Degradation Behavior of Zn-Cu Stents with Different Coatings in Sodium Chloride Solution

doi:10.1007/s40195-024-01721-0

Abstract

Abstract:

The Zn0.6Cu wires are fabricated into stents for the potential biodegradable application of nasal wound healing. The degradation behavior of Zn0.6Cu stents in 0.9 wt% NaCl at 36.5 °C is evaluated. It shows that the untreated Zn0.6Cu stent experiences severe crevice corrosion with acceleration and autocatalytic effects within the micro-cracks and ruptures at 4.67±1.15 d, with the average corrosion rate of 0.28 mm y⁻¹. Fortunately, the anodic polarization (AP)+hydrothermal (H) conversion coating, consisting of ZnCO₃, Zn(OH)₂ and ZnO, could inhibit the crevice corrosion significantly by reducing the cathode/anode ratio, extending the rupture time up to 16.50±2.95 d, with the average corrosion rate of 0.14 mm y⁻¹. This research indicates that the biodegradable Zn-based stent has some potential applications in nasal wound recovery area.

Key words: Zn alloys wires, Corrosion behavior, Biodegradable stents, Coating, Degradation characterization

Xingpeng Liao, Jialuo Huang, Zhilin Liu, Jingru Guo, Dajiang Zheng, Pengbo Chen, Fuyong Cao. Degradation Behavior of Zn-Cu Stents with Different Coatings in Sodium Chloride Solution[J]. Acta Metallurgica Sinica (English Letters), 2024, 37(9): 1564-1580.

Figures/Tables 18

Fig. 1 Overview surface appearance of Zn0.6Cu wires: a untreated, b AP treated, c H treated, d AP+H treated

Fig. 2 Microstructure and EDS mapping of Zn0.6Cu wires: a untreated, b AP treated, c H treated, d AP+H treated

Fig. 3 Cross-sections and EDS mapping of surface treated Zn0.6Cu wires: a AP treated, b H treated, c AP+H treated

Fig. 4 XPS of C 1s, O 1s, Zn 2p3/2 and Cu 2p of the surface treated Zn0.6Cu wires: a-d AP treated, e-h H treated, i-l AP+H treated

Fig. 5 Surface appearance of the Zn0.6Cu stents after the fabrication process: a untreated, b AP treated, c H treated, d AP+H treated

Fig. 6 Rupture time of the Zn0.6Cu stents in 0.9 wt% NaCl solution at 36.5±1 °C

Fig. 7 Pictures of the Zn0.6Cu stents taken during the immersion test in 0.9 wt% NaCl solution at 36.5±1 °C

Fig. 8 Equivalent circuit for EIS fitting of the Zn0.6Cu stents immersed in 0.9 wt% NaCl for 7 days

Fig. 9 Typical Nyquist plots of the Zn0.6Cu stent in 0.9 wt% NaCl solution for 7 days at 36.5±1 °C: a untreated, b AP treated, c H treated, d AP+H treated

Table 1 EIS fitting data of the untreated, AP, H and AP+H Zn0.6Cu stents at OCP in 0.9 wt% NaCl at 36.5±1 °C for 7 days

Sample	Time (h)	R_s (Ω cm²)	CPE_f Y_f×10⁻⁶ (S cm⁻² sⁿ)	n₁	R_f (Ω cm²)	CPE_dl Y_dl×10⁻⁶ (S cm⁻² sⁿ)	n₂	R_ct (Ω cm²)	R_t (Ω cm²)
Untreated	1	13	334	0.87	470	3671	0.97	333	803
	6	14	667	0.60	449	10,496	0.58	477	926
	24	18	245	0.63	141	2443	0.40	675	816
	48	16	73	0.75	164	1896	0.39	583	747
	72	14	129	0.72	195	3577	0.48	457	652
	96	14	2185	0.55	302	11,396	0.71	311	613
	120	14	1336	0.64	158	19,149	0.37	426	584
	144	15	3126	0.56	313	35,740	0.58	276	589
	168	14	4602	0.66	175	13,041	0.53	207	383
AP	1	16	48	0.81	462	4119	0.99	335	797
	6	15	508	0.67	477	4676	0.66	252	729
	24	14	120	0.73	114	1809	0.37	599	713
	48	14	119	0.76	171	2848	0.37	619	790
	72	13	139	0.70	254	3787	0.52	273	527
	96	15	1917	0.59	287	29,273	0.41	333	620
	120	18	483	0.64	254	11,670	0.40	376	631
	144	13	620	0.70	206	22,660	0.32	425	631
	168	13	343	0.71	218	12,677	0.47	304	522
H	1	13	227	0.77	335	5504	0.84	479	814
	6	15	610	0.72	272	7633	0.63	681	953
	24	17	345	0.65	187	3243	0.44	577	764
	48	12	216	0.68	158	4063	0.40	597	754
	72	12	170	0.70	199	3493	0.39	536	735
	96	18	442	0.67	134	7394	0.33	608	742
	120	14	1642	0.58	288	20,924	0.48	590	878
	144	17	1329	0.60	342	24,257	0.37	544	887
	168	17	1307	0.68	116	19,671	0.38	642	758
AP+H	1	14	232	0.81	335	4514	0.91	480	815
	6	11	943	0.71	380	12,338	0.65	4581	838
	24	14	271	0.67	181	1793	0.42	851	1032
	48	16	187	0.74	153	1648	0.36	816	969
	72	14	422	0.69	264	3689	0.39	746	1010
	96	14	625	0.69	294	8450	0.42	594	888
	120	13	319	0.64	323	3448	0.39	610	933
	144	15	1418	0.64	477	12,835	0.36	649	1126
	168	14	2408	0.62	327	13,438	0.30	531	858

Fig. 10 Polarization curves of the Zn0.6Cu stents after immersion in 0.9 wt% NaCl for 1 h and 168 h at 36.5±1 °C

Table 2 Electrochemical data by fitting the polarization curves of the Zn0.6Cu stents in 0.9 wt% NaCl at 36.5±1 °C

Sample	1 h
Sample	E_corr (V)	i_corr (μA cm⁻²)	V (mm y⁻¹)	E_corr (V)	i_corr (μA cm⁻²)	V (mm y⁻¹)
Untreated	−0.947	28	0.42	−0.866	9	0.13
AP	−0.937	20	0.31	−0.894	7	0.11
H	−0.940	19	0.28	−0.911	9	0.13
AP+H	−0.946	14	0.21	−0.882	4	0.06

Fig. 11 Corroded morphologies of Zn0.6Cu stents after the immersion test: a, b the untreated stent after 4 d immersion with degradation products, c, d the untreated stent without degradation products, e, f the AP treated stent after 6 d immersion with degradation products, g, h the AP treated stent without degradation products

Fig. 12 Corroded morphologies of Zn0.6Cu stents after the immersion test: a, b the H treated stent after 7 d immersion with degradation products, c, d the H treated stent without degradation products, e, f the AP+H treated stent after 21 d immersion with degradation products, g, h the AP+H treated stent without degradation products

Fig. 13 Typical surface appearance and EDS mapping of Zn0.6Cu stent after immersion test in 0.9 wt% NaCl: a the fracture morphology, b partial enlarged view of the fracture area, c-f EDS mapping results of the fracture area

Fig. 14 XPS of C 1s, O 1s, Zn 2p3/2 and Cu 2p of the surface treated Zn0.6Cu stents after immersion test: a-d untreated, e-h AP, i-l H, m-p AP+H

Fig. 15 Schematic illustration for the formation of the conversion coatings on Zn0.6Cu wire: a AP, b H, c AP+H treated

Fig. 16 Schematic illustration of the degradation mechanism of the Zn0.6Cu stents in 0.9 wt% NaCl: a untreated stent, b AP+H treated stent

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