Fabrication and characterization of novel biodegradable Zn-Mn-Cu alloys

doi:10.1016/j.jmst.2017.11.026

Abstract

Abstract:

Zn-Mn-Cu alloys with micro-alloying of Mn and Cu in Zn are developed as potential biodegradable metals. Although the as-cast alloys are very brittle, their ductilities are significantly improved through hot rolling. Among the as-cast and the as-hot-rolled alloys, as-hot-rolled Zn-0.35Mn-0.41 Cu alloy has the best comprehensive property. It has yield strength of 198.4 ± 6.7 MPa, tensile strength of 292.4 ± 3.4 MPa, elongation of 29.6 ± 3.8% and corrosion rate of 0.050-0.062 mm a^-1. A new ternary phase is characterized and determined to be MnCuZn₁₈, which is embedded in MnZn₁₃, resulting in a coarse cellular/dendritic MnZn₁₃-MnCuZn₁₈ compound structure in Zn-0.75 Mn-0.40Cu alloy. Such a coarse compound structure is detrimental for wrought alloy properties, which guides future design of Zn-Mn-Cu based alloys. The preliminary research indicates that Zn-Mn-Cu alloy system is a promising candidate for potential cardiovascular stent applications.

Key words: Zn alloys, Biodegradability, Strength, Ductility, Corrosion behavior

Zhang-Zhi Shi, Jing Yu, Xue-Feng Liu, Lu-Ning Wang. Fabrication and characterization of novel biodegradable Zn-Mn-Cu alloys[J]. J. Mater. Sci. Technol., 2018, 34(6): 1008-1015.

Figures/Tables 11

Fig. 1. Data of mechanical and corrosion properties of biodegradable Zn and its alloys collected from references [12], [13], [14], [15], [16], [17], [18], [19], [20], [21], [22], [23], [24], [25], [26]: (a) elongation and yield strength; (b) elongation and tensile strength; (c) electrochemical corrosion rate and tensile strength; (d) immersion corrosion rate and tensile strength.

Table 1 Order, amounts, weighting containers, purities and formula weights of reagents for preparing 1000 ml of SBF.

Order	Reagent	Amount	Container	Purity	Formula weight
1	NaCl	8.035 g	Weighing paper	99.5%	58.4430
2	NaHCO₃	0.355 g	Weighing paper	99.5%	84.0068
3	KCl	0.225 g	Weighing bottle	99.5%	74.5515
4	K₂HPO4·3H₂O	0.231 g	Weighing bottle	99.0%	228.2220
5	MgCl₂·6H₂O	0.311 g	Weighing bottle	98.0%	203.3034
6	1.0 mol L^-1 HCl	39 ml	Graduated cylinder	-	-
7	CaCl₂	0.292 g	Weighing bottle	95.0%	110.9848
8	Na₂SO₄	0.072 g	Weighing bottle	99.0%	142.0428
9	Tris	6.118 g	Weighing paper	99.0%	121.1356
10	1.0 mol L^-1 HCl	0 to 5 ml	Syringe	-	-

Fig. 2. Changes in pH value of SBF during immersion test for 336 h (14 d).

Fig. 3. Engineering strain-stress curves of Zn-Mn-Cu alloys. The inserted figure is the enlargement of the curves of the as-cast alloys.

Fig. 4. Microstructures of Zn-Mn-Cu alloys observed by metallurgical microscopy: (a) as-cast Zn-0.35Mn-0.41Cu alloy; (b) as-cast Zn-0.75Mn-0.40Cu alloy; (c) as-hot-rolled Zn-0.35Mn-0.41Cu alloy; (d) as-hot-rolled Zn-0.75Mn-0.40Cu alloy.

Fig. 5. Microstructures of Zn-Mn-Cu alloys observed by SEM: (a) as-cast Zn-0.35Mn-0.41Cu alloy; (b) a representative EDS result of MnZn13 phase; (c) as-cast Zn-0.75Mn-0.40Cu alloy, in which a region enclosed by solid lines is enlarged at the upper right corner; (d) a representative EDS result of Zn-Mn-Cu ternary phase; (e) as-hot-rolled Zn-0.35Mn-0.41Cu alloy; (f) as-hot-rolled Zn-0.75Mn-0.40Cu alloy, in which a region enclosed by solid lines is enlarged at the upper right corner.

Fig. 6. (a) DSC cooling curves of as-cast Zn-0.75Mn-0.40Cu alloy, (b) a sketch of formation process of MnZn13-MnCuZn18 compound structure during solidification of Zn-0.75Mn-0.40Cu alloy and (c) DSC cooling curves of as-cast Zn-0.35Mn-0.41Cu.

Fig. 7. Polarization curves of as-hot-rolled Zn-0.75Mn-0.40Cu and Zn-0.35Mn-0.41Cu alloys in SBF at 37 °C.

Table 2 Corrosion rates of as-hot-rolled alloys obtained from fitting results of polarization curves and immersion test for 336 h (14 d).

Alloy	Electrochemical test			Immersion test
	E_cor (V)	i_cor (μA cm^-2)	CR (mm a^-1)	CR (mm a^-1)
Zn-0.35Mn-0.41Cu	-1.06 ± 0.04	4.1 ± 0.6	0.062 ± 0.009	0.050 ± 0.004
Zn-0.75Mn-0.40Cu	-1.03 ± 0.02	6.5 ± 0.3	0.098 ± 0.005	0.065 ± 0.006

Fig. 8. SEM micrographs of as-hot-rolled alloys after immersion in SBF for 336 h (14 d): (a) Zn-0.35Mn-0.41Cu alloy; (b) Zn-0.75Mn-0.40Cu alloy; (c) cleaned Zn-0.35Mn-0.41Cu alloy; (d) cleaned Zn-0.75Mn-0.40Cu alloy.

Table 3 Composition of corrosion products after immersion test measured by EDS (representative points marked with letters A and B with subscripts 1-6 in Fig. 8).

Alloy	Point	Element (at.%)
		Zn	C	O	P	Ca	Mn	Cl	Mg	Cu
	A₁	34.2	28.8	33.2	2.0	1.6	0.2	0	0	0
	A₂	46.1	22.7	28.5	1.9	0.6	0.2	0	0	0
Zn-0.35Mn-0.41Cu	A₃	37.4	37.6	20.3	2.3	0.9	0	0.9	0.6	0
	A₄	56.6	27.5	13.8	1.4	0.5	0.2	0	0	0
	A₅	56.4	30.8	11.3	1.0	0.3	0.2	0	0	0
	A₆	30.7	34.8	30.2	1.8	0.7	0.9	0	0	0.9
	B₁	23.6	28.1	42.7	4.7	0.8	0.1	0	0	0
	B₂	31.3	26.7	37.3	3.6	1.1	0	0	0	0
Zn-0.75Mn-0.40Cu	B₃	50.9	24.7	21.6	1.8	0.5	0.5	0	0	0
	B₄	49.9	24.4	23.5	1.6	0.5	0.1	0	0	0
	B₅	53.1	25.3	15.5	1.2	0.4	4.5	0	0	0

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