聚酰亚胺-二氧化硅杂化膜的制备及表征

 采用溶胶－凝胶法制备了两类具有不同二氧化硅含量的聚酰亚胺－二氧化硅（PI－SiO2）杂化膜,并用SEM,IR,TG－DTA,氮吸附和气体渗透性能测试等手段对该膜材料的表面形貌、结构、热性能、孔径分布和气体渗透性能进行了表征．结果表明,PI－SiO2膜材料中SiO2粒子的分散良好,与有机相之间存在着分相和键联;膜材料的玻璃化温度θg均随SiO2含量的增加而升高．相比之下,在酸性条件下制备的T系列杂化膜比在碱性条件下合成的S系列杂化膜对θg的影响更大一些;杂化膜具有较好的气体渗透性能和亲水性能,其H2O／N2和H2O／CH4的分离系数远大于努森扩散的理论值．     

氧化铝中空纤维膜的制备与表征

 介绍了铝氧化反应结合技术与干湿法纺丝工艺相结合制备氧化铝中空纤维膜的方法．采用热重分析、能量色散谱、X射线衍射、热机械分析和扫描电镜等手段对烧结过程中的反应行为、相转变及膜的微观结构进行了研究．结果表明,所制备的氧化铝中空纤维膜具有非对称结构的特点,其孔隙率高（50．1％）、孔径分布窄（平均孔径0．88μm）、机械强度高（压缩强度和弯曲强度分别为89．6和41．1MPa）．气体的渗透实验结果表明,所制备的膜无针孔、裂纹等缺陷,并且具有良好的渗透性．     

TiO_2/PVDF复合中空纤维膜的制备和表征

采用相转化法制备了二氧化钛 (TiO2 ) 聚偏氟乙烯 (PVDF)复合中空纤维膜 .应用牛血清白蛋白截留实验、扫描电子显微镜、热重分析、X射线衍射分别对复合膜的分离性能、微观结构、热稳定性和晶相组成进行了分析 .结果表明复合膜的性能与纯PVDF膜的相比有显著的改善 ,其中对牛血清白蛋白的截留率从 3 2 7%提高到 86 6 7% ,单根纤维的断裂应力从 3 35MPa提高到 4 70MPa ,提高了 4 0 3% .氮气吸附实验测定的孔径分布进一步表明复合膜的孔径分布变窄 ,孔径变小 .     

膜相渗透原位化学聚合法制备PAn/CA复合透膜

采用膜相渗透原位化学聚合法,使苯胺(An)原位化学聚合于醋酸纤维素(CA)基体膜的微孔壁中,得到均匀分布的PAn/CA复合导电透膜.通过研究聚合反应条件对复合透膜的导电性能和CO₂/O₂表观分离性能的影响,获得了制备性能较优的PAn/CA复合导电透膜的适宜条件.结果表明,采用膜相渗透化学原位聚合法制备的PAn/CA复合导电透膜,平均孔径明显变小,孔径分布变窄,具有优于CA基体膜的微孔结构形态.     

制膜条件对PVDF膜形态结构的影响

对干湿相转换法制备聚偏氟乙烯微孔膜进行了研究。利用光透射仪研究了不同制膜条件下成膜分相速度及其变化规律，用气体渗透法测定了膜的平均孔径和有效孔隙率，并结合电镜照片对不同制膜条件下膜的结构和性能进行了表征。实验结果表明较低的铸膜液温度和凝胶浴温度、较短的蒸发时间和较低聚合物浓度有利于增加膜的有效孔隙率。在铸膜液中加入非溶剂是提高膜性能的一种手段，但非溶剂的加入量需足够大，以抵消铸膜液温度提高引起的相反的效应。     

聚乙二醇对聚醚砜微孔膜致孔作用的研究

以聚醚砜聚乙二醇溶剂为铸膜液体系、采用干湿相转化法制备微孔滤膜,研究了各种制膜条件对膜孔径结构的影响.实验发现聚乙二醇在体系中起到分散稳定的作用,只有到浓度大于70%时,才会对铸膜液的粘度产生明显影响,聚合物在铸膜液中的溶解状态也随之改变,进而影响膜的结构.不同溶剂NMP、DMF、DMAc、DMSO等极性溶剂或固体溶剂己内酰胺均可制得开孔率较高的微孔膜,但对膜的结构和性能影响差别不大.在本研究体系中,膜的结构取决于聚乙二醇、溶剂的浓度比例关系.     

干／湿相转换法制备聚芳醚砜致密皮层不对称膜

以聚芳醚砜为膜材料，采用干／湿相转换法．在非挥发性溶剂－挥发性添加剂以及挥发性溶剂／共溶剂－弱挥发性添加剂两种溶剂体系中研究了致密皮层不对称膜的制备和形成条件，并对它们的结构及氮、氢气体透过性能进行了测试。结果表明，采用前一种溶剂体系。虽然可以在一定范围内控制膜平均孔径的变化，却难以得到致密皮层不对称膜。而后一种溶剂体系，在控制铸膜液组成、适当的制膜条件下可以得到具有海绵状支撑结构的不对称气体分离膜。     

高分子辅助倒相法制备聚乙烯醇多孔膜

采用高分子辅助倒相法制香了多孔的ＰＶＡ－ＰＶＡｃ膜,并测得其孔隙率,最大孔径,平均孔径及孔径分布。研究了影响这些孔特性的各种因素,在扫描电镜下考察了多孔膜的微观形态,制得的膜孔隙率可调节,孔径分布窄。     

溶胶凝胶法合成聚酰亚胺二氧化钛杂化膜

溶胶凝胶法制备了负载型聚酰亚胺 二氧化钛杂化膜 ,采用扫描电镜、红外光谱、TG DTA、压汞法和气体渗透性能测试装置对膜材料的表面形貌、表面结构、热性能、孔径分布和气体渗透性能进行了表征 .结果表明 ,杂化膜材料形成了有机相包裹无机相的交联结构 ;聚酰亚胺与二氧化钛粒子形成了新型键联结构 ;其热分解温度随二氧化钛含量的增加而降低 ,在 4 5 0℃以下热稳定性优于聚酰亚胺膜材料 ;平均孔径随二氧化钛含量增大而增大 ,孔径分布趋于弥散 ;N2 、H2 和CO2 在膜内渗透由Knudsen扩散控制 ,H2 O N2 分离因子均大于Knudsen扩散值 ,表现出良好的亲水性 .     

过滤成膜制备氧化铝中空纤维超滤膜

 介绍了在α－Al2O3中空纤维微滤膜上采用过滤成膜技术制备γ－Al2O3超滤膜的方法．应用热重分析、差热分析、X射线衍射和扫描电子显微镜等测试手段对膜的热稳定性、结构及形貌进行了表征．扫描电子显微镜结果表明，采用过滤成膜方式制备的担载中空纤维超滤膜表面无针孔，无裂纹．气体渗透实验进一步表明，所得中空纤维超滤膜完整、无缺陷，具有一定的气体选择性．经700℃焙烧后的膜在0．3和0．4MPa条件下对氮／氩的分离因子分别为1．133和1．139，说明气体通过膜的扩散以Knudsen扩散传质为主．用等温氮气吸附实验测定了非担载膜的孔径大小和分布，其比表面积为228．9m2／g，最可几孔径约为4．5nm．     

Preparation and characterizations of asymmetric sulfonated polysulfone membranes by wet phase inversion method

This paper presents an original approach to prepare the asymmetric sulfonated polysulfone membranes by using wet phase inversion method and their applications for dehydrating a water/ethanol mixture by pervaporation. The separation performances of sulfonated membranes were strongly affected by the degree of sulfonation and the degree of swelling of membranes. The substitution degree of sulfonic group enhanced the permselectivity of sulfonated polysulfone membranes by increasing the hydrophilicity of polymer backbone. Based on the observations of membrane morphology and light transmittance measurements, the degree of sulfonation of polysulfone presented less influence on the membrane formation pathway and the final structure of membrane in wet phase inversion process. It was also found that the sulfonated membranes showed well hydrophilic properties and facilitated water adsorption in the membranes. The sorption and permeation properties also showed that the permselectivity of asymmetric membrane was dominated by the permeate diffusion rather than the permeate sorption in the skin layer. The high separation performance of pervaporation membrane can be achieved by phase inverse method with sulfonated polysulfone.     

An experimental investigation of evaporation time and the relative humidity on a novel positively charged ultrafiltration membrane via dry–wet phase inversion

In this paper, a novel positively charged asymmetrical membrane was manufactured from brominated polyphenylene oxide (BPPO)/N-methyl-2-pyrrolidone (NMP)/H₂O via in situ amination with triethanolamine (TEOA) and a dry–wet phase inversion. The casting solution was exposed to the humid surroundings before immersing into the coagulation bath. The positive charge character of the membrane surface was examined by streaming potential and the effect of the evaporation time and the relative humidity (RH) on the membrane properties and microstructure were investigated, respectively. It was interestingly found that the role of evaporation time and the relative humidity on the membrane performance and morphologies for a positively charged casting system was different from the conventional rule. This was mainly due to the competition of two influence factors, i.e., evaporation of solvent and water absorption of the casting solution. The results were conformed to SEM observation and pore size distribution. Furthermore, the process of water absorption of the casting solution was monitored by attenuated total reflectance infrared (ATR-FTIR) spectroscopy technique. Additionally, in order to compare to the dry–wet phase inversion method, the membranes were obtained by prolonging the exposure time to more than 12 h (which was similar to vapor-induced phase inversion) at different RH. Polymer nodules on the membrane surface and a symmetrical morphology were observed by SEM.     

非对称结构的CO2分离膜成膜过程的研究

采用干/湿相转化法制备了一系列非对称结构的气体分离膜。动态监测成膜过程的不同阶段,用傅立叶变换红外光谱仪来研究干相转化的蒸发过程,采用数码相机连续照相的方法,用光学显微镜来研究湿相转化的凝胶过程,并探讨成膜动力学过程对膜的最终结构及性能的影响。结果表明,对流蒸发和凝胶过程溶剂/非溶剂的交换速率对形成非对称结构的高渗透性能气体分离膜有着重要的影响。     

Formation and characterization of asymmetric nanofiltration membrane: Effect of shear rate and polymer concentration

In this study, we report the effects of shear rates and polymer concentrations in the formation of asymmetric nanofiltration membrane using a simple dry/wet phase inversion technique. Employing the combination of irreversible thermodynamic model, solution-diffusion model (Spiegler–Kedem equation), steric-hindrance pore (SHP) model and Teorell–Meyers (TMS) model, the transport mechanisms and membrane structural properties were determined and have been characterized for different cases of those formation parameters. The experimental and modeling showed very promising results in terms of membrane performance with interesting structural details. The optimum shear rate (critical shear rate) was found to be at about 203.20 s⁻¹ and the best polymer concentration toward the formation of high performance nanofiltration membrane is in the range of 19.60–23.10%. The modeling results suggested that the pore radius of the membranes produced lies within the range of pore radius of 29 commercial available membranes. This study also proposed that the electrolytes transport through nanofiltration membrane was dominated by a convection factor which accounted approximately 30% more than a diffusion factor. This study also indicated that shear rate and polymer concentration were found to affect the membrane performance and structural properties by providing, to a certain extent, an oriented membrane skin layer which in turn exhibiting an improvement in membrane separation ability.     

制膜液黏度对单皮层PVDF中空纤维膜纺制的影响

以二甲基乙酰胺(DMAc)为溶剂,制备聚偏氟乙烯(PVDF)浓度为15%的制膜液,考察了DMAc同时作为内凝胶浴时膜结构的变化.为保持纺膜过程中的稳定性,分别考察了添加剂LiCl、水以及表面活性剂对制膜液黏度的影响.实验发现添加LiCl可以大大提高制膜液的黏度,而水作为添加剂时对黏度的影响与制膜液本身的浓度有关.在不提高制膜液浓度的基础上,通过提高制膜液黏度克服了膜在纺制过程中的不稳定问题,得到阻力较小的,指状孔贯穿的单外皮层中空纤维膜.     

PVDF and HYFLON AD membranes: Ideal interfaces for contactor applications

Super-hydrophobic fluorinated membranes were tailored by combining traditional dry-wet phase inversion and wet chemical treatment techniques. PVDF and HYFLON AD 60X were selected as raw polymers for their chemical and mechanical resistance as well as hydrophobic and solvophobic properties. Membranes with modulated pore size, narrow distribution and high overall porosity were manufactured without using additional additives or modifiers. High resistance to liquid water entry pressure (LEPw), high mass transfer and low surface free energy of the membrane surfaces were fully achieved. The combination of these two fluorinated polymers improved dramatically the mechanical resistance and the water repellence of the PVDF membranes. Well-controlled structure combined with aimed supra-molecular chemistry makes these porous layers ideal interfaces to be processed in membrane contactor devices.     

Effects of organic solvents on ultrafiltration polyamide membranes for the preparation of oil-in-water emulsions

Hydrophilic ultrafiltration membranes made of polyamide with molecular weight cutoff 10 and 50 kDa have been studied for the preparation of oil-in-water emulsions by a cross-flow membrane emulsification technique. Isooctane and phosphate buffer were used as disperse and continuous phase, respectively. The permeation of apolar isooctane through the polar hydrophilic membrane was achieved by pretreatment of membranes with a gradient of miscible solvents of decreasing polarity to remove water from the pores and replace it with isooctane. Four different procedures were investigated, based on the solvent mixture percentage and contact time with membranes. After pretreatment, the performance of the membranes in terms of pure isooctane permeate flux and emulsion preparation was evaluated. The influence of organic solvents on polyamide (PA) membranes has been studied by SEM analysis, which showed a clear change in the structure and morphology of the thin selective layers. The effects proved stronger for PA 10 kDa than for 50 kDa. In fact, similar pretreatment procedures caused larger pore size and pore size distribution for PA 10 kDa than for 50 kDa. The properties of emulsions in terms of droplet size distribution reflected the membrane pore sizes obtained after pretreatment. The correlation between pore size and droplet size, for the physicochemical and fluid dynamic conditions used, has been evaluated.