chemical structure: oxygen-containing functional groups, in particular, carboxyl groups, are formed.
[59] [60] [61, 62]
[38] [63] [64–67] [68]
[69]
[70] [71]
When various organic vapors are used for the plasma treatment of membranes, a thin polymer film is deposited on their surface as a result of polymerization. In this case, composite membranes consisting of the porous substrate (parent membrane) and a plasmadeposited polymer layer are produced. Depending on the plasma treatment time and the pore diameter of the parent membrane, composite ultra- and nanofiltration membranes and reverse-osmosis membranes can be obtained [7, 15]. In the latter case, a thin semipermeable layer, which completely covers the pores, is deposited on the surface. The possibility for controlling the thickness of the plasma-deposited layer, which determines the elective properties of membranes, and a wide choice of organic compounds suitable for this process make this method especially promising. Note that the structure and properties of the plasma-deposited polymer layer substantially differ from those of the polymer obtained by conventional chemical polymerization processes. Macromolecules of a conventional polymer are composed of repeating units of the reactant monomer and are quite mobile in the surface layer. The polymer obtained in plasma has a highly crosslinked structure in which the mobility is retarded. This determines characteristic changes in the transport properties of plasmamodified membranes and, first of all, their permeability for water and selectivity. HIGH ENERGY CHEMISTRY
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The surface properties of composite membranes obtained via plasma modification depend on the chemical compound used (Table 2). For example, when hydrocarbons or fluorinated organic compounds are used as a plasma gas, a hard, chemically resistant polymer film without functional groups is formed [31–33]. This treatment makes it possible to prepare hydrophobic composite membranes with enhanced mechanical and chemical strengths, which are widely used in distillation processes. Plasma modification of membranes in a mixture of hydrocarbons with nitrogen leads to the incorporation of nitrogen atoms into the polymer film though the formation of nitrogen–carbon bonds [34, 35]. As a result, the membrane surface acquires the hydrophilic character. For example, the treatment of a PTFE membrane, which had an initial contact angle of θ = 126°, in an acetylene–nitrogen plasma caused a decrease in θ to 34° [34]. This significantly improved the hydrodynamic properties of the product composite membrane. Improvement in the hydrodynamic properties of a PTFE membrane was observed after the deposition of a thin polymer film onto its surface in cyclohexane–nitrogen plasma [35]. A decrease in the concentration of COOH groups on the surface did not result in a considerable decline in the water permeability of the modified membrane; thus, the volume of the filtrate was increased. When acrylic acid is used for polymer-layer deposition, hydrophilic composite membranes with a high concentration of carboxyl groups in the surface layer are formed [36–42]. The surface wettability of the membranes substantially increases in this case; in addition, membranes manufactured in this way exhibit a high cation-exchange capacity and permselectivity. During membrane treatment in allylamine, butylamine, dimethylaniline, diaminocyclohexane, or acrylamide plasma, a polymer film with nitrogen-containing functional groups (NH2, NH, etc.) is deposited on the surface [40–53]. Such composite membranes have a hydrophilic surface and are characterized by high biocompatibility with blood and a decreased protein adsorption from solutions. When a poly(vinylidene fluoride) membrane is treated in mixed tetramethylsilane– ammonia plasma, an organosilicon film containing a considerable amount of amino groups is deposited on the surface [54]. This results in a composite membrane with a high anion-exchange capacity and permselectivity. Polymer film deposition on the membrane surface in allyl alcohol plasma improves the hydrodynamic properties of the obtained hydrophilic composite membranes [55, 56]. In addition, a high concentration of hydroxyl groups in the surface layer noticeably enhances the immobilization of biologically active compounds. One of the most interesting lines of plasma modification of polymer membranes is the creation of smart (intelligent) membranes. These are the membranes whose transport properties can be controlled by varying external conditions, e.g., temperature, composition and pH of solution, pressure, electric and magnetic fields, HIGH ENERGY CHEMISTRY
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etc. Investigations in this area are of great theoretical and practical importance, since they not only make it possible to manufacture membrane with unique properties but also open opportunities for the synthesis of materials imitating biological membranes. For example, composite membranes with the pH-dependent water permeability were obtained by plasma polymerization of dimethylaniline and acrylic acid on the surface of track PET membranes [37, 38, 52, 53]. Their behavior is determined by the reversible conformational transition of macromolecules of the plasmadeposited polymer from the loose hydrated state, which decreases the pore diameter of the membranes, to the compact dehydrated state, which increases the pore diameter. It was shown that the discharge in dimethylaniline vapor leads to the formation on the membrane surface of a polymer (PPDMA) layer capable of swelling in low-pH solutions; correspondingly, the water permeability of composite membranes with the PPDMA layer is reduced in an acidic medium. In contrast, the polymer layer produced in an acrylic acid vapor discharge (PPAA) can swell in solutions with high pH values; thus, a composite membrane with a PPAA layer has a low water permeability in an alkaline medium. The introduction of iodine into the polymer layer prepared by plasma polymerization of dimethylaniline leads to the formation of the polyelectrolyte whose swelling in an acidic medium results in the complete closure of membrane pores [52, 53]. At low pressures, such a membrane is impermeable to aqueous solution. An increase in the pressure leads to the collapse of the gel; as a result, the water permeability of the modified membrane abruptly increases; i.e., the obtained composite membranes are responsive to a change in pressure. Composite membranes with unique properties were also obtained on the basis of PET track membranes via deposition of polymer layer in aniline [57] or thiophene plasma [58]. The specific feature of such membranes is the presence of two layers with antipolar conductivity. There are cation-exchanging carboxyl groups on the surface of the substrate membrane; the layer formed by plasma polymerization includes anion-active nitrogenor sulfur-containing groups when aniline or thiophene vapor, respectively, is used as a plasma gas. When these layers contact with the membrane matrix, a unique phenomenon of conductivity asymmetry kindred to the p−n transition in semiconductors is observed, which is due a change in the transfer numbers of ions upon the transition from one membrane layer to another. The membranes exhibit diode-like properties; i.e., they are capable of rectifying current and can be used for fabrication of chemical and biochemical sensors. To enhance the adhesion of the plasma-deposited polymer layer to the membrane surface, preliminary treatment in a nonpolymerizable-gas plasma resulting in the formation of polymer macroradicals in the membrane surface layer is used. For example, Toufik et al. [40] treated a PET membrane in oxygen plasma before
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the polymerization of acrylic acid and allylamine form their vapors and Hamerli et al. [45] used argon for this purpose. It was shown that this procedure is the most effective for the manufacture of composite materials on the basis of hydrophobic membranes, since it substantially increases the adhesion of the plasma-deposited polymer layer. Argon was also used for the preactivation of the PES membrane surface [51], and pretreatment in é2 plasma was used for the deposition of an organosilicon film on the PVDF membrane surface [54]. Pretreatment in oxygen plasma was used not only for the surface activation of PET track membranes [55]. It was shown that this treatment results in an asymmetric membrane with enhanced porosity. The deposition of a thin polymer layer in allyl alcohol plasma on its surface leads to the creation of an asymmetric composite membrane displaying a high water filterability over a wide pH range. The application of these membrane makes it possible to considerably increase the efficiency of filtration processes. The preliminary activation of the membrane surface in nonpolymerizable-gas plasmas is also used for the subsequent grafting of a polymer by means of the conventional polymerization techniques from the gas or liquid phase (Table 3). This is the so-called postprocess, according to which a polymer is grafted onto the membrane surface by virtue of the active sites that appear as a result of plasma treatment. Depending on the properties of the monomer, both hydrophobic composite membranes (polystyrene grafting) [59] and membrane with a hydrophilic surface poly-N-vinyl-2-pyrrolidone grafting [60] can be obtained. As a result of grafting of poly(acrylic acid) onto the surface of PES and PAN membranes, hydrophilic composite membranes [61, 62] were prepared. The use of membranes of this type in the processes of separation of biologically active substances decreases their loss during filtration. The plasma activation of the surface followed by the chemical grafting of a polymer makes it possible to prepare intelligent membranes as well. For example, we have shown that the grafting of acrylic acid [38] and poly-2-methyl-5-vinylpyridine [63] onto the surface of PET track membranes pretreated in air plasma leads to the creation of the chemomechanical “chemicalvalve”composite membranes. For example, the transition to the chemical-valve operation was observed for a membrane with a poly-2-methyl-5-vinylpyridine grafting ratio of 7.2% at pH 3: the membrane was impermeable to molecules of the solution at low pH values of the filtrate and became water-permeable at high pH values. For a membrane with a poly(acrylic acid) grafting ratio of 7.4%, the transition to the chemical-valve operation mode was observed at pH 8. The membrane was impermeable at pH > 8 and became permeable to molecules of the solution when the pH of the solution was decreased. The appearance of such a property in membranes in due to substantial swelling of the grafted
polymer layer because of the presence of charge on macromolecules. Temperature-responsive smart membranes were prepared via the grafting of poly(N-isopropylacrylamide) [64–67] or its copolymers [68] on the surface of polymer membranes after their preliminary activation in argon plasma. The principle of operation of such membranes is based on the phenomenon of phase separation (at the lower critical solution temperature) of a grafted temperature-responsive polymer due to the reversible conformational transition of macromolecules from the unfolded “coil” conformation to the compact “globule.” This process is accompanied by a decrease in the volume of the polymer grafted on the surface of the membrane or their pore walls; as a result, the water permeability of the composite membranes changes. Membranes with such properties can be used for the fabrication of chemical sensors and for controlled drug delivery in the human body. By means of plasma surface activation followed by polymer grafting via the conventional chemical process, pervaporation and ion-exchange composite membranes can be prepared. In the former case, the grafting ratio should be sufficient for complete pore closure on the membrane surface [69]; in the latter case, a hydrophilic monomer whose polymerization will yield a polymer with a high ionic capacity should be selected. For example, hydrophilic composite membranes with a moderate cation-exchange capacity and a high permselectivity were obtained as a result of poly(glycidyl methacrylate) grafting onto the surface of PP and PE membranes [70]. Greene and Tannenbaum [71] prepared cation- and anion-exchange PE-based composite membranes via adsorption of polyelectrolytes from an aqueous solution after preliminary plasma activation, thereby achieving a high permselectivity of the membranes as well. The technique of direct grafting of a polymer (polyethylene glycol, polyvinylpyrrolidone), preliminarily adsorbed on the surface of PES [72] or PP [73], in nonpolymerizable gas (nitrogen or air) plasma was used to prepare hydrophilic composite membranes. Strong immobilization of the polymer on the surface was reached in this way; as a result, the wettability of the membranes substantially increased. The surveyed examples of the use of low-temperature plasma for modification of porous polymer membranes testify that the plasma-chemical method can be successfully used for modification of their surface and structure properties, as well as for manufacture of smart membranes with unique properties. ACKNOWLEDGMENTS The work was supported by the Russian Foundation for Basic Research, project no. 08-08-12207. HIGH ENERGY CHEMISTRY
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HIGH ENERGY CHEMISTRY
Vol. 43
No. 3 2009
