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Frontiers of Materials Science

ISSN 2095-025X

ISSN 2095-0268(Online)

CN 11-5985/TB

Postal Subscription Code 80-974

2018 Impact Factor: 1.701

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Front. Mater. Sci.    2014, Vol. 8 Issue (3) : 295-306    https://doi.org/10.1007/s11706-014-0255-7
RESEARCH ARTICLE
Biocorrosion resistance of coated magnesium alloy by microarc oxidation in electrolyte containing zirconium and calcium salts
Ya-Ming WANG1,*(),Jun-Wei GUO1,Yun-Feng WU2,Yan LIU2,Jian-Yun CAO1,Yu ZHOU1,De-Chang JIA1
1. Institute for Advanced Ceramics, Harbin Institute of Technology, Harbin 150001, China
2. Key Laboratory of Bionic Engineering of Ministry of Education, Jilin University, Changchun 130022, China
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Abstract

The key to use magnesium alloys as suitable biodegradable implants is how to adjust their degradation rates. We report a strategy to prepare biocompatible ceramic coating with improved biocorrosion resistance property on AZ91D alloy by microarc oxidation (MAO) in a silicate--K2ZrF6 solution with and without Ca(H2PO4)2 additives. The microstructure and biocorrosion of coatings were characterized by XRD and SEM, as well as electrochemical and immersion tests in simulated body fluid (SBF). The results show that the coatings are mainly composed of MgO, Mg2SiO4, m-ZrO2 phases, further Ca containing compounds involve the coating by Ca(H2PO4)2 addition in the silicate--K2ZrF6 solution. The corrosion resistance of coated AZ91D alloy is significantly improved compared with the bare one. After immersing in SBF for 28 d, the Si--Zr5--Ca0 coating indicates a best corrosion resistance performance.
Keywords magnesium alloy      coating      microstructure      biocorrosion     
Corresponding Author(s): Ya-Ming WANG   
Online First Date: 11 August 2014    Issue Date: 12 September 2014
 Cite this article:   
Ya-Ming WANG,Jun-Wei GUO,Yun-Feng WU, et al. Biocorrosion resistance of coated magnesium alloy by microarc oxidation in electrolyte containing zirconium and calcium salts[J]. Front. Mater. Sci., 2014, 8(3): 295-306.
 URL:  
https://academic.hep.com.cn/foms/EN/10.1007/s11706-014-0255-7
https://academic.hep.com.cn/foms/EN/Y2014/V8/I3/295
CompositionContent /(g?L-1)
Na2SiO3?9H2O15
NaOH10
K2ZrF65, 10
Ca(H2PO4)20, 0.5, 1
Tab.1  Electrolyte composition for MAO treatment of AZ91D alloy
Coating systemCoating codeElectrolyte compositionApplied voltage /VOxidation time /minCoating thickness /μm
Si–ZrSi–Zr5–Ca0Na2SiO3?9H2O (5 g/L)NaOH (10 g/L)K2ZrF6 (5 g/L)500519
Si–Zr10–Ca0Na2SiO3?9H2O (5 g/L)NaOH (10 g/L)K2ZrF6 (10 g/L)500517
Si–Zr–CaSi–Zr5–Ca0.5Na2SiO3?9H2O (5 g/L)NaOH (10 g/L)K2ZrF6 (5 g/L)Ca(H2PO4)2 (0.5 g/L)500521
Si–Zr5–Ca1Na2SiO3?9H2O (5 g/L)NaOH (10 g/L)K2ZrF6 (5 g/L)Ca(H2PO4)2 (1 g/L)500523
Tab.2  MAO process parameters and the corresponding coatings formed on AZ91D alloy
Fig.1  Effect of K2ZrF6 and Ca(H2PO4)2 additives with different concentration on current density during MAO applied on AZ91D alloy: Si–Zr10–Ca0 (a); Si–Zr5–Ca0 (b); Si–Zr5–Ca0.5 (c); Si–Zr5–Ca1 (d).
Fig.2  Surface morphologies of coatings formed on AZ91D alloy after adding K2ZrF6 into the based silicate electrolyte: (a) Si–Zr5–Ca0; (b) Si–Zr10–Ca0.
Fig.3  Effect of K2ZrF6 with different concentration on phase composition of MAO coating formed on AZ91D alloy.
Fig.4  Surface morphologies of coatings formed on AZ91D alloy with Ca(H2PO4)2 additive in the electrolyte: (a) Si–Zr5–Ca0; (b) Si–Zr5–Ca0.5; (c) Si–Zr5–Ca1. (Deposition products containing Ca were indicated by arrows).
CoatingElement composition /at.%
OFNaMgAlSiCa
Si–Zr5–Ca051.512.280.8733.962.678.610
Si–Zr5–Ca0.551.292.640.6533.113.278.990.13
Si–Zr5–Ca150.642.440.6934.062.489.550.14
Tab.3  Effect of Ca(H2PO4)2 with different concentration on the elements content of MAO coating formed on AZ91D alloy
Fig.5  Effect of Ca(H2PO4)2 with different concentration on phase composition of MAO coating formed on AZ91D alloy.
Fig.6  Potentiodynamic polarization curves of Mg alloy and MAO coatings formed in silicate electrolyte with different concentration of K2ZrF6 and Ca(H2PO4)2 measured in SBF solution.
Sampleba /mVbc /mVEcorr /VIcorr /(A?cm-2)Rp /(Ω?cm2)
Bare Mg82.4-84.0-1.92.6×10-546.9
Si–Zr5–Ca032.3-46.7-1.42.6×10-63.2×103
Si–Zr5–Ca0.544.4-93.1-1.63.1×10-64.3×103
Si–Zr5–Ca133.3-24.9-1.59.4×10-86.6×104
Si–Zr10–Ca090.1-72.4-1.73.6×10-74.9×104
Tab.4  Corrosion parameters of bare Mg and MAO coated Mg specimen immersing in SBF
Fig.7  Surface appearance of bare and MAO treated Mg alloy samples after the immersion tests in SBF solution for 28 d: (a) bare Mg substrate; (b) Si–Zr5–Ca0; (c) Si–Zr5–Ca1. (Visional corrosion site is indicated by circle).
Fig.8  Slightly attacked surface morphologies of MAO coating formed on AZ91D alloy after 28 d of immersion in SBF: (a)(b) Si–Zr5–Ca0; (c)(d) Si–Zr5–Ca1.
Fig.9  Ion concentration evolutions of Ca, Mg and P in the SBF bath with the increasing immersion time for the different coating samples.
ElementContent /at.%
Before immersionAfter immersion
O50.6459.95
F2.242.84
Na0.693.64
Mg34.066.67
Al2.376.47
Si9.5516.13
K0.110.90
Ca0.142.59
P0.000.82
Tab.5  Element composition of Si–Zr5–Ca1 coating surface after immersion in SBF for 28 d
Fig.10  Cross-section morphologies of Si–Zr5–Ca1 coating formed on AZ91D alloys after immersing in SBF: (a) the compact inner layer is penetrated and crack tends to propagate along the coating/substrate interface, and the inset image shows the corresponding surface crack; (b) corrosion products accumulate by consuming the Mg underlined the coating.
Fig.11  Corrosion mechanism schematic of coated AZ91D alloy by immersing in SBF.
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