两性离子基团改性分离膜的抗污染机理及研究进展

抗污染机理的研究对设计和合成抗污染膜材料具有指导意义。两性离子聚合物作为一种新型的抗污染膜材料逐渐受到人们的关注。本文从研究膜污染的成因及其影响因素出发,阐述了分离膜的抗污染机理及两性离子基团改性分离膜的抗污染特点,同时根据两性离子基团改性分离膜方式的不同,系统总结了近年来此类分离膜的研究进展,并对分离膜抗污染机理的研究和两性离子改性高分子分离膜未来的发展趋势作出展望。     

正渗透膜支撑层结构优化的研究进展

随着世界经济高速发展和人口不断增长,全球淡水资源和能源危机日渐加剧。为了改善这一状况,人们将目光投向了海洋,海水淡化显示出强大的生命力。正渗透技术由于其低能耗,少污染,成为一种极具发展潜力的海水淡化新技术。正渗透膜作为其关键技术之一,已引起全世界相关学者的广泛关注。然而,正渗透膜支撑层中存在严重的内浓差极化现象,大幅降低了正渗透性能,是正渗透膜进一步发展和应用的瓶颈。针对此,本文以内浓差极化现象为线索,围绕支撑层材料与结构,介绍了传统支撑层(传统相转化支撑层和织物支撑层)的优化方法和新型支撑层(包括静电纺丝支撑层、纳米颗粒掺杂支撑层及新型相转化支撑层等)的特点、制备方法及结构对提高正渗透性能的贡献等。最后展望了未来正渗透膜支撑层材料和结构的发展趋势,以提高正渗透膜性能及在更多领域中的应用。     

基于XDLVO理论解析MBR膜污染研究进展

膜污染问题严重制约了膜生物反应器(MBR)的广泛应用,因此膜污染机制的研究对于有效控制膜污染十分重要。XDLVO理论合理地解析了范德华力、极性作用力、双电层作用力在膜污染过程中的贡献,有效地揭示了膜污染机理。本文首先阐述了XDLVO理论;然后运用XDLVO理论,解析界面微距离范围内膜表面凝胶层及泥饼层形成过程;最后总结了XDLVO理论在MBR膜污染方面的应用,并对该领域未来的研究方向进行了展望。     

聚偏氟乙烯膜改性方法研究进展

膜污染是聚偏氟乙烯(PVDF)膜在污水处理工程应用中的主要障碍,膜亲水改性是改善膜污染的主要方法。本文根据改性方法的异同,按照表面涂覆、表面接枝、共混改性、共聚改性等方法进行了综述。通过分析不同改性方法对PVDF亲水效果、渗透能力、抗污能力及长期有效性等方面的影响,讨论了各种改性方法的优缺点,为PVDF膜处理的应用提供技术和理论支持。     

紫外接枝聚合聚乙二醇甲基丙烯酸甲酯制备抗污染聚砜超滤膜

以二苯甲酮(BP)为紫外引发剂,将聚乙二醇甲基丙烯酸甲酯(PEGMA)接枝在聚砜超滤膜表面以提高膜的抗污染性能.在二苯甲酮存在的条件下,波长较长(λ300nm)的紫外光(UV)辐射下发生提氢反应,可以有效防止聚砜分子主链的剪切,保持改性膜的分离性能.考察了PEGMA浓度、UV辐射时间和BP浓度对改性超滤膜接枝度、亲水性和抗污染性能的影响.用表面全反射红外光谱(ATR/FTIR)表征改性前后膜表面化学组成的变化.表面改性膜的纯水通量略有降低而牛血清白蛋白(BSA)截留率有所提高.随着接枝度的提高,PEGMA接枝改性膜的抗污染性能增加.     

防污膜的表面改性方法研究进展

膜分离技术具备高效、节能的优势,广泛应用于生物、水处理、仿生等领域。然而,选择性分离膜在使用过程中产生的膜污染会导致分离效率显著降低,成本提高。膜污染是指微粒及大分子在膜孔吸附、沉积,使膜通量变小的过程。通过对膜结构及膜表面电荷、亲水性、粗糙度的调控可以有效降低膜污染程度,提高分离膜的处理效率。本文总结了近期膜表面改性方法研究进展,重点介绍了化学接枝、物理涂覆、聚合反应改性以及表面分离的防污改性方法。     

改性超滤膜技术在水处理中的应用研究进展

膜技术由于其兼具较好的处理效果和较小的环境影响的特点,在水处理领域的应用前景广阔,其中超滤膜因其抗污染能力强、使用寿命长的特点广泛应用于水处理中。本文针对不同的应用场景总结梳理了聚偏氟乙烯超滤膜、TiO₂管式复合超滤膜、聚醚砜超滤膜这三种常见的超滤膜材料的改性方法和改性膜特点,讨论了这些改性膜材料在水处理过程中的应用现状和亟需解决的问题,以期为膜处理技术中的发展和应用提供科学支撑和理论依据。     

木质素磺酸钠改性聚砜膜的制备及其在正渗透膜中的应用

采用木质素磺酸钠作为亲水添加剂,通过浸没沉淀相转化法制备了木质素磺酸钠共混改性聚砜膜,以改善聚砜膜的亲水性,并用作正渗透膜的支撑层,以降低内浓差极化效应.利用扫描电子显微镜、衰减全反射傅里叶变换红外光谱仪、水接触角仪等研究了不同木质素磺酸钠添加量对聚砜膜的结构和表面性质的影响.结果表明,添加木质素磺酸钠后,聚砜膜的指状孔变得规整且狭长.水接触角实验证实添加木质素磺酸钠能改善聚砜膜的亲水性,当木质素磺酸钠含量为0.4 wt%时,聚砜膜的表面水接触角可降低至65°.正/反渗透测试装置分别用于表征正渗透膜的传质性质和结构参数.结果表明,以0.4 wt%木质素磺酸钠改性聚砜膜为支撑层的正渗透膜的水渗透性能(A=3.12×10~(-5) LMH×Pa~(-1))优于纯聚砜基底正渗透膜(0.76×10~(-5)LMH×Pa~(-1)),而且前者的结构参数(S=2010mm)远小于后者(3450mm),说明木质素磺酸钠改性聚砜膜有效弱化了正渗透膜的内浓差极化效应.     

表面活性剂对PVDF-SiO_2超滤膜的性能与结构的影响

在PVDF-SiO_2共混膜中添加不同种类的表面活性剂以及两种复配的表面活性剂,通过相转化法制备了一系列的改性膜。实验通过测定未改性膜及改性膜的纯水通量、牛血清白蛋白的截留率、接触角大小、拉伸强度来表征表面活性剂对膜性能的影响,同时通过测试改性膜的通量恢复率来表征膜的抗污染能力。采用扫描电镜(SEM)、X射线衍射(XRD)及热分析(DSC)对膜的微观形貌和晶体结构进行了表征。结果表明,添加单一表面活性剂及复配表面活性剂均可使膜的渗透性能提高,能够改善膜的机械性能、亲水性,对膜的结晶度没有明显的影响,微观结构观察得到改性膜呈现出优化的表面及断面结构,微孔数目变多,孔间的连通性趋好,纳米颗粒在表面分散的更加均匀,改性膜的抗污染性能得到改善。     

聚多巴胺/聚乙烯亚胺共沉积中间层增强薄膜复合正渗透膜性能

以聚多巴胺/聚乙烯亚胺(PDA/PEI)共沉积于三醋酸纤维素(CTA)多孔支撑膜表面形成中间层,再结合界面聚合法获得聚酰胺薄膜,构建了PDA/PEI共沉积中间层改性薄膜复合(TFC)正渗透(FO)膜.通过傅里叶变换衰减全反射红外光谱法、扫描电子显微镜、原子力显微镜、溶质截留法、水接触角仪等研究了PDA/PEI共沉积中间层对CTA膜和TFC膜的表面结构和性质的影响.研究结果表明,PDA/PEI共沉积使得CTA膜表面变得更为平滑,表面孔径减小至(30.0±4.1) nm,且表面孔径分布趋于均一.同时,在PDA/PEI共沉积改性CTA膜表面界面聚合得到的聚酰胺层呈现出更均匀的叶片状结构和优异的亲水性.基于此,具有PDA/PEI共沉积中间层的TFC正渗透膜显著提高了水通量(FO模式:(7.1±2.3) L/(m^2·h)),较空白TFC膜提升了57.6%.同时,中间层改性TFC膜具有更低的反向盐通量(FO模式:1.4±0.1 g/(m^2·h))和"净盐通量"(FO模式:(0.2±0.06) g/L),与空白TFC膜相比分别下降了83.9%和90.6%.说明PDA/PEI共沉积中间层不仅能有效提升TFC正渗透膜的水渗透性,而且大幅提升了膜的截盐性和渗透选择性.     

Ion redistribution in an electric double layer

The structure of a single flat electric double layer (EDL) is studied by grounding a symmetric electrolyte (NaCl), which is in contact with a planar positively corona-treated polypropylene film. Because the profiles of the electrostatic potential distribution and ion distribution in the solution are altered when the solution is grounded, some mobile counterions in the diffuse layer of the electrolyte solution will go into the Helmholtz layer and thus decrease the electric potential psi(a/2) at the Stern plane in order to obtain a new equilibrium. After the system is grounded for a long time, the representation of the electric double layer changes from a Stern model to a Helmholtz model. Theoretical and experimental analyses are given in this study.     

液——液界面双电层统计力学处理

应用巨正则系综统计法处理液／液界面（ＩＴＩＥＳ）双电层体系。根据ＭＶＮ模型,假定溶液中离子可穿入界面内层（定向溶剂分子层）,由体系（内层）巨正则配分函数导出内层微分电容（Ｃ１）统计表达式,拟合计算Ｃ１随该层表面电荷密度（σｍ）变化关系。理论同时表明,Ｃ１与σｍ涨落存在确定关系     

Single Polyelectrolyte Microcapsules Fabricated By Glutaraldehyde‐Mediated Covalent Layer‐By‐Layer Assembly

Summary: Single polyelectrolyte component microcapsules and multilayers, exemplified by poly(allylamine hydrochloride) (PAH), have been prepared using a method of glutaraldehyde (GA)‐mediated covalent layer‐by‐layer (LbL) assembly. The GA cross‐linking of the adsorbed PAH results in surfaces covered by reactive aldehyde groups, which can then react with PAH to result in another layer of covalently linked PAH. The repeated assembly of single polyelectrolyte in an LbL manner can be thus achieved. The PAH multilayers can grow linearly along with the layer number, and their thickness can be controlled at the nanometer scale, as verified by UV‐vis absorption spectrometry and ellipsometry. Single polyelectrolyte microcapsules are obtained after removal of the template cores at low pH. The morphology and integrity are confirmed by scanning force microscopy and confocal laser scanning microscopy.

Schematic illustration of the preparation of a single polyelectrolyte component microcapsule by GA‐mediated covalent LbL assembly.     

Layer-by-layer assembly and electrically controlled disassembly of water-soluble Poly(3,4-ethylenedioxythiophene) derivatives for bioelectronic interface

Poly(3,4-ethylenedioxythiophene (PEDOT) derivatives display a multitude of attractive properties such as high conductivity, biocompatibility, ease of functionalization, and high thermal stability. As a result, they show promise for applications in materials and biomedical engineering. In order to increase their applications in the practical domain, trivial fabrication techniques are required. Here, we present a simple layer-by-layer dip methodology to assemble water-soluble PEDOT derivatives that can then be disassembled via electrical stimulation. As a result, a dynamic PEDOT layered system is fabricated and could be applied as responsive materials for bioengineering. PEDOT-SO₃ and PEDOT-NMe₃ are synthesized via direct C-H arylation polymerization and chemical polymerization, respectively. The electrostatic interactions between oppositely charged SO₃⁻ and NMe₃⁺ enabled the stacking of PEDOT derivatives. The layer-by-layer assemblies are confirmed by ultraviolet–visible spectroscopy and profilometer. Morphological analyses are performed using scanning electron microscopy and atomic force microscopy, which revealed that the polymer coatings are uniform without any cracks. In situ material assembly is studied using quartz crystal microbalance, and we also demonstrate that these PEDOT-derivative assemblies can be disintegrated by electrical stimulation. Cyclic voltammetry shows a proportional increase in stored charge density with the increase in bilayer thickness, confirming stable electroactivity of these assemblies. Using this approach, we can assemble conductive bio interface on both conductive and nonconductive surfaces, expanding the capability to fabricate bioelectronic electrodes.     

超薄层在白色有机电致发光器件中的应用

以DCJTB为掺杂剂, 以BCP为空穴阻挡层, 研究了两种结构的有机电致发光器件ITO/NPB/BCP/Alq3:DCJTB/Alq3/Al(结构A)和ITO/NPB/BCP/Alq3/Alq3:DCJTB/Alq3/Al(结构B)的电致发光光谱. 实验结果显示, 在结构A器件的电致发光光谱中, 绿光的相对发光强度较弱,增加Alq3层的厚度对绿光的相对发光强度的影响也很小; 而在结构B器件的电致发光光谱中, BCP层与掺杂层(Alq3:DCJTB)之间的Alq3薄层对绿光的相对发光强度影响显著, 用很薄的Alq3层就可以得到强的绿光发射. 进一步改变器件结构, 利用有机超薄层就可以得到稳定的白光器件ITO/NPB(50 nm)/BCP(3 nm)/Alq3(3 nm)/Alq3:DCJTB(1%(w))(5 nm)/Alq3(7 nm)/Al. 随着电压的增加(14-18 V), 该器件的色坐标基本保持在(0.33, 0.37)处不动; 在432 mA·cm-2的电流密度下, 该器件的发光亮度可达11521 cd·m-2.     

Effect of TiCl4‐based TiO2 compact and blocking layers on efficiency of dye‐sensitized solar cells

The effect of the number and arrangement of TiO₂‐based photoanode layers on the efficiency of dye‐sensitized solar cells (DSSCs) was investigated. Compact, mesoporous, and blocking layers of TiO₂ were prepared to form monolayer, bilayer, and trilayer photoanodes. Compact and blocking TiO₂ layers were prepared using dip‐coating technique, whereas the doctor‐blade method was employed to prepare TiO₂ paste layers using nanoparticles prepared by the sol–gel method. The crystalline structure of photoanodes was characterized by X‐ray diffraction (XRD) measurements and their morphology and thickness were characterized by the scanning electron microscopy (SEM) technique. The photovoltaic performance of constructed DSSC devices was investigated and the optimum arrangement was identified and explained in terms of dye loading enhancement and recombination reduction at the fluorine‐doped tin oxide (FTO)/electrolyte interface.     

界面修饰策略在钙钛矿太阳能电池中的应用

目前钙钛矿太阳能电池的认证效率已达25.2%,被认为是下一代最有希望的薄膜太阳能电池候选者。但通过溶液加工方法制备的钙钛矿薄膜不可控的形貌与较差的结晶性是制约器件稳定性提升和大面积生产的主要原因。为了有效解决这一难题,研究者们通常在电荷传输层与钙钛矿层之间进行界面修饰。本文从界面修饰的角度出发,总结了不同界面修饰策略在钙钛矿太阳能电池中的应用,并展望了界面修饰在低成本和大面积钙钛矿太阳能电池的应用前景。     

可溶性聚合物电致发光材料PDHPV的合成及单、双层发光二极管器件的发光性能比较

可溶性聚合物电致发光材料ＰＤＨＰＶ的合成及单、双层发光二极管器件的发光性能比较李晨曦，尹春，黄文强，印寿根，张会旗，何炳林，郑军，华玉林（南开大学高分子化学研究所，天津，３０００７１）（天津理工学院材料物理研究所）关键词ＰＤＨＰＶ共轭聚合物；电致发光...     

Synthesis of a nanocomposite containing a water‐soluble polythiophene derivative and gold nanoparticles

This paper reports on a facile method for synthesizing gold nanoparticles (AuNps) with diameter around 5 nm encapsulated with water‐soluble polythiophene sulfonate poly[2‐(3‐thienyl)ethyloxy‐4‐butylsulfonate] sodium salt (PTS) and their physical–chemical characterization. The synthesis of hybrid materials of polythiophene derivatives and gold nanoparticles is a way to improve the polymer properties, mainly in application for chemical and optical sensing platforms. The AuNps were prepared by reducing gold salt with acid aqueous sodium citrate by the Turkvich method in the presence of PTS, and both PTS and citrate helped to stabilize the AuNps. The suspensions of AuNp:PTS presented good chemical and photostability for long period of storage. The nanoparticles encapsulated with the polymer presented smaller diameters than those obtained using only sodium citrate, according to scanning electron microscopy images. The AuNps obtained were used for fabrication LbL films with commercial chitosan, which were characterized by impedance spectroscopy measurements. The results showed that the charge transfer resistance values (R_ct) decrease as the average diameter of the AuNps decreases and the proportion of PTS increases in the nanocomposite. Such increase of the nanocomposite conductivity, given by the low values of R_ct, indicates that the novel film architecture developed is promising for chemical sensing applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1245–1254     

Influence of Side‐Chain Composition on Polythiophene Properties and Supramolecular Assembly of Anionic Polythiophene Derivatives

A series of 10 polythiophene derivatives is reported, in which each polymer has a different percentage of carboxylic acid‐bearing repeat units. The properties of these polymers are explored under acidic conditions, where the carboxylic acid moieties remain neutral, and under basic conditions, where the carboxylic acid units become anionic carboxylates. The properties that are examined for both solutions and films include UV–vis absorption spectroscopy, photoluminescence spectroscopy, and red‐edge optical band gaps. All the properties studied are strongly dependent both on protonation state and percentage of carboxylic acid/carboxylate side chains along the polymer backbone. The anionic form of each polythiophene derivative was also used in layer‐by‐layer film deposition with a cationic phosphonium polyelectrolyte. The film growth process was studied by spectroscopic techniques to assess the influence of side‐chain composition on the film growth and optical properties. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019