Abstract
Cellulose and its derivatives films are increasingly used in paper, packaging, and other fields, but there is limited research on its films with anti-counterfeiting patterns. Here, we demonstrate an approach to prepare cellulose film with a micro-millimeter scale pattern by lithium chloride (LiCl) crystal template, which grows out by the in-situ generation in the film formation process. The surface morphologies of the as-prepared film were systematically controlled by regulating the solution viscosity (η) and the surrounding temperature. The imprinting of LiCl crystal was retained on the film surface after rinsing. Moreover, the crystallinity of patterned film was significantly improved, and about 62 MPa increased tensile strength than the film without a pattern. Incredibly, these patterns were similar to fingerprint size, which exhibited an excellent function to unlock fingerprint locked phones and showed potential in the anti-counterfeiting yield.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Azeredo HMC, Rosa MF, Mattoso LHC (2017) Nanocellulose in bio-based food packaging applications. Ind Crops Prod 97:664–671. https://doi.org/10.1016/j.indcrop.2016.03.013
Bae HJ, Bae S, Park C, Han S, Kim J, Kim LN, Kim K, Song S-H, Park W, Kwon S (2015) Biomimetic microfingerprints for anti-counterfeiting strategies. Adv Mater 27:2083–2089. https://doi.org/10.1002/adma.201405483
Baughman RH, Zakhidov AA, de Heer WA (2002) Carbon nanotubes–the route toward applications. Science 297:787–792. https://doi.org/10.1126/science.1060928
Bazrafshan Z (2020) Multi-functional coating of polymeric spherulites for chiral photonic cellulose nanocrystal films. Cellulose 27:6235–6247. https://doi.org/10.1007/s10570-020-03233-3
Braeckmans K, De Smedt SC, Roelant C, Leblans M, Pauwels R, Demeester J (2003) Encoding microcarriers by spatial selective photobleaching. Nat Mater 2:169–173. https://doi.org/10.1038/nmat828
Buchanan JD, Cowburn RP, Jausovec AV, Petit D, Seem P, Xiong G, Atkinson D, Fenton K, Allwood DA, Bryan MT (2005) Forgery: ‘fingerprinting’ documents and packaging. Nature 436:475. https://doi.org/10.1038/436475a
Cazón P, Vázquez M (2021) Bacterial cellulose as a biodegradable food packaging material: A review. Food Hydrocoll 113:106530. https://doi.org/10.1016/j.foodhyd.2020.106530
Feng J, Wen W, Wei X, Jiang X, Cao M, Wang X, Zhang X, Jiang L, Wu Y (2019) Random organic nanolaser arrays for cryptographic primitives. Adv Mater 31:1807880. https://doi.org/10.1002/adma.201807880
Gassend B, Clarke D, Van Dijk M, Devadas S (2002) Silicon physical random functions. In: Proceedings of the 9th ACM conference on computer and communications security, pp 148–160. https://doi.org/10.1145/586110.586132
Geng Y, Noh J, Drevensek-Olenik I, Rupp R, Lenzini G, Lagerwall JP (2016) High-fidelity spherical cholesteric liquid crystal Bragg reflectors generating unclonable patterns for secure authentication. Sci Rep 6:26840. https://doi.org/10.1038/srep26840
Han S, Bae HJ, Kim J, Shin S, Choi SE, Lee SH, Kwon S, Park W (2012) Lithographically encoded polymer microtaggant using high-capacity and error‐correctable QR code for anti‐counterfeiting of drugs. Adv Mater 24:5924–5929. https://doi.org/10.1002/adma.201201486
Herder C, Yu M-D, Koushanfar F, Devadas S (2014) Physical unclonable functions and applications: a tutorial. Proc IEEE 102:1126–1141. https://doi.org/10.1109/JPROC.2014.2320516
Huang C, Lucas B, Vervaet C, Braeckmans K, Van Calenbergh S, Karalic I, Vandewoestyne M, Deforce D, Demeester J, De Smedt SC (2010) Unbreakable codes in electrospun fibers: digitally encoded polymers to stop medicine counterfeiting. Adv Mater 22:2657–2662. https://doi.org/10.1002/adma.201000130
Jing Y, Mahmud S, Wu C, Zhang X, Su S, Zhu J (2021) Alginate/gelatin mineralized hydrogel modified by multilayers electrospun membrane of cellulose: preparation, properties and in-vitro degradation. Polym Degrad Stab 192:109685. https://doi.org/10.1016/j.polymdegradstab.2021.109685
Lee H, Kim J, Kim H, Kim J, Kwon S (2010) Colour-barcoded magnetic microparticles for multiplexed bioassays. Nat Mater 9:745–749. https://doi.org/10.1038/nmat2815
Lee J, Bisso PW, Srinivas RL, Kim JJ, Swiston AJ, Doyle PS (2014) Universal process-inert encoding architecture for polymer microparticles. Nat Mater 13:524–529. https://doi.org/10.1038/nmat3938
Liu Y, Ahmed S, Sameen DE, Wang Y, Lu R, Dai J, Li S, Qin W (2021) A review of cellulose and its derivatives in biopolymer-based for food packaging application. Trends Food Sci Technol 112:532–546. https://doi.org/10.1016/j.tifs.2021.04.016
Mahmud S, Wang J, Shao N, Xiong Z, Zhang R, Zhu J (2020) Nucleation and crystallization of poly(propylene 2,5-furan dicarboxylate) by direct blending of microcrystalline cellulose: improved tensile and barrier properties. Cellulose 27:9423–9436. https://doi.org/10.1007/s10570-020-03448-4
Mahmud S, Hasan KF, Jahid MA, Mohiuddin K, Zhang R, Zhu J (2021) Comprehensive review on plant fiber-reinforced polymeric biocomposites. J Mater Sci 56:7231–7264. https://doi.org/10.1007/s10853-021-05774-9
Ohtsubob KNaJ (2012) Optical security device providing fingerprint and designed pattern indicator using fingerprint texture in liquid crystal. Opt Eng 51(4):040506. https://doi.org/10.1117/1.OE.51.4.040506
Pappu R, Recht B, Taylor J, Gershenfeld N (2002) Physical one-way functions. Science 297:2026–2030. https://doi.org/10.1126/science.1074376
Tian L, Liu K-K, Fei M, Tadepalli S, Cao S, Geldmeier JA, Tsukruk VV, Singamaneni S (2016) Plasmonic nanogels for unclonable optical tagging. ACS Appl Mater Interfaces 8:4031–4041. https://doi.org/10.1021/acsami.5b11399
Zhang J, Zhang S, Wang Z, Zhang Z, Wang S, Wang S (2011) Hopper-like single crystals of sodium chloride grown at the interface of metastable water droplets. Angew Chem Int Ed 50:6044–6047. https://doi.org/10.1002/anie.201101704
Zhang X, Meng D, Guo M, Mahmud S, Peng X, Su S, Shu Y, Zhu J, Yu N (2020) Fabrication of natural cellulose films with pattern by viscosity regulation of its solution. Cellulose 27:3947–3956. https://doi.org/10.1007/s10570-020-03051-7
Zhang M, Li M, Yu N, Su S, Zhang X (2021) Fabrication of AgCl@ tannic acid-cellulose hydrogels for NaBH 4-mediated reduction of 4-nitrophenol. Cellulose 28:3515–3529. https://doi.org/10.1007/s10570-021-03721-0
Zhang X, Huang C, Mahmud S, Guo X, Hu X, Jing Y, Su S, Zhu J (2021) Sodium alginate fasten cellulose nanocrystal Ag@ AgCl ternary nanocomposites for the synthesis of antibacterial hydrogels. Compos Commun 25:100717. https://doi.org/10.1016/j.coco.2021.100717
Zhao G, Lyu X, Lee J, Cui X, Chen W-N (2019) Biodegradable and transparent cellulose film prepared eco-friendly from durian rind for packaging application. Food Packag Shelf Life 21:100345. https://doi.org/10.1016/j.fpsl.2019.100345
Acknowledgments
The authors are grateful for the support from the Large-scale instrument opening fund of Hunan Normal University (21CSZ076); Science and Technology Innovation 2025 Major Project of Ningbo (2018B10013); Opening Fund of Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Hunan Normal University (KLCBTCM R201811); The Key fund of Hunan Educational Committee, China, for financial support (18B025); Changsha Natural Foundation of Hunan Provincial, China (kq2202245).
Funding
The authors have not disclosed any funding.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that there is no conflict of interest.
Additional information
Publisher’s Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Supplementary Material 2
Rights and permissions
About this article
Cite this article
Jing, Y., Wu, C., Zhang, X. et al. Construction of anti-counterfeiting pattern on the cellulose film by in-situ regulation strategies. Cellulose 29, 7751–7760 (2022). https://doi.org/10.1007/s10570-022-04729-w
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-022-04729-w