Fatigue and Corrosion Fatigue Properties of Mg-Zn-Zr-Nd Alloys in Glucose-Containing Simulated Body Fluids

doi:10.1007/s40195-024-01730-z

Abstract

Abstract:

Medical bone implant magnesium (Mg) alloys are subjected to both corrosive environments and complex loads in the human body. The increasing number of hyperglycemic and diabetic patients in recent years has brought new challenges to the fatigue performance of Mg alloys. Therefore, it is significant to study the corrosion fatigue (CF) behavior of medical Mg alloys in glucose-containing simulated body fluids for their clinical applications. Herein, the corrosion and fatigue properties of extruded Mg-Zn-Zr-Nd alloy in Hank’s balanced salt solution (HBSS) containing different concentrations (1 g/L and 3 g/L) of glucose were investigated. The average grain size of the alloy is about 5 μm, which provides excellent overall mechanical properties. The conditional fatigue strength of the alloy was 127 MPa in air and 88 MPa and 70 MPa in HBSS containing 1 g/L glucose and 3 g/L glucose, respectively. Fatigue crack initiation points for alloys in air are oxide inclusions and in solution are corrosion pits. The corrosion rate of the alloy is high at the beginning, and decreases as the surface corrosion product layer thickens with the increase of immersion time. The corrosion products of the alloy are mainly Mg(OH)₂, MgO and a small amount of Ca-P compounds. The electrochemical results indicated that the corrosion rate of the alloys gradually decreased with increasing immersion time, but the corrosion tendency of the alloy was greater in HBSS containing 3 g/L glucose. On the one hand, glucose accelerates the corrosion process by adsorbing large amounts of aggressive Cl⁻ ions. On the other hand, glucose will be oxidized to form gluconic acid, and then reacts with Mg(OH)₂ and MgO to form Mg gluconate, which destroys the corrosion product film and leads to the aggravation of corrosion and the accumulation of fatigue damage.

Key words: Mg alloys, Corrosion fatigue, Glucose, Gluconic acid, Corrosion product

Xue Han, Dan Zhang, Song Zhang, Mohammed R. I. Abueida, Lili Tan, Xiaopeng Lu, Qiang Wang, Huanye Liu. Fatigue and Corrosion Fatigue Properties of Mg-Zn-Zr-Nd Alloys in Glucose-Containing Simulated Body Fluids[J]. Acta Metallurgica Sinica (English Letters), 2024, 37(9): 1533-1550.

Figures/Tables 19

Fig. 1 Equipment diagram of fatigue test a, stress-life (S-N) curves of extruded Mg-2Zn-0.5Zr-0.5Nd alloy in air and HBSS containing different concentrations of glucose b, diagram of fatigue sample c

Table 1 Formulation of Hank’s balanced salt solution (g/L)

Components	NaCl	CaCl₂	KCl	MgCl₂·6H₂O	MgSO₄·7H₂O	Na₂HPO₄·12H₂O	KH₂PO₄	NaHCO₃	C₆H₆O₆
Concentration	8.00	0.14	0.40	0.10	0.10	0.12	0.06	0.35	1.00

Fig. 2 Grain of the extruded Mg-2Zn-0.5Zr-0.5Nd alloy a, XRD phase analysis b, tensile stress-strain curve c, mechanical properties of the alloy d, diagram of tensile sample e

Table 2 Comparison of fatigue and corrosion fatigue testing of Mg alloys

Materials	Sample type	Cycle mode	Frequency (Hz)	Medium	Fatigue strength in air (MPa)	Corrosion fatigue strength (MPa)	References
Mg-Y-Zn	As extruded	Push-pull	100	0.9% NaCl	95 (N_f=10⁶)	28 (N_f=10⁶)	[57]
AZ91D	Die-cast	-	10	SBF	50 (N_f=10⁷)	20 (N_f=10⁶)	[42]
AZ91D	Sand-cast	Fully reversed	5	m-SBF	57 (N_f=10⁷)	17 (N_f=5×10⁵)	[36]
HP-Mg	As extruded	Tension-compression	10	SBF	89 (N_f=10⁶)	52 (N_f=10⁶)	[37]
Mg-2Zn-0.2Ca	As extruded	Tension-compression	10	SBF	87 (N_f=4×10⁶)	68 (N_f=10⁶)	[37]
Mg-2Zn-0.5Zr-0.5Nd	As extruded	Tension-compression	2	HBSS (contains different concentrations of glucose)	127 (N_f=10⁶)	88, (1 g/L glucose) 70, (3 g/L glucose) (N_f=10⁶)	Present work

Fig. 3 Fracture morphologies of Mg-2Zn-0.5Zr-0.5Nd alloy after fatigue failure in air: a, d σ=151 MPa, Nf=4.2396×104; b, e σ=151 MPa, Nf=4.2396×104; c, f σ=135 MPa, Nf=5.26513×105

Fig. 4 SEM-EDS elemental distribution in the crack initiation zone of the fatigue fracture specimen in air (σ=151 MPa, Nf=4.2396×104)

Fig. 5 Fracture morphologies of Mg-2Zn-0.5Zr-0.5Nd alloy failed by fatigue in HBSS containing 1 g/L glucose: a-d σ=127 MPa, Nf=2.3240×104; e-h σ=111 MPa, Nf=8.7085×104; i-l σ=100 MPa, Nf=8.55101×105

Fig. 6 Fracture morphologies of Mg-2Zn-0.5Zr-0.5Nd alloy failed by fatigue in HBSS containing 3 g/L glucose: a-d σ=104 MPa, Nf=1.7878×104; e-h σ=88 MPa, Nf=1.11128×105; i-l σ=72 MPa, Nf=8.49961×105

Fig. 7 Lateral corrosion morphologies of specimens after fatigue fracture in HBSS containing different concentrations of glucose: 1 g/L glucose: a, b σ=127 MPa, Nf=2.3240×104; c, d σ=111 MPa, Nf=8.7085×104; e, f σ=100 MPa, Nf=8.55101×105; 3 g/L glucose: g, h σ=104 MPa, Nf=1.7878×104; i, j σ=88 MPa, Nf=1.11128×105; k, l σ=72 MPa, Nf=8.49961×105

Fig. 8 Polarization curves of the alloy in HBSS containing different concentrations of glucose a, Nyquist plots of the alloy after immersion in HBSS containing different concentrations of glucose for 7 days b, Bode plots c, equivalent circuit d, pH value of the alloy after immersion in HBSS containing different concentrations of glucose for 14 days e, corrosion rate obtained by weight loss f

Table 3 Electrochemical parameters of the alloy in HBSS solution

Samples	E_corr (V)	I_corr (μA/cm²)	Corrosion rate (mm/y)
1 g/L glucose	−1.51±0.02	6.56±0.82	0.15±0.02
3 g/L glucose	−1.52±0.01	10.9±1.15	0.25±0.03

Table 4 Fitted EIS parameters of alloys immersed for 7 days in HBSS containing different concentrations of glucose

Conditions	R_s (Ω·cm²)	CPE₁ (Ω⁻¹·cm⁻² ·sⁿ)	n₁	R₁ (Ω·cm²)	CPE₂ (Ω⁻¹·cm⁻² ·sⁿ)	n₂	R₂ (Ω·cm²)	R₃ (Ω·cm²)	L (H·cm⁻²)
1 g/L-1 h	17.27	1.45×10⁻⁵	0.68	187.9	1.21×10⁻⁵	0.94	1.62×10³	874.8	5.06×10³
3 g/L-1 h	18.31	1.89×10⁻⁵	0.60	145.5	1.92×10⁻⁵	0.90	846.6	504	3.05×10³
1 g/L-1 d	17.6	2.6×10⁻⁵	0.62	142.2	1.48×10⁻⁵	0.86	2.8×10³	1.23×10³	3.44×10³
3 g/L-1 d	19.1	1.3×10⁻⁵	0.87	155.1	3.16×10⁻⁵	0.62	2.2×10³	1.24×10³	5.75×10³
1 g/L-3 d	16.8	6.62×10⁻⁶	0.60	781.7	1.08×10⁻⁵	0.78	9.03×10³	3.24×10⁴	6.2×10³
3 g/L-3 d	19.2	8.11×10⁻⁶	0.79	645	1.44×10⁻⁵	0.70	8.32×10³	4.04×10⁴	4.19×10³
1 g/L-7 d	18.52	2.27×10⁻⁶	0.61	2.07×10³	4.76×10⁻⁶	0.83	1.33×10⁴	6.48×10⁴	7.27×10⁴
3 g/L-7 d	20.37	2.85×10⁻⁶	0.63	1.53×10³	7.07×10⁻⁶	0.84	9.62×10³	3.15×10⁴	7.42×10⁴

Fig. 9 SEM photographs of cross-sectional corrosion product layers of Mg-2Zn-0.5Zr-0.5Nd alloy after immersion in HBSS containing 1 g/L glucose and 3 g/L glucose for 1, 3, 7 and 14 days

Fig. 10 EDS surface scanning of cross-section corrosion product layers of Mg-2Zn-0.5Zr-0.5Nd alloy after immersion in HBSS containing 1 g/L glucose for 1, 3, 7 and 14 days

Fig. 11 EDS surface scanning of cross-section corrosion product layers of Mg-2Zn-0.5Zr-0.5Nd alloy after immersion in HBSS containing 3 g/L glucose for 1, 3, 7 and 14 days

Table 5 EDS surface scanning elemental composition of cross-section corrosion product layers of Mg-2Zn-0.5Zr-0.5Nd alloy after immersion in HBSS containing different concentrations of glucose

Condition	Elemental composition (wt%)
Condition	Mg	O	Ca	P
1 g/L-1 d	84.3	5.7	4.2	0.6
1 g/L-3 d	65.6	15.4	3.2	0.5
1 g/L-7 d	41.8	33.5	11.9	3.1
1 g/L-14 d	36.6	31.5	17.3	9.9
3 g/L-1 d	36.6	43.9	8.3	2.3
3 g/L-3 d	62.4	12.5	9.4	2.3
3 g/L-7 d	67.3	16.9	8.5	1.3
3 g/L-14 d	51.7	19.4	14.9	9.5

Fig. 12 XPS spectra of corrosion products of Mg-2Zn-0.5Zr-0.5Nd alloy after 7 days immersion in HBSS containing 1 g/L glucose: total energy spectrum a, C1s b, O1s c, Mg1s d, Mg2p e, Ca2p f

Fig. 13 XPS spectra of corrosion products of Mg-2Zn-0.5Zr-0.5Nd alloy after 7 days immersion in HBSS containing 3 g/L glucose: total energy spectrum a, C1s b, O1s c, Mg1s d, Mg2p e, Ca2p f

Fig. 14 Failure mechanism diagram of Mg-2Zn-0.5Zr-0.5Nd alloy in HBSS containing glucose: low-glucose environment a, high-glucose environment b

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