甲醇气氛静态呼吸图法制备蜂窝状有序多孔膜

以原子转移自由基聚合方法合成的聚二甲基硅氧烷-b-聚苯乙烯(PDMS-b-PS)为铸膜材料,在静态呼吸图的基础上,首次在甲醇氛围下利用PDMS-b-PS的二硫化碳溶液铸膜得到了高度规整的蜂窝状有序多孔结构.研究了聚合物溶液浓度对孔径的影响,并与水蒸汽氛围制备的孔结构进行了比较.结果表明,甲醇气氛下制备的多孔膜的孔径比水蒸汽氛围下的大,且孔的断面形貌呈“U”形;孔径随着溶液浓度的增大而减小.该研究有利于呼吸图法制备有序结构材料技术的进一步发展,有助于人们更加准确与全面地认识呼吸图机理.     

Influence of vacuum on the formation of porous polymer films via water droplets templating

We report on the formation of ordered arrays of micron-sized holes on the surface of polymer films cast from volatile solvents in the presence of humidity in vacuum. A lower pressure in a vacuum chamber can accelerate the evaporation of solvent in the same way as the accelerating action of the air flowing across the solvent surface and results in the formation of porous films via the “breath figure” templating method. This vacuum technique has a good reproductiveness for the fabrication of the well-ordered porous films in a large area. It is very controllable to prepare the porous films in a vacuum chamber via controlling the vacuum level. The pore sizes can be easily tuned from 5.6 to 17.1 μm by changing the vacuum level. The mechanism for the formation of the porous films in vacuum was also discussed. The polymer films with ordered porous structure and tunable pore sizes have potential applications in many areas such as microarrays and as scaffolds for tissue engineering. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

界面上蜂窝状多孔薄膜的构建、性质和应用

综述了以Breath Figure(呼吸图案)法制备聚合物及纳米颗粒蜂窝状多孔结构的研究现状.当潮湿的气流吹到聚合物或纳米颗粒的有机溶液表面时,溶剂蒸发导致水微滴在液体表面冷凝重排成六角阵列结构.溶剂和水微滴蒸发完毕后,聚合物或纳米颗粒在基底上形成具有六角阵列的蜂窝状多孔结构.该技术是自组装领域的一大进展,在生物技术、组织工程、微图像技术、高端分离技术、光催化及医药等领域有望获得重要应用.本文系统阐述了规整蜂窝状孔结构材料的构建方法、构建材料、形成机理以及影响因素(包括湿度、浓度、气流方向和速度、溶剂、基底曲率等),评述了蜂窝状多孔薄膜的性质和应用,并对其在化学和材料科学领域的应用前景作了展望.     

Electrochemical formation of conducting polymer coating on porous p‐ and n‐silicon substrates

Electrochemical synthesis of polyaniline was carried out in aqueous sulfuric acid solutions of aniline on porous p‐ and n‐silicon under galvanostatic, potentiostatic and potential pulse regimes. It is shown that the introduction of catalytic quantities of oxidants, potassium hexachloroiridate, potassium dichromate, potassium permanganate and chloranilic acid, in electrolytes accelerates the formation of polymer films and lowers the overvoltage of electrosynthesis. The resulting polymer coatings are characterized by cyclic voltammetry and IR spectroscopy. It is shown that polyaniline coatings on porous p‐ and n‐silicon electrodes are electroactive and conducting in anodic and cathodic ranges. Copyright © 2000 John Wiley & Sons, Ltd.     

利用呼吸图案法制备聚(苯乙烯-b-丙烯腈)有序多孔薄膜

以自制的聚(苯乙烯-b-丙烯腈)(PS-b-PAN)嵌段共聚物为成膜材料, 采用呼吸图案法制备了有序多孔薄膜, 采用扫描电子显微镜(SEM)对薄膜形貌进行了分析, 研究了聚合物浓度、溶剂种类及共聚物结构对薄膜结构的影响. 结果表明, 薄膜表层为多孔结构, 且孔为圆形、以六方阵列形式排列; 薄膜表层下面是蜂窝状结构.以三氯甲烷(CHCl₃)为溶剂时, 在较高浓度下制备的薄膜表层孔间距较大, 蜂窝结构尺寸较小, 且形成了多层结构. 与CHCl₃为溶剂时相比, 挥发速度较快的二硫化碳(CS₂)作溶剂时制备的多孔薄膜有序性较好, 薄膜表层孔径和孔间距均较大, 蜂窝结构尺寸较小. 以没有PAN链段的聚苯乙烯大分子引发剂(PS-Cl)为成膜材料时, 制备的薄膜表层没有形成多孔结构, 而是形成了窝状结构. 同时, 通过对薄膜表层晕的研究证明了多孔薄膜表层缺陷是由水滴处于液膜下较深的位置造成的.     

Electroless plating of honeycomb and pincushion polymer films prepared by self-organization

This report describes the fabrication and electroless plating of regular porous and pincushion-like polymer structures prepared by self-organization. Honeycomb-patterned films were prepared by simple casting of polymer solution under applied humid air and pincushion structures by peeling off the top layer of the former films. Silver-deposited honeycomb-patterned films and pincushion films were obtained by simple electroless plating of the respective original structures. XPS revealed Ag deposition on the honeycomb-patterned film. After thermal decomposition or solvent elution of the template polymer, unique metal mesoscopic structures were obtained.     

Role of each part of cyanobiphenyl-containing polymers in porous-film preparation by using the breath-figure method

ABSTRACT

The breath-figure method using the condensation of water droplets can easily fabricate regular porous films. Although the method is simple, the phenomenon itself requires the control of many parameters that change throughout the process. Therefore, we require a unified understanding of polymers for the fabrication of ordered porous films. In this study, to clarify the required molecular structures of polymers to form a regular porous structure, we systematically explored poly(methacrylate)s with cyanobiphenyl moieties connected by dodecyl groups in the side chain (P11CB); these could form a hexagonal ordered porous structure on the entire film surface. The comparison of P11CB and P11B, which is a P11CB without cyano groups, showed that the local polar groups in hydrophobic polymers promote the formation of ordered porous films. Furthermore, no holes were formed in films of P0CB which is a P11CB without alkyl spacers due to its hydrophilicity. Long alkyl chains resulted in changed hydrophilic polymers to hydrophobic polymers. The introduction of long alkyl chains as a spacer between the biphenyl moiety and polymer backbone is preferred in the cases of particularly few amounts of biphenyl groups in the polymer. The biphenyl groups showed the ability to improve film formability.     

Nanostructure formation in polymer thin films influenced by humidity

The influence of relative humidity (RH) during the film preparation on the surface morphology and on the material distribution of the resulting technical polymer blend films consisting of poly (methyl methacrylate) (PMMA) and poly (vinyl butyral) (PVB) is investigated by atomic force microscopy. Both pure polymers and polymer blends with different compositions of PVB/PMMA dissolved in tetrahydrofuran (THF) were used. Polymer films prepared under dry conditions (RH < 20%) are compared with those that have the same polymer composition but were prepared under increased humidity conditions (RH > 80%). The films consisting of the pure polymers showed a nonporous surface morphology for low‐humidity preparation conditions, whereas high‐humidity preparation conditions lead to porous PVB and PMMA films, respectively. These pores are explained as the result of a breath figure formation. In the case of the polymer blend films containing both polymers, porous or phase‐separated surface structures were observed even at low‐humidity conditions. A superposition of the effects of phase separation and breath figure formation is observed in the case of polymer blend films prepared under high‐humidity conditions. Atomic force microscopy (AFM) images taken before and after the treatment with ethanol as a selective solvent for PVB indicate that PMMA is deposited on top of a PVB layer in the case of the low‐humidity preparation process whereas for high‐humidity conditions the silicon substrate is covered with a PMMA film. Copyright © 2006 John Wiley & Sons, Ltd.     

Porous structures of polymer films prepared by spin coating with mixed solvents under humid condition

We investigate the effects of interfacial energy between water and solvent as well as polymer concentration on the formation of porous structures of polymer films prepared by spin coating of cellulose acetate butyrate (CAB) in mixed solvent of tetrahydrofuran (THF) and chloroform under humid condition. The interfacial energy between water and the solvent was gradually changed by the addition of chloroform to the solvent. At a high polymer concentration (0.15 g/cm3 in THF), porous structures were limited only at the top surfaces of CAB films, regardless of interfacial energies, due to the high viscosity of the solution. At a medium concentration (approximately 0.08 g/cm3 in THF), CAB film had relatively uniform pores at the top surface and very small pores inside the film because of the mixing of the water droplets with THF solution. When chloroform was added to THF, pores at the inner CAB film had a comparable size with those at the top surface because of the reduced degree of the mixing between the water droplets and the mixed solvent. A further decrease in polymer concentration (0.05 g/cm3 in THF) caused the final films to have a two-layer porous structure, and the size of pores at each layer was almost the same.     

聚合物孔材料的制备*

聚合物孔材料的制备和应用研究已经成为聚合物科学和材料科学热点,制备聚合物孔材料的方法发展很快。本文综述了聚合物孔材料的制备方法,包括胶体晶模版法、水模版法、超临界二氧化碳发泡法、自组装法等。其中本课题组首次提出的无模版自组装法操作简单、无需模版、环境友好,具有广阔的发展前景。     

冷等离子体制备铝的氧化物膜

冷等离子体制备铝的氧化物膜张勇，周坤，曹伟民，文晓刚（中国科学院成都有机化学研究所，成都，６１００４１）氧化铝是一种重要的无机材料，在微电子工业、机械工业及化学工业等方面有着广泛的应用前景。采用冷等离子体制备的氧化铝膜具有独特的性能：采用干法制膜，升...     

Preparation and properties of silicon- and titanium-containing hybrid nanocomposite films based on ethyl cellulose

Nanocomposite hybrid films containing silicon and titanium compounds in the polymer matrix are prepared through the sol-gel method via the hydrolytic polycondensation of Si and Ti alkoxides (tetraethoxysilane and titanium tetrabutoxide) in the THF solution of a hydrophobic polymer, ethyl cellulose. Their structure and properties are studied with the use of a complex of physicochemical methods. During the hydrolysis of tetraethoxysilane and the subsequent polycondensation of the reaction products, silicon atoms are incorporated into the polymer and form -O-Si-O-bonds involving hydroxyl groups of ethyl cellulose. In the sol-gel method, titanium alkoxide yields nanosized particles of titanium dioxide that play the role of fillers in the polymer matrix. Titanium-containing films show solubility in THF and, after prolonged contact with the solvent, precipitate titanium dioxide from the solution. Hybrid films containing silicon are insoluble owing to the formation of a chemical network between polymer molecules and Si-OH groups of the products of hydrolysis of silicon alkoxide, as confirmed by the IR data. It is shown that the amounts and types of alkoxides and the diameters of the structures formed in the polymer matrix via the sol-gel procedure affect the hydrophilicity levels of ethyl cellulose hybrid films and their abilities to swell in water and aqueous solutions of organic dyes (brilliant blue and methylene blue). Ethyl cellulose hybrid films are hydrophilic, and they facilitate the removal of dye molecules from aqueous solutions. The best properties are featured by the films containing nanosized particles of titanium dioxide in the polymer matrix.     

A study on the polymer structures and electro-optical properties of epoxy-mercaptan-based polymer dispersed liquid crystal films

ABSTRACT

In this paper, polymer dispersed liquid crystal (PDLC) films based on epoxy-mercaptan system were prepared by thermal-initiated polymerization. The effects of the liquid crystal (LC) content, the proportion and the functionality of epoxy monomers on the polymer structures and electro-optical properties of the as-made PDLC films were investigated systematically. It was found that the morphologies of the polymer matrix can be altered from polymer meshes to polymer balls by increasing the LC content as well as the functionality of epoxy monomers. Accordingly, the electro-optical properties could be regulated by the morphologies of polymer networks. Especially, the as-made PDLC films with homogeneous porous structures exhibited the optimal electro-optical properties. Consequently, this work offers a meaningful approach to control the microstructures and optimize the electro-optical properties of PDLC films, which indeed can form a wonderful footstone for the wide application of PDLC.     

以多孔CaCO3微球为模板制备聚乙烯超疏水表面

以聚苯乙烯磺酸钠（PSS）掺杂的多孔碳酸钙（CaCO3）微球层为模板,通过热压低密度聚乙烯（LDPE）并结合酸蚀刻的方法制得了具有多层粘联微球结构、而非常见蜂窝状多孔结构的LDPE稳定超疏水表面（接触角152.8±2.5°,滚动角约6°）。元素分析表明,表面粘联微球为纯LDPE而非LDPE包覆的CaCO3。将多孔CaCO3微球稀疏地撒在LDPE表面并加热熔融,发现微球会自发沉降到熔体内部,酸蚀刻后形成了类似莲蓬的表面微结构,即坑内包含小球。结合CaCO3微球生成原理和多孔结构,认为粘联微球结构和莲蓬结构均是由于LDPE熔融大分子自发沉积到多孔CaCO3微球内部,“反模”形成了LDPE微球所致。本发现为多孔CaCO3微球的应用开辟了新方向。     

基于粒子辅助水滴模板法制备仿生复眼结构的研究

将微粒“皮克林乳化效应”(Pickering emulsions)和水滴模板法(breath figure method)有机结合,探索通过建立粒子辅助的水滴模板法,实现纳米粒子在蜂窝状多孔膜内壁的自组装复合,构建微纳复合的多级仿生结构.并进一步利用聚二甲基硅氧烷(PDMS)复制转移技术,获得类似于复眼结构的多级微纳复合界面仿生结构.     

Controllable fabrication of porous free-standing polypyrrole films via a gas phase polymerization

A facile gas phase polymerization method has been proposed in this work to fabricate porous free-standing polypyrrole (PPy) films. In the presence of pyrrole vapor, the films are obtained in the gas/water interface spontaneously through the interface polymerization with the oxidant of FeCl(3) in the water. Both the thickness of the film and the size of the pores could be controlled by adjusting the concentrations of the oxidant and the reaction time. The as-prepared PPy films exhibited a superhydrophilic behavior due to its composition and porous structures. We have demonstrated a possible formation mechanism for the porous free-standing PPy films. This gas phase polymerization is shown to be readily scalable to prepare large area of PPy films.     

Recent advances in honeycomb-structured porous polymer films prepared via breath figures

Since its introduction in 1994, the preparation of ordered porous polymer films by the breath figure (BF) method has received a considerable interest. The so-called “honeycomb” (HC) films exhibit a hexagonal array of micrometric pores obtained by water droplet condensation during the fast solvent evaporation performed under a humid flow. The main focus of this feature article is to describe the recent advances in the design of honeycomb polymer films by the BF process. We first review the recent studies related to the honeycomb film formation through the exploration of different parameters such as the relative humidity, the polymer concentration, the drying rate, the substrate or the role of interfacial tension. The influence of the architecture and microstructure of the polymer is examined through examples. In this contribution, a special attention is given to the recent articles focused on the preparation of elaborate functional honeycomb-structured polymer films obtained via the simple BF method. In this context, we review the preparation of hierarchical HC films showing either sub- or super-structure, the formation of hybrid HC films by self-assembly of nanoparticles or in situ generation of the inorganic matter, the fluorescence in HC films introduced either by a fluorescent polymer or by fluorescent chemical groups, the elaboration of biomaterials from HC films decorated by glycopolymer and/or showing sensing ability and finally the design of functional polymeric surfaces with either stimuli-responsive or superhydrophobic properties.     

Formation of Supramolecular Structure of Electropolymerized Acryl Films

The studies on the mechanism and kinetics of formation of a polymer layer on metallic cathodes by electropolymerization of acrylamide, formaldehyde, and N-methylolacrylamide in an aqueous environment are reviewed. A model for the formation of a supramolecular structure of films is described. The coating growth occurs in conditions of continuous synthesis of high- and low-molecular-weight polymer fractions. Removing low-molecular-weight products out of the film results in the formation of a porous structure. The orientation of monomer molecules and growing macrochains along the electric-field lines leads to a perpendicular arrangement of pores and channels with respect to the film surface and to the formation of an ordered crystalline phase of the polymer. The synthesized films exhibit an asymmetric three-layered structure, whose dense barrier layer forms at the metal/polymer film interface. The polymer comprises crystalline and amorphous phases.     

Synthesis of star-shaped polyhedral oligomeric silsesquioxane (POSS) fluorinated acrylates for hydrophobic honeycomb porous film application

Two different eight-arm star-shaped polyhedral oligomeric silsesquioxane (POSS) fluorinated acrylates were synthesized through atom transfer radical polymerization (ATRP) and applied for hydrophobic honeycomb-patterned porous films through the breath figure (BF) method. The structure of polymers was characterized by Fourier transform infrared (FT-IR) spectroscopy, nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC), and surface analysis was featured by X-ray photoelectron spectroscopy (XPS). Depending on the influences of polymer architectures, solvents utilized, and solution concentrations, honeycomb-patterned porous films were obtained. It could be found that the introduction of fluorine components was a favorable condition for BF formation and chloroform (CHCl₃) utilized as solvent with an appropriate concentration of 30 mg/mL was the best condition for these hydrophobic honeycomb-patterned porous films. Meanwhile, the obtained honeycomb films could be retained after long-time preservation in an acid-base condition, which shows a great potential in filtration, cell culture, tissue engineering, and marine antifouling applications.     

Use of a self-assembling organogel as a reverse template in the preparation of imprinted porous polymer films

The concept of reverse templating of an organogel to form imprinted porous divinylbenzene polymer films with submicrometer channels is demonstrated. The organogel comprising a 1:1 molar ratio of two organogelators, that is, bis(2-ethylhexyl) sodium sulfosuccinate and 4-chlorophenol, was formed in divinylbenzene. The gel was cast as a thin film before UV polymerization of the solvent, and the organogelators were later removed by simple washing with water and isooctane. The integrity of the fiber bundles of the organogel was preserved during polymerization, and an exact hollow replica was obtained after the organogelators were leached away. It is easily possible to imprint gel fiber bundle structures into polymeric films through this technique. The gel can also be formed on macroporous substrates to yield supported thin porous polymeric films. With the incorporation of functional nanoparticles in AOT inverse micelles and hence the organogel, nanoparticle-containing porous polymer films exhibiting luminescence or magnetic properties are envisioned.