等离子体聚合法制备膜蒸馏用疏水微孔复合膜

本文以八氟环丁烷为单体,采用等离子体聚合法将亲水性硝酸纤维素微孔膜改性,制得疏水硝酸纤维素微孔复合膜。所得疏水微孔复合膜可用于膜蒸馏,并具有优良的膜蒸馏性能,其通量达到反渗透水平。利用扫描电镜、X-射线显微分析和XPS等分析手段研究了聚合条件对所得复合膜结构性能的影响.     

亲水膜的表面改性及在膜蒸馏中的应用

膜的微孔性和疏水性是水溶液膜蒸馏的两个基本条件,迄今人们均采用疏水性高分子材料制成疏水微孔膜用于膜蒸馏研究。本文采用辐照接枝聚合和等离子体表面聚合的方法,将亲水的醋酸纤维素微孔膜和硝酸纤维素微孔膜表面疏水化改性,成功地用于膜蒸馏研究,大大扩展了疏水微孔膜的材料来源。实验结果表明,亲水膜表面改性得到的疏水膜,其膜蒸馏性能不低于疏水材料制成的膜,尤其是等离子体聚合法可以实现多种特殊单体在多孔的材料表面聚合,成为制备高性能疏水微孔膜的有效手段,为膜蒸馏的深入发展和实用化创造了有利条件。     

氯化锂为添加剂制得的疏水聚偏氟乙烯不对称微孔膜的形态结构及其膜蒸馏性能

结合膜的形态结构研究了以 LiCl为添加剂制得的疏水 PVDF膜的膜蒸馏性能。与来用水溶液高分子添加剂制得的PVDF微孔膜相比,膜蒸馏性能有了较大提高,尤其具有更高的截留率。制得的微孔膜的蒸馏通量已接近商品膜的膜蒸馏通量,表明以LiCl为添加剂制得的PVDF疏水微孔膜是一种适用于膜蒸馏的较理想的疏水微孔膜。     

新型聚合物／液晶复合膜的研究 Ⅱ．二氧化碳气体的分离性能

以顺丁橡胶（ｃｉｓ－ＰＢ）为高分子基质材料，与具有反应性基团的低分子液晶化合物溶液共混后成膜，后经Ｓ２Ｃｌ２气相硫化制得交联型聚合物／液晶复合膜．研究了测试温度、压力、交联时间以及成膜条件对膜的气体分离性能的影响。结果发现，制得的复合膜在５０℃以下有很好的富二氧化碳性能．在此实验条件下，Ｎ２、Ｏ２的透过系数很小，而ＣＯ２的透过系数为２．０－４．０×１０－８ｃｍ３（ＳＴＰ）ｃｍ／ｃｍ２·ｓ·ｃｍＨｇ。     

应用于膜蒸馏过程的F26微孔膜的初步研究

以N-甲基吡咯酮作为溶剂 ,丙酮为溶胀剂 ,聚乙二醇 4 0 0为添加剂利用相转换法制备出偏氟乙烯 六氟丙烯共聚物 (F2 6 )的疏水微孔膜并且应用在膜蒸馏过程中 .研究了丙酮以及N 甲基吡咯酮 丙酮体系对膜参数以及结构的影响 .通过SEM观察了膜的微观结构 ,发现用N 甲基吡咯酮 丙酮体系制得的微孔膜兼具指状孔和海绵状孔结构 .无添加剂条件下制得的F2 6膜其对蒸馏水的接触角比相同条件下制备的PVDF膜大 .在用相转换法制备的F2 6和PVDF的疏水膜中 ,选择具有适当孔径结构的微孔膜用于膜蒸馏实验 ,F2 6膜的膜蒸馏系数比PVDF膜来得大 ,相同操作条件下的膜蒸馏通量也比PVDF膜高 .     

聚偏氟乙烯膜蒸馏技术在水处理中的应用研究进展

膜蒸馏是一种以膜为介质,利用传统蒸发工艺开发的新型膜分离技术。随着高分子材料行业的进步和制膜工艺的成熟,膜蒸馏技术取得了巨大的进展,在水处理领域拥有十分广阔的市场前景。膜蒸馏技术的核心是膜的通量和使用寿命,而性能优良的膜材料是膜蒸馏技术发展的关键。聚偏氟乙烯(PVDF)因具有成膜性能好、表面张力大、化学稳定性强等优点,在膜蒸馏技术应用研究中备受青睐。同时PVDF与其他聚合物具有良好的相容性,为膜的改性研究奠定了基础,极大地扩展了应用范围。本文介绍了膜蒸馏技术的工作原理及工艺特点以及PVDF膜材料的特点及改性方法,重点对PVDF膜蒸馏技术在水处理领域的应用进行了梳理和总结,讨论了该技术亟待研究和解决的问题,以期为该工艺技术的进一步发展提供科学支撑和理论依据。     

聚酰亚胺气体分离膜的进展

本文叙述了近年来聚酰亚胺气体分离膜的发展概况。讨论了聚合物结构、共聚改性、交联改性和成膜历史对聚酰亚胺透气性能的影响。脂环族聚酰亚胺和六氟二酐(6FDA)型聚酰亚胺兼具有高透气性和高透气选择性,是一类具有发展前途的气体分离膜材料。     

渗透汽化型酯化膜反应器研究——PVA/PSSA共混聚合物管式复合膜的膜反应性能

聚合物共混是制备具有预定性能的功能膜材料的有效方法．报道了以惰性素烧陶瓷管为支撑体的ＰＶＡ／ＰＳＳＡ共混聚合物管式复合膜的制备及其在渗透汽化型酯化膜反应器中不同实验条件下的膜催化反应性能．探讨了共混膜的组成,反应温度等对膜反应和分离性能的影响以及同步膜分离过程对反应转化率的促进作用．交联ＰＶＡ／ＰＳＳＡ管式复合膜具有良好的催化和分离性能．     

含氟聚合物修饰碳纳米管及其聚氨酯复合疏水膜的研究

利用羟基碳纳米管上的羟基与2-溴异丁基酰溴之间的简单反应, 在碳纳米管上引入了含溴ATRP引发剂, 并进一步引发含氟丙烯酸酯的ATRP聚合, 从而在碳纳米管表面接枝上了低表面能的含氟聚合物. 红外光谱(FT-IR)、热重分析(TGA)和透射电镜(TEM)的研究结果表明碳纳米管与含氟聚合物之间为化学键连接. 以此低表面能聚合物包裹的碳纳米管作为填充粒子, 采用溶液浇铸方法制备了聚氨酯/碳纳米管复合膜, 并利用溶剂四氢呋喃(THF)刻蚀表面获得了不同碳纳米管裸露程度的复合膜材料. 静态接触角测试结果表明, 无论是羟基碳纳米管还是低表面能修饰的碳纳米管均可提高其复合膜的疏水性能, 且其疏水性能随碳纳米管含量的增加而增加; 相同含量时, 含氟聚合物接枝后的碳纳米管使复合膜具有更佳的疏水性能, 膜表面经溶剂刻蚀后可显著提高其疏水性能. 采用扫描电子显微镜(SEM)研究了加入碳纳米管和溶剂刻蚀对聚合物表面微观结构以及材料表面疏水性能的影响. 上述结果表明: 利用接枝聚合物可改变碳纳米管本身的疏水性能, 并可进一步制备新型的具有表面疏水性能的聚合物纳米复合材料.     

微孔PI气体分离膜的研究进展

自具微孔材料(PIMs)由于自身刚性分子链的扭曲折叠等会产生高比表面积的微孔结构,相应的膜材料具有优异的气体分离性能。将刚性扭曲的结构单元引入到聚酰亚胺(PI)主链中就得到自具微孔PI。微孔型PI是近年来发展的一种新型PI,其微孔结构使得PI膜的气体分离性能得到很大提升,其中气体渗透系数的提升尤为显著,且保持了传统PI良好的热稳定性、化学稳定性及高力学强度等性质。本文重点介绍了微孔PI以及基于微孔PI复合膜的最新研究进展,并对其未来发展趋势进行了展望。     

质子交换膜燃料电池用膜材料的性能表征

质子交换膜(PEM)是质子交换膜燃料电池(PEMFC)的关键组件之一,其性能的好坏在很大程度上决定了PEMFC的性能。本文对PEMFC膜材料的性能表征进行了综述,讨论了膜材料的孔隙率、密度、粘度、磺化率、稳定性、选择透过性及导电性等性能的表征。     

Membrane electrochemistry

Electrochemistry and biomembranes are interface science in that both are concerned with the phenomena at, as well as across, the interfaces. Membrane electrochemistry may be defined as the application of electrochemistry to biomembrane studies. Additionally, transport processes within the membrane are involved in biomembranes. Since biomembranes are diverse and are usually not amenable to probing by electrochemicophysical techniques, model membrane systems have been developed for their investigation.

The introduction of experimental bilayer lipid membranes (BLM) technique and its modifications have been instrumental in the development and testing of membrane transport concepts (carriers vs channels) and electronic processes in membranes. Instead merely viewing a biomembrane as a physical barrier containing carriers or channels to carry out ionic processes, an ultrathin lipid or biological membrane can also be considered as a complete ‘electrochemical cell’ with one membrane/solution interface reducing (as a cathode) and the other membrane/solution interface oxidizing (as an anode). It is now possible to understand energy transduction (charge generation, separation, and redox reactions) in terms of ultrathin lipid membranes separating two aqueous solutions.

In this paper, we shall discuss the basic principles of electrochemistry as they are applied to membrane studies. Emphasis will be on experimental bilayer lipid membranes (BLM) which have been extensively investigated as models of biomembranes.     

纳米复合膜在膜分离领域的研究进展

基于纳米材料的独特性质,将其引入高分子膜所制得的纳米复合滤膜有望解决目前制约膜技术发展的“上限平衡”问题。 本文综述了碳纳米管、石墨烯、SiO2、TiO2、分子筛、ZrO2以及纳米银颗粒等纳米复合膜在膜分离领域的研究进展。 这些纳米材料对于提高复合膜的机械稳定性、亲水性、选择性、渗透性及抗污染能力等有显著的效果。 此外,对纳米复合膜的发展与应用做了展望,也对其研究中存在的问题和解决方法进行了阐述。     

自交联聚乙烯亚胺-聚砜高温质子交换膜研究

为了制备出兼具高电导率和优异力学性能的高温质子交换膜,本工作采用化学自交联的方法将含氮功能基团聚乙烯亚胺（PEI,平均分子量200）接枝到氯甲基化聚砜（CMPSF）高分子链上制备磷酸掺杂型高温质子交换膜的基膜（PEI-PSF）.其中,PEI上的含氮功能基团既作为磷酸吸附位点,使高温质子交换膜获得高的质子传导率,同时又作为交联位点与CMPSF高分子链上的苄氯基团发生自交联反应,使聚合物膜具有优良的力学性能.傅里叶变换红外光谱和X-射线光电子能谱测试结果表明,CMPSF高分子链上的苄氯基团与PEI上的含氮功能基团发生完全反应,且随着聚砜氯甲基化程度的增加,膜中引入的PEI含量相应增加,进而提升了PEI-PSF膜的磷酸掺杂水平.氯甲基化程度为58%的PEI-PSF膜（PEI-PSF-58）磷酸吸附量达到122 wt%,在180℃无水条件下质子电导率达到3.4×10^-2 S·cm^-1,同时该复合膜拉伸强度达到30 MPa.基于磷酸掺杂的PEI-PSF-58复合膜的高温质子交换膜燃料电池在150℃干气条件下的输出峰功率达到200 mW·cm^-2,并且在78 h的测试时间内展示出了良好的稳定性.     

Membrane Potential of Composite Bipolar Membrane in Ethanol-Water Solutions: The Role of the Membrane Interface

The membrane potential across a composite bipolar membrane (CBM) composed of a cation-exchange membrane with an anion-exchange membrane is theoretically and experimentally analyzed for LiCl ethanol-water solutions. The theoretical approach is based on an extension of the Donnan equilibrium and the Nernst-Planck equation of monopolar charged membranes for the case of two ion-exchange layers by considering the effect of electrolyte ion pairing in the external solution. The experimental results show that the effective membrane charge densities of the two ion-exchange layers will become smaller than those which are separately estimated for each layer. We have introduced a contact factor, zeta, into the theoretical approach to clarify this phenomenon in this study, and the theoretical predictions were in good agreement with the experimental data. The membrane potential measurements show that CBM has the characteristics of a bipolar membrane and can significantly contribute to a better electrochemical characterization of the CBMs. Copyright 1999 Academic Press.     

质子交换膜燃料电池有序化膜电极

质子交换膜燃料电池的核心部件--膜电极经历了两代传统制备方法后,已经进入第三代有序化膜电极发展阶段.有序化膜电极包括质子导体有序化膜电极和电子导体有序化膜电极两大类,而电子导体有序化膜电极包括催化剂材料有序化膜电极和催化剂载体材料有序化膜电极.有序化膜电极具有良好的电子、质子、水和气体等多相物质传输通道,从而可以大大降低膜电极中Pt载量、提升燃料电池的发电性能和延长燃料电池寿命.本文整理了近几年有关有序化膜电极的研究报道,梳理了有序化膜电极研究进展,归纳比较了各种有序化膜电极制备方法的优缺点,对未来高性能、低成本和长寿命的膜电极制备技术开发具有指导意义.     

Membrane capacitive deionization

Membrane capacitive deionization (MCDI) is an ion-removal process based on applying an electrical potential difference across an aqueous solution which flows in between oppositely placed porous electrodes, in front of which ion-exchange membranes are positioned. Due to the applied potential, ions are adsorbed in the electrodes and a product stream with a reduced salt concentration is obtained. Including the membranes in the process has two advantages: first, they block co-ions from leaving the electrodes, thereby increasing the salt removal efficiency of the process, and second, when during ion release a reversed voltage is used, counterions can be more fully flushed from the electrode region, thereby increasing the driving force for ion removal in the next cycle. Here we present pilot-plant experimental data for salt removal in MCDI as function of inlet ionic strength and flow rate. In the subsequent stage of ion release the flow rate is temporarily reduced to zero and the voltage sign reversed. This “stop-flow” operation mode results in a small and concentrated product stream. We present a theoretical process model for MCDI which describes the time-dependent electric current and effluent ion concentration, both during the deionization stage and during the subsequent stage of ion release. The process model describes the MCDI cell as a number of stirred volumes placed in-series, and includes the transport resistance of the ion-exchange membrane and of the stagnant diffusion layer in front of the membrane. Ion storage in the electrodes is described according to the equilibrium Gouy–Chapman–Stern model for the electrostatic double layer.     

Carbon Whisker Membrane

We report a recent developed membrane called carbon whisker membrane (CWM). The CWMs consist of a tubular ceramic membrane covered by a layer of carbon film and carbon whiskers formed on the surface of the carbon film. Hydrocarbons such as methane and a modified chemical vapor deposition apparatus were employed for fabricating uniformed CWMs. Because of the unique feature of the CWMs, the filtration performance of the CWMs was investigated and it was found that the CWMs possess a function of anti-attachment of particles and/or biomaterials on the membranes so that the permeate flux and the cleaning process of the membrane can be improved.     

Mechanosensitive Membrane Probes

This article assembles pertinent insights behind the concept of planarizable push–pull probes. As a response to the planarization of their polarized ground state, a red shift of their excitation maximum is expected to report on either the disorder, the tension, or the potential of biomembranes. The combination of chromophore planarization and polarization contributes to various, usually more complex processes in nature. Examples include the color change of crabs or lobsters during cooking or the chemistry of vision, particularly color vision. The summary of lessons from nature is followed by an overview of mechanosensitive organic materials. Although often twisted and sometimes also polarized, their change of color under pressure usually originates from changes in their crystal packing. Intriguing exceptions include the planarization of several elegantly twisted phenylethynyl oligomers and polymers. Also mechanosensitive probes in plastics usually respond to stretching by disassembly. True ground‐state planarization in response to molecular recognition is best exemplified with the binding of thoughtfully twisted cationic polythiophenes to single‐ and double‐stranded oligonucleotides. Molecular rotors, en vogue as viscosity sensors in cells, operate by deplanarization of the first excited state. Pertinent recent examples are described, focusing on λ‐ratiometry and intracellular targeting. Complementary to planarization of the ground state with twisted push–pull probes, molecular rotors report on environmental changes with quenching or shifts in emission rather than absorption. The labeling of mechanosensitive channels is discussed as a bioengineering approach to bypass the challenge to create molecular mechanosensitivity and use biological systems instead to sense membrane tension. With planarizable push–pull probes, this challenge is met not with twistome screening, but with “fluorescent flippers,” a new concept to insert large and bright monomers into oligomeric probes to really feel the environment and also shine when twisted out of conjugation.     

质子交换膜燃料电池梯度化膜电极

为实现质子交换膜燃料电池的高性能(高功率密度或大电流密度)、低成本(低铂载量)、长寿命发电,人们尝试在燃料电池的核心部件膜电极结构中引入梯度化设计的概念。梯度化膜电极包括膜电极中各组件的梯度化:气体扩散层的PTFE含量与孔隙率的梯度化,催化层的催化剂与Nafion用量的梯度化以及微孔层的疏水性与孔隙率的梯度化。梯度化膜电极中催化剂分布、孔隙率分布、亲/疏水性分布合理,具有良好的三相反应界面以及质子、电子、反应气体、水等多相物质高效传输通道,从而能满足在低铂载量、低加湿以及高电流密度条件下高性能稳定工作。本文整理了近几年来有关燃料电池梯度化膜电极研究的相关文献,梳理了梯度化膜电极研究发展脉络,归纳总结了各种梯度化膜电极的制备方法、性能以及构效关系,并展望了梯度化膜电极下一步研究方向,对高性能、低成本、长寿命的燃料电池开发具有指导意义。