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Topological instability and

electronegativity effects on the glass-
forming ability of metallic alloys
a b a a
W. J. Botta , F. S. Pereira , C. Bolfarini , C. S. Kiminami &
b
M. F. de Oliveira
a
Departamento de Engenharia de Materiais , Universidade
Federal de São Carlos , São Carlos, SP, Brazil
b
Escola de Engenharia de São Carlos , Universidade de São Paulo ,
São Carlos, SP, Brazil
Published online: 21 Oct 2008.

To cite this article: W. J. Botta , F. S. Pereira , C. Bolfarini , C. S. Kiminami & M. F. de Oliveira

(2008) Topological instability and electronegativity effects on the glass-forming ability of metallic
alloys, Philosophical Magazine Letters, 88:11, 785-791, DOI: 10.1080/09500830802375622

To link to this article: http://dx.doi.org/10.1080/09500830802375622

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 Philosophical Magazine Letters
Vol. 88, No. 11, November 2008, 785–791

Topological instability and electronegativity effects on the glass-forming

ability of metallic alloys
W.J. Bottaa*, F.S. Pereirab, C. Bolfarinia, C.S. Kiminamia and M.F. de Oliveirab
a
Departamento de Engenharia de Materiais, Universidade Federal de São Carlos,
São Carlos, SP, Brazil; bEscola de Engenharia de São Carlos, Universidade de
São Paulo, São Carlos, SP, Brazil
Downloaded by [University of Auckland Library] at 15:24 16 October 2014

(Received 21 May 2008; final version received 28 July 2008)

The glass-forming ability (GFA) of metallic alloys is associated with a topological

instability criterion combined with a new parameter based on the average
electronegativity difference of an element and its surrounding neighbours. In this
model, we assume that during solidification the glassy phase competes directly
with the supersaturated solid solution having the lowest topological instability
factor for a given composition. This criterion is combined with the average
electronegativity difference among the elements in the alloy, which reflects the
strength of the liquid. The GFA is successfully correlated with this combined
criterion in several binary glass-forming systems.
Keywords: topological instability; electronegativity; amorphous metals; rapidly
solidified materials

In a previous work [1], we have shown that a topological instability criterion, as defined
by the  parameter [2,3], can be a useful criterion for design and selection of easy
glass-forming compositions in metallic systems. The strategy proposed for using the 
criterion for the selection of good glass-forming compositions was to avoid the
composition fields associated with primary crystallization in any particular metallic
alloy composition. In our assumption, primary crystallization was defined as the first
phase to appear during crystallization of the amorphous bulk metallic glass (bmg)
independently of whether one has a solid solution or an intermetallic compound. In this
article, we propose the combined use of the topological  criterion with a new factor based
on the average electronegativity difference of the elements and their surrounding
neighbours in the alloy as a better indication of good glass-forming compositions in
binary systems.
The topological instability  is calculated from the atomic radii (in simple solid
solutions) or molar volumes of the compounds according to Equation (1):
X  Vmi 

ffi 
i   1, ð1Þ
Vm0

*Corresponding author. Email: wjbotta@ufscar.br

ISSN 0950–0839 print/ISSN 1362–3036 online

ß 2008 Taylor & Francis
DOI: 10.1080/09500830802375622
http://www.informaworld.com
 786 W.J. Botta et al.

where i and Vmi are the molar fraction and molar volume, respectively, of the solute
element in the compound and Vm0 is the molar volume of the compound. Large values of
 indicate a greater topological instability of the phase under consideration. In order for
a liquid alloy cooled fast enough to avoid long-range diffusion to result in polymorphic
solidification, the solid solution with the smallest  (i.e. the least unstable) in comparison
with all competing crystalline phases around the alloy composition, is the most likely to be
stable during solidification. Such an assumption implies that the best glass-forming
compositions should be around those with the largest values of , in which case the
competing phases are simultaneously more unstable.
We exemplify this situation for the Zr–Cu binary system in Figure 1. The solid lines
show the variation with composition of , calculated according to Equation (1),
considering the de-stabilization by solute addition of each stable phase in this system,
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either the solid solutions in the Zr-rich and Cu-rich ends or the intermediate phases. For
each composition, the minimum calculated  is taken and therefore the line represents the
minimum value of  among the surrounding stable phases, that is, min. The peaks in the
min plot then correspond to compositions where the topological instability reaches a local
maximum and therefore a better glass-forming ability (GFA) is expected. The higher the
peak, the better is the GFA.
The min plot of Figure 1 includes only phases that are stable at low temperatures.
Thus, it does not include the CuZr intermetallic compound, which is stable only at
temperatures higher than 715 C, far above Tg, with no driving force to be formed at the
glass transition in comparison with the Cu30Zr7 and CuZr2 stable phases. Therefore, in our
proposal, only crystalline phases stable at low temperatures are considered to be
competing phases against glass formation and for the calculation of  values.

Figure 1. Values of min (solid line) and average electronegativity difference (dashed line) in the
Zr–Cu system.
 Philosophical Magazine Letters 787

Also, as we have already discussed for the Zr–Cu system [1], compositions near the
terminal solid solutions are not good glass formers (contrary to what we should expect by
the min values shown in Figure 1) and one of the reasons is certainly the facility to
crystallize the simple structure of a solid solution. Such a condition can also be indicated
by any factor describing the strength of the liquid and we here propose to combine the
topological  parameter with a new parameter based on the average electronegativity
difference of an element and its surrounding neighbours (
e).
The effect of the electronegativity of the solute atoms on the stabilization of the
supercooled liquid region in Al-based glassy alloys has been already reported [4,5]. In that
case, within a certain composition range, the electronegativity difference between Al and
the solute leading to a more metallic type of bonding was observed to be associated with
the stability of the supercooled liquid. The electronegativity difference among the elements
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of an alloy is directly related to its formation enthalpy (
H) [6] and its glass stability [7].
It is also well known that large negative formation enthalpies among the main constitutive
elements are important for glass formation as firstly introduced by Inoue in his classical
empirical rules [8].
The correlation between electronegativity difference among the elements and the
formation of certain types of clusters has also been previously discussed [9,10]. Small
differences in electronegativity tend to lead to the formation of solid solutions while large
differences tend to lead to stoichiometric compounds, in both cases resulting in a low
GFA. However, a proper mismatch in electronegativity can promote the formation of
specific clusters which can enhance the GFA. Thus, it is reasonable to assume that the
average electronegativity difference among the elements is a useful parameter to help in
predicting the GFA, although it cannot be used alone. Other parameters should be
properly combined with the electronegativity difference in order to promote a synergetic
effect that allows a better prediction of GFA. The criterion we propose in this work takes
into account two factors, the atomic size mismatch, i.e. the mutual topological instability
of competing crystalline phases, and the chemical affinity indicated by the electro-
negativity difference amongst the elements.
The average electronegativity difference among the constitutive elements in the alloy
can be calculated considering the random packing of neighbours around a central atom.
We assume, however, that the neighbourhood is dependent on the surface concentrations
of atoms, instead of simple atomic fractions, as in Miedema’s model for calculations of
enthalpies [11]. In this approach, the surface concentrations are used to weight the
electronegativity difference among a central atom and its neighbours and the overall
average is weighted by the atomic fraction of each element as indicated in the following
Equation (2):
X X  

e ¼ i Sj ei  ej : ð2Þ
Here
e is the average electronegativity difference, i is the atomic fraction of each
element, ei is the Pauling’s electronegativity of a central atom, ej is the electronegativity of
each neighbour and Sj is the surface concentration according to Equation (3):
 2=3
j Vmj
Sj ¼ P  2=3 , ð3Þ
j Vmj
where j is the atomic fraction of each element in the alloy and Vmj the molar volume.
 788 W.J. Botta et al.
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Figure 2. Variation of (min
e) against Cu content in the Zr–Cu diagram. The vertical dashed lines
indicate the experimental range of bmgs reported for the Zr–Cu system.

Figure 1 also shows (dashed line) the variation of
e, the average electronegativity,
for the Zr–Cu system. Figure 2 plots for the Zr–Cu system the simple multiplication
of the values (min
e) against Cu content, assuming a synergetic effect among them.
The consideration of the average electronegativity significantly changed the peaks, with an
important decrease in the peaks around compositions near both ends of the diagram. Also
indicated in Figure 2 the composition ranges where bmgs with thickness up to 2 mm have
been reported for the Zr–Cu system [12–16]. The agreement with the two highest peaks of
min
e is remarkable.
The same agreement was observed for many other different binary alloys. Figure 3
indicates the peaks of min
e for 10 binary systems which form amorphous phases. The
vertical lines in the figure indicate the composition ranges reported to form an amorphous
phase [12–23] under the cooling conditions specified by the following code: sc – splat
cooled samples, ms – melt spun ribbons, ms/Tg – melt spun ribbons with glass transitions
and bmg (up to 2 mm).
In addition to the good agreement shown in Figures 2 and 3, the combined criterion of
min
e appears to rank the best glass-forming compositions among different systems.
Figure 4 classifies the highest values of min
e for the 11 compositional ranges evaluated
in our work suggesting that the GFA, as shown by the reported sample thickness, can be
directly related to the absolute value of our criterion.
The amorphous alloys obtained only by sc are from systems with the lowest values of
min
e. Amorphous alloys in systems with increasing values of min
e can be obtained by
corresponding lower cooling rates as indicated by the alloys obtained by ms or produced in
bulk with thickness up to 2 mm (bmg).
Two interesting cases are Ca–Al and Ca–Zn systems. From eight binary systems
that have been investigated in the original work [22], detection of the glass transition in
ms ribbons has been reported only for these systems. The supercooled liquid range
Tx
 Philosophical Magazine Letters 789
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Figure 3. Plots of min
e in 10 binary systems. The respective glass-forming composition ranges
occurs between the vertical lines [12–23]. The atomic fraction of the right hand element of each
atomic pair is indicated at the bottom. The sample thickness is indicated as follows: sc – splat cooled
samples, ms – melt spun ribbons, ms/Tg – melt spun ribbons with glass transition, bmg – bulk
metallic glasses (up to 2 mm). Dashed line in Al–Ca refers to the old assessed phase diagram.

(¼Tx  Tg), where Tx is the crystallization temperature and Tg the glass transition
temperature, which is associated with the stability of the glass, was reported to be around
15 K for the alloys Ca65Al35 and Ca65Zn35. A recent report [23] presents bulk glass
formation (1 mm in size) for Al–Ca alloys with 33–35 at.% Al. In good agreement with our
combined criteria, the bmg composition lies quite close to the highest min
e peak in the
Ca–Al system. If one considers the old assessment from the Al–Ca phase diagram, the
prediction lies exactly in the experimental compositional range. Regarding the Ca–Zn
system, the Ca65Zn35 composition corresponds to the second highest peak. These
experimental data and the ranking of min
e values presented in Figure 4 suggest the
possibilities of obtaining bulk binary (1 mm) alloys around the compositions Zn58Ca42
and Al85Ca15, and amorphous ms ribbons around the compositions Pd50Si50, Zn72Mg28,
Co57Ti43 and Mg76Ca24.
 790 W.J. Botta et al.
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Figure 4. Highest values of min
e in 10 binary systems. The sample thickness is indicated as
follows: sc – splat cooled samples, ms – melt spun ribbons, ms/Tg – melt spun ribbons with glass
transition and bmg – bulk metallic glasses (up to 2 mm).

In summary, the GFA of binary systems can be successfully correlated with a new
parameter which combines the topological instability  criterion with the average
electronegativity difference of the elements and their surrounding neighbours.

Acknowledgements
This work was financially supported by CAPES, CNPq and FAPESP (Brazil).

References

[1] C.S. Kiminami, R.D. Sá Lisboa, M.F. de Oliveira et al., Mat. Trans. JIM 48 (2007) p.1739.
[2] R.D. Sá Lisboa, C. Bolfarini, W.J. Botta F. et al., Appl. Phys. Lett. 86 (2005) p.211904.
[3] T. Egami and Y. Waseda, J. Non-Cryst. Solids 64 (1984) p.113.
[4] D.V. Louzguine and A. Inoue, Appl. Phys. Lett. 79 (2001) p.3410.
[5] D.V. Louzguine-Luzgin, A. Inoue and W.J. Botta, Appl. Phys. Lett. 88 (2006) p.011911.
[6] S.S. Fang, Z.Q. Zhou, J.L. Zhang et al., J. Alloys Compd. 293–295 (1999) p.10.
[7] S.S. Fang, X.S. Xiao, L. Xia et al., J. Non-Cryst. Solids 321 (2003) p.120.
[8] A. Inoue, Acta Mater. 48 (2000) p.279.
[9] Z.P. Lu, C.T. Liu and Y.D. Dong, J. Non-Cryst. Solids 341 (2004) p.93.
[10] W.Y. Liu, H.F. Zhang, A.M. Wang et al., Mat. Sci. Eng. A 459 (2007) p.196.
[11] F.R. Boer, Cohesion in Metals, Vol. 1, North-Holland, Amsterdam, 1988.
[12] M.B. Tang, D.Q. Zhao, M.X. Pan et al., Chin. Phys. Lett. 5 (2004) p.901.
[13] P. Yu, H.Y. Bai, M.B. Tang et al., J. Non-Cryst. Solids 351 (2005) p.1328.
[14] A. Inoue, W. Zhang and J. Saida, Mat. Trans. JIM 45 (2004) p.1153.
[15] W.H. Wang, J.J. Lewandowski and A.L. Greer, J. Mat. Res. 20 (2005) p.2307.
[16] D. Xu, B. Lohwongwata, G. Duan et al., Acta Mater. 52 (2004) p.2621.
 Philosophical Magazine Letters 791

[17] L.E. Tanner and R. Ray, Acta Met. 27 (1979) p.1727.

[18] P. Duwez, R.H. Willens and R.C. Crewdson, J. App. Phys. 36 (1965) p.2267.
[19] A. Calka, D.E. Polk, B.C. Giessen et al., Scripta Met. 11 (1977) p.65.
[20] L.C.R. Aliaga, M.F. de Oliveira, C. Bolfarini et al., J. Non-Cryst. Solids 354 (2008) p.1932.
[21] A. Inoue, K. Kobayashi, C. Suryanarayana et al., Scripta Met. 14 (1980) p.119.
[22] R.S. Amand and B.C. Giessen, Scripta Met. 12 (1978) p.1021.
[23] F.Q. Guo, S. Poon and G.J. Shiflet, Appl. Phys. Lett. 84 (2004) p.37.
Downloaded by [University of Auckland Library] at 15:24 16 October 2014