Photonic Elastomer Films Constructed by PDMS/SiO2/PDMS-PDA via Fast Lifting Method
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摘要: 采用快速提拉法制备出SiO2结构色薄膜，将其嵌入到聚二甲基硅氧烷（PDMS）中，然后将掺杂聚多巴胺（PDA）的PDMS（PDMS-PDA）涂覆在SiO2结构色薄膜表面制备了PDMS/SiO2/PDMS-PDA光子弹性体薄膜。采用扫描电子显微镜、纳米激光粒度仪、分光光度计、光纤光谱仪、拉力机和手机相机对SiO2结构色薄膜的微观结构和光学性能以及PDMS/SiO2/PDMS-PDA薄膜的力致变色性能和力学性能进行了表征。结果表明：SiO2结构色薄膜为短程有序的非晶光子晶体薄膜，其结构色在漫射光下无角度依赖性，在直射光下有角度依赖性。通过表面涂覆黑色PDMS-PDA层，有效提高了光子弹性体薄膜在拉伸过程中结构色的饱和度，当应变为20%时，薄膜出现明显的结构色，并随着应变的增加反射峰位置不断蓝移。该薄膜具有较好的力学性能，其断裂伸长率达140%。Abstract: Monodisperse SiO2 microspheres with particle size in the range of 208—368 nm were prepared by the Stöber method and used to construct structural color films via fast lifting method. The as-prepared structural color films were then embedded in polydimethylsiloxane (PDMS), on which polydopamine (PDA)-doped PDMS (PDMS-PDA) was coated to obtain stretchable color-changing PDMS/SiO2/PDMS-PDA photonic elastomer films. Both the structural color films and photonic elastomer films were explored with techniques including scanning electron microscope, nanoscale laser particle size analyzer, spectrophotometer, fiber optic spectrometer, tensile testing machine and digital camera to elucidate the microstructure and optical properties of the former and the strain response and mechanical properties of the latter. Results show that the structural color films belong to amorphous photonic crystals consisting of long-range disordered and short-range ordered arrangements of SiO2 microspheres, and their structural colors are angle-independent under diffuse light. But interestingly, the structural colors are angle-dependent under sunlight due to the surface of SiO2 microspheres arranged flatly. As for the photonic crystal elastomer films surface-coated with a black PDMS-PDA layer, the saturation of the structural color of the films during stretching is greatly improved. When the tensile strain reaches 20%, the films start to show apparently structural color, which undergo a continuous blue-shift with increasing strain, and the color returns to the initial state when the strain is restored. Moreover, the film has good mechanical properties with an elongation at the break of 140%, and can be applied to the field of visualized flexible sensing, smart wearable devices and other fields.
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图 1 SiO2微球的SEM图片和粒径分布
Figure 1. SEM images and particle size distribution of SiO2 microspheres
图 2 不同粒径SiO2微球制备的结构色薄膜的SEM图片
Figure 2. SEM images of structural color films prepared by SiO2 microspheres with different particle sizes
图 3 (a) 不同SiO2粒径的结构色薄膜的反射光谱；(b) 漫射光下不同角度SiO2结构色薄膜的数码照片； (c)微球粒径为288 nm的结构色薄膜在不同角度下的透射光谱；(d) 直射光下不同角度SiO2结构色薄膜的数码照片
Figure 3. (a) Reflection spectra of structural color films with different SiO2 particle sizes; (b) Digital photos of SiO2 structural color films at different angles under diffused light; (c) Transmission spectra of structural color films with microsphere size of 288 nm at different angles; (d) Digital photos of SiO2 structural color films at different angles under direct sunlight
图 4 （a）PDMS/SiO2薄膜表面的SEM图；（b）PDMS/SiO2薄膜在不同拉伸应变时的数码照片；（c～e）PDMS/SiO2/PDMS-PDA薄膜截面SEM图及局部放大图
Figure 4. (a) SEM image of PDMS/SiO2 film surface; (b) Digital photographs of PDMS/SiO2 film at different tensile strains; (c−e) SEM image of PDMS/SiO2/PDMS-PDA film and its partially enlarged images
图 5 PDMS/SiO2、PDMS/SiO2/PDMS-PDA光子弹性体的应力-应变曲线
Figure 5. Stress-strain curves of PDMS/SiO2 and PDMS/SiO2/PDMS-PDA photonic elastomers
图 6 (a) SiO2粒径为234、246、288 nm的 PDMS/SiO2/PDMS-PDA光子弹性体薄膜在不同应变下的数码照片及(b～d)其相应的反射光谱
Figure 6. (a) Digital photos of PDMS/SiO2/PDMS-PDA photonic elastomer films with particle sizes of 234, 246 nm and 288 nm under different strains and (b−d) their corresponding reflection spectra
图 7 PDMS/SiO2/PDMS-PDA光子弹性体薄膜在拉伸过程中的微观结构示意图
Figure 7. Schematic illustration of the microstructure of PDMS/SiO2/PDMS-PDA photonic elastomer films during the tensile stretching-releasing process
表 1 SiO2微球的平均粒径、Z均粒径及PDI值
Table 1. D、Dz and PDI of SiO2 microspheres
Sample D/nm $ {D}_\mathrm{z} $/nm PDI 1 208 207 0.012 2 234 231 0.029 3 246 247 0.034 4 288 303 0.032 5 321 308 0.030 6 368 365 0.041 
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