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State Key Laboratory of Solidication Processing, Northwestern Polytechnical University, Xi'an 710072, Shaanxi Province, PR China
Universit de Lyon, CNRS, INSA-Lyon, MATEIS UMR5510, F-69621 Villeurbanne, France
SIMAP, INP Grenoble/CNRS/UJF, 38402, Saint-Martin d'Hres, Cedex, France
a r t i c l e
i n f o
Article history:
Received 16 April 2014
Received in revised form 17 July 2014
Available online 10 August 2014
Keywords:
Bulk metallic glass;
Crystallization kinetics;
Activation energy;
Kissinger and JohnsonMehlAvrami;
Local Avrami exponent
a b s t r a c t
The crystallization kinetics of Cu38Zr46Ag8Al8 bulk metallic glass in non-isothermal mode and isothermal mode
are investigated by differential scanning calorimetry. In non-isothermal conditions, the average value of
activation energy is determined by Kissinger equation, and the value is around 310 kJ/mol. The crystallization
enthalpy is about 28.69 J/g. In addition, the local Avrami exponent is adopted to describe the crystallization
process. In isothermal route, the average value of activation energy for crystallization is calculated by the Arrhenius
equation, and the value is about 451 kJ/mol. The crystallization enthalpy is about 1.63 J/g. And the Avrami
exponent n ranges from 4.10 to 4.74, which indicates that the crystallization mechanism is mainly governed by
constant nucleation rate. The created phases in the two conditions are different which can be conrmed by the
X-ray diffraction test, this result is in accordance with the different crystallization enthalpies, but it's different
with other investigations.
2014 Elsevier B.V. All rights reserved.
1. Introduction
Compared with their crystalline counterparts, bulk metallic glasses
(BMGs) have a series of special combination of structural and functional
properties, such as higher strength, larger elasticity, lower elastic
modulus and excellent corrosion resistance due to the lack of translational
or orientational long-range order [1,2]. Namely, there are no conventional
defects in bulk metallic glasses [38], such as grain boundary and
dislocations. Therefore, bulk metallic glasses are potential materials
which can be applied on structural and functional materials.
In recent years, Cu-based bulk metallic glasses have been widely
investigated due to their excellent glass forming ability, good thermal
stability, wide supercooled liquid region (SLR) and high mechanical
properties at room temperature, as well as the containing of relatively
low cost elements [911]. Therefore, it is an ideal candidate which can
be applied in near shape fabri cation of precise and complex-shaped
components by means of the thermal plastic forming (TPF) method.
During the process of TPF, crystallization of BMGs must be avoided,
since crystallization or partial crystallization of BMGs will lead to a
drastic degradation of mechanical properties at room-temperature
[12]. In other words, crystallization makes BMG parts unsafe. Based on
this discussion, if we want to avoid crystallization effectively, it's
meaningful to understand the crystallization kinetics of BMG.
Corresponding author. Tel.: +86 29 8846 0568; fax: +86 29 8846 0294.
E-mail address: nwpuwj@nwpu.edu.cn (J. Wang).
http://dx.doi.org/10.1016/j.jnoncrysol.2014.07.029
0022-3093/ 2014 Elsevier B.V. All rights reserved.
Cu50Zr45Ti5 BMG. Moreover, this method also can be used for any kind
of phase transformation.
Therefore, the main purpose of this work is to investigate crystallization transformation kinetics in the non-isothermal and isothermal
modes of Cu 38 Zr46 Ag 8Al8 bulk metallic glass by DSC. In addition,
the research can provide some new insight to further understand
crystallization transformation kinetics, relevant thermal stability
and physical properties in bulk metallic glasses.
2. Experimental procedure
2.1. Sample preparation
The pre-alloyed ingot of Cu38Zr46Ag8Al8 (at%) BMG was prepared
by arc melting under a puried argon atmosphere in a water-cooled
copper crucible and in situ suction casting into a water-cooled
copper mold, then the rods of BMG with a diameter around 3 mm
were fabricated. Purity of the elements was above 99.9%. The ingot
was re-melted several times in order to ensure the homogeneity.
The DSC samples were mechanically cut from as-cast rods, and the
surfaces of samples were carefully polished and nally washed in
ethanol by an ultrasonic cleaning machine in order to remove the
surface oxidation before the DSC experiments. The amorphicity of
Cu38 Zr46 Ag8 Al 8 BMG was detected by means of X-ray diffraction
(XRD, DX-2700).
2.2. DSC experiments
The information of thermal properties and phase transformation
were determined by differential scanning calorimetry (DSC, Perkin
Elmer, Diamond) under a high purity owing argon gas atmosphere
with the owing rate of 20 ml/min and alumina pans were used as
sample holders, and the temperature accuracy is 0.01 K.
The non-isothermal DSC experiments were carried out by using
different steady heating rates from 2.5 K/min to 20 K/min. The isothermal
crystallization experiments were performed in the supercooled liquid
region (SLR) of Cu38Zr46Ag8Al8 BMG. The samples were heated up to
the annealing temperature at a heating rate of 20 K/min, then holding
at the selected temperatures until the crystallization completed, after
that, samples were cooled down to room temperature.
3. Results and discussion
3.1. Non-isothermal crystallization behavior
The crystallization peaks of DSC curves in Cu38Zr46Ag8Al8 BMG
performed at different heating rates are shown in Fig. 1. The heating
Fig. 1. The crystallization part of DSC curves in Cu38Zr46Ag8Al8 bulk metallic glass with
various heating rates.
rates are chosen as 2.5 K/min, 5 K/min, 10 K/min and 20 K/min, respectively. As can be seen from Fig. 1, crystallization only induces a single
pronounced exothermic peak at each heating rate, and the position of
peak shifts to higher temperature with the increase of heating rate.
Therefore, the crystallization process in this alloy is simple, and the
crystallization kinetics can be analyzed directly. By contrast with the
single exothermic peak, there are also complex exothermic peaks that
exist in other kinds of BMGs. For example, double exothermic peaks
can be obtained in classical VIT1 BMG [29], and three exothermic
peaks can be obtained in Cu52.5Ti30Zr11.5Ni6 BMG [30], all of these
peaks correspond to the multiplestage crystallization modes. For these
alloys, the crystallization kinetics is difcult to analyze, since all the
contributions have to be discussed separately. The XRD patterns of the
crystallized BMG are shown in Fig. 2, from which we can see that
there are two created phases in non-isothermal condition: CuZr phase
and AlAg phase, and three created phases in isothermal condition:
CuZr phase, AlAg phase and AgZr phase. The different created phases
in the two heating conditions can also be conrmed by the different
crystallization enthalpy, which have been done in the following sections.
And the result is different with the former research by Wei, et al. [31].
If we want to analyze the crystallization kinetics during the whole
process, the activation energy of the BMG in different crystallization
volume fraction must be obtained. Before that, the crystallization
volume fraction for non-isothermal crystallization, , should be
obtained, which can be deduced as a function of temperature from
DSC curves by using the following equation [3235]:
Z
Z
T
T0
T
T0
dHc =dT dT
dHc =dT dT
A0
A
1
Rh
T
T0
W T dT
ln
Rh
T p2
Ea
C
RT p
R ln ln 1
:
Ea 1=T
Fig. 6. Relationship between local Avrami exponent n() and crystallization volume
fraction at different heating rates as a guide to the eyes.
10
A
dHc =dtdt
t0
where t0 and t are the time when crystallization begins and ends in
amorphous materials, dHc/dt is heat ow, and A0, A are also the areas
under DSC curves. Fig. 9 exhibits the relationship between crystallization fraction and annealing time. The plots all display an S-shaped
trend, and the crystallization process becomes slow with the decrease
of annealing temperature.
Almost the similar with non-isothermal condition, the crystallization quantity in isothermal condition can be identied by calculating
the area of crystallization enthalpy using the following equation:
H
1
Rh
t
t0
W t dt:
Ea
RT
7
Fig. 7. DSC curve of Cu38Zr46Ag8Al8 bulk metallic glass (heating rate: 20 K/min). Glass
transition temperature (Tg) and onset crystallization temperature (Tx) are dened.
Fig. 8. The crystallization part of DSC curves in Cu38Zr46Ag8Al8 bulk metallic glass at
different annealing temperatures.
Fig. 9. Relationship between crystallization volume fraction and annealing time at different annealing temperatures in Cu38Zr46Ag8Al8 bulk metallic glass as a guide to the eyes.
11
Fig. 10. Plots of Cu38Zr46Ag8Al8 bulk metallic glass for activation energy in isothermal
conditions. The ts have R2 values all above 0.99.
ln ln 1
:
ln t
10
After this stage, the local Avrami exponent is larger than 4.0 which
means that the nucleation rate increases with time. Meanwhile, the
crystallization quantity increased rapidly and the n() value almost
maintains a stable state until the reaches 80%, after that the n()
value is back to 4.0, which means that the nucleation rate decreased to
a constant small value; the main reason is due to the lack of solvend.
After this stage, with the increase of crystallization fraction, the nucleation
rate decreases until the crystallization process is completed. Similar
phenomenon has been reported by Sun et al. [52] in the work of
Fe33Zr67 metallic glass.
4. Conclusion
The crystallization kinetics of Cu38Zr46Ag8Al8 BMG is investigated by
DSC in both non-isothermal and isothermal conditions. The main results
of this work are shown as follows:
In non-isothermal condition, the average crystallization enthalpy is
about 29.36 3.44 J/g, and the average activation energy is about
310 kJ/mol.
In non-isothermal condition, when the crystallization fraction is
between 20% and 80% the Avrami exponent is larger than 4, which
means that the nucleation rate increased with time, and the crystallization quantity increased rapidly. When the crystallization fraction
reaches 80%, the Avrami exponent value is back to 34, which
means that the crystallization progresses with a decreasing crystallization rate, the main reason is due to the lack of solvend.
In isothermal condition, the average crystallization enthalpy is about
1.63 0.12 J/g, and the average value of activation energy is about
451 23 kJ/mol.
In isothermal condition, the Avrami exponent n ranges from 4.10 to
4.74, the crystallization mechanism is mainly governed by constant
nucleation rate.
Table 1
The Avrami exponent n, reaction rate constant K and incubation time at different annealing
temperatures in Cu38Zr46Ag8Al8 bulk metallic glass. The Avrami exponent and reaction rate
constant K are obtained by tting Fig. 12, and the ts all have the same R2 value of 0.999.
Fig. 11. Activation energy of Cu38Zr46Ag8Al8 bulk metallic glass for different crystallization
volume fractions in isothermal heating conditions by tting the experimental points in
Fig. 10. The average activation energy is 451 23 kJ/mol.
(min)
755
761
767
773
779
4.74
4.24
4.09
4.54
4.72
3.12
2.48
1.15
0.55
0.12
0.19
0.35
0.50
0.77
1.21
12
Fig. 13. Relationship between local Avrami exponent n() and crystallization volume
fraction at different annealing temperatures as a guide to the eyes.
Acknowledgments
This work was supported by the Fundamental Research Fund of
Northwestern Polytechnical University (JC20120203) and the Program
of Introducing Talents of Discipline to Universities (B08040). One of
the authors J. Cui wants to acknowledge China Scholarship Council
(CSC) (2011629115) for the nancial support.
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