Abstract
A Cu- and Ni-free Zr-based metallic glass with high glass-forming ability was found in the Zr-Al-Co ternary system. The eutectic Zr56Al16Co28 alloy could be cast into glassy cylindrical rods with diameters up to 18 mm. The glassy alloy exhibited high tensile fracture strength of 1830 MPa and low Young’s modulus of 83 GPa in conjunction with better corrosion resistance compared with the glassy Zr57Nb5Al10Ni12.6Cu15.4 in a simulated body fluid. Hydrothermal-electrochemical treatment in the aqueous 5M-NaOH solution resulted in the formation of amorphous sodium cobaltate layer on the surface of glassy Zr56Al16Co28 alloy. Hydroxyapatite was spontaneously formed on the surface of the alloy, indicating bioactivity after surface modification. The discovery of a Cu- and Ni-free Zr-based metallic glass with a critical diameter larger than 1 cm in conjunction with excellent mechanical properties, superior corrosion resistance, and good bioactivity may open up the application field as biomaterials.
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References
A. Inoue: Stabilization of metallic supercooled liquid and bulk amorphous alloys. Acta Mater. 48, 279 (2000).
W.L. Johnson: Bulk glass-forming metallic alloys: Science and technology. MRS Bull. 24, 42 (1999).
A. Inoue, T. Zhang and T. Masumoto: Preparation of bulky amorphous Zr-Al-Co-Ni-Cu alloys by copper mold casting and their thermal and mechanical properties. Mater. Trans., JIM 36, 391 (1995).
T. Zhang and A. Inoue: New glassy Zr-Al-Fe and Zr-Al-Co alloys with a large supercooled liquid region. Mater. Trans., JIM 43, 267 (2002).
Y. Yokoyama, K. Fukaura and A. Inoue: Cast structure and mechanical properties of Zr-Cu-Ni-Al bulk glassy alloy. Intermetallics 10, 1113 (2002).
A. Inoue and T. Zhang: Fabrication of bulk glassy Zr55Al10-Ni5Cu30 alloy of 30 mm in diameter by a suction casting method. Mater. Trans. 37, 185 (1996).
A. Peker and W. Johnson: A highly processable metallic glass: Zr41.2Ti13.8Cu12.5Ni10.0Be22.5. Appl. Phys. Lett. 63, 2342 (1993).
Q. Zhang, W. Zhang and A. Inoue: New Cu-Zr-based bulk metallic glasses with large diameters of up to 1.5 cm.Scr. Mater. 55, 711 (2006).
N. Nishiyama, K. Amiya and A. Inoue: Bulk metallic glasses for industrial products. Mater. Trans. 45, 1245 (2004).
S. Hiromoto, A.P. Tsai, M. Sumita and T. Hanawa: Corrosion behavior of Zr65A7.5Ni10Cu17.5 amorphous alloy for biomedical use. Mater. Trans. 42, 656 (2001).
S. Buzzi, K. Jin, P.J. Uggowitzer, S. Tosatti, I. Gerber and J.F. Löffler: Cytotoxicity of Zr-based bulk metallic glasses. Inter-metallics 14, 729 (2006).
J. Park and R.S. Lakes: Biomaterials, An Introduction, 3rd ed. (Springer, New York, 2007), pp. 99, 137.
L.L. Hench: Bioceramics. J. Am. Ceram. Soc. 80, 1705 (1998).
T. Kokubo, H.M. Kim and M. Kawashita: Novel bioactive materials with different mechanical properties. Biomaterials 24, 2161 (2003).
N. Ohtsu, K. Sato, A. Yanagawa, K. Saito, Y. Imai, T. Kohgo, A. Yokoyama, K. Asami and T. Hanawa: CaTiO3 coating on T. Wada et al.: Formation and bioactivation of Zr-Al-Co bulk metallic glasses titanium for biomaterial application—Optimum thickness and tissue response. J. Biomed. Mater. Res. 82A, 304 (2007).
H.M. Kim, F. Miyaji, T. Kokubo and T. Nakamura: Effect of heat treatment on apatite-forming ability of Ti metal induced by alkali treatment. J. Mater. Sci. - Mater. Med. 8, 341 (1997).
N. Sugiyama, H.Y. Xu, T. Onoki, Y. Hoshikawa, T. Watanabe, N. Matsushita, X.M. Wang, F.X. Qin, M. Fukuhara, M. Tsukamoto, N. Abe, Y. Komizo, A. Inoue and M. Yoshimura: Bioactive titanate nanomesh layer on the Ti-based bulk metallic glass by hydrothermal-electrochemical technique. Acta Biomater. 5, 1367 (2009).
M. Yoshimura, T. Onoki, M. Fukuhara, X.M. Wang, K. Nakata and T. Kuroda: Formation of growing integrated layer [GIL] between ceramics and metallic materials for improved adhesion performance. Mater. Sci. Eng., B 148, 2 (2008).
ASM Alloy Phase Diagrams Center: http://www.asminternational.org/asmenterprise/apd/.
H.S. Chen: Glassy metals. Rep. Prog. Phys. 43, 353 (1980).
A. Inoue: Bulk Amorphous Alloys, Preparation and Fundamental Characteristics (Trans Tech Publication, Zurich, 1999), pp. 6, 15.
R.T. DeHoff and F.N. Rhines: Quantitative Microscopy (McGrawHill, New York, 1968).
A. Takeuchi and A. Inoue: Classification of bulk metallic glasses by atomic size difference, heat of mixing and period of constituent elements and its application to characterization of the main alloying element. Mater. Trans. 46, 2817 (2005).
S. Pang, T. Zhang, K. Asami and A. Inoue: Formation, corrosion behavior, and mechanical properties of bulk glassy Zr-Al-Co-Nb alloys. J. Mater. Res. 18, 1652 (2003).
I. Catelas, A. Petit, D.J. Zukor and O.L. Huk: Cytotoxic and apoptotic effects of cobalt and chromium ions on J774 macro-phages—Implication of caspase-3 in the apoptotic pathway. J. Mater. Sci.-Mater. Med. 12, 949 (2001).
Y.G. Shi, Y.L. Liu, H.X. Yang, C.J. Nie, R. Jin and J.Q. Li: Raman spectroscopy study of NaxCoO2 and superconducting NaxCoO2 [C2]yH2O. Phys. Rev. B 70, 052502 (2004).
M. Pouraix: Atlas of Electrochemical Equilibria in Aqueous Solutions (Cebelcor, Houston, 1974).
J.R.V. Wazer: Phosphorous and Its Compounds: Chemistry, vol. 1 (Interscience Publisher, New York, 1958), pp. 510, 538.
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Wada, T., Qin, F., Wang, X. et al. Formation and bioactivation of Zr-Al-Co bulk metallic glasses. Journal of Materials Research 24, 2941–2948 (2009). https://doi.org/10.1557/jmr.2009.0348
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DOI: https://doi.org/10.1557/jmr.2009.0348