NUCLEATION AND CRYSTALIZATION IN BULK METALLIC GLASSES

Ramsha Khan
MECE 6364 Phase Transformation in Materials
April 2016
INTRODUCTION
Nucleation is defined as the formation of a new thermodynamic phase in a material. It
could either be homogenous, or heterogeneous. Heterogeneous nucleation occurs at a surface
within the material called the nucleation site, which could be a grain boundary or an impurity.
Whereas homogenous nucleation occurs without any preferential nucleation sites, and is
therefore spontaneous and random.
A glass is an amorphous solid, which means its non-crystalline like a liquid but still holds
its shape like a solid. Glass is usually formed when you cool a liquid rapidly, hence avoiding the
nucleation of a crystal structure and any further crystallization. Recently scientists have found a
new class of materials called Metallic Glasses, which is an amorphous structure of metal alloys.
The first synthesis of an amorphous phase in an Au-Si system was done in 1960 by Duwez at
Caltech USA [1]. They achieved very high cooling rates of 105-106 K/s, essentially freezing liquid
metal and avoiding any nucleation of a crystalline phase.
Interest in the research and development of this new class of material spiked due to
their superior strength, large ductility in bending, lower friction coefficients, high hardness, high
corrosion resistance and wear resistance. However the downside to BMGs is the lack of their
ability to undergo homogenous plastic deformation, as there are no slip dislocations to absorb
the elastic energy.
Initially in the 1960s only thin films of metallic glass could be formed, because of the
extremely high cooling rate required. However in 1974 the first Bulk Metallic Glass (BMG) was
formed by using a suction-casting method. Here bulk means rods of diameter in the millimeter
scale, instead of the micro-meter thin plates.

Many classes of BMG materials have now been developed, with critical cooling rate of
as low as 0.10 K/s for the Pd40Cu30Ni10P20 alloy, and sample thickness of as large as 10cm. Table
1 lists some typical BMG families and the year they were developed.

BMG system
PdCuSi
PtNiP
AuSiGe
PdNiP
MgLnCu (Ln = lanthanide metal)
LnAlTM (TM = group transition metal)
ZrTiAlTM
TiZrTM
ZrTiCuNiBe
Nd(Pr)AlFeCo
Zr(Nb, Pd)AlTM
CuZrNiTi
Fe(Nb, Mo)(Al, Ga)(P, C, B, Si, Ge)
PdCu(Fe)NiP
Co(Al, Ga)(P, B, Si)
Fe(Zr, Hf, Nb)B
CoFe(Zr, Hf, Nb)B
Ni(Zr, Hf, Nb)(Cr, Mo)B
TiNiCuSn
LaAlNiCuCo
NiNb
Ni(Nb, Cr, Mo)(P, B)
Zr-based glassy composites
ZrNbCuFeBe
FeMnMoCrCB
NiNb(Sn, Ti)
Pr(Nd)(Cu, Ni)Al

Years
1974
1975
1975
1982
1988
1989
1990
1993
1993
1994
1995
1995
1995
1996
1996
1996
1996
1996
1998
1998
1999
1999
1999
2000
2002
2003
2003

Table 1: Bulk metallic glasses and the year they were developed. Source [2]

NUCLEATION AND GROWTH OF CRYSTALS IN

According to S Banerjee [4] three situations of nucleation can occur when we undercool a metal
alloy system:
1. No nucleation of crystalline phase: can be achieved by laser glazing, and the glass
produced is absolutely free of any quenched-in-nuclei.

2. Limited nucleation of crystals but no growth: can be achieved by melt spinning method,
and glass has some quenched-in-nuclei, where the nucleation rate depends on the rate
of cooling.
3. Nucleation of a limited number of crystals and their substantial growth: the metal glass
has some crystalline ribbons.

Figure 1: Comparison of critical cooling rate and reduced glass transition temperature for BMG, silicate glasses and conventional
metallic glasses. Source [2] & [3]

THERMODYNAMIC AND KINETIC ASPECT OF GLASS FORMATION AND CRYSTALLIZATION

Some terms that need to be defined for understanding the Glass forming ability or GFA
of metal alloys:

Tg is glass transition temperature.

Tm is melting temperature, or the liquidis line temperature for alloys

Trg = Tg/Tm, which is the ratio of glass to melting temperature is defined as reduced glass
transition temperature. Higher Trg values means better GFA.

Three empirical rules were summarized by Inoue in [3] as follows:

1. GFA (Glass forming ability) in BMGs tends to increase by increasing the number of
elements in the system because the competing crystalline phases which may form
increases with increased components, and actually destabilizes the system.
2. To have elements with varying atomic size, having more than a 12% size ratio.
3. Having negative heats of mixing values for the three main constituent elements.
Assuming steady state nucleation, the nucleation rate is given by:
=

. 1)

Where k is the Boltzmanns constant, T is the absolute temperature, A is a constant, D is

discursivity and

is the activation energy for the formation of a stable nuclei.

16
3(

. 2)

Where is the interfacial energy between the nuclei and liquid phase, and

is the

free-energy difference between the liquid state and the crystalline state.
( )=

Where

! "!

)*

# $ %& ( )' + $
)

)* %
&

( )

' (

. 3)

is enthalpy of fusion at # , "! is the entropy of fusion at # , %& ( ) is

delta of the specific heat capacity, and

is the temperature at which the crystal and liquid are

in equilibrium.
Smaller values of

makes

favor high GFA. A smaller enthalpy and higher entropy of fusion

smaller. Increasing the number of alloy components in the BMG increases the "!

term, and having a variation of atomic sizes causes a denser atomic packing of the atoms in the
liquid state which in turn results in a lower enthalpy

!.

Hence Inoues empirical rules for

increased glass forming ability in metallic glasses are seen to hold true for the above equations.

ZIRCONIUM-BASED METALLIC GLASSES

Figure 2: Free energy diagram of liquid

phase in Zr-Ni system. Source [4]

Figure 3: Temperature time-transformation curve for Zr-Ni

system. Source [4]

In figure 2 the free energy difference G for Zr 33% and Ni 67% is lower than that for Zr
24% and Ni 76%. This shows that super-cooling of 33% Zr alloy will have a higher amorphous
transformation as compared to Zr 24%. This observation is also confirmed by the T-T-T
(temperature, time, transformation curve) in figure 3. We see that the nose of the Zr 33% alloy
is further out on the time scale, which means that a slower cooling rate will suffice for an
amorphous transformation as compared to Zr 24% that has a much faster cooling rate. And we
have discussed earlier how slower cooling rates result in a better amorphous glass material, as
no nucleation occurs.
CONCLUSION
BMG materials have a high potential for being used in many applications such as die
materials (Pd-Cu-Ni-P), sporting equipment (ZrTiCuNiBe and ZrTiNiCu), electrode materials
(PdCuSiP) or Fe-based BMGs for soft magnetic applications. [2] BMG materials will become more
significant as further research and development is conducted on for this class of materials.

References
[1] Klement, W., Willens, R. H., & Duwez, P. (1960, 09). Non-crystalline Structure in Solidified Gold-Silicon Alloys.
Nature, 187(4740), 869-870.
[2] W.H. Wang, C. D. (2004, May 10). Bulk metallic glasses. Materials Science and Engineering, R 44, 45-89.
[3] Inoue, A. (2000). STABILIZATION OF METALLIC SUPERCOOLED LIQUID AND BULK AMORPHOUS ALLOYS. Acta
Mater, 48, 279-306.
[4] G.K. Dey, S. B. (1992, December). Rapid solidification of zirconium-based alloys. Bulletin of Materials Science,
15(6), 543-556.