PREPARATION OF HIGH DENSITY POLYETHYLENE/POLYETHYLENE-ΒLOCK- POLY(ETHYLENE GLYCOL) COPOLYMER BLEND POROUS MEMBRANES VIA THERMALLY INDUCED PHASE SEPARATION PROCESS AND THEIR PROPERTIES

High density polyethylene (HDPE)/polyethylene-Wock-poly(ethylene glycol) (PE-b-PEG) blend porous membranes were prepared via thermally induced phase separation (TIPS) process using diphenyl ether (DPE) as diluent. The phase diagrams of HDPE/PE-b-PEG/DPE systems were determined by optical microscopy and differential scanning calorimetry (DSC). By varying the content of PE-b-PEG, the effects of PE-b-PEG copolymer on morphology and crystalline structure of membranes were studied by scanning electron microscopy (SEM) and wide angle X-ray diffraction (WAXD). The chemical compositions of whole membranes and surface layers were characterized by elementary analysis, Fourier transform infrared spectroscopy-attenuated total reflection (FTIR-ATR) and X-ray photoelectron spectroscopy (XPS). Water contact angle, static protein adsorption and water flux experiments were used to evaluate the hydrophilicity, antifouling and water permeation properties of the membranes. It was found that the addition of PE-b-PEG increased the pore size of the obtained blend membranes. In the investigated range of PE-b-PEG content, the PEG blocks could not aggregate into obviously separated domains in membrane matrix. More importantly, PE-b-PEG could not only be retained stably in the membrane matrix during membrane formation, but also enrich at the membrane surface layer. Such stability and surface enrichment of PE-b-PEG endowed the blend membranes with improved hydrophilicity, protein absorption resistance and water permeation properties, which would be substantially beneficial to HDPE membranes for water treatment application.     

Improving hydrophilicity and protein resistance of poly(vinylidene fluoride) membranes by blending with amphiphilic hyperbranched-star polymer

To endow hydrophobic poly(vinylidene fluoride) (PVDF) membranes with reliable hydrophilicity and protein resistance, an amphiphilic hyperbranched-star polymer (HPE-g-MPEG) with about 12 hydrophilic arms in each molecule was synthesized by grafting methoxy poly(ethylene glycol) (MPEG) to the hyperbranched polyester (HPE) molecule using terephthaloyl chloride (TPC) as the coupling agent and blended with PVDF to fabricate porous membranes via phase inversion process. The chemical composition changes of the membrane surface were confirmed by X-ray photoelectron spectroscopy (XPS), and the membrane morphologies were measured by scanning electron microscopy (SEM). Water contact angle, static protein adsorption, and filtration experiments were used to evaluate the hydrophilicity and anti-fouling properties of the membranes. It was found that MPEG segments of HPE-g-MPEG enriched at the membrane surface substantially, while the water contact angle decreased as low as 49 degrees for the membrane with a HPE-g-MPEG/PVDF ratio of 3/10. More importantly, the water contact angle of the blend membrane changed little after being leached continuously in water at 60 degrees C for 30 days, indicating a quite stable presence of HPE-g-MPEG in the blend membranes. Furthermore, the blend membranes showed lower static protein adsorption, higher water and protein solution fluxes, and better water flux recovery after cleaning than the pure PVDF membrane.     

An efficient nanofiltration membrane based on blending of polyethersulfone with modified (styrene/maleic anhydride) copolymer

In this study, styrene–maleic anhydride (SMA) copolymer was modified by ring opening reaction of its anhydride groups with diethanolamine (DEA). The modified SMA copolymer was blended in different concentrations (2.5, 4 and 5.5 %) with Polyethersulfone (PES) to improve the hydrophilicity of PES membranes and the corresponding blend membrane was prepared through phase inversion. The influence of SMA copolymer on morphology, mechanical properties, water flux, rejection and anti-fouling properties of blend membrane were investigated. The modified SMA and their composition were confirmed by FT-IR and ¹HNMR techniques. The asymmetric structure of membrane was revealed by SEM. The water flux and contact angle results show that the hydrophilicity of membrane surface was increased by addition of SMA copolymer. The better anti-fouling properties of the PES/modified SMA blend membranes in comparison with the PES membrane also confirmed that the hydrophilicity of blend membrane enhances.     

Improving the properties of HDPE based separators for lithium ion batteries by blending block with copolymer PE-b-PEG

To improve the performances of HDPE-based separators, polyether chains were incorporated into HDPE membranes by blending with poly(ethylene-block-ethylene glycol) (PE-b-PEG) via thermally induced phase separation (TIPS) process. By measuring the composition, morphology, crystallinity, ion conductivity, etc, the influence of PE-b-PEG on structures and properties of the blend separator were investigated. It was found that the incorporated PEG chains yielded higher surface energy for HDPE separator and improved affinity to liquid electrolyte. Thus, the stability of liquid electrolyte trapped in separator was increased while the interfacial resistance between separator and electrode was reduced effectively. The ionic conductivity of liquid electrolyte soaked separator could reach 1.28 × 10-3 S.cm-1 at 25℃, and the electrochemical stability window was up to 4.5 V (versus Li + /Li). These results revealed that blending PE-b-PEG into porous HDPE membranes could efficiently improve the performances of PE separators for lithium batteries.     

Remarkable reduction of irreversible fouling and improvement of the permeation properties of poly(ether sulfone) ultrafiltration membranes by blending with pluronic F127

Hydrophilic modification of ultrafiltration membranes was achieved through blending of Pluronic F127 with poly(ether sulfone) (PES). The chemical composition and morphology changes of the membrane surface were confirmed by water contact angle, X-ray photoelectron spectroscopy, scanning electron microscopy, and protein adsorption measurements. The decreased static water contact angle with an increase in the Pluronic F127 content indicated an increase of surface hydrophilicity. XPS analysis revealed enrichment of PEO segments of Pluronic F127 at the membrane surface. The apparent protein adsorption amount decreased significantly from 56.2 to 0 microg/cm(2) when the Pluronic F127 content varied from 0% to 10.5%, which indicated that the blend membrane had an excellent ability to resist protein adsorption. The ultrafiltration experiments revealed that the Pluronic F127 content had little influence on the protein rejection ratio and pure water flux. Most importantly, at a high Pluronic F127 content membrane fouling, especially irreversible fouling, has been remarkably reduced. The flux recoveries of blend membranes reached as high as 90% after periodic cleaning in three cycles.     

木质素磺酸钠改性聚砜膜的制备及其在正渗透膜中的应用

采用木质素磺酸钠作为亲水添加剂,通过浸没沉淀相转化法制备了木质素磺酸钠共混改性聚砜膜,以改善聚砜膜的亲水性,并用作正渗透膜的支撑层,以降低内浓差极化效应.利用扫描电子显微镜、衰减全反射傅里叶变换红外光谱仪、水接触角仪等研究了不同木质素磺酸钠添加量对聚砜膜的结构和表面性质的影响.结果表明,添加木质素磺酸钠后,聚砜膜的指状孔变得规整且狭长.水接触角实验证实添加木质素磺酸钠能改善聚砜膜的亲水性,当木质素磺酸钠含量为0.4 wt%时,聚砜膜的表面水接触角可降低至65°.正/反渗透测试装置分别用于表征正渗透膜的传质性质和结构参数.结果表明,以0.4 wt%木质素磺酸钠改性聚砜膜为支撑层的正渗透膜的水渗透性能(A=3.12×10~(-5) LMH×Pa~(-1))优于纯聚砜基底正渗透膜(0.76×10~(-5)LMH×Pa~(-1)),而且前者的结构参数(S=2010mm)远小于后者(3450mm),说明木质素磺酸钠改性聚砜膜有效弱化了正渗透膜的内浓差极化效应.     

Preparation and characterisation of novel polysulfone membranes modified with Pluronic F-127 for reducing microalgal fouling

In this study, hydrophilic and fouling-resistant polysulfone (PS) membranes were fabricated using the phase inversion method to reduce membrane fouling caused by microalgal culture. The Pluronic F-127 polymer, which is used as a hydrophilic co-polymer, was added to the membranes to improve the membrane properties. Characteristic specifications of the fabricated membranes, such as morphology, surface roughness, chemical structures and hydrophobicity/hydrophilicity, were studied using scanning electron microscopy, atomic force microscopy (AFM), energy-dispersive X-ray spectroscopy (EDS), attenuated total reflection-fourier infrared (ATR-FTIR) spectroscopy and contact angle devices. According to the results obtained, it was observed that, with the increase of the Pluronic F-127 concentration in the membranes, the surface roughness of the membranes decreased and hydrophilicity and permeation fluxes increased notably. Furthermore, it was observed that the addition of the Pluronic F-127 polymer into the membranes reduced reversible/irreversible membrane fouling. Additionally, a characterisation of the fouled membranes was performed for the purpose of comprehensively understanding the membrane fouling mechanism caused by microalgal culture.     

Fabrication and characterization of a novel TiO2 nanoparticle self-assembly membrane with improved fouling resistance

A novel TiO₂ nanoparticle self-assembly membrane was prepared based on ultrahigh molecular weight poly(styrene-alt-maleic anhydride)/poly(vinylidene fluoride) (SMA/PVDF) blend membrane. TiO₂ nanoparticle solution was beforehand prepared via the controlled hydrolysis of titanium tetraisopropoxide. The diameter (10 nm or less) and anatase crystal structure were analyzed using transmission electron microscopy (TEM) and X-ray diffraction (XRD). The SMA/PVDF blend membranes prepared by the phase inversion method were immersed into the TiO₂ nanoparticle solution for a week to produce TiO₂ self-assembly membranes. The chemical compositions in membrane surface were analyzed by X-ray photoelectron spectroscopy (XPS). The membrane morphologies were measured by scanning electron microscopy (SEM). Finally, the membrane hydrophilicity, protein anti-fouling property and the molecular weight cutoff (MWCO) were characterized by water contact angle measurement, static protein absorption and filtration experiments, respectively. It is demonstrated that, in comparison to PVDF/SMA blend membrane, the permeability and anti-fouling ability of TiO₂ self-assembly membranes were significantly improved.     

SYNTHESIS OF AMPHIPHILIC COMB-SHAPED COPOLYMERS USED FOR SURFACE MODIFICATION OF PVDF MEMBRANES

The synthesis of a novel amphiphilic comb-shaped copolymer consisting of a main chain of styrene-(N-(4- hydroxyphenyl) maleimide)(SHMI) copolymer and poly(ethylene glycol) methyl ether methacrylate(PEGMA) side groups was achieved by atom transfer radical polymerization(ATRP).The amphiphilic copolymers were characterized by ~1H-NMR, Fourier transform infrared(FTIR) spectroscopy and gel permeation chromatography(GPC).From thermogravimetric analysis (TGA),the decomposition temperature of SHMI-g-PEGMA is low...     

ANTIFOULING PROPERTIES OF POLYVINYL CHLORIDE) MEMBRANES MODIFIED BY AMPHIPHILIC COPOLYMERS P(MMA-A-MAA)

Three well-defined diblock copolymers of poly(methyl methacrylate-b-methacrylic acid)(P(MMA-b-MAA))were synthesized using atom transfer radical polymerization method and varying poly(methacrylic acid)(PMAA)chain lengths. These copolymers were blended with PVC to fabricate porous membranes via phase inversion process.Membrane morphologies were observed by scanning electron microscopy(SEM),and chemical composition changes of the membrane surfaces were measured by X-ray photoelectron spectroscopy(XPS).Static and dynamic protein adsorption experiments were used to evaluate antifouling properties of the blend membranes.It was found that,the blend membranes containing longer PMAA arm length showed lower static protein adsorption,higher water permeation flux and better protein solution flux recovery.     

铅(Ⅱ)离子印迹复合膜的制备及其性能研究

以聚丙烯微孔膜(MPPM)为支撑,采用共价表面修饰和离子印迹技术,制备了Pb(Ⅱ)离子印迹复合膜.首先通过紫外光引发丙烯酸接枝聚合,在MPPM表面引入羧基;然后基于羧基和氨基的反应,将壳聚糖共价接枝到MPPM表面;再以Pb(Ⅱ)为模板离子、环氧氯丙烷为交联剂,通过配位键作用形成离子印迹位点.制备过程通过ATR-FTIR和XPS分析得到了证实.利用扫描电子显微镜(SEM)-能量色散X射线光谱仪(EDX)对膜表面及截面的形貌及元素分布进行了分析.静态水接触角和纯水通量实验结果显示,印迹复合膜具有良好的表面亲水性和渗透性,在离子印迹聚合物接枝率为174.4μg/cm2时,水通量高达2659±58 L/(m2.h).印迹复合膜对Pb(Ⅱ)离子的吸附亲和性和渗透选择性分别通过平衡结合实验和竞争渗透实验进行评价.与非印迹复合膜相比,印迹复合膜对Pb(Ⅱ)离子展现出更强的吸附亲和性,更快的吸附速率及更好的渗透选择性,以Cu(Ⅱ)和Zn(Ⅱ)作为竞争离子,其渗透选择性因子分别为3.43和3.93.     

Improved protein-adsorption resistance of polyethersulfone membranes via surface segregation of ultrahigh molecular weight poly(styrene-alt-maleic anhydride)

A styrene-maleic anhydride (SMA) alternating copolymer with ultrahigh molecular weight (M_w > 10⁶) synthesized in super critical carbon dioxide (SC CO₂) medium was used as hydrophilic polymeric additive in the preparation of polyethersulfone (PES) membranes. The PES/SMA blend membranes were prepared by immersion precipitation process. X-ray photoelectronic spectroscopy (XPS) measurements confirmed that the hydrolyzed SMA preferentially segregated to membrane–coagulant interface during membrane formation. For the PES/SMA blend membranes, no big change was observed in the cross-sectional structure and the mechanical properties were well maintained after SMA addition except that a thicker top layer was formed. The surface morphology analysis by atomic force microscopy (AFM) showed that the membrane surface roughness increased with the added SMA amount. The results of water contact angle, water absorbance measurements and static protein adsorption experiments revealed that the surface enrichment of SMA endowed PES/SMA blend membranes with significantly improved surface hydrophilicity and protein-adsorption resistance.     

Poly(vinyl alcohol)/polyelectrolyte complex blend membrane for pervaporation dehydration of isopropanol

Poly(vinyl alcohol) (PVA) was blended with soluble polyelectrolyte complex (PEC) made from poly(diallyldimethylammonium chloride) (PDDA) and sodium carboxymethyl cellulose (CMCNa). Crystallinity, thermal transition, and thermal stability of the PVA/PEC blends were characterized by using wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), and thermal gravity analysis (TGA), respectively. Surface morphology, cross-section and phase structure of the blend membranes were examined by field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). Surface hydrophilicity and swelling behavior of the blend membranes were examined by water contact angle (CA) and swelling tests. Blend membranes were subjected to isopropanol dehydration, and effects of blend composition, feed composition and feed temperature on pervaporation performance are discussed in terms of phase structures of blend membranes. A performance of J = 1.35 kg/m² h, α = 1002, was obtained for blend membrane containing 50 wt% PEC in dehydrating 10 wt% water–isopropanol at 70 °C.     

Amphiphilic graft copolymers based on ultrahigh molecular weight poly(styrene-alt-maleic anhydride) with poly(ethylene glycol) side chains for surface modification of polyethersulfone membranes

Amphiphilic graft copolymers having ultrahigh molecular weight poly(styrene-alt-maleic anhydride) (SMA) backbones and methoxyl poly(ethylene glycol) (MPEG) grafts were synthesized via the esterification between anhydride groups with hydroxyl groups. The synthesized graft copolymers, SMA-g-MPEGs, were used as additives in the preparation of polyethersulfone (PES) membranes via phase inversion process. X-ray photoelectron spectroscopy (XPS) analysis showed the comb-like graft copolymers spontaneously segregated to membrane surface during membrane formation. Water contact angle measurements and water absorbance experiments indicated the PES/SMA-g-MPEG blend membranes were much more hydrophilic than pure PES membrane. The blend membranes had stronger protein adsorption resistance than pure PES membrane did. After washed using de-ionized water for 25 days, the blend membranes exhibited higher hydrophilicity and stronger protein adsorption resistance. This phenomenon was attributed to the further accumulation of SMA-g-MPEG additives on membrane surface in aqueous conditions. SMA-g-MPEGs can be well preserved in membrane near-surface and not lost during membrane washing due to their high molecular weight and comb-like architecture.     

Temperature-sensitive membranes prepared from blends of poly(vinylidene fluoride) and poly(N-isopropylacrylamides) microgels

In this study, temperature-sensitive membranes were prepared by phase transition of the mixture of the temperature-sensitive poly(N-isopropylacrylamides) (PNIPAAM) microgels and poly(vinylidene fluoride). The results of Fourier transformed infrared spectrometer, X-ray photoelectron spectroscopy, elemental analysis, and scanning electron microscope photographs indicate that the PNIPAAM microgels are distributed more in the inner membrane than on the surface. The scanning electron microscope photographs reveal the blend membranes having porous surfaces with nanometer sizes and porous cross-sections with micrometer sizes. The addition of the PNIPAAM microgels is found to improve the porosity, the pore size, water flux, as well as to enhance the hydrophilicity and anti-fouling property of the blend membranes. The blend membrane shows temperature-sensitive permeability and protein rejection with the most dramatic change at around 32 °C which is the lower critical solution temperature of PNIPAAM, when water or bovine serum albumin solution flow through. Specifically, below 32 °C, the blend membrane shows a high protein rejection ratio which decreases with increasing temperature and a low water flux which increases with increasing temperature; above 32 °C, the blend membrane shows a low protein rejection ratio which decreases with increasing temperature and a high water flux which increases with increasing temperature.     

Preparation of Hydrophilic UHMWPE Hollow Fiber Membranes by Chemically Bounding Silica Nanoparticles

In this work, ultra-high molecular weight polyethylene (UHMWPE) microfiltration hollow fiber membranes prepared via the thermally induced phase separation (TIPS) method were modified by chemically bounding hydrophilic silica (SiO_2) nanoparticles onto the surface to improve anti-fouling performance. A range of testing techniques including attenuated total reflection Flourier transformed infrared spectroscopy(ATR-FTIR), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), water contact angle, mechanical test,filtration and anti-fouling performance were carried out to discuss the influence of different modification conditions on the properties of the membranes. The prepared hollow fiber membranes display the significantly excellent performance when the vinyl trimethoxy silane (VTMS) concentration was 13%, the pH value of the hydrolyzate was 4 and the hydrolysis reaction time was 6 h. In particular, the hydrophilicity of modified membranes was improved effectively, resulting in the enhancement of membrane anti-fouling properties. The results of this work can be consulted for improving the anti-fouling performance of the UHMWPE microfiltration hollow fiber membrane applied in the field of water purification.     

Dehydration of water-alcohol mixtures by pervaporation and vapor permeation through surface resintering expanded poly(tetrafluoroethylene) membranes

For the purpose of separating aqueous alcohol mixtures by the use of the pervaporation and vapor permeation techniques, a surface resintering expanded poly(tetrafluoroethylene) (e-PTFE), membrane was investigated. The surface properties of the modified e-PTFE membranes were characterized by atomic force microscopy, scanning electron microscopy, and contact angle meter. The X-ray diffraction measurements show that the crystallinity of the e-PTFE membrane decreases with increasing the surface resintering temperature. The surface roughness decreases with the surface resintering temperature increases. The membrane exhibited water selectivity during all process runs. The effects of feed composition, surface resintering temperature, and molar volume of the alcohols on pervaporation and vapor permeation were investigated. Compared with the e-PTFE membrane without surface modified, the e-PTFE membrane with surface resintering treatment effectively improve the separation factor for pervaporation of aqueous alcohol mixtures. The separation performances of e-PTFE membranes in vapor permeation are higher than that in pervaporation.     

SYNTHESIS OF AN AMPHIPHILIC PPESK-g-P(PEGMA) GRAFT COPOLYMER VIA ATRP AND ITS USE IN BLEND MODIFICATION OF PPESK MEMBRANES

Preparation of an amphiphilic graft copolymer having poly(phthalazinone ether sulfone ketone)(PPESK) as main chains was carried out by atom transfer radical polymerization(ATRP).The precursor,chloromethylated PPESK (CMPPESK),was prepared by using chioromethylether as chloromethylation agent.Then,poly(ethylene glycol) methyl ether methacrylate(PEGMA) was used as monomer to synthesize PPESK-g-P(PEGMA) by ATRP method under the catalysis of a cuprous chloride/2,2'-bipyridyl system.PPESK/PPESK-g-P(PEGMA) blen...     

Protein-adsorption-resistance and permeation property of polyethersulfone and soybean phosphatidylcholine blend ultrafiltration membranes

Novel ultrafiltration membranes were prepared by simple blending of polyethersulfone (PES) and soybean phosphatidylcholine (SPC). X-ray photoelectron spectroscopy (XPS) and water contact angle measurements indicated SPC enrichment at the membrane surfaces. The immobilization and arrangement of PC groups at surfaces rendered the membranes more hydrophilic. BSA adsorption amount decreased from 56.2 μg/cm² for SPC-free PES membrane to 2.4 μg/cm² for PES/SPC blend membrane. The fouling-resistant property of the blend membranes was improved considerably with an increase of SPC content while the pure water permeation flux decreased remarkably. Using PEG/PVP mixture instead of PEG as pore-forming agent increased pure water flux of PES/SPC blend membrane to some extent.     

Pervaporation dehydration of ethylene glycol with chitosan–poly(vinyl alcohol) blend membranes: Effect of CS–PVA blending ratios

Chitosan–poly(vinyl alcohol), CS–PVA, blended membranes were prepared by solution casting of varying proportions of CS and PVA. The blend membranes were then crosslinked interfacially with trimesoyl chloride (TMC)/hexane. The physiochemical properties of the blend membranes were determined using Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy (ATR-FTIR), X-ray diffraction (XRD), differential scanning calorimetry (DSC), tensile test and contact angle measurements. Results from ATR-FTIR show that TMC has crosslinked the blend membranes successfully, and results of XRD and DSC show a corresponding decrease in crystallinity and increase in melting point, respectively. The crosslinked CS–PVA blend membranes also show improved mechanical strength but lower flexibility in tensile testing as compared to uncrosslinked membranes. Contact angle results show that crosslinking has decreased the surface hydrophilicity of the blend membranes. The blend membrane properties, including contact angle, melting point and tensile strength, change with a variation in the blending ratio. They appear to reach a maximum when the CS content is at 75 wt%. In general, the crosslinked blend membranes show excellent stability during the pervaporation (PV) dehydration of ethylene glycol–water mixtures (10–90 wt% EG) at different temperatures (25–70 °C). At 70 °C, for 90 wt% EG in the feed mixture, the crosslinked blend membrane with 75 wt% CS shows the highest total flux of 0.46 kg/(m² h) and best selectivity of 986. The blending ratio of 75 wt% CS is recommended as the optimized ratio in the preparation of CS–PVA blend membranes for pervaporation dehydration of ethylene glycol.