PVDF/TiO_(2)@MoS_(2)纤维复合膜的制备及光催化性能

含大量有机染料的废水对环境的污染日益严重,光催化分离膜的研究备受关注。本研究先通过静电纺丝法制备了PVDF/PEMA膜,后进行酸处理制备出富羧基PVDF纤维复合膜,最后通过水热反应在膜表面原位沉积TiO_(2)@MoS_(2)微纳米颗粒,制备出在太阳光下具有较高催化活性的PVDF/TiO_(2)@MoS_(2)纤维复合膜。结果表明MoS_(2)的加入可以有效降低纤维复合膜禁带带隙能量,从而提高纤维复合膜的光催化活性;在光照4 h后对RhB的降解率达到97.1%;连续5次吸附-降解实验,纤维复合膜对RhB的降解率仍达到95%以上,表明该纤维复合膜具有优异的可重复使用性。因此,该膜在染料降解方面具有潜在的应用前景。

废弃PVDF管式超滤膜修复再生技术研究

为了减少管式超滤膜系统的膜更换成本,延长膜使用寿命,利用亲水修复剂对废弃PVDF管式超滤膜进行修复再生。通过XPS、SEM、AFM、孔径表征分析、过滤通量、截留率、机械强度等测试,探讨了废弃膜和再生膜的结构和性能。结果表明,经过膜修复实验,可补充废弃膜表面损失成分,修复剂所含DMAc还能溶解废弃膜孔隙中的有机污染物。在亲水剂、致孔剂和PVDF的共同作用下,再生膜表面可形成新的孔隙结构,平均孔径从0.0873μm增大至0.2355μm。确定了综合性能最优的再生膜修复剂成分为15%PVDF、75%DMAc、5%PEG和5%PVP,修复后的膜接触角降低了31.1%,在满足渗滤液中COD、NH3-N和TN截留率处理要求的同时,膜纯水通量提升近4倍,拉伸强度和断裂伸长率分别增加了52.5%和137.5%。

TA对基于DA/PEI的PVDF复合疏松纳滤膜的结构与性能影响的研究

为了对染料废水中染料和盐进行有效地分离与回收,以聚偏氟乙烯(PVDF)超滤膜为基膜,以多巴胺(DA)、单宁酸(TA)及聚乙烯亚胺(PEI)为共沉积物,以均苯三甲酰氯(TMC)为有机相,采用界面聚合法制备了PVDF复合疏松纳滤膜,探讨了DA与TA及PEI与TA的质量浓度比对PVDF复合疏松纳滤膜结构与性能及处理模拟RB5染料废水效果的影响。结果表明,当ρ(DA)/ρ(TA)与ρ(PEI)/ρ(TA)分别为2/8和4/6时,膜性能最佳,此时纯水通量较不添加TA时分别提高36%和114%;模拟RB5染料废水通量较不添加TA时分别提高37%和87%;染料截留率分别为95.5%、95.4%,盐(NaCl)的截留率分别为3.95%、3.15%。PVDF复合疏松纳滤膜在处理模拟RB5染料废水中运行稳定性良好。

Surface Modification of Polyvinylidene Fluoride (PVDF) Membranes by Low-Temperature Plasma with Grafting Styrene

In order to control the surface pore sizes of polyvinylidene fluoride membranes and their distribution, low temperature plasma-induced grafting modifications of PVDF were studied to prepare hydrophobe membranes. By argon （Ar） treating and subsequent grafting reaction, a hydrophobe monomer, styrene, was introduced into the PVDF membrane. Fourier transform infrared attenuated total reflection （FTIR-ATR） was utilized to characterize the chemical and physical changes in the Ar plasma modified membrane. The surface modifications of PVDF membranes were investigated by using scanning electron microscopy （SEM）, atomic force microscopy （AFM） and differential scanning calorimeter （DSC）. The water permeability and the solute rejection were measured by PVDF membrane modified in different graft conditions. Results demonstrated that the pores in the modified membranes get smaller and the distribution of pores gets narrowed with the increase in grafting reaction duration. Longer graft time caused the water flux of PVDF membrane to decrease from 578 kg/（m^2· h） to 23 kg/（m^2· h） and the solute rejection to increase from 73% to 92%.

双凝固浴条件下TiO_(2)/PVDF-g-PEGMA/PVDF膜的制备及性能

将TiO_(2)和两亲聚合物PVDF-g-PEGMA一起加入铸膜液中,以乙醇溶液为第1凝固浴,利用其较高的成孔能力使改性膜表面生成大量孔洞,之后将改性膜放入第2凝固浴中,利用NaCl溶液对膜孔生长的抑制作用,制备孔隙率高、孔洞较小的亲水性TiO_(2)/PVDF-g-PEGMA/PVDF超滤膜。试验结果表明,第1凝固浴乙醇溶液质量分数为20%时,随着第2凝固浴NaCl溶液浓度的升高,α晶相的生长受到抑制,β晶相数量占比增大,表面粗糙度出现下降,改性膜的抗污染性能增强。试验中,m^(2)凝固浴条件(20%乙醇溶液,20 g/L NaCl溶液)下制备的改性膜性能最好,孔隙率达到1.94%,海藻酸钠截留试验中膜通量和截留率分别为288 L/(m^(2)·h)和68.08%;跨膜压力为10 psi(0.07 MPa)时的纯水通量和通量恢复率分别为1862 L/(m^(2)·h)和76.25%,较M0(仅20%乙醇溶液)均有所提高,trade-off效应得以缓解,牛血清蛋白吸附量下降到961.56μg/cm^(2),抗污染性能升高。

Adaptive Shape Control for Thermal Deformation of Membrane Mirror with In-plane PVDF Actuators

Optical membrane mirrors are promising key components for future space telescopes. Due to their ultra-thin and high flexible properties, the surfaces of these membrane mirrors are susceptible to temperature variations. Therefore adaptive shape control of the mirror is essential to maintain the surface precision and to ensure its working performance. However, researches on modeling and control of membrane mirrors under thermal loads are sparse in open literatures. A 0.2 m diameter scale model of a polyimide membrane mirror is developed in this study. Three Polyvinylidene fluoride(PVDF) patches are laminated on the non-reflective side of the membrane mirror to serve as in-plane actuators. A new mathematical model of the piezoelectric actuated membrane mirror in multiple fields,(i.e., thermal,mechanical, and electrical field) is established, with which dynamic and static behaviors of the mirror can be analyzed.A closed-loop membrane mirror shape control system is set up and a surface shape control method based on an influence function matrix of the mirror is then investigated. Several experiments including surface displacement tracking and thermal deformation alleviation are performed. The deviations range from 15 μm to 20 μm are eliminated within 0.1 s and the residual deformation is controlled to micron level, which demonstrates the effectiveness of the proposed membrane shape control strategy and shows a satisfactory real-time performance. The proposed research provides a technological support and instruction for shape control of optical membrane mirrors.

Fouling behavior of poly(vinylidene fluoride)(PVDF)ultrafiltration membrane by polyvinyl alcohol(PVA)and chemical cleaning method

Severe fouling to poly(vinylidene fluoride)(PVDF)membrane is usually caused as filtrating the papermaking wastewater in the ultrafiltration(UF)process.In the paper,fouling behavior and mechanism were investigated,and the low-concentration polyvinyl alcohol(PVA)contained in the sedimentation tank wastewater was found as the main foulant.Consequently,the corresponding cleaning approach was proposed.The experiment and modeling results elaborated that the fouling mode developed from pore blockage to cake layer along with filtration time.Chemical cleaning conditions including the composition and concentration of reagents,cleaning duration and trans-membrane pressure were investigated for their effect on cleaning efficiency.Pure water flux was recovered by over 95% after cleaning the PVDF membrane using the optimal conditions 0.5 wt% NaClO(as oxidant)and 0.1 wt% sodiumdodecyl benzene sulfonate(SDBS,as surfactant)at 0.04MPa for 100 min.In the chemical cleaning method,hypochlorite(ClO−)could first chain-scissor PVA macromolecules to small molecules and SDBS could wrap the fragments in micelles,so that the foulants were removed from the pores and surface of membrane.After eight cycling tests,pure water flux recovery maintained above 95% and the reused membrane was found intact without defects.

聚多巴胺涂覆LDH/PVDF改性膜的制备及性能测试

聚偏氟乙烯(PVDF)具有特殊的疏水性,在分离废水的过程中,污染物覆盖膜表面并堵塞膜孔会导致膜的渗透性能下降。使用浸没沉淀相转化法,通过调整水滑石(LDH)添加剂的配比和改性膜浸泡在含有盐酸多巴胺缓冲溶液中的时间,制备了LDH/PVDF改性膜及聚多巴胺(PDA)涂覆LDH/PVDF改性膜。测试了改性膜孔隙率、平均孔径、水通量、截留率、接触角、抗污染性等性能的变化。结果表明:当LDH添加量为3%时,孔隙率最大,比纯膜提升15.35%,平均孔径增加8.48 nm;膜通量最大为943.22 L·m^(-2)·h^(-1),比纯膜增加了382.95 L·m^(-2)·h^(-1),膜孔中污染物沉积减少,可逆污染占比升高,抗污染能力最强,清洗后通量恢复率为81.5%,相比纯膜M0提升了34.2%。

Insight into fouling behavior of poly(vinylidene fluoride)(PVDF)hollow fiber membranes caused by dextran with different pore size distributions

Membrane fouling is the key problem that occurs in membrane process for water treatment. However, how membrane microstructure influences the fouling behavior is still not clear. In this study, fouling behavior caused by dextran was deeply and systematically investigated by employing four poly（vinylidene fluoride） （PVDF） membranes with different pore sizes, ranging from 24 to 94 nm. The extent of fouling by dextran was accurately characterized by pore reduction, flux decline, and the change of critical flux. The result shows that membrane with the smallest pore size of 24 nm experienced the smallest fouling rate and the lowest fouling extent. As the membrane pore size increased, the critical flux ranges were 105-114, 63-73, 38-44 and 34- 43 L. m 2. h t, respectively. The critical flux and fouling resistances indicated that the fouling propensity in- creases with the increase of membrane pore size. Two pilot membrane modules with mean pore size of 25 nm and 60 nm were applied in membrane filtration of surface water treatment. The results showed that serious ir- reversible membrane fouling occurred on the membrane with pore size of 60 nm at the permeate flux of 40.5 L.m 2.h 1. On the other hand, membrane with pore size of 25 nm exhibited much better anti-fouling per- formance when permeate flux was set to 40.5, 48 and 60 L-m 2-h- 1.

Cake models applied to evaluate the fouling mechanism in separation of anionic polyacrylamide using modified PVDF ultrafiltration membranes

In the present study,nano-sized TiO2 /Al2O3 modified PVDF membranes (MM) were fabricated and utilized for anionic polyacrylamide ( APAM) separation. The results showed that,compared with PVDF membrane (OM) ,the contact angle of MM decreases from 83. 64° to 67. 42°,which indicates the increase of the hydrophilicity of MM. The relative flux (RF) decline curve of this ultrafiltration of APAM in water with time shows an obvious two stage properties. The cake filtration models were used to predict the performance of different time over the complete range of filtration times. All the four cake models could simulate this UF process to a certain extent,and the suitability of the two kinds of membranes was: cake filtration > intermediate pore blocking > standard pore blocking > complete pore blocking models. However,they became more and more unsuited to this process with time extending. Surface and cross-sectional morphology of membrane was investigated by SEM to make an advanced certificate of this UF mechanism.

基于混合胺的PVDF复合疏松纳滤膜及其在染料废水处理中的应用

为了对染料废水中的染料和盐进行有效的分离、促进染料的回收利用,文章探讨了在共沉积与界面聚合组合法制备PVDF复合疏松纳滤膜过程中,GAZ/PEI对PVDF复合疏松纳滤膜选择层的微观结构、表面粗糙度、过滤性能及其在模拟活性黑5(RB5)染料废水处理中的应用等情况的影响。研究结果表明随着GAZ/PEI的增加,PVDF复合疏松纳滤膜表面结节减小,选择层厚度降低,表面粗糙度减小,纯水通量增大,PEG800截留率降低,染料废水通量增大,GAZ/PEI为9/91时,膜性能最佳,此时纯水通量和染料溶液通量较单一胺分别提高了91.6%和109.1%,RB5和NaCl的截留率分别为94.3%和2.1%,在运行时间内,基于混合胺的PVDF复合疏松纳滤膜体现了较好的运行稳定性。

ETPTA复合PVDF-HFP基聚合物固态电解质膜的制备与性能研究

固态电池因其优异的性能备受关注,但是与传统的液态电池相比,离子传输能力偏弱,原因是固-固界面离子传输困难。本文制备了以聚偏氟乙烯-六氟丙烯(PVDF-HFP)为基的固态电解质膜,并探究PVDF-HFP和增塑剂乙氧基化三羟甲基丙烷三丙烯酸酯(ETPTA)质量比为1.0∶0.3、1.0∶0.4、1.0∶0.5时对电解质膜离子传输的影响,并组装成以磷酸铁锂为正极、锂片为负极的固态电池,研究其电化学性能。研究发现:当PVDF-HFP和ETPT质量比为1.0∶0.4时,锂离子迁移数达0.89,电化学窗口可达4 V,离子电导率达到8×10^(-5)S/cm,表现出良好的稳定性。将质量比为1.0∶0.4的电解质膜装配成固态电池,经过激活之后,首先在0.1C的倍率下进行测试,首圈充电比容量为133 m A·h/g,首圈放电比容量为129 m A·h/g,在20圈循环测试后,放电比容量也能保持在120 mA·h/g以上,容量保持率为92%。

PVDF-HFP与LATP不同配比对固态电解质膜的影响

液态电解质锂离子电池因其潜在的安全性问题,发展新的固态电解质锂离子电池是目前所研究的热点。磷酸铝钛锂(Li_(1.5)Al_(0.5)Ti_(1.5)(PO_(4))_(3),LATP)是一种NASICON型陶瓷材料,由于其空气稳定性和较好的Li^(+)导电性而备受关注。然而,为了达到良好的离子导电性并降低晶界阻抗,LATP需要950℃以上的高温来实现致密化,这对于大规模应用来说耗时且昂贵。本文使用简单的溶液浇铸法,通过将LATP嵌入共聚物PVDF-HFP(聚偏氟乙烯-六氟丙烯)基体,合成新的复合固态电解质膜。在此基础上,以磷酸铁锂(LiFePO_(4))为正极,使用PVDF-HFP/LATP复合固态电解质膜进行电池组装。在室温下,利用X射线衍射仪(X-ray diffractometer,XRD)、扫描电子显微镜(scanning electron microscope,SEM)对不同质量比的固态电解质膜进行物理特性研究,并进行相关电化学测试。结果表明,PVDF-HFP/LATP质量比为5∶1的复合固态电解质膜,其LATP的NASICON型晶体结构得到了很好的保持;制备的聚合物固态电解质膜具有阻燃性;组装的半电池在常温条件下锂离子迁移数达到0.70。全电池在20次充放电循环下,放电比容量保持率为85%。

Comparison of PVDF porous membranes modified by two different methods using composite nano-particles

To improve the hydrophilicity and anti-fouling performance in water treatment,both entrapped method and deposited method were used to modify polyvinylidene fluoride(PVDF)porous membrane with composite Al2O3/TiO2 nano-particles.Neat PVDF membrane was prepared and its property was also compared with that of the modified membranes.Membrane permeation flux and anti-fouling performance were measured using a membrane cell.The contact angle between water and membrane surface was detected in order to denote the membrane hydrophilicity.Membrane morphology and surface structure were examined by atomic-force microscopy(AFM)and scanning electron microscopy(SEM).Experimental results showed that modified membranes had higher permeation fluxes than that of the neat PVDF membrane.The addition of nano-particles altered membrane surface morphology and increased surface roughness.Due to the hydrophilicity of nano-particles,however,the membrane anti-fouling performance was improved instead of worsened.The entrapped membrane exhibited better anti-fouling performance than the deposited membrane and the neat membrane.

Synthesis of Organic Modified SiC_w/PVDF Composite Membrane and Its Dielectric Properties under Low Temperature

Cetyltrimethylammonium bromide(CTAB) was incorporated into silicon carbide whiskers(SiCw) to improve their hydrophobicity. The solution casting method was employed to develop composite membranes of polyvinylidene fluoride(CTAB-SiCw/PVDF) with different feed ratios. FT-IR spectroscopic studies proved that CTAB was successfully incorporated into the SiCw. SiCw phase structure was maintained after modification by CTAB according to XRD results. SEM studies indicated that the surface became smoother with CTAB dispersal in the PVDF membrane. The dielectric properties of the composite membranes containing various amounts of CTAB-SiCw were measured at low temperature. It was found that the dielectric constant of the composite membranes with 13.0 wt% whiskers reached a maximum value of 25 at low frequency, and decreased to nine at high frequency(from 500 Hz to 1 MHz) at 0 ℃. The dielectric loss of each composite membrane increased with increasing temperature and reached a maximum value. The value shifted with corresponding frequency increases. In addition, the dielectric loss reached a maximum value of 0.2 when 16.7 wt% of CTAB-SiCw was fed at each frequency(from-30 ℃ to 10 ℃). At room temperature, the dielectric constant could be maintained at 42 and the loss factor decreased to 0.8 at 100 Hz when 13.0 wt% of CTABSiCw was incorporated. Additionally, TGA experiments indicated that the decomposition temperature of a PVDF membrane was increased by 10 ℃ and its heat resistance was improved by adding 13.0 wt% of CTAB-SiCw. This PVDF composite membrane has potential for use as an insulator and capacitor.

PVDF催化膜的制备及去除水中盐酸四环素性能研究

将具有芬顿催化活性的普鲁士蓝类似物Fe-Co PBA负载到聚偏氟乙烯(PVDF)膜内,采用浸没沉淀相转化法制备了一种新型PVDF催化膜,用于去除水中盐酸四环素污染物。结果表明:负载Fe-Co PBA纳米粒子既能提高PVDF膜表面亲水性、孔隙率和水通量,又能赋予PVDF膜催化活性;当Fe-Co PBA负载量为10%(质量分数)时,PVDF催化膜的纯水通量达到418.47L/(m^(2)·h),与纯PVDF膜相比提高了3.24倍。PVDF催化膜具有优异的抗生素去除性能和催化稳定性,当H_(2)O_(2)浓度为400mmol/L时,基于芬顿反应的PVDF催化膜对质量浓度20mg/L盐酸四环素的去除率达到90%;重复使用10次后,PVDF催化膜对盐酸四环素去除率仍保持在85%以上。

MXene/PVDF复合膜的制备、性能调控及其应用研究进展

二维过渡金属碳(氮)化物(MXene)是一种新型二维碳化纳米材料,具有横向比率大、传输途径短和纳米通道多等独特优点。该文综述了MXene/聚偏氟乙烯(PVDF)膜的制备工艺,并分析了MXene与PVDF膜的电性能、机械性能、热性能、抗菌性能、环境稳定性等性能之间的调控关系;综述了MXene/PVDF复合膜在分离膜、高介电膜、电磁屏蔽膜等领域中的应用进展;最后,对MXene/PVDF膜的发展方向进行了展望:在当前研究阶段中,对PVDF膜进行抽滤处理仍是发挥MXene优异性能的有效途径之一;进一步深入研究MXene对PVDF膜定向调控的多功能性机制,有助于更好地理解MXene与PVDF膜之间的相互作用规律;此外,应该加强应用型研究,形成较完善的实际应用体系,有助于更好地理解MXene/PVDF复合膜的自身性质和性能,推动MXene/PVDF复合膜在各领域的应用研究和实际发展。

Composite Polymer Electrolyte Membranes based on Nafion and Modified PVDF Electrospun Nanofiber Mats

We fabricated the nanofiber composite membranes by impregnating Nafion into the modified polyvinylidene fluoride(PVDF) electrospinning nanofiber mat for proton exchange membrane fuel cells applications.The hydrophobic PVDF nanofibers mat became to the hydrophilic state by alkali treatment for the full embedding of Nafion into the PVDF network.The fabricated composite membranes exhibit significantly enhanced thermal stabilities,swelling resistance,and observably improved mechanical property compared to the pristine Nafion membrane.When the content of PVDF nanofiber mat is 15.1wt% in the membrane,the proton conductivity of the nanofiber composite membrane is nearly equal to that of pristine Nafion membrane with the same condition.The experimental results show that the prepared composite membrane can be used as a promising polyelectrolyte membrane for fuel cell applications.

共混β-环糊精改性PVDF膜的制备及性能

以N,N-二甲基乙酰胺(DMAc)为溶剂、聚乙二醇20000(PEG 20000)和聚乙烯吡咯烷酮K30(PVP K30)为致孔剂,以β-环糊精(β-CD)为添加剂进行共混改性,采用非溶剂致相分离法(NIPS)制备了β-CD共混改性聚偏氟乙烯(PVDF)膜。考察了β-CD添加量对改性膜微观形貌、渗透性能和截留性能、亲水性和抗污染性能的影响。结果表明,添加β-CD后改性膜表面开孔数量及孔径增加,膜截面皮层变薄,亚层发展出小指状孔,贯通的大指状孔数量降低,指状孔壁上出现更为疏松的大孔结构。添加β-CD后改性PVDF膜的纯水通量和牛血清蛋白(BSA)截留率均大幅提高,其中β-CD添加量为4%时改性膜的综合性能最佳,其纯水通量为1848 L/(m^(2)·h·bar),BSA截留率为90.43%。添加β-CD后改性膜动态水接触角下降为0°的时间减少,说明其内在湿润性增强。改性膜在渗透性能和分离性能提高的同时保持了较好的抗污染性能,所有膜的通量恢复率均达到98%以上。

DCMC/PEI涂层改性PVDF超滤膜的分离和抗污染性能研究

为了减轻膜污染和提高膜的分离性能,采用一步沉积法将双醛羧甲基纤维素(DCMC)和聚乙烯亚胺(PEI)涂覆在聚偏氟乙烯(PVDF)超滤膜的表面.DCMC上的醛基可以和PEI上的氨基在膜表面发生席夫碱反应,形成化学交联.与纯PVDF膜相比,DCMC/PEI涂层改性膜具有更高的亲水性(水接触角<40°)和收缩的孔径(平均孔径≈20.32 nm).以腐殖酸(HA)、牛血清白蛋白(BSA)和海藻酸钠(SA)为代表,研究DCMC/PEI涂层改性膜的分离和抗污染性能.涂层膜对HA、BSA和SA具有超过93%的截留率和通量恢复率(FRR),相比原PVDF膜提升了38%.这种兼具高分离和抗污染性能的纤维素涂层膜,为废水净化提供了新的思路.