A Comparative Study of Hydrophilic Modification of Polypropylene Membranes by Remote and Direct Ar Plasma

Surface modification of polypropylene membrane by argon （Ar） plasma-induced graft polymerization with hydrophilic monomer [acrylic acid （AA） in this work] was investigated. It was found that both the distance of the membrane from the Ar plasma center and the plasma power had a strong influence on the surface modification, hydrophilieity and graft yield （GY） of the treated membrane. Results suggest that remote plasma treatment with a proper sample position, plasma power and graft polymerization leads to a membrane surface with not only less damage, but also more permanent hydrophilicity, than direct plasma treatment does. By analyzing the morphology and the chemical composition of the membrane surface by scanning electron microscopy （SEM） and X-ray photoelectron spectroscopy （XPS）, as well as Fourier transform infrared attenuated total reflection spectroscopy （FTIR-ATR） respectively, a possible mechanism was tentatively revealed.

Plasma Modified Polypropylene Membranes as the Lithium-Ion Battery Separators

To reduce the thermal shrinkage of the polymeric separators and improve the safety of the Li-ion batteries,plasma treatment and plasma enhanced vapor chemical deposition（PECVD）of SiO_x-like are carried out on polypropylene（PP）separators,respectively.Critical parameters for separator properties,such as the thermal shrinkage rate,porosity,wettability,and mechanical strength,are evaluated on the plasma treated PP membranes.O_2 plasma treatment is found to remarkably improve the wettability,porosity and electrolyte uptake.PECVD SiO_x-like coatings are found to be able to effectively reduce the thermal shrinkage rate of the membranes and increase the ionic conductivity.The electrolyte-philicity of the Si Ox-like coating surface can be tuned by the varying O_2 content in the gas mixture during the deposition.Though still acceptable,the mechanical strength is reduced after PECVD,which is due to the plasma etching.

SURFACE MODIFICATION OF MICROPOROUS POLYPROPYLENE MEMBRANES BY GRAFT POLYMERIZATION OF N,N-DIMETHYLAMINOETHYL METHACRYLATE

Surface modification of microporous polypropylene hollow fiber membranes was performed by radical-induced graft polymerization of N,N-dimethylaminoethyl methacrylate (DMAEMA). The influences of temperature, monomer concentration and pre-adsorbed amount of benzoyl peroxide on grafting degree were studied respectively. It was found that the appropriate graft temperature was 75 'C, at which the grafting degree was the highest and the hydrolytic decomposition of DMAEMA the lowest. Scanning electron photomicrography and the average pore diameters of the modified membranes demonstrated that part of the micropores on the membrane surface was plugged by the grafted polyDMAEMA chains, especially at high grafting degree. Contact angle and water swelling experiments showed that a moderate grafting degree could improve the hydrophilicity of the membranes. In the range of 11.3%-12.0% grafting degree, the water swelling percentage reached its maximum (51.1%) and the contact angle reached its minimum (74 degrees). The bovine serum albumin (BSA) adsorption experiment indicated that the grafted polyDMAEMA had a dual effect on protein adsorption. At the first stage, the BSA adsorption decreased with increasing of DMAEMA grafting degree. As the interaction between BSA and polyDMAEMA on membrane surface increased, the BSA adsorption increased with increasing of DMAEMA grafting degree.

INTERACTION BETWEEN THE SURFACE GLYCOSYLATED POLYPROPYLENE MEMBRANE AND LECTIN

A glycopolymer bearing glucose residues was tethered onto the surface of polypropylene microporous membrane by UV-induced graft polymerization ofα-allyl glucoside.Concanavalin A (Con A),a glucose recognizing lectin,could be specifically adsorbed to the membrane surface.On the other hand,the membrane surface showed no recognition ability to another lectin peanut agglutinin.Moreover,the recognition complex between the glycosylated membrane surface and Con A could be inhibited by glucose and mannose solution.T...

A polypropylene melt-blown strategy for the facile and efficient membrane separation of oil-water mixtures

Porous materials with selective wettability and permeability have significant importance in oil-water separation,but complex fabrication processes are typically required to obtain the desired structures with suitable surface chemistry.In this work,an industrial melt-blown strategy that utilized commercially available polypropylene(PP)was used for the large-scale fabrication of superhydrophobic/superoleophilic membranes with staggered fabric structures.These membranes could readily separate different oils including pump oil and crude oil from various aqueous solutions such as strongly acidic,alkaline,and saline media.In addition,the separation efficiencies of these membranes exceeded 99%,and they could remain functional even after exposure to corrosive media.We anticipate that this work will further the design of membranes and enhance their applicability in oil-water separation,and provide researchers and engineers with a more effective tool for performing challenging separations and mitigating pollution.

Mussel-inspired Modification of Microporous Polypropylene Membranes for Functional Catalytic Degradation

In this manuscript, an easy method of anchoring Au nanoparticles onto a polypropylene （PP） membrane to prepare a composite Au-PP membrane with catalytic activity was demonstrated. The surface of the PP membrane was first modified with a primary amine by mussel-inspired dopamine polymerization. Then, the modified PP membrane was used to reduce chloroauric acid to anchor Au nanoparticles onto the surface, forming a Au-PP membrane. The surface morphology and composition of the modified PP membrane were characterized with SEM, ATR-FTIR and XPS. The catalytic activity of the Au-PP membrane was also evaluated by the degradation of a model dye solution of methylene blue. The fabricated membrane shows excellent catalytic performance, and the catalytic activity can be effectively regenerated.

Grafting Branch Length and Density Dependent Performance of Zwitterionic Polymer Decorated Polypropylene Membrane

Branch length and density have critical effects on membrane performances; however, it is regarded to be traditionally difficult to investigate the relationship due to the uncontrolled membrane modification methods. In this study, zwitterionic polymer with controlled grafting branch chain length（degree of polymerization） and grafting density（grafting chains per membrane area） was tethered to the microporous polypropylene membrane surface based on the combination of reversible addition-fragmentation chain transfer（RAFT） polymerization technique with click reaction. The modified membranes were tested by filtrating protein dispersion to highlight the correlations of branch chain length and grafting density with the membrane permeation performances. The pure water flux, the flux recovery ratio are positively and significantly, and the irreversible fouling negatively and significantly correlated with grafting density. These results demonstrate that the larger the coverage of the membrane with poly{[2-（methacryloyloxy）ethyl]-dimethyl-（3-sulfopropyl） ammonium hydroxide}（PMEDSAH）, the higher the pure water flux and the higher the flux recover ratio, and the lower the irreversible fouling, which shows that high grafting density is favorable to fouling reducing.

TiO_(2) Coated Polypropylene Membrane by Atomic Layer Deposition for Oil-Water Mixture Separation

Polypropylene(PP)membrane has been widely used in water purification and other fields owing to special pore structure,excellent mechanical properties and resistance to acids,alkalis and organic solvents.However,it is difficult for PP to introduce the hydrophilic chemical compositions for oil-water separation.Herein,superhydrophilic and underwater superoleophobic PP membranes were prepared by ALD for efficient gravity-driven oil-water separation.Owing to synergistic effect,oil contact angle of TiO_(2) coated PP membrane under water can reach above 150°.Hence,TiO_(2) coated PP membrane has great oil-repelling performance.Because of the superwetting property,TiO_(2) coated PP membrane can easily separate oil-water mixture and have high separation efficiency(more than 95%).The outstanding recyclability and mechanical stability of TiO_(2) coated PP membrane suggest the promising potential application in practical oil-water separation.

Improvement of antifouling characteristics in a bioreactor of polypropylene microporous membrane by the adsorption of Tween 20

Surface modification by physical adsorption of Tween 20 was accomplished on polypropylene microporous membranes （PPMMs）. Attenuated total reflection-Fourier transform infrared spectroscopy （ATR/FT-IR） and field emission scanning electron microscope （FE- SEM） were used to characterize the chemical and morphological changes on the membrane surfaces. Water contact angles and relative pure water fluxes were measured. The data showed that the hydrophilic performance for the modified membranes increased with the increase in the adsorption amount of Tween 20 onto the surface or into the pores of polypropylene microporous membranes. To test the antifouling property of the membranes by the adsorption of Tween 20 in a membrane bioreactor （MBR）, filtration for active sludge was performed using synthetic wastewater. With the help of the data of water fluxes and the FE-SEM photos of the modified PPMMs before or after operating in a MBR for about 12 d, the PPMMs with monolayer adsorption of Tween 20 showed higher remained flux and stronger antifouling ability than unmodified membrane and other modification membranes studied.

Surface Modification of Polypropylene Microporous Membrane by Atmospheric-pressure Plasma Induced N-vinyl-2-pyrrolidone Graft Polymerization

Membrane surfaces modified with poly（N-vinyl-2-pyrrolidone） （PNVP） can be endowed with hydrophilicity, biocompatibility and functionality. In this work, atmospheric pressure dielectric barrier discharge plasma graft polymerization of N-vinyl-2-pyrrolidone （NVP） onto polypropylene （PP） microporous membrane surface was studied. The experimental results reveal that plasma treatment conditions, such as discharge power, treatment time and adsorbed NVP amount, have remarkable effects on the grafting degree of NVP. Structural and morphological changes on the membrane surfaces were characterized by attenuated total reflection-Fourier transform infrared spectroscopy （FT-IR/ATR）, X-ray photoelectron spectroscope （XPS） and field emission scanning electron microscopy （FE-SEM）. Water contact angles of the membrane surfaces were also measured by the sessile drop method. Water contact angles on the membrane surfaces decrease with the increase of NVP grafting degree, which indicates an enhanced hydrophilicity for the modified membranes. The effects of grafting degrees on pure water fluxes were also measured. It is shown that pure water fluxes increase with grafting degree firstly and then decrease adversely. Finally, filtration of bovine serum albumin （BSA） solution and platelets adhesion of the PNVP modified membranes show good protein resistance and potential biocompatibility due to the enhancement of surface hydrophilicity.

SURFACE MODIFICATION OF POLYPROPYLENE MICROPOROUS MEMBRANES BY THE ADSORPTION OF NON-IONIC SURFACTANTS

Surface modification by physical adsorption of a series of non-ionic surfactants including Tween 20, Tween 40, Tween 60, Tween 80 and Tween 85, was accomplished on polypropylene microporous hollow fiber and flat membranes. The adsorption curve of the membrane surface was analyzed by weight measurements and the typical results showed a twoplatform character similarly. Differences in the degree and curve shape of adsorption resulting from such factors as concentration, temperature, as well as water cleaning time were observed for Tween 85 among other Tweens. Attenuated total reflection - Fourier transform infrared spectroscopy analysis and field emission scanning electron microscopy observation showed that the adsorption of Tween on polypropylene microporous membrane （PPMM） is effective and occurs mainly in the pores of PPMMs at low adsorption amount, and on the membrane surface also at high adsorption value.

SURFACE MODIFICATION OF POLYPROPYLENE MICROPOROUS MEMBRANE BY TETHERING POLYPEPTIDES

Two kinds of polypeptides were tethered onto the surface of polypropylene microporous membrane （PPMM） through a ring opening polymerization of L-glutamate N-carboxyanhydride initiated by amino groups which were introduced by ammonia plasma and y-aminopropyl triethanoxysilane treatments. X-ray photoelectron spectroscopy （XPS）, attenuated total reflectance Fourier transform infrared spectroscopy （FT-IR/ATR）, scanning electron microscopy （SEM）, together with water contact angle measurements were used to characterize the modified membranes. XPS analyses and FT-IR/ATR spectra demonstrated that polypeptides are actually grafted onto the membrane surface. The wettability of the membrane surface increases at first and then decreases with the increase in grafting degrees of polypeptide. Platelet adhesion and murine macrophage attachment experiments reveal an enhanced hemocompatibility for the polypeptide modified PPMMs. All these results give evidence that polypeptide grafting can simultaneously improve the hemocompatibility as well as reserve the hydrophobicity for the membrane, which will provide a potential approach to improve the performance of polypropylene hollow fiber microporous membrane used in artificial oxygenator.

Surface Modification of Polypropylene Microporous Membrane by Atmospheric-Pressure Plasma Immobilization of N,N-dimethylamino Ethyl Methacrylate

Surface modification of polypropylene microporous membrane （PPMM） was performed by atmospheric pressure dielectric barrier discharge plasma immobilization of N,Ndimethylamino ethyl methacrylate （DMAEMA）. Structural and morphological changes on the membrane surface were characterized by attenuated total reflection-Fourier transform infrared spectroscopy （FT-IR/ATR）, X-ray photoelectron spectroscope （XPS） and field emission scanning electron microscopy （FE-SEM）. Water contact angles of the membrane surfaces were also measured by the sessile drop method. Results reveal that both the plasma-treating conditions and the adsorbed DMAEMA amount have remarkable effects on the immobilization degree of DMAEMA. Peroxide determination by 1,1-diphenyl-2-picrvlhydrazyl （DPPH） method verifies the exsistence of radicals induced by plasma, which activize the immobilization reaction. Pure water contact angle on the membrane surface decreased with the increase of DMAEMA immobilization degree, which indicates an enhanced hydrophilicity for the modified membranes. The effects of immobilization degrees on pure water fluxes were also measured. It is shown that pure water fluxes first increased with immobilization degree and then decreased. Finally, permeation of bovine serum albumin （BSA） and lysozyme solution were measured to evaluate the antifouling property of the DMAEMA-modified membranes, from which it is shown that both hydrophilicity and electrostatic repulsion are beneficial for membrane antifouling.

Enhancement of the flux for polypropylene hollow fiber membrane in a submerged membrane-bioreactor by surface modification

To improve its limiting flux and antifouling characteristics in a submerged membrane-bioreactor （SMBR） for wastewater treatment, polypropylene hollow fiber microporous membrane （PPHFMM） was surface-modified by the plasma-induced immobilization of poly （N-vinyl-2-pyrrolidone） （PVP） and the plasma treatment with different gases respectively. Attenuated total reflection-Fourier transform infrared spectroscopy （FT-IR/ATR）, X-ray photoelectron spectroscopy （XPS） and field emission scanning electron microscope （FE-SEM） were used to characterize the structural and morphological changes on the membrane surface. Water contact angle was measured by the sessile drop method. It was found that the water contact angle was 128.8, 72.3, 62.7, 74.4, 79.1, 86.3, and 71.3° for the nascent, PVP-immobilized, air, 02, Ar, CO2 and H2O plasma treated PPHFMM, respectively. The SMBR was operated at fixed transmembrane pressure to determine the limiting flux for the PPHFMM before and after surface modification. Results showed that the limiting flux appeared to be 103, 159, 117, 133, 136, 121 and 152 L/（m^2· h） for the nascent, PVP-immobilized, air, O2, At, CO2 and H2O plasma treated PPHFMM, respectively. After continuous operation for about 50 h in the SMBR, the antifouling characteristics were improved to some extent.

Fabrication of Microporous Membranes from Melt Extruded Polypropylene Precursor Films via Stretching: Effect of Annealing

In this work, the effects of annealing conditions on the microstructure of polypropylene（PP） precursor films and further on the porous structure and permeability of stretched membranes were investigated. Combinations of WAXD, FTIR, DSC and DMA results clearly showed the crystalline orientation and crystallinity of the precursor film increased with annealing temperature, while the molecular chain entanglements in the amorphous phase decreased. Changes in the deformation behavior suggested more lamellar separation occurred for the films annealed at higher temperatures. Surface morphologies of the membranes examined by SEM revealed more pore number and uniform porous structure as the annealing temperature increased. In accordance with the SEM results, the permeability of the membranes increased with annealing temperature. On the other hand, it was found that 10 min was almost enough for the annealing process to obtain the microporous membranes with an optimal permeability.

Preparation and characterization of antibacterial microporous membranes fabricated by poly(AMS-co-DMAEMA)grafted polypropylene via melt-stretching method

Polypropylene microporous membranes are typical hydrophobic separation membranes, but the high hydrophobicity and lack of functionality easily cause bacterial adhesion, thus inducing membrane pollution. Poly（AMS-co-DMAEMA） （PAD） was designed and synthesized by copolymerization of a-methyl styrene （AMS） and functional monomer 2-（dimethylamino）ethyl methacrylate （DMAEMA）, and then grafted onto PP chains by melt blending. Microporous membranes of blended PP containing different contents of PAD are made by casting and stretching, and the polycation microporous membrane is then obtained via quaternization. The permeability and porosity of the microporous membrane achieve the best when the grafting efficiency reaches 42.16%, and the hydrophilicity of the microporous membrane is improved. The results show that the modified membranes fabricated in this method have good antibacterial properties.