高透光性有序银网阵列的制备

以水珠为模板制备了聚己内酯(PCL)有序多孔膜. 利用水珠在冷的高分子溶液表面凝结形成有序阵列, 溶剂蒸发后, 高分子材料按照水珠排列的形貌形成了有序多孔膜. 改变蒸发溶液的体积可得到具有透光性的有序贯通膜, 对该膜喷金后在银溶液中置换得到了有序银网阵列膜. 这种银网阵列不仅能够导电, 而且比聚己内酯阵列膜具有更高的透光性和柔韧性.     

聚丁二烯有序多孔膜在热缩型聚乙烯膜上的收缩

采用溶剂散逸自组装制备了聚丁二烯(PB)有序多孔膜。水珠能在冷的高分子溶液表面凝结形成有序的阵列,溶剂蒸发后,高分子材料按照水珠排列的形貌形成了有序多孔膜。两性共聚物的加入能够起到稳定水滴的作用,从而确保多孔膜成为有序的结构。利用聚乙烯可收缩膜将聚丁二烯多孔膜收缩2次,得到长方形、梭形、条形和哑铃形的孔。孔的尺寸从微米级收缩至亚微米级,并对产生各种形状的机理进行了研究。     

溶剂散逸自组装制备高分子有序微透镜阵列

利用水珠为模板制备了聚苯乙烯有序多孔膜.在溶剂挥发的制冷作用下,水珠能够在冷的高分子溶液表面凝结形成有序的阵列,溶剂蒸发完毕后,高分子材料按照水珠排列形貌空隙形成有序多孔膜,一种两性共聚物被加入到溶液中稳定水珠而获得有序的多孔结构. 将聚乙烯醇水溶液填充入多孔膜中,蒸干后用氯仿洗去聚苯乙烯,得到聚乙烯醇的整球微透镜阵列. 聚苯乙烯有序针垫阵列是由有序多孔膜撕掉上层制备的,这种针垫结构内部具有半球结构的空间,并以此为模板制备了聚乙烯醇半球微透镜阵列. 2种微透镜阵列均具有微观显影功能. 通过2种微透镜的显像对比证实,半球微透镜阵列比整球微透镜阵列具有更为清晰的多重显像效果.     

溶剂散逸自组装法制备具有电致收缩性能的聚苯胺/聚氨酯凹透镜阵列

以水珠为模板,采用溶剂散逸自组装法制备了表面具有特殊形貌的有序多孔膜. 以此多孔膜为模板制备了聚苯胺/聚氨酯（PANI/PU）的凹透镜阵列. 采用红外光谱（FTIR）和扫描电子显微镜（SEM）对界面聚合得到的PANI/PU纳米复合物的结构和凹透镜阵列的形貌进行了表征,研究了不同合成条件对纳米复合物导电性能的影响,并对PANI/PU凹透镜阵列的电学和光学性能进行了研究. 结果表明,PANI/PU凹透镜阵列同时具有导电性、电致收缩性和光衍射性质;其收缩率与外加电压成反比,而透光率与收缩率成正比.     

聚苯乙烯-嵌段-聚丁二烯有序多孔膜在可收缩膜上的形变研究和光学性质

利用溶剂散逸自组装法在潮湿的条件下,制备了聚苯乙烯-聚丁二烯嵌段聚合物（PS-b-PB）有序多孔膜。 利用聚乙烯可收缩膜将PS-b-PB多孔膜进行两次收缩,形成小孔径的有序多孔膜。 通过收缩,膜上的孔由圆形变为长方形或者梭形,孔的尺寸从微米级收缩至亚微米级。 利用扫描电子显微镜对膜收缩过程中2种形状产生的机理进行了研究。 结果表明,PS-b-PB结合了聚苯乙烯（PS）和聚丁二烯（PB）两个均聚物的优点,收缩后仍然保持膜结构的平整性,从而将不可见的热场变化转变为可见的光学变化。     

基于静态呼吸图技术的图案化方法

对呼吸图技术制备二维有序多孔结构的研究进展进行了综合评述, 并重点介绍了本课题组发展的静态呼吸图技术. 利用静态呼吸图法, 可制备高度有序的聚合物、聚合物/无机物微孔膜. 这些有序的结构可以直接应用于光掩膜. 进一步, 多孔聚合物膜可以被紫外光交联和改性. 表面改性的多孔聚合物膜可以用于细胞支架. 而交联的聚合物/无机物前驱体微孔膜可以用来制备无机纳米材料阵列. 结果表明, 静态呼吸图技术是一种简单、高效的对聚合物、聚合物/无机物薄膜进行图案化的通用方法,并展示了图案化薄膜广阔的功能化前景.     

阳极氧化法制备TiO2多孔薄膜

本文综述了制备TiO₂薄膜的各种方法,详细介绍了阳极氧化法制备TiO₂多孔膜的进展,在非含氟电解液体系中,对纯钛进行阳极氧化处理可制得表面呈无规则生长的多孔膜结构;在含氟电解液体系中,则可自组织形成高度有序的TiO₂纳米管阵列,并指出阳极氧化法是可在常温低压下进行、操作工艺简单、薄膜性能稳定、再现性好的一种最具工业化应用潜力的制备方法。     

溶剂散逸自组装制备超疏水针垫阵列膜

利用溶剂散逸自组装方法,以聚苯乙烯、聚十二烷基丙烯酰胺-6-丙烯酰胺基己酸（CAP）和三氯甲烷为原料,在平滑的固体基质上制备了有序多孔膜,该膜上下表面可在外力作用下发生分离,得到具有微米级超疏水针垫阵列膜。 结果表明,制得的聚苯乙烯膜具备超疏水性质,与水接触角达158°。     

阳极氧化法制备TiO2多孔薄膜

本文综述了制备TiO2薄膜的各种方法,详细介绍了阳极氧化法制备TiO2多孔膜的进展,在非含氟电解液体系中,对纯钛进行阳极氧化处理可制得表面呈无规则生长的多孔膜结构;在含氟电解液体系中,则可自组织形成高度有序的TiO2纳米管阵列,并指出阳极氧化法是可在常温低压下进行、操作工艺简单、薄膜性能稳定、再现性好的一种最具工业化应用潜力的制备方法。     

溶剂散逸自组装法制备超疏水针垫阵列膜

利用溶剂散逸自组装方法,以聚苯乙烯、聚十二烷基丙烯酰胺-6-丙烯酰胺基己酸(CAP)和三氯甲烷为原料,在平滑的固体基质上制备了有序多孔膜,该膜上下表面可在外力作用下发生分离,得到具有微米级超疏水针垫阵列膜。结果表明,制得的聚苯乙烯膜具备超疏水性质,与水接触角达158°。     

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.     

Preparation of a unique microporous structure via two step phase separation in the course of drying a ternary polymer solution

A unique porous polymeric film was prepared by drying a ternary polymer solution: a polystyrene (PS), polyethylene glycol (PEG), and toluene solution. Highly ordered micropores, ranging from 5 to 12 mum in diameter, were formed on the film surface, and the rim of each micropore was surrounded by a ring of PEG. The effects of the weight ratio of the polymer blend and molecular weight of the polymer (PEG) on the porous structure were investigated. Based on in situ visual observation and light scattering measurements, the formation mechanism of the porous structure was speculated to be a two step phase separation: the phase separation into PEG-rich and PEG-poor (i.e., PS-rich) phases occurred first at the surface area of the ternary solutions, where polymers were condensed due to solvent evaporation. The PEG-rich phase became droplets and had an ordered structure on the surface. The PEG-poor phase became a matrix where PS and solvent coexisted as a single phase solution. Secondary phase separation then followed in the PEG droplets, which was induced by further solvent evaporation, and formed into solvent-rich and PEG-rich domains within the droplets. Solvent evaporation and secondary phase separation created a cavity structure in each PEG droplet structured on the film surface.     

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.     

Superhydrophobic and lipophobic properties of self-organized honeycomb and pincushion structures

This report describes the simple preparation of superhydrophobic and lipophobic surfaces by self-organization. Microporous polymer films of a fluorinated polymer with hexagonally arranged pores were prepared by casting from solution under humid conditions. Hexagonally packed water microdroplets were formed by evaporative cooling on the surface of the casting solution. After solvent evaporation, a honeycomb-patterned polymer film was formed with the water droplet array acting as a template; the water droplets themselves evaporated soon after the solvent. Two porous polymer layers were stacked vertically, separated by pillars at the hexagon vertexes. After peeling off the top layer using adhesive tape, a pincushion-like structure was obtained. Here, we show that superhydrophobic behavior was achieved, with the maximum contact angle, 170 degrees, observed using these pincushion structures. Theoretical calculations fit the experimental results well. The lipophobic properties of the films are also discussed.     

Fabrication of Ordered Arrays of Biodegradable Polymer Pincushions Using Self-Organized Honeycomb-Patterned Films

Nano- and micropatterned structures of tissue engineering scaffolds made of biodegradable and biocompatible polymers profoundly influence cell behavior. The present study describes a technically simple and inexpensive method to rapidly fabricate hexagonal arrays of biodegradable polymer pillars (pincushions). As precursors to these polymer pincushion arrays, highly regular porous biodegradable polymer films (self-organized honeycomb-patterned films, called honeycomb films) were prepared on a glass substrate using a simple casting technique. Scanning electron microscope observations revealed that the honeycomb film was composed of a top and bottom layer. This double-layered structure is attributable to the self-organization of hexagonally packed arrays of water droplets that form the template. When we peeled off the top layer of the honeycomb film under ambient conditions using adhesive tape, we obtained arrays of polymer pincushions on both side of the glass substrate and on the adhesive tape. Each air hole is surrounded by six pincushions, each with a diameter of 0.1-1 µm. We also studied factors that determine the morphology of the pincushions, such as the thermal and mechanical properties of the polymers used. It was shown that the heights, widths, and distances of separation between the pincushions could be controlled by the choice of polymer and the pore structure of the original honeycomb film. Such well-ordered, biologically inspired pincushion structures could find application in biomedical, photonic, and electronic materials.     

Honeycomb micropatterning of proteins on polymer films through the inverse microemulsion approach

Here we report the rapid and convenient patterning of proteins on porous polymer film using the inverse microemulsion approach. Following this method, proteins, which were dissolved in water, were transferred into dichloromethane solution of polymers through the formation of inverse microemulsion by mixing the two solutions. The protein-containing microemulsion droplets accumulated automatically into large and stable ones on the surface of organic solution casting on solid substrates, and formed tightly packed microemulsion droplet arrays driven by surface tension. With the evaporation of organic solvent and water, the microemulsion droplet arrays, which act as the template, turn to honeycomb patterned pores bearing proteins in them. The formed protein patterns can be locally applied for the detection of other proteins through specific recognition. The generality and reproducibility for the formation of BSA/PS microporous film and protein patterning by using different polymers and solvents were demonstrated by investigating surfactant addition, polymer and solvent types, and casting volume on the morphology of the microporous films. A preliminary mechanism for the protein patterning is discussed based on the analysis of the experimental results.     

Porous thin films based on photo-cross-linked star-shaped poly(D,L-lactide)s

Self-assembly processes and subsequent photo-cross-linking were used to generate cross-linked, ordered microporous structures on the surfaces of well defined four-arm star-shaped poly(D,L-lactide) (PDLLA) thin films. The four-arm star-shaped PDLLAs were synthesized using an ethoxylated pentaerythritol initiator. Solutions of the PDLLAs were cast in a humid environment, and upon solvent evaporation, ordered honeycomb structures (or breath figures) were obtained. Correlations between molar mass, polymer solution viscosity, and pore dimensions were established. The average pore dimension decreased with increasing polymer solution concentration, and a linear relationship was observed between relative humidity and average pore dimensions. Highly ordered microporous structures were also developed on four-arm star-shaped methacrylate-modified PDLLA (PDLLA-UM) thin films. Subsequent photo-cross-linking resulted in more stable PDLLA porous films. The photo-cross-linked films were insoluble, and the honeycomb structures were retained despite solvent exposure. Free-standing, structured PDLLA-UM thin films were obtained upon drying for 24 h. Ordered microporous films based on biocompatible and biodegradable polymers, such as PDLLA, offer potential applications in biosensing and biomedical applications.     

Tunable morphology of 2D honeycomb-patterned films and the hydrophobicity of a ferrocenyl-based oligomer

Honeycomb-patterned polymer films with tunable pore size and regularity of ordered two- or three-dimensional hexagonal arrays have met with widespread interest in recent years in different areas, for instance as separation and superhydrophobic materials. Herein, 2D honeycomb-patterned films of amphiphilic ferrocenyl-based oligomer with cholesterol as side chains were prepared by the breath-figure method on solid surfaces and their surface-wetting behavior were tested. These films can be simply prepared by spreading a mixture of polymer and organic solvents on a solid surface under moist airflow and at an air/water interface without any extra moist airflow. An ordered 2D hexagonal array of pores with monodisperse size distribution can be obtained over a large area by changing various influencing factors, including humidity, wet volume, concentration, selective solvent, and spreading method, which provides a facile route to regulate the morphology of patterned porous films. The surface-wetting behavior indicates that a higher hydrophobicity of the ferrocenyl-based oligomer honeycomb films can be obtained by modulating the pore size and regularity. It is expected that this could promote the potential application of ordered porous polymer films in hydrophobic materials and biochemistry.     

Micropatterned polymer surfaces induced by nonsolvent

In this work, we present a facile method for fabricating polymer thin films with micropatterned surfaces by evaporating polymer solution containing a small amount of nonsolvent of polymer in air. Poly(methyl methacrylate) (PMMA) and polystyrene (PS) films with densely packed micropores on the surfaces were fabricated. This method was also used to prepare three-dimensional PMMA films with micropatterned surfaces. The effects of nonsolvent content; evaporation temperature; and interactions between the polymer, solvent, and nonsolvent on the specific patterns were investigated, and the formation mechanism of the pores is discussed. This simple route can potentially be used, for example, in the large-scale production of patterned surfaces, three-dimensional painting, and hydrophobicity-enhancing coatings.