Topological instability as a criterion for design and selection of aluminum-based glass-

former alloys
R. D. Sá Lisboa, C. Bolfarini, W. J. Botta F., and C. S. Kiminami

Citation: Applied Physics Letters 86, 211904 (2005); doi: 10.1063/1.1931047

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 APPLIED PHYSICS LETTERS 86, 211904 共2005兲

Topological instability as a criterion for design and selection

of aluminum-based glass-former alloys
R. D. Sá Lisboa,a兲 C. Bolfarini, W. J. Botta F., and C. S. Kiminami
Departamento de Engenharia de Materiais, Universidade Federal de São Carlos, CEP 13565-905, São
Carlos, SP, Brazil
共Received 15 December 2004; accepted 6 April 2005; published online 16 May 2005兲
This letter proposes a criterion to quantitatively correlate chemical composition with crystallization
behaviors of Al-based glass-former alloys. By extending to multicomponent systems the topological
instability model of Egami and Waseda 关J. Non-Cryst. Solids 64, 113 共1984兲兴, we introduce a
“lambda 共␭兲 criterion” according to which amorphous alloys with ␭ ⬎ 0.1 exhibit glassy behavior,
whereas alloys with ␭ ⬍ 0.1 are nanocrystalline. Nanoglassy alloys occur when ␭ ⬇ 0.1. A large
number of experimental findings in the literature supports the ␭ criterion, rendering it a useful tool
for the design and selection of glass-former systems and compositions. © 2005 American Institute
of Physics. 关DOI: 10.1063/1.1931047兴

Since the production of fully amorphous, ductile
aluminum-based alloys by Inoue et al.1 and He et al.,2 a large
number of Al-based alloys has been cast into the fully amor-
phous state when rapidly quenched from the liquid3 or made
amorphous by solid-state processing.4–6 A rough estimate
from the literature indicates more than 200 different amor-
phous alloys, within over 40 different systems, from binary1
to up to six solute elements;7 this multitude of alloys may
comprehensively and suitably be referred to as Al-TM-RE
共TM: transition metals; RE: rare-earth elements兲. Glass for-
mation is favored for multicomponent compositions
typically containing 80– 94 at. % Al, 3 – 20 at. % RE and
1 – 15 at. % TM, though limited glass formation was also re-
ported for binary Al-共Y,La,Ce,Sm兲 共Refs. 1, 8, and 9兲 and
pseudobinary Al-TM alloys with multiple TM additions.10
Strikingly, those innumerable Al-TM-RE glass-former
alloys may be grouped into only three categories of alloys,
distinguished from each other and defined by the crystalliza-
tion reactions11 and unique combinations of thermal, calori-
metric, mechanical, 共micro兲structural, and kinetics features
of their thermally induced crystallization process. Within the
scope of the present letter, thermal features—as effected by
and probed with a differential scanning calorimeter under
continuous heating—and crystallization reactions—as deter-
mined by x ray or electron diffractometry—suffice to define
the nanocrystalline, glassy, and nanoglassy crystallization
behaviors or categories of alloys as follows.
Nanocrystalline alloys undergo primary crystallization of
toughening fcc-Al nanocrystals12 with no clearly resolved
glass transition temperature Tg preceding the first crystalliza-
tion onset temperature Tx1. A large temperature interval sepa-
rates Tx1 from the precipitation of intermetallic phase共s兲 at a
second crystallization onset temperature Tx2. Glassy alloys
undergo either eutectic-like or polymorphic reactions at Tx1,
whereby fcc-Al and intermetallic phase共s兲 or a single meta-
stable intermetallic phase, respectively, crystallize from the
parent amorphous phase. Glassy alloys usually devitrify after
a clearly resolved Tg, and thus often exhibit a supercooled
liquid region ⌬Tx 共⌬Tx = Tx1 − Tg兲. Intermediate to the above-
mentioned, nanoglassy alloys exhibit a unique and promising
a兲
Author to whom correspondence should be addressed; electronic mail:
salisboa@iris.ufscar.br
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combination of primary nanocrystallization of fcc-Al pre-
ceded by a clear glass transition phenomenon, rendering
these alloys potential candidates for the synthesis of high-
strength, bulk nanocrystalline alloys by exploiting the vis-
cous flow of matter within ⌬Tx 共Ref. 13兲.
Despite the scientific and technological significance in-
trinsic to each of these categories of alloys being
broadly acknowledged, there is presently no systematic pro-
cedure for the design and selection of systems and/or com-
positions other than trial and error-based methods.14,15 Nano-
crystalline behavior is empirically related to Al-rich
compositions 共⬎88 at. % Al兲,16 yet primary crystallization
has been observed in compositions with as low an aluminum
content as 73 at. % 共Ref. 17兲. Conversely, the glassy behav-
ior has been experimentally found in TM- or RE-richer al-
loys, although it is occasionally observed in Al-rich alloys
such as Al88Ni4La6Gd2 共Ref. 7兲. Nanoglassy behavior has
been reported for a number of alloys,18–22 though no corre-
lation with chemical composition is apparent.
While these distinct crystallization behaviors are directly
related to and ultimately determined by chemical composi-
tion and the resulting atomic-level amorphous structure, no
definite picture of this structure has yet been proposed, de-
spite the current progress in the field.23 Graphical procedures
based on tentative topological aspects of atomic-level struc-
ture have also been recently proposed that distinguish ordi-
nary from bulk glass-former systems and successfully de-
scribe glass-forming ranges,24,25 but from which no inference
of crystallization reactions can be made. Hence, prediction of
crystallization behavior is not possible based on the current
knowledge of the amorphous structure. The use of computer-
aided thermodynamic modeling has only been able to a pos-
teriori explain a number of experimental findings of glass-
forming ability and crystallization reactions of some binary
systems.26 While no straightforward prediction of crystalliza-
tion behavior is implied by this method, attempts to model
multicomponent systems are restricted to but a few ternary
alloys,15,27 further limiting the applicability of this numerical
procedure as a guideline on alloy design and selection.
In this letter we describe and propose the extension of
the Egami-Waseda28 topological instability model as a crite-
rion for the prediction of crystallization behavior in multi-
component Al-TM-RE glass-former alloys, irrespective of
86, 211904-1 © 2005 American Institute of Physics
 211904-2 Sá Lisboa et al. Appl. Phys. Lett. 86, 211904 共2005兲

TABLE I. Experimental 共cexp B

兲 and predicted 共cmin
B
兲 solute concentrations for Metallic radii used in this letter are taken from Ref. 25.
amorphization by melt spinning of selected binary Al-based systems. Values Alloys of hypocritical compositions 共cexp B
⬍ cmin
B
; ␭0
B
of cmin are calculated for ␭0 = 0.1 in Eq. 共1兲, and ␭0 values correspond to the
B
limits of cexp ranges. Metallic radii taken from Ref. 25.
⬍ 0.100兲 have also been made amorphous, noticeably in
Al-Sm and Al-Ce systems; see Table I. This relaxation in the
Alloy system B
cexp B
cmin 共␭0 = 0.1兲 condition expressed by Eq. 共1兲 evokes the kinetic nature of
Al–B 共at. %兲 共at. %兲 ␭0 关Eq. 共1兲兴 amorphization: were high enough cooling rates available,
even pure metals would be made amorphous by quenching
Al–Sm 8–14a 9.8 0.082–0.143
from the liquid.
Al–Y 9–13b 10.1 0.089–0.129
Thorough inspection of references given in Ref. 28 and
Al–La 7–10c 7.9 0.088–0.126
Table I further suggests a correlation between ␭0 and the
Al–Ce 7–10c 9.3 0.075–0.107
previously defined crystallization behaviors: ␭0 ⬎ 0.100 re-
a
Data taken from Refs. 9 and 29–31. sulted in either polymorphous or eutectic crystallization—
b
Data taken from Refs. 1, 8, and 32. usually preceded by a clear Tg under continuous heating in a
c
Data taken from Refs. 1 and 33.
differential scanning calorimeter, while nanocrystalline be-
havior occurred whenever ␭0 ⬍ 0.100. For instance, Al92Sm8
identity or number of TM and RE elements, in advance of 共␭0 = 0.082兲 alloy underwent primary crystallization of fcc-Al
their production. The herein proposed “lambda 共␭兲 criterion” nanocrystals dispersed within a remaining amorphous
rationalizes the trial and error-based methods of systems matrix;9,29–31 Al90Sm10 共␭0 = 0.102兲 alloy exhibited polymor-
and/or composition selection by correlating chemical compo- phous crystallization to a metastable phase that subsequently
sition and crystallization behavior in a clear, predictable decomposed into a eutectic-like mixture of fcc-Al and
manner. intermetallic phases;9,30,31 both Al88Sm12 共␭0 = 0.122兲
In 1984, Egami and Waseda put forward a topological and Al86Sm14 共␭0 = 0.143兲 alloys underwent eutectic
instability model28 that successfully described the minimum crystallization.9,30,31
solute concentrations for amorphization by rapid quenching The topological instability condition expressed by Eq.
共melt-spun ribbons and vapor-deposited thin films兲 of a num- 共1兲 for binary systems may be extended to multicomponent
ber of binary systems. Within the framework of this model, a Al-based alloys of generic composition AlBcBCcCDcD . . . ZcZ,
minimum solute concentration 共cmin B
, given in at. %兲 exists at where B through Z represent different TM and/or RE solute
which average atomic-level elastic strains throughout the elements, with corresponding ci atomic concentrations and ri
system equal the limiting or critical value for topological metallic radii. By dropping the condition of a minimum sol-
instability of the single-phase, crystalline solid solution of ute amount from the definition of ␭0, a unique parameter, ␭,
the same composition as the liquid or vapor 共i.e., polymor- is obtained,
phous solidification is ruled out兲. Amorphization of
共hyper兲critical compositions 共cB 艌 cmin B
兲 would thus become Z
feasible provided a cooling rate high enough was employed
to hinder the competing solute segregation triggering pri-
␭= 兺
i=B
ci兩共ri/rAl兲3 − 1兩. 共2兲
mary or eutectic solidification. Supported by literature results
on over 60 binary amorphous alloys, the ratio of solute 共B兲 to Only chemical composition and metallic radii of constituent
solvent 共A兲 metallic radii 共rB / rA兲 was found to be empirically elements of any given alloy are required for its ␭ to be de-
B
correlated with cmin through a topological instability param- termined.
eter, ␭0, such that ␭0 ⬇ 0.1 共Ref. 28兲, It is instructive to apply Eq. 共2兲 to ternary systems, Al–
Ni–Y given as an example in Fig. 1共a兲. The line of compo-
␭0 = cmin
B
兩共rB/rA兲3 − 1兩 ⬇ 0.1. 共1兲 sitions whose ␭ is exactly equal to 0.1 is plotted in the figure
and describes the “␭0.1 line,” the ends of which are defined
While no binary Al-based systems were originally con- Ni
by cmin Y
and cmin as calculated using the original Eq. 共1兲 with
sidered, the topological instability condition expressed by ␭0 = 0.1. This particular iso-␭ line divides the compositional
Eq. 共1兲 also applies to alloys of these systems. Predictions of triangle into regions where ␭ is either higher or lower than
Eq. 共1兲 共cmin
B
兲 are compared with experimental results 共cexp
B
兲 0.1, above or below the ␭0.1 line, respectively.
for selected binary Al-based systems in Table I; good agree- By superimposing over Fig. 1共a兲 points representing Al–
ment between prediction and experiments is observed, since Ni–Y alloys for which thermal crystallization results are
the composition range for experimental glass formation en- available in the literature, a remarkable, selective distribution
compasses the predicted values for all of the examples given. of points around the ␭0.1 line is obtained: alloys reported to

FIG. 1. Compositional triangles for 共a兲

Al–Ni–Y and 共b兲 Al–Ni–Gd systems.
Plotted points, corresponding to actual
compositions reported in the literature,
selectively distribute around the ␭0.1
line 共—兲 depending on crystallization
behavior; 共䉭兲 glassy, 共䊊兲 nanoglassy,
and 共䉲兲 nanocrystalline alloys. The ar-
rows in 共b兲 identify Al93−xNi7Gdx and
Al93−xNixGd7 alloys 共Ref. 22兲.
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 211904-3 Sá Lisboa et al. Appl. Phys. Lett. 86, 211904 共2005兲

TABLE II. Compositional dependence of reported crystallization behaviors criterion as a tool to design best glass-former compositions
for Al88Ni4共La, Er兲8−xGdx alloys. Data taken from Ref. 7. in other Al-based systems.
In forthcoming articles we will 共i兲 provide structural and
Al88Ni4Er8−xGdx 0艋x艋8 ␭ 艋 0.093 Nanocrystalline
thermodynamic support to the empirical findings presented
x=8 ␭ = 0.093 Nanocrystalline in this letter, 共ii兲 further detail the ␭ criterion by addressing
Al88Ni4La8−xGdx 6艋x艋7 0.096艋 ␭ 艋 0.098 Nanoglassy its major implications and limitations, and 共iii兲 evaluate its
0艋x艋5 ␭ 艌 0.101 Glassy validity as a quantitative index of glass-forming ability and
stability of Al-based alloys.

be glassy fall above 共␭ ⬎ 0.1兲, whereas nanocrystalline alloys This work was financially supported by FAPESP
lie below 共␭ ⬍ 0.1兲 this newly derived dividing line. This 共Brazil兲.
selective distribution occurs for any Al-TM-RE ternary sys- 1
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given with Al–Ni–Gd alloys in Fig. 1共b兲. These data, particu- 4
I. Borner and J. Eckert, Scr. Mater. 45, 237 共2001兲.
5
larly those taken from systematic analyses of Al93−xNi7Gdx G. Wilde, H. Sieber, and J. H. Perepezko, J. Non-Cryst. Solids 250–252,
22 621 共1999兲.
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zation behavior as compositions cross the ␭0.1 line is not as 7
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sudden as suggested by a dividing line. Instead, a narrow 8
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transition region exists where specific compositions of ␭ 9
Philos. Mag. B 66, 427 共1992兲.
⬇ 0.1 共0.096⬍ ␭ ⬍ 0.103 in this system兲 undergo primary J. Q. Guo, K. Ohtera, K. Kita, J. Nagahora, and N. S. Kazama, Mater. Lett.
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nanocrystallization of fcc-Al preceded by a clear Tg, the very 10
F. Q. Guo, S. J. Enouf, S. J. Poon, and G. J. Shiflet, Philos. Mag. Lett. 81,
definition of nanoglassy behavior. 203 共2001兲.
Although lacking the possibility of easy graphical pre- 11
U. Köster and U. Herold, in Glassy Metals I, edited by H. Beck and H.-J.
sentation, the correlation between ␭ and crystallization 12
Güntherodt 共Springer-Verlag, Berlin, 1981兲, p. 225.
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Y. Kawamura, H. Mano, and A. Inoue, Scr. Mater. 44, 1599 共2001兲.
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Al88Ni4共La, Er兲8−xGdx alloys in Table II; despite the seem- 14
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range of crystallization behaviors while Al88Ni4Er8−xGdx al- 50, 2245 共2002兲.
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共Al84Y9Ni5Co2兲100−xScx and Al85Y8−xScxNi5Co2 共Ref. 18兲 or 18
A. Inoue, S. Sobu, D. V. Louzguine, H. Kimura, and K. Sasamori, J.
Al85Y8−xRExNi5Co2 共Ref. 20兲. Mater. Res. 19, 1539 共2004兲.
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A large number of experimental results available in the V. Rontó, L. Battezzati, A. R. Yavari, M. Tonegaru, N. Lupu, and G.
Heunen, Scr. Mater. 50, 839 共2004兲.
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J. Q. Wang, H. W. Zhang, X. J. Gu, K. Lu, F. Sommer, and E. J. Mitte-
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22
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23
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O. N. Senkov and D. B. Miracle, Mater. Res. Bull. 36, 2183 共2001兲.
26
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30
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Al87Ni7Sm6 共␭ = 0.085兲.19 One additional, remarkable ex- 31
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nanocrystalline behavior caused by a compositional change J. Antonowicz, P. Jaśkiewicz, L. Nowiński, and K. Pȩkała, J. Non-Cryst.
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36 J. Q. Guo, K. Kita, J. Nagahora, N. S. Kazama, and K. Ohtera, Mater. Lett.
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It is finally pertinent to mention that alloys attested to be
35
M. Kusy, P. Riello, and L. Battezzatti, Acta Mater. 52, 5031 共2004兲.
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or Alis85copyrighted
This article Y8Ni5Co2 as 共Ref. 37兲, stressing
indicated theReuse
in the article. usefulness of the ␭
of AIP content is subject共1990兲.
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