Exfoliation Resistance, Microstructure, and Oxide Formation Mechanisms of the White Oxide Layer on CP Ti and Ti–Nb–Ta–Zr Alloys
Abstract
:1. Introduction
2. Materials and Methods
3. Results
3.1. Exfoliation Resistance, Fretting Wear, and Nanoindentation Hardness of Oxide Layers
3.2. Results of Cross-Sectional SEM Observations and the Au Marker Method
3.3. Microstructural Observations by TEM
4. Discussion
4.1. Exfoliation Stress of Oxide-Coated Ti-Alloys
4.2. Relationship between Oxidation Direction and Exfoliation Resistance in Terms of the Pilling–Bedworth Ratio
4.3. Oxide Layer Formation Mechanisms
5. Summary and Conclusions
- 1.
- The exfoliation stress, σf, of the oxide layer on CP Ti is always <7 MPa, and its fracture is always caused by cohesion failure. The σf of the oxide layer on Ti–36Nb–2Ta–3Zr–0.3O is much higher than that of the oxide layer on CP Ti, and the maximum σf is approximately 70 MPa, which is approximately equal to the maximum stress of the epoxy adhesives. In the case of Ti–36Nb–2Ta–3Zr–0.3O, interfacial fracture occurs.
- 2.
- The high exfoliation resistances of Ti–36Nb–2Ta–3Zr–0.3O and Ti–29Nb–13Ta–4.6Zr are attributed to their dense and robust oxide microstructures; in addition, fine particles and a composition-graded interfacial microstructure may contribute to their high exfoliation resistance. In the case of CP Ti, its weak “piecrust-like” layered structure is broken prior to exfoliation at the interface.
- 3.
- The nanoindentation hardness of the oxide layers appears to decrease gradually and continuously with increasing depth toward the substrate; the hardness in the substrate also gradually decreases.
- 4.
- According to the results of the fretting frictional tests, both the static and dynamic friction coefficients obviously decrease as a consequence of the oxide layer formation.
- 5.
- The Au marker method indicates that out-diffusion plays a predominant role in oxide formation on CP Ti. Both in- and out-diffusion are involved in oxide formation on Ti–29Nb–13Ta–4.6Zr and Ti–36Nb–2Ta–3Zr–0.3O.
- 6.
- TEM observations of Ti−29Nb−13Ta−4.6Zr revealed that the transition layer consists of nanograins of a Ti-rich oxide phase and an Nb-, Ta-, and Zr-rich oxide phase at the interface between the oxide and the metal substrate. The oxide layer consists of dense submicron-sized TiNb2O7 and TiO2 grains, whereas the oxide layer on CP Ti consists of a layered structure with micron-sized TiO2 grains.
- 7.
- For Ti−29Nb−13Ta−4.6Zr and Ti−36Nb−2Ta−3Zr−0.3O, a robust oxidation layer with a multiphase equiaxed subnanomicrostructure forms continuously on the substrate through the nanostructured transition layer, and the high exfoliation resistance can be attributed to this strong and smooth graded structure.
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Miura-Fujiwara, E.; Yamada, S.; Mizushima, K.; Nishijima, M.; Watanabe, Y.; Kasuga, T.; Niinomi, M. Exfoliation Resistance, Microstructure, and Oxide Formation Mechanisms of the White Oxide Layer on CP Ti and Ti–Nb–Ta–Zr Alloys. Materials 2021, 14, 6599. https://doi.org/10.3390/ma14216599
Miura-Fujiwara E, Yamada S, Mizushima K, Nishijima M, Watanabe Y, Kasuga T, Niinomi M. Exfoliation Resistance, Microstructure, and Oxide Formation Mechanisms of the White Oxide Layer on CP Ti and Ti–Nb–Ta–Zr Alloys. Materials. 2021; 14(21):6599. https://doi.org/10.3390/ma14216599
Chicago/Turabian StyleMiura-Fujiwara, Eri, Soichiro Yamada, Keisuke Mizushima, Masahiko Nishijima, Yoshimi Watanabe, Toshihiro Kasuga, and Mitsuo Niinomi. 2021. "Exfoliation Resistance, Microstructure, and Oxide Formation Mechanisms of the White Oxide Layer on CP Ti and Ti–Nb–Ta–Zr Alloys" Materials 14, no. 21: 6599. https://doi.org/10.3390/ma14216599