Preparation of Biodegradable Mg/β-TCP Biofunctional Gradient Materials by Friction Stir Processing and Pulse Reverse Current Electrodeposition

doi:10.1007/s40195-019-00956-6

Abstract

Abstract:

Mg alloys, as a new generation of biodegradable bone implant materials, are facing two tremendous challenges of enhancing strength and reducing degradation rate in physiological environment to meet clinical needs. In this study, tricalcium phosphate (β-TCP) particles were dispersed in Mg-2Zn-0.46Y-0.5Nd alloy by friction stir processing (FSP) to produce Mg-based functional gradient materials (Mg/β-TCP FGM). On the surface of Mg/β-TCP FGM, the hydroxyapatite (HA) coating was prepared by electrodeposition. The effects of FSP and electrochemical parameter on the microstructure, microhardness, bonding strength and corrosion performance of the Mg/β-TCP FGM were investigated. After four passes of FSP, a uniform and fine-grained structure was formed in Mg/β-TCP and the microhardness increased from 47.9 to 76.3 HV. Compared to the samples without β-TCP, the bonding strength of the Mg/β-TCP FGM increased from 23.1?±?0.462 to 26.3?±?0.526 MPa and the addition of degradable β-TCP contributed to the in situ growth of HA coating. The thickness of HA coating could be dominated by controlling the parameters of electrodeposition. According to the results of immersion tests and electrochemical tests in simulated body fluid, it indicated that the degradation rate of the Mg/β-TCP FGM could be adjusted.

Key words: Biodegradable magnesium alloy, Biofunctional gradient materials, Friction stir processing, Tricalcium phosphate (β-TCP);, Electrodeposition

Yabo Zhang, Huiling Yang, Shaoqian Lei, Shijie Zhu, Jianfeng Wang, Yufeng Sun, Shaokang Guan. Preparation of Biodegradable Mg/β-TCP Biofunctional Gradient Materials by Friction Stir Processing and Pulse Reverse Current Electrodeposition[J]. Acta Metallurgica Sinica (English Letters), 2020, 33(1): 103-114.

Figures/Tables 17

Fig. 1 Preset diagram of β-TCP (mm) a, schematic of FSP b

Fig. 2 Schematic of Mg/β-TCP FGM

Fig. 3 Schematic diagram of the bonding strength test

Table 1 Amount of reagents for preparing 1000 ml of the SBF solution

NaCl	NaHCO₃	KCl	K₂HPO₄·3H₂O	MgCl₂·6H₂O	HCl	CaCl₂	Na₂SO₄	Tris
8.035 g	0.355 g	0.225 g	0.231 g	0.311 g	39 ml	0.292 g	0.072 g	6.118 g

Fig. 4 OM images of as-cast Mg-Zn-Y-Nd and Mg/β-TCP: a annealed Mg-2Zn-0.46Y-0.5Nd; b FSP-1; c FSP-3; d FSP-4; e FSP-5; f FSP-6

Fig. 5 SEM image and EDS mapping of Mg/β-TCP composite by FSP-4

Fig. 6 Microhardness curve and cross-sectional structure of Mg/β-TCP composite by FSP-n; test points along yellow dotted line

Fig. 7 Electrochemical test results of the experimental samples in SBF solution: a polarization curves; b Nyquist plots

Table 2 Electrochemical data for the experimental samples in SBF solution derived from the polarization curves

Sample state	E_corr (V)	i_corr (A cm^-2)
Annealed Mg-2Zn-0.46Y-0.5Nd	-?1.590	9.65?×?10^-4
Mg/β-TCP?+?FSP-4	-?1.671	1.07?×?10^-4
Mg/β-TCP FGM	-?1.575	1.57?×?10^-5

Fig. 8 SEM images of the coatings on Mg/β-TCP by FSP-1 deposited at 0.1 mA/cm2 with 0 s a, 5 s b, 15 s c, 60 s d, 300 s e, respectively; regions 1 and 2 represent the presence of β-TCP and the absence of β-TCP

Fig. 9 Element contents of P and Ca distributed in area 1 a, 2 b in Fig. 8

Fig. 10 Cross-sectional morphologies and corresponding liner element distribution curves of the coatings on Mg/β-TCP?+?FSP-4 deposited at 10 mA/cm2 with 5 min a, 15 min b, 30 min c, respectively

Fig. 11 SEM micrograph and EDS form of the coating of Mg-HA a, Mg/β-TCP FGM b deposited at 10 mA/cm2 with 30 min

Fig. 12 Corrosion rate: a Mg alloy, Mg/β-TCP and Mg/β-TCP FGM-30 min immersed in SBF for 14 days; b Mg/β-TCP FGM-5 min/Mg/β-TCP FGM-15 min immersed in SBF for 12 days

Fig. 13 Corrosion morphology immersed in SBF for 336 h: a annealed Mg-2Zn-0.46Y-0.5Nd; b Mg/β-TCP?+?FSP-4

Fig. 14 Corrosion morphology of Mg/β-TCP FGM-30 min immersed in SBF for 72 h a, 168 h b, 288 h c; Mg/β-TCP FGM-15 min for 24 h d, 96 h e, 288 h f; Mg/β-TCP FGM-5 min for 24 h g, 72 h h, 288 h i; the area of white box is the place of EDS

Table 3 Element content of Mg/β-TCP FGM in Fig. 13 white area (at.%)

	Time (h)	C	O	Mg	P	Ca
Mg/β-TCP FGM-30 min	72	26.07	33.88	6.11	16.93	17.01
	168	36.01	40.25	8.72	8.11	6.91
	288	30.39	51.42	8.08	7.43	2.68
Mg/β-TCP FGM-15 min	24	23.28	36.84	14.89	11.99	11.66
	96	24.36	39.69	29.40	3.23	1.49
	288	25.20	45.98	6.32	10.39	9.96
Mg/β-TCP FGM-5 min	24	23.63	42.39	7.49	13.86	11.16
	72	21.38	43.10	29.97	3.05	0.92
	288	36.52	32.33	3.71	13.98	12.21

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