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.

FORMATION AND MICROSTRUCTURE OF POLYETHYLENE MICROPOROUS MEMBRANES THROUGH THERMALLY INDUCED PHASE SEPARATION

Microporous membranes of low-high density polyethylene and their blends were prepared bythermally-induced phase separation of polymer/long-aliphatic chain alcohol (diluent) mixtures.The microstructures of this particular membrane, which depends on the diluent properties,polymer concentration and cooling rate, were observed by scanning electron microscopy.'Beehive-type,'leafy-like, and lacy porous structure morphologies can be formed,depending onthe blend composition and phase separation conditions, which were discussed by the polymer anddiluent crystallization processes.

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.

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.

PREPARATION AND CHARACTERIZATION OF PVDF-HFP MICROPOROUS MEMBRANE BY TEMPLATE METHOD

Porous poly（vinylidene fluoride-co-hexafluoropropylene） （PVDF-HFP） membranes were successfully prepared using dibutyl phthalate （DBP）, polyvinylpyrrolidone （PVP-K30）, polyethylene glycol 200 （PEG200） as templates. SEM was used to examine the morphology of the PVDF-HFP porous membranes. It was found that these membranes have an asymmetric structure and the blends of PVDF-HFP/DBP formed nanoporous membranes, whereas the blends of PVDF- HFP/PVP-K30 formed ＂sponge-like＂ and microporous membranes. Moreover, the average pore size and porosity was about 0.3 μm and 48.7%, respectively. The crystallinity, thermal stability and mechanical strength of membranes were characterized by XRD, DSC, TGA and stress-strain tests. The results showed that the membranes are a crystals with excellent thermal stability. It was an effective way to regulate pore size and morphology of the PVDF-HFP membranes.

THEORETICAL EFFECTS OF MOLECULAR DIMENSION AND CONFIGURATION ON EFFECTIVE DIFFUSION COEFFICIENT OF MACROMOLECULES IN MICROPOROUS MEMBRANES

This paper presents a theoretical method for predicting the effective diffusion coefficient of macromolecules in the microporous membrfines in view of the effects of molecular dimension and configuration. On the basis of the hindered diffusion theory of spherical neutral macromolecules in a micropore of a long cylinder, the effects of molecular dimension and configuration are studied by defining two molecular dimensions:the mean projected radius to predict the concentration partition and the ' hydrodynamically equivalent sphere' radius to evaluate the hydrodynamic reverse drag force. The quantitative comparison shows that the effective diffusion coefficients for different macromolecules predicted by the present method are more consistent with the available published experimental data.

PREPARATION OF EVOH MICROPOROUS MEMBRANES via THERMALLY INDUCED PHASE SEPARATION USING BINARY SOLVENTS

Microporous ethylene-vinyl alcohol copolymer （EVOH） flat membranes and hollow-fiber membranes with 38 mol% ethylene content were prepared via thermally induced phase separation （TIPS） using the mixture of 1,4-butanediol and poly（ethylene glycol）（PEG400） as diluents. Effects of the ratio of 1,4-butanediol to PEG400 on the phase diagrams, phase separation mechanism and membrane morphology were studied by small angle light scattering （SALS） measurements, differential scanning calorimetry （DSC）, and scanning ele~：tron microscopy （SEM）. It was found that by varying the composition of the binary solvent, the phase diagrams and membrane morphology can be controlled successfully. Moreover, the phase diagrams showed that broader regions of Liquid-Liquid （L-L） phase separation were obtained, as well as closer distances between L-L phase separation lines and Solid-Liquid （S-L） phase separation lines, Interconnected structures observed both in the flat membrane and hollow fiber membrane consist with the above results.

In situ Synthesis of Oligonucleotides on Plasma Treated Polypropylene Microporous Membrane

Polypropylene microporous membranes were treated with plasma in a mixture of N2 and H2 (1:2 in volume). Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FT1R), X-ray photoelectron spectroscopy (XPS) and ultra-violet (UV) spectra demonstrated the success of grafting amino groups. The density of the polar amino groups on the membrane surface is about 0.59 μmol/cm2. The as-treated membranes were successively applied to the in situ synthesis of oligonucleotides and an average coupling yield was more than 98%. The surface feature of the treated membrane is suggested to be responsible for its advantage over a glass slide.

Influence of Heat-setting Temperature on the Microporous Structure and Properties of PP/HDPE Bilayer Microporous Membranes

Due to the mechanical stability of PP layer,the PP/HDPE double-layer microporous mem brane could be prepared at a higher heat-setting temperatu re than that of PE monolayer membrane.In this work,the effects of heat-setting temperature on the pore structure and properties of PP/HDPE dou ble-layer membrane were studied.With the increase of heat-setting temperature from 120℃to 130℃,the length of connecting bridge crystal and crystallinity in the PE layer increase due to the melting of thin lamellae and the stability of connecting bridge structure during heat-setting.The corresponding air permeability,po rosity,wetta bility of liquid electrolyte and mechanical property of the heat-set microporous membrane increase,exhibiting better electrochemical performance.However,when the heat-setting temperature is further increased to 140℃,higher than the melting point of PE resin,some pores are closed since the lamellae and connecting bridges melt and shrink during heat-setting,resulting in a decrease of air permeability and porosity.In contrast,there is negligible change in the PP layer within the above heat-setting temperature region.This study successfully builds the relationship between the stable pore structure and property of microporous membrane during heat-setting,which is helpful to guide the production of high-pe rformance PP/PE/PP lithium batteries separator.

Effect of Fumed SiO_2 on Pore Formation Mechanism and Various Performances of β-iPP Microporous Membrane Used for Lithium-ion Battery Separator

In this work, four samples containing different contents of fumed SiO_2 were prepared to improve the pore size distribution and various properties of b nucleated isotatic polypropylene（b-i PP） biaxial membrane used for lithium-ion battery separator. The wide-angle X-ray diffraction（WAXD） and differential scanning calorimetry（DSC） results show that the fumed SiO_2 promotes the formation of b-crystal slightly and narrows down the thickness distribution of b-lamellae; meanwhile, evenly distributed SiO_2 within b-i PP can be inspected by scanning electron microscopy（SEM）. Moreover, further detailed characterization of morphological evolutions during biaxial stretching by tensile testing and SEM manifests that SiO_2 can strengthen b-i PP and make the samples deform more homogeneously, resulting in a gradually elaborate and finer oriented microfibril structure after longitudinal stretching, in which more uniform defects distribute between fibrils and restrain the formation of coarse fibrils effectively. Therefore, more superior microporous structure emerges with the addition of SiO_2, accompanied by narrower pore size distribution and better connectivity between microvoids, which is confirmed by mercury porosimeter and diminished Gurley value. Moreover, the lower thermal shrinkage, decreased shrinkage rate and suppressed porosity reduction indicate that fumed SiO_2 improves thermal and dimensional stability of membrane dramatically. Furthermore, due to the excellent wettability of SiO_2 with electrolyte, the microporous membranes doped with SiO_2 have higher electrolyte uptake, even after heat treatment at elevated temperature.

MICROPOROUS PVDF-HFP-BASED POLYMER MEMBRANES FORMED FROM SUPERCRITICAL CO_2 INDUCED PHASE SEPARATION

Microporous poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)membranes following supercritical CO_2 induced phase separation process were prepared using four solvents.The solid electrolytes of PVDF-HFP were formed by microporous PVDF-HFP membranes filled and swollen by a liquid electrolyte.The effect of the solvents on the morphology and structure,electrolyte absorptions and lithium ionic conductivity of the activated membranes were investigated.It was approved that all the membrane had the similar...

Inorganic microporous membranes for hydrogen separation:Challenges and solutions

Porous membrane separation is a competitive hydrogen purification technology due to the advantages of environmental friendliness,energy-saving,simple operation,and low cost.Benefiting from the booming development of materials science and chemical science,great progress has been made in H_(2) separation with porous membranes.This review focuses on the latest advances in the design and fabrication of H_(2) separation inorganic microporous membranes,with emphasis on the synthetic strategies to achieve structural integrity,continuity and stability.This review starts with a brief introduction to the membrane separation mechanisms,followed by an elaboration on the synthetic challenges and corresponding solutions of various high-performance inorganic microporous membranes based on zeolites,silica,carbon,and metal-organic frameworks(MOFs).At last,by highlighting the prospects of ultrathin two-dimensional(2D)porous membranes,we wish to shed some light on the further development of new materials and membranes for highly efficient hydrogen separation.

Synthesis of microporous membranes and films on various substrates by novel electrospinning method

The introduction of electrospinning technique in synthesis of supported microporous membranes and films opens bright pro- spects for mass production and practical applications. This novel and promising strategy has wide suitable range for various substrates with the possibility of large-area processing. We successfully synthesized several kinds of microporous materials into high quality membranes and films on different shaped supports by this method, such as zeolite NaA and pure-silica-zeolite Beta membranes on porous A1203 tube, zeolite NaY membrane on stainless steel net and a metal-organic framework Eu（BTC）（H20） DMF （JUC-32） film on porous silica disc. X-ray diffraction （XRD） and scanning electron microscopy （SEM） were used as characterization means. The results verified the effectiveness of this new approach in fabrication of membranes and films.

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.

Gas separation using sol–gel derived microporous zirconia membranes with high hydrothermal stability

A microporous zirconia membrane with hydrogen permeance about 5 × 10-8mol·m-2·s-1·Pa-1, H2/CO2 permselectivity of ca. 14, and excellent hydrothermal stability under steam pressure of 100 k Pa was fabricated via polymeric sol–gel process. The effect of calcination temperature on single gas permeance of sol–gel derived zirconia membranes was investigated. Zirconia membranes calcined at 350 °C and 400 °C showed similar single gas permeance, with permselectivities of hydrogen towards other gases, such as oxygen, nitrogen, methane, and sulfur hexa fluoride, around Knudsen values. A much lower CO2permeance（3.7 × 10-9mol·m-2·s-1·Pa-1）was observed due to the interaction between CO2 molecules and pore wall of membrane. Higher calcination temperature, 500 °C, led to the formation of mesoporous structure and, hence, the membrane lost its molecular sieving property towards hydrogen and carbon dioxide. The stability of zirconia membrane in the presence of hot steam was also investigated. Exposed to 100 k Pa steam for 400 h, the membrane performance kept unchanged in comparison with freshly prepared one, with hydrogen and carbon dioxide permeances of 4.7 × 10-8and ~ 3 × 10-9mol·m-2·s-1·Pa-1, respectively. Both H2 and CO2permeances of the zirconia membrane decreased with exposure time to 100 k Pa steam. With a total exposure time of 1250 h, the membrane presented hydrogen permeance of 2.4 × 10-8mol·m-2·s-1·Pa-1and H2/CO2 permselectivity of 28, indicating that the membrane retains its microporous structure.

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.

Effect of sol size on nanofiltration performance of a sol-gel derived microporous zirconia membrane

This paper reports the effect of sol size on nanofiltration performances of sol–gel derived microporous zirconia membranes. Microstructure, pure water flux, molecular weight cut-off(MWCO) and salt retention of zirconia membranes derived from zirconia sols with different sizes were characterized. Thermal evolution, phase composition, microstructure and chemical stability of unsupported zirconia membranes(powder) were determined by thermogravimetric and differential thermal analysis, X-ray diffraction, nitrogen adsorption–desorption and static solubility measurements. Results show that nanofiltration performance of zirconia membranes is highly dependent on sol size. The sol with an average size of 3.8 nm, which is smaller than the pore size of the γ-Al2O3support(pore size: 5–6 nm), forms a discontinuous zirconia separation layer because of excessive penetration of sol into the support. This zirconia membrane displays a MWCO value towards polyethylene glycol higher than 4000 Da. A smooth and defect-free zirconia membrane with a MWCO value of 1195 Da(pore size: 1.75 nm) and relative high retention rates towards Mg Cl2(76%) and Ca Cl2(64%) was successfully fabricated by dip-coating the sol with an appropriate size of 8.6 nm. Zirconia sol with an average size of 12 nm exhibits colloidal nature and forms a zirconia membrane with a MWCO value of 2332 Da(pore size: 2.47 nm). This promising microporous zirconia membrane presents sufficiently high chemical stability in a wide p H range of 1–12.

Surface Functionalization of Microporous Polypropylene Membrane with Polyols for Removal of Boron Acid from Aqueous Solution

Affinity membranes are fabricated for boric acid removal by the surface functionalization of microporous polypropylene membrane(MPPM)with lactose-based polyols.The affinity is based on specific complexation between boric acid and saccharide polyols.A photoinduced grafting-chemical reaction sequence was used to prepare these affinity membranes.Poly(2-aminoethyl methacrylate hydrochloride)[poly(AEMA)]was grafted on the surfaces of MPPM by UV-induced graft polymerization.Grafting in the membrane pores was visualized by dying the cross-section of poly(AEMA)-grafted MPPM with fluorescein disodium and imaging with confocal laser scanning microscopy.It is concluded that lactose ligands can be covalently immobilized on the external surface and in the pores by the subsequent coupling of poly(AEMA)with lactobionic acid(LA).Physical and chemical properties of the affinity membranes were characterized by field emission scanning electron microscopy and Fourier Transform Infrared/Attenuated Total Refraction spectroscopy(FT-IR/ATR).3-Aminophenyl boric acid(3-APBA)was removed from aqueous solution by a single piece of lactose-functionalized MPPM in a dynamic filtration system.The results show that the 3-APBA removal reaches an optimal efficiency(39.5%)under the alkaline condition(pH9.1),which can be improved by increasing the immobilization density of LA.Regeneration of these affinity membranes can be easily realized through acid-base washing because the complexation of boric acid and saccharide polyol is reversible.