Self-catalytic degradation of iron-bearing chemical conversion coating on magnesium alloys ---- Influence of Fe content

doi:10.1007/s11706-020-0512-x

Front. Mater. Sci.

2020, Vol. 14

Issue (3) : 296-313 https://doi.org/10.1007/s11706-020-0512-x

RESEARCH ARTICLE

Self-catalytic degradation of iron-bearing chemical conversion coating on magnesium alloys ---- Influence of Fe content

Zheng-Zheng YIN¹, Wei HUANG¹, Xiang SONG¹, Qiang ZHANG¹, Rong-Chang ZENG^1,²(

)

¹. Corrosion Laboratory for Light Metals, College of Materials Science and Engineering, Shandong University of Science and Technology, Qingdao 266590, China
². School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450002, China

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Abstract

A number of industrial and biomedical fields, such as hydraulic fracturing balls for gas and petroleum exploitation and implant materials, require Mg alloys with rapid dissolution. An iron-bearing phosphate chemical conversion (PCC) coating with self-catalytic degradation function was fabricated on the Mg alloy AZ31. Surface morphologies, chemical compositions and degradation behaviors of the PCC coating were investigated through FE-SEM, XPS, XRD, FTIR, electrochemical and hydrogen evolution tests. Results indicated that the PCC coating was characterized by iron, its phosphates and hydroxides, amorphous Mg(OH)₂ and Mg₃₋_n(H_nPO₄)₂. The self-catalytic degradation effects were predominately concerned with the Fe concentration, chemical composition and microstructure of the PCC coating, which were ascribed to the galvanic corrosion between Fe in the PCC coating and the Mg substrate. The coating with higher Fe content and porous microstructure exhibited a higher degradation rate than that of the AZ31 substrate, while the coating with a trace of Fe and compact surface disclosed a slightly enhanced corrosion resistance for the AZ31 substrate.

Keywords magnesium alloy iron-bearing chemical conversion coating self-catalytic degradation galvanic corrosion

Corresponding Author(s): Rong-Chang ZENG

Online First Date: 31 July 2020 Issue Date: 10 September 2020

Cite this article:

Zheng-Zheng YIN,Wei HUANG,Xiang SONG, et al. Self-catalytic degradation of iron-bearing chemical conversion coating on magnesium alloys ---- Influence of Fe content[J]. Front. Mater. Sci., 2020, 14(3): 296-313.

URL:

https://academic.hep.com.cn/foms/EN/10.1007/s11706-020-0512-x
https://academic.hep.com.cn/foms/EN/Y2020/V14/I3/296

Fig.1 Thermo-equilibrium predominance area diagram for Fe²⁺ ions calculated using the MEDUSA software package at c(

P O 4 3 −

) = 0.1 mol·L⁻¹, c(Fe²⁺) from 10⁻⁶ to 10 mol·L⁻¹ and pH from 0 to 12. The different formulations were indicated by I, II and III, respectively.

Tab.1 Compositions and pH values of the coatings fabricated in three different solutions

Fig.2 SEM images of (a)(b) coating I, (c)(d) coating II and (e)(f) coating III. Results obtained from (g) EDS, (h) XRD and (i) FTIR.

Fig.3 Cross-sectional morphologies and corresponding elemental mappings of (a) coating I, (b) coating II and (c) coating III.

Fig.4 Coating I on the AZ31 Mg alloy: (a) XPS survey; (b)(c)(d)(e) high resolutions of O 1s, Mg 1s, P 2p and Fe 2p; (f) element contents after different etch time.

Fig.5 OCP as a function of immersion time in 3.5 wt.% NaCl.

Fig.6 EIS results of (a) Nyquist plots, (b) enlarged Nyquist plots, (c) Bode plots of Z_mod, and (d) phase angles of coatings and the bare AZ31 substrate in 3.5 wt.% NaCl. ECs of (e) the AZ31 substrate and (f) coatings.

Tab.2 Electrochemical data obtained via equivalent circuit fitting of the EIS curves

Fig.7 Polarization curves after OCP (lasting for 1000 s) and EIS tests for AZ31 and coatings (I–III) immersed in 3.5 wt.% NaCl solution.

Tab.3 Electrochemical parameters of the polarization curves

Fig.8 (a) pH value, (b) HEV and (c) HER as a function of the immersion time in 3.5 wt.% NaCl for 78 h.

Fig.9 SEM images of (a)(b) the AZ31 substrate and (c)(d)(e)(f)(g)(h) coatings. Results of (i) EDS, (j) XRD and (k) FTIR after immersion in 3.5 wt.% NaCl solution for 78 h.

Fig.10 Nanoscratch test results of (a) coating I, (b) coating II, and (c) coating III.

Fig.11 SEM images of coating I with different times and magnifications: (a)(b) 2 min; (c)(d) 10 min; (e)(f) 20 min; (g)(h) 30 min.

Fig.12 EDS results of coatings for (a) different preparation time, (b) different immersion time in 3.5 wt.% NaCl, and (c) point scanning in Fig. 11(b).

Fig.13 Schematic representation of the Fe coating formation.

Fig.14 SEM images of coating I with different immersion time in 3.5 wt.% NaCl solution: (a)(b) 20 min; (c)(d) 1 h; (e)(f) 20 h; (g)(h) 80 h.

Fig.15 Schematic diagram of the coating accelerating the AZ31 alloy degradation.

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