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.     

软模板印刷法制备超疏水性聚苯乙烯膜

首次利用软模板印刷的方法,以微米-亚微米-纳米复合结构的PDMS为软模板,在平滑聚苯乙烯表面上成功制备了同样具有微米-亚微米-纳米复合结构的超疏水表面,该表面与水的接触角高达161.2º。软模板印刷方法可以用在其它热塑性聚合物如聚丙烯、聚甲基丙烯酸甲酯和聚碳酸酯等材料上,是一种简单有效地制备超疏水性表面的方法。     

利用反相乳液-水滴模板法制备功能性生物基图案化结构

通过将传统水滴模板法中的单相成膜液改造为反相乳液体系,引进乳液水滴来加载蛋白质组分,实现了对亲水组分直接实施水滴模板法从而获得其阵列组装结构.利用壳聚糖纳米粒子作为皮克林反相乳液的乳化剂制备了稳定的反相乳液体系,并进一步得到聚乳酸/壳聚糖/牛血清白蛋白的杂化蜂窝状多孔薄膜,考察了壳聚糖粒子对于乳液稳定和所制备多孔阵列结构形貌的影响,研究了加入蛋白质浓度和乳液中的水相/油相比例对于所成膜孔形貌的影响,利用荧光标记蛋白质跟踪确认基于蜂窝状多孔阵列结构上的图案化蛋白质阵列组装形貌.     

喷砂-阳极氧化-氟化处理构筑铝合金超疏水表面

为研究复合法制备超疏水表面过程中主要工艺参数对表面形貌及超疏水性能的影响, 开发了一种喷砂-阳极氧化复合方法, 在铝合金表面构筑了微米-纳米二级结构, 经氟化处理后获得了超疏水特性. 结果表明, 喷砂处理在铝合金表面通过冲蚀的凹坑构筑出微米结构, 阳极氧化则在铝合金表面通过蜂窝状氧化膜构筑纳米结构. 但单纯构筑粗糙结构或单纯改变表面化学组成均不能在铝合金表面获得超疏水特性. 单纯的微米结构或纳米结构, 即使有低表面能聚合物修饰也不能获得超疏水特性. 只有微米-纳米二级结构和低表面能聚合物的协同作用, 才能有效构筑铝合金超疏水表面. 这种铝合金与水滴接触时, 形成的气阱可减小固体表面与水滴的接触面积, 降低表面与水滴间的热量交换, 从而减缓水分子的凝结, 提高铝合金的抗霜冻性. 同时, 气阱还可有效减缓海水的腐蚀, 提高铝合金的耐海水腐蚀性.     

阵列凹坑结构分布与水滴黏附性质的关系

以新鲜玫瑰花花瓣正面为模板, 采用模板印刷法制备具有微米级阵列凹坑和纳米级沟壑结构的聚二甲基硅氧烷(PDMS)薄膜, 通过对该薄膜逐级拉伸改变其微观结构的分布; 采用场发射扫描电子显微镜(SEM)和原子力显微镜(AFM)观察了不同拉伸程度下薄膜表面微观结构的变化, 采用高敏感性微电力学天平测试了样品表面微观结构变化过程中水滴的黏附力, 分析了其微观结构分布与水滴黏附性质的关系; 采用接触角测量仪表征不同拉伸条件下薄膜的浸润性. 结果表明, 随着PDMS薄膜被逐次拉伸, 单位面积内的凹坑结构数目减少, 且凹坑逐渐分离, 凹坑的深度逐渐降低, 水滴更容易浸入到凹坑结构中, 因此水滴与薄膜的黏附力急剧增大; 随着薄膜进一步拉伸, 纳米级沟壑结构会随着凹坑的拉伸而不断伸展, 纳米级沟壑结构的面积增加, 纳米沟壑结构诱捕的空气量逐渐上升, 导致水滴与薄膜表面的接触面积降低, 使得水滴与薄膜的黏附力下降; 继续拉伸PDMS薄膜, 纳米级沟壑结构进一步伸展, 水滴逐渐浸入纳米级沟壑结构中, 水滴与薄膜的黏附力缓慢增大, 当水滴完全进入到纳米级沟壑中时, 水滴与薄膜的黏附力达到极大值, 此时继续拉伸PDMS薄膜, 纳米级沟壑结构随着拉伸程度的增加继续伸展, 水滴与薄膜的接触面积稍有减少, 黏附力将有所下降, 直至薄膜被完全破坏. 由此可见, 微米级凹坑结构和纳米级褶皱结构的分布是影响PDMS薄膜对水滴黏附性质的主要因素.     

基于热模塑法制备HDPE仿生超疏水表面

研究了热模塑法在制备超疏水高密度聚乙烯(HDPE)膜中的应用。以高岭土增强的聚二甲基硅氧烷(PDMS)为软模板,采用热模塑技术,将荷叶表面的微结构信息复制到HDPE膜表面。接触角测量结果显示,10%掺杂量的PDMS软模板复制得到的HDPE膜表面,与水的接触角高达156°,呈现超疏水性。扫描电镜照片显示,PDMS软模板具有与荷叶表面互补的"负型结构",而HDPE膜表面则具有与荷叶类似的微米—纳米复合粗糙结构。此法无需溶剂,可推广制备其它热塑性高聚物的超疏水表面。     

蜂窝状有序膜功能化研究进展*

水滴模板法是近年来引人瞩目的一种制备有序微结构材料的方法,所制备的蜂窝状有序膜在微容器和微反应器、图案化模板、细胞培养支架、光学材料、超疏水表面、分离膜等领域具有十分重要的应用前景。本文对蜂窝状有序膜功能化研究的最新进展进行了系统总结,详细介绍和分析了原位多层次自组装、表面接枝、生物活性分子固定、交联、模板法成膜以及表面填充等蜂窝状有序膜的功能化方法。     

超疏水低粘着铜表面制备及其防覆冰性能

用喷砂处理在铜片表面形成微米级丘陵状凹坑,再用表面氧化处理在铜片表面制备菊花花瓣状CuO纳米片.通过喷砂-表面氧化处理在铜片表面成功构建了微米-纳米复合结构,这种表面氟化后与水滴的接触角高达161°,滚动角低至1°,显示出优异的超疏水性和很低的粘着性.低温下,这种表面与水滴间的热量交换较小,水滴不易凝结,有效地提高了抗结霜性.抗结霜性良好的超疏水铜有望在热交换器或低温运行设备等领域获得应用,这种简便的超疏水铜表面的制备方法也给其它工程材料超疏水表面的工业化制备提供了一个思路.     

复合SiO2粒子涂膜表面结构及超疏水性能

采用溶胶-凝胶法制备不同粒径SiO₂粒子，通过表面改性得到不同形状复合粒子，并利用氟硅氧烷的表面自组装功能制备了具有“荷叶效应”的超疏水涂膜。通过原子力显微镜、扫描电镜和水接触角的测试对膜结构及性能进行了表征，探讨了SiO₂粒子的粒径和形状与表面微观结构、表面粗糙度和表面疏水性能的关系。结果表明含单一粒径粒子涂膜表面水接触角符合Wenzel模型，而复合粒子构成了符合Cassie模型的非均相界面;单纯的粗糙度因子不能反映水接触角的变化，复合粒子在膜表面的无规则排列赋予涂膜表面不同等级的粗糙度，使得水滴与涂膜表面接触时能够形成高的空气捕捉率和较小的粗糙度因子;其与在涂膜表面能形成自组装分子膜的氟硅氧烷共同作用赋予了涂膜超疏水性能，而这种超疏水性能与复合粒子的粒径大小和形状基本无关。     

双级微结构上二氧化硅粒子对微注压成型PP表面润湿特性的影响

提出一种柔性复制法,采用微注射压缩(μ-ICM)成型具有微拓扑结构的仿生聚丙烯(PP)表面.通过复制模板上的双级微结构,所成型的PP材料表面上呈现具有锥形顶面的双级微结构,即微棱和高纵横比的微锥体.由于微锥体之间的间隙较大,水滴浸润其间隙的上方,这使该表面呈现中等黏附的超疏水特性.在μ-ICM过程中,涂覆在模板上的二氧化硅纳米粒子(SNPs)被转移到熔体中,并牢牢附着于微结构表层,赋予其表面亚微米或微米粗糙度,形成多层次微结构.在附着有亲水SNPs的微结构上,高表面自由能使水滴完全浸润微锥体之间的间隙,表面的水接触角为161.9°、滚动角大于90°,呈现极高黏附的超疏水特性(花瓣效应);在附着有疏水SNPs的微结构上,水滴受疏水SNPs的排斥而减弱与表面之间的黏附作用,表面的水接触角为163.5°、滚动角为3.5°,呈现极低黏附的超疏水特性(荷叶效应).     

两亲性Janus粒子在蜂窝状多孔聚合物膜上的自组装性能

采用具有两亲性的两面体(Janus)粒子实现稳定的粒子界面组装与水滴模板法自组装过程相结合的方法获得了粒子在蜂窝状多孔聚合物薄膜内壁的高效定向修饰.通过与均质粒子组装形貌的对比,证明了Janus粒子因其特殊的界面自组装活性,可以获得高粒子加量条件下的规则多孔结构,解决了使用均质粒子时存在的结构有序性和粒子修饰密度之间的矛盾.而在较低粒子加量的条件下,Janus粒子也展示出与均质粒子极为不同的组装形貌.这一方法的建立,为新型表面功能化材料的制备提供了一个新的思路.     

Rings of nanoparticle-decorated honeycomb-structured polymeric film: the combination of pickering emulsions and capillary flow in the breath figures method

The self-assembly of nanoparticles at the fluid/fluid interface (Pickering emulsions) in the breath figures (BF) method have been explored to direct nanoparticles onto BF microarrays and adjust the BF assembly in microsize. Circular rings of nanoparticle-decorated honeycomb-structured polymeric film can be obtained by a one-step process. The combination of Pickering emulsions and capillary flow in the BF method may be responsible for the formation of this intriguing structure.     

Direct breath figure formation on PMMA and superhydrophobic surface using in situ perfluoro-modified silica nanoparticles

Breath figure formation was carried out directly on the surface of poly(methylmethacrylate) using a mixture of a good solvent, tetrahydrofuran, and a nonsolvent, water. Direct breath figure formation was coined for this method and a mechanism was proposed to describe the figure formation by the method based on hypothesizes available for the normal breath figure formation. The proposed mechanism is such that the sonication effect, immersion time, and water content on characteristics of the obtained figures can be explained. The figured surface was then made superhydrophobic with a water contact angle of 175° using in situ growing of perfluoro modified silica nanoparticles inside the figure cell by one-pot method. The spherical modified silica nanoparticles were detected being trapped by figure features providing a mechanical entrapment of the low-surface energy nanoparticles. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

利用去湿现象制备具有SERS活性的银纳米粒子图案

构建了具有表面增强拉曼散射(SERS)活性的二维有序环状与盘状的银纳米粒子结构, 利用CTAB包覆银纳米粒子的氯仿溶液直接在图案化的金基底上进行去湿, 当改变银纳米粒子的浓度时可以得到不同的图案. 利用原子力显微镜(AFM)对其结构进行了表征, 以4-巯基吡啶作为探针分子, 采用表面增强拉曼成像技术研究了这种基底的SERS活性, 这将为SERS的研究开拓新的领域.     

Facile patterning of upconversion NaYF4:Yb,Er nanoparticles

Different kinds of highly ordered patterns of NaYF(4):Yb,Er nanoparticles on gold substrates were fabricated using a simple method combining micro-contact printing and "breath figures" techniques. Ordered arrays of water droplets were first formed in the hydrophilic regions of patterned self-assembled monolayers (SAMs). This was subsequently submerged in a chloroform solution of NaYF(4):Yb,Er nanoparticles. The particles were spontaneously assembled at the interface of chloroform/water droplet surface, leading to different kinds of uniform patterns after solvent evaporation. The structures of NaYF(4):Yb,Er particles patterns depended on the dimension of the substrate, the concentration of the NaYF(4):Yb,Er nanoparticles and the water condensation process.     

Superhydrophobic polyimide films with a hierarchical topography: combined replica molding and layer-by-layer assembly

Artificial superhydrophobic surfaces with a hierarchical topography were fabricated by using layer-by-layer assembly of polyelectrolytes and silica nanoparticles on microsphere-patterned polyimide precursor substrates followed with thermal and fluoroalkylsilane treatment. In this special hierarchical topography, micrometer-scale structures were provided by replica molding of polyamic acid using two-dimensional arrays of polystyrene latex spheres as templates, and nanosized silica particles were then assembled on these microspheres to construct finer structures at the nanoscale. Heat treatment was conducted to induce chemical cross-linking between polyelectrolytes and simultaneously convert polyamic acid to polyimide. After surface modification with fluoroalkylsilane, the as-prepared highly hydrophilic surface was endowed with superhydrophobicity due to the bioinspired combination of low surface energy materials and hierarchical surface structures. A superhydrophobic surface with a static water contact angle of 160 degrees and sliding angle of less than 10 degrees was obtained. Notably, the polyimide microspheres were integrated with the substrate and were mechanically stable. In addition, the chemical and mechanical stability of the polyelectrolyte/silica nanoparticle multilayers could be increased by heat-induced cross-linking between polyelectrolytes to form nylon-like films, as well as the formation of interfacial chemical bonds.     

Langmuir monolayers of Co nanoparticles and their patterning by microcontact printing

In this paper, we describe an easy and reliable method for the production of patterned monolayers of Co nanoparticles. A two-dimensional monolayer of Co nanoparticles is fabricated by spreading a nanoparticle solution over an air-water interface and then transferring it to a hydrophobic substrate by using the Langmuir-Blodgett (LB) method. Transmission electron microscopy (TEM) was used to show that, with increasing surface pressure, the Co nanoparticles become well-organized into a Langmuir monolayer with a hexagonal close-packed structure. By controlling the pH of the subphase, it was found that a monolayer of Co nanoparticles with long-range order could be obtained. Further, by transferring the Langmuir monolayer onto a poly(dimethoxysilane) (PDMS) mold, the selective micropatterning of the Co nanoparticles could be achieved on a patterned electronic circuit. The electronic transport properties of the Co nanoparticles showed the ohmic I-V curve.     

Photoreactive azido-containing silica nanoparticle/polycation multilayers: durable superhydrophobic coating on cotton fabrics

In this study, we report the functionalization of silica nanoparticles with highly photoreactive phenyl azido groups and their utility as a negatively charged building block for layer-by-layer (LbL) electrostatic assembly to produce a stable silica nanoparticle coating. Azido-terminated silica nanoparticles were prepared by the functionalization of bare silica nanoparticles with 3-aminopropyltrimethoxysilane followed by the reaction with 4-azidobenzoic acid. The azido functionalization was confirmed by FTIR and XPS. Poly(allylamine hydrochloride) was also grafted with phenyl azido groups and used as photoreactive polycations for LbL assembly. For the photoreactive silica nanoparticle/polycation multilayers, UV irradiation can induce the covalent cross-linking within the multilayers as well as the anchoring of the multilayer film onto the organic substrate, through azido photochemical reactions including C-H insertion/abstraction reactions with surrounding molecules and dimerization of azido groups. Our results show that the stability of the silica nanoparticle/polycation multilayer film was greatly improved after UV irradiation. Combined with a fluoroalkylsilane post-treatment, the photoreactive LbL multilayers were used as a coating for superhydrophobic modification of cotton fabrics. Herein the LbL assembly method enables us to tailor the number of the coated silica nanoparticles through the assembly cycles. The superhydrophobicity of cotton fabrics was durable against acids, bases, and organic solvents, as well as repeated machine wash. Because of the unique azido photochemistry, the approach used here to anchor silica nanoparticles is applicable to almost any organic substrate.     

三维有序多孔图案化SiC陶瓷的制备

结合毛细管微模塑技术、模板技术和先驱体转化技术, 以图案化聚二甲基硅氧烷(PDMS)弹性体为模具,以氧化硅凝胶小球为模板, 以液态聚碳硅烷(PCS)为先驱体, 经过氧化硅凝胶小球图案化模板的形成, 先驱体的渗入, 模板中先驱体的交联, 弹性模具的去除, 图案化先驱体的无机化和模板的去除, 制备了图案化多孔SiC 陶瓷.研究结果表明：所制备的图案化多孔陶瓷中, 图案的尺寸受图案化PDMS 弹性模具的控制, 球形孔的孔径可由氧化硅凝胶小球来调节. 图案化陶瓷中球形孔不仅三维有序排列, 而且由于模板中小球的相互接触形成的“窗 口”使球形孔三维贯通.