Lignin/graphene oxide composite coating loaded with zinc ions and its photothermal conversion and self-healing anticorrosion properties

Abstract

At present, using biomass materials to modify graphene oxide (GO) to enhance the anticorrosion performance of coatings meets the requirements of future sustainable development. In order to endow lignin/GO coatings with self-healing function to reduce maintenance costs and avoid accidents caused by material corrosion failure, this work utilized electrostatic interactions to load zinc ions onto lignin/GO (Zn@LGO). Experimental results indicated that the cured coating exhibited both self-healing anticorrosion and photothermal conversion properties. When the content of Zn@LGO was 0.4 wt%, the surface temperature of the cured coating rose to 139.2 °C after 180 s of near-infrared radiation. The cured coating was left for 100 days in salt water, the Z_0.01Hz value of coating VER-3 was up to 1.3 × 10⁹ Ω cm², which was two orders of magnitude higher than that of pure resin coating, and fewer corrosion products were observed on the metal surface. The scratch test showed that the damaged coating was soaked in 3.5 wt% sodium chloride for 72 h; the charge transfer impedance of coating VER-3 was 2.61 × 10⁴ Ω cm², which was one order of magnitude higher than that of pure resin coating. This was mainly because during metal corrosion, the hydroxide generated by the combination of hydroxide ions at the cathode and zinc ions covered the damaged area of cured coating, hindering the penetration of the corrosive medium. All in all, this research promoted the application of lignin, and also provided a reference for the design of composite coatings with both photothermal conversion and self-healing anticorrosion properties.

Keywords

Self-healing / microstructure / anticorrosive / coating / graphene oxide / lignin

References

[1] Zhu X,Cheng L,Zhao H.Self-alignment of cationic graphene oxide nanosheets for anticorrosive reinforcement of epoxy coatings.Chem Eng J2020;389:124435

[2] Mohammadkhani R,Saadatmandi S.Designing a dual-functional epoxy composite system with self-healing/barrier anti-corrosion performance using graphene oxide nano-scale platforms decorated with zinc doped-conductive polypyrrole nanoparticles with great environmental stability and non-toxicity.Chem Eng J2020;382:122819

[3] Zafar S,Shakoor RA.Silane functionalization of titania-graphene oxide nanocomposite for superior anticorrosion polyurethane coatings on steel.Colloid Surface A2024;703:135434

[4] Jena G.A review on recent advances in graphene oxide-based composite coatings for anticorrosion applications.Prog Org Coat2022;173:107208

[5] Wu Y,Sun Y,Wang L.2D nanomaterials reinforced organic coatings for marine corrosion protection: state of the art, challenges, and future prospectives.Adv Mater2024;36:e2312460

[6] Ding X,Xu X,Xu X.A novel epoxy resin composite coating containing polyaniline modified GO with triple anti-corrosion effects of barrier, passivation and corrosion inhibition.Prog Org Coat2024;194:108564

[7] Rabchinskii MK,Besedina NA.Guiding graphene derivatization for covalent immobilization of aptamers.Carbon2022;196:264-79

[8] Yang Z,Yuwen C.Preparation and performance studies of modified graphene oxide/polyaniline composite anticorrosive coatings.Prog Org Coat2024;197:108855

[9] Li X,Liu J.Bi-functional epoxy coating with long-term protection for Q235 steel prepared by incorporating melamine-grafted and carbon-black-modified graphene oxide.Surf Coat Technol2024;485:130883

[10] Ge S,Peng W.A comprehensive review of covalent organic frameworks (COFs) and their derivatives in environmental pollution control.Chem Soc Rev2024;53:11259-302

[11] Cao Y,Zheng B.Synthesis of lignin-based polyols via thiol-ene chemistry for high-performance polyurethane anticorrosive coating.Compos Part B Eng2020;200:108295

[12] Shi Y,Ge S.Advanced functional electromagnetic shielding materials: a review based on micro-nano structure interface control of biomass cell walls.Nanomicro Lett2024;17:3 PMCID:PMC11415337

[13] Wang J,Shi X,Huang Y.Unveiling the potential of dual-extrinsic/intrinsic self-healing lignin-based coatings for anticorrosion applications.Int J Biol Macromol2025;285:138073

[14] Xu CA,Tong Z.Mimosa inspired intelligent anti-corrosive composite coating by incorporating lignin and pyridine derivatives grafted graphene oxide.Chem Eng J2024;483:149316

[15] Wang S,Shi J.Green synthesis of graphene with the assistance of modified lignin and its application in anticorrosive waterborne epoxy coatings.Appl Surf Sci2019;484:759-70

[16] Yu X,Chen H.Superhydrophobic anticorrosion coating with active protection effect: graphene oxide-loaded inorganic/organic corrosion inhibitor for magnesium alloys.Surf Coat Technol2024;480:130586

[17] Ma Y,Zhou H.Superior anti-corrosion and self-healing bi-functional polymer composite coatings with polydopamine modified mesoporous silica/graphene oxide.J Mater Sci Technol2021;95:95-104

[18] Habibiyan A,Mahdavian M,Kasaeian M.Rational assembly of mussel-inspired polydopamine (PDA)-Zn (II) complex nanospheres on graphene oxide framework tailored for robust self-healing anti-corrosion coatings application.Chem Eng J2020;391:123630

[19] Yimyai T,Rohwerder M.Corrosion-responsive self-healing coatings.Adv Mater2023;35:e2300101

[20] Gu F,Yuan Y.External field-responsive ternary non-noble metal oxygen electrocatalyst for rechargeable zinc-air batteries.Adv Mater2024;36:e2313096

[21] Xu CA,Li X.Vanillin and organosilicon functionalized graphene oxide modified ester resin composite coatings with excellent anti-corrosion properties.Prog Org Coat2023;183:107804

[22] Luo ZG,Wang H.Modified nano-lignin as a novel biomass-derived corrosion inhibitor for enhanced corrosion resistance of carbon steel.Corros Sci2024;227:111705

[23] Sun W,Zhao L.The waterborne epoxy composite coatings with modified graphene oxide nanosheet supported zinc ion and its self-healing anticorrosion properties.Prog Org Coat2023;182:107609

[24] Rabchinskii MK,Brzhezinskaya M.Rationalizing graphene-ZnO composites for gas sensing via functionalization with amines.Nanomaterials2024;14:735 PMCID:PMC11085583

[25] Fu X,Fan Y.Anticorrosion coating with near-infrared light triggered precisely controllable self-healing performances.J Colloid Interface Sci2025;683:587-99

[26] Ding J,Zhou M,Yu H.Super-anticorrosive inverse nacre-like graphene-epoxy composite coating.Carbon2021;181:204-11

[27] Wang X,Nayanathara RMO.Anticorrosive epoxy coatings from direct epoxidation of bioethanol fractionated lignin.Int J Biol Macromol2022;221:268-77

[28] Zhang C,Liu C.Effect of covalent organic framework modified graphene oxide on anticorrosion and self-healing properties of epoxy resin coatings.J Colloid Interface Sci2022;608:1025-39

[29] Lei Y,Liu Q.Nacre-mimetic strategy to fabricate waterborne FrGO/Zn/epoxy coatings with dual corrosion protection.ACS Appl Mater Interfaces2023;15:28570-80

[30] Zhu Q,Liu X.Synergistic effect of polypyrrole functionalized graphene oxide and zinc phosphate for enhanced anticorrosion performance of epoxy coatings.Compos Part A Appl Sci Manuf2020;130:105752

[31] Li F,Chen K.Improvement in adhesion and corrosion resistance of Ce-based coating on micro-arc oxidized AZ31B Mg alloy via employing graphene oxide as an effective interlayer.Mater Today Commun2024;40:109862