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Metallic Glasses - No Disdain for Disorder

Metallic glasses were borne out from rapid cooling experiments with binary metallic alloys in the late 1950s at the California Institute of Technology under the aegis of Pol Duwez. The idea was to quench molten metal mixtures very rapidly and thereby bypass crystallization of the liquid alloy1. If crystallization, i.e., the formation of a crystalline phase from a parent liquid phase can be avoided, the atomic movement will be sufficiently restricted below a critical temperature for the liquid to be "frozen-in".

The concept of metallic glass as a frozen-in liquid suggests an atomic arrangement that resembles the atomic structure of a liquid. It is indeed the hallmark of glasses that atoms are not arranged periodically over distances of several interatomic distances or more. A transmission-electron microscopy (TEM) image of a bulk metallic Fe50Cr15Mo14C15B6 glass is shown in Fig. 1. The image is typical for metallic glasses in that it does not reflect periodicity but instead a pattern that is often referred to as "salt and pepper" structure. The question how exactly the atoms in metallic glasses are arranged has captivated the glass research community for decades2-6. The recent, mostly computer simulation-based research indicates that a significant fraction of atoms in metallic glasses are arranged in clusters with sizes of a few nanometers. These clusters might reveal some connectivity3,4. It has furthermore been demonstrated that even small amounts of alloying additions can drastically affect the fraction of atoms that are arranged in clusters3. Advances in computer simulations, first principle calculations, and atomic level experimental characterization of materials promises further advances and insight in the near future into the "structure" of metallic glasses, the dependence of cluster volume fractions on composition, and the thermal history.

TEM image of bulk metallic Fe50Cr15Mo14C15B6 glass.
Fig.1: TEM image of bulk metallic Fe50Cr15Mo14C15B6 glass.

Synthesis of Metallic Glasses

A common strategy to synthesize metallic glasses is to quickly limit the mobility of atoms and thus to prevent atoms from moving into crystal lattice positions. Atomic mobility can be limited, for example, with rapid quenching from the liquid7 or vapor state8,9 onto substrates with a high thermal conductivity. Deposition techniques, including electro-deposition or vapor phase deposition are additional synthesis techniques that have proven successful for metallic glass synthesis. An entirely different approach is based on the destabilization of crystalline materials. Intense deformation10-12, irradiation with electrons13 or ions14, or even loading with hydrogen15 are approaches that destabilized crystalline pre-cursor materials and induced amorphous phases.

Even at the highest cooling rates not all alloys can be quenched into glassy phases. Only specific compositions can form metallic glasses. The necessity to avoid crystallization during quenching suggests a low liquidus temperature for glass forming compositions, i.e. a low solidification onset temperature during quenching. The liquid transforms into a frozen-in liquid when the viscosity exceeds about 1015 poise16 and the temperature range at which the viscosity crosses this critical value represents the glass transition range. For most glass forming compositions, the ratio of liquidus and glass transition temperature exceeds a value of about 0.5-0.6. To synthesize bulk metallic glasses Inoue proposed three empirical rules: the number of components in the alloy should exceed two, the size difference should be more than 12 %, and the heat of mixing between the major alloy components should be negative17. Exceptions to these rules are known and several additional criteria have been developed to address these exceptions18.

From the requirement for high cooling rates to bypass crystallization, it is clear that metallic glasses can not be cast in large sizes. Currently, the "record" size is 72 mm diameter for a Pd40Cu30Ni10P20 bulk metallic glass19.

Properties and Applications of Metallic Glasses

The lack of long-range periodicity in metallic glasses precludes the plastic deformation mechanisms that are operative in crystalline materials. The mechanical properties of metallic glasses are characterized by a large elastic limit of about 2 %--compared with about 0.2 % for crystalline metallic materials-and yield strength values that are about 1.5 to twice of those of their crystalline counterparts20. For example, tensile strength levels were reported for Al-based metallic glasses of up to 1500 MPa21 compared to about 750 MPa for the strongest crystalline Al alloys. Co-based bulk metallic glasses were measured with yield strengths of about 5 GPa22. These strength levels, however, only occur in compression. In tension much lower strength levels are observed. The lack of tensile strength follows from the deformation mechanism of metallic glasses that is based on shear bands. During deformation at room temperature, metallic glasses slide internally along bands with thicknesses of about 10-20 nm that can propagate through the entire sample if they are not impeded, for example, by precipitates. The challenge will remain for the foreseeable future to design metallic glasses with improved ductility but without loss in strength and elastic limit.

Metallic glasses differ greatly in their solute content compared with engineering alloys. The solute content in metallic glasses is typically on the order of tens of percent and thus far exceeds the solute content of conventional engineering alloys. At the same time, fully amorphous alloys are homogeneous. The combination of homogeneity, lack of grain boundaries, and concentrated solute content can play out very favorably for corrosion properties23.

The unique properties of metallic glasses appeal to a range of applications24,25. Structural applications include sporting goods such as baseball bats or tennis rackets, where metallic glasses excel with their high elastic limits, micro-meter sized gears and springs that reveal exceptional wear resistance26, biomedical applications such as tooth implants, or casings for electronic devices. Metallic glasses have been used since the late 1960s for magnetic applications, for example, as transformer core materials27. With an ever expanding range of glass-forming systems, processing improvements, and a better understanding of fundamental properties the number of applications continues to increase28. Once thought of as a lab curiosity, metallic glasses have come a long way, but still provide ample opportunities for new discoveries.

References

  1. Duwez, P., The Edward DeMille Campbell Memorial Lecture for 1967. Transactions of the ASM, 1967. 60: p. 606-633.
  2. Bakai, A.S., et al., Field emission microscopy of the cluster and subcluster structure of a Zr-Ti-Cu-Ni-Be bulk metallic glass. Low Temperature Physics, 2002. 28(4): p. 400-5.
  3. Cheng, Y.Q., E. Ma, and H.W. Sheng, Atomic level structure in multicomponent bulk metallic glass. Physical Review Letters, 2009. 102(24): p. 245501 (4 pp.).
  4. Takeuchi, A., et al., Molecular dynamics simulations of critically percolated, cluster-packed structure in Zr-Al-Ni bulk metallic glass. J. Mat. Sci., 2010. 45: p. 4898-4905.
  5. Bernal, J.D., Geometry of the structure of monatomic liquids. Nature, 1960. 185: p. 68-70.
  6. Polk, D.E., The structure of glassy metallic alloys. Acta met., 1972. 20: p. 485-491.
  7. Falkenhagen, G. and W. Hofmann, Die Auswirkung extrem hoher Abkuehlungsgeschwindigkeit auf die Erstarrung und Gefuege binaerer Legierungen. Z. Metallkde., 1952. 43: p. 69.
  8. Buckel, W., Z. Phys., 1954. 138: p. 136.
  9. Kramer, J., The amorphous state of metals. Z. Phys., 1936. 106: p. 675-691.
  10. Koch, C.C., et al., Preparation of 'amorphous' Ni60Nb40 by mechanical alloying. Appl. Phys. Lett., 1983. 43(11): p. 1017-1019.
  11. Sagel, A., et al., Synthesis of an amorphous Zr-Al-Cu-Ni alloy with large supercooled liquid region by cold-rolling of elemental foils. Acta mater., 1998. 46(12): p. 4233-4241.
  12. Atzmon, M., K.M. Unruh, and W.L. Johnson, Formation and characterization of amorphous erbium-based alloys preapred by near-isothermal cold-rolling of elemental composites. J. Appl. Phys., 1985. 58(10): p. 3865-3870.
  13. Mori, H., H. Fujita, and M. Fujita, Electron irradiation induced amorphization at dislocations in NiTi. Japanese Journal of Applied Physics, Part 2 (Letters), 1983. 22(2): p. 94-6.
  14. Hung, L.S., et al., Ion-induced amorphous and crystalline phase formation in Al/Ni, Al/Pd, and Al/Pt thin films. Applied Physics Letters, 1983. 42(8): p. 672-4.
  15. Aoki, K. and T. Masumoto, Hydrogen-induced amorphization of intermetallics. Journal of Alloys and Compounds, 1995. 231(1-2): p. 20-28.
  16. Turnbull, D., Under what conditions can a glass be formed? Contemp. Phys., 1969. 10(5): p. 473-488.
  17. Inoue, A., Bulk amorphous alloys: preparation and fundamental characteristics. Materials Science Foundations. Vol. 4. 1998, Uetikon-Zuerich: Trans-Tech Publications.
  18. Suryanarayana, C. and A. Inoue, Glass-forming ability of alloys, in Bulk metallic glasses. 2011, CRC Press. p. 49-135.
  19. Inoue, A., N. Nishiyama, and H. Kimura, Preparation and thermal stability of bulk amorphous Pd40Cu30Ni10P20 alloy cylinder of 72 mm in diameter. Mater. Trans. JIM, 1997. 38: p. 179-183.
  20. Schuh, C.A., T.C. Hufnagel, and U. Ramamurty, Overview No.144 - Mechanical behavior of amorphous alloys. Acta Materialia, 2007. 55(12): p. 4067-4109.
  21. Yeong-Hwan, K., A. Inoue, and T. Masumoto, Ultrahigh mechanical strengths of Al88Y2Ni10-xMx (M=Mn, Fe or Co) amorphous alloys containing nanoscale FCC-Al particles. Materials Transactions, JIM, 1991. 32(7): p. 599-608.
  22. Inoue, A., et al., Ultra-high strength above 5000 MPa and soft magnetic properties of Co-Fe-Ta-B bulk glassy alloys. Acta mater., 2004. 52: p. 1631-1637.
  23. Scully, J.R., A. Gebert, and J.H. Payer, Corrosion and related mechanical properties of bulk metallic glasses. Journal of Materials Research, 2007. 22(2): p. 302-313.
  24. Telford, M., The case for bulk metallic glass. Materials Today, 2004. 7(3): p. 36-43.
  25. www.liquidmetal.com.
  26. Ishida, M., et al., Wear resisitivity of super-precision microgear made of Ni-based metallic glass. Mater. Sci. Engr. , 2007. A 449-451: p. 149-154.
  27. McHenry, M.E., M.A. Willard, and D.E. Laughlin, Amorphous and nanocrystalline materials for applications as soft magnets. Progress in Materials Science, 1999. 44(4): p. 291-433.
  28. Greer, A.L., Metallic glasses...on the threshold. Materials Today, 2009. 12(1-2): p. 14-22.

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