Hostname: page-component-5db6c4db9b-fdz9p Total loading time: 0 Render date: 2023-03-23T02:57:08.640Z Has data issue: true Feature Flags: { "useRatesEcommerce": false } hasContentIssue true

Oxidation resistance of the supercooled liquid in Cu50Zr50 and Cu46Zr46Al8 metallic glasses

Published online by Cambridge University Press:  21 February 2012

Ka Ram Lim
Center for Non-crystalline Materials, Department of Materials Science and Engineering, Yonsei University, Seoul 120-749, Korea
Won Tae Kim
Department of Optical Engineering, Cheongju University, Cheongju 360-764, Korea
Eun-Sung Lee
Materials Research Center, Samsung Advanced Institute of Technology (SAIT), Gyeonggi-do 446-712, Korea
Sang Soo Jee
Materials Research Center, Samsung Advanced Institute of Technology (SAIT), Gyeonggi-do 446-712, Korea
Se Yun Kim
Materials Research Center, Samsung Advanced Institute of Technology (SAIT), Gyeonggi-do 446-712, Korea
Do Hyang Kim*
Center for Non-crystalline Materials, Department of Materials Science and Engineering, Yonsei University, Seoul 120-749, Korea
Annett Gebert
IFW Dresden, Institute for Complex Materials, D-01171 Dresden, Germany
Jurgen Eckert
IFW Dresden, Institute for Complex Materials, D-01171 Dresden, Germany; and TU Dresden, Institute of Materials Science, D-01062 Dresden, Germany
a)Address all correspondence to this author. e-mail:
Get access


The oxidation behavior of Cu50Zr50 and Cu46Zr46Al8 glasses during continuous heating up to 1073 K has been investigated, with special emphasis on the oxidation resistance in the supercooled liquid (SCL) state. For Cu50Zr50, the oxide layer mostly consists of monoclinic ZrO2 (m-ZrO2), while for Cu46Zr46Al8, the oxide layer consists of two different layers: an outer layer consisting of tetragonal ZrO2 (t-ZrO2) + Al2O3 + metallic Cu (oxidation product from the SCL state of the glass matrix) and inner layer comprised of m-ZrO2 + metallic Cu islands (oxidation product from the crystallized matrix). Cu-enriched regions consisting of Cu51Zr14 (in Cu50Zr50) or AlCu2Zr + Cu70Zr15Al15 + Cu51Zr14 (in Cu46Zr46Al8) are present below the oxide layer. The present study shows that the addition of Al (8 at.%) in Cu50Zr50 results in a significant deterioration of the oxidation resistance in the SCL state since the solutionizing of Al in t-ZrO2 leads to a higher oxygen ion vacancy concentration, thus providing a higher activity of oxygen ions.

Copyright © Materials Research Society 2012

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)



1.Salimon, A.I., Ashby, M.F., Brechet, Y., and Greer, A.L.: Bulk metallic glasses: What are they good for? Mater. Sci. Eng., A 375, 385 (2004).CrossRefGoogle Scholar
2.Ashby, M.F. and Greer, A.L.: Metallic glasses as structural materials. Scr. Mater. 54, 321 (2006).CrossRefGoogle Scholar
3.Hofmann, D.C.: Shape memory bulk metallic glass composites. Science 329, 1294 (2010).CrossRefGoogle ScholarPubMed
4.Pauly, S., Gorantla, S., Wang, G., Kuhn, U., and Eckert, J.: Transformation-mediated ductility in CuZr-based bulk metallic glasses. Nat. Mater. 9, 473 (2010).CrossRefGoogle ScholarPubMed
5.Kumar, G., Tang, H.X., and Schroers, J.: Nanomoulding with amorphous metals. Nature 457, 868 (2009).CrossRefGoogle ScholarPubMed
6.Schroers, J.: Processing of bulk metallic glass. Adv. Mater. 22, 1566 (2010).CrossRefGoogle ScholarPubMed
7.Saotome, Y., Imai, K., Shioda, S., Shimizu, S., Zhang, T., and Inoue, A.: The micro-nanoformability of Pt-based metallic glass and the nanoforming of three-dimensional structures. Intermetallics 10, 1241 (2002).CrossRefGoogle Scholar
8.Schroers, J., Pham, Q., Peker, A., Paton, N., and Curtis, R.V.: Blow molding of bulk metallic glass. Scr. Mater. 57, 341 (2007).CrossRefGoogle Scholar
9.Schroers, J.: The superplastic forming of bulk metallic glasses. JOM 57, 35 (2005).CrossRefGoogle Scholar
10.Fukushige, T., Hata, S., and Shimokohbe, A.: A MEMS conical spring actuator array. J. Microelectromech. Syst. 14(2), 243 (2005).CrossRefGoogle Scholar
11.Schroers, J., Nguyen, T., and Desai, A.: Superplastic Forming of Bulk Metallic Glass—A Technology for MEMS and Microstructure Fabrication (IEEE-MEMS 2006, Istanbul, Turkey, 2006), p. 298.Google Scholar
12.Carmo, M., Sekol, R.C., Ding, S.Y., Kumar, G., Schroers, J., and Taylor, A.D.: Bulk metallic glass nanowire architecture for electrochemical applications. ACS Nano 5(4), 2979 (2011).CrossRefGoogle ScholarPubMed
13.Kim, S.Y., Jee, S.S., Lim, K.R., Kim, W.T., Kim, D.H., Lee, E.S., Kim, Y.H., Lee, S.M., Lee, J.H., and Eckert, J.: Replacement of oxide glass with metallic glass for Ag screen printing metallization on Si emitter. Appl. Phys. Lett. 98, 222112 (2011).CrossRefGoogle Scholar
14.Kimura, H.M., Asami, K., Inoue, A., and Masumoto, T.: The oxidation of amorphous Zr-based binary alloys in air. Corros. Sci. 35, 909 (1993).CrossRefGoogle Scholar
15.Tam, C.Y. and Shek, C.H.: Oxidation behavior of Cu60Zr30Ti10 bulk metallic glass. J. Mater. Res. 20(6), 1396 (2005).CrossRefGoogle Scholar
16.Koster, U., Jastrow, L., and Meuris, M.: Oxidation of Cu60Zr30Ti10 metallic glasses. Mater. Sci. Eng.,A 449, 165 (2007).CrossRefGoogle Scholar
17.Tam, C.Y. and Shek, C.H.: Oxidation-induced copper segregation in Cu60Zr30Ti10 bulk metallic glass. J. Mater. Res. 21(4), 851 (2006).CrossRefGoogle Scholar
18.Kai, W., Kao, P.C., Lin, P.C., Ren, I.F., and Jang, J.S.C.: Effects of Si addition on the oxidation behavior of a Cu–Zr-based bulk metallic alloy. Intermetallics 18, 1994 (2010).CrossRefGoogle Scholar
19.Tam, C.Y. and Shek, C.H.: Effects of alloying on oxidation of Cu-based bulk metallic glasses. J. Mater. Res. 20(10), 2647 (2005).CrossRefGoogle Scholar
20.Tam, C.Y., Shek, C.H., and Wang, W.H.: Oxidation behaviour of a Cu-Zr-Al bulk metallic glass. Rev. Adv. Mater. Sci. 18, 107 (2008).Google Scholar
21.Kai, W., Ho, T.H., Hsieh, H.H., Chen, Y.R., Qiao, D.C., Jiang, F., Fan, G., and Liaw, P.K.: Oxidation behavior of CuZr-based glassy alloys at 400 °C to 500 °C in dry air. Metall. Mater. Trans. A 39A, 1838 (2008).CrossRefGoogle Scholar
22.Liu, L. and Chan, K.C.: Oxidation of Zr55Cu30Al10Ni5 bulk metallic glass in the glassy state and the supercooled liquid state. Appl. Phys. A 80, 1737 (2005).CrossRefGoogle Scholar
23.Sun, X., Schneider, S., Geyer, U., Johnson, W.L., and Nicolet, M.A.: Oxidation and crystallization of an amorphous Zr60Al15Ni25 alloy. J. Mater. Res. 11(11), 2738 (1996).CrossRefGoogle Scholar
24.Zhang, Q., Zhang, W., Xie, G., and Inoue, A.: Glass-forming ability and mechanical properties of the ternary Cu–Zr–Al and quaternary Cu–Zr–Al–Ag bulk metallic glasses. Mater. Trans. 48(7), 1626 (2007).CrossRefGoogle Scholar
25.Pauly, S., Das, J., Mattern, N., Kim, D.H., and Eckert, J.: Phase formation and thermal stability in Cu–Zr–Ti(Al) metallic glasses. Intermetallics 17, 453 (2009).CrossRefGoogle Scholar
26.Sun, Y.F., Wei, B.C., Wang, Y.R., Li, W.H., Cheung, T.L., and Shek, C.H.: Plasticity-improved Zr–Cu–Al bulk metallic glass matrix composites containing martensite phase. Appl. Phys. Lett. 87, 051905 (2005).CrossRefGoogle Scholar
27.Ho, S.M.: On the structural chemistry of zirconium oxide. Mater. Sci. Eng. 54, 23 (1982).CrossRefGoogle Scholar
28.Lu, X., Liang, K., Gu, S., Zheng, Y., and Fang, H.: Effect of oxygen vacancies on transformation of zirconia at low temperatures. J. Mater. Sci. 32, 6653 (1997).CrossRefGoogle Scholar
29.Shukla, S. and Seal, S.: Mechanisms of room temperature metastable tetragonal phase stabilisation in zirconia. Int. Mater. Rev. 50(1), 1 (2005).CrossRefGoogle Scholar
30.Ganduglia-Pirovano, M.V., Hofmann, A., and Sauer, J.: Oxygen vacancies in transition metal and rare earth oxides: Current state of understanding and remaining challenges. Surf. Sci. Rep. 62, 219 (2007).CrossRefGoogle Scholar
31.Khan, M.S., Islam, M.S., and Bates, D.R.: Cation doping and oxygen diffusion in zirconia: A combined atomistic simulation and molecular dynamics study. J. Mater. Chem. 8(10), 2299 (1998).CrossRefGoogle Scholar
32.Arhammar, C., Araujo, C.M., and Ahuja, R.: Energetics of Al doping and intrinsic defects in monoclinic and cubic zirconia: First-principles calculations. Phys. Rev. B 80, 115208 (2009).CrossRefGoogle Scholar
33.Levin, E.M., Robbins, C.R., and McMurdie, H.F.: Phase diagrams for ceramists, 1969 Supplement (American Ceramic Society, Columbus, Ohio, 1969).Google Scholar