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。     

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。     

PVDF中空纤维换热管亲/疏水组合表面强化蒸汽冷凝传热

针对塑料换热管热导率低的问题,采用非溶剂致相分离法（NIPS）,通过控制铸膜液中磺化聚醚砜（SPES）添加量,制备出具有致密层/非致密层复合结构,外表面接触角分别为49.8°、78.1°的中空纤维表面亲水（PVDF/SPES）、表面疏水（PVDF）换热管,在非致密层内填充水,从而提高换热管导热性能。将单根的表面亲水、疏水换热管编织,在列管式塑料换热器壳程,利用两根换热管的外表面,构建蒸汽冷凝用亲/疏水组合表面,研究该表面上蒸汽冷凝传热强化效果。研究表明,较熔融拉伸法制备的致密PVDF换热管疏水表面,NIPS法制备的亲水表面、疏水表面及亲/疏水组合表面上的蒸汽冷凝总传热系数分别提高46.6%、56.5%、99.7%。可见,较单一的亲水或疏水表面而言,亲/疏水组合表面能够显著强化蒸汽冷凝传热性能。     

溶胀辊轧法PVDF膜表面的疏水强化：溶胀剂的影响

提出了一种简便、低成本的聚偏氟乙烯（PVDF）微孔膜表面疏水增强方法——溶胀辊轧法,以微结构辊筒对表面喷涂溶胀剂的PVDF成品微孔膜辊轧后,采用浸没凝胶法成膜。以N-甲基吡咯烷酮/水（非溶剂）为溶胀体系,采用扫描电子显微镜（SEM）、原子力显微镜（AFM）、水接触角（WCA）、最大孔径、平均孔径、N₂通量、耐磨性、液体穿透压（LEP）等表征手段,系统地研究了溶胀剂体系、溶胀剂容量对PVDF微孔膜结构与性能的影响。结果表明：辊轧膜表面呈现微米-亚微米层次特征,溶胀辊轧操作起到了疏水增强、透过能力提升的效果。溶胀剂中水（非溶剂）质量分数为6%、喷涂密度为0.03mL/cm²时,膜性能最优。连续运行30h的真空膜蒸馏（VMD）对比实验表明,辊轧膜较未辊轧膜具有更高的产水通量、脱盐率及更好的耐污染性能。该方法为低成本、连续化进行成品膜表面疏水强化提供了一种新选择。     

金属表面PDA/PTFE超疏水涂层抑垢与耐腐蚀性能

超疏水涂层具有极广的应用前景，然而在金属表面制备稳定的超疏水涂层具有一定挑战。为提高涂层稳定性，本文通过简单浸泡法在不锈钢表面形成稳定的聚多巴胺（PDA）中间涂层，随后采用电泳沉积法在PDA修饰后的表面制备聚四氟乙烯（PTFE）超疏水涂层。测试中采用场发射扫描电镜、接触角测试仪及电化学测试仪进行PDA/PTFE涂层分析和表征。制备的PDA/PTFE涂层表面呈现凸起结构，提高电沉积制备时间与溶液中水含量，涂层表面水接触角呈现先增加后降低的变化趋势，制备涂层中最大水接触角为160.2°±1.3°，相应涂层的表面能为5.57mN/m。胶带剥离与砂纸磨损试验表明，PDA/PTFE涂层具有较好的稳定性。污垢沉积试验表明，浸泡在50℃、70℃与90℃碳酸钙过饱和溶液12h后，与不锈钢相比，涂层抑垢率分别为64.71%、72.22%与81.25%。电化学测试表明，PDA/PTFE超疏水涂层具有较好的耐腐蚀性能，与不锈钢相比，涂层缓蚀率为95.1%。     

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。     

界面增强型PVDF/PET膜的制备及性能

通过对支撑材料进行表面改性处理和浸入凝胶法制备了界面增强型聚偏氟乙烯/聚对苯二甲酸乙二醇酯（PVDF/PET）超滤膜。用电导率在线测量法确定了硅烷偶联剂 3-氨丙基三乙氧基硅烷（KH550）水解液的制备条件,考察了改性处理条件对PVDF/PET膜的界面性能和力学性能的影响。通过180°剥离试验测试PVDF膜与支撑层间的剥离强度,用扫描电镜观察PET无纺布及PVDF膜破坏底面的微观形貌,用傅里叶红外光谱仪表征PET表面化学组成。结果表明,水解液中KH550用量较少时（≤3%）,处理时间延长,PVDF/PET间的剥离强度增大,水解液中KH550用量较多时（>3%）,处理时间延长,PVDF/PET间的剥离强度先增大后减小;PVDF/PET膜的拉伸强度随水解液中KH550用量的增加或处理时间的延长先增大后略减小。改性前后PVDF/PET膜的分离与透过性能对比表明,PET表面改性后,PVDF膜的牛血清白蛋白（BSA）截留率几乎不受影响,水通量略增。     

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%。     

亲水和疏水改性膜的抗结垢和润湿能力的对比

膜蒸馏过程受料液盐度的影响较小，可以处理高矿化度的矿井水，但膜污染和润湿制约其工业化应用。本文首次全面比较了两种商业化的疏水膜，即平板聚四氟乙烯（PTFE）和聚偏氟乙烯（PVDF），以及分别进行亲水和疏水表面改性后制备的PVA-PAA/PTFE和Teflon/PVDF两种复合膜，在直接接触式膜蒸馏（DCMD）中浓缩饱和硫酸钙溶液时的结垢和润湿程度。重点分析了两种基膜和复合膜的结垢和润湿机理，探讨它们在矿井水浓缩中的应用潜力和最佳膜结构。实验结果显示，饱和硫酸钙浓缩过程中，膜表面结垢是主要影响因素，PTFE膜和PVDF膜尽管膜微观结构差别巨大，但抗结垢能力接近；Teflon/PVDF复合膜因其表面有滑移特性而表现出完美的抗结垢性能，PVA-PAA/PTFE复合膜尽管有致密的亲水表面，抗结垢能力并不强。     

PVDF-PFTS/SiO2膜制备及抗混合污染性能

采用表面接枝技术制备了PVDF-PFTS/SiO₂超疏水复合膜,通过扫描电子显微镜（SEM）和红外光谱（FTIR）分析了膜污染前后的表面结构和组成,考察了直接接触式膜蒸馏（DCMD）装置出水电导率和膜通量的变化,利用XDLVO理论分析了PVDF-PFTS/SiO₂超疏水复合膜的抗混合污染性能和机理。结果表明：在1H, 1H, 2H, 2H-全氟辛基三氯硅烷（PFTS）和SiO₂共同作用下,PVDF-PFTS/SiO₂超疏水复合膜表面形成微纳米复合乳突结构,水接触角（WCA）由99°增至155°。与PVDF基膜相比,PVDF-PFTS/SiO₂超疏水复合膜对混合污染物具有较好的抗污染性能;连续运行10h,膜通量和截留率分别保持在10.06kg/(m²·h)和99.80%。XDLVO理论分析表明,PVDF-PFTS/SiO₂超疏水复合膜表面与污染物之间的作用力由引力转变为斥力是其抗混合污染性能增强的主要原因之一。     

Study on the influence of reaction time on the structure and properties of the PVDF membrane modified through the method of atom transfer radical polymerization

A thermo‐responsive membrane, poly(vinylidene fluoride) (PVDF‐g‐PNIPAAm), was successfully prepared from PVDF membrane through surface‐initiated atom transfer radical polymerization (ATRP) of a thermo‐responsive monomer, N‐isopropyl acrylamide (NIPAAm). The influence of the reaction time on ATRP was studied in detail. The grafting membrane was characterized by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) and X‐ray photoelectron spectroscopy (XPS). The results showed that NIPAAm was successfully grafted on the PVDF membrane, the membrane pores became smaller and the reaction time of 36 h was in favor of surface‐initiated ATRP. The thermal stability of PVDF membrane and PVDF‐g‐PNIPAAm membranes was characterized by differential scanning calorimetry (DSC). Contact angles of membrane surface, water penetration and protein solution permeation were tested. Water contact angles of PVDF membrane reduced after the surface grafting of NIPAAm, which illuminated that the hydrophilicity of the grafted membrane was improved. The PVDF‐g‐PNIPAAm membranes exhibited good thermo‐responsive permeability and antifouling property. POLYM. ENG. SCI., 54:1013–1018, 2014. © 2013 Society of Plastics Engineers     

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%。     

Hydrophilic modification of poly(vinylidene fluoride) membrane with poly(vinyl pyrrolidone) via a cross‐linking reaction

A highly hydrophilic hollow fiber poly(vinylidene fluoride) (PVDF) membrane [PVDF‐cl‐poly(vinyl pyrrolidone) (PVP) membrane] was prepared by a cross‐linking reaction with the hydrophilic PVP, which was immobilized firmly on the outer surface and cross‐section of the PVDF hollow fiber membrane via a simple immersion process. The cross‐linking between PVDF and PVP was firstly verified via nuclear magnetic resonance measurement on PVP solution after cross‐linking. The hydrophilic stability of the modified PVDF membrane was evaluated by measuring the pure water flux after different times of immersion and drying. The anti‐fouling properties were estimated by cyclic filtration of protein solution. When the cross‐linking time was as long as 6 hr and the PVP content reached 5 wt %, the pure water flux (J_v) was constant as ～ 600 L m^?2 hr^?1. The hydrophilicity of the PVDF‐cl‐PVP membrane was significantly enhanced and exhibited a good stability. The PVDF‐cl‐PVP membrane showed an excellent anti‐protein‐fouling performance during the cyclic filtration of bovine serum albumin solution. Therefore, a highly hydrophilic and anti‐protein‐fouling PVDF hollow fiber membrane with a long‐term stability can be prepared by a simple and economical cross‐linking process with PVP. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Dye removal using hydrophobic polyvinylidene fluoride hollow fibre composite membrane by vacuum membrane distillation

Hydrophobic polyvinylidene fluoride (PVDF) hollow fibre composite membranes were prepared by the dilute solution coating process to build a special surface structure that was similar to the dual micro‐nano structure on the lotus leaf. Poly(vinylidene fluoride‐co‐hexafluoropropene) was chosen as the hydrophobic polymer candidate in dilute solution. Membrane morphology and surface hydrophobicity were evaluated by scanning electron microscopy and dynamic water contact angle measurement. The prepared PVDF hollow fibre membranes were employed to separate dyes (Congo Red and Methylene Blue) from water by vacuum membrane distillation. The effects of operational conditions (feed temperature, vacuum pressure and feed flow rate) on the vacuum membrane distillation performance of different PVDF membranes were investigated. The results indicated that the water contact angle values of PVDF composite membrane surfaces improved from 93.6° to 130.8°, which was mainly attributed to the formation of micro‐nano rods. This structure was similar to the dual micro‐nano structure on the lotus leaf. Under test feed temperature, vacuum pressure and feed flow rate conditions, the dye rejection rate of Congo Red and Methylene Blue by the hydrophobic PVDF hollow fibre membrane remained above 99.5% and 99%, which was higher than that of the pristine PVDF membrane (99% and 98%, respectively). In addition, the hydrophobic PVDF hollow fibre composite membrane showed higher permeation flux under different conditions compared with the pristine PVDF membrane, which was attributed to membrane surface hydrophobicity and the electrostatic interactions between dyes and the PVDF membrane surface.     

聚乙烯阴离子交换膜掺混聚偏氟乙烯改性表征

聚偏氟乙烯（PVDF）因含氟乙烯基单体,拥有良好的化学稳定性、热学稳定性和机械性能,与其他高分子膜材料相比更容易提高离子交换膜的性能。本实验采用热压法制备PVDF聚乙烯阴离子交换膜,探讨了PVDF含量对膜性能的影响,如膜电阻、离子交换容量、耐破度、含水率和选择透过性。利用红外光谱仪及扫描电子显微镜表征手段对PVDF膜表面性质和结构进行了分析。结果表明,当PVDF含量增加时,膜面电阻、耐破度升高。离子交换容量、含水率,反离子选择透过性降低。虽然PVDF的添加导致含水率、交换容量等膜性能的下降,但耐破度的升高表明膜稳定性和机械性能得到了提升,这赋予PVDF聚乙烯膜一定的使用价值。     

Synthesis and characterization of low content of different SiO2 materials composite poly (vinylidene fluoride) ultrafiltration membranes

A comparison of the morphology and performance of virgin poly (vinylidene fluoride) (PVDF) ultrafiltration (UF) membrane, and PVDF-composite membranes with low content of two different SiO₂ (N-SiO₂ and M-SiO₂ particles) was carried out. Cross-sectional area and surface morphology of the membranes were observed by scanning electron microscopy and atomic force microscopy. Surface hydrophilicity of the porous membranes was determined through the measurement of a contact angle. Performance tests were conducted on the composite membranes through water flux and bovine serum albumin (BSA) retention. Average pore size and surface porosity were calculated based on the permeate flux. Thermal stability and mechanical stability were determined by thermogravimetric analysis and tensile stress tests. The results indicate that N-SiO₂/PVDF (P-N) membranes possessed larger average pore size and porosity, which led to higher water flux and a slight decline in BSA retention. On the other hand, M-SiO₂/PVDF (P-M) membranes had better mechanical stability and anti-fouling performance with enhanced membrane hydrophilicity and decreased membrane surface roughness. Both of the P-N and P-M membranes exhibited typical asymmetric morphology and improved thermal stability.     

KMnO4溶液pH调控对PVDF膜物化性能和污染行为影响

膜材料形貌结构和物化性能对膜过滤系统的安全和稳定至关重要。以聚偏氟乙烯(PVDF)改性中空纤维膜为研究对象，考察了预氧化剂高锰酸钾(KMnO₄)在pH分别为5、7、9条件下对膜材料表面形貌、亲疏水性、机械强度、纯水通量及膜污染行为的影响。结果表明，在不同pH条件下，KMnO₄对PVDF膜表面的改性层及分离层造成了破坏，导致了膜表面不同的形貌结构、化学成分、亲疏水性及抗污染性的演变。酸性条件下，由于高锰酸钾的氧化性，PVDF膜材料的CC遭到破坏，同时引入羟基(OH)，继续氧化生成了醛类和酮类化合物；而在碱性条件下，膜表面发生了脱氟化氢反应，生成了羰基(CO)。膜污染实验表明，膜分离界面的物化性质变化严重影响了膜污染行为。此研究为预氧化膜过滤工艺中pH的变化对PVDF膜材料形貌结构和性能的影响提供了数据参考。     

纳米氧化石墨烯改性PVDF微滤膜在MBR中的抗污染性能

利用强亲水性氧化石墨烯（GO）作为添加剂,自制了PVDF/GO复合微滤膜,并将其应用于MBR系统中,进行长期应用研究。研究发现,共混膜的表面性质得到改善,其表面含氧基团达到29.33%（GO=3%）;共混膜与PVDF膜对污染物的去除效果相近,但共混膜（GO=3%）仅进行了一次清洗,清洗周期是PVDF的4倍;PVDF/GO共混膜的膜阻力要低于PVDF膜,并且共混膜的不可逆污染阻力显著下降,其数值仅仅是PVDF膜的9.0%（GO=3%）;EPS分析发现,共混膜表面的EPS浓度明显减少,其降幅分别达到59.98%（GO=1%）和69.57%（GO=3%）,抗污染性能显著提高;通过SEM与CLSM分析发现,随着氧化石墨烯加入量的提高,共混膜表面形成了滤饼层变得疏松,厚度也变薄,甚至露出了部分膜表面（GO=3%）,保证了共混膜稳定的渗透率。