Article(id=1315743836958208646, tenantId=1146029695717560320, journalId=1315121910733963395, issueId=1315743733992243595, articleNumber=null, orderNo=null, doi=10.3788/gzxb20265501.0131002, pmid=null, cstr=32255.14.gzxb20265501.0131002, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1753027200000, receivedDateStr=2025-07-21, revisedDate=null, revisedDateStr=null, acceptedDate=1757001600000, acceptedDateStr=2025-09-05, onlineDate=1791627376069, onlineDateStr=2026-10-10, pubDate=1769270400000, pubDateStr=2026-01-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1791627376069, onlineIssueDateStr=2026-10-10, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1791627376069, creator=13701087609, updateTime=1791627376069, updator=13701087609, issue=Issue{id=1315743733992243595, tenantId=1146029695717560320, journalId=1315121910733963395, year='2026', volume='55', issue='1', pageStart='1', pageEnd='316', issueExtLink='null', onlineDate='null', pubDate='1769270400000', pubDateStr='2026-01-25', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1791627351520, creator='13701087609', updateTime=1791627555456, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1315744589420540350, tenantId=1146029695717560320, journalId=1315121910733963395, issueId=1315743733992243595, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1315744589420540351, tenantId=1146029695717560320, journalId=1315121910733963395, issueId=1315743733992243595, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=214, endPage=224, ext={EN=ArticleExt(id=1315743837146952327, articleId=1315743836958208646, tenantId=1146029695717560320, journalId=1315121910733963395, language=EN, title=Preparation and Anti-counterfeiting Performance of Flexible Photonic Crystal Films based on TPU/EP, columnId=1315743807417729940, journalTitle=Acta Photonica Sinica, columnName=Thin Films, runingTitle=null, highlight=null, articleAbstract=
With the increasingly serious problem of commodity forgery, it is of great significance to develop new anti-counterfeiting technologies. Photonic crystals have shown broad application prospects in the field of anti-counterfeiting due to their unique optical properties, especially structural color effects. However, traditional photonic crystal materials generally have problems such as poor mechanical properties and insufficient thermal stability, which limit their practical application.
In this study, a flexible composite film of photonic crystals based on epoxy resin (EP) and thermoplastic polyurethane (TPU) interpenetrating network structure was innovatively proposed. Monodisperse silica colloidal microspheres were prepared by the improved Stöber method, and photonic crystal arrays with opal structure were assembled by the vertical deposition method. On this basis, TPU/EP-based photonic crystal structural color films were prepared by a filling and curing process using TPU and EP mixture as flexible substrates. The optical properties and mechanical properties of the composite films were systematically studied by adjusting the ratio of TPU to EP.
The experimental results show that when the mass ratio is 1∶1, the film exhibits excellent structural color rendering and flexibility, with a clear reflectance peak that shifts little after multiple bending. Furthermore, through optical and mechanical tests, it is confirmed that the film exhibits dynamic structural color change at different angles and has excellent durability and environmental stability. By combining the iridescence effect of photonic crystals with fluorescence recognition technology, the film exhibits iridescence under natural light and displays specific fluorescence patterns under ultraviolet light excitation, achieving dual anti-counterfeiting through the combination of “iridescence + fluorescence”.
The practical application tests show that the film can effectively adhere to the surface of the shoes, and the anti-counterfeiting label is difficult to replicate. It can be quickly verified and has good practicability and market potential. It also provides an innovative solution for dynamic anti-counterfeiting certification of footwear products.
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提出了一种基于环氧树脂(EP)和热塑性聚氨酯(TPU)互穿网络结构的光子晶体柔性复合薄膜,调控TPU/EP的复合比例,实现了较高温度下稳定结构色与弯折耐久性的统一。将光子晶体的虹彩效应与荧光识别技术相结合,使薄膜在自然光下呈现虹彩性,同时在紫外光激发下显示出特定的荧光图案,实现了“虹彩+荧光”的双重防伪,为鞋类产品的防伪认证提供了解决方案。
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1Hebei Key Laboratory of Special Fiber and Fiber Sensor, School of Information Science and Engineering, Yanshan University, Qinhuangdao 066004, China), AuthorCompanyExt(id=1315743839256687263, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, companyId=1315743839239910045, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=
1燕山大学 信息科学与工程学院 河北省特种光纤与光纤传感重点实验室,秦皇岛 066004)])], figs=[ArticleFig(id=1315743841689383619, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=EN, label=Fig.1, caption=
Preparation flowchart of TPU/EP-based opal photonic crystal structural color film, figureFileSmall=R28FstH2E5hZOfUUlvPWFQ==, figureFileBig=Ubf+Aw2DxcH5eHsknWxobQ==, tableContent=null), ArticleFig(id=1315743841760686788, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=CN, label=图1, caption=
TPU/EP基蛋白石光子晶体结构色薄膜的制备流程, figureFileSmall=R28FstH2E5hZOfUUlvPWFQ==, figureFileBig=Ubf+Aw2DxcH5eHsknWxobQ==, tableContent=null), ArticleFig(id=1315743841978790597, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=EN, label=Fig.2, caption=
Characterization of SiO₂ microspheres and the film. (a) XRD pattern of the microspheres; (b) TEM image of the microspheres; (c) SEM image of the film, figureFileSmall=Onf1xDDhdIwgjpffxuP9Gg==, figureFileBig=hvX8mgIODdv1q68BYcUMoQ==, tableContent=null), ArticleFig(id=1315743842045899462, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=CN, label=图2, caption=
SiO2微球和薄膜表征。(a)SiO2微球的XRD形貌图;(b)SiO2微球的透射电镜图像;(c)SiO2薄膜的扫描电镜图像, figureFileSmall=Onf1xDDhdIwgjpffxuP9Gg==, figureFileBig=hvX8mgIODdv1q68BYcUMoQ==, tableContent=null), ArticleFig(id=1315743842113008327, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=EN, label=Fig.3, caption=
The reaction mechanism of crosslinked network structure formation between TPU and EP[32]. (a) Structural formula of TPU; (b) Isocyanate groups in TPU react with hydroxyl groups in EP; (c) Isocyanate groups in TPU react with epoxy groups in EP, figureFileSmall=zUjEO5jUIY/mZOhiAtklXg==, figureFileBig=rKmHMIE4UYgYiKIeICMuYg==, tableContent=null), ArticleFig(id=1315743842192700104, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=CN, label=图3, caption=
TPU与EP形成交联网络结构的反应机理[32]。(a)TPU的结构式;(b)TPU中的异氰酸酯基团与EP中的羟基反应关系式;(c)TPU中的异氰酸酯基团与EP中的环氧基团反应关系式, figureFileSmall=zUjEO5jUIY/mZOhiAtklXg==, figureFileBig=rKmHMIE4UYgYiKIeICMuYg==, tableContent=null), ArticleFig(id=1315743842264003273, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=EN, label=Fig.4, caption=
FT-IR spectra and the spatial distribution of N element. (a) FT-IR spectra of OTE films with different TPU/EP ratios; (b) Spatial distribution maps of N element, figureFileSmall=wGoo3yKPNQ94orvZQMnq9w==, figureFileBig=b2o91H02kHvUl/VtgTMjCw==, tableContent=null), ArticleFig(id=1315743842326917834, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=CN, label=图4, caption=
傅里叶变换红外光谱及N元素空间分布图。(a)不同TPU/EP配比的OTE薄膜的傅里叶变换红外光谱;(b)N元素空间分布示意图, figureFileSmall=wGoo3yKPNQ94orvZQMnq9w==, figureFileBig=b2o91H02kHvUl/VtgTMjCw==, tableContent=null), ArticleFig(id=1315743842414998219, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=EN, label=Fig.5, caption=
Optical photographs, reflectance spectra and CIE plots of OTE films with different TPU/EP ratios. (a) Optical photographs of SiO2 opal templates and OTE films; (b) Reflectance spectra of OTE films; (c) CIE chromaticity diagrams of OTE films, figureFileSmall=8kJjUWbwTbvxzuxeCV7Ixg==, figureFileBig=+rmKzkTxmF1/u51/Pzq4CA==, tableContent=null), ArticleFig(id=1315743842498884300, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=CN, label=图5, caption=
不同TPU/EP配比的OTE薄膜光学照片、反射光谱图和CIE色度图。(a)SiO₂蛋白石模板与OTE薄膜的光学显微照片;(b)OTE薄膜的反射光谱;(c)OTE薄膜的CIE色度图, figureFileSmall=8kJjUWbwTbvxzuxeCV7Ixg==, figureFileBig=+rmKzkTxmF1/u51/Pzq4CA==, tableContent=null), ArticleFig(id=1315743842582770381, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=EN, label=Fig.6, caption=
Stress-strain curves of OTE Films with different TPU/EP ratios, figureFileSmall=Rq3sF0O0IuBmP+HrbGIsGw==, figureFileBig=UcpSHRJakS8GkHKkVc9GNQ==, tableContent=null), ArticleFig(id=1315743842662462158, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=CN, label=图6, caption=
不同TPU/EP配比的OTE薄膜的应力-应变曲线, figureFileSmall=Rq3sF0O0IuBmP+HrbGIsGw==, figureFileBig=UcpSHRJakS8GkHKkVc9GNQ==, tableContent=null), ArticleFig(id=1315743842742153935, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=EN, label=Fig.7, caption=
Bending test and reflectance spectra of OTE films. (a) Schematic diagram of the bending test; (b) Comparison pictures of the bending test; (c) Reflectance spectra, figureFileSmall=pudn3veaoyP9i1QnoniS5Q==, figureFileBig=KumYFqiSutOzsTYVVatYiw==, tableContent=null), ArticleFig(id=1315743842826040016, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=CN, label=图7, caption=
OTE薄膜的弯曲实验和反射光谱。(a)OTE薄膜的弯曲试验示意图;(b)OTE薄膜的弯曲试验对比图;(c)OTE薄膜的反射光谱, figureFileSmall=pudn3veaoyP9i1QnoniS5Q==, figureFileBig=KumYFqiSutOzsTYVVatYiw==, tableContent=null), ArticleFig(id=1315743842901537489, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=EN, label=Fig.8, caption=
Reflectance spectra of OTE films under varied environmental humidity, figureFileSmall=CJbhR9YzyvFw3Fj9iQ+JYA==, figureFileBig=sIaaGvFcQiTDDerVLRLb1w==, tableContent=null), ArticleFig(id=1315743842964452050, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=CN, label=图8, caption=
环境湿度变化下的OTE薄膜反射光谱, figureFileSmall=CJbhR9YzyvFw3Fj9iQ+JYA==, figureFileBig=sIaaGvFcQiTDDerVLRLb1w==, tableContent=null), ArticleFig(id=1315743843031560915, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=EN, label=Fig.9, caption=
Performance changes of OTE film before and after aging at 90 ℃. (a) Reflectance spectra variation before and after aging; (b) Stress-strain curves before and after aging, figureFileSmall=R31Fb/wi887e11AlgacN4Q==, figureFileBig=zY7IUfRShL3RHhjsHh+SPw==, tableContent=null), ArticleFig(id=1315743843111252692, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=CN, label=图9, caption=
90 ℃老化前后OTE薄膜的性能变化。(a)OTE薄膜老化前后反射率光谱变化;(b)OTE薄膜老化前后应力—应变曲线, figureFileSmall=R31Fb/wi887e11AlgacN4Q==, figureFileBig=zY7IUfRShL3RHhjsHh+SPw==, tableContent=null), ArticleFig(id=1315743843178361557, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=EN, label=Fig.10, caption=
Flow chart and visualization of the dual anti-counterfeiting label's preparation. (a) Flow chart for preparation of the dual anti-counterfeiting label; (b) Visualization of the dual anti-counterfeiting label; (c) Visualization of the dual anti-counterfeiting label applied to shoes, figureFileSmall=FqwYEviATzDyp6i2tZfGaA==, figureFileBig=TwD/DYp6Dvnak5lzu9h4AQ==, tableContent=null), ArticleFig(id=1315743843266441942, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=CN, label=图10, caption=
双重防伪标签制备流程图和效果图。(a)双重防伪标签的制作流程图;(b)双重防伪标签的可视化;(c)对鞋类采用的双重防伪标签的可视化, figureFileSmall=FqwYEviATzDyp6i2tZfGaA==, figureFileBig=TwD/DYp6Dvnak5lzu9h4AQ==, tableContent=null), ArticleFig(id=1315743843333550807, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=EN, label=Table 1, caption=
Optical properties of OTE films
, figureFileSmall=null, figureFileBig=null, tableContent=
| Sample | Maximum reflectance/% | Full width at half maximum/nm | Refractive index (n) | Chromaticity coordinates (x) | Chromaticity coordinates (y) | Color purity/% |
|---|
| A(SiO2) | 26.30±0.21 | 64.06±0.05 | 1.27±0.01 | 0.30±0.02 | 0.51±0.02 | 48.65±0.12 |
| B(EP) | 25.64±0.42 | 51.18±0.14 | 1.53±0.02 | 0.48±0.01 | 0.33±0.01 | 48.57±0.24 |
| C(1∶7) | 36.15±0.39 | 42.12±0.14 | 1.48±0.02 | 0.39±0.03 | 0.36±0.03 | 30.47±0.35 |
| D(1∶4) | 43.01±0.52 | 36.32±0.16 | 1.47±0.01 | 0.43±0.01 | 0.36±0.01 | 42.48±0.32 |
| E(1∶1) | 56.07±0.26 | 34.42±0.09 | 1.45±0.02 | 0.46±0.01 | 0.37±0.01 | 53.45±0.18 |
| F(4∶1) | 44.73±0.18 | 42.36±0.02 | 1.44±0.01 | 0.42±0.02 | 0.35±0.02 | 38.62±0.16 |
| G(7∶1) | 33.06±0.36 | 45.28±0.10 | 1.44±0.02 | 0.37±0.02 | 0.35±0.02 | 22.11±0.43 |
| H(TPU) | 23.68±0.49 | 45.24±0.15 | 1.43±0.01 | 0.38±0.01 | 0.38±0.01 | 32.33±0.47 |
), ArticleFig(id=1315743843417436888, tenantId=1146029695717560320, journalId=1315121910733963395, articleId=1315743836958208646, language=CN, label=表1, caption=
OTE薄膜的光学特性
, figureFileSmall=null, figureFileBig=null, tableContent=
| Sample | Maximum reflectance/% | Full width at half maximum/nm | Refractive index (n) | Chromaticity coordinates (x) | Chromaticity coordinates (y) | Color purity/% |
|---|
| A(SiO2) | 26.30±0.21 | 64.06±0.05 | 1.27±0.01 | 0.30±0.02 | 0.51±0.02 | 48.65±0.12 |
| B(EP) | 25.64±0.42 | 51.18±0.14 | 1.53±0.02 | 0.48±0.01 | 0.33±0.01 | 48.57±0.24 |
| C(1∶7) | 36.15±0.39 | 42.12±0.14 | 1.48±0.02 | 0.39±0.03 | 0.36±0.03 | 30.47±0.35 |
| D(1∶4) | 43.01±0.52 | 36.32±0.16 | 1.47±0.01 | 0.43±0.01 | 0.36±0.01 | 42.48±0.32 |
| E(1∶1) | 56.07±0.26 | 34.42±0.09 | 1.45±0.02 | 0.46±0.01 | 0.37±0.01 | 53.45±0.18 |
| F(4∶1) | 44.73±0.18 | 42.36±0.02 | 1.44±0.01 | 0.42±0.02 | 0.35±0.02 | 38.62±0.16 |
| G(7∶1) | 33.06±0.36 | 45.28±0.10 | 1.44±0.02 | 0.37±0.02 | 0.35±0.02 | 22.11±0.43 |
| H(TPU) | 23.68±0.49 | 45.24±0.15 | 1.43±0.01 | 0.38±0.01 | 0.38±0.01 | 32.33±0.47 |
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