Corrosion resistance of Ca-P coating induced by layer-by-layer assembled polyvinylpyrrolidone/DNA multilayer on magnesium AZ31 alloy

doi:10.1007/s11706-021-0560-x

Front. Mater. Sci.

2021, Vol. 15

Issue (3) : 391-405 https://doi.org/10.1007/s11706-021-0560-x

RESEARCH ARTICLE

Corrosion resistance of Ca-P coating induced by layer-by-layer assembled polyvinylpyrrolidone/DNA multilayer on magnesium AZ31 alloy

Zhen-Yu ZHANG¹, Duo WANG¹, Lu-Xian LIANG¹, Shen-Cong CHENG¹, Lan-Yue CUI¹(

), Shuo-Qi LI¹, Zhen-Lin WANG³, Rong-Chang ZENG^1,²

¹. 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
³. College of Materials Science and Engineering, Chongqing University of Technology, Chongqing 400065, China

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Abstract

A hydrothermal deposition method was utilized to fabricate Ca-P composite coating induced by the layer-by-layer (LbL) assembled polyvinylpyrrolidone/deoxyribonucleic acid (PVP/DNA)₂₀ multilayer on AZ31 alloy. The surface morphology and compositions were characterized by SEM, EDS, FTIR and XRD. Besides, the corrosion resistance and degradation behavior of the coating were tested via electrochemical polarization, impedance spectroscopy and immersion measurements. Results show that the main components of Ca-P coatings are hydroxyapatite, Ca₃(PO₄)₂ and Mg₃(PO₄)₂·nH₂O. The LbL-assembled DNA and PVP promote the adsorption of Ca-P deposits on the sample surface, and structures and functional groups of the polyelectrolyte in the outermost layer are the primary influencing factor for the induction of the Ca-P coating. Carboxyl groups have the best biomineralization effect among all related functional groups. The enhanced corrosion resistance and adhesion highlight a promising use of (PVP/DNA)₂₀-induced Ca-P coatings in the field of biomedical magnesium alloys.

Keywords magnesium alloy biomaterial corrosion layer-by-layer assembly Ca-P coating

Corresponding Author(s): Lan-Yue CUI

Online First Date: 13 July 2021 Issue Date: 24 September 2021

Cite this article:

Zhen-Yu ZHANG,Duo WANG,Lu-Xian LIANG, et al. Corrosion resistance of Ca-P coating induced by layer-by-layer assembled polyvinylpyrrolidone/DNA multilayer on magnesium AZ31 alloy[J]. Front. Mater. Sci., 2021, 15(3): 391-405.

URL:

https://academic.hep.com.cn/foms/EN/10.1007/s11706-021-0560-x
https://academic.hep.com.cn/foms/EN/Y2021/V15/I3/391

Fig.1 Schematic diagram of Coating II by the LbL assembly and hydrothermal treatment process.

Fig.2 SEM images of (a)(b) Coating I and (c)(d) Coating II corresponding with elemental analysis and Ca/P ratio on AZ31 alloys.

Fig.3 Cross-sectional images and corresponding EDS mapping of (a)(b)(c)(d)(e)(f) Coating I and (g)(h)(i)(j)(k)(l) Coating II.

Fig.4 (A) FTIR spectra and (B) XRD patterns of Coating I (a) and Coating II (b).

Fig.5 Scratch track view of the AZ31 substrate in comparison to (a) Coating I and (b) Coating II.

Fig.6 SEM images of Coating II during the film formation: (a)(b) 10 min, (c)(d) 30 min, (e)(f) 1 h, (g)(f) 2 h, and (i)(j) 3 h. (k) EDS spectra and Ca/P ratio of Coating II in the process of formation (Points 16–18 to be equivalent to Points 4–6 in Fig. 2).

Fig.7 (a) FTIR spectra and (b) XRD patterns of Coating II during the film formation.

Fig.8 Potentiodynamic polarization of the AZ31 substrate (a), Coating I (b), the DNA-(Ca-P) coating (c) and Coating II (d) in HBSS.

Tab.1 Electrochemical parameters of polarization curves for samples in HBSS

Fig.9 (A) Nyquist curves (inset: the corresponding EC model) and (B) Bode plots of the AZ31 substrate (a), Coating I (b), the DNA induced Ca-P coating (c) and Coating II (d) in HBSS.

Tab.2 Electrochemical data obtained by EC fitting of EIS curves

Fig.10 HER curves with an immersion of 249 h and photographs of the samples after a 249 h immersion in HBSS: (a) the AZ31 substrate; (b) Coating I; (c) Coating II.

Fig.11 SEM images of (a)(b) the AZ31 substrate, (c)(d) Coating I and (e)(f) Coating II after immersion for 249 h in HBSS.

Fig.12 (A) FTIR spectra and (B) XRD patterns of the AZ31 substrate (a), Coating I (b) and Coating II (c) after an immersion of 249 h in HBSS.

Fig.13 The Ca-P ratio and the i_corr value of Ca-P coatings by different inducers [26,44,53–57].

Fig.14 Comparison of the Ca/P ratio, thickness, i_corr value and HER of Coating II and Ca/P/(PVP/PAA)_5.5 coating [26].

Fig.15 Schematic diagram of film formation mechanism for Coating II.

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