Vacuum 174 (2020) 109223

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Vacuum
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Mechanical properties and crystallization kinetics of Er-containing

Cu–Zr–Al bulk metallic glasses with excellent glass forming ability
Mehdi Malekan a, *, Reza Rashidi a, Saeed G. Shabestari b
a
School of Metallurgy and Materials Engineering, College of Engineering, University of Tehran, P.O. Box 11155-4563, Tehran, Iran
b
School of Metallurgy and Materials Engineering, Iran University of Science and Technology (IUST), 16846-13114, Narmak, Tehran, Iran

A R T I C L E I N F O A B S T R A C T

Keywords: Investigations were carried out to explore the consequences of Er adding on the glass forming ability (GFA),
Bulk metallic glass mechanical properties, and crystallization kinetics of Cu50Zr43Al7 bulk metallic glass (BMG). It is found that the
Glass forming ability (Cu50Zr43Al7)100-xErx (x ¼ 0, 2, 4, 6 at %) BMGs reflects its best GFA at x ¼ 2 and correlate well with GFA in­
Crystallization kinetics
dicator (γ and K) and thermal stability parameter (ΔTx). The Er-containing BMGs showed high compressive
Rare-earth elements
strength and Young module in the range of 1816–1890 Mpa and 116–120 GPa, respectively, but no plastic
deformation observed in them. The crystallization kinetics lagged with 2 at % Er addition. The large atomic
radius of Er and large negative mixing enthalpy of Er with the other constituent elements causes the significant
atomic size mismatch and the formation of short-range order in the melt which restrict the long-range diffusion
and ordering of atoms that lead to improving GFA and lagging the crystallization kinetics of (Cu50Zr43Al7)98Er2.

1. Introduction transformation and thermal stability of BMGs. The John­

Bulk metallic glasses (BMGs) have been regarded as promising
advanced materials due to their distinguishing characteristics like the
superior strength, sizeable elastic strain, and outstanding corrosion and
wear resistance relative to conventional crystalline alloys [1–6].
Meanwhile, some drawbacks of BMGs such as the limited size of speci­
mens (glass forming ability (GFA)), low plastic strain at room temper­
ature and crystallization at high temperatures restricted the extensive
use of them; several attempts have been conducted to circumvent these
limitations [7–13].
An increase in element number is a practical method to improve GFA
[14]. In this regard, Rare-earth (RE) elements are the influential addi­
tion materials and have a significant influence on the industries [15,16].
The addition of RE elements has a constructive result on the GFA of
BMGs [16–21]. Yttrium addition significantly enhanced the GFA of
Zr-based BMG [21]. Deng et al. [19] investigated the effects of RE ele­
ments on the GFA, and mechanical properties of a Cu–Zr–Al BMG.
Adding RE elements, including Ce, Nd, Gd, Y, Dy, and Lu increased the
GFA of Cu47Zr45Al8 BMG [19].
To circumvent the crystallization of BMGs during the high-
temperature processing and to determine the safe processing tempera­
ture range [22], it is essential to survey the kinetics of crystallization
son–Mehl–Avrami (JMA) method [23,24] is generally applied to study
crystallization kinetics in isothermal condition [25–27]. A large number
of efforts have been conducted to study the crystallization trans­
formation and thermal properties of BMGs [28–32]. Yue et al. [33] re­
ported that minor addition of Y increased the crystallization activation
energy of Cu–Zr–Al BMG.
In the present research, the effects of Er adding on the glass forming
ability, mechanical properties, and crystallization kinetics of Cu50Z­
r43Al7 bulk metallic glass studied. Differential scanning calorimetry
(DSC) and differential thermal analysis (DTA) techniques are adopted to
study glass forming ability and thermal properties, and isothermal
crystallization kinetics of the Cu–Zr–Al–Er BMGs.
2. Materials and methods
Alloy ingots with a nominal composition of (Cu50Zr43Al7)100-xErx (, x
¼ 0, 2, 4 and 6 at. %) prepared through arc melting a mixture of high
purity elements (purity �99.9 wt %) on a water-cooled copper heart
under Ti-gettered high purity argon (99.9999%) atmosphere. All ingots
were inverted and remelted minimum four times to certify composition
homogeneity. Cylindrical rods were fabricated from the ingots by in­
jection casting (for diameter up to 5 mm) and tilt casting (for diameter

* Corresponding author.
E-mail address: mmalekan@ut.ac.ir (M. Malekan).

https://doi.org/10.1016/j.vacuum.2020.109223
Received 16 September 2019; Received in revised form 20 January 2020; Accepted 22 January 2020
Available online 24 January 2020
0042-207X/© 2020 Elsevier Ltd. All rights reserved.
M. Malekan et al.
larger than 5 mm) into a copper mold in a chamber with the high-
vacuum (4 � 10 5 torr) and under argon atmosphere. The purity (or
cleanliness) of the melt is very important in achieving the desired GFA.
With a contaminated melt, the GFA of the alloy will be reduced and at
very high levels of impurity concentration, it may not be possible to
achieve formation of a glassy phase at all. Hence, in order to eliminate
(or significantly reduce) the contamination (especially oxygen), the
casting chamber equipped with rotary vacuum pump (reduces the
pressure of the chamber up to 10 3 torr) and oil diffusion vacuum pump
(reduces the pressure of the chamber up to 4 � 10 5 torr). Chemical
composition of samples including the contaminant elements (O, C, and N
˂ 0.1 at.%) confirmed that there was an insignificant uptake of
contamination.
X-ray diffraction (XRD, Rigaku, Cu Kα radiation) was used to detect
the amorphous and crystalline structures, and the high-resolution
transmission electron microscopy (HRTEM, JEOL 2010, 200 kV) was
operated to confirm structures. Thermal analysis was performed using
Differential Scanning Calorimetry (DSC, TA DSCQ 100) and Differential
Thermal Analysis (DTA, TA SDTQ 600) under high purity argon atmo­
sphere during continuous heating at 20 K min 1. Crystallization kinetics
study was investigated with DSC examinations at isothermal conditions
in a temperature range between the glass transition temperature (Tg)
and the crystallization temperature (Tx), which called the supercooled
liquid region (SLR). The BMG samples were heated at a heating rate of
40 K min 1 up to the analysis temperature and afterwards held at this
temperature to occur the full crystallization transformation. In the end,
the samples have been cooled to the ambient temperature. To guarantee
repeatability, rods segmented to 10–15 mg samples, and ground up to
2000 grit SiC paper, and finally, the oxidation and contamination of
surfaces were eliminated by washing samples into ethanol bath by an
ultrasonic cleaning machine before the DSC examinations.
Mechanical properties determined with an Instron testing machine.
Uniaxial compression experiments were performed on BMG specimens
with the 4 mm in height and 2 mm in diameter (aspect ratio of 2:1) at
environment temperature and under strain rate of 5 � 10 4 s 1. Strain
gages fastened to the sample surface were employed to measure the
elastic modulus of BMG samples. Scanning electron microscopy (SEM,
HITACHI, S-4800) was used to examine the fracture and lateral surfaces.
3. Results and discussion
3.1. Glass forming ability
Fig. 1 (a) displays the XRD patterns of the as-cast (Cu50Zr43Al7)100-
Fig. 1. (a) XRD patterns of the (Cu50Zr43Al7)100-xErx (x ¼ 0, 2, 4 and 6 at. %) BMGs, (b) XRD pattern (inset shows optical microscopy image) of the 12 mm in
diameter Cu50Zr43Al7 alloy.
2
Vacuum 174 (2020) 109223
xErx (x ¼ 0, 2, 4 and 6 at. %) BMGs. The critical diameters (dc) of BMGs
are presented in Fig. 1 (a) and Table 1. XRD patterns reveal wide
diffraction maxima with no discernible diffraction feature of the crys­
talline peak, indicating the fully amorphous nature of samples.
The Cu50Zr43Al7 BMG has a considerable GFA with a 10 mm critical
diameter that should be attributed to its low melting point and the near
eutectic composition. Therefore, the solidified structure of Cu50Zr43Al7
alloy with 12 mm in diameter was studied. Fig. 1 (b) shows the center of
the cross-section of the 12 mm in diameter Cu50Zr43Al7 sample. As can
be seen, the microstructure is composed of a homogenous lamellar
structure that suggests the eutectic solidification has happened under
homogenous nucleation. XRD pattern confirmed the mentioned claim.
As shown in Fig. 1 (b), sharp crystalline peaks related to Cu10Zr7, CuZr,
and CuZr2 are the main phases in the Cu50Zr43Al7 alloy structure. It has
been made clear that these crystalline phases are stable eutectic phases
that have reported in several crystallized CuZr-based BMGs [34–37]. So
based on Inoue criteria [14], it is reasonable to expect a high GFA from
Cu50Zr43Al7 alloy.
Addition of Er to the base BMG causes to increase the dc from 10 mm
for the Cu50Zr43Al7 BMG to 15 mm for the (Cu50Zr43Al7)98Er2 BMG.
With the addition of 4 at% of Er, the dc reaches 12 mm while further
addition of Er up to 6 at% does not affect the dc of the BMG. So, the
(Cu50Zr43Al7)98Er2 has the highest dc in the Cu–Zr–Al–Er alloy system. In
other words, the addition of a proper amount of Er significantly restrict
crystalline phase formation and triggers the enhancement of GFA. This
improvement of GFA is considerable, regarding the reported literature
on RE-containing BMGs [38–40].
HRTEM observations were used to confirm the amorphous structure
of Cu50Zr43Al7 and (Cu50Zr43Al7)98Er2 BMGs with 10 mm and 15 mm in
diameters, respectively. As shown in the inset of Fig. 2, the selected area
electron diffraction (SAED) patterns with a diffused halo ring imply a
fully amorphous and homogeneous microstructure without any crys­
talline characteristics for both BMGs. The lack of any long-range order
pattern in HRTEM images (Fig. 2) confirms the disordered nature of the
BMGs. Also, comparison between Fig. 2 (a) and (b) shows that there is no
segregation effects through the Er addition.
Fig. 3 (a) and (b) depict the DSC and DTA curves of the (Cu50Z­
r43Al7)100-xErx (x ¼ 0, 2, 4 and 6 at. %) BMGs at a heating rate of 20 K
min 1. All alloys have an endothermic glass transition transformation
with the SLR followed by an exothermic transformation corresponded to
crystallization, and an endothermic melting event. Characteristic tem­
peratures of BMGs, including Tg, Tx, the melting temperature (Tm) and
the liquidus temperature (Tl) are recognized and reported in Table 1.
According to Fig. 3 (a) and Table 1, with the Er addition, Tg and Tx
M. Malekan et al. Vacuum 174 (2020) 109223

Table 1
Characteristic temperatures (Tg, Tx, Tm and Tl in Kelvin), thermal properties, GFA indicators and mechanical properties (σc,f in MPa, E in GPa) of the (Cu50Zr43Al7)100-
xErx (x ¼ 0, 2, 4 and 6 at. %) BMGs.

BMG Tg Tx ΔTx Tm Tl ΔTm Trg γ K dc σc,f E

Cu50Zr43Al7 717 784 67 1152 1205 53 0.595 0.408 0.159 10 2006 122
(Cu50Zr43Al7)98Er2 697 773 76 1122 1172 50 0.595 0.412 0.182 15 1890 120
(Cu50Zr43Al7)96Er4 687 751 64 1075 1154 79 0.595 0.408 0.159 12 1852 117
(Cu50Zr43Al7)94Er6 653 700 47 1078 1150 72 0.568 0.388 0.104 10 1816 116

Fig. 2. (a) and (b) HRTEM images of the Cu50Zr43Al7 and (Cu50Zr43Al7)98Er2 BMGs.

Fig. 3. (a) DSC curves, and (b) DTA curves of the (Cu50Zr43Al7)100-xErx (x ¼ 0, 2, 4 and 6 at. %) BMGs at a heating rate of 20 K min 1.

gradually decline from 717 K to 784 K–653 K and 700 K for the
Cu50Zr43Al7 and (Cu50Zr43Al7)94Er6 BMGs, respectively. Erbium adding
has a significant effect on the melting behavior of Cu–Zr–Al alloy system.
The Tm and Tl have been steadily decreased with increase in Er content
and decline from 1152 K to 1205 K–1078 K and 1150 K for Cu50Zr43Al7
and (Cu50Zr43Al7)94Er6 BMGs, respectively. The Cu50Zr43Al7 BMG has a
single step endothermic melting process with a melting/freezing range
(ΔTm ¼ Tl–Tm) equal to 53 K. As mentioned earlier, the Cu50Zr43Al7
BMG has a near ternary eutectic composition. In the case of the
(Cu50Zr43Al7)98Er2 BMG, ΔTm of near quaternary eutectic BMG de­
creases to 50 K, and the melting behavior is still a single step endo­
thermic process. With further adding of Er up to 4 and 6 at %, ΔTm
increase to 79 K and 72 K, respectively. In the case of (Cu50Zr43Al7)96Er4
and (Cu50Zr43Al7)94Er6 BMGs, the melting process turns to multi-step
endothermic process that attributed to the presence of primary phases
within the eutectic structure. This phenomenon leads to widening the
melting/freezing range for the (Cu50Zr43Al7)96Er4 and
(Cu50Zr43Al7)94Er6 BMGs. These results show that the
(Cu50Zr43Al7)98Er2 BMG with the lowest freezing range has the closest
composition to the quaternary eutectic composition among the
Cu–Zr–Al–Er BMG system. This phenomenon justifies the high GFA of
the (Cu50Zr43Al7)98Er2 BMG.
It has been found that Cu46Zr54 [41,42], Cu50Zr43Al7 and
(Cu50Zr43Al7)98Er2 BMGs possess the eutectic compositions in their alloy
systems. With the increase in constitute elements of an alloy system, the
temperature of the eutectic composition declined, and consequently, the
GFA of the BMGs is promoted. This chain concurs entirely with the
confusion principle [43]. Several studies with the thermodynamic and
kinetic principles have been performed to elucidate the relevance of
high GFA and deep eutectics [34,44–49]. Regarding the thermodynamic
approach, achieving a high GFA requires a lower tendency for crystal­
lization, which means a smaller driving force for crystallization trans­
formation. In a deep eutectic composition, the driving force for
crystallization is comparatively small in comparison to the non-eutectic

3
M. Malekan et al.
mixture; therefore, in the case of eutectic compositions, the glass for­
mation is more comfortable [50]. Regarding the kinetic approach, there
is a competitive state among various crystalline phases in the eutectic
composition [42]. The formation of crystalline phases demands simul­
taneous rearrangement and redistribution of different atoms in the
long-range, which restricts the kinetics of the crystallization process and
consequently enhances GFA.
Therefore, the high GFA of (Cu50Zr43Al7)98Er2 quaternary alloy is
due to the effect of Er addition, which drops the Tl of the alloy system,
and draws the chemical composition to a near-eutectic mixture.
To further investigate GFA, a number of GFA indicators such as Trg ¼
Tg/Tl [51], γ ¼ Tx/(Tg þ Tl) [52], K¼ (Tx- Tg)/(Tl- Tx) [53] were
calculated. GFA indicators values versus Er content are plotted in Fig. 4
(a) and listed in Table 1. According to Fig. 4 (a) and Table 1, Trg has no
specific correlation with dc. Therefore, Trg does not show sensitivity to
GFA in the Cu–Zr–Al–Er alloys. There is a good correlation between ΔTx,
γ, and K with dc and GFA. Based on the results, the (Cu50Zr43Al7)98Er2
BMG has the highest thermal stability and GFA indicator values that
correspond to its high GFA.
Erbium addition and enhancement of GFA in Cu–Zr–Al–Er BMGs can
be interpreted through the Inoue criteria [14]. Fig. 4 (b) shows mixing
enthalpy between components, atomic radius, and atomic size ratio of
elements in Cu–Zr–Al–Er BMGs. Er has the largest atomic radius in the
system that leads to significant atomic size mismatch, and the interplay
between large atoms of Er and other smaller atoms. Formation of crys­
tals requires rearrangement and redistribution; in other words, the
diffusion of Er atoms in the undercooled molten alloy. According to the
Hume-Rothery criterion [54], due to the sizeable atomic size of Er, its
solubility in the forming crystalline phases is restricted. Then, the low
diffusion rate of Er atoms delays the formation of the crystalline phase.
Also, the significant negative mixing enthalpy among the ingredients of
BMG system affects the GFA. Based on Fig. 4 (b), the significant negative
mixing enthalpy between Er with Cu and Al causes atomic interactions
and formation of short-range order of atoms in the undercooled liquid,
which locally increases the atomic packing efficiency, and restrict the
diffusion and ordering of atoms in the long-range. As a result, significant
atomic size mismatch and large negative mixing enthalpy hinder the
formation of crystalline phases in Er-containing supercooled liquid.
It has been proven that the formation of glassy alloys is sensitive to
the presence of oxygen [16,55–58]. The Cu and Zr oxides are amenable
sites for the heterogeneous nucleation of crystalline phases, which de­
grades the GFA of BMGs. The enthalpy of the formation of Erbium oxide
(Er2O3, 1899.1 kJ/mol [59]) is significantly higher than that of the
oxides of other constituent elements (Cu2O, 167.5 kJ/mol; CuO, 155.3
kJ/mol; ZrO2, 1101.5 kJ/mol; Al2O3, 1678.5 kJ/mol [59]). Hence, the
Fig. 4. (a) Variation of GFA indicators with Er content for the (Cu50Zr43Al7)100-xErx (x ¼ 0, 2, 4 and 6 at. %) BMGs, (b) mixing enthalpy between constituent el­
ements, atomic radius size and atomic size ratio in the Cu–Zr–Al–Er system.
4
Vacuum 174 (2020) 109223
formation of Er oxide is thermodynamically preferred in comparison
with the oxides of Zr, Cu, and Al. Accordingly, adding a small amount of
Er can cause the absorption of oxygen in the molten alloy. Consequently,
eliminating the harmful element of oxygen through the formation of
harmless oxides of erbium can be another reason for improving GFA in
the Cu–Zr–Al–Er system.
Thermal stability is of great importance since it determines the
processable temperature limit for BMGs. ΔTx value (ΔTx ¼ Tx-Tg) as the
thermal stability parameter is equal to 67 K for the Cu50Zr43Al7 BMG and
increases to 76 K for the (Cu50Zr43Al7)98Er2 BMG. Approximately, the
same values of ΔTx have been reported for other RE-containing BMGs
[19]. Further addition of Er up to 4 and 6 at % changed the crystalli­
zation mode from a single stage to two stages (Fig. 3 (a)), thus short­
ening the SLR and the ΔTx declines to 47 K in the case of
(Cu50Zr43Al7)94Er6 BMG. As can be seen, the (Cu50Zr43Al7)98Er2 BMG
has the best thermal stability in this Cu–Zr–Al–Er alloy system. To
further investigate the processability of Cu50Zr43Al7 and the
(Cu50Zr43Al7)98Er2 BMGs, their crystallization kinetics in the SLR were
studied.
3.2. Mechanical properties
Fig. 5 displays the compressive stress-strain curves of (Cu50Z­
r43Al7)100-xErx (x ¼ 0, 2, 4 and 6 at. %) BMGs. The compressive fracture
strength (σc,f) and Young module (E) of these BMGs are presented in
Table 1. Er-containing BMGs show a high compressive fracture strength
and Young module in the range of 1816–1890 MPa and 116–120 GPa,
respectively, without any plastic deformation. In other words, with 2 at
% Er addition to the base alloy, σc,f value decreased from 2006 MPa to
1890 MPa, and with the further addition of Er up to 4 at% and 6 at%, this
value decreased to 1852 MPa and 1816 MPa, respectively. Also, E values
have no considerable change with Er addition. As a result, the
Cu–Zr–Al–Er BMG alloys present desirable GFA and high mechanical
properties, which enhance their structural applicability.
Fig. 6 (a) and (b) shows SEM images of lateral and fracture surfaces
and fracture morphology of (Cu50Zr43Al7)98Er2 BMG as a representative
of other Cu–Zr–Al–Er BMGs, which investigated in the present study. As
shown in Fig. 6 (a), the deformation and fracture in this BMG were in
shear mode with an approximate fracture angle of 45 ̊. Seemingly, the
Er-doped BMG fractures catastrophically along one dominate shear
plane, while there are no other visible shear bands on the lateral surface.
These pieces of evidence justify the lack of plasticity of Er-containing
BMGs. Also, the fracture surface of these alloys includes a fully devel­
oped vein-like pattern that is known as a characteristic in monolithic
BMGs [14].
M. Malekan et al. Vacuum 174 (2020) 109223

(Cu50Zr43Al7)98Er2 BMG indicates shorter time lag and broader crys­

tallization peak compared to the Cu50Zr43Al7 BMG, suggesting a decel­
eration in the kinetics of crystallization. For example, at the equal
treating temperature of 735 K, the crystallization process for the base
BMG lasts 16 min, while for the (Cu50Zr43Al7)98Er2 BMG, this time in­
creases to 16.8 min. Namely, with the addition of Er, the crystallization
transformation becomes sluggish.
Further crystallization kinetics analysis can be performed by
applying the Johnson–Mehl–Avrami (JMA) method [23,24]:

αðtÞ ¼ 1 exp½ Kðt τ Þn � (2)

The α(t) is the degree of crystallization at time t, τ is the time lag.
Avrami exponent, n, elucidates the mechanism of nucleation and growth
of crystals. K is a reaction rate constant. As can be seen in Fig. 8 (a) and
(b), and Table 2, the plot of ln½ lnð1 αðtÞÞ� versus lnðt τÞ for Cu50Z­
r43Al7 BMG shows nonlinear Avrami plots with average slopes (Avrami
exponents, n) of 5.7, while in the case of (Cu50Zr43Al7)98Er2 BMG,
Avrami plots are linear with average n of 3.3. The Avrami exponent
values suggest the three-dimensional growth with an increasing nucle­
Fig. 5. Compressive stress-strain curves of (Cu50Zr43Al7)100-xErx (x ¼ 0, 2, 4
ation rate for Cu50Zr43Al7 BMG and constant (or) decreasing nucleation
and 6 at. %) BMGs.
rate for (Cu50Zr43Al7)98Er2 BMG [65].
An Avrami exponent, n, bigger than 4 is only possible for non-
3.3. Isothermal crystallization kinetics
constant crystallization processes. When crystallization initiates, a
non-linear increase in nucleation rate towards the steady-state nucle­
The isothermal crystallization behavior of the Cu50Zr43Al7 and
ation rate is frequently observed. If the crystal growth velocity remains
(Cu50Zr43Al7)98Er2 BMGs was examined through DSC experiments at
constant, Avrami exponent, n, becomes n ¼ 4 þ m. For the Cu50Zr43Al7
various treating temperatures that selected in the SLR of BMGs. Tem­
BMG with n ¼ 5.7, the exponent m must then sequel to 1.7. Thus, if the
peratures of {735 K, 740 K, 745 K, 750 K} and {730 K, 735 K, 740 K, 745
time for complete crystallization is small enough, i.e. smaller than the
K} were selected for isothermal annealing of the Cu50Zr43Al7 and
time to reach steady-state nucleation, only an Avrami exponent of larger
(Cu50Zr43Al7)98Er2 BMGs, respectively. Fig. 7 (a) and (b) show DSC
than 4 is observed. On the other hand, if the time to reach the steady-
curves of the Cu50Zr43Al7 and (Cu50Zr43Al7)98Er2 BMGs at the
state was smaller than the time for full crystallization, the Avrami
isothermal conditions. All DSC curves exhibit a time lag or incubation
exponent, n, should reduce to a value of 4 as soon as the steady-state is
time followed by a distinct exothermic peak, while time lag declines
reached and remain constant afterwards. Meanwhile, as the crystalli­
with a rise in the treatment temperature.
zation of samples has different products, including CuZr, Cu10Zr7, and
In the isothermal conditions, the degree of crystallization, α, as a
CuZr2, so the anomalous n values may be related to simultaneously
function of time can be computed as [60]:
crystallization processes that occurred at the same time.
� �
R t dHc The nonlinearity of Avrami plots of Cu50Zr43Al7 reveals that Avrami
dt
t0 dt exponent, n, is not constant as the crystallization process proceed. The
α¼R � � (1)
t∞ dHc local Avrami exponent n(α) can be calculated to study crystallization in
dt
t0 dt detail [66]:

The dHc =dt defined as the heat flow, t0, and t∞ are the starting and ∂ln½ lnð1 αÞ�
nðαÞ ¼ (3)
finishing times of crystallization, respectively. Fig. 7 (c) and (d) reveal ∂lnðt τÞ
that the development of the crystallization transformation for all treat­
Fig. 8 (c) and (d) depict the n(α) as a function of the degree of
ing temperatures exhibit a sigmoidal shape. A similar trend has been
crystallization, α, at the various treating temperature. The Cu50Zr43Al7
observed in BMGs [28,61–64].
BMG demonstrates anomalous local Avrami exponents larger than 3,
As can be seen in Fig. 7, at the same treating temperature, the
which justify the three-dimensional growth and increasing nucleation

Fig. 6. SEM images of (a) lateral surface and (b) fracture surface of (Cu50Zr43Al7)98Er2 BMG.

5
M. Malekan et al.
Fig. 7. Isothermal DSC curves and degree of crystallization as a function of time for (a), (c) the Cu50Zr43Al7 BMG and (b), (d) the (Cu50Zr43Al7)98Er2 BMG performed
at the various annealing temperature.
rate of the crystallization transformation. At different treating temper­
atures, Cu50Zr43Al7 BMG shows different local Avrami exponent varia­
tion trends. The (Cu50Zr43Al7)98Er2 BMG at different annealing
temperatures shows a same local Avrami exponent variation trends,
which in the early degrees of crystallization (0 ˂ α ˂ 0.2) the n(α) values
are smaller than 2.5, followed by a constant local Avrami values around
2.6 in the middle stage of crystallization (0.2 ˂ α ˂ 0.8), and eventually
anomalous local Avrami values larger than 4 in the final degrees of
crystallization (0.8 ˂ α ˂ 1). Thus, (Cu50Zr43Al7)98Er2 BMG has a three-
dimensional growth with a decreasing, constant, and increasing nucle­
ation rate in the early stage, middle stage, and final stage of crystalli­
zation, respectively.
However, the determination of the crystallization mechanism using
the Avrami exponent necessitates some circumspect. Due to the het­
erogeneous distribution of nuclei, the local Avrami exponents at low
degrees of crystallization are meaningful to specify the mechanism of
crystallization [67]. Hence, based on n(α) values at low α values,
Cu50Zr43Al7 and (Cu50Zr43Al7)98Er2 BMGs have an increasing and
decreasing nucleation rate, respectively. The whole Avrami exponent
discussions satisfy the slower crystallization process of
(Cu50Zr43Al7)98Er2 BMG than that of Cu50Zr43Al7 BMG.
4. Conclusion
The effect of Er adding on the GFA, compressive mechanical prop­
erties, and crystallization kinetics of the Cu–Zr–Al BMG investigated:
6
Vacuum 174 (2020) 109223
The addition of 2 at. % of the Er to the Cu–Zr–Al glassy alloy can
effectively hinder the formation of order phases, and improve stability of
supercooled liquid, and GFA. The (Cu50Zr43Al7)98Er2 BMG shows the
highest values of GFA indicators and thermal stability (γ, K and ΔTx)
which have a reasonable correlation with its critical diameter of 15 mm
that shows an increase in diameter of 5 mm regard to the base BMG with
10 mm in critical diameter.
The mechanical properties of BMGs were investigated by uniaxial
compressive testing at ambient temperature. Er-containing BMGs have
high compressive strength and Young module in the range of 1816–1890
Mpa and 116–120 GPa, respectively, but no plastic deformation
observed in them.
Crystallization kinetics studies imply that with the addition of Er, the
crystallization process became sluggish. Regard the three-dimensional
growth for the base and Er-containing BMGs, the nucleation mecha­
nism of the base BMG from increasing rate changed to the decreasing
and constant rates for (Cu50Zr43Al7)98Er2 BMG.
Declaration of competing interest
The authors declare no conflict of interest with regard to the sub­
mitted manuscript.
M. Malekan et al. Vacuum 174 (2020) 109223

Fig. 8. Avrami plot and local Avrami exponent for (a), (c) the Cu50Zr43Al7 BMG, and (b), (d) the (Cu50Zr43Al7)98Er2 BMG.

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