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.     

One-step route to the fabrication of highly porous polyaniline nanofiber films by using PS-b-PVP diblock copolymers as templates

We report a new method to control both the nucleation and growth of highly porous polyaniline (PANI) nanofiber films using porous poly(styrene-block-2-vinylpyridine) diblock copolymer (PS-b-P2VP) films as templates. A micellar thin film composed of P2VP spheres within a PS matrix is prepared by spin coating a PS-b-P2VP micellar solution onto substrates. The P2VP domains are swollen in a selective solvent of acetic acid, which results in the formation of pores in the block copolymer film. PANI is then deposited onto the substrates modified with such a porous film using electrochemical methods. During the deposition, the nucleation and growth of PANI occur only at the pores of the block copolymer film. After the continued growth of PANI by the electrochemical deposition, a porous PANI nanofiber film is obtained.     

Formation of ordered microphase-separated pattern during spin coating of ABC triblock copolymer

In this paper, the authors have systematically studied the microphase separation and crystallization during spin coating of an ABC triblock copolymer, polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO). The microphase separation of PS-b-P2VP-b-PEO and the crystallization of PEO blocks can be modulated by the types of the solvent and the substrate, the spinning speed, and the copolymer concentration. Ordered microphase-separated pattern, where PEO and P2VP blocks adsorbed to the substrate and PS blocks protrusions formed hexagonal dots above the P2VP domains, can only be obtained when PS-b-P2VP-b-PEO is dissolved in N,N-dimethylformamide and the films are spin coated onto the polar substrate, silicon wafers or mica. The mechanism of the formation of regular pattern by microphase separation is found to be mainly related to the inducement of the substrate (middle block P2VP wetting the polar substrate), the quick vanishment of the solvent during the early stage of the spin coating, and the slow evaporation of the remaining solvent during the subsequent stage. On the other hand, the probability of the crystallization of PEO blocks during spin coating decreases with the reduced film thickness. When the film thickness reaches a certain value (3.0 nm), the extensive crystallization of PEO is effectively prohibited and ordered microphase-separated pattern over large areas can be routinely prepared. When the film thickness exceeds another definite value (12.0 nm), the crystallization of PEO dominates the surface morphology. For films with thickness between these two values, microphase separation and crystallization can simultaneously occur.     

Micellar transitions in solvent-annealed thin films of an amphiphilic block copolymer controlled with tunable surface fields

We investigated the response of symmetric poly(styrene-block-4vinylpyridine) P(S-b-4VP) diblock copolymer micelles to surface fields of variable strength at free surfaces and substrate interfaces when the micelles as spun were subjected to solvent annealing. Free surface interactions were controlled with solvent annealing in solvents of varied selectivity. On exposure to vapors of a solvent strongly selective for PS, the micelles retained their spherical shape but grew into cylindrical micelles or lamellar nanostructures via fusion on exposure to slightly selective or neutral solvent vapors. Giant 2D disks that completely wetted PS-grafted substrates resulted when spherical micelles were exposed to vapors of a highly selective solvent for P4VP. The interfacial interactions were controlled through subjecting them to UV/ozone (UVO) substrates initially coated with an end-grafted layer of short PS chains, with which the grafted PS chains became oxidized, degraded, or totally removed through UVO treatment for a controlled duration. When thin films were annealed in vapors of THF, the structural transition from spherical to cylindrical micelles depended on the interfacial field. On applying selective UVO exposure of optimal duration, we fabricated a substrate with two interfacial chemistries that promoted varied micellar species (spherical and cylindrical micelles) with a sharp boundary developed within thin films through solvent annealing for a controlled duration.     

Transformation from ordered islands to holes in phase-separating P2VP/PS blend films by adding Triton X-100

Our previous investigation showed that the ordered hexagonal island pattern in the phase-separating polymeric blend films of polystyrene and poly(2-vinylpyridine) (PS/P2VP) formed due to the convection effect by proper control of PS molecular weight, solvent evaporation rate, and the weight ratio of PS to P2VP. In this paper, we further illustrate that, by adding a proper amount of the surfactant Triton X-100 to the PS/P2VP toluene solution, the ordered hexagonal island pattern can be transformed to the ordered honeycomb pattern. The effects of the amount of Triton X-100 on the surface morphology evolution and the pattern transformation are discussed in terms of the collapse of Triton X-100, phase separation between Triton X-100/P2VP and PS, the interfacial interaction between Triton X-100/P2VP and the mica substrate, and the Bénard-Marangoni convection.     

智能蜂窝状有序多孔薄膜：体系构建、响应性能及应用探索

蜂窝状有序多孔膜是一种典型的具有微、纳米尺寸的图案化高分子薄膜材料,在超疏水表面、光电材料、组织工程、生物医学、传感器等领域都具有良好的应用前景。表面形貌或性质具有可逆刺激响应特性的智能型多孔膜不仅拥有常规多孔膜的性能,而且还拥有独特的"开-关"功能,因此受到广泛关注。本文回顾了智能有序多孔膜近年的研究进展,重点对其体系构建、响应方式、机理、性能和相关应用进行了归纳与分析,评述了不同刺激响应多孔膜的特点及优劣势,探讨了智能多孔膜的优化设计及提高响应性能等问题,指出了目前面临的挑战,并展望了未来的发展方向。     

Intelligent reversible nanoporous antireflection film by solvent-stimuli-responsive phase transformation of amphiphilic block copolymer

An erasure-reconstruction porous structure with reversible antireflection (AR) property at near-infrared region (NIR) was prepared for the first time based on solvent-stimuli-responsive phase transformation of polystyrene-block-poly(4-vinypyridine) (PS-b-P4VP). The inhomogeneous porous structure with a dense skin and porous underneath, which was obtained by the nonsolvent-induced phase separation of PS-b-P4VP film from micelle solution with mixed solvents (tetrahydrofuran and dimethylformamide), was used as starting porous film. Then, the film was annealed by PS-selective solvent to erase the nanopores because the PS block was swollen effectively by its selective solvent. Afterward, the nonporous film was immersed in linear aliphatic acid to reconstruct the nanoporous structure (loosely packed micelles) by the combination of the hydrogen bond interaction and the positively charge-induced repulsion between each chain. Thus, an intelligent reversible AR property in the NIR region between a high-transmittance porous state (～99.0%) and a low-transmittance nonporous state (～90.0%) was realized by alternate treatments of PS-selective solvent and linear aliphatic acids. This reversible erasure-reconstruction porous structure for switching between AR (98.0%) and non-AR (90.0%) properties could be recycled by at least four times.     

聚乳酸蜂窝状多孔膜的形成与控制

以单一组分聚L-乳酸(PLLA)为成膜材料,利用水辅助法制备了聚乳酸(PLLA)蜂窝状多孔膜.利用扫描电镜(SEM)和原子力显微镜(AFM)观察多孔膜形貌.研究溶剂、溶液浓度、环境温度和湿度等因素对所成多孔膜结构的影响.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.环境相对湿度由43%增加到91%,PLLA多孔膜的孔径由(1.75±0.24)μm增加到(11.50±1.43)μm,且孔呈现六边形的蜂窝状结构.扫描电镜断面和AFM表明:膜表面形成了深度约为1.8μm的单层孔结构.通过控制溶液浓度、环境温度和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.最佳的成膜条件为溶剂CH2Cl2,湿度75%RH,温度34℃,浓度3 wt%.讨论了蜂窝状多孔膜的形成机理.     

Fabrication of an open Au/nanoporous film by water-in-oil emulsion-induced block copolymer micelles

Water-in-oil (W/O) emulsion-induced micelles with narrow size distributions of approximately 140 nm were prepared by sonicating the polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) block copolymer in the toluene/water (50:1 vol %). The ordered nanoporous block copolymer films with the hydrophilic P2VP interior and the PS matrix were distinctly fabricated by casting the resultant solution on substrates, followed by evaporating the organic solvent and water. The porous diameter was estimated to be about 70 nm. Here, we successfully prepared the open nanoporous nanocomposites, the P2VP domain decorated by Au (5+/-0.4 nm) nanoparticles based on the methodology mentioned. We anticipate that this novelty enhances the specific function of nanoporous films.     

聚苯乙烯-聚(4-乙烯基吡啶)嵌段共聚物LB膜结构形态的研究

采用氯仿作为铺展溶剂,将嵌段共聚物聚苯乙烯-聚(4-乙烯基吡啶)(PS-b-P4VP)稀溶液铺展于空气与水界面上,利用Langmuir-Blodgett(LB)膜技术转移至固体基底.研究了不同的嵌段比、表面压和小分子1-芘丁酸(PBA)的加入对嵌段共聚物气液界面聚集组装的影响.研究发现随着亲水段(P4VP)的增加,聚集组装结构由纳米片状、带状转变成纳米条状、纳米点状结构.表面压对纯PS-b-P4VP聚集组装产生影响,表面压增大,组装体排列紧密;随着表面压的继续增大,单层聚集结构遭到破坏,发生堆叠.加入PBA小分子后,PBA与PS-b-P4VP形成氢键,形态发生明显变化,原来的片状结构转变为条状或点状结构.     

Facile fabrication of porous pure and Ag nanoparticle-doped poly(4-vinylpyridine) films at the liquid-liquid interfaces

We reported an interfacial self-assembly of regularly layered porous poly(4-vinylpyridine)(P4VP) films at the interfaces of water-chloroform or -dichloroethane.The porous diameters were in the range from hundred nanometers to several micrometers.It was revealed that formation of such kind of porous materials was solvent dependent.Moreover,cyclic Ag nanoparticles could be grown in the porous P4VP films to form Ag-P4VP nanohybrids under radiation.     

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.     

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.     

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。     

Stabilization of self‐assembled microdroplets using short chain alcohols

The condensation of water vapor on a volatile polymeric solution leads to a porous surface after evaporation of both solvent and water. However, the stabilization of the water microdroplet is of great importance, which can be achieved using specific polymer or adding a third substance to the polymer solution. Short chain alcohols (methanol, ethanol, and n‐propanol) are utilized to fabricate a self‐assembled porous honeycomb film of linear, low molecular weight polystyrene using the breath figure technique. A combination of breath figure processing and the effect of alcohol on a water droplet can stabilize the pattern and make pores on the surface of the polymer film. The quality of the porous honeycomb film is strongly dependent on the type of alcohols and the concentration of polymer. In a specific range of polymer and alcohol concentration, pores cover all the surface of the polymer film. This method offers the possibility of producing a honeycomb structure with no trace of additive residual after the fabrication process and avoiding polymer modification. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 709–718     

The influence of casting parameters on the surface morphology of PS‐b‐P4VP honeycomb films

The “breath figures” method provides an efficient and cost‐effective method to produce highly ordered honeycomb patterns in polymeric films at micrometer and sub‐micrometer dimensions. The size and regularity of the pores can be adjusted through a series of physical and chemical parameters. In this study, amphiphilic diblock copolymers, polystyrene‐block‐poly(4‐vinyl pyridine) (PS‐b‐P4VP) with different lengths of P4VP, were synthesized through Reversible Addition‐Fragmentation Chain Transfer polymerization. The honeycomb‐patterned films were prepared from these well‐defined polymers through the dynamic breath figures method. A series of physical parameters including solution concentration, flow rate, humidity of the flow, and the humidity of the casting environment, were delicately adjusted to systematically investigate their effects on the morphology of the films. These studies identified four key factors which were found to influence the formation of the pattern. No obvious effect was found on the pore size by changing the length of P4VP block. The result provides clear direction on the fabrication of PS‐b‐P4VP honeycomb‐patterned films and more broadly contributes a deeper understanding of the processes involved in the formation of honeycomb patterns. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3721–3732     

A simple method to prepare highly ordered PS-b-P4VP block copolymer template

A control strategy for tuning the film morphology of asymmetric polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) block copolymers (BCPs) is reported. After preparation of the film by spin-coating method, the as-cast films were annealed in different solvent vapor. It is found that chloroform is a wonderful solvent for forming PS-b-P4VP regular pattern. Otherwise, with changing the concentration of PS-b-P4VP, cylindrical or parallel nanostructures could be attained. The PS-b-P4VP films with cylindrical structure are used as template to deposit FePt nanoparticles into the pores. Nanoparticles reaching the bottom of the holes form a disordered magnetic array.     

Controlled Nanopores in Thin Films of Nonstoichiometrically Supramolecularly Assembled Graft Copolymers

Herein, nanometer‐scale morphologies of graft‐copolymer‐like supramolecular thin films, composed of sulfonic acid terminated polystyrene (SPS) and poly(2‐vinylpyridine) (P2VP), and their application to antireflection coatings were investigated. The intermolecular complexes of SPS and P2VP, formed through nonstoichiometric multiple hydrogen bonding between the sulfonic acid group of SPS and the nitrogen atom in pyridine unit of P2VP, occurring in film deposition allowed for the formation of spherical micelles (with SPS and P2VP as the corona and core, respectively) in the thin film. Interestingly, the domain size of the micelles was tunable from approximately 20 to 90 nm on average by controlling either the blend ratio of components or the concentration of polymer solution. Furthermore, nanoporous thin films could be easily prepared by removing the core of micelle‐based nanostructures by using a simple solvent etching process, leaving sulfonic acid groups on the surface of nanopores, which can be utilized as potential functional sites. Those resultant nanoporous thin films were conveniently employed as an antireflection layer on a glass substrate, giving a maximum 97.8 % transmittance in the visible wavelength range.     

利用Breath Figures法制备具有蜂窝状结构的 PMMA/TBT复合膜

以聚甲基丙烯酸甲酯(PMMA)和钛酸四丁酯(TBT)的氯仿溶液为铸膜溶液,采用Breath Figures法制备了蜂窝状结构的PMMA/TBT多孔阵列薄膜,采用SEM、JR、XRD对制备的多孔膜进行了表征,探讨了聚合物浓度、PMMA/TBT配比以及水解抑制剂对膜蜂窝状结构的影响.实验结果表明,起始溶液浓度为20～30m...