Effect of Cu on In-Stent Restenosis and Corrosion Resistance of Ni-Ti Alloy
XU Linjie1,2, LIU Hui1, REN Ling1, YANG Ke1()
1Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China 2School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China
Cite this article:
XU Linjie, LIU Hui, REN Ling, YANG Ke. Effect of Cu on In-Stent Restenosis and Corrosion Resistance of Ni-Ti Alloy. Acta Metall Sin, 2023, 59(4): 577-584.
Ni-Ti alloys are used widely as a self-expanding vascular stent material because of their unique shape memory effect and superelasticity. However, after implantation, there is a risk of in-stent restenosis (ISR) because of insufficient endothelialization and coagulation problems. As a biological functional metal element, the proper addition of Cu endows vascular stent materials, such as stainless steel and cobalt-based alloys, with significant endothelialization promotion and anticoagulant effect, which can effectively inhibit the occurrence of ISR. Based on the alloying strategy, a biofunctional Ni-Ti-Cu alloy was prepared by adding the proper amount of Cu into medical Ni-Ti alloys. The inhibition effect of ISR and corrosion resistance of the Ni-Ti-Cu alloy were studied via OM, SEM, XRD, surface free energy test, electrochemical test, and in vitro cell experiment. Results showed that compared with the Ni-Ti alloy, the Ni-Ti-Cu alloy promoted the transformation of an equiaxed austenite grain structure to fine lath martensite, reduced the surface free energy, and improved corrosion resistance in simulated human blood. In addition, the extract of the Ni-Ti-Cu alloy could promote the proliferation, migration, and tube formation of human umbilical vein endothelial cells. Furthermore, compared with the Ni-Ti alloy, the Ni-Ti-Cu alloy decreased the blood coagulation rate, presenting better anticoagulation ability, which has an application potential for inhibiting the occurrence of ISR.
Fund: National Key Research and Development Program of China(2022YFC2406003);National Natural Science Foundation of China(81873918);National Natural Science Foundation of China(82272099);Natural Science Foundation of Liaoning Province(2021020399-JH2/103);Natural Science Foundation of Liaoning Province(2022-YGJC-34)
Corresponding Authors:
YANG Ke, professor, Tel: (024)23971628, E-mail: kyang@imr.ac.cn
Fig.1 XRD spectra (a) and SEM images of Ni-Ti (b) and Ni-Ti-Cu (c) alloys
Alloy
θ1 / (°)
θ2 / (°)
θ3 / (°)
/ (mJ·m-2)
/ (mJ·m-2)
Ni-Ti
53.44 ± 1.94
55.53 ± 3.27
18.59 ± 0.37
11.94 ± 1.31
39.31 ± 0.83
Ni-Ti-Cu
58.36 ± 3.60
65.73 ± 3.58
19.12 ± 0.88
8.99 ± 1.12
37.56 ± 1.08
Table 1 Measurement results of contact angle and surface free energy of different samples with deionized water, glycerin, and bromonaphthalene
Fig.2 Electrochemical test results of Ni-Ti and Ni-Ti-Cu alloys (a) open circuit potential curves (Eocp—open circuit potential) (b) potentiodynamic polarization curves (i—current density, E—potential) (c) Nyquist diagram and fitting circuit diagram (Inset shows the equivalent circuit diagram. Z'—real impedance, Z''—imaginary impedance, R.E.—reference electrode, W.E.—working electrode, Rs—solution resistance, Rc1—passive film resistance, Qc1—constant-phase element) (d) Bode diagram (|Z|—impedance modulus)
Alloy
Ecorr / mV
icorr / (nA·cm-2)
Epit / mV
Rs / (Ω·cm2)
Rc1 / (104 Ω·cm2)
Qc1 / (μΩ-1·s n ·cm-2)
Ni-Ti
-399 ± 62
99.7 ± 13.4
828 ± 30
13.73 ± 1.64
6.41 ± 1.20
52.3 ± 1.5
Ni-Ti-Cu
-283 ± 52
59.5 ± 16.3
862 ± 25
11.79 ± 1.22
67.32 ± 3.42
51.5 ± 1.2
Table 2 Electrochemical parameters obtained from polarization curves of driven potential and EIS diagram
Fig.3 In vitro cell test results of Ni-Ti (a1-c1) and Ni-Ti-Cu (a2-c2) alloys (a1, a2) scratch (b1, b2) Transwell (c1, c2) tube formation
Fig.4 Results of dynamic coagulation experiment of Ni-Ti and Ni-Ti-Cu alloys (y—fitted value of absorbance of residual free hemoglobin in streamer solution measured at 545 nm wavelength, x—dynamic coagulation time, R2—fitting correlation coefficient)
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