埃洛石纳米管的表面修饰及其在包装薄膜中的研究进展

钱自强; 刘征; 杨秀秀; 莫书森; 杨顺; 郑华明

doi:10.19554/j.cnki.1001-3563.2025.21.001

PDF(3671 KB)

包装工程（技术栏目） ›› 2025, Vol. 46 ›› Issue (21) : 1-10. DOI: 10.19554/j.cnki.1001-3563.2025.21.001

先进材料

埃洛石纳米管的表面修饰及其在包装薄膜中的研究进展

钱自强¹, 刘征², 杨秀秀², 莫书森¹, 杨顺¹, 郑华明^1*

作者信息 +

Surface Modification of Halloysite Nanotubes and Its Research Progress in Packaging Films

QIAN Ziqiang¹, LIU Zheng², YANG Xiuxiu², MO Shusen¹, YANG Shun¹, ZHENG Huaming^1*

Author information +

文章历史 +

摘要

系统探讨了埃洛石纳米管（Halloysite Nanotubes,HNTs）的结构特性、提纯方法及其表面功能化改性策略,开发高性能HNTs复合薄膜材料,拓展其在食品包装薄膜领域的应用潜力。阐述了HNTs的提纯工艺,基于HNTs内/外表面不同的化学性质,重点分析了刻蚀扩孔、表面活性剂修饰、封端等多种功能化改性策略,以及不同表面改性方法对材料界面特性的影响机制。深入探讨了HNTs在食品包装薄膜领域的应用。研究表明,酸/碱刻蚀可精准调控HNTs的管径与比表面积,显著提升了HNTs对活性分子的负载能力;硅烷偶联剂改性有效增强了HNTs与聚合物基体的界面相容性,为高性能纳米复合薄膜的设计提供了新思路;HNTs的药物封端技术可延长活性成分释放周期,展现出在缓释包装薄膜的应用潜力;HNTs-植物精油复合薄膜可显著延长食品货架期,在食品包装领域具有良好的应用前景。

Abstract

The work aims to systematically investigate the structural characteristics, purification methods, and surface functionalization strategies of Halloysite Nanotubes (HNTs), so as to develop high-performance HNTs composite film materials, and expand their potential applications in food packaging films. The purification processes of HNTs were elaborated. Based on their distinct chemical properties of the inner and outer surfaces, a detailed analysis of various functional modification strategies such as etching, pore expansion, surfactant modification, end-capping and the mechanisms by which different surface modification methods influence the material's interfacial characteristics was provided. The application of HNTs in food packaging films was also discussed. The results demonstrate that acid/alkali etching can precisely control the tube diameter and specific surface area of HNTs, significantly enhancing their active molecule loading capacity; Modification with silane coupling agents effectively improves the interfacial compatibility between HNTs and the polymer matrix, providing a new approach for designing high-performance nanocomposite film; The end-capping technology for HNTs can prolong the release cycle of active ingredients, demonstrating its potential application in sustained-release packaging films; HNTs-plant essential oil composite films can significantly extend the shelf life of food, showing promising application prospects in the food packaging.

导出引用

钱自强, 刘征, 杨秀秀, 莫书森, 杨顺, 郑华明. 埃洛石纳米管的表面修饰及其在包装薄膜中的研究进展[J]. 包装工程. 2025, 46(21): 1-10 https://doi.org/10.19554/j.cnki.1001-3563.2025.21.001

QIAN Ziqiang, LIU Zheng, YANG Xiuxiu, MO Shusen, YANG Shun, ZHENG Huaming. Surface Modification of Halloysite Nanotubes and Its Research Progress in Packaging Films[J]. Packaging Engineering. 2025, 46(21): 1-10 https://doi.org/10.19554/j.cnki.1001-3563.2025.21.001

中图分类号： TB332

参考文献

[1] SENYEL M, DIKE A S.Contribution of Silane Modification of Halloysite Nanotube to Its Poly(butylene terephthalate)-Based Nanocomposites: Structural, Mechanical and Thermal Properties[J]. Polymer Bulletin, 2024, 81(11): 9851-9870.
[2] ZHAO X J, ZOU D H, LIU Y F, et al.Electrospun Polylactic Acid Nanofibers Membrane with Copper Ion-Loaded Clay Nanotubes for Fresh-Keeping Packaging[J]. International Journal of Biological Macromolecules, 2024, 267: 131651.
[3] CINÀ G, MASSARO M, CAVALLARO G, et al.Development of Alginate Film Filled with Halloysite-Carbon Dots for Active Food Packaging[J]. International Journal of Biological Macromolecules, 2024, 277(Pt 2): 134375.
[4] DING M K, WU W J, LIU R L, et al.Preparation and Application of Thyme Essential Oil@halloysite Nanotubes-Loaded Multifunctional Pullulan/Gelatin/PVA Aerogels[J]. International Journal of Biological Macromolecules, 2025, 309: 142917.
[5] ZHOU M Y, TIAN Y H, MO S S, et al.Cinnamon Essential Oil-Loaded Halloysite Nanotubes Applied in Degradable Film: Characterization and Non-Contact Antimicrobial Activity[J]. Polymers, 2025, 17(9): 1144.
[6] YAH W O, XU H, SOEJIMA H, et al.Biomimetic Dopamine Derivative for Selective Polymer Modification of Halloysite Nanotube Lumen[J]. Journal of the American Chemical Society, 2012, 134(29): 12134-12137.
[7] LOURENÇO M P, DE OLIVEIRA C, OLIVEIRA A F, et al. Structural, Electronic, and Mechanical Properties of Single-Walled Chrysotile Nanotube Models[J]. The Journal of Physical Chemistry C, 2012, 116(17): 9405-9411.
[8] CERDÁ-GANDIA R, AGÜERO Á, ARRIETA M P, et al. Effect of Different Porous Size of Porous Inorganic Fillers on the Encapsulation of Rosemary Essential Oil for PLA-Based Active Packaging[J]. Polymers, 2024, 16(18): 2632.
[9] CHEN X Y, DING F, HOU X L, et al.Halloysite-Based Inorganic-Organic Hybrid Coatings for Durable Flame Retardant, Hydrophobic and Antibacterial Properties of Cotton Fabrics[J]. International Journal of Biological Macromolecules, 2024, 277: 134357.
[10] HU M Y, LI X H, TAO R, et al.Highly Permeable Polyamide Nanofiltration Membranes with Crumpled Structures Regulated by Polydopamine-Piperazine-Halloysite Interlayer[J]. Desalination, 2023, 565: 116862.
[11] 曾丽, 韵勤柏, 鲁启鹏, 等. 埃洛石纳米管的疏水改性及其复合材料的研究进展[J]. 工程科学学报, 2021, 43(6): 732-744.
ZENG L, YUN Q B, LU Q P, et al.Research Progress of Hydrophobically Modified Halloysite Nanotube-Based Composite Materials[J]. Chinese Journal of Engineering, 2021, 43(6): 732-744.
[12] FRÍAS GALLARDO L, MONTEMARTINI P E, PENOFF M E. Enhanced Slurry Erosion Resistance of Low Friction and Highly Hydrophobic Halloysite-Fluoro-Polysilsesquioxane Coatings[J]. Wear, 2023, 526: 204875.
[13] ZHANG Q, SHU Y J, ZHANG Y H, et al.Effect of Functionalized Halloysite Nanotubes on Fire Resistance and Water Tolerance of Intumescent Fire-Retardant Coatings for Steel Structures[J]. Progress in Organic Coatings, 2024, 197: 108843.
[14] WU S Y, ZHAO S F, ZHAI Z, et al.Robust Halloysite Nanotubes Modified PVDF Membranes with Improved Wetting Resistance for Hypersaline Wastewater Treatment via Membrane Distillation[J]. Journal of Environmental Chemical Engineering, 2024, 12(6): 114872.
[15] STOR M, CZELEJ K, KRASIŃSKI A, et al. Exceptional Sorption of Heavy Metals from Natural Water by Halloysite Particles: A New Prospect of Highly Efficient Water Remediation[J]. Nanomaterials, 2023, 13(7): 1162.
[16] 田大惠, 郝佳瑞, 肖国琪. 多级分离纯化纳米管状埃洛石性能对比研究[J]. 山西大学学报(自然科学版), 2022, 45(6): 1624-1631.
TIAN D H, HAO J R, XIAO G Q.Study on Properties of Halloysite Nanotubes by Multistage Separation and Purification[J]. Journal of Shanxi University (Natural Science Edition), 2022, 45(6): 1624-1631.
[17] EKHLASI A, SOLOUK A, HAGHBIN NAZARPAK M, et al.Electrospun Polyacrylonitrile/Halloysite Nanofibrous Membranes for Creatinine Removal from Kidney Failure Patients[J]. Applied Clay Science, 2023, 243: 107083.
[18] NIGIZ F U, KARAKOCA B.Halloysite Nanotube Doped Poly Lactic Acid Membrane Preparation and Seawater Desalination[J]. Applied Clay Science, 2023, 231: 106721.
[19] 韩利雄, 严春杰, 赵俊, 等. 天然纳米管状埃洛石的提纯研究[J]. 矿产保护与利用, 2011, 31(4): 36-40.
HAN L X, YAN C J, ZHAO J, et al.Study on Purification of Halloysite Nanotubes[J]. Conservation and Utilization of Mineral Resources, 2011, 31(4): 36-40.
[20] 秦丰, 孙青, 张俭, 等. 酸浸提纯埃洛石的研究[J]. 非金属矿, 2016, 39(4): 11-13.
QIN F, SUN Q, ZHANG J, et al.Research on Acid Leaching Purification of Halloysite[J]. Non-Metallic Mines, 2016, 39(4): 11-13.
[21] 张原菘, 甘雯馨, 曾钦志, 等. 埃洛石纳米管负载芳樟醇及其防霉抗菌性能[J]. 复合材料学报, 2025, 42(5): 2854-2865.
ZHANG Y S, GAN W X, ZENG Q Z, et al.Antibacterial and Antifungal Properties of Halloysite Nanotubes by Loaded Linalool[J]. Acta Materiae Compositae Sinica, 2025, 42(5): 2854-2865.
[22] WHITE R D, BAVYKIN D V, WALSH F C.The Stability of Halloysite Nanotubes in Acidic and Alkaline Aqueous Suspensions[J]. Nanotechnology, 2012, 23(6): 065705.
[23] TOSATTI S, MICHEL R, TEXTOR M, et al.Self-Assembled Monolayers of Dodecyl and Hydroxy-Dodecyl Phosphates on both Smooth and Rough Titanium and Titanium Oxide Surfaces[J]. Langmuir, 2002, 18(9): 3537-3548.
[24] YAH W O, TAKAHARA A, LVOV Y M.Selective Modification of Halloysite Lumen with Octadecylphosphonic Acid: New Inorganic Tubular Micelle[J]. Journal of the American Chemical Society, 2012, 134(3): 1853-1859.
[25] TARONI T, MERONI D, FIDECKA K, et al.Halloysite Nanotubes Functionalization with Phosphonic Acids: Role of Surface Charge on Molecule Localization and Reversibility[J]. Applied Surface Science, 2019, 486: 466-473.
[26] LISUZZO L, CAVALLARO G, MILIOTO S, et al.Coating of Silk Sutures by Halloysite/Wax Pickering Emulsions for Controlled Delivery of Eosin[J]. Applied Clay Science, 2024, 247: 107217.
[27] ZHANG X Y, LI C Q, YUAN F, et al.Preparation and Carrier Preference of Synergistic Antibacterial Cetylpyridinium/Cu²⁺/Halloysite Composite[J]. Applied Surface Science, 2025, 681: 161519.
[28] HAYEEMASAE N, MASA A, OTHMAN N, et al.Viable Properties of Natural Rubber/Halloysite Nanotubes Composites Affected by Various Silanes[J]. Polymers, 2022, 15(1): 29.
[29] WANG X, ZHU C S, HU Y L, et al.Development and Application of Cinnamaldehyde-Loaded Halloysite Nanotubes for the Conservation of Stone Cultural Heritage[J]. Applied Clay Science, 2023, 236: 106886.
[30] WEI Y N, ZHANG Y L.Catalytic Conversion of Mannose to 5-Hydroxymethylfurfural Promoted by Hydrophobic Halloysite-Based Catalyst in Biphasic System[J]. Applied Clay Science, 2024, 254: 107390.
[31] ZASYPALOV G, KLIMOVSKY V, ABRAMOV E, et al.Hydrodeoxygenation of Bio-Oil Model Compounds over Ni- and Pt-Catalysts Supported on Hydrophobized Halloysite Nanotubes[J]. Sustainable Energy & Fuels, 2024, 8(17): 3976-3993.
[32] YANG C K, HUANG Y P, DAN N H, et al.Polyglutamic Acid-Grafted Halloysite-Modified Collagen-Sodium Alginate Oxide Composite Membrane for Wound Dressing Application[J]. ACS Applied Polymer Materials, 2022, 4(5): 3994-4002.
[33] DUMAN O, DIKER C Ö, GÜREŞIR S M, et al. Superhydrophobic Melamine Sponge-Sorbent Fabricated Using WS₂, Halloysite Nanotube, Octyltriethoxysilane, Tetraethoxysilane, and Polydimethylsiloxane for the Selective Uptake of Oil from Water[J]. Journal of Water Process Engineering, 2023, 56: 104454.
[34] FENG J, LUO W L, HE W T, et al.Bio-Derived Phosphorous-Nitrogen-Silicon Decorated Halloysite Nanotube towards Enhancing Flame Retardant, UV-Blocking and Mechanical Properties of Poly(lactic acid)[J]. Polymer Degradation and Stability, 2023, 217: 110509.
[35] ZIA-UL-HAQ M, WU J, HAQ Z U, et al. Enhanced Mechanical, Thermal Performance and Kinetics of Thermal Degradation of Silicone Rubber/Ethylene-Vinyl Acetate Copolymer/Halloysite Nanoclay Nanocomposites Compatibilized by Ethylene-Acrylic Acid Copolymer[J]. Journal of Polymer Research, 2023, 30(8): 306.
[36] MASA A, HAYEEMASAE N.Dual Modification of Natural Rubber/Halloysite Nanotubes Composites by Silane and Maleated Natural Rubber[J]. International Journal of Polymer Analysis and Characterization, 2023, 28(8): 714-725.
[37] BAO Z G, YAN Y X, HAN W J.Investigation of Γ-Aminopropyltriethoxysilane (APTES)-Modified Halloysite Nanotubes on the Reinforcement of Halloysite/Polypropylene (PP) Nanocomposites[J]. Polymers, 2024, 16(23): 3332.
[38] LIU M, HU M M, LI P P, et al.An Alkali-Responsive Mineral Self-Healing Agent with Mechanical Property Enhancement for Cementitious Composites[J]. Composites Part B: Engineering, 2023, 266: 110986.
[39] MA Q, LIU L L, WANG P, et al.Preparation and Corrosion Resistance Study of a pH-Responsive Plasma Electrolytic Oxidation Coating Modified by Halloysite Nanotubes[J]. Materials Today Communications, 2024, 38: 108541.
[40] LEI X J, ZHU K, LIU H, et al.Eco-Friendly Packaging Film with Integrated Functions of High-Efficiency Radiation Cooling and Sustained-Release Antimicrobial Activity[J]. Chemical Engineering Journal, 2024, 496: 153430.
[41] WANG S S, ZHANG Y.Fire Alarm Nano-Coating with the Controlled Release of Phosphorus-Containing Free Radical for Considerable Flame Retardant Performance[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2024, 701: 134951.
[42] GARCIA-HERNANDEZ C, GARCIA-CABEZON C, RODRIGUEZ-MENDEZ M L, et al. Effect of Nanoclays on the Electrochemical Performance of LbL Catechol Sensors[J]. Electrochimica Acta, 2024, 476: 143717.
[43] JOSHI A, ABDULLAYEV E, VASILIEV A, et al.Interfacial Modification of Clay Nanotubes for the Sustained Release of Corrosion Inhibitors[J]. Langmuir, 2013, 29(24): 7439-7448.
[44] DECHER G.Fuzzy Nanoassemblies: Toward Layered Polymeric Multicomposites[J]. Science, 1997, 277(5330): 1232-1237.
[45] VEERABADRAN N G, MONGAYT D, TORCHILIN V, et al.Organized Shells on Clay Nanotubes for Controlled Release of Macromolecules[J]. Macromolecular Rapid Communications, 2009, 30(2): 99-103.
[46] TAŞ C E, GUNDOGDU S O, ÜNAL H.Polydopamine-Coated Halloysite Nanotubes for Sunlight-Triggered Release of Active Substances[J]. ACS Applied Nano Materials, 2022, 5(4): 5407-5415.
[47] FRIULI V, URRU C, FERRARA C, et al.Design of Etched- and Functionalized-Halloysite/Meloxicam Hybrids: A Tool for Enhancing Drug Solubility and Dissolution Rate[J]. Pharmaceutics, 2024, 16(3): 338.
[48] ZHENG Z X, WANG S, YANG F, et al.Controlled Surface Multifunctional Groups over Halloysite Nanotube Enabling Reinforced Lead Adsorption in Vitro[J]. Separation and Purification Technology, 2024, 339: 126632.
[49] JAMALPOOR Z, AHMADI H, HEYDARI M, et al.Chitosan Based Niosomal Hydrogel with Polyethylene Glycol and Halloysite Nanotubes for Curcumin Delivery[J]. Journal of Molecular Liquids, 2024, 401: 124640.
[50] LI X Y, LI H R, ZHAO X Q, et al.Amine-Impregnated Natural Inorganic Nanotubes via Layer-by-Layer Electrostatically Self-Assembly Approach for Efficient CO₂ Adsorption[J]. Separation and Purification Technology, 2024, 349: 127864.
[51] WANG J H, ZHANG X, ZHANG B, et al.Rapid Adsorption of Cr (VI) on Modified Halloysite Nanotubes[J]. Desalination, 2010, 259(1/2/3): 22-28.
[52] CHENG D K, DAI X H, CHEN L, et al.Thiol-Yne Click Synthesis of Polyamide-Amine Dendritic Magnetic Halloysite Nanotubes for the Efficient Removal of Pb(II)[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(2): 771-781.
[53] CASIELLO M, SAVINO S, MASSARO M, et al.Multifunctional Halloysite and Hectorite Catalysts for Effective Transformation of Biomass to Biodiesel[J]. Applied Clay Science, 2023, 242: 107048.
[54] ZHU J, LIN T, NIU S L, et al.Synthesis of HNTS-Ca/Zn Catalyst for Biodiesel Production from Acidulated Palm Oil: Optimized by GA-BP[J]. Industrial Crops and Products, 2024, 213: 118450.
[55] MASSAD-IVANIR N, SAND A, NITZAN N, et al.Scalable Production of Antimicrobial Food Packaging Films Containing Essential Oil-Loaded Halloysite Nanotubes[J]. Food Packaging and Shelf Life, 2023, 37: 101079.
[56] DENG Z P, MENG X, LI C Y, et al.Effects of Halloysite Nanotubes Modified by Organic Phosphate on the Performance Improvement for Polypropylene[J]. Journal of Applied Polymer Science, 2023, 140(19): e53703.
[57] 黎柯君, 陈展鹏, 刘仁, 等. 水果废弃物活性成分提取方法及其在食品包装的应用进展[J]. 包装工程, 2024, 45(17): 50-59.
LI K J, CHEN Z P, LIU R, et al.Advances in Extraction Methods of Active Ingredients from Fruit Waste and Their Application in Food Packaging[J]. Packaging Engineering, 2024, 45(17): 50-59.
[58] CHAKRABORTY P, HATI S, MISHRA B K.Preparation and Characterization of Nanobiocomposite Films from Sodium Caseinate, Halloysite Nanoclay, and Geraniol and Application on Capsicum (Capsicum Annuum) Fruits as a Case Study[J]. Food Bioscience, 2024, 61: 104665.
[59] DHARINI V, BISWAL A, SELLAMUTHU P S, et al.PVA/Essential Oil-Based Active Food Packaging Films Functionalised with Halloysite Nanotubes and Cellulose Nanocrystals as Filler Materials for the Shelf-Life Extension of Papaya Fruits[J]. International Journal of Food Science & Technology, 2024, 59(1): 318-332.
[60] SHAFIEI H, SAEI-DEHKORDI S, MORADI M, et al.Preparation and Antibacterial Performance of Bacterial Nanocellulose Sachet Containing Zataria Multiflora Essential Oil Loaded Halloysite Nanotubes on Escherichia Coli O157: H7 in Cheese[J]. LWT, 2024, 194: 115812.
[61] ZHENG Y, LI L, SHEN H M, et al.Preparation of Slow-Release Polylactic Acid Antibacterial Active Packaging Films and Its Application in Spinach Preservation[J]. Food and Bioprocess Technology, 2025, 18(2): 1346-1364.
[62] SHAHABI N, SOLEIMANI S, GHORBANI M.Investigating Functional Properties of Halloysite Nanotubes and Propolis Used in Reinforced Composite Film Based on Soy Protein/Basil Seed Gum for Food Packaging Application[J]. International Journal of Biological Macromolecules, 2023, 231: 123350.
[63] HU X, TIAN M Y, CHEN M M, et al.Humidity-Responsive Smart Active Chitosan/Poly(vinyl alcohol) Based Membrane with Cinnamaldehyde@halloysite Nanotubes for Strawberry Preservation[J]. International Journal of Biological Macromolecules, 2025, 314: 144344.