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。     

凝固浴组成和温度对PVDF疏水微孔膜结构与性能的影响

利用非溶剂相转化法(NIPS),以聚偏氟乙烯(PVDF)/磷酸三乙酯(TEP)-N,N-二甲基乙酰胺(DMAc)为铸膜液体系,乙醇水溶液为凝固浴制备高性能的PVDF疏水微孔膜。考察了凝固浴中乙醇(EtOH)含量及凝固浴温度对PVDF成膜分相速率、膜结构和膜疏水性的影响。实验结果表明,在20℃的凝固浴温度下,凝固浴中乙醇含量的升高减慢了铸膜液体系的分相速率,提高了PVDF膜的孔隙率;在凝固浴中添加60%(wt)的乙醇,可形成表面荷叶状结构和截面对称的海绵状结构,膜表面的接触角为130.3°,呈很强的疏水性,并具有较优的膜强度。     

膜蒸馏用PDMS/PVDF/PTFE三元共混微孔膜制备

采用浸没沉淀相转化法制备了聚二甲基硅氧烷/聚偏氟乙烯/聚四氟乙烯（PDMS/PVDF/PTFE）三元共混微孔膜,并用于20 g/L NaCl水溶液的膜蒸馏脱盐实验。通过扫描电子显微镜观察以及接触角、膜孔隙率和膜平均孔径分析,研究了PTFE含量对膜结构与性能的影响。结果表明,随着PTFE含量的增加,共混微孔膜断面的指状孔逐渐被海绵状取代,平均孔半径由0.234 μm增加到0.354 μm,膜孔隙率由53.4 %增加到81.3 %;膜下表面与水接触角从118.52 °增加到131.11 °;膜蒸馏过程中通量逐渐增加,截留率先稳定后降低,PTFE含量为40 %（质量分数,下同） 时达最大,为99.99 %,此时膜蒸馏通量达16.60 kg/(m2·h)。     

倒相法制备聚偏氟乙烯多孔膜大孔的研究

利用倒相法制备了聚偏氟乙烯(PVDF)多孔膜,扫描电镜表征了膜的微观结构。研究发现,在w(PVDF)=5 0%～20 0%的铸膜液中,大孔孔隙率及孔径尺寸随着PVDF质量分数的升高而降低;在乙醇与水组成的凝固浴中,膜的大孔孔隙率及孔径尺寸随乙醇体积分数的增加而降低,在φ(ethanol)=50%时大孔结构消失,多孔膜由指状大孔结构转变为海绵状结构。分析了大孔形成机理。     

聚偏氟乙烯/聚离子液体共混膜的优化制备

研究制备了由聚离子液体(PIL)改性的聚偏氟乙烯(PVDF)共混膜,探讨了凝固浴组成的变化对PVDF共混膜的影响。通过FTIR、XPS、SEM分析了膜表面的组成及膜孔结构;通过水接触角和机械强度测试分析了膜的性能,并研究了膜对橙黄Ⅳ的吸附容量。实验表明:随着凝固浴中DMF含量的增加,膜的水接触角从77.79°减小到51.94°,亲水性显著增强,膜对橙黄Ⅳ的吸附容量从7.7 mg/g增加到16.1 mg/g,实现对PVDF膜的优化改性。     

PVDF共混亲水膜的制备及其性能研究

通过自由基聚合法将甲基丙烯酸羟乙酯（HEMA）接枝到预处理的聚偏氟乙烯（PVDF）上，制备一种新型的聚合物PVDF-g-PHEMA。以PVDF-g-PHEMA作为亲水性添加剂，利用非溶剂致相分离法（NIPS）制备PVDF共混亲水膜，并研究铸膜体系PVDF-g-PHEMA含量对PVDF共混膜亲水性能的影响。实验结果表明，铸膜体系中PVDF-gPHEMA为25%的共混膜表面水接触角103±1°降低到45.6°，膜表面抗污染性增强。通过X射线光电子能谱、傅里叶红外光谱仪、扫描电子显微镜和孔径分析仪对制备的亲水膜表面进行表征，PVDF共混亲水膜表面含有羟基、酯基、膜孔径增加。抗污染和稳定性测试表明，PVDF共混亲水膜具有优异的抗蛋白质吸附性能和良好的稳定性。     

双凝固浴对膜蒸馏聚偏氟乙烯膜结构性能的影响

以聚偏氟乙烯(PVDF)、磷酸-N,N-二甲基乙酰胺为铸膜液体系,采用非溶剂相转化法,通过双凝固浴制备高性能的PVDF疏水微孔膜。采用正交实验的方法,考察凝固浴条件对PVDF膜结构和性能的影响。结果表明,双凝固浴法对膜的结构和性能有很大的影响,随着第1凝固浴中乙醇含量的增加,固液分相逐渐占据主导,促进了膜表面微纳米粗糙结构的形成,提高了膜表面的疏水性。以温度为60℃的质量分数40%乙醇作为第1凝固浴,浸泡时间20 s,温度60℃的水作为第2凝固浴所制备的PVDF膜,其直接接触膜蒸馏通量为28.3 kg/(m2·h),孔隙率为84.5%,平均孔径为1.05μm,接触角为116.8°。     

化学浴沉积制备防污自洁型PVDF/PMMA共混膜研

使用NaOH溶液亲水改性聚偏氟乙烯(PVDF)/聚甲基丙烯酸甲酯(PMMA)共混膜,在共混膜表面化学浴沉积烷基氯硅烷,构筑微纳米结构,制备出具有超疏水能力的PVDF/PMMA共混膜,对共混膜的微观结构和性能进行了表征。结果表明,亲水改性提升了PVDF/PMMA共混膜表面烷基氯硅烷的化学浴沉积效果;亲水改性的最佳工艺条件为：NaOH的浓度为40 %、反应时间为60 min、反应温度为70 ℃;化学沉积后的PVDF/PMMA共混膜接触角高达154.6 °;集灰实验表明,倾斜角度约为1 °时水滴能将膜表面的灰尘带走,膜的防污自洁性能优良。     

PDMS接枝共聚物改性PVDF膜的制备及其膜蒸馏性能研究

采用自由基聚合法制备了PDMS接枝共聚物（PMMA-g-PDMS）,并用PDMS接枝共聚物对聚偏氟乙烯（PVDF）膜进行疏水改性,使用傅立叶红外光谱仪、毛细管流动孔径分析仪、接触角测定仪和场发射电子显微镜对不同浓度改性的PVDF膜进行表征,并测试了其在直接接触式膜蒸馏（DCMD）中的分离性能。结果表明,经过PMMAg-PDMS改性后,膜的通量、疏水性和截留性有所提高,稳定性大幅提升。当PMMA-g-PDMS浓度为8%时,膜的静态接触角由118.68°增加至157.47°,在以温度为70℃,质量分数3.5%的NaCl溶液为进料液的DCMD实验中,改性膜的通量由基膜的11.28 kg/（m²·h）提高至15.44 kg/（m²·h）,通量衰减降低了35%.     

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.     

Characterization of poly(vinylidene fluoride) flat sheet membranes prepared in various ratios of water/ethanol for separator of li‐ion batteries: Morphology and other properties

PVDF, poly(vinylidene fluoride), membranes were prepared and investigated by a scanning electron microscope, a universal testing machine, and capillary porometer for its potential use as a separator in lithium ion batteries. The membranes were prepared by phase inversion with different polymer types, concentrations of solution, amounts of additive, and nonsolvent ratios of water/ethanol. The morphology of membranes is affected by the ratio of both the coagulation bath (water/ethanol) and a low molecular weight additive (polymer/solvent/additive). The results showed that significant variations in the membrane were detected when adding an additive to the casting solution or ethanol to the coagulation bath. With an increased concentration of ethanol, the upper structure was found to be transformed into a sponge‐like arrangement. In the case of Solef®1015 of the same polymer concentration, despite the higher molecular weight of 1015, a relatively small sized nucleus is formed, resulting in a denser network and relatively uniform membrane structure being formed. Mechanical testing showed that the tensile strength of the PVDF membranes increased when added to a 25 wt % ethanol coagulation bath, whereas it is decreased when added to higher concentrations of ethanol in the bath or additives in the casting solution. In a bath condition of water/ethanol = 75/25 wt % (Bath no. 2), the value of tensile strength is 7.11 and 7.52 MPa, for Solef®6010 20 wt % and Solef®1015 17 wt %, respectively. The thickness of the prepared membrane is 21–34 μm and the porosity is up to 50%. The electrolyte absorption changes of the fabricated membranes at different conditions are measured from 151 to 223 ± 15%. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

PDMS/PVDF microporous membrane with semi‐interpenetrating polymer networks for vacuum membrane distillation

In this article, using the non‐solvent induced phase separation process, a new microporous membrane with the semi‐interpenetrating polymer network (semi‐IPN) structure was produced. For this membrane, polydimethylsiloxane (PDMS) polymer is crosslinking and poly(vinylidene fluoride) (PVDF) polymer is linear, by changing the mass ratio of PDMS/PVDF, the structure and the performance of the prepared membranes were studied. The membranes were also investigated by attenuated total reflection‐Fourier transform infrared (ATR‐FTIR), scanning electron microscopy–energy‐dispersive X‐ray spectroscopy, X‐ray diffraction, thermogravimetric analysis, and water contact angle, etc. ATR‐FTIR spectroscopy confirmed the formation of semi‐IPN; compared with the PDMS/PVDF polymer without semi‐IPNs structure, the viscosity of the semi‐IPNs structured casting solution increased, membrane mechanical property increased but its hydrophobicity decreased. Using the resulting membranes for the vacuum membrane distillation desalt of the NaCl solution (30 g/L), 99.9% salt rejection and reasonable flux were obtained. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45792.     

High permeability poly(vinylidene fluoride) ultrafiltration membrane doped with polydopamine modified TiO2 nanoparticles

In order to improve the water permeability of poly(vinylidene fluoride) (PVDF) ultrafiltration (UF) membranes with low molecular weight cut-off (MWCO), polydopamine (PDA) was employed in the membrane preparation process. Owing to its merits of material-independent adhesion, PDA was coated on inorganic particles or added in coagulation bath to tailor the final membrane structure and property. The introduction of PDA broke through the permeability/selectivity trade-off of the PVDF membrane. By adding the PDA coated titanium dioxide (PDA/TiO₂) nanoparticles, water flux increased by 287% while MWCO kept similar with the pristine PVDF membrane. Thermodynamics and Kinetics of the PVDF/additives/non-solvent were analyzed and shown that nanoparticles reduced the thermodynamic stability and increased the phase separation speed, and the speed can be adjusted using different nanoparticles. Additionally, X-ray diffraction (XRD) test indicated that PVDF crystalline form changed from α phase to β phase after adding different nanoparticles. Permeability/selectivity trade-off was broken through by DA addition in coagulation bath. Compared with the original PVDF membrane, when the DA concentration of the coagulation bath was 2.0 g·L⁻¹, water flux increased by 312%, and MWCO of the PVDF membrane ranged in 10,000 to 20,000 Da as well as contact angle decreased from 81.4° to 45°.     

High permeability poly(vinylidene fluoride) ultrafiltration membrane doped with polydopamine modified TiO2 nanoparticles

In order to improve the water permeability of poly(vinylidene fluoride) (PVDF) ultrafiltration (UF) membranes with low molecular weight cut-off (MWCO), polydopamine (PDA) was employed in the membrane preparation process. Owing to its merits of material-independent adhesion, PDA was coated on inorganic particles or added in coagulation bath to tailor the final membrane structure and property. The introduction of PDA broke through the permeability/selectivity trade-off of the PVDF membrane. By adding the PDA coated titanium dioxide (PDA/TiO₂) nanoparticles, water flux increased by 287% while MWCO kept similar with the pristine PVDF membrane. Thermodynamics and Kinetics of the PVDF/additives/non-solvent were analyzed and shown that nanoparticles reduced the thermodynamic stability and increased the phase separation speed, and the speed can be adjusted using different nanoparticles. Additionally, X-ray diffraction (XRD) test indicated that PVDF crystalline form changed from α phase to β phase after adding different nanoparticles. Permeability/selectivity trade-off was broken through by DA addition in coagulation bath. Compared with the original PVDF membrane, when the DA concentration of the coagulation bath was 2.0 g·L^-1, water flux increased by 312%, and MWCO of the PVDF membrane ranged in 10,000 to 20,000 Da as well as contact angle decreased from 81.4° to 45°.     

Investigation on crystallization behavior and hydrophilicity of poly(vinylidene fluoride)/poly(methyl methacrylate)/poly(vinyl pyrrolidone) ternary blends by solution casting

Ternary blends composed of matrix polymer poly(vinylidene fluoride) (PVDF) with different proportions of poly(methyl methacrylate) (PMMA)/poly(vinyl pyrrolidone) (PVP) blends were prepared by solution casting. The crystallization behavior and hydrophilicity of ternary blends were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), wide angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), and contact angle test. According to morphological analysis, the surface was full of typical spherulitic structure of PVDF and the average diameter was in the order of 3 μm. The samples presented predominantly β phase of PVDF by solution casting. It indicated that the size of surface spherulites and crystalline phase had little change with the PMMA or PVP addition. Moreover, FTIR demonstrated special interactions among the ternary polymers, which led to the shift of the carbonyl stretching absorption band of PVP. On the other hand, the melting, crystallization temperature, and crystallinity of the blends had a little change compared with the neat PVDF in the first heating process. Except for the content of PVP containing 30 wt %, the crystallinity of PVDF decreased remarkably from 64% to 33% and the value of t_1/2 was not obtained. Besides, the hydrophilicity of PVDF was remarkably improved by blending with PMMA/PVP, especially when the content of PVP reached 30 wt %, the water contact angle displayed the lowest value which decreased from 98.8° to 51.0°. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

聚偏氟乙烯/纳米纤维素复合超滤膜的研究

以聚偏氟乙烯为原材料,聚乙烯吡咯烷酮( PVP K30)为添加剂,并向聚偏氟乙烯铸膜液中混入纳米纤维素,采用相转化工艺制备了复合超滤膜.通过正交试验分析了各因素对产品性能的影响,并得出了制备复合超滤膜的最优条件:聚偏氟乙烯质量分数为14％,添加剂PVP K30质量分数为0.5％,纳米纤维素加入量为0.7％,空气中溶剂蒸发时间为10s,凝胶浴为水.测定复合超滤膜的水通量、截留率、平均孔径、孔隙率、力学强度等一系列性能,膜的水通量为40.7 L/(m2·h),对牛血清蛋白的截留率为91.8％,孔隙率为52.3％,平均孔径为15.3 nm.     

辣素衍生物改性PVDF膜的制备及其抗菌性能

以甲基丙烯酸甲酯（MMA）和天然辣素8-甲基-N-香草基-6-壬烯酰胺（Capsa）为单体,通过自由基聚合合成辣素衍生物PMMA-Capsa。将PMMA-Capsa与聚偏氟乙烯（PVDF）共混,通过非溶剂诱导相转化法制备PVDF/PMMA-Capsa分离膜,系统地研究了PMMA-Capsa含量对所制备的分离膜表面化学组成、形态结构、亲水性能、抗菌性能及渗透性能的影响。结果表明在成膜过程中PMMA-Capsa倾向于分布在分离膜的表面和孔道表面。随着铸膜液中PMMA-Capsa含量的增加,所制备的分离膜断面结构中海绵层结构逐渐消失,分离膜容易形成粗糙的微孔状表面。PMMA-Capsa的引入使分离膜表面水接触角从88.4°降低到73.1°。渗透实验结果表明分离膜的纯水通量随着PMMA-Capsa含量的增加而增加,而对牛血清蛋白（BSA）的截留率逐渐降低,所制备的PVDF/PMMA-Capsa分离膜的通量恢复率高于纯PVDF膜。PVDF/PMMA-Capsa分离膜具有优异的抗菌性能,对金黄色葡萄球菌的抗菌效率最高可达97.2%。     

超疏水聚偏氟乙烯复合微孔膜的制备及性能

提出了一种超疏水聚偏氟乙烯（PVDF）复合微孔膜的制备方法。以相转化法制备的PVDF膜为基膜,通过恒压过滤将多壁碳纳米管（MWCNTs）沉积到PVDF基膜表面,再经聚二甲基硅氧烷（PDMS）溶液修饰,可制得接触角达162°、滚动角约10°的PVDF复合微孔膜。用原子力显微镜和扫描电镜对膜表面进行结构分析,并测试了膜的接触角、气通量和机械强度等性能,考察了MWCNTs及PDMS浓度对膜结构和性能的影响。研究表明,CNTs在具有微米级粗糙度的基膜上强化了纳米结构,提高了膜的粗糙度,PDMS降低了膜的表面能,二者协同作用使复合膜的接触角大幅提高,滚动角显著下降。与高度疏水的PVDF基膜相比,PVDF复合膜的疏水性大幅提高,断裂伸长率加倍,在模拟海水真空膜蒸馏过程中,保持了较高的传质通量和截留率,具有更好的操作稳定性和抗污染性能。