Intermetallics 15 (2007) 253e259

www.elsevier.com/locate/intermet

Competitive formation of glasses and glassematrix composites

Z.P. Lu a,*, D. Ma b, C.T. Liu a, Y.A. Chang b
a
Metals and Ceramic Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6115, USA
b
Department of Materials Science and Engineering, University of Wisconsin-Madison, WI 53706, USA
Received 31 March 2006; received in revised form 8 May 2006; accepted 29 May 2006
Available online 9 August 2006

Abstract

By systematically investigating the effect of chemical composition on the competitive formation of glasses in various systems, we attempt to
address two long-standing scientific puzzles upon metallic glasses, i.e., (i) which composition is the best for forming glasses and glassematrix
composites and (ii) what determines the easy glass-forming composition range in a given alloy system. Our findings have led to the construction
of a qualitative microstructure selection map, which is useful for guiding the design of bulkier metallic glasses and glassematrix composites. In
addition, our analysis demonstrates that the classical kinetic treatment of glass formation is insufficient; to analyze glass formation properly, it is
necessary to go beyond simple assumptions of single polymorphic solidification during crystallization.
2006 Elsevier Ltd. All rights reserved.

Keywords: B. Glasses, metallic; B. Phase transformations; B. Phase diagrams

1. Introduction (1) Glass formation occurs even after nucleation of crystalline

Scientific problems about metallic glasses, including (i)
which composition is the best for forming glasses and glasse
matrix composites and (ii) what determines the glass-forming
composition range in a given alloy system, have challenged
material scientists ever since metallic glass was first reported
in 1960 [1e4]. Based on the assumption that the nucleation
frequency of a melt scale as 1/h (h, viscosity of the liquid),
Turnbull [5] has suggested that an alloy would be an easier
glass former if its reduced glass transition temperature Trg
( Tg/Tl, where Tg and Tl are the glass transition temperature
and the liquidus temperature, respectively) is not less than 2/
3. The implication of this theory is that the greatest glass-
forming ability (GFA) is always associated with low-melting
eutectics (i.e., deep eutectics) [4,6], as has been demonstrated
in many binary systems (e.g., TieBe [7]). However, this sce-
nario is strongly challenged by two types of experimental find-
ings over the years:
* Corresponding author.
E-mail address: luzp@ornl.gov (Z.P. Lu).
phases, essentially due to the suppression of crystal growth
[8], and
(2) The best glass-forming compositions were found to be off-
eutectic rather than the eutectic points in some systems
such as GdeFe and TieSi [3].
It is Boettinger who first realized the importance of crystal
growth effect on glass formation and qualitatively analyzed
the relationship between glass formation and the growth veloc-
ities as a function of composition in a regular binary eutectic
system [9,10]. More recently, this constrained solidification
theory has been applied to study the competition between
crystal growth and glass formation in irregular eutectic sys-
tems [11,12]. It was found that the best glass former in an ir-
regular eutectic system is located at off-eutectic due to the
large kinetic difficulty in the growth of the faceted crystalline
phase, as demonstrated in the CueZr system [11]. Despite its
success, however, such analysis appears to be inapplicable to
the cases where solidification of competing crystalline phases
is unconstrained (i.e., with limited nucleation and/or undergo-
ing a negative thermal gradient), such as the glass formation in
electromagnetically levitated undercooled melts and from the

0966-9795/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.intermet.2006.05.015
254 Z.P. Lu et al. / Intermetallics 15 (2007) 253e259
free side of melt-spun ribbons. In these cases, nucleation ef-
fects on glass formation cannot be neglected. Thus, there is
an urgent need to extend the principle of competitive forma-
tion of glasses to a more general situation where both the nu-
cleation and crystal growth of competing crystalline phases
play important roles in glass formation.
The first attempt to incorporate the effects of both nucle-
ation and crystal growth on glass formation is the classical ki-
netic treatment established by Uhlmann [13] and Davies [14].
The recent discovery of multi-component bulk metallic glasses
which possess an extremely high thermal stability with respect
to crystallization has made the experimental determination of
a timeetemperature-transformation (TTT) diagram for glass-
forming liquids in the undercooled state possible. Direct ob-
servation of TTT diagrams for glass formation will indicate
the validity and feasibility of the classical kinetic treatment.
It was found that, however, the measured TTT diagram can
be exactly fitted over the entire temperature range by the clas-
sical kinetic treatment in bulk glass-forming Pd40Cu30Ni10P20
(at.%) alloy [13]. In contrast, the same treatment fails to pre-
dict the experimentally determined TTT diagram for the fa-
mous Vitreloy 1 (Zr41.2Ti13.8Cu12.5Ni10Be22.5, at.%) because
of its significant high nose temperature [16]. Up to date,
this theoretical dilemma remains unresolved.
In this paper, we will present a unique conceptual approach
to predict the formation of glasses and glassematrix compos-
ites. A comprehensive understanding of where glasses and
glassematrix composites are located in a given eutectic sys-
tem will be elucidated with considerations of both the nucle-
ation and crystal growth. The insufficiencies of the classical
kinetic treatment of glass formation will also be discussed.
2. Theoretical analysis
2.1. Basic concept of competitive formation of glass
Glass formation is always a competitive process between
a liquid phase and the competing crystalline phases, as demon-
strated by Lu and Liu [17]. As pointed out by Turnbull [4] and
Davies [14], any liquid can form a glass as long as the cooling
rate is fast enough to suppress the crystallization event. In this
sense, glass formation can be well explained by TTT diagrams
[18]. In a typical binary eutectic system [see the phase dia-
gram in Fig. 1(a)], the competitive formation between the
glass phase and its competing crystalline phases during the
cooling of an off-eutectic alloy (toward the b-phase side) can
be schematically illustrated by Fig. 1(b). The solid curves (de-
noted as the starting TTT curve hereafter) indicate the begin-
ning of the crystallization with a barely detectable volume
fraction of crystallites (usually w106) while the dashed
curves (denoted as the ending TTT curve hereafter) represent
the end of the crystallization event. At small undercoolings be-
tween Tl and TE, formation of primary b phase dominates the
crystallization event, while, at large undercoolings between TE
and Tg, formation of the eutectic structure dominates (i.e., the
coupled growth of b and another equilibrium phase). In this
case, in order to form a glass upon cooling, the liquid must
(b)
Temperature
Liquid Liquid
Tl
TE
Eu End
Tg Start
Rc Rcom
(a) Cooling
Composition Log (time)
Fig. 1. (a) A typical binary phase diagram and (b) timeetemperature-transfor-
mation (TTT) diagrams showing the competitive formation between compet-
ing crystalline phases and glass. To form a glass, the cooling curve from the
liquid state must avoid intersecting the leftmost start curve. Eu stands for
eutectic.
be undercooled to below the glass transition temperature
with no formation of both b and the eutectic. In other words,
the liquid must be cooled fast enough from the liquidus tem-
perature through the glass transition temperature without inter-
secting the starting TTT curve of any competing crystalline
phase (e.g., b and the eutectic for this particular case). The
minimum cooling rate required to form a full glass (i.e., the
critical cooling rate) is the one needed to bypass the leftmost
nose of all the TTT curves in the entire undercooling, as de-
picted by Rc in Fig. 1. Additionally, the composite structure
(i.e., the phase b embedded in the amorphous matrix) would
be formed if the applied cooling rate were in-between Rc
and Rcom. When cooled at rates between Rc and Rcom, the liq-
uid starts to form the crystalline phase b. However, this trans-
formation is not complete because the cooling curve bypasses
the ending TTT curve for the a-phase formation. Thus, upon
further cooling, the remaining liquid turns into an amorphous
phase. At cooling rates lower than Rcom, b would form first and
then the remaining liquid will solidify into the eutectic struc-
ture at a constant temperature (formation of the eutectic causes
the system to cease cooling until solidification is complete
[19]). Therefore, Rcom is actually the critical cooling rate
(i.e., the minimum cooling rate) for forming the composite
structure.
2.2. Glass and composite formation in a regular
eutectic system
It is generally believed that glasses form preferentially in
systems with deep eutectics [3,4]. In general, eutectic alloys
can be divided into two main types [20,21]: regular and ir-
regular. For a regular eutectic system, studies have indicated
that a symmetrical phase diagram is favored, as illustrated in
Fig. 2(a) [20]. At the eutectic composition Ce, two phases
(e.g., a and b) will grow in a coupled manner to form a stable
eutectic structure of these two phases [19,20]. Therefore, only
one TTT curve for the eutectic formation in this alloy is seen,
as demonstrated in Fig. 2(b). In order to form a fully
 Z.P. Lu et al. / Intermetallics 15 (2007) 253e259 255

(a) (b) (c)

L T T
Ce C1

TL

TE TE
Temperature Ce Eu Start

End
Rc Rc Eu
Tg Tg
C2
Log (time) Log (time)
A C2 Ce C1 C3 B
Composition

(f) (d) (e)

T T C3
C2 TL
Am
+ Am Am
+ TL

TE TE
Rcom
Cooling rate

Rc

Eu+ Eu Eu+
Rc Eu Rc Rcom Eu
Tg Tg
C2
Log (time) Log (time)
A C2 Ce C1 C3 B
Composition

Fig. 2. The composition effect on glass formation in a regular eutectic system; (a) phase diagram with glass-forming range, (b)e(e) competitive formation between
glass and primary phases as a function of composition and (f) final microstructure as a function of cooling rate and composition. Eu and Am stand for eutectic and
amorphous structures, respectively.

amorphous structure in this alloy, the applied cooling rate has
to be large enough to bypass the nose of the TTT curve (i.e.,
larger than Rc) so that the formation of the eutectic structure
can be avoided. As the alloy composition is moved from Ce
toward C3, the liquidus temperature of this off-eutectic alloy
is increased and the composition difference between the liquid
and the b phase is decreased [see Fig. 2(a)]. Thermodynami-
cally, the driving force for crystallization of the b phase is en-
hanced due to the increase of the liquidus temperature.
Kinetically, the decreased composition difference between
the liquid and the b phase requires less diffusion of atoms.
Thus, the formation of the b phase is greatly facilitated
when the alloy composition is moved toward the b-phase
side [20]. As a result, for these off-eutectic alloys, there are
two TTT curves (as the case shown in Fig. 1): one due to
the b-phase formation at small undercoolings (i.e., close to
the liquidus temperature) and the other due to the eutectic for-
mation at relatively large undercoolings (i.e., close to the glass
transition temperature). In addition, with the increase of the
constituent B, the starting TTT curve of the b phase will grad-
ually shift to the top-left (i.e., high-temperature and short-time
regimes), as illustrated in Fig. 2(cee). In order to form a glass
in these off-eutectic alloys, the formation of both b and the eu-
tectic has to be completely suppressed. In the case of Fig. 2(c)
and (d), the critical cooling rate for full glass formation is still
determined by the starting TTT curve of the eutectic forma-
tion, although b can be formed at slow cooling rates. With fur-
ther shifting of the composition toward the b-phase side, full
glass formation starts to compete primarily with b-phase for-
mation, as shown in Fig. 2(e). C2 is actually the critical com-
position beyond which full glass formation competes
essentially with the formation of the b phase rather than the
eutectic. It is noted that composite materials, consisting of
a mixture of amorphous matrix and b phase, can be obtained
with cooling rates between Rcom and Rc for compositions
larger than C2 [see Fig. 2(e)]. In analogy with the b-phase
side, similar results can be obtained when the alloy composi-
tion is shifted toward the a-phase side and C02 is the composition
limit over which the GFA starts to be determined by the a-
phase formation.
2.3. Glass and composite formation in
an irregular system
For an irregular eutectic system, studies indicate that an
asymmetrical phase diagram is encouraged, as shown in
Fig. 3(a) [20]. Such kinds of eutectic usually consist of one
non-faceted phase (i.e., the a phase) and one faceted phase
256 Z.P. Lu et al. / Intermetallics 15 (2007) 253e259

(a) (b) (c)

L
T T
Ce C1

TL
TE TE

Temperature

Ce
Start

End
Rc Rcom Eu Rc Eu
Tg Tg

C1 Log (time) Log (time)

A Ce C2 C3 B
composition

(f) (d) (e)

T T C3
Am C2
Am+ Am+ TL
TL

TE TE
Cooling rate

Eu+ Eu Eu+
Rc Eu Rc Rcom Eu
Tg Tg
C1
Log (time) Log (time)
A Ce C2 C3 B
Composition

Fig. 3. The composition effect on glass formation in an irregular eutectic system; (a) phase diagram with glass-forming range, (b)e(e) competitive formation be-
tween glass and primary phases as a function of composition and (f) final microstructure as a function of cooling rate and composition. Eu and Am stand for
eutectic and amorphous structures, respectively.

(i.e., the b phase) which has anisotropic growth characteristics
[20,21]. It is well known that a fully eutectic structure cannot
be obtained when an alloy with the eutectic composition [i.e.,
Ce in Fig. 3(a)] is rapidly solidified because the a phase can be
formed prior to the eutectic and the b phase at large undercool-
ings [20,21]. Therefore, there exist two TTT curves for the
undercooled liquid in this alloy [as schematically demon-
strated in Fig. 3(b)]: one due to the formation of the coupled
eutectic and the other caused by the formation of a at rela-
tively large undercoolings. In order to form a full glass without
a, the applied cooling rate has to be fast enough without inter-
secting both TTT curves, while the composite will be obtained
at cooling rates in-between Rc and Rcom. Similar to the case of
the regular eutectic, as the alloy composition is moved from Ce
toward the b-phase side, the tendency for forming the b phase
would become greater (concurrently, the formation of a is
relatively retarded) [20]. As a result, the TTT curve for the
a-phase formation at low temperatures is moved to the
bottom-right (i.e., long-time and low-temperature regimes)
and eventually vanishes, while the TTT curve for b-phase for-
mation is gradually shifted toward the top-left (i.e., short-time
and high-temperature regimes) in the temperatureetime coor-
dinate as schematically demonstrated in Fig. 3(cee). Thus for
alloys whose compositions are between C1 and C2 [see
Fig. 3(c)], glass-forming ability is controlled no longer by
the a phase but solely by the formation of the eutectic. C2 is
the critical composition where the critical cooling curve for
full glass formation just barely intersects the noses of both
TTT curves for the eutectic and primary b phase.
At compositions above C2 [e.g., C3 in Fig. 3(e)] the tendency
for forming the faceted b phase, is much stronger than that of
the eutectic, and their glass-forming ability is thus much de-
creased as compared with that of compositions C1 and C2. As
shown in Fig. 3(e), in order to form a glass, the applied cooling
rates have to be large enough to bypass the nose of the starting
TTT curve for b-phase formation. Similarly, composite mate-
rials, consisting of b phase embedded in the glass matrix, will
be obtained with cooling rates ranging from Rcom to Rc.
2.4. Composition effects on glass formation
As a result of the above analysis, we have attempted to con-
struct a qualitative microstructure selection map, as shown in
Fig. 2(f), for a typical regular eutectic system in terms of com-
position and cooling rate. As can be seen, the best composition
for fully glass formation in such a system is located exactly at
the eutectic composition. Nevertheless, the formation of full
glass for all other compositions between C02 and C2 also
 Z.P. Lu et al. / Intermetallics 15 (2007) 253e259
compete primarily with the eutectic, and the critical cooling
rate for the full glass formation is just slightly larger than
that of the eutectic composition Ce. The discrepancies in Rc
of these alloys are caused by the variations in their liquidus
temperatures. Outside the composition interval between C02
and C2, the critical cooling rates for forming a fully glassy
structure are increased sharply due to the strong competition
from the much easier formation of primary phases. In other
words, the composition band between C2 and C02 as indicated
in Fig. 2(a), actually represents the easy glass-forming range
for regular eutectic systems. Outside the easy glass-forming
range, in-situ composite materials (i.e., primary phase of either
a or b embedded in an amorphous matrix) can be obtained.
Similarly, a microstructure selection diagram can also be
established for an irregular eutectic system, as shown in
Fig. 3(f) which schematically illustrates the resultant phase/
microstructure as a function of cooling rate and alloy compo-
sition. For compositions below C1 (e.g., Ce), the critical cool-
ing rate for forming a full glass is very high due to the much
easier formation of the a phase, although composite materials
(i.e., primary non-faceted a phase embedded in the amorphous
matrix) can be formed at relatively lower cooling rates. For
compositions ranging from C1 to C2, the critical cooling rate
for full glass formation is much reduced and shows a minimum
at the composition C1 (i.e., composition C1 has the largest
GFA in the entire system). Nevertheless, the difference be-
tween the critical cooling rates for all the compositions in
the range from C1 to C2 is not striking. For compositions
above C2, the critical cooling rate is steeply increased again
due to the easier formation of the faceted b phase. Thus, the
composition interval between C1 and C2 is the easy glass-
forming range for the irregular eutectic system, as indicated
in Fig. 3(a). Composite materials can also be formed at com-
positions above C2 (e.g., C3) but the primary phase is switched
from the non-faceted a to the faceted b.
It is necessary to point out that the microstructure selection
maps as a function of cooling rate shown in Figs. 2(f) and 3(f)
are slightly different from those as a function of growth veloc-
ity obtained with sole consideration of crystal growth [12].
Our analysis successfully incorporates the nucleation effects
on glass formation and can thus be applied to various solidifi-
cation processes. In addition, actual glass-forming range that
is a function of cooling rate as shown in Figs. 2(f) and 3(f)
could be enlarged with high-cooling capacity vitrification
techniques. Nevertheless, the shaded area in Figs. 2(a) and
3(a) represents the composition range for easy glass formers
that have relatively larger GFA (i.e., lower critical cooling
rate) than the rest of the alloys in the system.
3. Direct experimental validation of the current approach
Our current analysis has been directly confirmed by a few
experimental observations in literature. As one example,
Fig. 4 shows continuous cooling transformation curves of
B2O3 fluxed Pd40Ni40P20 alloy reported previously in literature
[22]. As shown, there indeed exist two curves for phase com-
petition over the temperature range between Tl and Tg, one is
257
1000
950 Tl=970K
900 Te=885K
850
Primary Ni3P
Temperature, K
800
750
700
650
Eutectic
600
Tg=580K
103 104
Time, t/s
Fig. 4. Experimentally determined TTT curves of the B2O3 fluxed Pd40Ni40P20
alloy during the entire undercooling.
for the formation of primary phase Ni3P and the other is for
the formation of eutectic structure. Glass competes with the
Ni3P phase at high temperatures (i.e., small undercoolings)
and with the eutectic at low temperatures (i.e., large under-
coolings). This particular experimental observation clearly
verifies that glass formation is really a competing process
and our analysis is well ground. More recently, work
on non-contact measurement of TTT curves using the
electrostatic levitation method for glass-forming liquids
Zr55Al20Co25, Zr55Al22.5Co22.5 and Zr55Al19Co19Cu7 without
doubt further validate our analysis; double-nose TTT
curves were actually experimentally observed in the under-
cooled Zr55Al20Co25 and Zr55Al19Co19Cu7 alloys [23]. For ex-
ample, the alloy Zr55Al20Co25 simultaneously crystallizes into
a mixture of two crystalline phases Zr6Al2Co and ZrAl0.6Co1.4
(i.e., the eutectic formation) at small undercoolings while sin-
gle phase Zr6Al2Co is formed at relatively large undercool-
ings. In this alloy, the critical cooling rate for glass
formation can be determined by avoiding the leftmost nose
of the eutectic TTT curve [23]. On the other hand, only one
single TTT curve of the alloy Zr55Al22.5Co22.5 is seen during
the undercooling below the melting temperature TE. The alloy
was found to crystallize also simultaneously into a mixture of
Zr6Al2Co, ZrAl0.6Co1.4 and other unidentified phases, indicat-
ing that the glass phase in this alloy competes primarily with
the eutectic structure and can be formed if the nose of the eu-
tectic TTT curve is bypassed [23].
It is important to point out that the microstructure selection
maps determined from our current analysis is also consistent
with experimental data reported in various glass-forming
eutectic systems. Fig. 5 presents GFA data as a function of
composition in two representative eutectic systems, i.e.,
Ti2CueTiCu and bTieTi5Si3. As can be seen, Fig. 5(a) is
a typical regular eutectic in the TieCu binary system, which
258
1005C
Temperature
790C
Ti2Cu
Ti
Fig. 5. Experimental data in two typical eutectic systems clearly verifying the current analyses; (a) regular eutectic Ti2CueTiCu system with glass-forming range
[24] and (b) irregular bTieTi5Si3 system with glass-forming range [24].
consists of two intermetallic phases Ti2Cu and TiCu with sim-
ilar melting points. The glass-forming composition range de-
termined using a melt-quenching technique (the cooling rate
is w 106 K/s) was found to be 40e45 at.% Cu, almost equally
distributing on both sides of the eutectic (i.e., 43 at.% Cu)
[24]. This experimental finding is exactly consistent with the
analysis shown in Fig. 2(a) for a regular eutectic system. In
the irregular eutectic system like bTieTi5Si3, the melting
points of the two phases differ greatly and the phase diagram
is asymmetrical [see Fig. 5(b)]. The glass-forming range ex-
perimentally determined using the melt-spinning technique is
from 15 to 20 at.% Si, which is skewed toward the hypereutec-
tic (Ce 13.5 at.% Si) [24]. This experimental observation is
also in excellent agreement with the analysis shown in
Fig. 3(a). As pointed out earlier, actual glass-forming range
in a system is dependent on the used vitrification technique.
With high-cooling capacity, for example, even intermetallic
compositions could be amorphized in the TieCu system
[25]. Nevertheless, easy glass-forming range in this particular
system is indeed around the eutectic [24].
4. Insufficiency of the classical kinetic treatment of
glass formation
As mentioned earlier, the classical kinetic treatment of
glass formation was established based on the assumption
that glass formation occurs via the avoidance of the polymor-
phic crystallization over the entire undercooling, i.e., the trans-
formation from liquid to one type of crystal which is
congruently melting without a change of composition [5,14].
Therefore, two prerequisite conditions for applying this partic-
ular theory are as follows:
(1) The crystallization event is a polymorphic transformation,
and
(2) Only single type crystallization phase is kinetically fa-
vored during the entire undercooling.
As a result, a single C-shaped TTT curve is always con-
structed using the classical kinetic treatment. For the alloys
Z.P. Lu et al. / Intermetallics 15 (2007) 253e259
(a) (b)
2130C
982C 1670C
43 13.5
Temperature
1330C
Ti5Si3
TiCu
40-45 Ti 15-20
Zr55Al22.5Co22.5 [23] and Pd40Cu30Ni10P20 [15], phase compe-
tition during undercooling is similar to the cases of either Ce in
Fig. 2 or C1 in Fig. 3. Glass formation in these alloys is pri-
marily limited by the eutectic formation during the tempera-
ture interval TE and Tg. The eutectic formation could be
treated as a polymorphic transformation because the melting/
solidification behavior of eutectics is similar to that for
a pure metal, i.e., congruently melting without significant
change of average composition [19,20]. Therefore, the classi-
cal kinetic treatment of glass formation is valid and suitable
for predicting the GFA in these alloys.
As mentioned earlier, however, multi-component glass-
forming liquids such as the alloy Zr55Al20Co25 could have
a non-C-shaped TTT curve with multiple noses. In this
case, description of glass-formation kinetics using the classical
crystallization theory is insufficient. The main reason is that
different phases could be kinetically selected to form at differ-
ent undercoolings. The classical kinetic treatment could only
be applied to predict the eutectic TTT curve, but composition
effects on the nucleation and crystal growth for formation of
other crystalline phases have to be taken into account. Desre
and his co-workers [26e28] have attempted to discuss the
roles of concentration fluctuations in multi-component sys-
tems on nucleation. Wu [29] and others [30,31] have investi-
gated barrier crossing in multi-component systems which
involves correlated fluctuations of composition and topologi-
cal nucleus growth. Nevertheless, for a multi-component
glass-forming liquid with n competing crystalline phases, the
time, t, for forming a small volume fraction, X, of crystal at
temperature, T, can be simply expressed as follows:
tT; X minteutectic T; X; t1 T; X; t2 T; X; .; tn T; X
1
where teutectic(T, X ) is the time needed for simultaneously form-
ing a small portion X of the mixture of all n crystalline phases
(i.e., the eutectic structure) and tn(T, X ) is the time required
for forming the small fraction X of individual crystalline phase
at the temperature T. In order to form glass, crystallization must
be avoid at all undercoolings in the time scale of t(T, X ). With
modern computation approaches, crystallization dynamics and
 Z.P. Lu et al. / Intermetallics 15 (2007) 253e259
solidification kinetics of each phase or structure is more readily
available than before. It can thus be foreseen that prediction of
kinetics of glass formation in metallic alloys in a quantitative
manner is highly possible.
5. Conclusions
In this paper, it was found that the competition between pri-
mary phases, the eutectic and the amorphous phase at different
undercoolings determines the best glass formers, possible easy
glass-forming range and glassematrix composite formation in
any given systems. Our analysis has led to the construction of
the microstructure selection map, which can be used as guide-
lines for developing new metallic glasses and composites in
various material systems. In addition, our analysis has demon-
strated that the classical kinetic treatment of glass formation
can be applied only to the cases where the glass phase com-
petes primarily with the eutectic phase. For the other cases,
however, it is necessary to go beyond simple assumptions of
single polymorphic crystallization.
Acknowledgements
This research was sponsored partly (Lu and Liu) by the
Division of Materials Sciences and Engineering, Office of Basic
Energy Sciences, US Department of Energy under contract
DE-AC05-00OR-22725 with UT-Battelle, LLC. Two authors,
D. Ma and Y.A. Chang, gratefully acknowledge financial sup-
port for this work from the Defense Advanced Research Pro-
jects Agency (DARPA), under ARO Contract No. DAAD
19-01-1d525, and with Dr. Leo Christodoulou as Program
Manager.
259
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