聚丙烯酸对含聚氧化乙烯链段嵌段共聚物微相分离形貌的调控作用

采用原子转移自由基聚合(ATRP)制备了两嵌段共聚物聚氧化乙烯-b-聚苯乙烯(PEO-b-PS)和三嵌段共聚物聚氧化乙烯-b-聚苯乙烯-b-聚丙烯酸丁酯(PEO-b-PS-b-PBA),再将聚丙烯酸(PAA)分别与PEO-b-PS和PEO-b-PS-b-PBA进行溶液共混和旋涂成膜,通过原子力显微镜研究了PAA对2种嵌段共聚物薄膜微相分离形貌的调控作用。结果表明,PEO-b-PS/PAA共混薄膜呈现PEO/PAA为分散相以柱状形态垂直分布在PS连续相中的微相分离形貌,柱状微区尺寸随着PAA含量及相对分子质量的增加而不断增大。当PAA质量分数达到30%后,PEO/PAA分散相向层状形态转变。PEO-b-PS-b-PBA与PAA共混后,PEO/PAA相区从原先平行于薄膜表面排列的层状形态向随机取向的柱状形态转变,PS微相区在薄膜表面形成细小的锥状突起,随着PAA质量分数增加,PEO/PAA柱状微区向薄膜表面垂直排列取向得到增强,PS微相区的突起程度降低。     

嵌段共聚物PEO-b-PS与聚苯乙烯共混薄膜的表面形貌及性能

通过原子转移自由基聚合(ATRP)制备了嵌段共聚物聚氧化乙烯(PEO-b-聚苯乙烯(PS)),将PEO-b-PS与PS溶液共混成膜,使用接触角测试仪(CA)和原子力显微镜(AFM)考察了PEO-b-PS含量与共混薄膜表面形貌及性能之间的关系。研究发现,嵌段共聚物在薄膜中发生微相分离并在薄膜表面形成PEO微相区,随PEO-b-PS含量增加,薄膜表面PEO相区尺寸增大,但分布密度下降。通过共混薄膜表面形貌的变化,解释了共混薄膜的亲水性和表面张力随PEO-b-PS含量增加的变化趋势。     

PCL-b-PMMA/PEO共混薄膜的微相分离形貌

通过聚氧化乙烯(PEO)与聚己内酯-聚甲基丙烯酸甲酯嵌段共聚物(PCL-b-PMMA)的共混来调节聚己内酯(PCL)与聚甲基丙烯酸甲酯(PMMA)嵌段的微相分离行为。采用原子力显微镜研究了PEO的质量分数和相对分子质量对PCL-b-PMMA/PEO共混薄膜微相分离形貌的影响。结果表明,共混薄膜形成了以PMMA/PEO为连续相,PCL呈柱状微区垂直于薄膜表面的微相分离形貌,PMMA/PEO链段无法在PCL柱状微区上方形成完全覆盖,导致薄膜表面形成许多孔洞。随着PEO含量增加,PCL链段聚集趋势增强,柱状微区尺寸不断增大;随着PEO相对分子质量的增加,PMMA/PEO在PCL微区上方形成的有效覆盖减少,薄膜表面的孔洞数量和尺寸增大;当PEO与不同嵌段比PCL-b-PMMA共混后,随嵌段共聚物中PCL链段体积分数增加,柱状微区向层状形态转变,薄膜表面孔洞消失。     

PEO-b-PS嵌段共聚物的合成与有序纳米膜的制备

以聚环氧乙烷-溴(PEO-Br)大分子引发剂引发苯乙烯(St)的原子转移自由基聚合(ATRP),制备了聚环氧乙烷-b-聚苯乙烯(PEO-b-PS).1H NMR分析表明嵌段共聚物中聚环氧乙烷嵌段和聚苯乙烯嵌段的数均分子量分别是5500和37000,PEO的质量分数为12.9％.考察了旋涂环境和溶剂熏蒸后处理方法对此嵌段共聚物薄膜形貌的影响,结果表明在PS的良溶剂和PEO的良溶剂共同存在下旋涂成膜,并经过两种良溶剂共同蒸汽的后处理,PEO-b-PS嵌段共聚物可以制得具有规则纳米圆柱图案的薄膜.     

嵌段共聚物PCL-b-PMMA薄膜的微相分离形貌

通过开环聚合(ROP)和原子转移自由基聚合(ATRP)制备了不同嵌段结构的嵌段共聚物PCL-b-PMMA,使用核磁共振(1H-NMR)和凝胶渗透色谱(GPC)对其结构进行了表征,通过原子力显微镜(AFM)研究了嵌段共聚物薄膜的微相分离形貌。结果表明,嵌段共聚物发生了微相分离,聚ε-己内酯(PCL)链段形成柱状微区;PCL链段体积分数较低时,薄膜表面以聚甲基丙烯酸甲酯(PMMA)链段聚集为主,但未在PCL柱状微区上方形成覆盖,从而在薄膜表面形成孔洞;随PCL链段体积分数增加及PMMA链段分子量下降,PCL柱状微区面积增加,向薄膜表面迁移并逐渐形成覆盖,造成薄膜表面孔洞消失。     

双酚A型聚砜-聚氧化丙烯多嵌段共聚物的形态结构

用示差扫描量热仪(DSC)和透射式电子显微镜(TEM)研究了双酚A型聚砜-聚氧化丙烯多嵌段共聚物的形态结构。结果表明,硬段和软段的分子量大小对这种嵌段共聚物的形志结构的影响很大,可以从三相结构变为单相结构。热处理会加速其相分离过程,使分散相微区增大。动态力学性能的研究结果亦支持了这种嵌段共聚物有三相结构的存在。     

PMTFPSb-PEO-b-PMTFPS含氟三嵌段共聚物的合成及其溶液性质研究

通过阴离子开环聚合制备了Si-H封端聚[1,3,5-三甲基-1,3,5(3,3,3-三氟丙基)硅氧烷](PMTFPS)大分子单体,进而与双烯丙基聚氧乙烯醚(PEO)进行硅氢加成反应合成了不同亲水/疏水嵌段比例的PMTFPS-b-PEO-b-PMTFPS三嵌段共聚物。分别利用GPC和1H-NMR等手段表征了嵌段共聚物的结构组成,测定了不同结构嵌段共聚物的平衡表面张力及临界胶束浓度(cmc)。研究表明,当疏水嵌段链长一定时,临界胶束浓度(cmc)值随聚醚嵌段的增长而下降;当聚醚嵌段长度一定时,cmc值不随疏水嵌段长度的变化而变化。     

AFM针尖在嵌段共聚物薄膜表面锻造纳米图案

介绍了在原子力显微镜(AFM)轻敲模式下使用普通硅针尖在球形结构的苯乙烯-乙烯/丁烯-苯乙烯三嵌段共聚物(SEBS)薄膜表面锻造凹痕和凸痕纳米图案的工艺方法;从嵌段共聚物薄膜的微观结构出发,研究了SEBS薄膜表面的不同相分离形态对锻造压痕的影响,结果证实,只有六角状球形结构的薄膜才能用于制备压痕,其原因是由于该结构样品具有较低的硬度和模量;通过与均聚物PS薄膜比较得出,球形相分离形态的SEBS薄膜具有容易发生变形、压痕精度高、无边界堆积等优点。     

聚丁二烯段1,2结构含量对SBS表面相分离形貌的影响

本文以三嵌段共聚物聚(苯乙烯-丁二烯-苯乙烯)(SBS)为研究对象,原子力显微镜(AFM)为研究手段,对PB段1,2结构的含量对SBS表面微相分离形貌的影响进行了研究,研究结果表明,无论采用甲苯还是环己烷为成膜溶剂,PS呈都圆柱状分散在连续的橡胶相中,但是随着聚丁二烯段1,2结构含量由28%增加到33%,其结构排列的有序性会发生相应下降.此外,本文还对制膜所选择的溶剂种类对嵌段共聚物形貌的影响进行了讨论.     

基于胶体晶体构筑银纳米薄膜及其抑制微放电性能研究

近年来,微放电效应的抑制研究在加速器、大功率微波器件等领域得到了广泛的关注。采用聚苯乙烯(PS)胶体晶体模板辅助磁控溅射法制备了类空心球结构的银薄膜,通过调节PS模板尺寸及溅射时间(镀银层厚度),得到具有抑制微放电效应的银薄膜。采用SEM表征银薄膜的形貌与结构,并用二次电子发射系数(SEY)测试平台表征银薄膜的SEY。结果表明,PS模板尺寸及溅射时间对银薄膜形貌及其二次电子抑制作用有显著的影响,当溅射时间为600s,模板尺寸为1 000nm时,银薄膜的SEY较小,即对二次电子的抑制作用较为显著,与初始镀银铝合金样品相比,其SEY值降低了48%。     

Heparin-containing block copolymers

Newly synthesized heparin-containing block copolymers, consisting of a hydrophobic block of polystyrene (PS), a hydrophilic spacer-block of poly(ethylene oxide) (PEO) and covalently bound heparin (Hep) as bioactive block, were coated on aluminium, glass, polydimethylsiloxane (PDMS), PS or Biomer substrates. Surfaces of coated materials were characterized by transmission electron microscopy (TEM), contact angle measurements and X-ray photoelectron spectroscopy for chemical analysis (XPS). It was demonstrated by TEM that thin films of PS-PEO and PS-PEO-Hep block copolymers consisted of heterogeneous microphase separated structures. Using sessile-drop and Wilhelmy plate dynamic contact angle measurements, insight was provided into the hydrophilicity of the surfaces of the coatings. Measurements with hydrated coatings of PS-PEO and PS-PEO-Hep block copolymers revealed that the surfaces became more hydrophilic during immersion in water, due to relaxation/reorientation, or swelling of PEO or PEO-Hep domains, respectively. XPS results for PS, PEO, heparin and PS-PEO as powder agreed well with qualitative and quantitative predictions. XPS results for films of PS-PEO and PS-PEO-Hep block copolymers showed enrichments of PEO in the top layers of the coatings. This effect was more pronounced for hydrated surfaces. Only small amounts of heparin were detected at the surface of coatings of PS-PEO-Hep block copolymers.     

Highly ordered hierarchical poly(ethylene oxide)-b-polystyrene/organoclay nanocomposites

A lamellar forming poly(ethylene oxide)-b-polystyrene (PEO-b-PS)/organoclay nanocomposite with a unique hierarchical structure has been fabricated, by casting solution blends of the block copolymer and organoclay, with subsequent annealing at 180 °C for 8 h under uniaxial constraint. PEO-b-PS provided the nanocomposite lamellar structure with a slightly increased long period. Lamellar layers of the nanocomposite block copolymer were oriented parallel to the film plane. Fully exfoliated clay platelets were localized mostly in the aligned PEO layers, and all platelets were found to be parallel to the interface between PEO and PS layers. PEO crystals in the nanocomposite were oriented with the c-axis perpendicular to the phase-separated layers. The orientation function degree of the PEO crystals within the nanocomposite was lower than that of the crystals within the neat block copolymer.     

Three‐Dimensional Nanofabrication by Block Copolymer Self‐Assembly

Thin films of block copolymers are widely seen as enablers for nanoscale fabrication of semiconductor devices, membranes, and other structures, taking advantage of microphase separation to produce well‐organized nanostructures with periods of a few nm and above. However, the inherently three‐dimensional structure of block copolymer microdomains could enable them to make 3D devices and structures directly, which could lead to efficient fabrication of complex heterogeneous structures. This article reviews recent progress in developing 3D nanofabrication processes based on block copolymers.     

Directed Self‐Assembly of Star‐Block Copolymers by Topographic Nanopatterns through Nucleation and Growth Mechanism

Exploring the ordering mechanism and dynamics of self‐assembled block copolymer (BCP) thin films under confined conditions are highly essential in the application of BCP lithography. In this study, it is aimed to examine the self‐assembling mechanism and kinetics of silicon‐containing 3‐arm star‐block copolymer composed of polystyrene (PS) and poly(dimethylsiloxane) blocks as nanostructured thin films with perpendicular cylinders and controlled lateral ordering by directed self‐assembly using topographically patterned substrates. The ordering process of the star‐block copolymer within fabricated topographic patterns with PS‐functionalized sidewall can be carried out through the type of secondary (i.e., heterogeneous) nucleation for microphase separation initiated from the edge and/or corner of the topographic patterns, and directed to grow as well‐ordered hexagonally packed perpendicular cylinders. The growth rate for the confined microphase separation is highly dependent upon the dimension and also the geometric texture of the preformed pattern. Fast self‐assembly for ordering of BCP thin film can be achieved by lowering the confinement dimension and also increasing the concern number of the preformed pattern, providing a new strategy for the design of BCP lithography from the integration of top‐down and bottom‐up approaches.     

聚苯乙烯-聚氧乙烯-聚苯乙烯三嵌段共聚物的结晶行为研究

采用偏光显微镜和DSC技术研究了聚苯乙烯-聚氧乙烯-聚苯乙烯（PS-b-PEO-b-PS)三嵌段共聚物的结晶行为,实验结果表明,随着共聚物中聚氧乙烯含量的降低,形成清晰球晶的能力减弱,结晶度（Xc）、结晶熔融温度（Tm）、结晶温度（Tc）降低;先微相分离再结晶和微相分离与结晶同时进行两种热历史,前者会损失体系的Xc、Tm;当共聚物中聚氧乙烯的数均分子量为2000,质量分子数为18%和34%时,发现了等速降温双结晶体。     

One-step preparation of hierarchical porous carbons from poly(vinylidene chloride)-based block copolymers

A facile self-templating and activation-free method to fabricate the hierarchical porous carbons (HPCs) from poly(vinylidene chloride) (PVDC)-based block copolymers is reported in this article. A series of block copolymers consisted of PVDC and the polystyrene (PS) blocks were prepared via RAFT living radical polymerization. Effects of molar ratio between the PVDC and the PS blocks on the microphase separation and thermal degradation of the PVDC-b-PS copolymers, and the microstructure of the as-prepared porous carbons were investigated. The results show that the PVDC block acts as a good kind of carbon precursor capable of forming micropores (0.5–0.6 nm) due to the diffusion of small molecules eliminated during the degradation of the PVDC block, and the microdispersed PS block acts as a mesopore extender to generate the mesopores (3–30 nm) by the decomposition of the PS phase. The as-prepared HPCs have the unique structures with three-dimensionally interconnected micropores and mesopores. The high Brunauer–Emmett–Teller surface area (1220 m²/g) and total pore volume (0.92 cm³/g) were achieved through controlling the composition of block copolymer. The method is facile to prepare the HPCs and suitable to the PVDC-based copolymers with other pyrolyzable block.     

Controlling the Pore Size of Mesoporous Carbon Thin Films through Thermal and Solvent Annealing

Herein an approach to controlling the pore size of mesoporous carbon thin films from metal‐free polyacrylonitrile‐containing block copolymers is described. A high‐molecular‐weight poly(acrylonitrile‐block‐methyl methacrylate) (PAN‐b‐PMMA) is synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization. The authors systematically investigate the self‐assembly behavior of PAN‐b‐PMMA thin films during thermal and solvent annealing, as well as the pore size of mesoporous carbon thin films after pyrolysis. The as‐spin‐coated PAN‐b‐PMMA is microphase‐separated into uniformly spaced globular nanostructures, and these globular nanostructures evolve into various morphologies after thermal or solvent annealing. Surprisingly, through thermal annealing and subsequent pyrolysis of PAN‐b‐PMMA into mesoporous carbon thin films, the pore size and center‐to‐center spacing increase significantly with thermal annealing temperature, different from most block copolymers. In addition, the choice of solvent in solvent annealing strongly influences the block copolymer nanostructure and the pore size of mesoporous carbon thin films. The discoveries herein provide a simple strategy to control the pore size of mesoporous carbon thin films by tuning thermal or solvent annealing conditions, instead of synthesizing a series of block copolymers of various molecular weights and compositions.     

Photopatterning of Cross‐Linkable Epoxide‐Functionalized Block Copolymers and Dual‐Tone Nanostructure Development for Fabrication Across the Nano‐ and Microscales

The self‐assembly of block copolymers in thin films provides an attractive approach to patterning 5–100 nm structures. Cross‐linking and photopatterning of the self‐assembled block copolymer morphologies provide further opportunities to structure such materials for lithographic applications, and to also enhance the thermal, chemical, or mechanical stability of such nanostructures to achieve robust templates for subsequent fabrication processes. Here, model lamellar‐forming diblock copolymers of polystyrene and poly(methyl methacrylate) with an epoxide functionality are synthesized by atom transfer radical polymerization. We demonstrate that self‐assembly and cross‐linking of the reactive block copolymer materials in thin films can be decoupled into distinct, controlled process steps using solvent annealing and thermal treatment/ultraviolet exposure, respectively. Conventional optical lithography approaches can also be applied to the cross‐linkable block copolymer materials in thin films and enable simultaneous structure formation across scales—micrometer scale patterns achieved by photolithography and nanostructures via self‐assembly of the block copolymer. Such materials and processes are thus shown to be capable of self‐assembling distinct block copolymers (e.g., lamellae of significantly different periodicity) in adjacent regions of a continuous thin film.