Preparation and Corrosion Resistance Mechanism of Magnesium-Lithium Alloy Micro-arc Oxidation/Quaternary LDHs@GO Self-healing Composite Film

doi:10.1007/s40195-025-01892-4

Abstract

Abstract:

Micro-arc oxidation (MAO) film can only provide common mechanical protection for magnesium (Mg)-lithium (Li) alloys. These alloys are susceptible to severe localized corrosion, if the MAO film is disrupted. This work reports the successful hydrothermal preparation of a MgLiAlCe-LDHs@GO film on a MAO-coated Mg-Li alloy following Ce confinement. The graphene oxide (GO) sheet increased the diffusion path of the corrosive media, and the addition of rare-earth cerium ions (Ce³⁺) endowed the film with a certain self-healing ability, which significantly improved the corrosion resistance of the film, and the corrosion current density (i_corr) reached 3.27 × 10⁻⁸ A cm⁻². The synergistic action of GO and Ce³⁺ can achieve long-term corrosion protection for the substrate. The corrosion resistance mechanism of MgLiAlCe-LDHs@GO film was discussed by the scanning vibration electrode technique (SVET).

Key words: Micro-arc oxidation (MAO), Magnesium-lithium alloy, Quaternary layer doubled hydroxides (LDHs), Graphene oxide, Corrosion mechanism

Zhenzhen Tian, Rongqian Wu, Fubing Yu, Yan Zhou, Wenhui Yao, Yuan Yuan, Zhihui Xie, Yanlong Ma, Atrens Andrej, Liang Wu. Preparation and Corrosion Resistance Mechanism of Magnesium-Lithium Alloy Micro-arc Oxidation/Quaternary LDHs@GO Self-healing Composite Film[J]. Acta Metallurgica Sinica (English Letters), 2025, 38(9): 1545-1558.

Figures/Tables 16

Table 1 Chemical composition of the Mg-8Li alloy (wt%)

Li	Si	Ca	Ce	Ag	Mn	Zn	Mg
7.97	0.17	0.01	0.01	0.01	0.01	0.01	Bal.

Fig. 1 XRD spectra of MgLiAl-LDHs, MgLiAlCe-LDHs, MgLiAl-LDHs@GO, MgLiAlCe-LDHs@GO films samples and Mg-Li alloy

Fig. 2 SEM and EDS spectra of the surface of the films: a1-a3 MgLiAl-LDHs, b1-b3 MgLiAl-LDHs@GO, c1-c3 MgLiAlCe-LDHs, d1-d3 MgLiAlCe-LDHs@GO

Fig. 3 Cross-sectional SEM images and EDS element diagrams of the four films: a MgLiAl-LDHs, b MgLiAl-LDHs@GO, c MgLiAlCe-LDHs, d MgLiAlCe-LDHs@GO

Fig. 4 FT-IR of MgLiAl-LDHs film, MgLiAl-LDHs@GO film, MgLiAlCe-LDHs film, MgLiAlCe-LDHs@GO film

Fig. 5 XPS spectra of MgLiAl-LDHs film, MgLiAl-LDHs@GO film, MgLiAlCe-LDHs film, and MgLiAlCe-LDHs@GO film: a Al 2p, b C 1s, c O 1s, d Ce 3d

Fig. 6 Tafel curves for different samples

Table 2 Electrochemical parameters of different samples

Sample	E_corr (V_SCE)	i_corr (A cm⁻²)
Mg-Li	− 1.626 ± 0.11	(2.24 ± 0.17) × 10⁻⁵
MgLiAl-LDHs	− 1.56 ± 0.13	(1.55 ± 0.21) × 10⁻⁶
MgLiAl-LDHs@GO	− 1.49 ± 0.15	(5.72 ± 0.15) × 10⁻⁷
MgLiAlCe-LDHs	− 1.17 ± 0.10	(2.58 ± 0.13) × 10⁻⁷
MgLiAlCe-LDHs@GO	− 0.58 ± 0.17	(3.27 ± 0.18) × 10⁻⁸

Fig. 7 a Impedance-frequency curve, b phase angle-frequency curve, and c EIS fitting equivalent circuit of different films immersed for 30 min

Table 3 Fitted parameters for the EIS data of Fig. 7

Sample	Q_out (S sⁿ cm⁻²)	n₁	R_out (Ω cm²)	Q_in (S sⁿ cm⁻²)	n₂	R_in (Ω cm²)	Q_dl (S sⁿ cm⁻²)	n₃	R_ct (Ω cm²)	χ² (10⁻³)
MgLiAl-LDHs	5.4 × 10⁻⁵	0.9	9.3 × 10³	2.5 × 10⁻⁵	0.7	3.0 × 10³	2.7 × 10⁻³	0.9	2.3 × 10³	0.3
MgLiAl-LDHs@GO	3.4 × 10⁻⁶	0.5	1.3 × 10³	1.3 × 10⁻⁵	0.7	4.4 × 10³	2.7 × 10⁻⁵	0.8	5.6 × 10³	4
MgLiAlCe-LDHs	1.6 × 10⁻⁷	0.7	2.1 × 10²	1.5 × 10⁻⁶	0.7	3.6 × 10⁴	3.3 × 10⁻⁶	0.8	7.8 × 10³	0.5
MgLiAlCe-LDHs@GO	6.4 × 10⁻⁷	0.9	1.4 × 10²	2.4 × 10⁻⁶	0.3	1.1 × 10⁵	1.6 × 10⁻⁶	0.9	3.2 × 10⁴	1.7

Table 4 Fitted parameters for the EIS data of Fig. 8

Sample	Q_out (S sⁿ cm⁻²)	n₁	R_out (Ω cm²)	Q_in (S sⁿ cm⁻²)	n₂	R_in (Ω cm²)	Q_dl (S sⁿ cm⁻²)	n₃	R_ct (Ω cm²)	χ² (10⁻³)
MgLiAl-LDHs	3.3 × 10⁻⁵	0.7	2.7 × 10³	1.2 × 10⁻³	0.9	6.3 × 10²	1.2 × 10⁻²	0.9	1.2 × 10²	1.8
MgLiAl-LDHs@GO	9.1 × 10⁻⁶	0.6	4.0 × 10²	4.5 × 10⁻⁶	0.7	5.9 × 10³	2.5 × 10⁻⁴	0.8	1.2 × 10³	4.2
MgLiAlCe-LDHs	2.1 × 10⁻⁵	0.8	3.2 × 10³	1.5 × 10⁻³	0.9	3.9 × 10²	2.9 × 10⁻²	0.5	1.4 × 10³	6.8
MgLiAlCe-LDHs@GO	9.8 × 10⁻⁶	0.6	1.6 × 10²	5.8 × 10⁻⁷	0.9	2.0 × 10³	1.5 × 10⁻⁵	0.7	8.9 × 10³	3.3

Fig. 8 a Impedance-frequency curve, b phase angle-frequency curve, and c EIS fitting equivalent circuits of different films immersed for 10 days

Fig. 9 Hydrogen evolution of different samples after immersion in 3.5 wt% NaCl solution

Fig. 10 Surface morphology of scratches on a1-a3 Mg-Li alloy, b1-b3 MgLiAl-LDHs film, c1-c3 MgLiAl-LDHs@GO film, d1-d3 MgLiAlCe-LDHs film, e1-e3 MgLiAlCe-LDHs@GO film before and after a 24-h immersion in 3.5 wt% NaCl solution

Fig. 11 SVET three-dimensional potential gradient distribution of scratches film samples before and after immersing in a 3.5 wt% NaCl solution for 24 h: a1, a2 MgLiAl-LDHs film, b1, b2 MgLiAl-LDHs@GO film, c1, c2 MgLiAlCe-LDHs film, d1, d2 MgLiAlCe-LDHs@GO film

Fig. 12 Corrosion resistance mechanism representation of the MgLiAlCe-LDHs@GO film

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