Exfoliation Corrosion of As-Extruded Mg-1Li-1Ca: the Influence of the Superficial Layer

doi:10.1007/s40195-024-01708-x

Abstract

Abstract:

Exfoliation corrosion (EFC) has rarely been reported for wrought magnesium alloys. Enhanced EFC of the as-extruded Mg-1Li-1Ca alloy was observed after the removal of outermost fine-grained skins. The microstructure and corrosion products were investigated using optical microscopy, scanning electron microscopy, electron backscattered diffraction, X-ray diffraction, and Fourier transform infrared spectrometry. The corrosion behavior was analyzed using electrochemical polarization, electrochemical impedance spectroscopy, and scanning Kelvin probe techniques. The results indicated that the surface of Mg-1Li-1Ca, with the superficial layer removed, was more susceptible to EFC. A linear correlation between grain boundary density and corrosion resistance was established. Additionally, the influence of factors such as grain size, intermetallic compounds, different alloy surfaces, and corrosion products on EFC were discussed, and the corresponding EFC mechanism was clarified.

Key words: Magnesium alloys, Exfoliation corrosion, Microstructure, Intermetallic compound, Metamorphic skin

Ze-Song Wei, Zi-You Ding, Lei Cai, Shao-Xia Ma, Dong-Qing Zhao, Lan-Yue Cui, Cheng-Bao Liu, Yuan-Sheng Yang, Yuan-Ding Huang, Rong-Chang Zeng. Exfoliation Corrosion of As-Extruded Mg-1Li-1Ca: the Influence of the Superficial Layer[J]. Acta Metallurgica Sinica (English Letters), 2024, 37(8): 1339-1353.

Figures/Tables 15

Fig. 1 Shape of the extruded state Mg-1Li-1Ca sample

Fig. 2 Optical micrographs of as-extruded Mg-1Li-1Ca alloy: a TS, b SS, c, d LS

Fig. 3 a-c Orientation micrographs for TS, LS and SS, respectively; d-f KAM of TS, LS and SS, respectively; g grain distribution histograms; and h-j pole figures for TS, LS and SS, respectively, for the as-extruded Mg-1Li-1Ca alloy from the EBSD analysis

Table 1 Area fractions of specific misorientations with different ranges

Specimen	Area fraction of localized orientation difference (%)
Specimen	0°-1°	1°-2°	2°-3°	3°-4°	> 4°
TS	45.30	46.10	4.90	0.07	2.90
SS	43.90	48.70	6.00	0.08	0.05
LS	35.70	53.50	8.40	1.20	1.30

Fig. 4 a Curves of OCP versus immersion time, b polarization curves of as-extruded Mg-1Li-1Ca alloy in 3.5 wt% NaCl aqueous solution

Table 2 Fitting parameters of polarization curves

Sections of specimen	E_corr (V_SCE)	i_corr (A cm⁻²)	b_a (mV)	b_c (mV)	R_p (Ω cm²)	Chi-square
TS	−1.46	1.21 × 10^-5	177.80	219.99	3538.54	1.32
SS	−1.44	2.39 × 10^-4	105.93	209.32	127.73	5.19
LS	−1.39	2.06 × 10^-5	177.85	128.27	1567.09	4.78

Fig. 5 Occurrence of EFC of as-extruded Mg-1Li-1Ca immersed in 3.5 wt% NaCl aqueous solution: a 1 day, b, c 3 day; d, e 6 day; f 8 day; g, h 12 day; i-k 17 day; l, m 20 day

Fig. 6 As-extruded Mg-1Li-1Ca immersed in 3.5 wt% aqueous solution for 8 days: a OM graph, b, c SEM images and responding EDS mapping

Fig. 7 a XRD patterns of matrix and corrosion products, b FT-IR spectrums of (I) corrosion products in solution and (II) corrosion precipitations debris

Fig. 8 a Relationship between grain size and current density, b relationship between density of HAGBs and current density of as-extruded Mg-1Li-1Ca alloy

Fig. 9 Surface Volta potential mappings of a TS, b LS, c SS. The red areas correspond to higher potential, they usually act as cathodes, the blue area (usually Mg2Ca in this work) does the opposite. (Color figure online)

Fig. 10 SEM micrograph of fibrous texture and corrosion cracks after immersion test and etching

Fig. 11 a SEM images of corrosion debris of as-extruded Mg-1Li-1Ca alloy, b high magnification of white square frame in panel a with EDS mapping results. (Color figure online)

Fig. 12 Cross-sectional morphologies of as-extruded Mg-1Li-1Ca alloy immersed in 3.5 wt% NaCl solution for 15d: a OM graph, b, c high magnification of white square frame in panel, d selected areas SEM-BSE images, e, f high magnification images with EDS elemental mapping. (Color figure online)

Fig. 13 Schematic illustrations of EFC mechanism. Oxide a wedges and b cracks the grain boundaries leading to EFC corrosion. Corrosion occurring on c SS containing the superficial layer and d SS without the superficial layer

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