聚苯乙烯蜂窝状多孔膜的制备及应用

以线性聚苯乙烯(PS)为膜材料,采用Breath Figures法制备了高度规整的蜂窝状结构多孔膜.研究了溶液浓度、环境湿度、气体吹扫速度及不同溶剂对多孔膜结构的影响.结果表明,相比于苯和二氯甲烷,氯仿作为溶剂因其挥发度适宜,PS浓度在20～80mg/mL的铸膜溶液可形成规整的蜂窝状结构多孔膜,且膜孔分布均匀、大小均一;制膜的湿度需高于环境湿度,但随着湿度的增加孔径增大;气体吹扫速度可在400～1000mL/min范围,但吹扫速度较大时孔径略有降低.该膜可作为固定诸如辣根过氧化酶等活性酶的载体,用于酶催化反应.     

呼吸图案法制备高分子有序多孔膜的研究进展

主要综述了呼吸图案法制备高分子有序多孔膜的国内外研究进展,分析了多孔膜的形成过程和机理;着重讨论了环境湿度、非水气氛、溶剂种类、聚合物浓度、温度、基底和聚合物结构等因素,对呼吸图案法制备有序多孔膜的形貌和孔径尺寸的影响;分析了呼吸图案法制备有序多孔膜的改进方法以及有序多孔膜的应用,并对其未来的发展提出了展望。有序多孔膜的形成机理、纳米级小孔径的制备、大面积有序多孔膜的制备以及多孔膜智能化,将是呼吸图案法制备高分子有序多孔膜的主要研究方向。     

醋酸纤维素正渗透膜的制备及其性能研究

以醋酸纤维素(CA)作为成膜材料,以聚酯筛网作为支撑材料,利用相转化法制备正渗透膜,考察了正渗透膜制备过程中的影响因素,包括铸膜液中聚合物浓度以及制膜过程中环境湿度、凝胶浴温度及热处理温度对正渗透膜性能(水通量和截盐率)的影响规律。并利用SEM表征了膜表面和断面的形貌。结果表明,在原料液为0.1mol/L NaCl,汲取液为4mol/L葡萄糖,原料液面向分离层,室温的测试条件下,当聚合物浓度为10.4%、在60℃下热处理、凝胶浴温度为15℃、环境湿度为90%时所制备的正渗透膜通量为9.7～10.3L/(m2.h),截盐率在93%以上。     

层-层自组装制备三维蜂窝状醋酸纤维素多孔膜

以单一组分醋酸纤维素(CA)为成膜材质,不添加任何添加剂条件下,利用水蒸气辅助法层-层自组装制备了三维蜂窝状CA多孔膜。利用扫描电镜观察了多孔膜形貌;研究了溶剂、环境湿度和浓度等因素对所成多孔膜结构影响。实验结果表明,以二氯甲烷为溶剂,制备得到的孔结构规整、排列紧密;环境湿度由43%增加到91%,孔径大小由(1.36±0.24)μm增加到(3.71±0.18)μm;CA的质量分数为1%~2%有利于规整孔的形成。扫描电镜断面观察发现CA膜内部全部成孔,且内部孔径大小为(1.09±0.13)μm,约为表面孔径大小的一半。利用界面能最小化理论解释了三维蜂窝孔的形成机理。此三维多孔膜有利于细胞的粘附、铺展、分化和增殖,可作为一种良好的组织工程支架材料使用。     

聚醚砜蜂窝状多孔膜的研究

以聚醚砜(PES)为材料通过水蒸汽辅助法制备蜂窝状多孔膜,利用扫描电镜(SEM)观察膜表面形貌特征.研究溶剂、铸膜液浓度和湿度等因素对形成多孔膜结构的影响,通过控制铸膜液浓度、湿度等因素来控制膜的表面形貌及其所成蜂窝状孔的大小.实验结果表明,高湿度环境和具有一定浓度的聚合物溶液是制备蜂窝状多孔膜的必要条件;溶剂的挥发性是形成规整蜂窝状孔结构的关键因素,形成蜂窝状多孔膜的最佳条件为溶剂CH_2Cl_2,相对湿度93.5%,铸膜液中PES质量分数为2%,注射量为60μL.     

水蒸汽辅助法聚乳酸多孔膜的制备及性能研究

首先以聚乳酸(PLA)为成膜材料,采用水蒸汽辅助法制备了PLA多孔薄膜。利用电子显微镜(EM)和扫描电子显微镜(SEM)研究了有机溶剂、铸膜液浓度、环境湿度和表面活性剂等因素对多孔膜结构和形貌的影响;然后在铸膜液中添加TiO_2制备了PLA/TiO_2复合膜,采用SEM和X-射线衍射仪(XRD)对其表面形貌和结构进行表征,采用分光光度计评价了PLA/TiO_2复合多孔膜对亚甲基蓝染料的光催化降解性能。结果表明:水蒸汽辅助法制备PLA多孔膜的最佳条件为以CH_2Cl_2为溶剂、PLA质量浓度3%、环境湿度为83%、不添加表面活性剂;TiO_2的加入降低了多孔膜的有序性,使得PLA的结晶度略有降低,晶粒尺寸略有减小,复合膜对亚甲基蓝的光催化降解效果较好。     

层-层自组装制备三维蜂窝状醋酸纤维素多孔膜EI北大核心CSCD

以单一组分醋酸纤维素（CA）为成膜材质,不添加任何添加剂条件下,利用水蒸气辅助法层-层自组装制备了三维蜂窝状CA多孔膜。利用扫描电镜观察了多孔膜形貌;研究了溶剂、环境湿度和浓度等因素对所成多孔膜结构影响。实验结果表明,以二氯甲烷为溶剂,制备得到的孔结构规整、排列紧密;环境湿度由43%增加到91%,孔径大小由（1.36±0.24）μm增加到（3.71±0.18）μm;CA的质量分数为1%~2%有利于规整孔的形成。扫描电镜断面观察发现CA膜内部全部成孔,且内部孔径大小为（1.09±0.13）μm,约为表面孔径大小的一半。利用界面能最小化理论解释了三维蜂窝孔的形成机理。此三维多孔膜有利于细胞的粘附、铺展、分化和增殖,可作为一种良好的组织工程支架材料使用。     

利用水滴模板法制备蜂窝状有序多孔聚亚苯基砜膜的研究

聚亚苯基砜(PPSU)是一种具有高机械强度、热稳定性和耐化学性的膜材料,而利用水滴模板法制备蜂窝状有序多孔膜是分子自组装领域一个极大的发展。通过考察聚合物浓度、溶剂和添加剂等因素对蜂窝状有序多孔PPSU膜孔径的影响。结果表明:当聚合物浓度从20g/L上升到70g/L时,平均膜孔径由11.5μm减小到4.4μm,呈下降趋势;相比CH_2Cl_2和CH_2Cl_2/CHCl_3共混溶液,CHCl_3是最佳溶剂;丙酮作为添加剂,当丙酮与CHCl_3溶剂比由0.1∶20增加到0.5∶20时,膜孔径由8.9μm增加到13.3μm,但膜孔数量会减少。     

水辅助法制备左旋聚乳酸/聚乙烯醇复合多孔膜及其力学性能

以左旋聚乳酸(PLLA)/聚乙烯醇(PVA)为成膜材料,利用水辅助法制备了PLLA/PVA复合多孔膜。研究了溶剂及其组成、环境湿度和聚合物浓度对形成多孔膜的形貌影响。筛选出可完全溶解PLLA/PVA体系的二甲亚砜(DMSO)/二氯甲烷(DCM)混合溶剂。V(DMSO)/V(DCM)=1/9为溶剂得到孔径大小为(2.45±0.31)μm的规整蜂窝孔,且随着DMSO含量增多,孔径变小,孔分布变得无序。环境湿度从43%增加到91%,孔径大小由(1.43±0.63)μm增加到(4.30±0.63)μm,孔径与环境湿度基本上呈现一阶线性关系。与纯PLLA多孔膜相比,PLLA/PVA复合多孔膜的拉伸强度和断裂伸长率分别从33.32MPa和12.46%增加到40.66MPa和32.57%。PLLA/PVA复合多孔膜有利于细胞的粘附与生长,因而有望作为组织工程支架材料。     

呼吸图法制备三醋酸纤维素蜂窝状多孔膜

选用三醋酸纤维素(CTA)为膜材质,采用呼吸图法制备有序的蜂窝状多孔膜.考察了溶剂、浓度、温度、湿度等条件对蜂窝状微孔膜微观结构和孔径大小及孔径均匀性的影响.实验表明,湿度(RH)在70%~90%,以载玻片为基板可以制得孔径3μm左右的蜂窝状膜.     

Breath Figures法制备漆酚铜聚合物多孔膜

以漆酚铜聚合物(UCP)有机溶液为铸膜液,采用Breath Figures法制备漆酚铜聚合物多孔膜,探讨了溶剂、环境相对湿度和潮湿气体流速等因素对多孔膜形貌的影响,并使用红外光谱和扫描电镜等进行表征。结果表明,以二硫化碳为溶剂,在静态(潮湿气体流速为0mL/min,湿度为95%)或动态(潮湿气体流速为400mL/min,湿度为85%)时,均可制得孔分布均匀、孔型规整、优良耐热性和耐酸碱性的疏水性UCP多孔膜,其平均孔径分别为1.5和0.85μm。     

Assembly of ordered ZnO porous thin films by cooperative assembly method using polystyrene spheres and ultrafine ZnO particles

Ordered ZnO porous thin films were fabricated by cooperative assembly method using polystyrene sphere (PS) and ultrafine ZnO particles, in which ultrafine ZnO particles were directly assembled in the voids of PS while the template was being assembled by capillary forces. The influence of experimental parameters, such as evaporation temperature, ZnO concentration and the concentration ratio of PS/ZnO on morphology of the porous structure was mainly studied. The results showed that an ordered porous structure could be obtained by this method. X-ray diffraction (XRD) spectra indicated the porous ZnO thin film was wurtzite structure. The transmissivity decreased with the decrease of wavelength, but still kept above 80% beyond the wavelength of 550 nm. Optical band gap of the ZnO thin film was 3.13 eV.     

Morphological and physicochemical properties of spin-coated poly(3-octylthiophene)/polystyrene composite thin films

Poly(3-octylthiophene) (P3OT) was synthesized by direct oxidation of 3-octylthiophene with FeCl₃ as oxidant. Molecular weight of P3OT polymer was measured by size exclusion chromatography. Homogeneous poly(3-octylthiophene) (P3OT) and polystyrene (PS) composite films have been synthesized by spin-coating technique from toluene with different polymer concentrations. The doped films were obtained by immersion for 30 s in a 0.3 M ferric chloride (FeCl₃) solution in nitromethane. A classical percolation phenomenon was observed in the electrical properties of these blends, it was smaller than 5% of P3OT in the blend. Surface topographical changes were studied by atomic force microscopy (AFM). AFM images of the composite films revealed surface morphology variation as a function of different P3OT concentration in PS, phase segregation was observed, and PS is shown to segregate to the surface of the films. The higher PS solubility, in comparison with the P3OT solubility, in toluene resulted in PS/P3OT bilayers. The films exhibited pit and island like topography, the pit size changed with the polymer concentration. Optical absorption properties of the polymeric films were analyzed in pristine and doped state. In doped state, the bipolaronic bands at 0.5 and 1.6 eV are shown in a 4% conductive polymer in the PS/P3OT film. Finally thermogravimetric analysis was also made on the simple and composite polymers.     

One-pot preparation of surface-functionalized barium titanate nanoparticles for high-K polystyrene composite films prepared via floating method

An advanced and inexpensive one-pot method to prepare polystyrene (PS)–barium titanate (BT) films by solution mixing is reported. The process was developed to obtain free-standing films with an increased dielectric constant (ε′). Since PS is soluble in apolar solvents, BT nanoparticles (BT-NPs) were surface-modified with palmitic acid (PAc) and embedded within the polymer matrix without affecting homogeneity and smoothness of the composite. The films were prepared by floating method consisting in dropping BT-NPs dispersed in PS/toluene solution on the water surface. After the evaporation of toluene, smooth, free-standing and thermally stable films were obtained with a markedly higher ε′ compared to the neat PS. PAc modification improved the dispersion of BT-NPs in the apolar phase and prevented their diffusion into the aqueous phase during the toluene evaporation. The proposed film-forming technique makes it possible to modulate the thickness and shape of the films by selecting the quantity and concentration of the organic phase and using various templates, thus opening up a broad range of applications.     

Electrical behaviour of discontinuous silver films deposited on softened polystyrene and poly (4-vinylpyridine) blends

Results of the studies carried out on the electrical behaviour of silver island films deposited on the blends of polystyrene (PS) and poly (4-vinylpyridine) (P4VP) are presented here. The substrates were held at 457 K, much above the glass transition temperature of both the polymers to ensure sufficient polymer fluidity during deposition, to obtain a sub-surface particulate film. A constant deposition rate of 0.4 nm/s was used throughout the study. Films on softened PS gives rise to a very high room temperature resistance approaching that of the substrate resistance due to the formation of a highly agglomerated structure. On the other hand, films on softened P4VP gives rise to a room temperature resistance in the range of a few tens to a few hundred MΩ/, which is desirable for device applications. The blends of PS and P4VP show room temperature resistances in the desirable range even at a PS/P4VP ratio of 75:25. The films show an increase in resistance when they are exposed to atmosphere. This is attributed to the oxidation of silver islands. The film resistances in the desired range could be obtained even after exposure to atmosphere up to a PS concentration of 50%.     

电化学制备有序聚苯胺／聚苯乙烯复合材料

利用垂直沉积自组装技术在氧化铟锡（ITO）导电玻璃基底上制备出高度有序的聚苯乙烯（PS）薄膜,以此为模板,在三电极体系中应用循环伏安法,控制电势在-0．3-0．9V之间,以20mV／S的扫描速度,在有序排列PS薄膜的表面电化学沉积聚苯胺（PANI）,成功制备出了聚苯胺／聚苯乙烯（PS／PANI）有序导电高分子复合材料,通过紫外-可见光分光光度计、循环伏安法、场发射扫描电镜、x射线衍射仪进行表征,结果表明,制得的PS／PANI复合材料粒径均匀、排列有序、呈密堆积结构,可为制备具有有序中空或大孔膜产物提供较理想的模板。     

Template-directed preparation of bovine serum albumin microporous multilayer films

The fabrication of polymeric materials with ordered submicron-size void structures is potentially valuable for many applications such as catalysts, separation and adsorbent media. This paper reports the preparation of macroporous protein multilayer films with regular voids using silica nanospheres as templates. Both monodisperse silica colloids and highly ordered assembly silica multilayer films are used as templates to prepare microporous bovine serum albumin multilayer films with ruleless and ordered submicron-sized voids. Glutaraldehyde is used as a crosslinking agent to form a firm net-like protein film on the surface of silica templates. The microporous protein film is obtained after removing of silica templates. Compare with polymer film, protein film has good biocompatibility and biodegradability which will be beneficial to its biological applications.     

《二氧化硅孔材料的模板合成》化学综合实验的建设

化学综合实验"二氧化硅孔材料的模板合成"是为大学化学专业本科生开设的一个实验教学课程。其实验的主要内容是,首先合成制备单分散的聚苯乙烯乳胶粒子,然后以此单分散的聚苯乙烯乳胶粒子为初始材料,利用胶体晶模板法制备二氧化硅三维有序孔材料。利用透射电子显微镜和扫描电子显微镜对所制备的各级样品进行表征。教学实践发现,当作为初始材料的聚苯乙烯乳胶粒子尺寸较大时,三维有序孔材料的制备成功率高。文中介绍了此实验的建立以及对其进行改进的过程。     

A Nanoporous Cytochrome c Film with Highly Ordered Porous Structure for Sensing of Toxic Vapors

Creating well‐ordered nanoporosity in biomolecules promises stability and activity, offering access to an even wider range of application possibilities. Here, the preparation of nanoporous protein films containing cytochrome c protein molecules is reported through a soft‐templating strategy using polystyrene (PS) spheres of different sizes as templates. The stability of the cytochrome c film is demonstrated through electrochemistry studies to show a reusable nature of these films over a long period of time. The size of the PS spheres is varied to tune the pore diameter and the thickness of the cytochrome c films, which are quite stable and highly selective for sensing toxic acidic vapors. The fusion of the templating strategy and the self‐assembly of biomolecules may offer various possibilities by generating a new series of porous biomolecules including enzymes with different molecular weights and diameters, peptides, antibodies, and DNA with interesting catalytic, adsorption, sensing, and electronic properties.