Journal of Alloys and Compounds 790 (2019) 657e665

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

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

Stability of the B2 CuZr phase in Cu-Zr-Al-Sc bulk metallic glass matrix

composites
B. Escher a, *, I. Kaban a, b, U. Kühn a, J. Eckert c, d, S. Pauly a, **, 1
a
IFW Dresden, Institute for Complex Materials, Helmholtzstraße 20, D-01069 Dresden, Germany
b
TU Dresden, Institute of Materials Science, D-01062 Dresden, Germany
c
Erich Schmid Institute of Materials Science, Austrian Academy of Sciences, Jahnstraße 12, A-8700 Leoben, Austria
d
Montanuniversita€t Leoben, Department of Materials Science, Jahnstraße 12, A-8700 Leoben, Austria

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

Article history: This study investigates the effect, that replacing Zr in a glass-forming Cu47.5Zr47.5Al5 alloy by Sc (0e2 at.%)
Received 3 January 2019 has on the phase formation as well as on the thermal and mechanical properties. Even though it is not
Received in revised form reflected in the thermal data, the glass-forming ability (GFA) is significantly reduced. This originates from
25 February 2019
the increased tendency to precipitate the shape-memory phase B2 CuZr(Sc), which, in turn, promotes the
Accepted 7 March 2019
Available online 8 March 2019
formation of bulk metallic glass (BMG) matrix composites. Sc appears to be very effective in stabilizing
the B2 crystals because it forms the stable B2 CuSc phase with a similar lattice constant like B2 CuZr. By
adjusting the casting parameters, the composite microstructure of Cu47.5Zr46.5Al5Sc1 can be controlled to
Keywords:
A amorphous materials
a certain extent. The yield strength and the plasticity of the present composites depend on the crystalline
B casting volume fraction. In-situ high-energy X-ray diffraction reveals that deformation proceeds in three stages:
B liquid quenching (i) martensitic transformation of the B2 phase, (ii) yielding of the amorphous phase and continuing
C X-ray diffraction martensitic transformation, (iii) completion of the phase transformation and plastic deformation of all
E synchrotron radiation phases. Our work suggests that Sc is a promising candidate to adjust the microstructure and, thus, the
E thermal analysis mechanical properties of CuZr-based composites consisting of a glassy matrix and shape-memory
crystals.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction
Bulk metallic glasses (BMG) still are a relatively young class of
materials [1e3]. They show many excellent properties, especially
when compared to their crystalline counterparts. They have a low
Young's modulus and a large elastic limit [3], which, in combination
with yield strengths near the theoretical value, leads to a high
resilience [1]. Furthermore, bulk metallic glasses generally exhibit
high hardness and high wear resistance [2]. Above the glass-
transition temperature (Tg) they can be formed “superplastically”
like polymers [3]. Due to the negligible volume change accompa-
nying the glass transition, metallic glasses can be processed into
* Corresponding author.
** Corresponding author.
E-mail addresses: escher.benjamin@yahoo.de (B. Escher), s.pauly@ifw-dresden.
de (S. Pauly).
1 €t Ingenieurwissenschaften Hochschule Aschaffenburg
Present address: Fakulta
(University of Applied Sciences) Würzburger Str. 45, 63743 Aschaffenburg,
Germany.
near-net shape geometries without the need for intensive post-
processing [3]. Apart from all these advantages, their major draw-
back, however, is their macroscopic brittleness due to self-
promoting strain localization [2,3]. At the early stages of irrevers-
ible flow, plastic strain is solely accommodated in so-called shear
transformation zones, which eventually emerge into shear bands at
the later stages of plastic deformation [4]. Shear bands eventually
transform into cracks and cause catastrophic failure after limited
macroscopic plastic strain [4].
In order to distribute the strain more homogeneously, the
number or density of shear bands has to be increased. This can be
achieved, among other things, by embedding deformable crystals in
the glassy matrix [2,4,5]. The presence of crystals in such bulk
metallic glass matrix composites hinders the propagation of shear
bands, which enhances the overall plastic deformability [2,4,5].
Some glass-forming alloys already partially crystallize during
casting if the casting conditions are chosen properly. The challenge
thereby is to uniformly disperse the ductile crystalline precipitates
in the glass [5]. Among these bulk metallic glass matrix composites,
the ones in which the crystalline phase exhibits a shape-memory

https://doi.org/10.1016/j.jallcom.2019.03.139
0925-8388/© 2019 Elsevier B.V. All rights reserved.
658 B. Escher et al. / Journal of Alloys and Compounds 790 (2019) 657e665
effect have been subjected to intense research in the past years
[6e10]. The pronounced deformation-induced hardening in the
crystalline phase overcompensates the softening of the glassy
matrix and, moreover, the resultant overall work hardening is
accompanied by an enhanced plastic strain [7e10].
One prominent group of shape-memory BMG matrix compos-
ites is derived from binary Cu50Zr50 [6e10]. While these composites
possess desirable mechanical properties, their fabrication is not
straightforward. Because the B2 phase crystallizes polymorphically,
the crystal growth rates are comparatively high in these alloys
[11,12]. The consequence is a limited glass-forming ability and the
fact that, generally, only few but relatively large crystals precipitate
non-uniformly inside the glass. The composite microstructure can
be made more uniform by employing a rather tedious and time-
consuming remelting procedure [13], by flash-annealing [14,15]
or by careful alloy design [9]. Al is often added to CuZr-based alloys
[16e18] because it improves the glass-forming ability (GFA) by
electronic stabilization of the glass [19]. At the same time one has to
ensure that the B2 phase is not fully destabilized. Otherwise it
becomes impossible to prepare shape-memory BMG matrix com-
posites. In order to understand and tune the evolution of BMG
matrix composite microstructures and, with it, of the resulting
mechanical properties, it is important to explore and identify the
impact of additional alloying elements. They are, next to the casting
parameters, the main setscrew to influence the microstructural
evolution during quenching [1,3,5]. In the following paragraph, we
briefly dwell on this aspect with a focus on the stability of the B2
phase.
The shape-memory phase, B2 CuZr, is only stable above 988 K
[20] and only owing to the kinetic constraints imposed on
quenching it can be preserved at lower temperatures [6,21e23]. At
low cooling rates, however, the B2 phase decomposes below 988 K
into the compounds Cu10Zr7 and CuZr2 [24]. The thermodynamic
stability of B2 CuZr can be significantly enhanced by adding certain
alloying elements such as Co [8,21,22,24,25] and Zn [26]. Co forms a
B2 phase with Zr [27] and Zn forms B2 phases with both Zr and Cu
[28,29]. All these B2 phases are thermodynamically stable over a
much wider temperature regime and form at room temperature.
Even small amounts of Co and Zn, hence, suffice to stimulate the
precipitation of a B2 phase in CuZr-based alloys [21,22,26,30,31].
The efficacy of this effect seems to correlate with the lattice con-
stants of the respective B2 phase. B2 CoZr (a ¼ 0.3197 nm [27]) has a
lattice constant much closer to B2 CuZr (a ¼ 0.3259 nm [23]) than
B2 ZrZn (a ¼ 0.5825 nm [28]) or B2 CuZn (a ¼ 0.2949 nm [29]).
When Co or Zn are dissolved in B2 CuZr a smaller size mismatch
should reduce the local strains (lattice distortions due to differing
atomic radii) [32] and stabilize the crystalline phase accordingly.
Therefore, Co is believed to be more efficient in stabilizing the B2
phase than Zn [26].
In this work, we explore whether Sc can also be used to stabilize
the B2 phase in a glass-forming Cu-Zr-Al alloy and to produce more
uniform BMG matrix composite microstructures. Sc forms a ductile,
stable B2 phase with Cu [33] between room temperature and
1398 K having a lattice parameter of 0.3256 nm [34]. This is even
closer to the value of B2 CuZr (0.3259 nm [23]) than that of CoZr
(0.3197 nm [27]). In addition, Zr and Sc are fully miscible over a
wide temperature range [35]. Therefore, Sc is expected to be a
promising, novel element addition for enhancing the stability of the
B2 phase and, thus, for promoting its precipitation in the glassy
matrix. The B2 crystals might be dispersed more uniformly when
the cooling conditions are chosen properly. So far only the influence
of small Sc additions (0.02 at.%) on the welding structure of a Zr-
based glass has been analysed [36]. Next to the influence of Sc on
the GFA and the thermodynamic stability of the B2 phase, the
mechanical properties of different Cu47.5Zr47.5-xAl5Scx (x ¼ 0, 0.2,
0.5, 1 and 2 at.%) alloys are investigated. The influence of the B2
crystals on the deformation behaviour is revealed by means of in-
situ high-energy X-ray diffraction (XRD).
2. Experimental
Master alloy ingots (25 g) for all alloys were prepared by arc
melting of high-purity elements (Al: 99.99 wt%, Cu: 99.99 wt%, Co:
99.9 wt% Sc: 99.9 wt%, Zr: 99.8 wt%) in a titanium-gettered Ar at-
mosphere. A series of glass-forming Cu47.5Zr47.5-xAl5Scx (x ¼ 0, 0.2,
0.5, 1 and 2 at.%) was prepared. The ingots were re-melted at least
three times and their composition was controlled via inductively-
coupled plasma optical emission spectroscopy (ICP-OES, Thermo
Scientific IRIS Intrepid II XUV and iCAP 6000). The samples were
cast in a suction casting device (Bühler MAM1) into rods with di-
ameters of 1.5 mm, 2 mm, 2.5 mm and 3 mm. A single-roller melt
spinner (Edmund Bühler GmbH) was employed for preparing rib-
bons using a BN-coated SiO2 nozzle. The melts were ejected about
200 K above their respective liquidus temperatures.
Thermal analysis was conducted in a high-temperature differ-
ential scanning calorimeter (DSC, Netzsch DSC 404 C) and in con-
ventional DSCs (Perkin-Elmer Diamond & DSC 8500). For the
Netzsch DSC 404 C a heating and cooling rate of 20 K/min and
alumina crucibles were used up to a temperature of 1423 K. The
measurements in the conventional DSCs were done in aluminium
crucibles at a heating rate of 20 K/min up to a temperature of 863 K.
The calorimetric glass-transition temperatures Tg (half cp) and the
crystallization temperatures Tx (onset) were obtained from low-
temperature DSC measurements. Additionally, the start and end
temperatures of the eutectoid transformation (Ts and Tf, respec-
tively), the solidus temperature (Tsol) and the liquidus temperature
(Tliq) were determined from the high-temperature measurements
of rods having a diameter of 2 mm. The volume fractions of the B2
phase in rods with a diameter of 2 mm were extracted from the
crystallization enthalpies (at least 4 measurements from different
positions). Dilatometry was done in a Netzsch DIL 402C in the
temperature regime between 193 K and 673 K at a heating rate of
5 K/min on 3 mm rods pre-annealed at 1073 K for 16 h.
A STOE STADI P X-ray diffractometer with Mo-Ka1 radiation
(l1 ¼ 0.070932 nm) in transmission mode was used for structural
characterization. High-energy XRD measurements combined with
compression tests were carried out at the Beamline P07 (Petra III e
DESY Hamburg) using an energy of 100 keV and a Perkin Elmer XRD
1621 area detector. The samples with a diameter of 1.5 mm and a
height of 3 mm were deformed in a Kammrath & Weiss loading rig.
The displacement rate was set as 1 mm/s.
Additional compression tests were conducted on rods with a
diameter of 2 mm and a length of 4 mm in an Instron 5869 me-
chanical test machine applying a displacement rate of
4  104 mm/s using “Molykote” (Dow Corning Corporation) as
lubricant and WC-Co hard metal plates to protect the compression
plungers. At least three samples of each composition were tested.
The strain was determined by a laser extensometer (Fiedler Opto-
elektronik). The elastic constants were determined with the help of
an Olympus Panametrics-NDT 5900 PR ultrasound device for rods
with a diameter of 2 mm.
The amount of the B2 phase in the compression test samples
was extracted via the point counting method from optical micro-
graphs (Zeiss Axiophot microscope, Carl Zeiss AG) of the upper and
lower face of each sample. A scanning electron microscope (SEM)
Leo Gemini 1530 (Zeiss) equipped with an XFlash-Detector (Bruker)
was used for obtaining composition maps by energy-dispersive X-
ray spectroscopy (EDX).
 B. Escher et al. / Journal of Alloys and Compounds 790 (2019) 657e665 659

3. Results & discussion

Table 1 lists the nominal and the actual compositions of the

different alloys as obtained by ICP-OES. Both values agree well
within the experimental error. The first part of the following dis-
cussion covers the thermal properties of the alloys. Especially the
influence of Sc on the characteristic transformation temperatures
and on the phase formation will be addressed. The second part
deals with the influence of the resulting microstructures on the
mechanical behaviour and the deformation mechanisms. In doing
so, we focus on the B2 phase and the martensitic transformation
inherent to this phase during compression.

3.1. Thermal properties

Fig. 1 shows the high-temperature DSC traces of fully glassy

Cu47.5Zr47.5Al5 (alloy no. 1) and Cu47.5Zr46.5Al5Sc1 (alloy no. 4) rib-
bons revealing the glass-transition temperature (Tg), the crystalli-
zation temperature (Tx), the start and the end of the eutectoid
transformation (Ts and Tf), the solidus temperature (Tsol) and the
liquidus temperature (Tliq). There are no systematic changes in Tg,
Tx, Tf or Tliq but only the interval between Ts and Tsol gradually be-
comes larger when the Sc content is increased (Fig. 1, Table 2). This
indicates that the addition of Sc stabilizes the B2 phase. The values
of the austenite start (As) and martensite start temperatures (Ms) in
Table 2 corroborate this. As decreases almost linearly from about
509 ± 5 K for Cu47.5Zr47.5Al5 (alloy no. 1) to 422 ± 5 K for Cu47.5Z-
r45.5Al5Sc2 (alloy no. 5) and likewise Ms decreases, albeit in a less
pronounced manner.
The GFA parameter, gfTg þT Tx
liq
[37], and the K ¼ TTliqf [6] parameter,
which describes the tendency of a CuZr-based alloy to form a BMG
matrix composite containing the B2 phase, were also calculated.
Both parameters strongly depend on Tliq and, therefore, the changes
in g and K mostly reflect the variation in Tliq. Consequently, they
also do not follow a clear trend as a function of the Sc content. In
other words, even though Sc additions clearly influence the ther-
mal stability of the B2 phase, which competes with vitrification,
thermal parameters often used to characterize the glass-forming
ability of an alloy are hardly affected by them. One can thus
conclude that certain minor alloying elements in a given alloy
system have a much stronger effect on the phase formation and
thus on the glass-forming ability than their thermal parameters
suggest. In these cases, the corresponding parameters have to be
interpreted with care.
The X-ray diffraction patterns in Fig. 2a support this reasoning
and clearly demonstrate that there is an influence of the Sc content
on the solidification behaviour. This figure summarizes the XRD
patterns for all investigated rods with 2 mm diameter. While only a
broad diffraction maximum is found for the alloys with low Sc
contents (x ¼ 0, 0.2, 0.5), Cu47.5Zr46.5Al5Sc1 shows weak B2 re-
flections on top of the broad maxima coming from the amorphous
Fig. 1. High-temperature DSC traces (heating rate 20 K/min) of fully amorphous
Cu47.5Zr47.5Al5 and Cu47.5Zr45.5Al5Sc1 ribbons. The glass-transition temperature (Tg), the
crystallization temperature (Tx), the temperature at which the B2 transformation starts
(Ts) and finishes (Tf), as well as the solidus (Tsol) and liquidus temperature (Tliq) are
labelled. The interval of the eutectoid transformation between Ts and Tf is slightly
increased.
phase. At 2 at.% of Sc, the sample seems to be fully crystalline,
indicating a considerable deterioration of the glass-forming ability
primarily caused by the stabilization of the B2 phase. Interestingly,
the EDX results (not shown here) indicate that Sc is evenly
distributed over both crystalline and glassy phases. Hence, espe-
cially at intermediate Sc contents the tendency of the alloys to form
a BMG matrix composite containing the B2 phase should be
enhanced. For this reason Cu47.5Zr46.5Al5Sc1 was cast into different
diameters in order to follow the phase evolution as a function of
cooling rate (Fig. 2b). The B2 phase begins to precipitate in rods
with a diameter of 1.5 mm. Larger diameters (2 and 2.5 mm) lead to
a stronger intensity of the peaks corresponding to the B2 phase and,
thus, to a higher volume fraction of the B2 phase. The 3 mm rod
only shows B2 CuZr reflections and there is no trace of a glassy
phase. In other words, the amount of the B2 phase in the composite
is clearly influenced by the Sc content as well as the cooling rate. It
shows an abrupt rise when a critical cooling rate is crossed or the
critical Sc content is exceeded.
The micrographs of the end faces of two different Cu47.5Z-
r46.5Al5Sc1 (alloy no. 4) compression test rods are displayed
together with their respective B2 volume fraction in Fig. 3. Based on
the micrographs it is obvious, that the rods tend to show a larger
amount of crystals and coarser B2 particles at the sample top
(Fig. 3a and c) compared to the bottom (Fig. 3b and d). This
coarsening is a known phenomenon and has been attributed to
flow turbulences during casting [38]. The coarsening at the top of
the rods can be especially seen between Fig. 3b from the bottom of
one and Fig. 3c from the top of the other rod. Both micrographs

Table 1
Nominal and actual chemical compositions of the ingots of all investigated Cu47.5Zr47.5-xAl5Scx (x ¼ 0, 0.2, 0.5, 1 and 2 at.%) alloys.

x Cu (at.%) ± 0.2 Zr (at.%) ± 0.2 Al (at.%) ± 0.04 Sc (at.%) ± 0.04

0 Nominal 47.50 47.50 5.00 e

ICP-OES 47.66 47.37 4.97 e
0.2 Nominal 47.50 47.30 5.00 0.20
ICP-OES 47.54 47.26 5.00 0.20
0.5 Nominal 47.50 47.00 5.00 0.50
ICP-OES 47.73 46.76 5.01 0.50
1 Nominal 47.50 46.50 5.00 1.00
ICP-OES 47.68 46.26 5.06 1.00
2 Nominal 47.50 45.50 5.00 2.00
ICP-OES 47.79 45.29 5.00 1.92
660 B. Escher et al. / Journal of Alloys and Compounds 790 (2019) 657e665

Table 2
Glass-transition temperature, Tg, crystallization temperature, Tx, eutectoid transformation temperature, Tf, and liquidus temperature, Tliq, for the different glassy Cu47.5Zr47.5-
Tx T
xAl5Scx (x ¼ 0, 0.2, 0.5, 1 and 2 at.%) ribbons. Also the gf [37], and K ¼ f [6] parameter are listed. As and Ms represent the austenite start and martensite start
Tg þ Tliq Tliq
temperatures, respectively.

Alloy Tg (K) Tx (K) Ts (K) Tf (K) Tsol (K) Tliq (K) g K As (K) Ms (K)
±2 K ±2 K ±2 K ±2 K ±5 K ±5 K ±1  104 ±2  104 ±5 K ±5 K

Cu47.5Zr47.5Al5 692 755 973 994 1139 1183 0.409 0.859 509 296
Cu47.5Zr47.3Al5Sc0.2 707 757 970 990 1143 1193 0.403 0.847 e e
Cu47.5Zr47Al5Sc0.5 701 751 967 990 1144 1199 0.403 0.851 494 289
Cu47.5Zr46.5Al5Sc1 696 748 963 992 1149 1200 0.402 0.849 450 280
Cu47.5Zr45.5Al5Sc2 699 741 944 990 1150 1192 0.402 0.847 422 270

[39]. For example, the two samples in Fig. 3 were either overheated
(current was increased) just before filling the mould (Fig. 3a and b)
or directly cast from the melt (Fig. 3c and d). However the fast
growth and low nucleation rate of the B2 phase during the casting
process only allows a slight adjustment of the distribution and the
amount of the B2 phase in the glassy matrix [15].

3.2. Mechanical properties

Representative compression test curves for all compositions are

Fig. 2. (a) X-ray diffraction patterns of Cu47.5Zr47.5-xAl5Scx alloys obtained from 2 mm
diameter rods. The alloys with 0e0.5 at.% Sc are fully amorphous, the alloy with 1 at.%
Sc shows B2 phase peaks on top of broad diffraction maxima and the alloy with 2 at.%
Sc only shows the B2 peaks. (b) Cu47.5Zr46.5Al5Sc1 cast in different diameters or rather
quenched with different cooling rates. The diameters are indicated and MS represents
a melt-spun ribbon. Only the ribbon appears to be completely amorphous. B2 re-
flections with varying intensity are observed for the rods with increasing diameter.
When the diameter exceeds 3 mm, the alloy is fully crystalline.
show about the same fraction of B2 phase (25e29 vol%), but the
precipitates are larger and more strongly agglomerated in Fig. 3c,
whereas Fig. 3b reveals smaller and more homogeneously distrib-
uted precipitates. The differing amount of the B2 phase between
top and bottom is likely to be governed by the higher cooling rate at
the bottom due to the residual heat coming from the excess melt
above the rod. The amount of B2 phase increases from right to left
in Fig. 3, eventually leading to percolation of the B2 particles
(Fig. 3a) [7]. By adjusting the casting parameters, such as the mass,
the arc current and the suction force (pressure difference), the
resulting composite structures can be influenced to a certain extent
shown in Fig. 4. Up to 0.5 at.% Sc the yield strength and the plas-
ticity, as well as the Young's modulus (Table 3) are virtually unaf-
fected by the Sc additions. Yet, the standard deviation of the yield
strength rises with rising Sc content, which implies that the mi-
crostructures become less reproducible. The volume fraction of the
B2 phase obtained from optical microscopy remains below 1 vol%
for all three compositions. In contrast, the values extracted from
DSC indicate a steady increase of the average B2 phase content but
also a strong rise of the standard deviation. Especially for Cu47.5Z-
r47Al5Sc0.5 (alloy no. 3) there are large discrepancies between the
values of the crystalline volume fraction obtained by the two
different methods (Table 3). The DSC measurements are expected
to provide more reliable results because of the larger sample vol-
ume analysed compared to the thin slices used for XRD. Conse-
quently, the strong heterogeneity of the distribution of the B2
phase within one rod is taken into account to a greater extent [25].
Once the amount of Sc exceeds 1 at.%, the curves in Fig. 4 change
drastically. It is known that the amount and distribution of the B2
phase in BMG matrix composites strongly influences their me-
chanical behaviour: depending on the crystalline volume fraction,
the yield strength changes from a rule-of-mixtures-type to a load-
bearing behaviour [7,40,41]. The percolation threshold for the
present alloys should be near 40 vol% crystals [7,40,41]. Also the
plastic strain is enhanced for volume fractions above 10 vol% of the
B2 phase [7,40,41].
The yield strength in Cu47.5Zr46.5Al5Sc1 is lower than for the al-
loys with a smaller Sc content (Table 3). At the same time, the
standard deviations of the yield strength and the plastic strain are
much larger than for the other alloys. As discussed above, the B2
phase content and distribution in these rods with a diameter of
2 mm also suffer from large scattering (Fig. 3). Therefore, the strong
scatter in the yield strength and the plastic strain most likely is the
result of the varying crystalline volume fraction. The larger number
of B2 particles in Cu47.5Zr46.5Al5Sc1 simultaneously increases the
plastic strain compared to the alloys containing less Sc.
Interestingly, the Young's modulus remains constant within the
experimental error for all the alloys up to 1 at.% Sc regardless of the
amount of crystalline particles (Table 3). When the Sc content
reaches 2 at.% (Cu47.5Zr45.5Al5Sc2), the rods are exclusively
composed of the B2 phase. The compression curve reveals early
yielding (~590 MPa) and strong work hardening up to about
2000 MPa. For this alloy, no measurement of the elastic constants
 B. Escher et al. / Journal of Alloys and Compounds 790 (2019) 657e665
Fig. 3. Optical micrographs of the top and centre parts of two Cu47.5Zr46.5Al5Sc1 rods. The amount and the distribution of the B2 phase changes depending on the position within the
rod and to some extend on the casting parameters. (a) and (b) as well as (c) and (d) are from the same rod, respectively. Micrographs (a) and (c) were recorded at the top; (b) and (d)
from the centre of the rod. They were cast applying different casting parameters.
Fig. 4. True stressetrue strain curves of Cu47.5Zr47.5-xAl5Scx (x ¼ 0, 0.2, 0.5, 1 and 2 at.%)
samples with different crystalline volume fractions (measured by optical microscopy).
The plasticity and the B2 phase content increase and the yield strength decreases for a
Sc content of 1 at.% compared to 0 at.% to 0.5 at.%. For 2 at.% Sc this trend persists.
by ultrasound could be done because the signal was too weak.
Nevertheless, the Young's modulus in compression is clearly lower
than for the other alloys, which is in good agreement with literature
[7].
Most as-cast Cu47.5Zr46.5Al5Sc1 rods with a diameter of 2 mm
exhibit B2 phase volume fractions around and above 10 vol% (Fig. 3,
661
Table 3). To better understand the deformation behaviour of this
particular alloy, additional samples were compressed until fracture
and the mechanical properties were correlated with the respective
crystalline volume fractions (Fig. 5). As discussed in the preceding
section, the adjustment of the casting parameters has an influence
on the resulting microstructures. The samples with the lower
amount of B2 phase (D, E, F) were cast with a lower pressure dif-
ference, and thus less suction force than the ones with more B2
crystals.
The amount of B2 crystals ranges from 2 ± 0 vol% up to 42 ± 1 vol
% and the shapes of the compression curves clearly differ (Fig. 5)
[42]: Sample B (17 ± 8 vol% B2, Fig. 3b) shows much stronger work
hardening than sample C (20 ± 9 vol% B2, Fig. 3c). According to the
literature, there is a strain field around the precipitates that over-
lays the external field during compression and thus influences the
creation and movement of shear bands [43]. A more uniform or
finer distribution of the B2 phase, therefore, leads to a reduced
mean free path for the shear bands in the glassy matrix and,
consequently, enhances the interaction between the shear bands
and the crystalline particles [42e44]. This also strongly influences
the appearance of the serrations during plastic deformation
[8,43,45] (as can be seen in Fig. 5). The more homogeneous distri-
bution of the precipitates in sample B leads to smaller distances
between the crystallites and the load drop accompanying the stick-
slip propagation of shear bands apparently becomes smaller. In
other words, the characteristics of serrations in the stress-strain
662 B. Escher et al. / Journal of Alloys and Compounds 790 (2019) 657e665

Table 3
Mechanical properties for rods (diameter: 2 mm) of all compositions as obtained by compression tests (yield strength Rp0,2 (true), plastic strain εp, Young's modulus Ecomp) and
ultrasonic measurements (Young's modulus EUS, Poisson ratio nUS). The volume fraction of the B2 phase was determined by optical microscopy (OM) on all compression test
samples and calorimetry of four samples from the centre of the rods (DSC). The critical casting diameters, Øcrit, are also listed. At least 4 samples were tested in compression. For
the composition Cu47.5Zr46.5Al5Sc1 with a large scatter in the results even 8 samples.

Alloy Rp0,2 (true) (MPa) εp (%) Ecomp (GPa) EUS (GPa) nUS B2 content (vol%) OM B2 content (vol%) DSC Øcrit (mm)
±2 ±0.01

Cu47.5Zr47.5Al5 1721 ± 19 2.1 ± 2.5 88 ± 4 87 0.374 0.3 ± 0.5 0.5 ± 0.5 z2

Cu47.5Zr47.3Al5Sc0.2 1730 ± 29 2.8 ± 1.9 89 ± 4 87 0.374 0.6 ± 0.8 3.5 ± 3.0 z2
Cu47.5Zr47Al5Sc0.5 1711 ± 87 3.7 ± 1.8 87 ± 6 87 0.374 0.2 ± 0.4 4.7 ± 7.1 z2
Cu47.5Zr46.5Al5Sc1 1537 ± 397 9.3 ± 6.4 86 ± 5 85 0.377 12.9 ± 13.5 14.0 ± 14.2 1
Cu47.5Zr45.5Al5Sc2 589 ± 4 10.2 ± 2.0 82 ± 0.5 e e 100 ± 0.0 98.2 ± 3.4 <1

Apart from the serrations, the significant work hardening of the

Fig. 5. True stressetrue strain curves for Cu47.5Zr46.5Al5Sc1 samples with different
content of B2 phase (OM), displayed in the legend. An increasing B2 content leads to
increased work hardening, decreased yield strength and large plasticity. The micro-
graphs of Fig. 3b and c correspond to samples B and C, respectively.
curve change (Fig. 5) as a result the shorter mean free path for shear
band propagation. On the contrary, sample C shows a more pro-
nounced serrated flow due to the larger distances between the
crystallites (Fig. 5 and better visible in Fig. 6). The other samples
also show serrated flow but to a lesser extent than sample C, which
agrees well with their more uniform distribution of crystalline
precipitates and the resulting shorter distances between the par-
ticles. The present experiments do not allow for more detailed
conclusions than these qualitative statements.
Fig. 6. Engineering stresseengineering strain curves for the Cu47.5Zr46.5Al5Sc1 samples
measured using the Kammrath & Weiss rig and the samples measured using the
Instron device (see Fig. 5). The three characteristic yield stresses of the in-situ test are
marked in the curve. The strain differs strongly but the stress corresponds well to the
ex-situ measurement.
investigated samples becomes apparent, which also depends on
the crystalline volume fraction (Fig. 5). A martensitic trans-
formation is the origin of this work hardening in CuZr-based BMG
matrix composites during loading [44,46,47]. In order to follow this
phase transformation in situ, the alloy, which yields the BMG ma-
trix composites with the most promising mechanical properties
(Table 3), Cu47.5Zr46.5Al5Sc1, was investigated by high-energy X-rays
during compression. In doing so, the focus is on the question
whether the martensite develops a texture during loading. In Fig. 6,
the stress-strain curve of a sample with a crystalline volume frac-
tion of 19 ± 1 vol% tested in the Kammrath & Weiss loading rig is
compared with the stress-strain curves of two samples with similar
crystalline volume fractions (17 ± 8 and 20 ± 9 vol%), which were
tested in the Instron. The Kammrath & Weiss rig has a compara-
tively low stiffness and this leads to the clear deviation of the strain
in the nominally elastic regime. The stiffness of the load frame has
been reported to lower the plastic strain of BMGs [48]. However,
the fracture strain measured with the Kammrath & Weiss device is
only marginally smaller than the values obtained in the conven-
tional compression tests with the Instron (Fig. 6). Also the fracture
stresses are rather similar. All samples exhibit distinct changes in
the slope (arrows in Fig. 6), which indicate three different yield
stresses e a typical feature found in CuZr-based BMG matrix
composites [49].
Fig. 7 shows a sequence of diffraction patterns obtained at
increasing stresses parallel (Fig. 7a) and perpendicular (Fig. 7b) to
the loading axis. The diffraction patterns (marked in red) show the
characteristic stages of compression highlighted by arrows in Fig. 6.
In the beginning of deformation (s ¼ 0 MPa), the B2 reflections are
strongly anisotropic because of the non-uniform distribution of
crystals obeying the Bragg condition. The number of crystals
contributing to the diffraction pattern is low and varies over the
loading process since the crystals reorient during loading. There-
fore, the intensity of the B2 Bragg peaks does not show any sys-
tematic trend during compression in the elastic regime. Once the
compressive stress reaches about 600 MPa one additional peak
appears (Fig. 7a), which can be assigned to the martensitic phase
({111} B190 or {020} B33 [50]). The stress at which the martensitic
transformation sets in, corresponds well to the yield strength of the
pure B2 phase in Cu47.5Zr45.5Al5Sc2, thus the glassy matrix does not
seem to constrain the martensitic transformation severely even
though there is a volume expansion involved [43,51]. This yielding
is called the first yielding, following the nomenclature of [49].
Interestingly, there is only a small shoulder at the q-value, at which
the strongest martensite reflection occurs, but no distinct
martensite peak is visible perpendicular to the compression di-
rection. The intensities of the martensite peaks increase continu-
ously up to the stresses where macroscopic yielding of the
composite (second yielding [49]) is observed (Fig. 6). This holds
especially for the diffraction patterns recorded parallel to the
 B. Escher et al. / Journal of Alloys and Compounds 790 (2019) 657e665 663

Fig. 7. High-energy X-ray diffraction data obtained by partial integration of the 2-dimensional diffraction patterns (a) parallel to the compression direction and (b) perpendicular to
it. The three yield stresses indicated in Fig. 6 are marked in red. With increasing stress the phase transformation from B2 to martensite takes place. It starts earlier and is more
pronounced in the compression direction. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

loading axis. The second yielding corresponds to the yielding of the
metallic glass matrix and is lower than for monolithic BMGs due to
stress concentration around the deforming crystalline precipitates
[8,43]. Continuing deformation leads to a progressing martensitic
transformation and the formation and interaction of shear bands in
the glassy matrix [49]. The evidence of the ongoing martensitic
transformation after the second yielding is obvious in Fig. 7a and b.
Even though there are abrupt changes, the intensity of the B2 phase
peaks clearly tends to decrease after the second yielding compared
to the martensitic peaks. Around and after the third yielding (Fig. 6)
[7,49] the intensity of the crystalline phases exhibits no substantial
changes. The stress at which the third yielding is detected is in good
agreement with the stress (about 1950 MPa) of the second yielding
of fully crystalline (B2 phase) Cu47.5Zr45.5Al5Sc2. The deformation
mechanism at this stage has been reported to be altered from being
dominated by shear banding and the martensitic transformation to
detwinning of the martensite and formation of a high density of
dislocations [49]. Even though there seems to be a considerable
amount of B2 phase left, both in compression direction and
perpendicular to it, those crystals might not reach the local strain
necessary for the martensitic transformation due to their orienta-
tion with respect to the compression direction. In contrast, other
grains transform and already reach the strain necessary for det-
winning of the martensite [52]. These local differences in the
transformation lead to the observed pronounced texture of the
martensite in Fig. 7a and b. Prior to fracture, the B2 phase appears
to be completely transformed to martensite in the compression
direction. As opposed to this, a certain amount of the B2 phase
seems to remain perpendicular to the compression direction for the
above mentioned reasons.
4. Conclusions
A series of glass-forming Cu47.5Zr47.5-xAl5Scx (x ¼ 0, 0.2, 0.5, 1 and
664 B. Escher et al. / Journal of Alloys and Compounds 790 (2019) 657e665
2 at.%) alloys was prepared in this work and the effect of Sc on the
stability of the B2 CuZr phase, the glass-forming ability, the
microstructure and the deformation behaviour was investigated. Sc
is very efficient in stabilizing the B2 phase and, therefore, the glass-
forming ability deteriorates quickly when the Sc content exceeds
1 at.%. The critical casting diameter above 2 at.% Sc is below 1 mm.
Nonetheless, the thermal properties remain unaffected and pa-
rameters like gfTg þTTx
[37], and K ¼ TTliqf [6] are not capable to reflect
liq
these changes. The yield strength and the fracture strain both
strongly depend on the crystalline volume fraction and the distri-
bution of the crystals as does the serrated flow. The alloy Cu47.5Z-
r46.5Al5Sc1 exhibits the broadest possible range of microstructures.
This allows for tailoring the mechanical behaviour of this specific
BMG matrix composite to some extent. In-situ XRD reveals that the
B2 crystals in this composite gradually undergo a martensitic
transformation. The rigid glassy matrix transfers the load directly to
the crystals and facilitates the transformation in the direction
parallel to the compression axis. A pronounced texture of the
martensite is the outcome. Three different yield stresses can be
identified from the compression and the diffraction curves, corre-
sponding to the start of the martensitic transformation, the yielding
of the amorphous matrix and the end of the martensitic trans-
formation. Overall Sc is a suitable element to control the micro-
structure via B2 phase precipitation and thus the mechanical
properties of the glass-forming Cu47.5Zr47.5Al5 alloy.
Acknowledgements
Parts of this research were carried out at the light source Petra III
at DESY, a member of the Helmholtz Association (HGF). We thank U.
Rütt for her help using the beamline P07. We also thank S. Donath
for his advice concerning casting, B. Bartusch and A. Voss for
technical assistance as well as C. Rentenberger, C. Ebner, C.
Gammer, H.P. Karnthaler and K. Kosiba for stimulating discussions.
The authors gratefully acknowledge the funding by DFG (German
Science Foundation) under grant PA 2275/2-1 and also the Leibniz
Program (Grant EC 111/26-1) and the German Federal Ministry of
Education and Research BMBF (Bundesministerium für Bildung und
Forschung, Germany) (Project No. 05K12OD1). S.P. acknowledges
additional support by German Science Foundation under grant no
PA 2275/6-1. J. Eckert thanks for the additional support, which was
provided through the European Research Council under the ERC
(European Union) Advanced Grant INTELHYB (grant ERC-2013-
ADG-340025).
References
[1] A. Inoue, Bulk glassy and nonequilibrium crystalline alloys by stabilization of
supercooled liquid: fabrication, functional properties and applications (Part 2),
Proc. Jpn. Acad. Ser. B-Phys. Biol. Sci. 81 (2005) 172e188.
[2] M.M. Trexler, N.N. Thadhani, Mechanical properties of bulk metallic glasses,
Prog. Mater. Sci. 55 (2010) 759e839, https://doi.org/10.1016/
j.pmatsci.2010.04.002.
[3] A.L. Greer, Metallic glasses ... on the threshold, Mater. Today 12 (2009) 14e22.
https://doi.org/10.1016/S1369-7021(09)70037-9.
[4] A.L. Greer, Y.Q. Cheng, E. Ma, Shear bands in metallic glasses, Mater. Sci. Eng.
Rep. 74 (2013) 71e132, https://doi.org/10.1016/j.mser.2013.04.001.
[5] J. Eckert, J. Das, S. Pauly, C. Duhamel, Mechanical properties of bulk metallic
glasses and composites, J. Mater. Res. 22 (2007) 285e301, https://doi.org/
10.1557/Jmr.2007.0050.
[6] K.K. Song, S. Pauly, Y. Zhang, P. Gargarella, R. Li, N.S. Barekar, U. Kühn,
M. Stoica, J. Eckert, Strategy for pinpointing the formation of B2 CuZr in
metastable CuZr-based shape memory alloys, Acta Mater. 59 (2011)
6620e6630, https://doi.org/10.1016/j.actamat.2011.07.017.
[7] S. Pauly, G. Liu, G. Wang, J. Das, K.B. Kim, U. Kühn, D.H. Kim, J. Eckert, Modeling
deformation behavior of Cu-Zr-Al bulk metallic glass matrix composites, Appl.
Phys. Lett. 95 (2009) 101906, https://doi.org/10.1063/1.3222973.
[8] F.F. Wu, K.C. Chan, S.T. Li, G. Wang, Stabilized shear banding of ZrCu-based
metallic glass composites under tensile loading, J. Mater. Sci. 49 (2014)
2164e2170, https://doi.org/10.1007/s10853-013-7909-1.
[9] Y. Wu, Y. Xiao, G. Chen, C.T. Liu, Z. Lu, Bulk metallic glass composites with
transformation-mediated work-hardening and ductility, Adv. Mater. 22
(2010) 2770e2773, https://doi.org/10.1002/adma.201000482.
[10] P. Gargarella, S. Pauly, K.K. Song, J. Hu, N.S. Barekar, M. Samadi Khoshkhoo,
A. Teresiak, H. Wendrock, U. Kühn, C. Ruffing, E. Kerscher, J. Eckert, TieCueNi
shape memory bulk metallic glass composites, Acta Mater. 61 (2013)
151e162, https://doi.org/10.1016/j.actamat.2012.09.042.
[11] J. Orava, A.L. Greer, Fast and slow crystal growth kinetics in glass-forming
melts, J. Chem. Phys. 140 (2014) 214504, https://doi.org/10.1063/1.4880959.
[12] Q. Wang, L.-M. Wang, M.Z. Ma, S. Binder, T. Volkmann, D.M. Herlach,
J.S. Wang, Q.G. Xue, Y.J. Tian, R.P. Liu, Diffusion-controlled crystal growth in
deeply undercooled melt on approaching the glass transition, Phys. Rev. B 83
(2011) 14202, https://doi.org/10.1103/PhysRevB.83.014202.
[13] Z. Liu, R. Li, G. Liu, K. Song, S. Pauly, T. Zhang, J. Eckert, Pronounced ductility in
CuZrAl ternary bulk metallic glass composites with optimized microstructure
through melt adjustment, AIP Adv. 2 (2012) 32176e32178. https://doi.org/10.
1063/1.4754853.
[14] K. Kosiba, S. Pauly, Inductive flash-annealing of bulk metallic glasses, Sci. Rep.
7 (2017) 2151, https://doi.org/10.1038/s41598-017-02376-x.
[15] K. Kosiba, S. Scudino, R. Kobold, U. Kühn, A.L. Greer, J. Eckert, S. Pauly, Tran-
sient nucleation and microstructural design in flash-annealed bulk metallic
glasses, Acta Mater. 127 (2017) 416e425, https://doi.org/10.1016/
j.actamat.2017.01.059.
[16] T.A. Baser, J. Das, J. Eckert, M. Baricco, Glass formation and mechanical
properties of (Cu50Zr50)(100-x)Alx (x¼0, 4, 5, 7) bulk metallic glasses,
J. Alloys Compd. 483 (2009) 146e149, https://doi.org/10.1016/
j.jallcom.2008.07.147.
[17] J. Das, M.B. Tang, K.B. Kim, R. Theissmann, F. Baier, W.H. Wang, J. Eckert,
“Work–Hardenable” ductile bulk metallic glass, Phys. Rev. Lett. 94 (2005)
205501, https://doi.org/10.1103/PhysRevLett.94.205501.
[18] W.H. Wang, J.J. Lewandowski, A.L. Greer, Understanding the glass-forming
ability of Cu50Zr50 alloys in terms of a metastable eutectic, J. Mater. Res. 20
(2005) 2307e2313, https://doi.org/10.1557/Jmr.2005.0302.
[19] Z.D. Sha, Q.X. Pei, Ab initio study on the electronic origin of glass-forming
ability in the binary Cu–Zr and the ternary Cu–Zr–Al(Ag) metallic glasses,
J. Alloys Compd. 619 (2015) 16e19. https://doi.org/10.1016/j.jallcom.2014.09.
010.
[20] D. Arias, J.P. Abriata, Cu-Zr (Copper-Zirconium), Bull. Alloy Phase Diagr. 11
(1990) 452e459, https://doi.org/10.1007/BF02898260.
[21] K. Kosiba, P. Gargarella, S. Pauly, U. Kuhn, J. Eckert, Predicted glass-forming
ability of Cu-Zr-Co alloys and their crystallization behavior, J. Appl. Phys.
113 (2013) 123504e123505. Artn 12350510.1063/1.4798294.
[22] F.A. Javid, N. Mattern, S. Pauly, J. Eckert, Effect of cobalt on phase formation,
microstructure, and mechanical properties of Cu50–xCoxZr50 (x ¼ 2, 5, 10, 20
at. Pct) alloys, Metall. Mater. Trans. A 43 (2011) 2631e2636, https://doi.org/
10.1007/s11661-011-0945-z.
[23] E.M. Carvalho, I.R. Harris, Constitutional and structural studies of the inter-
metallic phase, ZrCu, J. Mater. Sci. 15 (1980) 1224e1230, https://doi.org/
10.1007/bf00551811.
[24] S. Pauly, K. Kosiba, P. Gargarella, B. Escher, K.K. Song, G. Wang, U. Kühn,
J. Eckert, Microstructural evolution and mechanical behaviour of metastable
CueZreCo alloys, J. Mater. Sci. Technol. 30 (2014) 584e589, https://doi.org/
10.1016/j.jmst.2014.05.006.
[25] B. Escher, U. Kühn, J. Eckert, C. Rentenberger, S. Pauly, Influence of Ag and Co
additions on glass-forming ability, thermal and mechanical properties of
CueZreAl bulk metallic glasses, Mater. Sci. Eng. A 673 (2016) 90e98. https://
doi.org/10.1016/j.msea.2016.06.081.
[26] D.Y. Wu, K.K. Song, P. Gargarella, C.D. Cao, R. Li, I. Kaban, J. Eckert, Glass-
forming ability, thermal stability of B2 CuZr phase, and crystallization kinetics
for rapidly solidified CueZreZn alloys, J. Alloys Compd. 664 (2016) 99e108.
https://doi.org/10.1016/j.jallcom.2015.12.187.
[27] K.H.J. Buschow, Crystallization of amorphous Zr1xCox alloys, J. Less Com-
mon Met. 85 (1982) 221e231. https://doi.org/10.1016/0022-5088(82)90073-
X.
[28] A.E. Dwight, Cscl-type equiatomic phases in binary alloys of transition ele-
ments, Trans. Am. Inst. Min. Metall. Eng. 215 (1959) 283e286.
[29] S.S. Rao, T.R. Anantharaman, Constitution of brasses below 500 C, Z. Met. 60
(1969) 312.
[30] T. Proffen, S.J.L. Billinge, T. Egami, D. Louca, Structural analysis of complex
materials using the atomic pair distribution function d a practical guide,
Z. Krist. J. Struct. Phys. Chem. Asp. Cryst. Mater. 218 (2003) 132, https://
doi.org/10.1524/zkri.218.2.132.20664.
[31] D. Wu, K. Song, C. Cao, R. Li, G. Wang, Y. Wu, F. Wan, F. Ding, Y. Shi, X. Bai,
I. Kaban, J. Eckert, Deformation-induced martensitic transformation in Cu-Zr-
Zn bulk metallic glass composites, Metals (Basel) 5 (2015) 2134. http://www.
mdpi.com/2075-4701/5/4/2134.
[32] T. Egami, Atomic level stresses, Prog. Mater. Sci. 56 (2011) 637e653. https://
doi.org/10.1016/j.pmatsci.2011.01.004.
[33] K.A. Gschneidner Jr., M. Ji, C.Z. Wang, K.M. Ho, A.M. Russell, Y. Mudryk,
A.T. Becker, J.L. Larson, Influence of the electronic structure on the ductile
behavior of B2 CsCl-type AB intermetallics, Acta Mater. 57 (2009) 5876e5881,
https://doi.org/10.1016/j.actamat.2009.08.012.
[34] A.T. Aldred, Intermediate phases involving scandium, Trans. Metall. Soc. Aime
224 (1962) 1082.
[35] B.J. Beaudry, A. Daane, The scandium-yttrium and scandium-zirconium
 B. Escher et al. / Journal of Alloys and Compounds 790 (2019) 657e665
system, Trans. Met. Soc. AIME 227 (1963) 865.
[36] S.H. Wang, P.H. Kuo, H.T. Tsang, R.R. Jeng, Y.L. Lin, The influence of Sc addition
on the welding microstructure of Zr-based bulk metallic glass: the stability of
the amorphous phase, Appl. Phys. Lett. 91 (2007) 171902e171903. https://
doi.org/10.1063/1.2795330.
[37] Z.P. Lu, C.T. Liu, A new glass-forming ability criterion for bulk metallic glasses,
Acta Mater. 50 (2002) 3501e3512, https://doi.org/10.1016/s1359-6454(02)
00166-0.
[38] C.N. Kuo, J.C. Huang, J.B. Li, J.S.C. Jang, C.H. Lin, T.G. Nieh, Effects of B2 pre-
cipitate size on transformation-induced plasticity of Cu–Zr–Al glassy alloys,
J. Alloys Compd. 590 (2014) 453e458. https://doi.org/10.1016/j.jallcom.2013.
12.156.
[39] K. Laws, B. Gun, M. Ferry, Influence of casting parameters on the critical
casting size of bulk metallic glass, Metall. Mater. Trans. A 40 (2009)
2377e2387, https://doi.org/10.1007/s11661-009-9929-7.
[40] Z.Q. Liu, G. Liu, R.T. Qu, Z.F. Zhang, S.J. Wu, T. Zhang, Microstructural perco-
lation assisted breakthrough of trade-off between strength and ductility in
CuZr-based metallic glass composites, Sci. Rep. 4 (2014). https://doi.org/10.
1038/srep04167.
[41] S. Pauly, G. Liu, G. Wang, U. Kühn, N. Mattern, J. Eckert, Microstructural het-
erogeneities governing the deformation of Cu47.5Zr47.5Al5 bulk metallic
glass composites, Acta Mater. 57 (2009) 5445e5453, https://doi.org/10.1016/
j.actamat.2009.07.042.
[42] F.F. Wu, K.C. Chan, S.H. Chen, S.S. Jiang, G. Wang, ZrCu-based bulk metallic
glass composites with large strain-hardening capability, Mater. Sci. Eng. A 636
(2015) 502e506. https://doi.org/10.1016/j.msea.2015.04.027.
[43] B.A. Sun, K.K. Song, S. Pauly, P. Gargarella, J. Yi, G. Wang, C.T. Liu, J. Eckert,
Y. Yang, Transformation-mediated plasticity in CuZr based metallic glass
composites: a quantitative mechanistic understanding, Int. J. Plast. 85 (2016)
34e51. https://doi.org/10.1016/j.ijplas.2016.06.004.
[44] Y. Wu, H. Wang, H.H. Wu, Z.Y. Zhang, X.D. Hui, G.L. Chen, D. Ma, X.L. Wang,
Z.P. Lu, Formation of Cu–Zr–Al bulk metallic glass composites with improved
tensile properties, Acta Mater. 59 (2011) 2928e2936, https://doi.org/10.1016/
665
j.actamat.2011.01.029.
[45] Y. Qin, X. Han, K. Song, L. Wang, Y. Cheng, Z. Zhang, Q. Xue, N. Sun, J. Wang,
B. Sun, B. Sarac, F. Spieckermann, G. Wang, I. Kaban, J. Eckert, Stability of shear
banding process in bulk metallic glasses and composites, J. Mater. Res. 32
(2017) 2560e2569, https://doi.org/10.1557/jmr.2017.243.
[46] F.-F. Wu, K.C. Chan, S.-S. Jiang, S.-H. Chen, G. Wang, Bulk metallic glass
composite with good tensile ductility, high strength and large elastic strain
limit, Sci. Rep. 4 (2015) 5302, https://doi.org/10.1038/srep05302.
[47] S. Pauly, J. Das, J. Bednarcik, N. Mattern, K.B. Kim, D.H. Kim, J. Eckert, Defor-
mation-induced martensitic transformation in Cu–Zr–(Al,Ti) bulk metallic
glass composites, Scr. Mater. 60 (2009) 431e434, https://doi.org/10.1016/
j.scriptamat.2008.11.015.
[48] Z. Han, Y. Li, H.J. Gao, Effect of frame stiffness on the deformation behavior of
bulk metallic glass, J. Mater. Res. 25 (2010) 1958e1962, https://doi.org/
10.1557/JMR.2010.0256.
[49] K.K. Song, S. Pauly, Y. Zhang, R. Li, S. Gorantla, N. Narayanan, U. Kühn,
T. Gemming, J. Eckert, Triple yielding and deformation mechanisms in
metastable Cu47.5Zr47.5Al5 composites, Acta Mater. 60 (2012) 6000e6012,
https://doi.org/10.1016/j.actamat.2012.07.015.
[50] A.V. Zhalkotitarenko, M.L. Yevlashina, V.N. Antonov, B.Y. Yavorskii, Y.N. Koval,
G.S. Firstov, Electronic and crystal-structure of the Zrcu intermetallic com-
pound close to the point of structural transformation, Phys. Status Solidi B-
Basic Res. 184 (1994) 121e127.
[51] M. Hasan, W.W. Schmahl, K. Hackl, R. Heinen, J. Frenzel, S. Gollerthan,
G. Eggeler, M. Wagner, J. Khalil-Allafi, A. Baruj, Hard X-ray studies of stress-
induced phase transformations of superelastic NiTi shape memory alloys
under uniaxial load, Mater. Sci. Eng. A 481e482 (2008) 414e419. https://doi.
org/10.1016/j.msea.2007.02.156.
[52] C.M. Wayman, T.W. Duerig, in: T.W. Duerig, K.N. Melton, D. Sto € ckel, C.M.B.T.-
E.A, S.M.A. Wayman (Eds.), An Introduction to Martensite and Shape Memory,
Butterworth-Heinemann, 1990, pp. 3e20. https://doi.org/10.1016/B978-0-
7506-1009-4.50005-6.