温度调控的动态湿度响应褶皱图案★

doi:10.6023/A23040108

摘要/Abstract

本工作利用光响应温敏聚合物构筑了温控湿度响应褶皱图案, 并探索其响应机制与应用. 将1-乙烯基-3-蒽甲基氯化咪唑鎓(IMAN)、N-异丙基丙烯酰胺(NIPAM)与聚乙二醇甲醚甲基丙烯酸酯(OEGMA)三元共聚物P(IMAN-co-NIPAM-co-OEGMA)作为表层, 与聚二甲基硅氧烷(PDMS)基底形成双层褶皱体系. 蒽基团的光二聚交联能够使体系区域选择性起皱, 含NIPAM结构的聚合物链则赋予其温度控制的湿度响应性. 在室温、加湿条件下, 该褶皱图案消失, 其响应机制是聚合物吸湿过程中的模量降低和应力松弛; 而在较高温度下, 褶皱图案无法由湿度擦除, 这是由于顶层聚合物链疏水性增强所导致的. 这种同时具有光敏性与温度控制的湿度响应性褶皱图案, 在湿度传感、智能显示、智能窗户等领域具有潜在的应用前景.

关键词: 动态褶皱图案, 湿度响应, 温度调控, 调控机制, 湿度传感

Here we reported temperature-controlled moisture responsive wrinkled patterns based on bilayer system, and explore its regulation mechanism and applications. The bilayer wrinkling system is comprising a copolymer P(IMAN-co-NIPAM-co-OEGMA) containing 1-vinyl-3-anthracenemethyl imidazolium chloride (IMAN), N-isopropylacrylamide (NIPAM) and poly(ethylene glycol) methyl ether methacrylate (OEGMA) as the skin layer and poly(dimethylsiloxane) (PDMS) as the substrate. After photodimerization of the AN group, the polymer network is crosslinked, and the modulus of the top film increases. According to the linear buckling theory, random wrinkles are formed under thermal treatment and subsequent cooling to room temperature owing to the mismatch in the moduli and thermal expansion coefficients between the stiff skin layer and the soft substrate. First, the photodimerization of AN group endows the system with the ability of region selective wrinkling. If the irradiation process is performed with a photomask, the exposed regions are rigid enough for wrinkles forming, while the unexposed areas are not. Furthermore, surface wrinkles caused strong light scattering while the flat surface limit it, which affects the visibility of an object. Thus, we could fabricate various images utilizing the selective wrinkled patterns. Second, the NIPAM-containing polymer chain endows the wrinkles with temperature-controlled moisture response. Under room temperature, the wrinkles can be eliminated by moisture, which is caused by the decreasing modulus and stress relaxation during absorbing moisture; while under a higher temperature, the wrinkles cannot be driven by moisture because the copolymer of top layer becomes hydrophobic, which is demonstrated by experimental results such as the laser scanning confocal microscope images. Furthermore, the wrinkled images and the transparence can be controlled by moisture and temperature during the switch between wrinkled and flat states. Besides, the poly(ethylene glycol) methyl ether methacrylate (OEGMA) is involved to tune the mechanical properties. The photosensitive and temperature- controlled moisture responsive wrinkled patterns may find potential applications in moisture sensing, smart display or smart windows.

Key words: dynamic wrinkle pattern, moisture response, temperature-regulation, regulation mechanism, moisture sensing

引用此文

马天骄, 李瑾, 马晓东, 姜学松. 温度调控的动态湿度响应褶皱图案^★[J]. 化学学报, 2023, 81(7): 749-756.

Tianjiao Ma, Jin Li, Xiaodong Ma, Xuesong Jiang. Temperature-controlled Dynamic Moisture-responsive Wrinkled Patterns^★[J]. Acta Chimica Sinica, 2023, 81(7): 749-756.

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图/表 5

图1. 湿度响应褶皱图案的构筑策略: (a)湿度响应褶皱图案的构筑及调控示意图; (b)湿度响应褶皱图案的激光共聚焦显微镜(LSCM)图像. 比例尺: 50 μm. 插图为蝴蝶形褶皱图案的宏观照片

Figure 1. Strategy for the production of moisture responsive surface wrinkles. (a) Schematic illustration of the production and regulation of moisture responsive surface wrinkles. (b) Laser scanning confocal microscope (LSCM) images of moisture responsive surface wrinkles. Scale bar: 50 μm. Inset picture is macrographs of a butterfly-shaped wrinkled pattern

图2. 在不同湿度下褶皱图案的演化过程: (a)~(c)褶皱图案在(a) 85%RH, (b) 59%RH, (c) 33%RH下处理不同时间时的激光共聚焦显微镜图片. 比例尺: 100 μm. (d)~(f)褶皱振幅与波长随在(d) 85%RH, (e) 59%RH, (f) 33%RH下处理时间的变化过程

Figure 2. Evolution process of the wrinkled pattern at different humidity. (a)~(c) LSCM images of wrinkles for different treatment times at (a) 85%RH, (b) 59%RH, and (c) 33%RH. Scale bar: 100 μm. (d)~(f) Wrinkle amplitude (A) and wavelength (λ) as a function of treatment time at (d) 85%RH, (e) 59%RH, and (f) 33%RH

图3. 动态褶皱图案的湿度响应机制: (a)不同厚度聚合物薄膜的吸湿比例随时间的变化. (b)聚合物薄膜的吸湿速率随薄膜厚度的变化过程. (c)过饱和潮湿条件下褶皱形貌的实时变化. 比例尺: 50 μm. (d)不同湿度下聚合物薄膜的应力随时间的变化过程. (e)聚合物薄膜的应变随加湿处理时间的变化过程

Figure 3. Humidity response mechanism of dynamic wrinkled patterns. (a) Humidity-sorption ratio of polymer film with different thicknesses as a function of moisture-treatment time. (b) Humidity-absorption rate of polymer film as a function of film thickness. (c) Real-time change of wrinkled topography at over 100%RH. Scale bar: 50 μm. (d) Stress of polymer film as a function of time at different humidity. (e) Strain of polymer film as a function of moisture-treatment time

图4. 温控与光控的湿度响应褶皱图案: (a) P(IMAN-co-NIPAM-co-OEGMA)/PDMS体系褶皱图案在不同温度下的湿度响应. 比例尺: 100 μm. (b)条形褶皱图案在不同温度下的湿度响应. 比例尺: 100 μm

Figure 4. Temperature and photo-controlled moisture responsive wrinkles. (a) Moisture response of wrinkles in P(IMAN-co-NIPAM-co-OEGMA)/PDMS system at different temperatures. Scale bar: 100 μm. (b) Moisture response of striped wrinkles at different temperatures. Scale bar: 100 μm

图5. 湿度响应褶皱图案的应用. (a)湿度响应褶皱图案在可视化湿度传感方面的应用. (b)动态褶皱图案对光信号的调控及其可视化传感机制. (c)湿度响应褶皱图案在智能窗户方面的应用. (d)湿度响应褶皱图案在智能显示方面的应用

Figure 5. The application of moisture responsive wrinkles. (a) The application of moisture responsive wrinkles in visualized moisture sensing. (b) Regulation of optical signal by dynamic wrinkles and the visualized sensing mechanism. (c) The application of moisture responsive wrinkles in smart window. (d) The application of moisture responsive wrinkles in smart display

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