Journal of Alloys and Compounds 832 (2020) 154997

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Ultrahigh thermal stability and hardness of nano-mixed fcc-Al and

amorphous phases for multicomponent Al-based alloys
Y. Jin a, A. Inoue a, b, c, d, e, *, F.L. Kong b, S.L. Zhu a, **, F. Al-Marzouki d, A.L. Greer f, ***
a
School of Materials Science and Engineering, Tianjin University, Tianjin, 300072, China
b
International Institute of Green Materials, Josai International University, Togane, 283-8555, Japan
c
Institute of Massive Amorphous Alloy Science, China University of Mining Technology, Xuzhou, 221116, China
d
Department of Physics, King Abdulaziz University, Jeddah, 22254, Saudi Arabia
e
MISiS, National University of Science and Technology, Moscow, 119049, Russia
f
Department of Materials Science and Metallurgy, University of Cambridge, Cambridge, CB3 0FS, UK

a r t i c l e i n f o a b s t r a c t

Article history: Fcc-Al (a-Al) þ amorphous phase mixtures with ultrahigh hardness are formed by a heating-induced
Received 28 January 2020 reverse transition from the primary precipitates of a-Al and AlxMy in residual amorphous phase for
Received in revised form melt-spun Al84Y9Ni4Co1.5Fe0.5TM1 (TM ¼ V, Nb, Cr, Mo, Mn, Fe, Co, Ni or Cu) amorphous alloys. The
10 March 2020
resulting particle diameter and volume fraction of the a-Al phase are 5e15 nm and 60e70%, and no
Accepted 29 March 2020
Available online 3 April 2020
internal defects are observed. The solute content in the a-Al phase is 8e11% for the TM ¼ V or Cu alloys.
In contrast, the reverse transition is not found for the TM ¼ Zr, Ag or Au alloys, presumably because these
elements have atomic radii larger than Al and positive heats of mixing with other solute elements
Keywords:
Thermal stability
hindering the atomic rearrangements to decompose the AlxMy compound. The [a-Al þ amorphous]
Hardness phase mixture is maintained up to about 700 K and exhibits a Vickers hardness of 550e580, much higher
Multicomponent than for the corresponding crystalline alloys. The high hardness at elevated temperature is due to the
Al-based amorphous alloy coexistence of perfect crystal a-Al and high solute-content residual amorphous phase. For a cast conical
rod of the TM ¼ Cu alloy, the microstructure is fully amorphous up to a diameter of 0.82 mm, and is an
[a-Al þ amorphous] phase mixture at larger diameters up to 1.2 mm. The formation of the highly stable
[a-Al þ amorphous] phase mixtures by the heating-induced reverse transition, as well as the bulk for-
mation (in cast rods) of similar phase mixtures for the TM ¼ V, Nb, Cr, Mo, Mn, Fe, Co, Ni or Cu alloys is
promising for future structural and coating materials owing to their high hardness and high elevated-
temperature strength.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction corrosion resistance, and high anti-erosion performance [1e3].

Savings of energy and natural resources motivate the develop-
ment of higher-performance alloys that permit miniaturization and
light-weighting. There is a particularly clear need for alloys with
high specific strength that can be maintained at elevated temper-
atures. Aluminum-based glassy alloys have attracted a steady in-
terest because they exhibit high specific strength, high wear and
* Corresponding author. School of Materials Science and Engineering, Tianjin
University, Tianjin, 300072, China.
** Corresponding author.
*** Corresponding author.
E-mail addresses: inoue@jiu.ac.jp (A. Inoue), slzhu@tju.edu.cn (S.L. Zhu), alg13@
cam.ac.uk (A.L. Greer).
With these advantages, they have recently been used as coating
materials in, for example, high-speed patrol boats and hydroplanes
[4], applications that benefit from the improved glass-forming
ability to over 1 mm in maximum diameter and improved spray-
coating techniques. For high strength and good corrosion resis-
tance, mixed amorphous þ fcc a-Al phase alloys are also attractive
because these can be formed over wider composition ranges, at
lower cooling rates and under a variety of preparation conditions.
Furthermore, they have higher strength, much higher heat-
resistant strength, and nearly the same corrosion resistance in
comparison to glassy single-phase alloys [5,6]. It is therefore
important to search for new heat-resistant alloys that can be
readily prepared with the desirable [amorphous þ a-Al] phase
mixture.

https://doi.org/10.1016/j.jallcom.2020.154997
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2 Y. Jin et al. / Journal of Alloys and Compounds 832 (2020) 154997
In 2017, Han et al. found a reverse transition in which the vol-
ume fraction of amorphous phase (am) increases on going from a
three-phase mixture [a-Al þ AlxMy (M ¼ Y, Ni, Co, Fe, Pd) þ residual
(am’)] to a two-phase mixture [a-Al þ residual (am00 )]. This occurs
during heating of Al-based amorphous alloys around the compo-
sition Al84Y9Ni4Co1.5Fe0.5Pd1 (at%), and the desirable two-phase
mixture [a-Al þ am00 ] is retained at high temperatures up to
650 K [7]. This phase mixture also retains high strength up to these
temperatures, which is significantly different from the poor heat
resistance associated with many Al-based amorphous alloys of
lower crystallization temperature. The [a-Al þ am00 ] alloy type is
thus attractive as a new type of coating for high-temperature ap-
plications. So far, however, all the reports of the reverse transition
([a-Al þ AlxMy þ am’] / [a-Al þ am00 ]) are for compositions con-
taining some noble metal. In the present work, we seek new Al-
based alloys showing the reverse transition, while having only
inexpensive components. We find that a similar reverse transition
does occur for Al84Y9Ni4Co1.5Fe0.5TM1, (TM ¼ V, Nb, Cr, Mo, Mn, Fe,
Co, Ni or Cu) multicomponent amorphous alloys which can be
regarded as less expensive and therefore more attractive for
application.
It is also important to derive a general rule for the appearance of
such an unusual reverse transition for multicomponent Al-based
amorphous alloys by examining the heating-induced phase
decomposition. This work examines the possibility of forming the
[a-Al þ am00 ] phase mixture during crystallization for a very wide
range of melt-spun amorphous alloys: Al84Y9Ni4Co1.5Fe0.5TM1
(TM ¼ Zr, V, Nb, Cr, Mo, Mn, Fe, Co, Ni, Cu, Ag or Au). The micro-
structural features, thermal stability and mechanical properties of
the [a-Al þ am00 ] samples are characterized, and the dominant
factors underlying the reverse transition are investigated.
2. Experimental procedures
Multicomponent Al-based alloys with compositions of Al84Y9-
Ni4Co1.5Fe0.5TM1 (TM ¼ Zr, V, Nb, Cr, Mo, Mn, Fe, Co, Ni, Cu, Ag or
Au) were chosen because the formation of [a-Al þ amorphous]
phase mixtures was expected to give higher mechanical strength
and higher thermal stability [5,6]. Transition-metal (TM) elements
were selected by considering the atomic size mismatches to Al and
the heat of mixing with the constituent base elements (Al, Y, Ni, Co
and Fe) [8,9]. The alloy compositions are given as nominal atomic
percentages. Mixed alloy ingots were prepared by arc-melting the
mixtures of pure metals with purities above 99.9 wt% under an
argon atmosphere. Alloy ribbons with a thickness of about 0.03 mm
and width of 1.5e1.7 mm were prepared by single-roller melt-
spinning. Conical alloy rods were also prepared by injection copper-
mold casting. Amorphicity was evaluated by X-ray diffraction, op-
tical microscopy (OM) and transmission electron microscopy
(TEM). The thermal stability associated with glass transition,
supercooled liquid region and crystallization was examined by
differential scanning calorimetry (DSC) at a heating rate of
0.67 K s1. The microstructures developed upon crystallization
were examined by X-ray diffraction, TEM combined with energy-
dispersion X-ray (EDX) analysis, high-resolution TEM and nano-
beam diffraction analysis, and crystallization kinetics was evalu-
ated by DSC at heating rates of 0.167e0.667 K s1. Hardness was
measured using a Vickers hardness indenter with a load of 0.49 N.
Bending ductility was evaluated by a simple bend test. Shear
markings around the Vickers indents and on the outer surface of
bent ribbons were examined by OM and scanning electron micro-
scopy (SEM).
3. Results
Fig. 1(a) and (b) show X-ray diffraction patterns and DSC curves,
respectively, of as-spun Al84Y9Ni4Co1.5Fe0.5TM1 (TM ¼ Zr, V, Nb, Cr,
Mo, Mn, Cu, Ag or Au) alloy ribbons. All of the X-ray patterns show
broad haloes without any appreciable crystalline peaks. However,
some of the halos (such as TM ¼ Ag and Nb) are not so symmetrical,
which are considered due to the presence of a small number of
clusters or nanocrystalline phases. The position of the maximum of
the main diffraction halo is not fixed, and appears to shift to lower
angle for the alloys containing TM elements with larger atomic
radius, as seen in particular for the Zr-containing alloy; this in-
dicates that the TM elements are incorporated into the amorphous
phase in each case. The DSC curves show an endothermic peak due
to the glass transition, followed by a narrow supercooled-liquid
region and then two or three exothermic peaks due to the phase
transitions for all the Al-based glassy alloys except the Mn-
containing alloy, as shown in Fig. 1 (b). The second exothermic
peak marked with arrows has always much lower area. The DSC
data indicate that the crystallization is completed through two or
three stages.
Fig. 2(aef) show X-ray diffraction patterns of the V-, Nb-, Cr-,
Mo-, Mn- and Cu-containing glassy alloys, annealed for 900 s at
temperatures just above the first, second and third exothermic
peaks. As identified in the corresponding diffraction patterns, the
first exothermic peak is due to the change from an amorphous
phase to fcc-Al (a-Al) þ AlxMy (M ¼ Y, Ni, Co, Fe and V, Nb, Cr, Mo,
Mn or Cu) þ residual amorphous (am’) phases, while the second
peak originates from the transition of this three-phase mixture to
an [a-Al þ am00 ] mixture for all the alloys. It is notable that the
multicomponent AlxMy compound disappears, and the volume
fractions of a-Al and amorphous phase increase during the second-
stage exothermic reaction. The third exothermic peak corresponds
to the complete crystallization of the sample, with the transition
from [a-Al þ am00 ] to [a-Al þ Al3Y þ Al9(Fe, Co, Ni, TM)2 (TM ¼ V, Nb,
Cr, Mo, Mn or Cu)] [10,11]. A similar heating-induced reverse
transition from [a-Al þ AlxMy (M ¼ Y, Fe, Co, Ni, TM) þ am’] to [a-
Al þ am00 ] is also recognized for Fe, Co and Ni as the added TM
element, as shown in Fig. 3(aec). The X-ray diffraction patterns
show clearly the sequence [am] / [a-Al þ AlxMy þ am’] / [a-
Al þ am00 ] / [a-Al þ Al3Y þ Al9(Fe, Co, Ni, TM)2] with increasing
temperature. Among all the alloys, the metastable [a-Al þ am00 ]
phase mixture is maintained over the wide range of 620e650 K
and, most notably up to the high temperatures of 600e660 K for
the Nb-, Cr- and Mo-containing alloys. These features indicate the
possibility that these Al-based alloys would retain extremely high
heat-resistant strength even at temperatures above 700 K.
To confirm the reverse transition from [a-Al þ AlxMy þ am’] to
[a-Al þ am00 ], bright-field TEM images and selected-area electron
diffraction patterns of the V-, Nb-, Cr- and Cu-containing glassy
alloys annealed for 900 s at 640, 630, 640 and 640 K, respectively,
corresponding to the temperature just above the second
exothermic peak, are shown in Fig. 4(aeh). A fine dispersion of
precipitates in the amorphous matrix can be identified as fcc a-Al
phase. The average diameter of the a-Al particles is about 7 nm for
TM ¼ V, 5 nm for TM ¼ Nb, 7 nm for TM ¼ Cr and about 15 nm for
TM ¼ Cu, indicating a tendency for the diameter to decrease with
increasing melting temperature and/or atomic radius of the TM
element.
We further tried to confirm the coexistence of only [a-Al þ am00 ]
phases for the Cr- and Cu-containing alloys annealed after the
second exotherm by high-resolution TEM (HRTEM) and nanobeam
diffraction methods. Fig. 5(aeh) show HRTEM images, nanobeam
diffraction patterns and EDX profiles with analytical sites and
compositions. The fringe contrast, as well as the atomic
 Y. Jin et al. / Journal of Alloys and Compounds 832 (2020) 154997 3

Fig. 1. (a) X-ray diffraction patterns and (b) DSC curves of melt-spun Al84Y9Ni4Co1.5Fe0.5TM1 (TM ¼ Zr, V, Nb, Cr, Mo, Mn, Cu, Ag or Au) alloy ribbons. The arrows in (a) and (b)
present the summit position of the maximum X-ray diffraction peak and the peak temperature of the second exothermic peak, respectively.

Fig. 2. X-ray diffraction patterns of (a) Al84Y9Ni4Co1.5Fe0.5V1, (b) Al84Y9Ni4Co1.5Fe0.5Nb1, (c) A84Y9Ni4Co1.5Fe0.5Cr1, (d) Al84Y9Ni4Co1.5Fe0.5Mo1, (e) Al84Y9Ni4Co1.5Fe0.5Mn1 and (f)
Al84Y9Ni4Co1.5Fe0.5Cu1 alloys annealed for 900 s at different temperatures.

configurations in the a-Al phase, does not indicate defects, sug-
gesting that this nanoscale phase formed through the reverse
transition has a perfect crystal structure. The nanobeam diffraction
patterns confirm that the precipitates are a-Al. Based on the data in
Figs. 2, 4 and 5, the lattice parameter of the a-Al phase is evaluated
to be 0.4053 nm for the Cr- and Cu-containing alloys, and no
appreciable change in the lattice parameter with TM elements is
recognized. This value is slightly larger than that (0.4049 nm) for
pure Al, indicating that the a-Al contains a small amount of Y with a
much larger atomic radius than Al, in addition to the other solute
elements with smaller atomic radii than Al. The perfect crystal a-Al
phase is surrounded by the residual amorphous phase and no AlxMy
intermetallic compound is recognized, even at the interface be-
tween the a-Al and am00 phases. Although the a-Al particle diam-
eter for the TM ¼ Cu alloy is about twice that for the TM ¼ Cr alloy,
the a-Al particles are still defect-free and the AlxMy compound is
still absent. Fig. 5 shows the EDX profiles of the a-Al (c and g) and
am00 phase (d and h) regions of the Cr- and Cu-containing alloys
obtained by annealing for 900 s at 640 K. The compositions are
evaluated to be approximately Al89.4Y3.2Ni3.8Co2.1Fe0.6Cr0.9 and
Al91.8Y0.9Ni5.2Co0.9Fe1Cu0.2 (at%) for the a-Al phase, and Al77.6Y11.5-
Ni7.0Fe0.4Co2.2Cr1.3 and Al78.8Y11.4Ni5.5Co2.6Fe0.7Cu1.0 for the am00
phase. The am00 phase has much higher Y, Ni and Co contents than
the a-Al phase, suggesting that the am00 phase was formed mainly
from the AlxMy compound phase regions. The other solute elements
except Y are also enriched into the am00 phase as shown in Fig. 5 (d
and h). Nevertheless, the a-Al phase has an overall solute content of
about 10.6 at% (Fig. 5 c) for TM ¼ Cr, and 8.2 at% (Fig. 5 g) for
TM ¼ Cu, values which are much higher than the equilibrium solid-
solubility limit (near zero at%) at room temperature for Al-(Fe, Co,
Ni, TM) binary alloys [12]. A similar partitioning of Y was also
recognized for the Nb-containing alloy, being independent of pe-
riodic group number and atomic size of the TM elements.
To investigate the ease of the reverse amorphization in
4 Y. Jin et al. / Journal of Alloys and Compounds 832 (2020) 154997
Fig. 3. X-ray diffraction patterns of (a) Al84Y9Ni4Co1.5Fe1.5, (b) Al84Y9Ni4Co2.5Fe0.5 and (c) Al84Y9Ni5Co1.5Fe0.5 alloys annealed for 900 s at different temperatures.
comparison with the first-stage crystallization, the activation en-
ergies for the three stages of decomposition were evaluated by the
Kissinger analysis [13]. As examples, Fig. 6(a) and (b) show the
Kissinger plots of the first, second and third exothermic peaks for
Al84Y9Ni4Co1.5Fe0.5TM1 (TM ¼ Nb or Cu) amorphous alloys, together
with the corresponding DSC curves measured at different heating
rates in Fig. 6 (c). Three exothermic peaks are seen in the DSC
curves. From the clear straight lines in the plots, the activation
energies for the first, second and third stages are estimated to be
286, 247 and 196 kJ mol1, respectively, for TM ¼ Nb, and 252, 227
and 174 kJ mol1, respectively, for TM ¼ Cu. The activation energies
are slightly larger for the Nb-containing alloy and the difference
seems to reflect much higher melting temperature and larger
atomic size for Nb than for Cu [14]. Although the activation energies
decrease in the order of first / second / third stage, the stability
of the metastable [a-Al þ am00 ] phase mixture is estimated to be
relatively high because of the high decomposition temperature as
well as the much larger temperature interval between the second
and the third stages than between the first and the second stages.
We also examined the possibility of forming a similar [a-
Al þ am00 ] phase mixture from [a-Al þ AlxMy þ am’] in the other
alloy series of Al84Y9Ni4Co1.5Fe0.5TM1 (TM ¼ Zr, Ag or Au). The se-
lection of these TM elements is because they have larger atomic
radii than those of Al and the other constituent elements [8] and
include atomic pairs with positive heats of mixing with the other
elements as exemplified for ZreY, AgeCo, AgeFe, Au-Co and AueFe
[9]. As shown by the X-ray diffraction patterns in Fig. 7(aec), no
reverse transition from [a-Al þ AlxMy þ am’] to [a-Al þ am00 ] is
recognized for the TM ¼ Zr, Ag or Au alloys.
Fig. 8 shows the changes in the structure, Vickers hardness (Hv)
and bending plasticity with annealing temperature for Al84Y9Ni4-
Co1.5Fe0.5TM1 (TM ¼ V, Nb, Cr, Mo, Mn or Cu) alloy ribbons, together
with previous data on the Al84Y9Ni4Co1.5Fe0.5Pd1 alloy [7]. The Hv is
360e430 in the as-spun glassy state, increases rapidly in the first-
stage crystallization to [a-Al þ AlxMy þ am’] and further to
maximum values of 550e580 at the temperatures around the
 Y. Jin et al. / Journal of Alloys and Compounds 832 (2020) 154997 5

Fig. 4. TEM bright-field images and selected-area electron diffraction patterns of (a, b) Al84Y9Ni4Co1.5Fe0.5V1, (c, d) Al84Y9Ni4Co1.5Fe0.5Nb1, (e, f) Al84Y9Ni4Co1.5Fe0.5Cr1 and (g, h)
Al84Y9Ni4Co1.5Fe0.5Cu1 alloys annealed for 900 s at 640 K, 630 K, 640 K and 640 K, respectively. The arrows present a-Al precipitates.

Fig. 5. HRTEM images, nanobeam diffraction patterns and EDX profiles with analytical sites and compositions of (aed) Al84Y9Ni4Co1.5Fe0.5Cr1 and (eeh) Al84Y9Ni4Co1.5Fe0.5Cu1
alloys annealed for 900 s at 640 K. The analyses were made in a-Al phase region for Fig. 5 (c) and (g) and the residual amorphous phase for Fig. 5 (d) and (h).

second-stage reverse amorphization reaction to [a-Al þ am00 ], and
then decreases significantly to 450e500 in the third decomposition
stage to [a-Al þ Al3Y þ Al9(Fe,Co,Ni,TM)2]. The Cr- and Mo-
containing alloys also exhibit the highest hardness values in the
annealing temperature range just before the phase decomposition
from [a-Al þ am00 ] to the three crystalline phases. It is notable that
the highest Vickers hardness is obtained for the metastable [a-
Al þ am00 ] phase mixture, and that the fully crystalline phase
mixtures including compounds exhibit much lower hardness. This
feature is recognized for all the present Al-based alloys except the
TM ¼ Zr, Ag or Au alloys, though the hardness values are slightly
different among the TM elements. The absence of a significant
difference in the maximum hardness values with TM elements
indicates that the metastable two-phase mixture [a-Al þ am00 ]
plays a dominant role in the achievement of the high hardness.
Fig. 9 shows SEM and optical micrographs revealing the shear
markings on the outer surface of bent ribbons and around the
Vickers hardness indents, for Al84Y9Ni4Co1.5Fe0.5TM1 (TM ¼ Cr or
Cu) ribbons in as-spun and annealed states. All the as-spun ribbons
have good plasticity: they can be bent through 180 without frac-
ture, as shown in Fig. 9 (a, c). Although the good plasticity can be
maintained nearly up to the glass-transition temperature, heating
6 Y. Jin et al. / Journal of Alloys and Compounds 832 (2020) 154997
Fig. 6. DSC curves measured at different heating rates and the corresponding Kissinger plots of the first-, second- and third-exothermic peaks for (a, b) Al84Y9Ni4Co1.5Fe0.5Nb1 and
(c, d) Al84Y9Ni4Co1.5Fe0.5Cu1 glassy alloys.
to higher temperature leads to embrittlement of the ribbons, which
then fracture during bending. In contrast, whatever the annealing
treatment, no cracking is detected around Vickers hardness in-
dents, and the observed shear traces indicate plasticity under this
loading condition.
4. Discussion
The Al84Y9Ni4Co1.5Fe0.5TM1 alloys with (TM ¼ V, Nb, Cr, Mo, Mn,
Fe, Co, Ni, Cu or Pd [7]) show the reverse transition, and those with
(TM ¼ Zr, Ag or Au) do not. The reverse transition appears to be
limited to the TM elements which have smaller atomic radii than Al
as well as negative or nearly zero heat of mixing with the other
constituent elements [7]. For all the studied alloys, however, AlxMy
is a primary precipitation phase that is metastable.
The absence of the reverse transition for (TM ¼ Zr, Ag or Au) is
presumably due to the difficulty of phase decomposition of the
AlxMy compound in these alloys. This may be because these ele-
ments have atomic radii larger than those for any of the other
constituent elements including Al [7], as well as large positive heats
of mixing with other solute elements [9], as exemplified by ZreY,
Ag-(Ni, Co or Fe) and Au-(Ni, Co or Fe) pairs [9]. The larger atomic
radii can suppress the mobility of the constituent elements thus
impeding the reverse transition, while the positive heat of mixing
can also suppress the formation of a compositionally uniform AlxMy
compound, impeding its decomposition to a-Al þ amorphous
phases. The ultimate decomposition of the AlxMy phase in these
three alloys occurs when the atomic mobility is sufficient at higher
temperatures just below the third exothermic peak, and it proceeds
directly to the equilibrium phases (Fig. 7).
We examined the possibility of forming a bulk rod, fully amor-
phous or with [am þ a-Al] phases, for the Al84Y9Ni4Co1.5Fe0.5Cu1
alloy which can be regarded as attractive for future application.
Fig. 10(aec) show photographs of the rod prepared by casting into a
mold with a conical inner cavity, and optical micrographs of regions
of the longitudinal cross-section of the rod. The cast microstructure
is fully glassy for rod diameters less than about 0.82 mm and shows
a [a-Al þ am] mixture for diameters up to about 1.2 mm. From the
X-ray-diffraction patterns of the longitudinal cross-section, we also
confirmed that coexistent [a-Al þ am] phases in the diameter range
1.0e1.2 mm, and then coexistent [a-Al þ Al3Y þ Al9(Fe, Co, Ni,
Cu)2 þ unknown phases] at larger diameters up to about 3 mm. We
further confirmed the formation of [a-Al þ am] phases without any
other phases in the region with a diameter of about 1 mm because
there are no previous data on the formation of nanoscale mixed [a-
Al þ am] phases in cast Al-based alloy rods. Fig. 11(aed) show
bright-field TEM image, selected-area electron diffraction pattern,
high-resolution TEM images and nanobeam diffraction patterns
taken from [a-Al] and [am] phases, respectively. The cast structure
consists of [a-Al þ am] phases and the particle size and inter-
particle spacing of [a-Al] phase are about 30 nm and 15e20 nm,
respectively, which are considerably larger than those (about
7e15 nm and 10e15 nm, respectively) for [a-Al] phase obtained by
the annealing-induced reverse transition of amorphous phase. No
appreciable other phases are observed in the region, indicating
clearly that the coexistent [a-Al þ am] phases are formed in the
1 mm diameter region of the conical cast alloy rod, in agreement
with the X-ray diffraction data. The EDX data in Fig. 11(e and f)
indicate that the total solute content is about 7.3 at% for the [a-Al]
phase and 20.4 at% for the [am] phase. In comparison with the EDX
data of the annealing-induced [a-Al þ am] phases shown in Fig. 5,
the solute content of [a-Al] phase in the cast alloy is nearly the same
as that for [a-Al] phase in the annealed alloy, while the solute
content in [am] phase is lower for the cast alloy, indicating that the
as-cast mixed phase structure is in a higher level of metastable
state. It is notable that metastable microstructures of [am] or [a-
Al þ am] phases are formed even for the alloy rod with a diameter
of about 1.2 mm, indicating that the microstructure of choice,
namely coexistent [a-Al þ am] phases with high strength, can be
obtained even in cast rod form. As shown in Fig. 10 (d), the Vickers
hardness is 420e430 for the amorphous single phase, increases to
about 510 for the [a-Al þ am] phases, and then decreases signifi-
cantly to about 265 for the completely crystalline microstructure.
The Hv values of the [am] as well as the [a-Al þ am] phases are
nearly the same as those for the as-spun amorphous ribbons and
the annealed ribbons with metastable [a-Al þ am00 ] microstructure.
It is promising that the high hardness and high thermal stability
characteristic of the [a-Al þ am] phase mixture can be exploited
 Y. Jin et al. / Journal of Alloys and Compounds 832 (2020) 154997
Fig. 7. X-ray diffraction patterns of Al84Y9Ni4Co1.5Fe0.5TM1 (TM ¼ Zr (a), Ag (b) or Au (c)) alloys annealed for 900 s at different temperatures including the first-, second- and third-
exothermic peak temperatures.
even for the bulk Al-based structural and coating materials with
high elevated-temperature strength.
As shown in Fig. 8, the metastable [a-Al þ am00 ] alloys exhibit
very high Hv values of 550e580 in the high annealing temperature
range of 620e680 K. The solute content is analyzed to be about
10 at% for a-Al and about 22 at% for am00 and the volume fractions of
a-Al and am00 phases are measured to be approximately 55% and
45%, respectively, from the TEM images. It is important to investi-
gate why these simple mixed-phase alloys exhibit high Hv values
exceeding those for phase mixtures that include intermetallic
compounds. The Hv has been reported to be about 250 for
Al88Y2Ni10-xMx (M ¼ Fe or Co) amorphous alloys [15] with similar
solute content as for the am00 phase in the present work. Applying
the rule of mixtures, the Hv of the a-Al phase is estimated to be
about 820 which is about 10 times the highest value reported for
conventional age-hardening Al 7075 alloys [16]. Furthermore, this
Hv value is almost comparable to the Hv value (about 800) for a-Al
phase with a size of about 3e10 nm which has been previously
7
reported for the a-Al þ residual amorphous phases in Al88Y2Ni9M1
(M ¼ Mn or Fe) [17], Al88Y12-xNix [18] and Al88Ni9Ce2Fe1 [19]
amorphous alloys obtained by cooling rate control. In earlier works,
the high strength of a-Al was attributed to the formation of su-
persaturated solid solution nanocrystals containing a large amount
of solute elements [18] and having perfect crystal without appre-
ciable internal defects [19]. The present a-Al phase formed by the
reverse transition appears very similar to that formed directly from
the supercooled liquid phase [17e19], though the annealing tem-
perature is considerably higher for the present alloys. The forma-
tion of the perfect crystal a-Al supersaturated solution phase as
well as the achievement of the ultrahigh strength appears to be
independent of the annealing process and alloy composition. On
the other hand, the Hv of the as-cast amorphous þ a-Al phase alloys
is as low as about 350, as shown in Fig. 10 (d). The Al phase has
much larger particle size of about 30 nm and appears to include a
high density of internal defects. The much lower Hv values for the
as-cast alloys are presumed to be due to the much lower strength of
8 Y. Jin et al. / Journal of Alloys and Compounds 832 (2020) 154997

Fig. 8. Changes in the structure, Vickers hardness (Hv) and bending ductility with annealing temperature (Ta) for Al84Y9Ni4Co1.5Fe0.5TM1 (TM ¼ V, Nb, Cr, Mo, Mn or Cu) alloys. The
previous data of Al84Y9Ni4Co1.5Fe0.5Pd1 alloy are also shown for comparison [6].

Fig. 9. Scanning electron micrographs of the outer bent surface and optical micrographs of the slip markings around Vickers hardness indentation trace for (a, b) Al84Y9Ni4-
Co1.5Fe0.5Cr1, and (c, d) Al84Y9Ni4Co1.5Fe0.5Cu1 alloys.

Al phase containing internal defects as compared with the perfect
crystal Al phase as well as the much lower Hv values of the lower
solute-content amorphous phase without distinct solute element
partitioning. Thus, the present high Hv values are presumed to
originate from the combination of two factors; (1) the formation of
nanoscale a-Al phase without appreciable internal defects, and (2)
the formation of a residual amorphous matrix with a solute content
much higher than the nominal overall content in the alloy. In
addition, the maintenance of the metastable nanoscale [a-
Al þ am00 ] phase mixture in the high and wide annealing temper-
ature range of 620e680 K is also due to the low atomic diffusivity
caused by the absence of internal defects for a-Al phase as well as
the high thermal stability of the am00 phase, itself resulting from the
high solute contents.
Based on the present experimental data, schematic illustrations
of continuous-cooling-transformation (CCT) and continuous-
heating-transformation (CHT) curves and the interrelation of the
Gibbs free energies of the constituent phases, composition and
temperature for Al84Y9Ni4Co1.5Fe0.5Cu1 glassy alloy are shown in
Fig. 12(a) and (b). On cooling, and considering the effects of larger
rod diameter, implying lower cooling rate, the fastest solidification
is to a single amorphous phase, then above a critical diameter of
 Y. Jin et al. / Journal of Alloys and Compounds 832 (2020) 154997 9

Fig. 10. (aec) Photos and optical micrographs of a wedge-shape Al84Y9Ni4Co1.5Fe0.5Cu1 alloy rod prepared by injection-type copper mold casting, and (d) Vickers hardness taken
from the longitudinal cross section of the cast alloy rod, and (e) the relation between the as-cast structure and the wedge-shaped cone rod prepared by injection copper mold
casting.

Fig. 11. (a) Bright-field TEM image, (b) selected-area electron diffraction pattern, HRTEM images and nanobeam electron diffraction patterns taken from (c) fcc-Al and (d)
amorphous phase regions, and EDX profiles, analytical sites and compositions of (e) fcc-Al and (f) amorphous phase regions for a wedge-shape Al84Y9Ni4Co1.5Fe0.5Cu1 alloy rod
prepared by injection-type copper mold casting.

about 0.82 mm the solidification is to [a-Al þ am] and above a concluded that the reverse transition occurs only in the decom-
diameter of about 1.2 mm to [a-Al þ Al3Y þ Al9(Ni,Co,Fe)2 þ an position stages from the amorphous phase. The reverse transition
unknown phase]. Thus, no structural change corresponding to the has been interpreted on the basis of the changes in the relative free
reverse amorphization is seen on continuous cooling. It is energies with alloy composition for the various phases relevant for
10 Y. Jin et al. / Journal of Alloys and Compounds 832 (2020) 154997
Fig. 12. Schematic illustrations of (a) continuous-cooling-transformation (CCT) and continuous-heating-transformation (CHT) curves and (b) the relation among the free energy,
composition and temperature for Al84Y9Ni4Co1.5Fe0.5Cu1 glassy alloy.
the first and second exotherms on heating an 84Al amorphous alloy
[7]. On a similar thermodynamic basis, we try to explain the
heating-induced reverse transition for the Cu-containing alloy
where the alloy contents in the precipitate phases in the first and
the second exotherms have been measured. As depicted in Fig. 12
(b), where the alloy is represented as a binary system, with all
solutes considered together, the free energy of all the phases de-
creases with increasing temperature, but that of the supercooled
liquid decreases faster because of its higher entropy. The faster
lowering of the free energy of the supercooled liquid permits
reverse amorphization to occur in the second exotherm. In the
figure, the free energies of the crystalline phases are shown fixed,
and relative to them the free energy of the supercooled liquid is
shown for the temperatures of the peaks of the first and second
exotherms. The free energy is lowered (arrow 1 in the figure) by
eutectic crystallization to a-Al and AlxMy in the first exotherm. In
the second exotherm, the free energy is further lowered (arrow 2 in
the figure) by the peritectic decomposition of AlxMy to a-Al and
supercooled liquid. With further increasing temperature, sufficient
atomic mobility would permit the formation of the equilibrium
phases (marked 3 in the figure): Al9(Ni, Co, Fe)2, Al3Y and an un-
known phase.
5. Summary
The formation, thermal stability and phase decomposition of
melt-spun amorphous Al84Y9Ni4Co1.5Fe0.5TM1 (TM ¼ Zr, V, Nb, Cr,
Mo, Mn, Fe, Co, Ni, Cu, Ag or Au) alloys were examined with the aim
of developing a-Al þ amorphous phase mixtures with high thermal
stability and high strength through the heating-induced reverse
transition from [a-Al þ AlxMy þ am’] to [a-Al þ am00 ] phases in their
crystallization reactions. For the alloys with TM ¼ V, Nb, Cr, Mo, Mn,
Fe, Co, Ni or Cu, the decomposition sequence is [am] / [a-
Al þ AlxMy þ am’] / [a-Al þ am00 ] / [a-
Al þ A3Y þ Al9TM2 þ unknown phases] and includes the reverse
transition. For the alloys with TM ¼ Zr, Ag or Au, the decomposition
sequence is [am] / [a-Al þ AlxMy þ am’] / [a-
Al þ Al3Y þ Al9TM2 þ unknown phases], showing no heating-
induced reverse amorphization. For these alloys, the solutes (Zr,
Ag or Au) have atomic radii larger than Al and positive heats of
mixing with other constituent elements. The a-Al phase formed by
the reverse transition has a nearly spherical morphology with a
diameter of 5e15 nm and no appreciable internal defects. The so-
lute contents in the a-Al and am00 phases in the TM ¼ V, Cr and Cu
alloys are 8.2e11.0 at% and 21.2e22.4 at%, respectively, and the Y
and Co elements are partitioned into the am00 phase. The a-Al phase
can be regarded as a metastable supersaturated solid solution, as its
overall solute content is much higher than the maximum solubility
limit for Al-based binary alloys. For the sequence of decomposition
reactions, the activation energy is measured to be
252e286 kJ mol1 for the first stage, 227e247 kJ mol1 for the
second stage, and 174e196 kJ mol1 for the third stage. There is a
tendency for the activation energy to be higher for a TM solute with
a higher melting temperature and larger atomic radius. The Vickers
hardness Hv is 360e430 in the as-spun state, increases significantly
for the [a-Al þ AlxMy þ am’] phase mixture, and further to
maximum values of 550e580 for the [a-Al þ am00 ] phase mixture,
and then decreases rapidly upon decomposition to the fully crys-
talline phase mixture. The [a-Al þ am00 ] phase mixture exhibits the
highest Hv and is significant in developing lightweight materials
with high elevated-temperature strength. That the reverse
amorphization is seen only for some TM solutes is presumably due
to the low mobility of TM solutes with atomic radii larger than Al
and positive heats of mixing. In a conical cast rod with TM ¼ Cu, an
amorphous single phase is formed for diameter up to about
0.82 mm, while the diameter for [a-Al þ am] phases extends to
about 1.2 mm. The cast [a-Al þ am] alloys exhibit a high hardness of
about 510, which decreases rapidly to 265 in the fully crystalline
phase mixture. The bulk-forming ability and high thermal stability
of the metastable [a-Al þ am] phase mixture are due to the low
atomic diffusivities in the co-existing perfect crystal a-Al phase and
high-solute-content amorphous phase.
Declaration of competing interest
We wish to confirm that there are no known conflicts of interest
associated with this publication and there has been no significant
financial support for this work that could have influenced its
outcome.
CRediT authorship contribution statement
Y. Jin: Methodology, Investigation, Writing - original draft,
Writing - review & editing. A. Inoue: Conceptualization, Investi-
gation, Writing - original draft, Writing - review & editing, Super-
vision, Funding acquisition. F.L. Kong: Investigation, Writing -
review & editing. S.L. Zhu: Data curation, Supervision. F. Al-Mar-
zouki: Formal analysis. A.L. Greer: Conceptualization, Methodol-
ogy, Writing - review & editing.
Acknowledgments
The authors are grateful for support from the Recruitment
Program of Global Experts “1000 Talents Plan” (WQ20121200052),
 Y. Jin et al. / Journal of Alloys and Compounds 832 (2020) 154997
the National Natural Science Foundation of China (51771131), the
Deanship of Scientific Research (DSR), King Abdulaziz University,
[8]
Jeddah, Saudi Arabia (1-1-435/HiCi) and the Ministry of Education [9]
and Science of the Russian Federation in the framework of the
program aimed to increase the competitiveness of the National
University of Science and Technology, “MISiS” (No. K2-2019-002). [10]
ALG acknowledges support from the European Research Council
under the European Union’s Horizon 2020 research and innovation [11]
[12]
program (grant ERC-2015-AdG-695487: Extend Glass).
[13]
References
[14]
[1] A. Inoue, Amorphous, nanoquasicrystalline and nanocrystalline alloys in Al-
based systems, Prog. Mater. Sci. 43 (1998) 365e520.
[15]
[2] A. Inoue, S. Sobu, D.V. Louzguine, H. Kimura, K. Sasamori, Ultrahigh strength
Al-based amorphous alloys containing Sc, J. Mater. Res. 19 (2004) 1539e1543.
[16]
[3] A. Inoue, A. Takeuchi, Recent development and application products of bulk
glassy alloys, Acta Mater. 59 (2011) 2243e2267.
[4] C. Fan, X.X. Yue, A. Inoue, C.T. Liu, X.P. Shen, P.K. Liaw, Recent topics on the
[17]
structure and crystallization of Al-based glassy alloys, Mater. Res.-Ibero-Am. J.
22 (2019), e20180619.
[5] Y. Kim, A. Inoue, T. Masumoto, Ultrahigh tensile strengths of Al88Y2Ni9M1 (M¼
[18]
Mn or Fe) amorphous alloys containing finely dispersed fcc-Al particles,
Mater. Trans., JIM 31 (1990) 747e749.
[6] F.F. Han, A. Inoue, Y. Han, F.L. Kong, S.L. Zhu, E. Shalaan, F. Al-Marzouki, High
[19]
formability of glass plus fcc-Al phases in rapidly solidified Al-based multi-
component alloy, J. Mater. Sci. 52 (2017) 1246e1254.
[7] F.F. Han, A. Inoue, Y. Han, F.L. Kong, S.L. Zhu, E. Shalaan, F. Al-Marzouki,
11
A.L. Greer, Novel heating-induced reversion during crystallization of Al-based
glassy alloys, Sci. Rep. 7 (2017) 46113.
J.C. Slater, Atomic radii in crystals, J. Chem. Phys. 41 (1964) 3199e3204.
A. Takeuchi, A. Inoue, Classification of bulk metallic glasses by atomic size
difference, heat of mixing and period of constituent elements and its appli-
cation to characterization of the main alloying element, Mater. Trans. 46
(2005) 2817e2829.
D. Bailey, The structure of two polymorphic forms of YAl3, Acta Crystallogr. 23
(1967) 729e733.
A. Douglas, The structure of Co2Al9, Acta Crystallogr. 3 (1950) 19e24.
H. Okamoto, Desk Handbook: Phase Diagrams for Binary Alloys, 2 ed., ASM
International, Materials Park, Ohio, 2010.
H.E. Kissinger, Reaction kinetics in differential thermal analysis, Anal. Chem.
29 (1957) 1702e1706.
W.D. Callister Jr., D.G. Rethwisch, Fundamentals of Materials Science and
Engineering: an Integrated Approach, 4 ed., John Wiley & Sons, Hoboken, NJ,
2012.
A.P. Tsai, A. Inoue, T. Masumoto, Ductile Al-Ni-Zr amorphous alloys with high
mechanical strength, J. Mater. Sci. Lett. 7 (1988) 805e807.
S.W. Kim, D.Y. Kim, W.G. Kim, K.D. Woo, The study on characteristics of heat
treatment of the direct squeeze cast 7075 wrought Al alloy, Mater. Sci. Eng. A-
Struct. 304e306 (2001) 721e726.
Y.H. Kim, A. Inoue, T. Masumoto, Ultrahigh tensile strengths of Al88Y2Ni9M1
(M¼Mn or Fe) amorphous alloys containing finely dispersed fcc-Al particles,
Mater. Trans., JIM 31 (1990) 747e749.
Y.H. Kim, A. Inoue, T. Masumoto, Increase in mechanical strength of Al-Y-Ni
amorphous alloys by dispersion of nanoscale fcc-Al particles, Mater. Trans.,
JIM 32 (1991) 331e338.
A. Inoue, Y. Horio, Y.H. Kim, T. Masumoto, Elevated-temperature strength of
an Al88Ni9Ce2Fe1 amorphous alloy containing nanoscale fcc-Al particles,
Mater. Trans., JIM 33 (1992) 669e674.