现代纺织技术 ›› 2024, Vol. 32 ›› Issue (3): 81-90.

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基于(PEA)2PbBr4单晶的光致发光防伪织物标贴制备与性能

  

  1. 1. 天津工业大学,a. 纺织科学与工程学院;b. 绍兴柯桥研究院,天津 300387;2. 唐山三友兴达化纤有限公司,唐山 063305
  • 出版日期:2024-03-10 网络出版日期:2024-03-20
  • 作者简介:胡晓亭(1998—),女,硕士研究生,主要从事光致发光钙钛矿单晶及智能纺织品方面的研究。
  • 基金资助:
    国家自然科学基金项目(51303131)

Preparation and performance of photoluminescence anti-counterfeiting fabric labeling based on (PEA)2PbBr4 single crystal

  1. 1a. School of Textile Science and Engineering; 1b. Research Institute of Keqiao District, Tiangong University, Tianjin 300387, China; 2. Tangshan Sanyou Xingda Chemical Fiber Co., Ltd., Tangshan 063305, China
  • Published:2024-03-10 Online:2024-03-20

摘要: 为制备高效轻质的荧光防伪织物标贴,采用反溶剂气相辅助结晶法生长不同尺寸和密度的苯乙胺溴化铅((PEA)2PbBr4)单晶,并将其旋涂封装于PVC薄膜内,与织物热轧复合,得到具有光致发光防伪功能的织物标贴;通过XRD、SEM、紫外可见光度计和瞬态荧光光谱仪等测试对单晶的结构、复合膜与织物标贴的发光特性进行分析。结果表明:采用简单温和的工艺即可有效制备晶体并调控其尺寸和密度,制作具有防伪功能的织物标贴。尺寸为5~10 μm的二维结构单晶,其厚度约200 nm;通过调节邻二氯苯与N,N-二甲基甲酰胺的溶剂比例能够有效控制(PEA)2PbBr4单晶尺寸。当单晶尺寸约为5 µm时,其分布状态、结晶性和发光性能最为优异,其复合膜的吸收峰和发射峰分别位于391 nm和414 nm处。超微量的防伪标贴即可在365 nm紫外光的激发下发出强烈均匀的蓝紫色光,并且,用于织物防伪能够达到洗可穿及耐磨标准,实现有效的防伪功能。

关键词: 苯乙胺溴化铅, 二维钙钛矿单晶, 光致发光, 荧光防伪, 织物标贴, 纺织品防伪

Abstract: The development and application of fabric security labels with identification function ensure the safety of textiles. Ultraviolet photoluminescent textiles refer to the fact that the fabric emits a specific color of light after being excited from a colorless state when it is irradiated by ultraviolet light, so as to achieve the purpose of anti-counterfeiting. Previous studies have shown that the (PEA)2PbBr4 single crystal with ultraviolet photoluminescence performance has excellent characteristics such as high color purity and high crystallinity, and can be prepared by simple process, mild conditions and mass production.
To prepare efficient and lightweight fluorescent anti-counterfeiting fabric labels, phenethylammonium bromide was prepared by β-phenethylamine and hydrobromic acid, and it was dissolved with lead bromide at a molar ratio of 2:1 to N, N-dimethylformamide to configure a precursor solution. By adjusting the solvent ratio of o-dichlorobenzene to N, N-dimethylformamide, two-dimensional layered (PEA)2PbBr4 single crystals of different sizes and densities were grown by anti-solvent gas-assisted crystallization. The single crystal with the best distribution and luminescence performance was selected, and the single crystal solution under this condition was spin-coated and encapsulated in a 0.1 mm thick PVC film to prepare a single crystal/PVC composite film, and a fabric label with photoluminescence anti-counterfeiting function was obtained by hot rolling with the fabric. The crystallization properties, distribution, morphological structure and luminescence characteristics of single crystals and composite films and fabric labels were studied by fluorescence microscopy, laser particle size analyzer, XRD, SEM, ultraviolet-visible photometer and transient fluorescence spectrometer, and their application effects in textiles were discussed through washable wearable and wear-resistant tests.
The results show that (PEA)2PbBr4 single crystals have a series of periodically repeated, uniformly spaced and well-defined strong diffraction peaks belonging to the two-dimensional layered perovskite structure, with excellent crystallinity and high preference orientation. And the morphology is regular, the edges are sharp, and the elements forming single crystals in the energy dispersive spectrum are evenly distributed; single crystals with a size of 5-10 μm are about 200 nm thick; the absorption and emission peaks are located at 394 nm and 412 nm, respectively. The larger the solvent ratio of o-dichlorobenzene to N, N-dimethylformamide, the smaller the single crystal size is; when the single crystal size is about 5 μm, its distribution state, crystallinity and luminescence performance are the best. The absorption peaks and emission peaks of the single crystal/PVC composite film are located at 391 nm and 414 nm, respectively, and the spectra shows that the single crystal inside the PVC film still has high quality and high color purity. The composite film used as the fabric security label uses ultra-small amounts of single crystals to emit a strong and uniform blue-violet light under the excitation of 365 nm ultraviolet light, realizing effective anti-counterfeiting function. It is tested and applied to fabric security labels to meet washable and wear-resistant standards.

Key words: phenylethylamine lead bromine, two-dimensional perovskite single crystal, PL photoluminescence, fluorescent anti-counterfeiting, fabric labeling, textile anti-counterfeiting

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