微模塑协同浸没凝胶法PVDF高度疏水微孔膜:添加剂的影响

采用微模塑协同浸没凝胶法制备聚偏氟乙烯（PVDF）高度疏水微孔膜,以呈现人工微结构的喷砂加工铝板、N-甲基吡咯烷酮（NMP）、水分别为制膜基底、溶剂和凝固剂。研究了添加剂对微结构制膜基底协同作用下的相分离行为、膜结构与性能的影响。添加剂加入形成混合溶剂,改变原溶剂与聚合物、非溶剂的相容性,并用Hansen溶解度的理论计算值进行比较,是筛选添加剂的依据。混合溶剂与非溶剂相容性比溶剂与非溶剂相容性好,发生L-L相分离,形成胞腔结构、致密皮层;混合溶剂与非溶剂相容性比溶剂与非溶剂相容性差,发生S-L相分离,形成粒子结构、孔结构;混合溶剂与聚合物相容性比溶剂与聚合物形容性好时,铸膜液体系比较稳定;混合溶剂与聚合物相容性比溶剂与聚合物形容性差时,铸膜液体系易形成预晶核,在慢过程S-L相分离过程中,使粒子结构和孔结构更明显。研究发现,添加剂加入形成的混合溶剂与非溶剂相容性比溶剂与非溶剂相容性好、混合溶剂与聚合物相容性比溶剂与聚合物形容性差时,膜底面的粗糙度最大,疏水性最好。     

强疏水性PDMS/PVDF微孔膜的制备及其性能研究

利用非溶剂相转化法（NIPS）,通过在聚偏氟乙烯(PVDF)铸膜液中加入聚二甲基硅氧烷(PDMS),制备了PDMS/PVDF共混疏水微孔膜,并研究了凝胶浴组成（水/乙醇）对铸膜液凝胶动力学、膜形貌、疏水性及力学性能的影响。结果表明,随着凝胶浴中乙醇百分含量由零增加至100 %时,PDMS/PVDF共混膜的断面上指状孔基本消失,海绵状孔结构贯穿断面;当凝胶浴中乙醇含量为100 %时,PDMS与PVDF发生分相;膜表面疏水性能增加,水接触角达到139.68 °;弹性模量、拉伸强度、断裂伸长率分别由（48.06±4.20）、（2.82±0.15） MPa、（92.90±2.53） %下降至（15.70±2.83）、（0.72±0.13） MPa、（15.47±1.63） %。     

CNCs增强相分离法构建PVDF/PDMS超疏水表面

采用非诱导相分离法，通过将纤维素纳米晶（CNCs）与两种聚合物（聚偏二氟乙烯和聚二甲基硅氧烷）进行结合，利用CNCs之间的静电排斥力及其高比表面积特性，有效降低相分离过程中聚合物的聚集，减小了颗粒尺寸，增强了颗粒分散性，在棉布、木板和玻璃表面构造了精细均匀的微纳米粗糙结构。采用FTIR、SEM、AFM、接触角测量仪、3D光学轮廓仪对CNCs和超疏水表面的形貌、结构和超疏水性进行表征。研究发现，棉布、木板和玻璃表面的水接触角分别最高可达158 °、156.8 °和153.8 °，滚动角最低分别为2 °、2.7 °和3.4 °，呈现出明显的超疏水特征。经过机械摩擦（500余次）、酸碱处理（pH 1～13）、温度变化（–40～40°C）以及紫外光照射（0～320 h）后，基材表面仍具有较好的超疏水性。此外，基材具有优异的自清洁性和油水分离效率，超疏水棉布的最高分离效率可达98.4%。     

PVDF中空纤维换热管超疏水表面强化蒸气滴状冷凝传热

为了提高塑料换热管的传热性能，通过两步涂覆法制备了具有超疏水表面的复合塑料换热管。首先采用多孔PVDF中空纤维膜为支撑层，以导热材料纳米ZnO填充聚二甲基硅氧烷（PDMS）为皮层，制备了具有致密外表皮层的复合塑料换热管。其次为了强化蒸气的滴状冷凝传热，通过考察正硅酸乙酯含量，氨水含量等条件的影响，制备出了具有超疏水表面的PVDF复合塑料换热管。结果表明，所制备的换热管表面接触角可达154°，与熔融法及NIPS法制备的换热管相比，总传热系数可提高85.3%～147.3%。     

膜蒸馏用PVDF抗复合污染膜的制备与测试

为提高膜的抗污染能力,对聚偏氟乙烯（PVDF）平板膜进行表面涂覆改性,得到超疏水PVDF平板膜,再将超疏水PVDF平板膜进行表面亲水化改性,制备出超疏水/亲水复合PVDF膜。当PVDF的质量浓度为2%、聚乙二醇（PG）的质量浓度为39%、涂敷液温度为50℃、蒸发时间为10 s、凝固浴温度为60℃时,超疏水PVDF平板膜接触角达到154.8°。表面亲水改性制得的PVDF超疏水/亲水复合膜的接触角为41°。然后研究了超疏水PVDF平板膜和PVDF超疏水/亲水复合膜的抗膜污染性能。结果显示,超疏水PVDF平板膜具有优良的抗无机污染性能和一定的抗有机污染性能;PVDF超疏水/亲水复合膜不仅具有优良的抗无机污染性能,而且其抗复合污染性能尤其是抗有机污染性能得到明显提升,为进一步构建高性能膜蒸馏抗污染膜提出了一个可行的技术方向。     

自组装法制备PVDF-SiO2/PVSQ超疏水复合膜及膜蒸馏抗污染性能

采用乙烯基三甲氧基硅烷(VTMOS)对SiO₂疏水改性,通过自组装法,将改性SiO₂接枝在商业PVDF(聚偏氟乙烯)膜表面,使其表面达到超疏水。利用场发射电子显微镜、红外光谱仪、接触角测量仪及毛细流孔径分析仪等仪器对改性前后膜的表面形貌、化学组成、接触角及孔径变化等性能参数进行表征。结果表明,VTMOS不仅对SiO₂疏水改性,还通过自身的水解缩聚反应,生成了规整圆球状的聚乙烯基倍半硅氧烷(PVSQ)微粒,纳米级SiO₂分布于微米级PVSQ表面,在改性膜表面构造了多层次微/纳米粗糙表面,在低表面能疏水基团乙烯基和甲氧基的共同作用下,成功实现了超疏水改性,改性膜水接触角达到159.5°,滚动角降至8.1°。以NaCl、HA和CaCl₂混合溶液为进料液,对商业PVDF膜和改性膜进行了长期直接接触式膜蒸馏(DCMD)实验,探究其抗污染性能。结果表明,改性膜适用于长期DCMD实验,并表现出比商业PVDF膜更稳定的通量,截盐率始终大于99.99%,具有良好的稳定性和抗污染性能。     

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。     

表面沉积化镁合金基底上超疏水聚偏氟乙烯微孔膜的制备与性能

用一步浸泡法制得表面沉积化镁合金板,再以此镁合金板为制膜基底,以聚偏氟乙烯（PVDF）/N,N-二甲基乙酰胺（DMAc）/辛醇/水为制膜体系,采用干-湿相转化法制备了超疏水PVDF膜,该膜的水接触角可达160°。用粗糙度仪、扫描电镜、能谱仪、红外光谱仪等对镁合金表面和PVDF膜底面的微观结构、化学组成进行表征和分析。研究表明,一步浸泡处理过的镁合金表面生成了均匀的十四酸铁沉积物,该沉积物可在膜制备中部分嵌入膜底面,增加了膜底面的粗糙度,从而使PVDF膜的疏水性大幅提高。对PVDF膜的磨损试验表明,所制备的超疏水膜表面具备良好的机械稳定性。真空膜蒸馏实验表明,所制备的PVDF膜具有较高的通量和截留率,在运行中保持了更好的操作稳定性。     

仿生水稻叶各向异性聚偏氟乙烯超疏水膜的构建及性能研究

通过静电纺丝技术制备了一种仿生水稻叶各向异性聚偏氟乙烯(PVDF)超疏水膜,研究了纺丝液配比、纺丝条件对聚偏氟乙烯纳米纤维膜的形貌、疏水性以及纤维取向的影响。结果表明,最优纺丝液溶剂配比为DMF/丙酮=5∶5,PVDF质量分数为22%。最优纺丝参数为：电压12 kV,纺丝液推注速度0.05 mm/min,滚筒接收转速2 200 r/min,接收距离15 cm。制备出的聚偏氟乙烯纳米纤维膜具有优异的疏水性和各向异性,其与水的接触角为149.5°。同时,膜的断后伸长率为94.90%,抗拉强度16 MPa。为超疏水膜及表面制备提供了一种新的可行方法。     

混合溶剂对TiO2/PVDF平板超滤膜性能和结构的影响

采用N,N-二甲基乙酰胺(DMAC)和N-甲基吡咯烷酮(NMP)为混合溶剂制备PVDF超滤膜。考察了不同混合比例的DMAC和NMP对膜性能及膜结构的影响,同时利用扫描电子显微镜(SEM)对膜表面及断面结构进行分析,原子力学显微镜(AFM)对膜表面粗糙度进行了分析,利用接触角测量仪对膜表面接触角进行了测量。结果表明,使用混合溶剂对膜孔径和膜亚层结构影响较大,但混合溶剂对膜孔隙率和接触角基本没有影响。当混合溶剂DMAC/NMP为1:2时,膜性能达到最优,孔隙率为70%,平均孔径为0.24μm,水通量为373 L.m-2.h-1,截留率为88%。     

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 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.     

TiO2纳米粒子对PVDF超滤膜的结构与性能影响研究

采用溶胶-凝胶法制备了不同纳米TiO2溶胶含量的TiO2/PVDF超滤膜,探讨TiO2溶胶及其含量对膜性能及结构的影响,并利用X射线衍射、扫描电子显微镜、红外光谱和接触角测量仪表征了复合膜的结构.结果表明,经纳米TiO2溶胶改性后,TiO2/PVDF复合膜的孔隙率、接触角和结构等都发生了显著的变化,在TiO2溶胶添加质量分数为4％时条件下,膜的孔隙率为74.5％,水通量为430.6L·m-2·h-1,截留率为82.5％.     

聚偏氟乙烯(PVDF)膜化学法亲水改性技术

通过化学表面改性的方法改善PVDF膜的亲水性,从化学处理的时间、体系的温度、碱液的浓度三个因素对改性的条件进行摸索、优化.采用静滴接触角、raman光谱法、傅里叶-红外(FT-IR)、差分扫描热分析(DSC)法、X-射线衍射强度法等方法研究改性后PVDF膜亲水性、结构、组成、晶型变化.结果显示:体系温度在60℃下,碱液...     

Modified silicone–PVDF composite hollow‐fiber membrane preparation and its application in VOC separation

Polydimethylsiloxane^vi–poly(vinylidene fluoride) (PDMS^vi–PVDF) composite membranes were prepared using asymmetric PVDF hollow‐fiber membranes as the substrate where a very thin layer of silicone‐based coating material was deposited via a developed dip coating method. The preparation of the composite membranes under various conditions were investigated. In the optimal coating procedure, homogenous and stable oligo‐PDMS^vi coating layers as thin as 1–2 μm were successfully deposited on the surface of PVDF membranes. The developed PDMS^vi–PVDF composite membranes were applied for separation of a wide variety of volatile organic compounds (benzene, chloroform, acetone, ethyl acetate, and toluene). The results showed that the PDMS^vi–PVDF hollow‐fiber composite membranes that had been developed exhibited very high removal efficiency (>96%) for all the VOCs examined under favorable operating conditions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

鼓气减压膜蒸馏过程研究

设计了新型鼓气减压膜蒸馏(AVMD)过程,在原水进入疏水膜组件前鼓入低压压缩空气,形成气液混合流进入疏水膜组件,在疏水膜组件的产汽出口外接负压系统,构成AVMD系统.采用疏水性聚偏氟乙烯中空纤维微孔膜,以自来水为测试液,研究了鼓气强度、进料温度、流速、冷侧真空度对AVMD过程性能的影响,考察了AVMD对不同NaCl含量溶液的分离性能.结果表明,随着鼓气量、进料液温度、流速,真空度的提高,AVMD过程通量有明显的增加,而产水电导率始终低于0.3 mS·m~(-1).当进料液温度70℃,冷侧真空度85 kPa,进料流速1.33 m·s~(-1)时,AVMD过程膜通量可高达45 kg·m~(-2)·h~(-1),而相同实验条件下减压膜蒸馏(VMD)过程的通量约为30 kg·m~(-2)·h~(-1).     

Effects of mixed solvents and PVDF types on performances of PVDF microporous membranes

Polyvinylidene fluoride (PVDF) microporous flat membranes were cast with different kinds of PVDFs and four mixed solvents [trimethyl phosphate (TMP)–N,N‐dimethylacetamide (DMAc), triethyl phosphate (TEP)–DMAc, tricresyl phosphate (TCP)–DMAc, and tri‐n‐butyl phosphate (TBP)–DMAc]. The effects of different commercial PVDFs (Solef® 1015, FR 904, Kynar 761, Kynar 741, Kynar 2801) on membrane morphologies and membrane performances of PVDF/TEP–DMAc/PEG200 system were investigated. The membrane morphologies were examined by scanning electron microscopy (SEM). The membrane performances in terms of pure water flux, rejection, porosity, and mean pore radius were measured. The membrane had the high flux of 143.0 ± 0.9 L m^?2 h^?1 when the content of TMP in the TMP–DMAc mixed solvent reached 60 wt %, which was 2.89 times that of the membrane cast with DMAc as single solvent and was 3.36 times that of the membrane cast with TMP as single solvent. Using mixed solvent with different solvent solubility parameters, different morphologies of PVDF microporous membranes were obtained. TMP–DMAc mixed solvent and TEP–DMAc mixed solvent indicated the stronger solvent power to PVDF due to the lower solubility parameter difference of 1.45 MPa^1/2 and the prepared membranes showed the faster precipitation rate and the higher flux. The less macrovoids of the membrane prepared with TEP (60 wt %)–DMAc (40 wt %) as mixed solvent contributed to the higher elongation ratio of 96.61% ± 0.41%. Therefore, using TEP(60 wt %)–DMAc (40 wt %) as mixed solvent, the casting solution had the better solvent power to PVDF, and the membrane possessed the excellent mechanical property. The microporous membranes prepared from casting solutions with different commercial PVDFs exhibited similar morphology, but the water flux increased with the increment of polymer solution viscosity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

PVC膜改性助剂PVDF/PS-SO3H/GMS的制备

将聚偏氟乙烯(PVDF)和阳离子交换树脂(PS-SO3H)、单甘酯(GMS)以适当的比例充分混合均匀,经造粒机挤出即得到新型PVC膜改性助剂。最佳工艺条件为:配比PVDF/PS-SO3H/GMS为82∶14∶4,用于PVC膜混合料,PVC树脂/PVC膜改性助剂的最佳配比为85∶15,加入膜改性助剂后,膜制品的透水率得到提高,力学性能也有所改善。