本文選題：偶氮苯聚合物 + 光異構(gòu)化��； 參考：《天津大學(xué)》2016年博士論文

【摘要】：具有軟/硬層復(fù)合結(jié)構(gòu)的膜/基系統(tǒng)表面起皺是自然界和實際工程應(yīng)用中經(jīng)常遇到的現(xiàn)象。一方面,材料表面起皺會影響材料結(jié)構(gòu)及使用性能,是一種須極力避免的工程危害;另一方面,表面起皺能廣泛應(yīng)用于膜材料物性表征、功能性表面構(gòu)筑及柔性光電器件等諸多領(lǐng)域。然而,如何有效消除材料表面皺紋或制備特定形貌的皺紋圖案,目前仍然是一個挑戰(zhàn)性難題。在本論文中,基于表面起皺機制,通過在表層膜材料中引入光響應(yīng)性組分構(gòu)建智能響應(yīng)性皺紋體系,實現(xiàn)了膜/基體系表面皺紋形貌的動態(tài)調(diào)控/擦除。根據(jù)膜/基體系的組成結(jié)構(gòu)不同,本論文工作主要分為:雙層膜/基體系和多層膜/基體系表面皺紋的光調(diào)控。在雙層膜/基體系中,本論文以偶氮苯聚合物(聚分散橙3,PDO3)為膜層,以聚二甲硅氧烷(PDMS)為彈性基底構(gòu)筑了光響應(yīng)性膜/基皺紋體系(PDMS/PDO3)。通過可見光照射,引發(fā)PDO3膜中偶氮苯基團發(fā)生可逆光致順反異構(gòu)化反應(yīng)進(jìn)行體系表面大面積皺紋形貌的動態(tài)調(diào)控/擦除。系統(tǒng)考察了光強、入射光波長、PDO3膜厚以及皺紋振幅等實驗參數(shù)對膜/基體系表面皺紋形貌光調(diào)控/擦除行為的影響;最終實驗和理論模擬表明:PDO3膜中偶氮苯基團可逆順反異構(gòu)引發(fā)的應(yīng)力/應(yīng)變松弛是PDMS/PDO3體系表面皺紋形貌光調(diào)控/擦除的主要原因。當(dāng)該體系進(jìn)行可見光選區(qū)曝光時,曝光區(qū)域的皺紋被擦除;而非曝光區(qū)域的皺紋形貌仍然能夠保持,但形貌演變?yōu)榇怪庇谄毓鈪^(qū)/非曝光區(qū)邊界的高度取向性皺紋形貌。此外,借助不同的銅網(wǎng)/光掩模選區(qū)曝光,進(jìn)行了表面皺紋微結(jié)構(gòu)的精細(xì)調(diào)控,實現(xiàn)了一系列高級皺紋圖案化表面的構(gòu)筑,并探索了該光敏性體系在光可擦寫信息存儲等方面的應(yīng)用。在多層膜/基體系中,本論文首先以PDO3膜作為中間層,以非光敏性聚苯乙烯(PS)膜為頂層,制備了光響應(yīng)性的多層膜/基體系(PDMS/PDO3/PS)。當(dāng)熱誘導(dǎo)制備的多層膜皺紋體系經(jīng)受可見光曝光處理時,中間層PDO3膜內(nèi)偶氮苯基團的可逆順反異構(gòu)引起體系表面皺紋形貌的動態(tài)演變。實驗和相關(guān)理論分析表明:可見光曝光導(dǎo)致PDO3膜內(nèi)發(fā)生光軟化效應(yīng)是多層膜/基體系表面皺紋形貌演變的主要原因。借助銅網(wǎng)/光掩模選區(qū)曝光,體系表面曝光區(qū)皺紋基于PDO3膜光軟化效應(yīng),呈現(xiàn)皺紋周期顯著降低的形貌演變;非曝光區(qū)皺紋則基于邊界效應(yīng)演變?yōu)楦叨扔行虻娜∠蛐园櫦y,由此實現(xiàn)了非光響應(yīng)性膜表面高級皺紋形貌的光調(diào)控制備。此選區(qū)曝光所形成的高級皺紋形貌,通過調(diào)節(jié)表層膜厚及銅網(wǎng)種類實現(xiàn)了精確調(diào)控。此外,這一光響應(yīng)性體系能通過改變頂層膜材料的種類進(jìn)一步拓展。借助于曝光前后多層膜/基體系表面皺紋形貌的變化,本論文對可見光曝光引起層狀多層膜中PDO3膜模量的變化進(jìn)行了詳細(xì)的考察;分析結(jié)果顯示:光照條件下偶氮苯膜的模量降低約為1個數(shù)量級。此外,本論文進(jìn)一步基于PDO3膜作為表面層,設(shè)計引入不同類型的中間層構(gòu)筑了兩種多層膜體系:PDMS/PS/PDO3體系以及PDMS/SiOx/PDO3體系。在選區(qū)曝光處理時,兩種多層膜體系表面曝光區(qū)皺紋呈現(xiàn)出不同的演變規(guī)律。通過系統(tǒng)考察中間層膜厚、PDO3膜厚以及中間層膜材料的種類對該體系表面皺紋形貌光調(diào)控演變的影響,由此分析探討了不同皺紋演變現(xiàn)象的內(nèi)在機理。結(jié)果表明:可見光曝光條件下,PDMS/PS/PDO3體系其曝光區(qū)皺紋呈現(xiàn)PDO3膜光軟化效應(yīng)主導(dǎo)的皺紋周期減小的演變規(guī)律;而PDMS/SiOx/PDO3體系其曝光區(qū)皺紋呈現(xiàn)應(yīng)力松弛效應(yīng)主導(dǎo)的皺紋光擦除的演變規(guī)律。同樣借助銅網(wǎng)選區(qū)曝光,結(jié)合兩種多層膜體系膜厚和銅網(wǎng)種類等實驗參數(shù)的調(diào)節(jié),實現(xiàn)了兩種多層膜體系表面多種不同高級皺紋圖案的精細(xì)構(gòu)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.
【學(xué)位授予單位】：天津大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：TB383.2

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1 宗傳永;含偶氮聚合物膜表面皺紋的光擦除與光調(diào)制研究[D];天津大學(xué);2016年

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本文編號：1967897