Improving bonding strength between a hydrophilic coating layer and poly(ethylene terephthalate) braid for preparing mechanically stable braid‐reinforced hollow fiber membranes

A braid‐reinforced hollow fiber membrane with mechanically stable coating layer was prepared by coating a blended polymer dope solution on an alkaline‐treated poly(ethylene terephthalate) (PET) braid. The alkaline treatment was carried out to endow the PET braid surface with more polar groups and better hydrophilicity. The results showed that the bonding strength between the hydrophilic coating layer and modified PET braid was about two times as great as that between the coating layer and original PET braid, while the pure water permeability (PWP) of the membrane remained unchanged when the PET braid was simply treated in 3 wt % potassium hydroxide (KOH) solution at 90 °C for 1 h or 1 wt % KOH solution for 6 h. The proposed modification approach proved to be a facile, low‐cost, and effective method to improve bonding strength between the coating layer and the braid, while other properties, such as PWP and morphology of the coating layer, of the braid‐reinforced hollow fiber membranes were not altered, indicating promising potential in membrane engineering. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46104     

Preparation and characterization of braided tube reinforced polyacrylonitrile hollow fiber membranes

Polyacrylonitrile (PAN) and polyester (PET) braided hollow tube that used as a special reinforcement are braided from their filaments via two‐dimensional weaving techniques. PAN braided tube reinforced homogeneous PAN hollow fiber membranes and PET braided tube reinforced heterogeneous PAN hollow fiber membranes are prepared by concentric circles squeezed‐coated spinning method. As for PAN hollow fiber membrane, the effects of PAN concentration on the performance of the prepared hollow fiber membranes are investigated in terms of pure water flux, protein rejection, mechanical strength, and morphology observations by a scanning electron microscope (SEM). The interfacial bonding state of the braided tube reinforced PAN hollow fiber membranes is studied by constant speed stretching method. Results show that the breaking strength of two‐dimensional braided tube reinforced PAN hollow fiber membranes is higher than 80 MPa. The structure of separation surface is similar to the structure of an asymmetric membrane. With the increase of polymer concentration, the membrane flux decreases while the retention rate of BSA increase. The membrane porosity and maximum pore size have the same decreasing tendency as the increase of PAN concentration. The results also show that the interfacial bonding state of the PAN two‐dimensional braided tube reinforced homogeneous PAN hollow fiber membranes is better than that of the PET two‐dimensional braided tube reinforced heterogeneous PAN hollow fiber membranes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41795.     

Fabrication and characterization of novel foaming polyurethane hollow fiber membrane

Foam-like materials had attracted great interest as promising absorbent. In this study, thermoplastic polyurethane(TPU) block sponge was synthesized. Polyester(PET) braid tubular reinforced polyurethane(PU) spongy hollow fiber membrane was prepared by a concentric circular spinning method. The method was woven from an outer coated water-blown PU separation layer and inner PET braid tubular. We have developed a simple and useful preparation technique for the PU spongy hollow fiber membrane. For the first time, the PU spongy hollow fiber membrane was prepared using a coating and controlled foaming technique. The influence of toluene isocyanate index on the physical properties, morphology, and structure of flexible PU sponge was discussed in terms of water contact angle(CA), pure water flux(PWF), Fourier Transform Infrared Analysis(FTIR),pressure-responsive property, and pull-out strength. The morphologies of the membranes were investigated by scanning electron microscopy. We have characterized the foams from an intuitive point of view and demonstrated that the dimensional morphology of the membrane was closely related to isocyanate index. The result showed that the surface cell size of the PU sponge hollow fiber membrane gradually decreased with an increase of the isocyanate index. Due to the elasticity of PU at room temperature, the pressure responsive characteristic of the membrane was prepared. When isocyanate index was 1.05, the interface bonding strength of PU spongy hollow fiber membranes reached as high as 0.37 MPa, porosity and PWF were 71.5% and 415.5 L·m~(-2)·h~(-1),respectively.     

Preparation of PET threads reinforced PVDF hollow fiber membrane

PET threads were incorporated in the support layer of hollow fiber membrane in axial direction as a special reinforcement material for the purpose of improving the mechanical properties of PVDF hollow fiber membranes. It was found that the reinforcement threads had a limited effect on the separation-related properties of the membrane, such as porosity and pore size, but the tensile strength of the reinforced membrane was improved several folds. Also, the criterion of choosing reinforced fiber materials was suggested.     

Poly(vinyl chloride) hollow‐fiber membranes for ultrafiltration applications: Effects of the internal coagulant composition

Poly(vinyl chloride) (PVC) hollow‐fiber membranes were spun by a dry/wet phase‐inversion technique from dopes containing 15 wt % PVC to achieve membranes with different pore sizes for ultrafiltration (UF) applications. The effects of the N,N‐dimethylacetamide (DMAc) concentration in the internal coagulant on the structural morphology, separation performance, and mechanical properties of the produced PVC hollow fibers were investigated. The PVC membranes were characterized by scanning electron microscopy, average pore size, pore size distribution, void volume fraction measurements, and solubility parameter difference. Moreover, the UF experiments were conducted with pure water and aqueous solutions of poly(vinyl pyrrolidone) as feeds. The mechanical properties of the PVC hollow‐fiber membranes were discussed in terms of the tensile strength and Young's modulus. It was found that the PVC membrane morphology changed from thin, fingerlike macrovoids at the inner edge to fully spongelike structure with DMAc concentration in the internal coagulant. The effective pores showed a wide distribution, between 0.2 and 1.1 μm, for the membranes prepared with H₂O as the internal coagulant and a narrow distribution, between 0.114 and 0.135 μm, with 50 wt % DMAc. The results illustrate that the difference in the membrane performances was dependent on the DMAc concentration. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Novel Hollow Titania Spheres‐Chitosan Hybrid Membranes with High Isopropanol Dehydration Performance

A new kind of hollow titania spheres‐chitosan (hTiO₂‐CS) hybrid membranes was prepared by a physical blending method. hTiO₂ spheres were found to disperse well in the as‐prepared hTiO₂‐CS hybrid membranes. Their incorporation can reduce the chitosan crystallinity and enhance slightly its hydrophilicity and thermal stability. Subsequently, hTiO₂‐CS/PAN composite membranes comprising of the hTiO₂‐CS hybrid membrane as separation layer and a polyacrylonitrile (PAN) membrane as support layer were fabricated. Compared to the CS/PAN membrane, all of them exhibit a much better flux and separation factor for a 90 wt % aqueous solution of isopropanol at 80 °C. This promising kind of composite membranes may find potential application in the dehydration of alcohols.     

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.     

Performance evaluation of polyvinylchloride/polyacrylonitrile ultrafiltration blend membrane

Polyvinylchloride (PVC) membranes were modified by blending with polyacrylonitrile (PAN) as a second polymer. The miscibility of PVC/PAN blend was examined using an incompressible regular solution (CRS) model in no need to make a membrane. The results showed that the PVC/PAN blend was immiscible for all compositions at a temperature range of ?25 to 225 °C. Furthermore, the prediction of the phase behavior of a PVC/PAN/DMF ternary system showed that the blend of two polymers was highly incompatible even in their common DMF solvent. However, this incompatibility led to a remarkable increase in the porosity of the blend membrane and pure water flux compared to those for pure PVC membrane. The pure water flux of the PVC membrane (37.9 ± 1.5 L/m² h) increased about 41 and 76% by adding 10 and 20 wt% PAN, respectively. The blend membranes also showed an enhanced flux recovery ratio (FRR) compared to a pure PVC membrane, although the PVC membrane rejection for Bovine serum albumin (BSA) was decreased after blending with PAN. The PVC/PAN (90/10) blend membrane was subjected to hydrolysis with NaOH alkaline solution at three different concentrations and contact times to further enhance its performance. The membrane, which was hydrolyzed with a 0.5 mol/L NaOH solution for 0.5 h, showed a highest pure water flux of 75.6 ± 7.2 L/m² h due to its increased hydrophilicity. This membrane also revealed an improved FRR and better thermal and mechanical properties compared to an unmodified membrane.     

Polymer membranes for separating organic mixtures

Polyvinyl alcohol (PVA), polyacrylonitrile (PAN), and cellulose ester were respectively chosen as the separation layer and the support in the composite membranes based on the concept of the solubility parameter and the permselectivities for separating ethanol/water mixture, isopropanol/water mixture, and caprolactam/water mixture. The effects of the membrane materials and the construction of the composite membrane on the separation performance were preliminary discussed. The separation performance of the membranes prepared by several making‐membrane techniques, i.e., the polymer solution making‐membrane technique, and the membrane treatment technique (heat treatment, organic solvent modification) were presented. The composite membranes of PVA/PAN and PVA/cellulose acetate, and cellulose triacetate hollow fiber membrane modified, which possess good performance in separating the organic systems, were developed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1160–1164, 2006     

全氟磺酸改性聚乙烯醇渗透汽化膜分离乙酸乙酯-水溶液

以聚乙烯醇(PVA)为原材料,全氟磺酸(PFSA)为共混改性材料,以聚丙烯腈(PAN)中空纤维超滤膜为底膜制备了PVAfPAN、PVA-PFSA/PAN复合膜,并用于乙酸乙酯脱水.考察了共混涂膜液中PVA、PFSA配比,交联剂酒石酸(Tat)用量以及原料液温度与浓度对PVA、PAN、PVA-PFSA、PAN复合膜分离件能的影响.实验结果表明,Tac交联的PVA,PAN、PVA-PFSA/PAN复合膜均对水具有较好的分离选择性.共混涂膜液中PVA/PFSA质量比为1/1、Tac/PVA质量比为l/5时所制备的PVA-PFSA/PAN复合膜渗透汽化分离性能最佳.40下℃此复合膜用于分离98%(wt)的乙酸乙酯水溶液时,其渗透通量和分离因予分别为81.1 g·m-2·h-1和1890.同样条件下,与交联PVA/PAN复合膜相比,交联PVA-PFSA/PAN复合膜的渗透通量显著提高.     

Hollow Fiber Ultrafiltration Membranes from Poly(Vinyl Chloride): Preparation,Morphologies, and Properties

Hollow fiber poly(vinyl chloride) membranes were prepared by using the dry/wet spinning method. Cross-section, internal, and external surfaces of the hollow fibers structure were studied by SEM. The pore size and pore size distribution of the hollow fibers were measured by a PMI capillary flow porometer. UF experiments of pure water and aqueous solution of PVP K-90 were carried out. The effect of the PVC concentration on the hollow fibers mechanical properties was also investigated. It was found that the PVC fibers cross-sectional structure was affected by the polymer concentration in the dope solution. In particular, reduction of macrovoids size was observed when increasing PVC concentration from 15 to 19 wt%. The pore size distribution of the PVC hollow fibers was controlled by adjusting the PVC concentration. Indeed, an increase of PVC concentration up to 19 wt% leads to fibers with sharp pore size distribution (the 99% of pores is about 0.15 µm).The pure water permeation flux decreased from 162 to 128 (l/m² · h · bar), while the solute separation performance increased from 82 to 97.5%, when increasing the PVC concentration. The elongation at break, the tensile strength, and the Young's modulus of the PVC hollow fibers were improved with PVC concentration in dope solution.     

建筑增强用聚丙烯腈纤维的耐海水腐蚀性研究

模拟混凝土应用的海洋环境,在常温(25℃)、氯化物浓度为5610 mg/L的海水中对建筑增强用聚丙烯腈(PAN)纤维进行浸泡处理,研究建筑增强用PAN纤维的耐海水腐蚀性,并与聚对苯二甲酸乙二醇酯(PET)增强纤维和聚丙烯(PP)增强纤维进行对比。结果表明:海水浸泡50 d后,建筑增强用PAN纤维的主要吸收特征峰无明显变化,且无新的吸收特征峰出现,纤维超分子结构变化较小,晶区取向度基本保持不变,结晶度略有增加;海水浸泡50 d后,建筑增强用PAN纤维的拉伸强度为1261 MPa、降幅0.63%,初始模量为18.6 GPa、增幅8.14%,其拉伸强度与PET增强纤维相当、约为PP增强纤维的1.8倍,初始模量约是PET增强纤维的1.4倍、PP增强纤维的3.2倍;建筑增强用PAN纤维、PET增强纤维、PP增强纤维的拉伸强度耐蚀系数分别为99.4%,99.2%,100.0%,建筑增强用PAN纤维的耐海水腐蚀性介于PP增强纤维和PET增强纤维之间,但其在海水中环境中具有优异的模量保持优势,可以更好地提高混凝土在海水环境中的耐受力。     

Hydrophilic modification of high‐strength polyvinylidene fluoride hollow fiber membrane

The polyvinylidene fluoride (PVDF)/polyvinyl alcohol (PVA) polymer solutions were coated on the outer surface of PVDF matrix hollow fiber membrane. On the principle of the homogeneous‐reinforced (HR) membrane technology, the reinforced PVDF/PVA (RFA) hollow fiber membranes prepared through the dry‐wet spinning method. The performance of the RFA membranes varies with the PVA concentration in the polymer solution and is characterized in terms of pure water flux (PWF), porosity, a mechanical strength test, and morphology observations by a scanning electron microscopy (SEM). The results of this study indicate that PVA can apparently improve the hydrophilicity of the PVDF hollow fiber membranes. The growing enrichment of the hydrophilic components PVA on the membrane surface is determined by X‐ray photoelectron spectroscopy. The RFA membranes have a favorable interfacial bonding between the coating layer (PVDF/PVA) and the matrix membrane (PVDF hollow fiber membrane), as shown by SEM. The elongation at break of the RFA membranes increases much more than that of the matrix membrane that is endowed with the better flexibility of the membrane performance. PWF decreases much more compared with that of the matrix membrane. The RFA membranes have a lower flux decline degree during the process of protein solution and ink solution filtration compared with that of the matrix membrane. POLYM. ENG. SCI., 54:276–287, 2014. © 2013 Society of Plastics Engineers     

影响渗透汽化中空纤维复合膜分离性能的制备工艺研究

采用聚乙烯醇（ＰＶＡ）为分离层的模材料,以浸涂工艺把ＰＶＡ复合到聚砜（ＰＳ）或聚丙烯腈（ＰＡＮ）的中空纤维支撑层上,在长度为０．４ｍ的不锈钢管中组装若干根中空纤维复合膜测定对乙醇水溶液的渗透汽化（ＰＶ）分离性能。结果表明,ＰＶＡ／ＰＡＮ中空纤维复合膜的性能优于ＰＶＡ／ＰＳ,内径较大（１．３ｍｍ）的优于内径上（０．４ｍｍ）者,ＰＶＡ水溶液在中空纤维支撑层上的涂复次数对复合膜ＰＶ分离性能、以及ＰＶＡ／     

PVA-TEOS/PAN渗透汽化膜的制备及其乙酸乙酯脱水

以聚丙烯腈(PAN)中空纤维超滤膜为底膜,以聚乙烯醇(PVA)和正硅酸乙酯(TEOS)的混合液为涂膜液,采用溶胶-凝胶法制备了PVA-TEOS/PAN渗透汽化复合膜,并用于乙酸乙酯脱水. FT-IR和XRD谱图证实复合膜表层中由于PVA与TEOS的交联反应而形成了Si?O?C共价键,且PVA的结晶度下降. 另外,利用静态接触角测量对复合膜表层的亲水性进行了表征. 考察了复合膜在乙酸乙酯水溶液中的溶胀性能及涂膜液中TEOS含量和料液温度与浓度对PVA-TEOS/PAN复合膜分离性能的影响. 结果表明,TEOS的加入有效降低了复合膜在乙酸乙酯水溶液中的溶胀度,使其对水具有较好的分离选择性. 40℃下,涂膜液中TEOS质量含量分别为5%和30%的PVA-TEOS/PAN复合膜分离98%的乙酸乙酯水溶液时,其分离因子分别为2830和4448,渗透通量分别为49.4和41.4 g/(m2×h).     

Preparation of dual‐layer acetylated methyl cellulose hollow fiber membranes via co‐extrusion using thermally induced phase separation and non‐solvent induced phase separation methods

Dual‐layer acetylated methyl cellulose (AMC) hollow fiber membranes were prepared by coupling the thermally induced phase separation (TIPS) and non‐solvent induced phase separation (NIPS) methods through a co‐extrusion process. The TIPS layer was optimized by investigating the effects of coagulant composition on morphology and tensile strength. The solvent in the aqueous coagulation bath caused both delayed liquid–liquid demixing and decreased polymer concentration at the membrane surface, leading to porous structure. The addition of an additive (triethylene glycol, (TEG)) to the NIPS solution resolved the adhesion instability problem of the TIPS and NIPS layers, which occurred due to the different phase separation rates. The dual‐layer AMC membrane showed good mechanical strength and performance. Comparison of the fouling resistance of the AMC membranes with dual‐layer polyvinylidene fluoride (PVDF) hollow fiber membranes fabricated with the same method revealed less fouling of the AMC than the PVDF hollow fiber membrane. This study demonstrated that a dual‐layer AMC membrane with good mechanical strength, performance, and fouling resistance can be successfully fabricated by a one‐step process of TIPS and NIPS. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42715.     

PVDF树脂的物性对中空纤维膜性能的影响

采用了不同特性粘度的PVDF树脂,通过非溶剂致相分离法(NIPS)制备了相应的PVDF中空纤维膜。通过力学性能、纯水通量、牛血清白蛋白(BSA)截留率等性能测试发现,不同特性粘度的PVDF树脂制备的中空纤维膜的性能差异较大。随着PVDF特性粘度的增加,PVDF中空纤维膜的拉伸强度及断裂伸长率逐渐增加,纯水通量逐渐降低,BSA截留率先降低后增加。通过扫描电镜(SEM)进一步发现,随着PVDF特性粘度的增加,PVDF树脂制备的中空纤维膜,其海绵层上的孔状结构逐渐减少且变小。     

Activated carbon‐filled cellulose acetate hollow‐fiber membrane for cell immobilization and phenol degradation

The activated carbon‐filled cellulose acetate (CA) hollow‐fiber membranes were prepared by using phase‐inverse technique and subsequently characterized by scanning electronic microscopy (SEM), atomic force microscopy (AFM), dynamic mechanical analysis (DMA), thermal mechanical analysis (TMA), and tensile analysis. The SEM observation demonstrated that the activated carbon‐filled CA hollow‐fiber membranes possess four‐layer structure, which consists of an external skin dense layer, an external void layer, a central sponge layer, and an internal skin dense layer, whereas the pure CA hollow‐fiber membranes lack the macrovoid layer. As the measurement of AFM, the roughness of both internal and external surface of activated carbon‐filled fibers is much higher than that of pure CA fiber, respectively. Higher Young's modulus and storage modulus of filled membranes indicate that the activated carbon particles were homogeneously dispersed in the polymeric matrix. To investigate the feasibility of the newly developed hollow‐fiber membranes for cell immobilization cells and to evaluate the inhibitory effect of phenol on immobilized cells, Pseudomonas putida ATCC 17484 was chosen to be immobilized on both pure CA and activated carbon‐filled hollow‐fiber membranes. Batch experiments for phenol biodegradation were carried out for both free suspension and immobilized cells at the initial concentration of 1500 mg/L phenol. In the case of free suspension, neither cell growth nor phenol degradation occurred to any measurable extent up to 35 h. We found that both pure CA fiber and activated carbon‐filled fiber immobilization systems can completely degrade the phenol. However, the biodegradation rate of activated carbon‐filled fiber system was higher than that of pure CA fiber system. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 695–707, 2000     

分离有机/有机混合物的PVA、CA系列膜及其渗透汽化性能研究(Ⅰ)膜材料与成膜工艺

依据溶度参数原则和分离甲基叔丁基醚(MTBE)/甲醇(MeOH)混合物的选择渗透性,选择了聚乙烯醇(PVA)为复合膜的分离层材料,聚丙烯腈(PAN)、醋酸纤维素(CA)系列为支撑层的膜材料.初步讨论了膜材料和复合膜结构对分离性能的影响,给出了用不同成膜工艺制备的膜性能,获得了可用于有机/有机体系分离的性能优良的PVA/PAN和PVA/CA复合膜,以及CTA中空纤维渗透汽化膜.     

纺丝条件对PVDF/PVC中空纤维膜性能的影响

采用干-湿法纺丝工艺制备PVDF/PVC共混中空纤维膜,通过对水通量、孔径、截留率等的测试,研究了挤出速率、芯液流量、干纺程对PVDF/PVC中空纤维膜性能及结构的影响,并进行了详细的理论分析。试验结果表明挤出速率与膜通量存在最大值,芯液流量与膜通量及截留率呈线性关系,干纺程的影响效果跟挤出速率类似。可以通过改变纺丝条件来制备性能不同的中空纤维膜。