含偶氮聚合物膜表面皱纹的光擦除与光调制研究

发布时间：2018-06-02 07:16

本文选题：偶氮苯聚合物 + 光异构化　；参考：《天津大学》2016年博士论文

【摘要】：具有软/硬层复合结构的膜/基系统表面起皱是自然界和实际工程应用中经常遇到的现象。一方面,材料表面起皱会影响材料结构及使用性能,是一种须极力避免的工程危害;另一方面,表面起皱能广泛应用于膜材料物性表征、功能性表面构筑及柔性光电器件等诸多领域。然而,如何有效消除材料表面皱纹或制备特定形貌的皱纹图案,目前仍然是一个挑战性难题。在本论文中,基于表面起皱机制,通过在表层膜材料中引入光响应性组分构建智能响应性皱纹体系,实现了膜/基体系表面皱纹形貌的动态调控/擦除。根据膜/基体系的组成结构不同,本论文工作主要分为:双层膜/基体系和多层膜/基体系表面皱纹的光调控。在双层膜/基体系中,本论文以偶氮苯聚合物(聚分散橙3,PDO3)为膜层,以聚二甲硅氧烷(PDMS)为弹性基底构筑了光响应性膜/基皱纹体系(PDMS/PDO3)。通过可见光照射,引发PDO3膜中偶氮苯基团发生可逆光致顺反异构化反应进行体系表面大面积皱纹形貌的动态调控/擦除。系统考察了光强、入射光波长、PDO3膜厚以及皱纹振幅等实验参数对膜/基体系表面皱纹形貌光调控/擦除行为的影响;最终实验和理论模拟表明:PDO3膜中偶氮苯基团可逆顺反异构引发的应力/应变松弛是PDMS/PDO3体系表面皱纹形貌光调控/擦除的主要原因。当该体系进行可见光选区曝光时,曝光区域的皱纹被擦除;而非曝光区域的皱纹形貌仍然能够保持,但形貌演变为垂直于曝光区/非曝光区边界的高度取向性皱纹形貌。此外,借助不同的铜网/光掩模选区曝光,进行了表面皱纹微结构的精细调控,实现了一系列高级皱纹图案化表面的构筑,并探索了该光敏性体系在光可擦写信息存储等方面的应用。在多层膜/基体系中,本论文首先以PDO3膜作为中间层,以非光敏性聚苯乙烯(PS)膜为顶层,制备了光响应性的多层膜/基体系(PDMS/PDO3/PS)。当热诱导制备的多层膜皱纹体系经受可见光曝光处理时,中间层PDO3膜内偶氮苯基团的可逆顺反异构引起体系表面皱纹形貌的动态演变。实验和相关理论分析表明:可见光曝光导致PDO3膜内发生光软化效应是多层膜/基体系表面皱纹形貌演变的主要原因。借助铜网/光掩模选区曝光,体系表面曝光区皱纹基于PDO3膜光软化效应,呈现皱纹周期显著降低的形貌演变;非曝光区皱纹则基于边界效应演变为高度有序的取向性皱纹,由此实现了非光响应性膜表面高级皱纹形貌的光调控制备。此选区曝光所形成的高级皱纹形貌,通过调节表层膜厚及铜网种类实现了精确调控。此外,这一光响应性体系能通过改变顶层膜材料的种类进一步拓展。借助于曝光前后多层膜/基体系表面皱纹形貌的变化,本论文对可见光曝光引起层状多层膜中PDO3膜模量的变化进行了详细的考察;分析结果显示:光照条件下偶氮苯膜的模量降低约为1个数量级。此外,本论文进一步基于PDO3膜作为表面层,设计引入不同类型的中间层构筑了两种多层膜体系:PDMS/PS/PDO3体系以及PDMS/SiOx/PDO3体系。在选区曝光处理时,两种多层膜体系表面曝光区皱纹呈现出不同的演变规律。通过系统考察中间层膜厚、PDO3膜厚以及中间层膜材料的种类对该体系表面皱纹形貌光调控演变的影响,由此分析探讨了不同皱纹演变现象的内在机理。结果表明:可见光曝光条件下,PDMS/PS/PDO3体系其曝光区皱纹呈现PDO3膜光软化效应主导的皱纹周期减小的演变规律;而PDMS/SiOx/PDO3体系其曝光区皱纹呈现应力松弛效应主导的皱纹光擦除的演变规律。同样借助铜网选区曝光,结合两种多层膜体系膜厚和铜网种类等实验参数的调节,实现了两种多层膜体系表面多种不同高级皱纹图案的精细构筑。
[Abstract]:Surface wrinkling of membrane / base system with soft / hard layer composite structure is often encountered in natural and practical engineering applications. On one hand, surface wrinkling will affect the structure and performance of material, and it is a kind of Engineering harm to avoid. On the other hand, surface wrinkling can be widely used in the characterization of membrane materials, functional surfaces. Construction and flexible optoelectronic devices and many other fields. However, it is still a challenging problem how to effectively eliminate the wrinkles on the surface of the materials or to prepare the wrinkle patterns of specific morphologies. In this paper, an intelligent responsive wrinkle system is constructed by introducing light responsive components into the surface membrane materials to achieve the film / film. Dynamic regulation / erasure of the surface wrinkle morphology of the base system. According to the composition and structure of the membrane / base system, this paper is mainly divided into the light regulation of the surface wrinkles of the double layer film / base system and the multilayer film / base system. In the double layer membrane / base system, the azobenzene polymer (polydisperse Orange 3, PDO3) is used as the film, and the poly (two methylene siloxane) (PDMS) is used in this paper. The photoresponsive membrane / basic wrinkle system (PDMS/PDO3) is constructed for the elastic substrate. The azobenzene group in the PDO3 film can be induced by the visible light irradiation, and the dynamic regulation / erasure of the large surface wrinkle morphology of the surface of the system is carried out. The experimental parameters of the light intensity, the radiation wavelength, the PDO3 film thickness and the wrinkle amplitude are systematically investigated. The effects of the light regulation / erasure on the surface wrinkle morphology of the membrane / base system, and the final experimental and theoretical simulation show that the stress / strain relaxation induced by the azobenzene group in the PDO3 film is the main reason for the light regulation / erasure of the surface wrinkle morphology of the PDMS/PDO3 system. The wrinkles were erased, while the wrinkle morphology in the non exposed area was still maintained, but the morphology evolved into a highly oriented wrinkle pattern perpendicular to the boundary of the exposure zone / unexposed area. In addition, the fine regulation of the surface wrinkle microstructures was carried out with the help of different copper mesh / photomask selection. A series of advanced wrinkled surfaces were realized. The application of the photosensitive system in the storage of optical erasable information is explored. In the multilayer film / base system, the PDO3 film is used as the middle layer and the non photosensitive polystyrene (PS) film is the top layer, and the light responsive multilayer film / base system (PDMS/PDO3/PS) is prepared. The reversible CIS and trans isomerization of azobenzene group in the middle layer of PDO3 film caused the dynamic evolution of the surface wrinkle morphology during the visible light exposure treatment. The experimental and related theoretical analysis showed that the optical softening effect in the PDO3 film caused by visible light exposure was the main reason for the evolution of the surface wrinkle morphology of the surface of the multilayer film / base system. The surface wrinkles of the system surface exposure are based on the light softening effect of PDO3 film, showing a significant decrease in the morphology evolution of the wrinkle cycle, while the unexposed area wrinkles are based on the highly ordered orientation wrinkles based on the boundary effect, thus realizing the optical modulation of the advanced wrinkle morphology on the surface of the non light responsive membrane. In addition, this photoresponse system can be further expanded by changing the types of the top layer membrane materials. With the help of the changes in the surface wrinkle morphology of the multilayer film / base system before and after exposure, the visible light exposure causes the PDO3 film in layered multilayer films. The results showed that the modulus of azobenzene film decreased by about 1 orders of magnitude under light conditions. Furthermore, based on the PDO3 film as the surface layer, two kinds of multilayer film systems were constructed by introducing different types of intermediate layers: the PDMS/ PS/PDO3 system and the PDMS/SiOx/PDO3 system. At the time of treatment, the surface wrinkles in the surface of the two multilayer films show a different evolution law. Through the systematic investigation of the influence of the thickness of the middle layer, the thickness of the PDO3 film and the type of the middle layer film on the light regulation and regulation of the surface wrinkle morphology, the internal mechanism of the different wrinkle evolution is analyzed and discussed. The results show that the visible light is visible. Under the exposure conditions, the wrinkles in the exposure zone of the PDMS/PS/PDO3 system show the evolution of the wrinkle cycle which is dominated by the light softening effect of the PDO3 film, while the PDMS/SiOx/PDO3 system has the light erasure dominated by the stress relaxation effect in the exposure zone of the PDMS/SiOx/PDO3 system. It is also exposed by copper mesh selection and combined with the thickness and copper of the membrane system. With the adjustment of experimental parameters such as net type, the fine structure of two kinds of high grade wrinkle patterns on the surface of the multilayer system has been realized.
【学位授予单位】：天津大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：TB383.2

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