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.

, authors=Zhaopeng XU, Jiaxin WANG, Taotao SUN, Shaorui HE, Qian YANG, authorsList=Zhaopeng XU, Jiaxin WANG, Taotao SUN, Shaorui HE, Qian YANG, authorCompany=null, correspAuthors=Zhaopeng XU, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1315743839017611932, articleId=1315743836958208646, tenantId=1146029695717560320, journalId=1315121910733963395, language=CN, title=基于TPU/EP的光子晶体柔性薄膜制备及防伪性能, columnId=1315743807635833750, journalTitle=光子学报, columnName=薄膜, runingTitle=null, highlight=null, articleAbstract=

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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(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=
SampleMaximum
reflectance/%
Full width at half maximum/nmRefractive
index (n)
Chromaticity
coordinates (x)
Chromaticity
coordinates (y)
Color purity/%
A(SiO2)26.30±0.2164.06±0.051.27±0.010.30±0.020.51±0.0248.65±0.12
B(EP)25.64±0.4251.18±0.141.53±0.020.48±0.010.33±0.0148.57±0.24
C(1∶7)36.15±0.3942.12±0.141.48±0.020.39±0.030.36±0.0330.47±0.35
D(1∶4)43.01±0.5236.32±0.161.47±0.010.43±0.010.36±0.0142.48±0.32
E(1∶1)56.07±0.2634.42±0.091.45±0.020.46±0.010.37±0.0153.45±0.18
F(4∶1)44.73±0.1842.36±0.021.44±0.010.42±0.020.35±0.0238.62±0.16
G(7∶1)33.06±0.3645.28±0.101.44±0.020.37±0.020.35±0.0222.11±0.43
H(TPU)23.68±0.4945.24±0.151.43±0.010.38±0.010.38±0.0132.33±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=
SampleMaximum
reflectance/%
Full width at half maximum/nmRefractive
index (n)
Chromaticity
coordinates (x)
Chromaticity
coordinates (y)
Color purity/%
A(SiO2)26.30±0.2164.06±0.051.27±0.010.30±0.020.51±0.0248.65±0.12
B(EP)25.64±0.4251.18±0.141.53±0.020.48±0.010.33±0.0148.57±0.24
C(1∶7)36.15±0.3942.12±0.141.48±0.020.39±0.030.36±0.0330.47±0.35
D(1∶4)43.01±0.5236.32±0.161.47±0.010.43±0.010.36±0.0142.48±0.32
E(1∶1)56.07±0.2634.42±0.091.45±0.020.46±0.010.37±0.0153.45±0.18
F(4∶1)44.73±0.1842.36±0.021.44±0.010.42±0.020.35±0.0238.62±0.16
G(7∶1)33.06±0.3645.28±0.101.44±0.020.37±0.020.35±0.0222.11±0.43
H(TPU)23.68±0.4945.24±0.151.43±0.010.38±0.010.38±0.0132.33±0.47
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基于TPU/EP的光子晶体柔性薄膜制备及防伪性能
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徐朝鹏 , 王佳昕 , 孙涛涛 , 贺绍瑞 , 杨乾
光子学报 | 薄膜 2026,55(1): 214-224
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光子学报 |薄膜 2026 , 55 (1) : 214 -224
基于TPU/EP的光子晶体柔性薄膜制备及防伪性能
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徐朝鹏,

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徐朝鹏 , 王佳昕, 孙涛涛, 贺绍瑞, 杨乾
作者信息
  • 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
通讯作者:
作者简介:
Preparation and Anti-counterfeiting Performance of Flexible Photonic Crystal Films based on TPU/EP
Zhaopeng XU , Jiaxin WANG, Taotao SUN, Shaorui HE, Qian YANG
Affiliations
  • 1Hebei Key Laboratory of Special Fiber and Fiber Sensor, School of Information Science and Engineering, Yanshan University, Qinhuangdao 066004, China
出版时间: 2026-01-25 doi: 10.3788/gzxb20265501.0131002
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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。

光子晶体  /  柔性薄膜  /  双重防伪  /  热塑性聚氨酯  /  环氧树脂

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.

Photonic crystal  /  Flexible film  /  Dual anti-counterfeiting  /  Thermoplastic polyurethane  /  Epoxy resin
徐朝鹏, 王佳昕, 孙涛涛, 贺绍瑞, 杨乾. 基于TPU/EP的光子晶体柔性薄膜制备及防伪性能. 光子学报, 2026 , 55 (1) : 214 -224 . DOI: 10.3788/gzxb20265501.0131002
Zhaopeng XU, Jiaxin WANG, Taotao SUN, Shaorui HE, Qian YANG. Preparation and Anti-counterfeiting Performance of Flexible Photonic Crystal Films based on TPU/EP[J]. Acta Photonica Sinica, 2026 , 55 (1) : 214 -224 . DOI: 10.3788/gzxb20265501.0131002
随着全球经济的快速发展和消费市场的持续升级,假冒伪劣产品对品牌权益、消费者安全及市场秩序的威胁日益严峻。尤其在奢侈品、电子产品、医药和鞋服等高附加值领域,仿制品不仅侵蚀企业利润,还可能引发健康与安全隐患。传统的防伪技术,如二维码[1, 2]、激光全息[3-6]和荧光油墨[7-9]等,因其技术门槛较低、易复制或易受环境因素影响等缺陷,已难以满足现代防伪的高安全性需求。在此背景下,基于结构色的新型防伪技术凭借其独特的光学不可复制性和环境稳定性,成为学术界与产业界共同关注的研究方向[10]。结构色是一种通过材料表面或内部微观结构与光相互作用产生的颜色效应,结构色显色不依赖化学色素[11],而是基于光子晶体[12]、薄膜干涉衍射[13]或表面等离激元[14]等物理机制实现颜色输出。与传统化学染料相比,结构色具有高色纯度、动态角度色彩及可编程性[15]等显著优势。其中,光子晶体作为典型的周期性介电材料,能够通过调控光子禁带特性实现可见光波段的选择性反射,生成高饱和度的结构色,成为高安全性防伪的理想载体[16]。然而,传统光子晶体材料多采用刚性基材或脆性聚合物,如玻璃[17]、硅片[18]、聚苯乙烯[19]和环氧树脂(EP)[20-21]等,其固有的强度和较差的抗疲劳特性制约了其在柔性场景中的应用。因此,开发兼具柔性、耐久性和高亮度的光子晶体薄膜,成为突破结构色防伪技术应用瓶颈的关键。
近些年,针对兼具柔性、耐久性和高亮度的光子晶体薄膜开发,国内外学者在材料设计[22]、制备工艺[23]及功能集成[24-25]等方面展开了大量研究,并且成功应用于防伪领域。然而,柔性结构色领域仍面临柔性基材与光学性能的协同优化、复杂环境耐受性不足及规模化制备成本等关键挑战。
传统的光子晶体和EP结合可以制备出结构稳定、颜色亮度高的结构色薄膜,但大部分该类结构色薄膜存在弹性和柔韧性差等缺点[26]。热塑性聚氨酯(Thermoplastic Polyurethane, TPU)具有弹性好、断裂伸长率大于50%、耐磨、耐油以及可加热塑化等特性,其大分子主链是由软段和硬段嵌段而成,在化学结构上几乎没有化学交联,基本呈线性结构[27],并且TPU与EP会在化学结构上形成互穿交联网络结构 [28]。因此,本文使用TPU对EP进行了增韧改性,制备了高柔韧性的TPU/EP基光子晶体薄膜。同时,鉴于光子晶体的制备技术及工艺相对透明,本文将高柔韧性结构色和透明荧光漆结合,设计并制备了可用于鞋类防伪的标签,实现了“虹彩+荧光”的双重柔性防伪。
实验中所用的正硅酸四乙酯(TEOS)、N,N-二甲基甲酰胺(DMF),购自上海阿拉丁生化科技股份有限公司。无水乙醇和氢氟酸(HF)购自于天津凯通化学试剂有限公司。氨水、TPU、竹制炭黑(CB)和环氧树脂AB胶分别购于上海麦克林生物化学有限公司、淄博华天橡塑科技有限公司、浙江旺林生物科技有限公司和浙江吉安丽姝科技有限公司。采用70 mm×27 mm×3 mm的聚乙烯板(PE)为基板。
单分散的SiO2胶体粒子通过经典的Stöber法制备,将160 mL无水乙醇、4 mL去离子水和10.5 mL氨水混合后[29],得到溶液A。将其在30 ℃下以600 r/min搅拌3~5 min后,分四次添加2 mL TEOS,每次间隔10 min,并将搅拌器加速至1 200 r/min,搅拌6 h,使混合溶液反应完全得到溶液B。使用中国湖南湘仪公司生产的GL-21M型离心机对溶液B进行离心5 min后倒掉上清液得到固体A,最后使用无水乙醇对固体A进行三次反复冲洗,再放置在烘箱中烘干8 h,得到固体B(255 nm球径的SiO2微球)。将得到的固体B研磨后与一定量的无水乙醇混合,形成质量分数为7%的胶体悬浊液。通过中国北京卓立汉光仪器公司生产的MC6003P-4B型步进电机以2 μm/s的速度缓慢提拉12 h后,在PE片上得到周期有序的蛋白石阵列。把环氧树脂A、B胶按照1∶3的比例混合后得到环氧树脂EP,之后将EP、TPU和DMF按不同的比例混合后,加入质量分数为1%的CB充分搅拌得到溶液C。在60 ℃的加热平台上将溶液C滴至有蛋白石光子晶体的PE片上,均匀加热5 h后,将固化的薄膜从PE片上揭下,即可得到TPU/EP蛋白石结构色薄膜(简称为OTE),制备流程如图1所示[30]。通过梯度掺杂实验,分别制备得到TPU/EP质量比为1∶7、1∶4、1∶1、4∶1、7∶1以及纯EP和TPU的蛋白石结构色薄膜。
采用日本Rigaku公司的Ultima IV X射线衍射仪(XRD)对制备的微球晶体结构进行测试,测试条件为:室温,辐射源Cu (Kα),管电流40 mA,管电压40 kV,扫描范围为20º-90º,扫描速度为10 (º)/min;采用日本电子公司的JEM-2100透射电子显微镜(TEM)对制备的微球粒径尺寸进行测试;采用德国蔡司公司的GeminiSEM 360扫描电子显微镜(SEM)对SiO2薄膜样品表面形貌进行测试;使用德国布鲁克公司的VERTEX 80/80v傅里叶变换红外光谱(FT-IR)对结构色薄膜的官能团进行表征,测试波长范围400~4 000 cm-1;使用美国赛默飞世尔公司的ARL™QUANT'X8能量色散X射线能谱仪(EDS)对结构色薄膜的N元素分布进行表征;使用中国上海仪电物理光学公司的WYA(2WAJ)阿贝折射仪、美国海洋光学公司的USB 2000光纤光谱仪对结构色薄膜的折射率与反射光谱(测试波长范围380~760 nm)进行测试。
制备的微球XRD测试结果如图2(a)所示,从图中可以看出,主要衍射峰出现在(1 0 1)、(2 0 0)、(2 1 0)晶面,与SiO2的标准卡片(CSD 46-1045)主要衍射峰基本一致,因此证明合成的微球为SiO2微球。TEM测试结果如图2(b)所示,通过Image J软件进行分析,得到SiO2微球的平均尺寸为(255±3.6)nm,并且形态规则,表面光滑,呈分散排布。SiO2薄膜的SEM测试结果如图2(c)所示,提拉后的SiO2微球呈现面心立方堆积排布,其中间隙也呈周期性排布,间隙被空气填充,由于SiO2和空气之间的折射率差异使薄膜呈现结构色。
TPU是一种(ABn)型嵌段线性共聚物,由刚性链段跟柔性链段组成。刚性链段由二异氰酸酯大分子和低分子多元醇反应生成,柔性链段由二异氰酸酯大分子和多元醇大分子反应得到,最后由刚性链段跟柔性链段交替组成嵌段共聚物,其结构式如图3(a)所示[31]。EP的分子式为(C11H12O3)n,其与TPU的改性属于化学共混改性,主要是利用TPU中的异氰酸酯基与EP中的羟基以及环氧基进行反应,生成氨基甲酸酯结构与烷酮,将环氧链段引入到TPU分子结构中,使得两者产生协同效应,最终形成两种网络相互贯穿,并借助永久缠结实现紧密结合的互穿交联网络结构。TPU与EP的化合反应机理如图3(b)、(c)所示[32]。
红外光谱可以分析物体中存在的官能团及化学键等,为了测试样品的聚合情况,采用FT-IR和EDS对结构色薄膜样品进行了表征,如图4所示。
从图4(a)中可以看出,纯TPU在1 697 cm-1处有很强的吸收峰,这是氨基甲酸酯基团[-NHCOO-]的C=O伸缩振动特征峰[33],纯EP在该波段未见明显吸收,而其他掺有TPU的样品,在1 697 cm-1处均出现吸收峰,并且吸收峰强度随着TPU含量增加而增加,因此说明TPU已经添加到体系中。同时我们在所有样品的3 319 cm-1(羟基特征峰)处均发现有吸收峰[34],这是环氧基在开环过程中所产生的羟基振动峰,而且在910 cm-1(环氧基特征峰)处未发现明显的吸收峰,这是因为EP中的环氧基与TPU中的异氰酸酯基反应所导致[35],表明制备的所有样品均固化完全。结合EDS对N元素分布进行了分析,将N元素用红色标记,从图4(b)中可以看出,N元素在TPU/EP体系中分布均匀,表明TPU与EP之间形成了稳定、均匀的共聚物。
采用HUAWEI NOVA 7型号手机对制备的结构色薄膜进行拍摄,如图5(a)所示,使用光纤光谱仪测试了薄膜的反射光谱,并进行了色度学分析,如图5(b)、(c)所示。
从图5(a)可以看出,球径为255 nm的SiO2微球自组装后形成的结构色呈现绿色,而其他薄膜均显示为红色结构色。相比于255 nm粒径的SiO2自组装形成的薄膜,EP、TPU及TPU/EP基蛋白石薄膜的最大反射峰位置均发生红移。OTE薄膜相比于纯EP、纯TPU结构色薄膜具有更高的反射峰,TPU/EP配比为1∶1的OTE薄膜的反射峰值达到最高,如图5(b)所示。为进一步分析反射峰红移的原因,对制得的样品折射率进行了测试,结果如表1所示。
由布拉格公式λ≈1.633Dneff2-sin2θ,其中λ为三维蛋白石光子晶体的特征衍射波长,D为微球直径,neff为光子晶体有效折射率,θ为光波入射角,可知,当入射光垂直照射SiO2薄膜,θ为0度,SiO2球径D为255 nm,纯SiO2薄膜和TPU/EP配比为1∶1的OTE薄膜折射率分别为1.27和1.45,计算可得λ分别为528.85 nm和603.80 nm,与图5(b)中实验得到的反射峰528.91 nm和610.20 nm基本符合,差异可能是薄膜中SiO2粒径存在一定的不均匀性所造成。
在图5(c)中,A点为255 nm粒径的SiO2结构色薄膜,B和H为纯EP和TPU结构色薄膜,C到G分别为TPU/EP配比从1∶7到7∶1的结构色薄膜,可以发现B—G点相比于A点均向红区移动。为进一步量化颜色特性,依据色坐标计算公式M≈k∑iSλiM¯λi∆λi,m=M/(X+Y+Z),计算了各样品点的光谱色坐标,其中M=X、Y、Z,i表示离散波长点的索引,∆λi是相邻波长点的间隔。并根据色纯度计算公式P=x-x02+y-y02xn-x02+yn-y02,计算了各样品点的色纯度,并将测试和计算得到的样品最高反射率、半峰宽、折射率、色度坐标和色纯度列于表1中,每个结构色薄膜均进行了5次测量,取平均值。
对表1的数据进行分析,可以发现OTE薄膜相比于纯EP、纯TPU结构色薄膜具有更窄的半峰宽,其中TPU/EP配比为1∶1的OTE薄膜半峰宽最窄,为34.42 nm。这表明1∶1掺杂的OTE薄膜反射特性能集中在较窄的波长范围内,该材料对特定波长的选择性反射能力大幅增强。从色度坐标值可以看出,x坐标分量的最大值出现在E点(1∶1),到达橙红色域;y坐标分量的最大值也出现在E点(1∶1),为0.37,此时色纯度最高,达到了53.45。
柔性结构色薄膜的力学性能对薄膜的应用具有重要的影响。评价柔性薄膜力学性能的指标包括拉伸强度、断裂伸长率和韧性。因此本节通过单轴拉伸试验,依据GB/T528-2009标准对OTE复合薄膜的拉伸强度和断裂伸长率进行了测试[36]。先将复合薄膜切割成1.5×0.6 cm的长条形试样,使用HF-50N和HF-500N数字测力计,配备平推夹具,拉伸速率设置为50 mm/min,通过Force软件实时采集和监控数据[37],得到OTE薄膜的应力—应变曲线,如图6所示。
从图6中可以看出,纯EP结构色薄膜、TPU/EP配比为1∶7和1∶4的OTE薄膜在应力很小的情况下就发生了断裂,几乎不会发生塑性形变,因此无法用于拉伸场合。TPU/EP配比在1∶1到7∶1之间时,随着TPU掺杂量的增加,拉伸强度增强,断裂伸长率增加,TPU/EP配比为1∶1时,抗拉强度为16.8 MPa,断裂伸长率达171.9%,相对于EP结构色薄膜,拉伸强度增加14.3 MPa,断裂伸长率增加120.8%,优于相关文献报道[38-39]。根据2.2.1节的分析,在TPU/EP配比为1∶1时,OTE薄膜的色纯度最高(见表1)。综上,本文选取TPU/EP配比为1∶1的结构色薄膜用于后续的研究。
为评估OTE薄膜的韧性,将薄膜样品按照图7(a)所示固定,前后分别弯曲一次作为一个弯曲周期,弯折次数选为200次,对OTE薄膜进行了弯曲测试[40]。每50次测量一次光谱数据,OTE薄膜在弯折前后的颜色和光谱变化如图7(b)、(c)所示。
从图7(b)中可以看出,测试前薄膜表面呈现均匀的红色,显色鲜艳且无明显缺陷;经过200次弯曲测试后,薄膜表面仍保持完整的显色效果,未出现明显的裂纹、分层或颜色褪变,表明其具有良好的变形耐久性。图7(c)中表明,经过200次弯折测试后,OTE薄膜的反射峰为610.91 nm,半峰宽为37.12 nm,峰值反射率为55.36%。相比于弯折前,反射峰仅偏移0.71 nm,半峰宽发生了一定展宽(2.70 nm),峰值反射率下降0.71%。反射光谱的微小变化表明,薄膜在弯折后,形成的光子晶体结构仍能保持稳定,未发生明显破坏。
为进一步评测结构色薄膜在实际环境中的应用耐久性,在密闭环境里分别放置75 wt.%CH₃COOK溶液、33 wt.%MgCl2溶液、54 wt.%Mg(NO3)2溶液、26 wt.%NaCl溶液,模拟出25%RH、35%RH、55%RH、75%RH四种湿度环境,并测试了OTE薄膜在这四种环境下放置24 h后的反射光谱变化,如图8所示。其中15%RH条件是实验室湿度条件。经过测试可知,在25%RH环境下OTE薄膜的反射峰值下降1.02%,35%RH环境下OTE薄膜的反射峰值下降1.15%,55%RH环境下OTE薄膜的反射峰值下降2.43%,而在75%RH环境下OTE薄膜的反射峰值下降4.58%,但在实际应用中出现持续24 h且环境都处于75%RH的情况极为少见,因此可以证明该薄膜具有良好的湿度耐受性。
防伪薄膜在应用过程中可能涉及到热贴合工艺,因此最好能够在高温处理后仍保持力学与光学性能的稳定。由于TPU和EP的软化温度大致在80~120 ℃ 之间,长期使用温度一般不超过80 ℃,因此将OTE薄膜的老化温度设为90 ℃,并测试薄膜在该温度下老化24 h后,反射光谱及拉伸强度的变化,如图9所示。
从图9(a)中可以看出,老化前的OTE薄膜反射峰为610.20 nm,半峰宽为34.42 nm,反射峰值为56.07%,而老化后的OTE反射峰波长位置蓝移8.64 nm,但半峰宽基本不变,且反射率为54.95%,仅下降了2.12%。表明90 ℃老化前后OTE薄膜的显色效果基本不变,薄膜具有优异的耐热性。图9(b)进一步展示了OTE薄膜的力学稳定性,经过90 ℃老化24 h后,OTE薄膜的拉伸强度及断裂伸长率波动幅度控制在5%以内。
综上所述,制备的薄膜具有良好的柔韧、耐高温性能以及稳定的结构色,可将其应用于防伪标签中。
结构色的颜色呈现由TPU/EP配比、纳米颗粒尺寸、组装有序性、薄膜厚度以及制备工艺共同决定,参数变化多,使得颜色变化和不同角度呈现的颜色也会发生不同的变化,同时,不同组分的荧光材料在不同波长光的激发下会呈现出不同颜色,在一定程度上会提高薄膜被仿造的难度。本文在上述结构色薄膜制备的基础上,采用喷涂法利用稀土铝酸锶透明荧光漆制备出具有荧光和结构色双重防伪的OTE薄膜,TPU/EP光子晶体可以实现虹彩效果,稀土铝酸锶在紫外光照射下会呈现绿色,防伪薄膜制备流程如图10(a)所示。
喷涂荧光物质前、后及用紫外灯照射后的OTE薄膜效果图如图10(b)所示,可以看到喷涂前后薄膜颜色无明显变化,且不显示星星图案,当用365 nm紫外灯照射后,荧光星星图案显现。图10(c)为双重防伪薄膜在实际应用中的效果图,展示了其通过热贴合技术固定在鞋舌上的效果。可以看出,经过热贴合处理后,防伪薄膜依然保持明显的虹彩效果,在不同视角下可产生明显的色彩跃变。此外,在紫外灯的照射下,薄膜表面能够清晰地显现出绿色的星星荧光图案。这种设计不仅增强了产品的美观性,还通过荧光图案的隐蔽性和虹彩效果的直观性,为防伪提供了双重保障。
采用Stöber法制备了粒径为255 nm的单分散SiO2微球,通过提拉自组装技术在PE基底上构建了高度有序的SiO2面心立方蛋白石结构模板,并进一步制备了不同比例的TPU/EP基光子晶体蛋白石薄膜。测试结果表明,TPU/EP配比为1∶1的TPU/EP基蛋白石结构色薄膜展现了优异的光学性能(平均反射率为56.07%,色纯度为53.45%,半峰宽为34.42 nm)、力学性能(抗拉强度为16.8 MPa,断裂伸长率为171.9%)以及良好的环境耐久性(反射峰位置和半峰宽基本不变,反射率下降≤2.43%@55%RH,24 h,反射率下降≤2.12%@90 ℃,24 h)。以该薄膜为基础,结合荧光材料发光特性,探究了其作为光子晶体柔性薄膜防伪标签的应用潜力。薄膜在自然光下呈现高饱和度的结构色,且随观察角度变化表现出明显的虹彩效应,在紫外光照射下荧光材料则显示出特定的荧光图案,经模拟实际使用环境测试后仍保持稳定的光学性能和结构完整性。与现有的防伪技术相比,该结构色薄膜不仅实现了“虹彩+荧光”的双重防伪,并且由于制造成本相对低廉,通过简单的热贴合技术即可实现与鞋舌等物品的牢固结合,通过不同蛋白石结构模板还可实现不同的结构色,因此在实际的防伪应用中具有广阔空间。

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2026年第55卷第1期
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doi: 10.3788/gzxb20265501.0131002
  • 接收时间:2025-07-21
  • 首发时间:2026-10-10
  • 出版时间:2026-01-25
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  • 收稿日期:2025-07-21
  • 录用日期:2025-09-05
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    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

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2种不同金属材料的力学参数
科
Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)
属
Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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