J. Mater. Sci. Technol. ›› 2022, Vol. 110: 227-238.DOI: 10.1016/j.jmst.2021.09.034
• Research Article • Previous Articles Next Articles
Pengfei Jia, Bohan Chena, Shuguang Liua,c, Bo Lia, Chaoqun Xiaa,b, Xinyu Zhanga,*(
), Mingzhen Maa, Riping Liua,*()
Received:2021-08-01
Revised:2021-08-27
Accepted:2021-09-13
Published:2021-11-26
Online:2021-11-26
Contact:
Xinyu Zhang,Riping Liu
About author:riping@ysu.edu.cn (R. Liu).Pengfei Ji, Bohan Chen, Shuguang Liu, Bo Li, Chaoqun Xia, Xinyu Zhang, Mingzhen Ma, Riping Liu. Controlling the mechanical properties and corrosion behavior of biomedical TiZrNb alloys by combining recrystallization and spinodal decomposition[J]. J. Mater. Sci. Technol., 2022, 110: 227-238.
Fig. 1. Schematic illustration of heat treatment process and naming.
Fig. 2. (a) X-ray diffraction (XRD) patterns of TiZrNb alloys; (b, b1) image quality (IQ) and inverse pole figure (IPF) map of TZN-600 alloy; (c, c1) IQ and IPF map of TZN-700 alloy; (d-f) and (d1-f1): IQ and pole figures for regions with GOS ≤ 2°, 2° 〈 GOS ≤ 5°, and GOS 〉 5° of TZN-700 alloy; (g, g1) IQ and IPF map of TZN-800 alloy; (h, h1) IQ and IPF map of TZN-900 alloy; (i) grain size distribution in TZN-800 and TZN-900 alloys. (Black areas in IPF map represent areas with low resolution or being screened.).
| Empty Cell | E (GPa) | σ0.2 (MPa) | σb (MPa) | ε (%) | G (GPa) | r (pm) |
|---|---|---|---|---|---|---|
| TZN-CR | 73±1.5 | 1123.1 ± 22.1 | 1159.1 ± 24.8 | 12.9 ± 0.7 | - | - |
| TZN-600 | 73±2 | 984.0 ± 19.2 | 1010.6 ± 17.3 | 14.8 ± 1.3 | - | - |
| TZN-700 | 72±1 | 916.3 ± 21.6 | 938.3 ± 12.5 | 16.5 ± 1.1 | - | - |
| TZN-800 | 60±1 | 876.1 ± 11.7 | 912.4 ± 15.6 | 20.3 ± 1.4 | - | - |
| TZN-900 | 61±2 | 882.4 ± 16.9 | 932.7 ± 12.3 | 13.9 ± 1.8 | - | - |
| Ti | - | 195 | - | - | 44 | 141.8 |
| Zr | - | 280 | - | - | 33 | 155.1 |
| Nb | - | 240 | - | - | 38 | 142.9 |
Table 1. Elastic modulus (E), yield strength (σ0.2), ultimate tensile strength (σb), and total elongation (%) of TiZrNb alloys, and σ0.2 atomic radius (r) and shear modulus (G) of Ti, Zr, and Nb metals.
| Empty Cell | E (GPa) | σ0.2 (MPa) | σb (MPa) | ε (%) | G (GPa) | r (pm) |
|---|---|---|---|---|---|---|
| TZN-CR | 73±1.5 | 1123.1 ± 22.1 | 1159.1 ± 24.8 | 12.9 ± 0.7 | - | - |
| TZN-600 | 73±2 | 984.0 ± 19.2 | 1010.6 ± 17.3 | 14.8 ± 1.3 | - | - |
| TZN-700 | 72±1 | 916.3 ± 21.6 | 938.3 ± 12.5 | 16.5 ± 1.1 | - | - |
| TZN-800 | 60±1 | 876.1 ± 11.7 | 912.4 ± 15.6 | 20.3 ± 1.4 | - | - |
| TZN-900 | 61±2 | 882.4 ± 16.9 | 932.7 ± 12.3 | 13.9 ± 1.8 | - | - |
| Ti | - | 195 | - | - | 44 | 141.8 |
| Zr | - | 280 | - | - | 33 | 155.1 |
| Nb | - | 240 | - | - | 38 | 142.9 |
Fig. 3. (a) Uniaxial tensile loading curves of TiZrNb alloys; (b) evolution of the mechanical properties of TiZrNb alloys.
Fig. 4. Representative transmission electron microscopy (TEM) images showing alloy morphology: (a, a1) TZN-CR alloy, (b) TZN-600 alloy, (c) TZN-700 alloy, (d) TZN-800 alloy, (e) TZN-900 alloy; (f) selected area diffraction pattern of β-phase matrix and nano-precipitated phase; (g) relationship between dislocations and precipitated phases; (h-h4) high-resolution TEM analysis of spinodal decomposition.
Fig. 5. (a-c) Geometric phase analysis (GPA) based on high-resolution transmission electron microscopy (TEM) pattern (Fig. 4(h)).
Fig. 6. Schematic diagrams: (a) dislocation motion without the effect of spinodal decomposition, (b) influence of spinodal decomposition on dislocation motion.
| Ti alloys | E (GPa) | σ0.2 (MPa) | σb (MPa) | ε (%) | Refs. |
|---|---|---|---|---|---|
| CP-Ti (grade 4) | 104.1 | 485 | 550 | 15 | [ |
| Ti-6Al-4 V ELI | 101-110 | 795-875 | 860-965 | 10-15 | [ |
| Ti-6Al-7Nb | 114 | 880-950 | 900-1050 | 8.1-15 | [ |
| Ti-13Nb-13Zr | 79-84 | 836-908 | 973-1037 | 10-16 | [ |
| As casted Ti-25-40.7Zr-24.8-34Nb alloys | 62-65 | 682-810 | 704-758 | 9.9-14.8 | [ |
| Cold rolded Ti-35.4Zr-28Nb alloy | 70-79 | 708-890 | 763-941 | 4-8 | [ |
| Cold rolded + Annealing Ti-35.4Zr-28Nb alloy | 63 | 611 | 633 | 13 | [ |
| TiZrNb alloy containing B | - | 621.3-739.1 | 622.3-764.1 | 7.8-11.6 | [ |
Table 2. Mechanical properties of Ti alloys developed and/or utilized as biomedical materials.
| Ti alloys | E (GPa) | σ0.2 (MPa) | σb (MPa) | ε (%) | Refs. |
|---|---|---|---|---|---|
| CP-Ti (grade 4) | 104.1 | 485 | 550 | 15 | [ |
| Ti-6Al-4 V ELI | 101-110 | 795-875 | 860-965 | 10-15 | [ |
| Ti-6Al-7Nb | 114 | 880-950 | 900-1050 | 8.1-15 | [ |
| Ti-13Nb-13Zr | 79-84 | 836-908 | 973-1037 | 10-16 | [ |
| As casted Ti-25-40.7Zr-24.8-34Nb alloys | 62-65 | 682-810 | 704-758 | 9.9-14.8 | [ |
| Cold rolded Ti-35.4Zr-28Nb alloy | 70-79 | 708-890 | 763-941 | 4-8 | [ |
| Cold rolded + Annealing Ti-35.4Zr-28Nb alloy | 63 | 611 | 633 | 13 | [ |
| TiZrNb alloy containing B | - | 621.3-739.1 | 622.3-764.1 | 7.8-11.6 | [ |
| Empty Cell | Ecorr (mV) | Icorr (nA cm-2) | Rs (Ω cm2) | Rp × 106 (Ω cm2) | CPE × 10-5 (Ω-1 s-n cm-2) | n | Ceff × 10-5 (F cm-2) | χ2 (× 10-3) |
|---|---|---|---|---|---|---|---|---|
| TZN-ST | -604.2 ± 23.5 | 31.4 ± 0.2 | 5.366±0.311 | 1.234±0.091 | 2.256±0.134 | 0.9454±0.0104 | 2.901±0.323 | 1.104±0.097 |
| TZN-CR | -492.6 ± 31.6 | 12.1 ± 0.4 | 5.673±0.272 | 1.751±0.107 | 1.960±0.083 | 0.9385±0.0119 | 2.602±0.263 | 1.288±0.102 |
| TZN-800 | -405.4 ± 17.2 | 6.12±0.2 | 5.651±0.347 | 2.606±0.151 | 1.471±0.065 | 0.9486±0.0083 | 1.864±0.158 | 0.736±0.046 |
Table 3. Corrosion potential (Ecorr), corrosion current density (Icorr), electrochemical impedance spectroscopy (EIS) fitting results, effective capacitance (Ceff), and chi-squared (χ2) values of TZN-ST, TZN-CR and TZN-800 alloys.
| Empty Cell | Ecorr (mV) | Icorr (nA cm-2) | Rs (Ω cm2) | Rp × 106 (Ω cm2) | CPE × 10-5 (Ω-1 s-n cm-2) | n | Ceff × 10-5 (F cm-2) | χ2 (× 10-3) |
|---|---|---|---|---|---|---|---|---|
| TZN-ST | -604.2 ± 23.5 | 31.4 ± 0.2 | 5.366±0.311 | 1.234±0.091 | 2.256±0.134 | 0.9454±0.0104 | 2.901±0.323 | 1.104±0.097 |
| TZN-CR | -492.6 ± 31.6 | 12.1 ± 0.4 | 5.673±0.272 | 1.751±0.107 | 1.960±0.083 | 0.9385±0.0119 | 2.602±0.263 | 1.288±0.102 |
| TZN-800 | -405.4 ± 17.2 | 6.12±0.2 | 5.651±0.347 | 2.606±0.151 | 1.471±0.065 | 0.9486±0.0083 | 1.864±0.158 | 0.736±0.046 |
Fig. 7. (a) Potentiodynamic polarization curves of TZN-ST, TZN-CR, and TZN-800 alloys; (b) corrosion potential (Ecorr) and corrosion current density (Icorr) of TZN-ST, TZN-CR, and TZN-800 alloys; (c) Nyquist plots of TZN-ST, TZN-CR, and TZN-800 alloys and equivalent circuit; (d) Bode plots of TZN-ST, TZN-CR, and TZN-800 alloys; (e) M-S plots of TZN-ST, TZN-CR, and TZN-800 alloys; (f) first derivative curve of the M-S plots.
Fig. 8. High-resolution spectra of the constituents of (a1-a3) TZN-ST alloy, (b1-b3) TZN-CR alloy, (c1-c3) TZN-800 alloy.
Fig. 9. (a) X-ray photoelectron spectroscopy (XPS) survey spectra of TZN-ST, TZN-CR and TZN-800 alloys; (b-d) O intensity transition of TZN-ST, TZN-CR, and TZN-800 alloys from the surface of the passivation film towards the inside of passivation film by XPS depth profilometry; (e) compositional transition of TZN-ST, TZN-CR, and TZN-800 alloys from the surface of the passivation film towards the inside by XPS depth profilometry; (f) inverse pole figure (IPF) map of TZN-ST alloy.
Fig. 10. Schematic illustration of (a) cation vacancy migration without the influence of spinodal decomposition and (b) cation vacancy migration with the influence of spinodal decomposition.
Fig. 11. (a) The relative cell viability of MC3T3-E1 pre-osteoblasts cultured on TZN-800 alloy for 1, 4 and 7 days; (b-d) the live/dead staining images of MC3T3-E1 pre-osteoblasts cultured on TZN-800 alloy for (b) 1, (c) 4 and (d) 7 days.
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