Structure- and Corrosion Resistance-evolution of Cr2O3 Passivation Film on Tinplate Surface in Neutral NaCl- and Acidic NaCl + Na2SO3-solution

doi:10.11902/1005.4537.2025.185

Journal of Chinese Society for Corrosion and protection

2026, Vol. 46

Issue (3): 756-766 DOI: 10.11902/1005.4537.2025.185

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Structure- and Corrosion Resistance-evolution of Cr₂O₃ Passivation Film on Tinplate Surface in Neutral NaCl- and Acidic NaCl + Na₂SO₃-solution

LIU Zhuang¹, QIAO Chuang², JIANG Jinli³, CHE Xin¹(

), DAI Chunli⁴, SHEN Yong⁴, HAO Long²(

)

^1.School of Materials Science and Engineering, Shenyang University of Technology, Shenyang 110870, China
^2.Materials Corrosion and Protection Center, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
^3.Lingyuan Iron and Steel Co. Ltd., Lingyuan 122500, China
^4.Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

Cite this article:

LIU Zhuang, QIAO Chuang, JIANG Jinli, CHE Xin, DAI Chunli, SHEN Yong, HAO Long. Structure- and Corrosion Resistance-evolution of Cr₂O₃ Passivation Film on Tinplate Surface in Neutral NaCl- and Acidic NaCl + Na₂SO₃-solution. Journal of Chinese Society for Corrosion and protection, 2026, 46(3): 756-766.

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Abstract

With the continuous improvement of the tin plating process for cold rolled steel plates, the amount of tin deposition on the tinplate surface has decreased in contrast to the traditional ones. This will directly affect the quality of the surface passivation film formed after the subsequent passivation treatment. Hence, it has been observed currently that corrosion troubles gradually occur during storage and transportation of tin-coated plates. Clearly, changes in the structure and corrosion characteristics of the surface passivation film will determine the corrosion behavior of the tinplate. Herein, the surface structure- and the corrosion performance-evolution of the surface passivation film on the tinplate in neutral NaCl solution and acidic NaCl + Na₂SO₃ solution was assessed by means of electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS). The results indicate that the as-received surface passivation film presents characteristics of "double-layered structure" with an outer layer rich in Cr and Sn oxides, while the inner layer is rich in Sn oxides. In addition, the EIS response of the tinplate in NaCl solution exhibits two time-constants characteristics, corresponding to the bi-layered structure of the passivation film. But the observed two time-constants locating at the low-frequency domain and high-frequency domain in NaCl + Na₂SO₃ solution are derived from the residual film layer/newly formed corrosion product layer and from the double layer at electrolyte/tinplate interface, respectively. Furthermore, the corrosion resistance of tinplate in NaCl solution is relatively high, and the surface passivation film thickness remains basically unchanged. However, in NaCl + Na₂SO₃ solution, the surface passivation film rapidly dissolves and thus the corrosion resistance decreases sharply. Therefore, the passivation film dissolution in acidic environment is the main reason for its reduced corrosion resistance. It follows that the EIS technique can effectively characterize and elucidate the structure of the passivation film on the tinplate surface and the evolution mechanism of its corrosion.

Key words: tinplate Cr₂O₃passivation film EIS corrosion resistance film structure

Received: 17 June 2025 32134.14.1005.4537.2025.185

ZTFLH:

TG172

Fund: National Natural Science Foundation of China(52401126);Liaoning Natural Science Foundation Program(2025-BS-0164)

Corresponding Authors: HAO Long, E-mail: lhao@imr.ac.cn;
CHE Xin, E-mail: xiaoxin2004068@163.com

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	LIU Zhuang
	QIAO Chuang
	JIANG Jinli
	CHE Xin
	DAI Chunli
	SHEN Yong
	HAO Long

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https://www.jcscp.org/EN/10.11902/1005.4537.2025.185 OR https://www.jcscp.org/EN/Y2026/V46/I3/756

Fig.1 Schematical diagram illustrating the cyclic EIS measurements^[25]

Fig.2 Composition and structure investigations on the passive film on as-received tinplate: (a) ToF-SIMS spetra, (b) EIS spectra

Fig.3 EIS evolutions of the passive film on tinplate immersed in different corrosive electrolytes. (a) 3.5% (mass fraction) NaCl electrolyte with pH ≈ 7.0, (b) 3.5% (mass fraction) NaCl + 0.1% (mass fraction) Na₂SO₃ electrolyte with pH ≈ 4.0

Fig.4 OCP (a) and |Z|_{0.01 Hz} (b) evolution of tinplate sample during immersion in different corrosive electrolytes

Fig.5 Electrolyte resistance (R_s) correction and complex capacitance conversion of the EIS data: (a) R_s correction of EIS data obtained in NaCl electrolyte, (b) R_s correction of EIS data obtained in NaCl + Na₂SO₃ electrolyte, (c) the complex capacitance conversion of the EIS data after R_scorrection

Fig.6 Equivalent circuits employed to fit the EIS data obtained in NaCl (a) and NaCl + Na₂SO₃ (b) electrolyte

Table 1 Electrical parameters obtained from fitting the EIS data in Fig.3a1 and a2

Fig.7 Thickness evolution of passive film on tinplate during immersion in different electrolyte

Table 2 Electrical parameter obtained from fitting the EIS data in Fig.3b1, b2

Fig.8 Deconvolutions of high-resolution spectra obtained from tinplate sample after immersion in NaCl electrolyte for 10 h: (a) Sn 3d_5/2, (b) Cr 2p, (c) O 1s

Fig.9 Deconvolutions of high-resolution spectra obtained from tinplate sample after immersion in NaCl + Na₂SO₃ electrolyte for 10 h: (a) Sn 3d_5/2, (b) Cr 2p, (c) O 1s

Table 3 Fitting results of the XPS spectra measured on tinplate after immersion in different corrosive solutions^[31,34,35]

Fig.10 Potential E-pH diagrams illustrate the stability of Sn-based (a) and Cr-based oxides (b)

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