聚偏氟乙烯有机膜的共混改性及性能研究

将聚偏氟乙烯和高分子聚合物共混,通过溶胶-凝胶相转化法研制综合性能良好的微孔膜,考察了铸膜液浓度、PVDF与共混添加剂的配比、凝胶浴温度、溶剂挥发时间和酸、碱、氧化处理对共混膜性能的影响.结果表明,随着铸膜液中聚合物总含量、膜液的黏度增加,纯水通量总体呈下降趋势,孔隙率先增加后减小,最后趋近平衡;随着共混添加剂在铸膜液中相对含量的增加,纯水通量先增加后减小,孔隙率可得到有效提高,平均孔径变化不大;凝胶浴温度对纯水通量没有较大影响;延长溶剂的挥发时间,使平均孔径减小;找到合适的共混添加剂并选择适当的膜液组成,能够使共混改性膜的纯水通量、孔隙率、抗酸、碱、氧化性能较改性前得到有效提高.其中纯水通量较改性前提高10％左右,孔隙率提高15％左右,说明共混化是一种改善PVDF膜性能的有效方法,具有极好的实用开发价值.     

凝胶浴条件对PVDF/CaCO3共混中空纤维膜性能和结构的影响

采用干-湿相转化法制备了PVDF/CaCO3共混中空纤维膜,考察了芯液组成和外凝胶浴温度对共混膜结构和性能的影响。结果表明,随芯液中酸含量增加,膜纯水通量迅速升高,BSA截留率略有下降;膜拉伸强度下降,断裂伸长率增加。SEM图显示,膜断面指状孔的数量增多、支撑层厚度变薄、膜亚层海绵孔增加;相应孔隙率升高,而泡点压力略微下降。当外凝胶浴温度较高时,膜支撑层和外皮层较为致密,导致膜纯水通量明显下降,同时BSA截留率在80℃高温外凝胶浴时,由于膜外皮层上出现少量大孔结构,而迅速下降为62.55%。     

PVDF/PVA亲水化改性超滤膜的制备及表征

采用聚乙烯醇(PVA)对PVDF超滤膜进行亲水化改性,研究不同PVDF/PVA优化配比(wt/wt)对共混超滤膜结构和的性能影响。结果表明,当PVDF/PVA配比为8/2时,纯水通量最大,为1542.3 L/m2·h,截留率最小,为56.30%,平均孔径为67.75 nm,孔隙率为78.61%,膜的接触角为41.68°,此时超滤膜的性能最好,膜表面多孔。     

γ-BL/TEP混合溶剂对PVDF膜结构和性能的影响

通过溶解度参数预测,膜渗透性能检测,及扫描电镜(SEM)对膜形貌观察,考察了聚偏氟乙烯(PVDF)在γ-丁内酯(γ-BL)、磷酸三乙酯(TEP)为混合溶剂,乙二醇(EG)、N,N-二甲基乙酰胺(DMAc)及其混合物为凝固浴时,相转化条件及溶剂配比对PVDF膜在孔隙率、纯水通量、BSA截留率,以及拉伸强度等性能方面的影响行为。结果表明,随混合溶剂中TEP质量分数的增加,凝胶浴中溶剂DMAc质量分数增大,PVDF膜皮层逐渐变薄,PVDF结晶球粒粒径变小,孔隙率增加,拉伸强度下降。当混合溶剂中TEP的质量分数为60%,凝胶浴DMAc含量30%时,膜纯水通量达2 100 L/(m2·h),BSA截留率仍保持58.7%,具有良好的超滤性能,可作为制备高通量、较高截留PVDF超滤膜的最佳条件。     

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。     

PVDF/编织管中空纤维复合膜的制备及其性能研究

以纤维编织管为支撑层,通过涂覆-浸没沉淀相转化技术,制备了超高强度、大通量的PVDF/编织管中空纤维复合膜,考察了铸膜液中PVDF和添加剂PVP含量等对膜性能的影响。结果显示,随铸膜液中PVDF含量增加,复合膜纯水通量下降,爆破强度增加,平均孔径减小;PVP的质量分数从2%增加至10%,膜通量呈现降低趋势,但爆破压力先增后减;当PVDF、PVP的质量分数分别为8%、6%时,复合膜纯水通量达4 300 L/(m2·h),爆破压力为0.32 MPa。研究范围内,复合膜孔隙率始终保持在45%以上,爆破压力高于0.30 MPa,且由于编织管的存在,而使复合膜的拉伸强度很高,显示了较好的过滤性能;添加PVP和PVA较PEG在膜性能方面的贡献更突出。     

凝固浴组成对PVDF/PVDF-g-PAA共混膜结构与性能的影响

为了进一步提高PVDF膜的亲水性及渗透性能,本文通过在膜内引入聚偏氟乙烯接枝聚丙烯酸(PVDF-g-PAA),提高共混膜的亲水性,并在凝固浴中加入N, N-二甲基乙酰胺(DMAc),改善聚偏氟乙烯/聚偏氟乙烯接枝聚丙烯酸(PVDF/PVDF-g-PAA)共混膜的结构与性能。利用浊点法对PVDF/PVDF-g-PAA共混膜的成膜热力学进行了研究,相比于水/乙醇凝固浴,水/DMAc凝固浴的使用会抑制PVDF/PVDF-g-PAA的相分离速度,体系变得更加稳定。采用傅里叶红红外光谱仪(FT-IR)和X-射线光电子能谱仪(XPS)表征聚合物及膜的化学结构,并通过原子力显微镜和扫描电镜观察膜的表断面结构。结果表明,随着凝固浴中DMAc含量的增加,膜的致密皮层逐渐变薄,膜断面中的指状孔结构逐渐向海绵状结构转变,膜表面变粗糙,平均孔径增加,共混膜纯水通量变大。当DMAc含量为50%时,膜的纯水通量最高,可达(1 084±74)L/(m~2·h),同时具备较高的断裂强度(2.6±0.1)MPa。     

凝胶相转化温度和空气预蒸发时间对PVDF超滤膜性能及结构的影响

利用非溶剂相转化法(NIPS),以聚偏氟乙烯(PVDF)/聚乙烯吡咯烷酮(PVP)/N,N-二甲基乙酰胺( DMAC)为铸膜液体系,水为凝固浴制备了大通量超滤膜.考察了铸膜液温度、凝胶浴温度、空气预蒸发时间等条件对超滤膜性能与结构的影响.研究结果显示,随着铸膜液和凝胶浴温度的提高,膜纯水通量增大,强度增强,截留率降低,膜的第一泡点压力减小,膜的孔隙率随铸膜液温度升高而增大,随凝胶浴温度升高先增大后减小,膜断面指状孔发育较为通透,海绵层致密.延长铸膜液在空气预蒸发时间,膜的第一泡点压力和孔隙率降低,超滤膜截留率提高,通量和强度变化不大.     

聚偏氟乙烯共混膜的制备和性能研究

主要讨论了聚偏氟乙烯(PVDF)膜以及聚甲基丙烯酸甲酯(PVDF/PMMA)、PVDF/PMMA/PS(聚砜)共混膜的制备及性能,并研究了不同添加剂对PVDF/PMMA/PS共混膜的结构和性能的影响。实验数据表明:PVDF/PMMA/PS共混膜的通量最大;PVPK 40成膜通量最大;T iO 2成膜截留率最大。     

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。     

聚偏氟乙烯中空纤维膜的制备

本丈研究了聚偏氟乙烯（PVDF）中空纤维微滤膜的制备。采用亲水聚合物材料（如PMMA、改性聚醚硅油等）对聚偏氟乙烯材料进行共混改性,显著提高了膜材料的亲水性;同时由于材料性质的改变,导致膜材料在成膜时的凝胶特性和相转化发生变化,所成膜的孔径、通水量、孔隙率、表面性能等也发生改变。通过选择合适的共混体系,可制备出高性能、高孔隙率、表面亲水的聚偏氟乙烯中空纤维膜。     

Effect of Additive Concentration on Cellulose Acetate Blend Membranes-Preparation,Characterization and Application Studies

Abstract

Ultrafiltration techniques have particular advantages for simultaneous purification, concentration, and fractionation of macromolecules. A comparative study is presented on novel ultrafiltration polymeric blend membranes based on cellulose acetate (CA) prepared in the absence and presence of polymeric additives such as polyethylene Glycol 200 (PEG) and polyvinylpyrrolidone (PVP) by phase inversion technique using N,N′-dimethylformamide (DMF) as solvent. Polymer blend composition, additive concentration and casting, and gelation conditions were standardized for the preparation of asymmetric membranes by pore statistics and morphology. These blend membranes were characterized for compaction in ultrafiltration experiments at 414 kPa pressure in order to attain steady state flux and is reached within 4–5 h. The pure water flux was measured at 345 kPa pressure. Membrane hydraulic resistance derived by measuring water flux at various transmembrane pressures and found to be inversely proportional to pure water flux. Water content is estimated by simple drying and weighing procedures and found proportional to pure water flux for all the membranes. The molecular weight cut-offs (MWCOs) of different membranes were determined with proteins of different molecular weights and found to vary from 20 to 69 kDa depending on the PEG 200 and PVP content in the blend in the casting solution. Skin surface porosity of the membranes was analyzed by scanning the samples at various magnifications. The characterized CA, CA/PEG200 and CA/PVP membranes were used for cadmium ion rejection studies at 345 kPa.     

Synthesis and characterization of cellulose acetate-polysulfone blend microfiltration membrane for separation of microbial cells from lactic acid fermentation broth

This work is focused on synthesis and characterization of a polymer blend microfiltration membrane for separation of microbial cells from lactic acid fermentation broth in a continuous process. The membranes were prepared by blending hydrophilic cellulose diacetate (CA) polymer with hydrophobic polysulfone (PSF) polymer in wet phase inversion method. Polymers were blended in N-methyl-2-pyrrolidone (NMP) solvent (70 wt.%) where polyethylene glycol was added as a pore former. The membranes were characterized in terms of morphology, porosity, flux and microbial separation capability. The best prepared membrane with PSF/CA weight ratio of 25/75 yielded a pure water flux of 1830 LMH (liter/m² h) and a fermentation broth flux of 1430 LMH at around 1.5 bar TMP (trans-membrane pressure). The membrane was successful in complete retention of microbial cells from the broth in a continuous crossflow membrane module integrated with the fermentor.     

PVDF/PES-C共混膜的结构与性能

以邻苯二甲酸二丁酯(DBP)和N,N-二甲基乙酰胺(DMAc)为混合稀释剂,采用热致相分离法(TIPS)制备了聚偏氟乙烯(PVDF)和酚酞型聚醚砜(PES-C)共混膜,采用扫描电镜观察了膜的截面结构,测试了膜的纯水通量。通过膜生物反应器处理生活污水,检验了膜的污水处理性能。与PVDF膜相比,共混膜具有一个较薄的致密的皮层和较为疏松的支撑层,共混膜的纯水通量约为纯聚偏氟乙烯膜的两倍。同时共混膜的污水通量较高,COD和NH4+-N的去除率与PVDF膜相比约增加10%,共混膜的通量衰减系数较小,具有更好的抗污染性能。     

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.     

聚醚砜质量分数对聚偏氟乙烯/聚醚砜共混膜性能和结构的影响

用与聚醚砜共混的方法来改善聚偏氟乙烯膜的抗收缩性能,以二甲基乙酰胺作溶剂,聚乙烯吡咯烷酮为添加剂,研究了聚醚砜(PES)质量分数对聚偏氟乙烯/聚醚砜共混膜的收缩率、水通量、截留率及形态结构的影响。聚醚砜的加入可以有效地降低共混膜的收缩率,在w(PES)=1.5%时,共混膜的水通量取得极大值,截留率取得极小值。     

Preparation and characterization of PES/CA microporous membranes via reverse thermally induced phase separation process

The blend polyethersulfone (PES)/cellulose acetate (CA) flat‐sheet microporous membranes were prepared by reverse thermally induced phase separation (RTIPS) process. The effects of CA content and coagulation bath temperature on membrane structures and properties were investigated in terms of membrane morphology, water contact angle, permeation performance, and mechanical properties. The cloud point results indicated that the cloud point decreased with the increasing content of CA. When the coagulation bath temperature was lower than the cloud point, the membrane formation process underwent nonsolvent induced phase separation (NIPS) process and dense skin layer and finger‐like structure were formed in membranes. These membranes had lower pure water flux and poor mechanical properties. But when the coagulation bath temperature was higher than the cloud point, the membrane formation process underwent RTIPS process. The porous top surface as well as porous cross‐section of the membranes were formed. Therefore, high pure water flux and good mechanical properties were obtained. The contact angles results indicated that the hydrophilicity of the prepared membranes improved obviously with the addition of CA. When the content of CA was 0.5 wt% and the membrane formation temperature was 323K, the PES/CA microporous membrane which was prepared via the RTIPS process displayed a optimal permeability of the pure water flux of 816 L m^?2 h^?1 and the BSA rejection rate of 49.5%, which showed an increase of 48.9% and 23.6% than that of pure PES membrane, respectively. Moreover, the mechanical strengths of the membranes obtained by RTIPS process were better than those membranes prepared by NIPS process. POLYM. ENG. SCI., 58:180–191, 2018. © 2017 Society of Plastics Engineers     

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.     

凝固浴温度对PVDF/PES-C共混膜结构及性能的影响

以邻苯二甲酸二丁酯(DBP)和N,N-二甲基乙酰胺(DMAc)为混合稀释剂,采用热致相分离法(TIPS)制备了聚偏氟乙烯(PVDF)/酚酞型聚醚砜(PES-C)共混膜,考察了不同凝固浴温度对膜结构和性能的影响。采用扫描电镜观察了膜的结构,测试了膜的纯水通量。运用DSC和XRD方法检测了膜的结晶性能。将制备的膜在膜生物反应器(MBR)中运行测试了膜的污水通量和出水指标。随凝固浴温度的升高,共混膜的最高熔融温度上升,膜中α晶型的含量增加。在凝固浴温度为25℃时,膜形成了较为致密的皮层结构和较为疏松的支撑层结构,此时共混膜的纯水通量和污水通量达到最大值,且MBR出水COD和NH4+-N含量达到排放要求。     

Fabrication of antifouling membranes by blending poly(vinylidene fluoride) with cationic polyionic liquid

Membrane fouling problem is now limiting the rapid development of membrane technology. A newly synthesized cationic polyionic liquid (PIL) [P(PEGMA-co-BVIm-Br)] was blended with poly(vinylidene fluoride) (PVDF) to prepare antifouling PVDF membranes. The PVDF/P(PEGMA-co-BVIm-Br) exhibited an increased surface hydrophilicity, the water contact angle was reduced from 77.8° (pristine PVDF) to 57.9°. More porous membrane structure was obtained by adding PIL into the blending polymers, as high as 478.0 L/m²·h of pure water flux was detected for the blend PVDF membrane in comparison with pristine PVDF (17.2 L/m²·h). Blending of the cationic PIL with PVDF gave a more positive surface charge than pristine PVDF membrane. Blend membranes showed very high rejection rate (99.1%) and flux recovery rate (FRR, 83.0%) to the positive bovine serum albumin (BSA), due to the electrostatic repulsion between the membrane surface and proteins. After three repeated filtration cycles of positive BSA, the blend PVDF membranes demonstrated excellent antifouling performance, the permeation flux of the membranes was recovered very well after a simple deionized water washing, and as high as 70% of FRR was obtained, the water flux was maintained at above 350 L/m²·h. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48878.