ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

Nanoprotective Layer-by-Layer Coatings with Epoxy Components for Enhancing Abrasion Resistance: Toward Robust Multimaterial Nanoscale Films

View Author Information
C.N.R.S., Institut Charles Sadron, 23 rue du Loess, F-67034 Strasbourg, France
Department of Chemistry, Quaid-i-Azam University, Islamabad - 45320, Pakistan
§ Université de Strasbourg, Faculté de Chimie, 1 rue Blaise Pascal, F-67008 Strasbourg, France
International Center for Frontier Research in Chemistry, 8 allée Gaspard Monge, F-67083 Strasbourg, France
*Address correspondence to [email protected]
Cite this: ACS Nano 2013, 7, 10, 9336–9344
Publication Date (Web):September 16, 2013
Copyright © 2013 American Chemical Society

Article Views





Read OnlinePDF (1 MB)
Supporting Info (1)»


Abstract Image

Layer-by-Layer (LbL) assembled films offer many interesting applications (e.g., in the field of nanoplasmonics), but are often mechanically feeble. The preparation of nanoprotective films of an oligomeric novolac epoxy resin with poly(ethyleneimine) using covalent LbL-assembly is described. The film growth is linear, and the thickness increment per layer pair is easily controlled by varying the polymer concentration and/or the adsorption times. The abrasion resistance of such cross-linked films was tested using a conventional rubbing machine and found to be greatly enhanced in comparison to that of classic LbL-films that are mostly assembled through electrostatic interactions. These robust LbL-films are then used to mechanically protect LbL-films that would completely be removed by a few rubbing cycles in the absence of a protective coating. A 45 nm thick LbL-film composed of gold nanoparticles and poly(allylamine hydrochloride) was chosen as an especially weak example for a functional multilayer system. The critical thickness for the protective LbL-coatings on top of the weak multilayer was determined to be about 6 layer pairs corresponding to about only 10 nm. At this thickness, the whole film withstands at least 25 abrasion cycles with a reduction of the total thickness of only about 2%.

Supporting Information

Jump To

UV–visible spectra for (PEI/CNER)n film build-up as a function of polymer concentration. This material is available free of charge via the Internet at

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

Cited By

This article is cited by 44 publications.

  1. Oyku Yildirimkaraman, Sezer Özenler, Ufuk Saim Gunay, Hakan Durmaz, Ümit Hakan Yıldız. Electroactive Nanogel Formation by Reactive Layer-by-Layer Assembly of Polyester and Branched Polyethylenimine via Aza-Michael Addition. Langmuir 2021, 37 (37) , 10902-10913.
  2. Kengo Manabe, Motomi Matsuda, Chiaki Nakamura, Keisuke Takahashi, Kyu-Hong Kyung, and Seimei Shiratori . Antifibrinogen, Antireflective, Antifogging Surfaces with Biocompatible Nano-Ordered Hierarchical Texture Fabricated by Layer-by-Layer Self-Assembly. Chemistry of Materials 2017, 29 (11) , 4745-4753.
  3. Xinglong Luan, Tao Huang, Yan Zhou, Qi An, Yue Wang, Yaling Wu, Xiangming Li, Haitao Li, Feng Shi, and Yihe Zhang . Controlled Interfacial Permeation, Nanostructure Formation, Catalytic Efficiency, Signal Enhancement Capability, and Cell Spreading by Adjusting Photochemical Cross-Linking Degrees of Layer-by-Layer Films. ACS Applied Materials & Interfaces 2016, 8 (49) , 34080-34088.
  4. David A. Hagen, Brendan Foster, Bart Stevens, and Jaime C. Grunlan . Shift-Time Polyelectrolyte Multilayer Assembly: Fast Film Growth and High Gas Barrier with Fewer Layers by Adjusting Deposition Time. ACS Macro Letters 2014, 3 (7) , 663-666.
  5. Sadia Batool, Wenwen Guo, Rohama Gill, Wang Xin, Yuan Hu. Chitin based multi-layered coatings with flame retardancy an approach to mimic nacre: Synthesis, characterization and mechanical properties. Carbohydrate Polymers 2022, 291 , 119488.
  6. Hebing Hu, Yun Meng, Jiarui Wang, Shancheng Wang, Tuan Duc Vu, Yi Long. Layer-by-layer self-assembled vanadium dioxide and its temperature-dependent light interference. Chemical Engineering Journal 2022, 431 , 133978.
  7. Wenyan Li, Xuejiao Lei, Hua Feng, Bingyun Li, Jiming Kong, Malcolm Xing. Layer-by-Layer Cell Encapsulation for Drug Delivery: The History, Technique Basis, and Applications. Pharmaceutics 2022, 14 (2) , 297.
  8. Li Chen, Gang Wu, Yin Huang, Changning Bai, Yuanlie Yu, Junyan Zhang. High Loading Capacity and Wear Resistance of Graphene Oxide/Organic Molecule Assembled Multilayer Film. Frontiers in Chemistry 2021, 9
  9. Ahed Almalla, Andreas Hertwig, Daniel Fischer, Ozlem Ozcan, Julia Witt. Development of layer‐by‐layer assembled thin coatings on aluminium alloy AA2024‐T3 for high resolution studies of local corrosion processes. Journal of Applied Polymer Science 2020, 137 (48) , 49826.
  10. Sadia Batool, Rohama Gill, Chao Ma, Gangireddy Chandra Sekhar Reddy, Wenwen Guo, Yuan Hu. Epoxy‐based multilayers for flame resistant flexible polyurethane foam (FPUF). Journal of Applied Polymer Science 2020, 137 (29) , 48890.
  11. Urvashi F. Gunputh, Huirong Le. A Review of In-Situ Grown Nanocomposite Coatings for Titanium Alloy Implants. Journal of Composites Science 2020, 4 (2) , 41.
  12. Hebing Hu, Shancheng Wang, Xueling Feng, Matthias Pauly, Gero Decher, Yi Long. In-plane aligned assemblies of 1D-nanoobjects: recent approaches and applications. Chemical Society Reviews 2020, 49 (2) , 509-553.
  13. Zhenlan Qin, Yanwei Zeng, Qianhui Hua, Qunjie Xu, Xixun Shen, Yulin Min. Synergistic effect of hydroxylated boron nitride and silane on corrosion resistance of aluminum alloy 5052. Journal of the Taiwan Institute of Chemical Engineers 2019, 100 , 285-294.
  14. Qi Xia, Shaofeng Pan, Yi Zhang, Qi An, Qian Zhang, Yihe Zhang. Preparation of Highly Loaded PAA/PAH Layer-by-layer Films by Combining Acid Transformation and Templating Methods. Chemical Research in Chinese Universities 2019, 35 (2) , 353-358.
  15. Ting Chen, Chaohua Peng, Cheng Liu, Conghui Yuan, Jing Hong, Guorong Chen, Yiting Xu, Lizong Dai. Modification of Epoxy Resin with a Phosphorus, Nitrogen, and Fluorine Containing Polymer to Improve the Flame Retardant and Hydrophobic Properties. Macromolecular Materials and Engineering 2019, 304 (3) , 1800498.
  16. Yihan Sun, Zhiguang Guo. Recent advances of bioinspired functional materials with specific wettability: from nature and beyond nature. Nanoscale Horizons 2019, 4 (1) , 52-76.
  17. Yanbao Guo, Deguo Wang, Siwei Zhang. Effect of heat treatment on the tribological behaviors of polyelectrolyte/Au nanoparticles composite films. Tribology International 2018, 126 , 249-257.
  18. Sadia Batool, Rohama Gill, Muhammad Arshad, Humaira Masood Siddiqi, Shahid Saeed Qureshi. Layer-by-layer fabrication of nacre inspired epoxy/MMT multilayered composites. Journal of Applied Polymer Science 2018, 135 (14) , 46079.
  19. S.N. Rao. Adsorption. 2018, 251-331.
  20. Qi An, Tao Huang, Feng Shi. Covalent layer-by-layer films: chemistry, design, and multidisciplinary applications. Chemical Society Reviews 2018, 47 (13) , 5061-5098.
  21. Sadia Batool, Anum Mahmood, Rohama Gill, Shahid Saeed Qureshi, Muhammad Mazhar, Mohamed Bououdina. Fabrication of covalently bonded nanostructured thin films of epoxy resin and polydimethylsiloxane for oil adsorption. Polymer Bulletin 2017, 74 (12) , 4827-4840.
  22. Jabal D. Thanki, Parsotam H. Parsania. Dynamic DSC curing kinetics and thermogravimetric study of epoxy resin of 9,9′-bis(4-hydroxyphenyl)anthrone-10. Journal of Thermal Analysis and Calorimetry 2017, 130 (3) , 2145-2156.
  23. Byoung Soo Kim, Hyun Jin Kim, Suyeong An, Sangwon Chi, Junseok Kim, Jonghwi Lee. Micro- and nano-porous surface patterns prepared by surface-confined directional melt crystallization of solvent. Journal of Crystal Growth 2017, 469 , 184-190.
  24. Xiaoxing Zhang, Ju Tang, Song Xiao, Cheng Pan. Application of Graphene Gas Sensors in Online Monitoring of SF6 Insulated Equipment. 2017
  25. Hai Hu, Yi He, Zhihang Long, Yingqing Zhan. Synergistic effect of functional carbon nanotubes and graphene oxide on the anti-corrosion performance of epoxy coating. Polymers for Advanced Technologies 2017, 28 (6) , 754-762.
  26. U. Gunputh, H. Le. Composite coatings for implants and tissue engineering scaffolds. 2017, 111-138.
  27. Joshua T. O’Neal, Matthew J. Bolen, Ethan Y. Dai, Jodie L. Lutkenhaus. Hydrogen-bonded polymer nanocomposites containing discrete layers of gold nanoparticles. Journal of Colloid and Interface Science 2017, 485 , 260-268.
  28. Keke Wu, Xiazhi Zhang, Wufeng Yang, Xiaoyan Liu, Yanpeng Jiao, Changren Zhou. Influence of layer-by-layer assembled electrospun poly (l-lactic acid) nanofiber mats on the bioactivity of endothelial cells. Applied Surface Science 2016, 390 , 838-846.
  29. Wenqi Yu, Jifang Fu, Liya Chen, Peisong Zong, Jintao Yin, Dapeng Shang, Qi Lu, Hua Chen, Liyi Shi. Enhanced thermal conductive property of epoxy composites by low mass fraction of organic–inorganic multilayer covalently grafted carbon nanotubes. Composites Science and Technology 2016, 125 , 90-99.
  30. Mingwei Tian, Xili Hu, Lijun Qu, Shifeng Zhu, Yaning Sun, Guangting Han. Versatile and ductile cotton fabric achieved via layer-by-layer self-assembly by consecutive adsorption of graphene doped PEDOT: PSS and chitosan. Carbon 2016, 96 , 1166-1174.
  31. Yuanyuan Zhang, Mary A. Arugula, Shannon T. Williams, Shelley D. Minteer, Aleksandr L. Simonian. Layer-by-Layer Assembly of Carbon Nanotubes Modified with Invertase/Glucose Dehydrogenase Cascade for Sucrose/O 2 Biofuel Cell. Journal of The Electrochemical Society 2016, 163 (6) , F449-F454.
  32. Xiaoxing Zhang, Lei Yu, Xiaoqing Wu, Weihua Hu. Experimental Sensing and Density Functional Theory Study of H 2 S and SOF 2 Adsorption on Au-Modified Graphene. Advanced Science 2015, 2 (11) , 1500101.
  33. Tommaso Nardi, Luis Pablo Canal, Michael Hausmann, Florian Dujonc, Véronique Michaud, Jan-Anders E. Månson, Yves Leterrier. Stress reduction mechanisms during photopolymerization of functionally graded polymer nanocomposite coatings. Progress in Organic Coatings 2015, 87 , 204-212.
  34. Tommaso Nardi, Chad Hammerquist, John A. Nairn, Ayat Karimi, Jan-Anders E. Månson, Yves Leterrier. Nanoindentation of Functionally Graded Polymer Nanocomposites: Assessment of the Strengthening Parameters through Experiments and Modeling. Frontiers in Materials 2015, 2
  35. Tarun Chand Vagvala, Gaurav Kapil, Shyam S. Pandey, Yuhei Ogomi, Shuzi Hayase. Nonisothermal curing kinetics of epoxy resin composite utilizing Ga (III) xanthate as a latent catalyst. Journal of Applied Polymer Science 2015, 132 (26) , n/a-n/a.
  36. Hanleem Lee, Guebum Han, Meeree Kim, Hyo-sok Ahn, Hyoyoung Lee. High Mechanical and Tribological Stability of an Elastic Ultrathin Overcoating Layer for Flexible Silver Nanowire Films. Advanced Materials 2015, 27 (13) , 2252-2259.
  37. Yan Hu, Kaiyong Cai. Polyelectrolyte Multilayer Film for the Regulation of Stem Cells in Orthopedic Field. 2015, 507-524.
  38. Zhaozhong Qiu, Rui Wang, Jinzhu Wu, Yushen Zhang, Yunfei Qu, Xiaohong Wu. Graphene oxide as a corrosion-inhibitive coating on magnesium alloys. RSC Advances 2015, 5 (55) , 44149-44159.
  39. Katsuhiko Sato, Mao Takahashi, Megumi Ito, Eiichi Abe, Jun-Ichi Anzai. Glucose-induced decomposition of layer-by-layer films composed of phenylboronic acid-bearing poly(allylamine) and poly(vinyl alcohol) under physiological conditions. Journal of Materials Chemistry B 2015, 3 (39) , 7796-7802.
  40. Steffi Sunny, Nicolas Vogel, Caitlin Howell, Thy L. Vu, Joanna Aizenberg. Lubricant‐Infused Nanoparticulate Coatings Assembled by Layer‐by‐Layer Deposition. Advanced Functional Materials 2014, 24 (42) , 6658-6667.
  41. João Borges, Luísa C. Rodrigues, Rui L. Reis, João F. Mano. Layer-by-Layer Assembly of Light-Responsive Polymeric Multilayer Systems. Advanced Functional Materials 2014, 24 (36) , 5624-5648.
  42. Weijiang Guan, Jun Lu, Wenjuan Zhou, Chao Lu. Aggregation-induced emission molecules in layered matrices for two-color luminescence films. Chem. Commun. 2014, 50 (80) , 11895-11898.
  43. Yunhe Dong, Fei Liu, Wenlong Yang, Jinghan Zhu, Jing Yu, Yanglong Hou. Layer-by-layer assembly of L1 0 -FePt nanoparticles with significant perpendicular magnetic anisotropy. CrystEngComm 2014, 16 (40) , 9430-9433.
  44. Tarun Chand Vagvala, Shyam Sudhir Pandey, Yuhei Ogomi, Shuzi Hayase. Gallium( iii ) xanthate as a novel thermal latent curing agent for an epoxy resin composite. RSC Adv. 2014, 4 (47) , 24658-24661.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Your Mendeley pairing has expired. Please reconnect