Chloride Ion Capture and Responsive Corrosion Inhibition Behavior of ZnAlCe-NO2 Hydrotalcite @ Silane Coating

doi:10.11902/1005.4537.2025.085

Journal of Chinese Society for Corrosion and protection

2026, Vol. 46

Issue (1): 207-219 DOI: 10.11902/1005.4537.2025.085

Current Issue | Archive | Adv Search

Chloride Ion Capture and Responsive Corrosion Inhibition Behavior of ZnAlCe-NO₂ Hydrotalcite @ Silane Coating

TAN Jingsha, GUO Yichao, CHEN Junlin, GAI Wenfeng, MENG Guozhe(

)

School of Chemical Engineering and Technology, Sun Yat-sen University, Zhuhai 519082, China

Cite this article:

TAN Jingsha, GUO Yichao, CHEN Junlin, GAI Wenfeng, MENG Guozhe. Chloride Ion Capture and Responsive Corrosion Inhibition Behavior of ZnAlCe-NO₂ Hydrotalcite @ Silane Coating. Journal of Chinese Society for Corrosion and protection, 2026, 46(1): 207-219.

Download:

HTML

PDF(12798KB)
Export: BibTeX | EndNote (RIS)

Abstract

The unique lamellar structure of cations and anions in hydrotalcite (LDH) endows the interlayer anions with the characteristic of easy ion exchange with the environment, making it an excellent inorganic nanocontainer. In this study, a corrosion inhibitor ZnAlCe-NO₂ LDH loaded with NO $2 -$ was prepared by one-step co-precipitation method and which then was added to the sol gel silane coating. It may be reasonably inferred that at defect sites of the coating Ce ions within the LDH lamellae may be response and release where local hydrolysis acidification environment has been generated during the coating service, which then act as a means to inhibit the corrosion of the substrate metal; Meanwhile, the NO $2 -$ of high energy state situated between the ZnAlCe-NO₂ LDH lamellae and will spontaneously exchange-react with the infiltrated chloride ions (Cl^-) in the coating, which result in not only capturing and fixing the free Cl^- in the LDH lamellar structure, but also releasing the pre-loaded corrosion inhibitor within the LDH lamellae so that to enhance the protective performance of the coating, just like a Chinese proverb “kill two birds with one stone”. Electrochemical tests in a 0.05 mol/L NaCl solution showed that ZnAlCe-NO₂ LDH had a corrosion inhibition efficiency of 97.57% for carbon steel. Compared with the blank sol gel coating, the corrosion protection performance of the sol gel coating doped with 2.5 mg/mL ZnAlCe-NO₂ LDH has been significantly improved.

Key words: hydrotalcite ion exchange corrosion inhibitor controlled release sol gel coating self repair

Received: 12 March 2025 32134.14.1005.4537.2025.085

ZTFLH:

TG174

Fund: National Natural Science Foundation of China(52171093);National Key Research and Development Program(2019YFE0111000)

	Service

	E-mail this article
	Add to citation manager
	E-mail Alert
	RSS
	（）
	Articles by authors
	TAN Jingsha
	GUO Yichao
	CHEN Junlin
	GAI Wenfeng
	MENG Guozhe

URL:

https://www.jcscp.org/EN/10.11902/1005.4537.2025.085 OR https://www.jcscp.org/EN/Y2026/V46/I1/207

Fig.1 Schematic illustration of the preparation of layered double hydroxide (LDH) and silane-based sol-gel coatings modified with NO $2 -$ -intercalated LDH

Fig.2 SEM images of ZnAl-LDH and ZnAlCe-NO₂ LDH, EDS spectra of ZnAlCe-NO₂ LDH (a), XPS spectra of different hydrotalcite samples (Zn 2p) (b), (Al 2p) (c), (N 1s) (d), (Ce 3d) (e) XRD images of different hydrotalcite samples (f), FT-IR figures (g), TG and DTG figures (h), Q235 carbon steel in blank solution and ZnAlCe-NO₂ added under different sodium chloride concentrations variation of corrosion potential (i) and low-frequency modulus (j) in LDH solution, chloride ion adsorption and corrosion inhibitor release curve (k) of ZnAlCe-NO₂ LDH hydrotalcite samples

Fig.3 Bode plots (a, b) and Nyquist plots (c) of carbon steel in ZnAlCe-NO₂ LDH-containing solution. Polarization curves of carbon steel after immersion in 0.05 mol/L NaCl blank solution and 0.05 mol/L NaCl solution containing ZnAlCe-NO₂ LDH for different durations: 24 h (d) and 48 h (e). Equivalent circuit models (a, b) for EIS fitting (f)

Table 1 Fitting parameters from EIS spectra of Q235 carbon steel soaked in NaCl mixed solution for different time

Fig.4 High-resolution micrographs of carbon steel after 24 h immersion in (a) 0.05 mol/L NaCl solution and (b) S/LDH-NO₂ solution. FT-IR spectrum (c) and XRD pattern (d) of carbon steel immersed in blank 0.05 mol/L NaCl solution and S/LDH-NO₂ solution for 24 h. XRD patterns of ZnAlCe-NO₂-LDH before and after ion exchange in NaCl solution (e)

Fig.5 SEM patterns (a), (b) of blank sol gel coating, ZnAlCe-NO₂ LDH-doped sol gel coating, cross-section and energy spectrum (c) of blank sol gel coating, ZnAlCe-NO2 LDH doped sol gel coating cross-section and energy spectrum (d)

Fig.6 Bode plots (a1-d1) and Nyquist plots (a2-d2) of different coatings after immersion in 0.05 mol/L NaCl solution for varying durations: SC (a1, a2), SC/NO₂-LDH₁ (b1, b2), SC/NO₂-LDH_2.5 (c1, c2), SC/NO₂-LDH₁₀ (d1, d2). Equivalent circuit Model a: R(Q(R(QR))) (e)

Fig.7 Variation curves of EIS-fitted parameters with immersion time: (a) coating resistance (R_cR_c), (b) coating capacitance (Q_cQ_c), (c) charge transfer resistance (R_ctR_ct). Low-frequency modulus variation curve (d) and open-circuit potential variation curve (e). Polarization curves of different coating samples after 6 h immersion in NaCl solution (f)

Fig.8 SKP (Scanning Kelvin Probe) maps of (a, b) blank silane coating (SC) and (c, d) sol-gel coating (SC/NO₂-LDH_2.5) measured after immersion in 0.05 mol/L NaCl solution for (a, c) 30 min and (b, d) 90 min

Fig.9 Corrosion protection mechanism of doped Sol-Gel coatings

[1]	You Y, Shang C J, Chen L, et al. Investigation on the crystallography of reverted structure and its effect on the properties of low carbon steel [J]. Mater. Sci. Eng., 2012, 546A: 111
[2]	Ali Gürten A, Keleş H, Bayol E, et al. The effect of temperature and concentration on the inhibition of acid corrosion of carbon steel by newly synthesized Schiff base [J]. J. Ind. Eng. Chem., 2015, 27: 68 doi: 10.1016/j.jiec.2014.11.046
[3]	Ataei S, Khorasani S N, Neisiany R E. Biofriendly vegetable oil healing agents used for developing self-healing coatings: a review [J]. Prog. Org. Coat., 2019, 129: 77
[4]	Zhang Y, Liu J H, Li Y D, et al. Enhancement of active anticorrosion via Ce-doped Zn-Al layered double hydroxides embedded in sol-gel coatings on aluminum alloy [J]. J. Wuhan Univ. Technol. Mater. Sci. Ed., 2017, 32: 1199 doi: 10.1007/s11595-017-1731-6
[5]	Karthik N, Lee Y R, Sethuraman M G. Hybrid sol-gel/thiourea binary coating for the mitigation of copper corrosion in neutral medium [J]. Prog. Org. Coat., 2017, 102: 259
[6]	Wu L K, Wu J J, Wu W Y, et al. Sol-gel-based coatings for oxidation protection of TiAl alloys [J]. J. Mater. Sci., 2020, 55: 6330 doi: 10.1007/s10853-020-04466-0
[7]	Chen H, Shen J, Deng J Z, et al. Sol-gel coatings with hydrothermal hydroxylation as pre-treatment for 2198-T851 corrosion protection performance [J]. App. Surf. Sci., 2020, 508: 145285 doi: 10.1016/j.apsusc.2020.145285
[8]	Akbarzadeh S, Paint Y, Olivier M G. A comparative study of different sol-gel coatings for sealing the plasma electrolytic oxidation (PEO) layer on AA2024 alloy [J]. Electrochim. Acta, 2023, 443: 141930 doi: 10.1016/j.electacta.2023.141930
[9]	Figueira R B. Hybrid sol-gel coatings for corrosion mitigation: A critical review [J]. Polymers, 2020, 12: 689 doi: 10.3390/polym12030689
[10]	Voevodin N N, Grebasch N T, Soto W S, et al. Potentiodynamic evaluation of sol-gel coatings with inorganic inhibitors [J]. Surf. Coat. Technol., 2001, 140: 24 doi: 10.1016/S0257-8972(01)00999-9
[11]	Zheludkevich M L, Serra R, Montemor M F, et al. Nanostructured sol-gel coatings doped with cerium nitrate as pre-treatments for AA2024-T3: Corrosion protection performance [J]. Electrochim. Acta, 2005, 51: 208 doi: 10.1016/j.electacta.2005.04.021
[12]	Liu Y H, Jin X H, Hu J M. Electrodeposited silica films post-treated with organosilane coupling agent as the pretreatment layers of organic coating system [J]. Corros. Sci., 2016, 106: 127 doi: 10.1016/j.corsci.2016.01.032
[13]	Hu C W, Li D F, Guo Y H, et al. Supermolecular layered double hydroxides [J]. Chin. Sci. Bull., 2001, 46: 1061 doi: 10.1007/BF02900678
[14]	Guo X X, Zhang F Z, Peng Q, et al. Layered double hydroxide/eggshell membrane: an inorganic biocomposite membrane as an efficient adsorbent for Cr(VI) removal [J]. Chem. Eng. J., 2011, 166: 81 doi: 10.1016/j.cej.2010.10.010
[15]	Mir Z M, Bastos A, Gomes C, et al. Numerical and experimental analysis of self-protection in reinforced concrete due to application of Mg-Al-NO₂ layered double hydroxides [J]. Adv. Eng. Mater., 2020, 22: 2000398 doi: 10.1002/adem.v22.11
[16]	Zheludkevich M L, Poznyak S K, Rodrigues L M, et al. Active protection coatings with layered double hydroxide nanocontainers of corrosion inhibitor [J]. Corros. Sci., 2010, 52: 602 doi: 10.1016/j.corsci.2009.10.020
[17]	Li W H, Liu A, Tian H W, et al. Controlled release of nitrate and molybdate intercalated in Zn-Al-layered double hydroxide nanocontainers towards marine anticorrosion applications [J]. Colloid Interface Sci. Commun., 2018, 24: 18 doi: 10.1016/j.colcom.2018.03.003
[18]	Alibakhshi E, Ghasemi E, Mahdavian M, et al. Fabrication and characterization of layered double hydroxide/silane nanocomposite coatings for protection of mild steel [J]. J. Taiwan Inst. Chem. Eng., 2017, 80: 924 doi: 10.1016/j.jtice.2017.08.015
[19]	Inayat A, Klumpp M, Schwieger W. The urea method for the direct synthesis of ZnAl layered double hydroxides with nitrate as the interlayer anion [J]. Appl. Clay. Sci., 2011, 51: 452 doi: 10.1016/j.clay.2011.01.008
[20]	Zhang Q, Zhang G J, Huang Y W, et al. Surface-modified LDH nanosheets with high dispersibility in oil for friction and wear reduction [J]. ACS Appl. Mater. Interfaces, 2024, 16: 5316 doi: 10.1021/acsami.3c17322
[21]	Yang M S, Gu L H, Yang B, et al. Antifouling composites with self-adaptive controlled release based on an active compound intercalated into layered double hydroxides [J]. Appl. Surf. Sci., 2017, 426: 185 doi: 10.1016/j.apsusc.2017.07.207
[22]	Roobottom H K, Jenkins H D B, Passmore J, et al. Thermochemical radii of complex ions [J]. J. Chem. Educ., 1999, 76: 1570 doi: 10.1021/ed076p1570
[23]	Ma G X, Xu J X, Han L, et al. Enhanced inhibition performance of NO 2 - intercalated MgAl-LDH modified with nano-SiO₂ on steel corrosion in simulated concrete pore solution [J]. Corros. Sci., 2022, 204: 110387 doi: 10.1016/j.corsci.2022.110387
[24]	Liu A, Tian H W, Li W H, et al. Delamination and self-assembly of layered double hydroxides for enhanced loading capacity and corrosion protection performance [J]. Appl. Surf. Sci., 2018, 462: 175 doi: 10.1016/j.apsusc.2018.08.109
[25]	Zuo J D, Wu B, Luo C Y, et al. Preparation of MgAl layered double hydroxides intercalated with nitrite ions and corrosion protection of steel bars in simulated carbonated concrete pore solution [J]. Corros. Sci., 2019, 152: 120 doi: 10.1016/j.corsci.2019.03.007
[26]	Carneiro J, Caetano A F, Kuznetsova A, et al. Polyelectrolyte-modified layered double hydroxide nanocontainers as vehicles for combined inhibitors [J]. RSC Adv., 2015, 5: 39916 doi: 10.1039/C5RA03741G
[27]	Cheng M, Liu J H, Liu Y Q, et al. Three birds with one stone: contemporaneously boosting passive, active and self-healing properties for long-term anticorrosion coatings [J]. Chem. Eng. J., 2023, 459: 141532 doi: 10.1016/j.cej.2023.141532
[28]	Bai Z H, Meng S, Cui Y X, et al. A stable anticorrosion coating with multifunctional linkage against seawater corrosion [J]. Composites, 2023, 259B: 110733
[29]	Liu S P, Zhang X F, Rao J S, et al. Ni-Co hydrotalcite modified diatom to achieve corrosion inhibition and Cl^- adsorption for long-term corrosion protection of steel [J]. Corros. Sci., 2023, 225: 111589 doi: 10.1016/j.corsci.2023.111589
[30]	Zhou Z Y, Pourhashem S, Wang Z Q, et al. Mxene structure: a key parameter in corrosion barrier performance of organic coatings [J]. J. Ind. Eng. Chem., 2022, 116: 310 doi: 10.1016/j.jiec.2022.09.021
[31]	Borisova D, Akçakayıran D, Schenderlein M, et al. Nanocontainer-based anticorrosive coatings: Effect of the container size on the self-healing performance [J]. Adv. Funct. Mater., 2013, 23: 3799 doi: 10.1002/adfm.v23.30
[32]	Zhang F, Pan J S, Claesson P M. Electrochemical and AFM studies of mussel adhesive protein (Mefp-1) as corrosion inhibitor for carbon steel [J]. Electrochim. Acta, 2011, 56: 1636 doi: 10.1016/j.electacta.2010.10.033
[33]	Mohamed A, Visco Jr D P, Bastidas D M. Effect of cations on the activity coefficient of NO 2 - /NO 3 - corrosion inhibitors in simulated concrete pore solution: an electrochemical thermodynamics study [J]. Corros. Sci., 2022, 206: 110476 doi: 10.1016/j.corsci.2022.110476
[34]	Zhang M, Xu F, Lin D, et al. A smart anti-corrosion coating based on triple functional fillers [J]. Chem. Eng. J., 2022, 446: 137078 doi: 10.1016/j.cej.2022.137078
[35]	Liu A, Tian H W, Li S C, et al. Bioinspired layered hybrid coatings with greatly enhanced barrier effect and active corrosion protection performance [J]. Prog. Org. Coat., 2021, 152: 106131
[36]	Tedim J, Kuznetsova A, Salak A N, et al. Zn-Al layered double hydroxides as chloride nanotraps in active protective coatings [J]. Corros. Sci., 2012, 55: 1 doi: 10.1016/j.corsci.2011.10.003
[37]	Chen H L, Li X J, Wei Y. Corrosion mechanism of carbon steel in chloride solution [J]. Corros. Prot., 2007, 28: 17
	陈惠玲, 李晓娟, 魏雨. 碳钢在含氯离子环境中腐蚀机理的研究 [J]. 腐蚀与防护, 2007, 28: 17
[38]	Ding C D, Tai Y, Wang D, et al. Superhydrophobic composite coating with active corrosion resistance for AZ31B magnesium alloy protection [J]. Chem. Eng. J., 2019, 357: 518 doi: 10.1016/j.cej.2018.09.133
[39]	Xu J H, Gao F, Wang H, et al. Organic/inorganic hybrid waterborne polyurethane coatings with self-healing properties for anticorrosion application [J]. Prog. Org. Coat., 2023, 174: 107244
[40]	Xie C, Jia Y, Xue M S, et al. Anti-corrosion and self-healing behaviors of waterborne polyurethane composite coatings enhanced via chitosan-modified graphene oxide and phosphate intercalated hydrotalcite [J]. Prog. Org. Coat., 2022, 168: 106881
[41]	Álvarez D, Collazo A, Hernández M, et al. Characterization of hybrid sol-gel coatings doped with hydrotalcite-like compounds to improve corrosion resistance of AA2024-T3 alloys [J]. Prog. Org. Coat., 2010, 68: 91
[42]	Chen C L, He Y, Xiao G Q, et al. Synergistic effect of graphene oxide@phosphate-intercalated hydrotalcite for improved anti-corrosion and self-healable protection of waterborne epoxy coating in salt environments [J]. J. Mater. Chem., 2019, 7C: 2318
[43]	Wang Z H, Wang C J, Fan W H, et al. A novel fly ash bifunctional filler for epoxy coating with long-term anti-corrosion performance under harsh conditions [J]. Chem. Eng. J., 2022, 430: 133164 doi: 10.1016/j.cej.2021.133164
[44]	Yasakau K A, Kuznetsova A, Kallip S, et al. A novel bilayer system comprising LDH conversion layer and sol-gel coating for active corrosion protection of AA2024 [J]. Corros. Sci., 2018, 143: 299 doi: 10.1016/j.corsci.2018.08.039
[45]	Wang Y B, Zhang Y S, Zhou B T, et al. In-situ observation of the growth behavior of ZnAl layered double hydroxide film using EQCM [J]. Mater. Des., 2019
[46]	Wang Y, Wei D B, Yu J, et al. Effects of Al₂O₃ Nano-additive on performance of micro-arc oxidation coatings formed on AZ91D Mg alloy [J]. J. Mater. Sci. Technol., 2014, 30: 984 doi: 10.1016/j.jmst.2014.03.006
[47]	Ganborena L, Vega J M, Özkaya B, et al. AN SKP and EIS study of microporous nickel-chromium coatings in copper containing electrolytes [J]. Electrochim. Acta, 2019, 318: 683 doi: 10.1016/j.electacta.2019.05.108
[48]	Zhang Y G, Chen Y L, Bian G X, et al. Electrochemical behavior and corrosion mechanism of anodized 7B04 aluminum alloy in acid NaCl environments [J]. J. Alloy. Compd., 2021, 886: 161231 doi: 10.1016/j.jallcom.2021.161231

[1]	YANG Shengjie, GAO Yan, GAO Xu, ZHAO Peng, WU Wei, YU Jinshan, ZHANG Junxi. Bifunctional Calcium Aluminate Modified Silica Sol Coating for Reinforced Bar[J]. 中国腐蚀与防护学报, 2024, 44(2): 405-412.
[2]	ZHAO Peng, HAO Chunyan, YANG Shengjie, YU Jinshan, WU Shuang, YU Ben, ZHANG Junxi. Silica Sol Coating Modified by Bifunctional Titanium Phosphate for Reinforce Bars[J]. 中国腐蚀与防护学报, 2024, 44(2): 413-421.
[3]	Xiankang ZHONG,Junying HU. Corrosion Behavior of X65 Carbon Steel in CO₂Containing Liquids with Constant pH and Ferrous Ion Concentration[J]. 中国腐蚀与防护学报, 2018, 38(6): 573-578.

No Suggested Reading articles found!

Viewed

Full text

Abstract

Cited

Shared

Discussed