Preparation of PVDF ultrafiltration membranes using PVA as pore surface hydrophilic modification agent with improved antifouling performance

Novel polyvinylidene fluoride (PVDF) ultrafiltration (UF) membranes were facilely fabricated using polyvinyl alcohol (PVA) aqueous solution as the coagulation bath through phase inversion method. In the process, PVA was introduced into the pore surfaces of the PVDF membranes via the interdiffusion of the non‐solvent water and the solvent. The effects of PVA content in the coagulation bath on membrane properties were systematically discussed. The results indicated that the increase of PVA content in coagulation bath resulted in the formations of the more sponge‐like structures and the higher surface hydrophilicity. Smaller pore size led to lower water flux and higher bovine serum albumin rejection. Fouling resistance measurement indicated that the membranes made in PVA/water coagulation bath had higher flux recovery ratio (92.1%) than the membrane made in a pure water bath (71.0%). Furthermore, mechanical property test revealed that the resulting membranes had high tensile strength and Young's modulus. In this work, we found that the morphology and the property of the novel PVDF membranes could be determined by the PVA content in the coagulation bath. POLYM. ENG. SCI., 59:E384–E393, 2019. © 2018 Society of Plastics Engineers     

氧化铝凝胶改性聚偏氟乙烯超滤膜的制备与表征

为提高聚偏氟乙烯超滤膜的亲水性,采用Al_2O_3凝胶对有机高分子聚偏氟乙烯膜进行改性,制备Al_2O_3凝胶改性聚偏氟乙烯超滤膜,并与非凝胶化无机纳米Al_2O_3颗粒改性进行对比。考察铸膜液中Al_2O_3凝胶加入量对改性聚偏氟乙烯超滤膜性能和结构的影响。采用扫描电镜、X射线能谱、傅里叶红外光谱和超滤实验等对超滤膜结构和性能进行表征,结果表明,Al_2O_3凝胶加入量1.0 g时,改性超滤膜水通量提高5.48倍;扫描电镜表明,改性超滤膜和未改性超滤膜均为典型的非对称结构,改性超滤膜表面孔数目明显增加,断面微观结构未发生改变;红外光谱及能谱分析表明,Al_2O_3凝胶与高分子聚偏氟乙烯之间为物理共混。Al_2O_3凝胶改性聚偏氟乙烯超滤膜,改善了膜表面亲水性,提高水通量,并保持较大截留率。     

Preparation and characterization of a novel hydrophilic PVDF/PVA UF membrane modified by carboxylated multiwalled carbon nanotubes

Polyvinylidene fluoride (PVDF)/polyvinyl alcohol (PVA) ultrafiltration (UF) membranes were prepared via a phase inversion method employing the modification of carboxylated multiwalled carbon nanotubes (MWCNTs‐COOH). Various contents of MWCNTs‐COOHs (0.00–0.15 wt%, weight of casting solution) were added into PVDF/PVA/dimethyl sulfoxide systems for the fabrication of the plate UF membrane. Fourier transform infrared spectroscopy spectra identified the successful introduction of carboxyl through the C?O peak at 1730 cm^?1. Scanning electron microscopy images exhibited the external surface and the asymmetric morphology with the appearance of a sponge‐like inner structure. Atomic force microscopy analysis determined the roughness values and rougher topography. The hydrophilicity of the composite membrane containing 0.09 wt% of MWCNTs‐COOHs improved the most. This sample has the highest pure water flux, approximately doubled (126.6 L·m^?2·h^?1) compared to the PVDF/PVA membrane (68.6 L·m^?2·h^?1), an enhanced bovine serum albumin flux recovery rate, showing an increase of 17%, and the best fouling resistance ability. Meanwhile, the porosity and dynamic contactangle also indicate the enhancement of membrane hydrophilicity. Dextran (DEX) 600k rejection reached 91.0%. Break strength, elongation at break, and Young's modulus also had improvements of 60%, 215.5%, and 56.7%, respectively, when the MWCNTs‐COOH content was 0.12 wt%. POLYM. ENG. SCI., 56:955–967, 2016. © 2016 Society of Plastics Engineers     

多巴胺及KH-561改性PVDF超滤膜的制备及性能

采用聚多巴胺与亲水物质前驱体同步水解的方法,在膜表面生成杂化涂层,通过调整3-(2,3-环氧丙氧基)丙基三乙氧基硅烷(KH-561)与多巴胺的配比,制备了PVDF超滤改性膜。测试了杂化涂层对改性膜的表面形貌、亲水性、纯水通量、截留率等性能的影响。结果表明,杂化涂层不仅提高了改性膜的表面亲水能力,也改善了膜内部孔道的亲水性,PVDF改性膜的水接触角降至37.8°。膜水通量达到174 L/(m²·h),蛋白截留率达90%以上。杂化涂层在膜表面形成一层水膜,使膜具有良好的抗污染性能,改性膜的衰减系数最低可达0.19。     

Preparation and properties of PVDF/PVA hollow fiber membranes

On principle of polymer blend phase separation, PVDF/PVA hollow fiber membranes were prepared using phase inversion method. The membrane morphology and performance varied with the blending ratio. The PVDF/PVA blends showed incompatibility by the results of dynamic mechanical analysis (DMA) and infrared attenuated total reflection (FTIR-ATR) sampling technique. Based on bursting pressure and tensile strengths results, we suggest that the mechanical properties of PVDF/PVA blend membranes are worse than that of PVDF membrane. PVA can improve the hydrophilicity of PVDF/PVA hollow fiber membranes, which could be illuminated by the decrease in contact angle, the increase in equilibrium water content (EWC) and the variety in dynamic moisture regain. The pure water flux increases while the rejection ratio decreases with PVA content increasing. Moreover, PVA can improve the anti-fouling property of PVDF/PVA hollow fiber membranes, which could be illuminated by the result of increase coefficient of resistance.     

氧化石墨烯改性PVDF超滤膜制备及分离性能

用N-（三甲氧基硅丙基）乙二胺三乙酸钠（EDTS）对氧化石墨烯进行修饰,制备出亲水的EDTS-GO纳米复合物。然后通过共混的方式将EDTS-GO添加到PVDF中,制备出EDTS-GO改性PVDF超滤膜。接触角分析和红外光谱结果表明,在相转化过程中EDTS-GO转移至膜表面,PVDF膜表面的亲水性增强。系统考察了不同EDTS-GO添加量对膜性能的影响。膜性能测试表明,随着EDTS-GO添加量的增加,PVDF膜的纯水通量先增大然后降低,当添加量为0.5%时,纯水通量达到最大值,711.2 L·（m²·h）^-1。此外,抗污染实验表明,EDTS-GO改性的PVDF超滤膜比未改性的PVDF超滤膜具有更强的抗污染性能。     

Preparation and performance of sulfonated polysulfone flat ultrafiltration membranes

Sulfonated polysulfone (SPSF) flat ultrafiltration membranes were successfully prepared by immersion precipitation phase inversion method. N‐Methyl pyrrolidone was used as a solvent, and polyvinylpyrrolidone (PVP) was used as a polymeric additive in the casting solution. The effects of casting solution formulation and preparation conditions on membrane structure and properties were investigated in present study, and the morphology of the membranes was analyzed by scanning electron microscopy. The results indicated that the performances of SPSF membranes made by chemical modification were better than polysulfone membrane. The SPSF concentration played a vital role in restricting the pure water flux (PWF), promoting the rejection coefficient, and improving the hydrophilicity. A maximum PWF and minimum egg albumin rejection coefficient were obtained when the PVP content was 10%. When the coagulation bath temperature was set to 25°C, the PWF reached 480 L·m^?2·h^?1 and the ovalbumin rejection coefficient reached 92%. Longer evaporation times improved the PWF. Specifically, when the evaporation time was 70 s, the comprehensive performance was good. POLYM. ENG. SCI., 55:1003–1011, 2015. © 2014 Society of Plastics Engineers     

选择性透过CO2气体PVA/淀粉膜制备及性能研究

对聚乙烯醇(PVA)/淀粉膜进行接枝改性,引入含有叔胺基团的甲基丙烯酸二甲氨基乙酯(DMAEMA),使其对CO₂气体具有选择性透过功能,并对CO₂透过量进行优化,研究其分子结构与性能的关系。红外光谱、X射线光电子能谱、原子力显微镜照片及透气测试结果证明,加入淀粉接枝DMAEMA共聚物后,PVA/淀粉改性膜对CO₂具有选择透过性。接枝共聚物的接枝率和添加量影响CO₂透过量,当添加1.5%(质量分数,下同)的接枝率为55.3%的接枝共聚物,膜的CO₂透过量由1.577 cm³/(m²·24 h·0.1 MPa)提高到45.786 cm³/(m²·24 h·0.1 MPa),提高了28.03倍。X射线光电子能谱测试结果显示,改性膜透过CO₂后,N1s谱图中399.8 eV处的结合能减小,在401.8 eV结合能增大,可能CO₂与膜上叔胺基团发生反应,实现...     

Characteristics and performance of new types of ultrafiltration membranes with chemically modified surfaces

A special “quo;coating”quo; technique for making new types of surface modified ultrafiltration membranes has been developed and evaluated. The preparation procedure comprises the following principle:

A suitable ultrafiltration support membrane made by the traditional phase inversion process is surface coated with an aqueous solution containing a hydrophilic polymer and/or monomer having reactive groups and a catalyst (the coating step). The membrane material is selected from the class of fluorine containing polymers. By raising the temperature, the hydrophilic components are chemically bonded to the membrane material at the exposed surface by an addition reaction (the curing step).

Using this method you can impart hydrophilic properties to an otherwise hydrophobic, high resistant synthetic polymeric ultrafiltration membrane.

The properties of the final membrane depend on the characteristics of the support membranes, the composition of the coating solution and the amount applied and the reaction conditions. The technique seems more or less universal - e.g. it is possible to make a series of membranes with different cut-off values.

Results from measurements on different test solutions and on relevant industrial products are described. Characterization is done by measuring hydraulic permeability and rejection of dextrans and proteins. Flux stability and fouling tendency have been examined using different model foulants.

Membrane surface structures are characterized by SEM-studies. Analytical investigations using infrared spectroscopy (FTIR/ATR) and X-ray photoelectron spectroscopy (ESCA) have been tried to get some information about the chemistry of the coating.

The main advantages of the new membranes are that higher flux values compared to a standard polyethersulfone UF membrane are generally obtained - e.g. on whey flux improvements in the order for 20 – 50% have been observed and for fermentation broths fluxes can be several times greater compared to results using the standard membrane.

Some of these new membranes are now commercially available and are supplied by DDS FILTRATION, designated ETNA series.     

Preparation,characterization and performance of cellulose acetate ultrafiltration membranes modified by charged surface modifying macromolecule

A charged surface modifying macromolecule (cSMM) was synthesized, characterized by FT-IR spectroscopy and blended into the casting solution of cellulose acetate (CA) to prepare surface modified UF membranes by phase inversion technique. With an increasing cSMM additive content from 1 to 4 wt%, pure water flux (PWF) and water content (WC) were increases whereas the hydraulic resistance decreases. Surface characteristic study reveals that the surface hydrophilicity increased in cSMM modified CA membranes. The pore size and surface porosity of the 4 wt% cSMM blend CA membranes increases to 41.26 Å and 0.015%, respectively. Similarly, the molecular weight cut-off (MWCO) of the membranes ranged from 20 to 45 kDa, depending on the various compositions of the prepared membranes. Lower flux decline rate (47.2%) and higher flux recovery ratio (FRR) (89.0%), exhibited by 4 wt% cSMM blend membranes demonstrated its fouling resistant characteristic compared to pristine CA membrane.     

Preparation of high‐flux ultrafiltration membranes by blending strongly charged polymer

Three kinds of high‐flux ultrafiltration membranes were fabricated by blending strongly charged polymer [sulfonated poly(phenylene oxide) (SPPO)] with neutral polymer [cellulose acetate (CA), polyethersulfone (PES), or polyvinylidene fluoride (PVDF)]. After blending with SPPO, the pure water flux of CA‐SPPO, PES‐SPPO, and PVDF‐SPPO membrane increase by 3, 76, and 30 times at a transmembrane pressure of 100 kPa. Compared with the unblended membranes, the pore radius of CA‐SPPO, PES‐SPPO, and PVDF‐SPPO membrane increased from 31.9 to 33.2 nm, 26.1 to 28.6 nm, and 19.8 to 25.7 nm, respectively. The addition of strongly charged polymer decreased the thermodynamic stability of casting solutions, promoting the phase inversion process and resulting in highly porous structure. The charged groups and hydrophilicity of the polymer facilitate the formation of an additive concentration gradient (more additive in the active layer), endowing the blend membrane with better hydrophilicity and greater wettability gradient. The high porosity, good hydrophilicity, and larger wettability gradient enable the high permeation of blend membranes. This work shows how the strongly charged polymer affects the formation and performance of blend membrane, which will be useful for designing high‐performance membrane. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44570.     

纳米氧化锌包覆SiO2和SiO2/Al2O3改性粉制备及表征

采用液相沉积法对纳米氧化锌进行表面包覆SiO2和SiO2/Al2O3改性,并用IR、XRD、TG-DSC对其表面结构进行了表征,用紫外-可见分光光度计对其紫外屏蔽性能进行了检测,采用Zeta电位测定仪、静态沉降实验等分析手段考察了改性前后纳米氧化锌在水体系中的分散稳定性。结果表明,在ZnO表面形成的包覆物是以非晶态形式存在的,通过表面包覆SiO2和SiO2/Al2O3改性后纳米氧化锌对紫外光的屏蔽性能有所下降,明显提高了氧化锌的表面羟基含量,有效改变了氧化锌的等电点,显著提高了纳米氧化锌在水中的分散稳定性。     

SiO2包覆TiO2复合纳米粒子的制备及防晒性能研究

通过溶胶-凝胶法在金红石型纳米二氧化钛（TiO₂）表面包覆二氧化硅（SiO₂）薄膜,对纳米TiO₂进行表面改性。通过优化聚乙烯吡咯烷酮（PVP）用量、硅钛比、氨水的用量确定最佳制备条件为:TiO₂用量为0.3 g,PVP用量为0.4 g,硅钛比为2∶1,氨水用量为5 m L,获得了粒径小,SiO₂包覆层薄,单分散性好的SiO₂-TiO₂复合纳米粒子。应用FT-IR,XRD,SEM,TEM和UV-vis等对改性前后的粒子进行表征。结果表明:红外光谱图中出现Si-O-Ti键的振动吸收峰,改性前后的纳米TiO₂均为金红石型,SEM及TEM显示改性后的粒子团聚现象减弱,其表面形成了约10 nm的SiO₂薄膜。经过表面改性,SiO₂成功包覆在纳米TiO₂表面,复合纳米粒子的光催化活性得到有效抑制,纳米TiO₂作为防晒剂的安全性大大提高。...     

Preparation of antibacterial polyvinylidene fluoride (PVDF) ultrafiltration membranes with direct addition of N-halamine polymers

In this study, novel antibacterial ultrafiltration polyvinylidene fluoride (PVDF) flat sheet membranes were produced with addition of synthesized N-halamine polymers. The ternary phase diagrams of PVDF and the synthesized polymers with N-methyl-2-pyrrolidone and water systems were prepared. The water flux and BSA rejection performances of the produced membranes were assessed both with and without PVP addition, and compared with a commercial membrane. The produced membranes were characterized with FTIR, XPS, DSC, and SEM analysis. Addition of N-halamine polymers to the membrane structure significantly improved the biocidal performance of the produced membranes against Staphylococcus aureus and Escherichia coli (10⁵ CFU).     

Preparation and characterization of hydrophilic and antifouling poly(ether sulfone) ultrafiltration membranes modified with Zn–Al layered double hydroxides

Zn–Al layered double hydroxide (LDH)‐entrapped poly(ether sulfone) (PES) ultrafiltration membranes with four different weight percentages, 0.5, 1.0, 2.0, and 3.0%, were prepared by a phase‐inversion method. Characterization by scanning electron microscopy, atomic force microscopy and contact angle (CA), equilibrium water content, porosity, average pore size, mechanical strength, and ζ potential measurement were used to evaluate the morphological structure and physical and chemical properties of membranes. Static protein adsorption, filtration, and rejection experiments were conducted to study the antifouling properties, water permeability, and removal ability of the modified membranes. The results show that significant change occurred in the membrane morphology and that better hydrophilicity, water permeability, and antifouling ability were also achieved for the PES/LDH membranes when a proper amount of LDH was used. For example, the CA value decreased from 66.60 to 50.21°, and the pure water flux increased from 80.21 to 119.10 L m^?2 h^?1 bar^?1 when the LDH loading was increased from 0 to 2.0 wt %. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43988.     

Brazing YSZ ceramics by a novel SiO2 nanoparticles modified Ag filler

Yttria-stabilized zirconia (YSZ) ceramics are soundly brazed in air using a novel amorphous SiO₂ nanoparticles (NPs) modified Ag filler. Scanning electron microscopy, transmission electron microscopy and X-ray diffraction are employed to characterize the interfacial microstructure of YSZ joints. A uniform amorphous SiO₂ layer is observed on the YSZ substrate surface. Micro-sized SiO₂ clusters are dispersed in the Ag braze matrix, which forms the brazing seam. The content of SiO₂ NPs and the brazing temperature exert significant effects on the formation of YSZ joints. The maximum shear strength of YSZ joints reaches 47 MPa under the optimized brazing conditions (Ag–2SiO₂, 1050 °C/30 min, 2 MPa load pressure).     

处理油库污水的改性PVDF超滤膜结构与性能

在PVDF/PVP体系中添加Al₂O₃和TiO₂两种无机纳米颗粒,利用沉浸凝胶相转化法制得纳米颗粒总量不同和比例不同的改性PVDF平板超滤膜。探讨了纳米颗粒比例和总量对膜性能的影响。利用SEM、XRD对改性膜的结构进行了表征。并利用该改性膜处理典型沿海油库含油污水。结果显示:两种无机纳米颗粒的加入,明显增强了纳米改性膜的亲水性,使膜的抗污染性能得到提高;膜的韧性和强度得到改进;膜表面及膜孔的微观结构、改性膜的结晶度没有受到无机纳米颗粒的明显影响。最佳的纳米颗粒总含量为3%,两种纳米颗粒最佳质量比例为1:2。采用改性膜处理油库含油污水,稳定时出水中悬浮物含量低于0.4 mg·L^-1;石油烃类含量低于0.5 mg·L^-1;COD值在60～70 mg·L^-1之间,达到了国家污水排放标准。     

Poly(vinylidene fluoride) ultrafiltration membranes containing hybrid silica nanoparticles: Preparation,characterization and performance

Poly(vinylidene fluoride) (PVDF) ultrafiltration membranes were prepared by immersion precipitation method using poly(hydroxyethyl methacrylate)-block-poly(methyl methacrylate) grafted silica (PHEMA-b-PMMA@SiO₂) nanoparticles as additives. The hybrid nanoparticles were synthesized by the surface initiated atom transfer radical polymerization (SI-ATRP), and they were characterized in detail by FT-IR, TEM, DLS and GPC. Results confirm that core–shell structure is formed after grafting PHEMA-b-PMMA brushes on the silica nanoparticles. Their average hydrodynamic diameter also increases with the prolongation of grafting time. After blending PVDF with the hybrid silica nanoparticles, the composite PVDF membranes exhibit high porosity and improved water permeation. Especially, when the molecular weight is 1.73 × 10⁵ g/mol for PHEMA-b-PMMA on the hybrid nanoparticles, the water flux of the PVDF composite membrane is 2.5 times than that of the control PVDF membrane, while the rejection to bovine serum albumin (BSA) remains at a high level (>90%). In addition, all the composite PVDF membranes show lower BSA adsorption and larger water flux recovery ratio than the control PVDF membrane. The improvement of membrane performance is attributed to the good hydrophilicity of PHEMA-b-PMMA@SiO₂ nanoparticles. Our results suggest that PHEMA-b-PMMA@SiO₂ nanoparticles with moderate molecular weight of PHEMA-b-PMMA are suitable for the property optimization of PVDF-based composite membranes.