Progress in Natural Science: Materials International 2012;22(1):21–25

Chinese Materials Research Society

Progress in Natural Science: Materials International

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ORIGINAL RESEARCH

Effect of cooling rate on plastic deformation of Zr-based

bulk metallic glasses
Chunyan Lia,nn, Shengzhong Koua,b,n, Yanchun Zhaoa, Guangqiao Liub, Yutian Dinga

a
State Key Laboratory of Gansu Advanced Non-ferrous Metal Materials, Lanzhou University of Technology, Lanzhou 730050, China
b
Key Laboratory of Non-ferrous Metal Alloys and Processing of the Ministry of Education, Lanzhou University of Technology,
Lanzhou 730050, China

Received 14 November 2011; accepted 9 December 2011

Available online 14 February 2012

KEYWORDS Abstract The effect of cooling rate on plastic deformation of Zr-based bulk metallic glasses has been
Bulk metallic glasses;
studied. The specimens with the diameters of 3 mm, 4 mm and 6 mm cut from the same ladder-shaped
Cooling rate; Zr55Al10Ni5Cu30 BMG rod were used in the present investigation. The experimental results indicated
Serration; that the different plastic strains were induced for the three type compression specimens. The
Plastic deformation; compressive plastic strain increased with the decreasing diameter for the as-cast specimens, which
Free volume means that the compressive plastic strain increased with the increasing cooling rate. The reason of the
difference is attributed to the free volume existed in the BMGs during the rapid solidification, and the
larger free volume was contained in the specimen fabricated with the higher cooling rate. It has been
found that the prominent serrations and multiple shear bands appeared during the compressive
deformation tests of the specimen with smaller diameter of 3 mm, indicating that the specimen with
smaller diameter exhibits better plasticity due to more free volume content.

& 2012. Chinese Materials Research Society. Production and hosting by Elsevier B.V. All rights reserved.

n
Corresponding author at: State Key Laboratory of Gansu Advanced
Non-ferrous Metal Materials, Lanzhou University of Technology,
Lanzhou 730050, China. Tel.: þ86 931 2976682; fax: þ86 931 2976578.
nn
Corresponding author. Tel.: þ86 931 2976646; fax: þ86 931 2976578.
E-mail addresses: licywz@163.com (C. Li), kousz@lut.cn (S. Kou).
1002-0071 & 2012. Chinese Materials Research Society. Production
and hosting by Elsevier B.V. All rights reserved.
Peer review under responsibility of Chinese Materials Research
Society.
doi:10.1016/j.pnsc.2011.12.004
Production and hosting by Elsevier
1. Introduction
Bulk metallic glasses (BMGs), as the promising structural and
functional materials, have received considerable attention owing
to their unique physical and mechanical properties. Being in a
metastable state, the amorphous structure of BMGs is most
likely to be influenced by different variables in the process of
materials preparation, such as, cooling rate, overheat tempera-
ture and impurities, among which the cooling rate was thought
to play an important role in the forming of BMGs [1–5]. The
macroscopic plastic deformation of most BMGs is limited
because of the lack of the dislocation or other structural defects
[6–10]. In recent years, multicomponent BMGs with improved
22 C. Li et al.

deformation have been successfully designed and fabricated

[11–15]. It has also been found that for metallic glasses with
the same compositions, the specimens with smaller sizes are
much softer than those with larger dimensions [16–18]. There-
fore, the cooling rate which determines the glassy structure of the
BMGs is directly influenced by the sizes of the as-cast specimens,
on the other hand, it seems to strongly affect the mechanical
properties of BMGs [8]. Recently, the effect of cooling rate on
mechanical properties of BMGs has attracted increasing atten-
tions [5,19]. However, the cooling-rate effect on plastic deforma-
tion and the plastic deformation mechanism of BMGs are still
need further research.
In this paper, ladder Zr55Al10Ni5Cu30 BMG rods with different
diameters were fabricated by copper mold suction casting.
The compressive deformation behavior of Zr55Al10Ni5Cu30
as-cast BMGs with different diameters from the same ladder rods
has been presented, the plastic deformation mechanism and the
relationships between compressive plastic strain and cooling rate Fig. 1 Morphology of ladder Zr55Al10Ni5Cu30 BMG rod:
have been discussed. (a) diameter: 3 mm specimen, (b) diameter: 4 mm specimen and
(c) diameter: 6 mm specimen.

2. Experimental procedures

Zr55Al10Ni5Cu30 alloy ingots were prepared by levitation melting.

The mixture was composed of pure elements Zr (99.8 mass%),
Cu (99.99mass%), Ni (99.99 mass%) and Al (99.99 mass%).
6mm
Ladder-shaped BMG rods with diameters of 3 mm, 4 mm and
Intensity (counts/s)

6 mm were fabricated by copper mold suction casting under an

argon atmosphere. The amorphous structure of specimens was
identified by Bruker Axs D8 Advance X-ray diffraction (XRD,
4mm
Cu Ka radiation). The glass transition and crystallization behavior
of the BMG was evaluated by STA409 thermal differential
calorimeter (DSC) at a heating rate of 0.33 K/s. Uniaxial
compression tests of the specimens were carried out by WDW- 3mm
100D universal testing machine at room temperature with the
strain rate of 2.7  104 s1, and the aspect ratio of all specimens
was about 2:1. The outer surfaces of specimens were carefully
polished in order to decrease the roughness effect on the plastic
20 40 60 80
deformation.
2θ (degrees)

Fig. 2 XRD patterns of Zr55Al10Ni5Cu30 BMG specimens with

3. Results and discussion different diameters.

Fig. 1 shows the ladder-shaped Zr55Al10Ni5Cu30 BMG rod

with the diameters of 3 mm, 4 mm and 6 mm. Fig. 2 shows 2.0 φ 3mm
XRD patterns of the Zr55Al10Ni5Cu30 rods with different
diameters. It can be seen that the XRD patterns of all the
three kinds specimens with the diameters of 3 mm, 4 mm and 1.5 φ 4mm
Stress  (GPa)

6 mm consist of only one broad diffuse peak between diffrac-

tion angles 301 and 451. This indicates that these specimens
have a perfect glassy structure. 1.0 φ 6mm
Fig. 3 shows compressive stress–strain curves of
Zr55Al10Ni5Cu30 BMG with different diameters. At the strain
rate of 2.7  104 s1, the specimens of diameter 3 mm and 1%
0.5
diameter 4 mm exhibited elastic–plastic behavior with the yield
strengths of 1.83 GPa and 1.65 GPa, and maximum strengths
of 1.91 GPa and 1.84 GPa, while their plastic deformation
0.0
differs prominently from each other. The plastic strain of 0.000 0.005 0.010 0.015 0.020 0.025 0.030 0.035 0.040
2.2% was obtained for the diameter 3 mm specimen, and Strain (%)
prominent serrations appeared on the compressive stress–
strain curve. The plastic strain decreases to 1% for the Fig. 3 Compressive stress–strain curves of Zr55Al10Ni5Cu30
diameter 4 mm specimen, and to 0.1% for the diameter 6 mm BMG specimens with different diameters.
Effect of cooling rate on plastic deformation of Zr-based metallic glasses 23

specimen. By comparing plastic strains and stress–strain curves

Table 1 Compressive mechanical property parameters of
of three specimens, it has been found that more plastic
Zr55Al10Ni5Cu30 BMG specimens with different diameters.
deformation was induced before fracture for the diameter
Diameters Yield Maximum Plastic Elastic 3 mm specimen, and only very limited plastic deformation
of strength, strength, strain, modulus, occurred (is produced) for the diameter 6 mm specimen with
specimens ss (GPa) smax (GPa) ep (%) E (GPa) the fracture strength of 1.69 GPa.
(mm) Compressive mechanical properties have been tested for three
times to ensure the data’s reliablility. The yield strength (ss),
3 1.83 1.91 2.20 115.20
maximum strength (smax), plastic strain (ep) and elastic modulus
4 1.65 1.84 1.00 110.11
6 1.685 1.690 0.10 100.02
(E) of the specimens with different diameters are listed in Table 1.
It can be seen clearly that, with the increasing diameter of the
specimens, smax, ep and E decreased gradually. Fig. 4 shows the
rules of smax and ep for specimens with different diameters.
Fig. 5 shows compressive fracture morphologies for
Zr55Al10Ni5Cu30 BMG specimens with different diameters.
The typical fracture morphology of full bulk metallic glass is
Compressive fracture strength shown in Fig. 5(a)–(c), which is a typical characteristic of
1.9 Plastic strain fracture feature with well-developed vein patterns. The local
2 melting and the softened alloy, which look like liquid droplets,
Plasic strain (%) can be observed on the fracture surface as shown in Fig. 5(b)
(GPa)

and (c). However, there is no liquid droplets in Fig. 5(a), and

1.8 vein patterns are shallow, and this is consistent with the good
plastic deformation of diameter 3 mm specimen. The previous
Stress

study reported that the density of the vein patterns can reflect
the changes of the strength and the plasticity of the specimen,
0
i.e., the larger the vein patterns density, the higher the strength
1.7
and the plasticity of the specimens [20]. Fig. 5 shows that the
density of the vein patterns of diameter 3 mm specimen was the
3 4 5 6 largest among the three specimens and hence diameter 3 mm
Diameters of specimens (mm) specimen has the highest strength and plasticity.
It is generally known that the plastic behavior of amorphous
Fig. 4 Compressive fracture strength and plastic strain for alloy is closely related to the free volume [21]. During plastic
Zr55Al10Ni5Cu30 BMG specimens with different diameters. deformation process, the difference of elastic modulus between the

10µm 10µm

10µm

Fig. 5 Compressive fracture morphologies for Zr55Al10Ni5Cu30 BMG specimens with different diameters: (a) diameter: 3 mm specimen,
(b) diameter: 4 mm specimen and (c) diameter: 6 mm specimen.
24 C. Li et al.

region with a lot of free volume and the adjacent region induces
local stress concentration, which leads to nucleation of shear
bands. For amorphous alloys with same chemical compositions,
the smaller the specimen is, the larger the cooling rate is in
solidification process, thus more excess free volume is obtained.

Exothermic heat flow(mW/mg)

Under compression, if the specimens contain more excess free
volume, more shear bands can be nucleated and propagated in the
deformation process, which contribute to more superior plasticity.
According to Cohen and Turnbull [22,23], the excess free
volume is arrested as a structural defect during the rapid
solidification. Different amorphous structures can be obtained
under different cooling rates, i.e., the content of excess free volume
is actually determined by the cooling rate. The higher the cooling
rate is, the more excess free volume will be quenched in. The
critical cooling rate T can be calculated by the following formula
T¼4K(TmTg)/CR2 [24], where K¼0.01 W mm1 s1 K1 is 500 600 700 800 900 1000 1100 1200
thermal coefficient, Tg (¼673 K) and Tm (1107 K) are glass Tempreture(K)
transition temperature and fusion temperature, respectively,
obtained from DSC curve shown in Fig. 4(a). And C is volume
heat capacity, C¼0.004 J mm3 K1, diameter of alloy is denoted
by R with unit mm. Based on the relationship between the critical
cooling rate and the specimen diameter, the cooling rates of

Exothermic heat flow(mW/mg)

diameter 3 mm, diameter 4 mm and diameter 6 mm specimens are
482, 272 and 120 K s1 respectively. The results indicate that, with
the increasing size of specimens, the cooling rate is almost multiply
decreasing, which suggests that the cooling rate is very sensitive to
the size changes of specimens. Accordingly, the amount of free
volume trapped in the amorphous alloys should be smaller in the
larger specimens than that in the specimen with a smaller size,
which explains the difference in plasticity of the Zr-based
BMGs with different diameters.
It is also known that, during heating amorphous alloys, the
heat release of the exothermic reaction occurred below glass
transition temperature Tg is attributed to structural relaxation 500 600 700
[25]. The heat release is sensitive to the cooling rate and Temperature (K)
proportional to the free volume changes during the structural Fig. 6 DSC curves of Zr55Al10Ni5Cu30 BMG specimens with
relaxation [26,27]. For a better understanding of the differences in different diameters (b) is the magnified figure of (a) in the
plastic deformation of the Zr55Al10Ni5Cu30 BMGs with different temperature range of 500–710 K.
diameters, thermal properties related to the free volume were
measured. The DSC curves of Zr55Al10Ni5Cu30 BMG specimens diameter 6 mm Zr55Al10Ni5Cu30 BMG as-cast specimens
with different diameters are shown in Fig. 4. The specimens with from the same ladder-shaped rod is attributed to the different
different diameters showed almost identical DSC curves with a cooling rates during the preparation of the specimens. The
distinct glass transition temperature (Tg) at 673 K, crystallization plastic strain of the specimens with the diameters of 3 mm,
temperature (Tx) at 757 K and fusion temperature (Tm) at 4 mm and 6 mm were 2.2%, 1% and 0.1%, respectively.
1107 K, as shown in Fig. 6(a). Fig. 6(b) shows the magnified 2) The better plastic deformation of the specimens with high
DSC curves in the temperature range of 500–710 K, the heat cooling rate may be attributed to the generation of more
releases are 2.8  104, 1.6  104 and 1.2  104 J kg1 for the free volume in the specimens to facilitate the formation of
diameter 3 mm, diameter 4 mm and diameter 6 mm specimens, multiple shear bands.
respectively. The results indicate that the specimens of larger size
possess a more relaxed structure, which means that the specimens
with larger size possess smaller free volume than that of the Acknowledgments
specimens with smaller dimension. Therefore, when the diameter
3 mm specimen is compressed, the regions concentrating more This work was supported by the National Natural Science
free volume facilitates the forming of multiple shear bands, and Foundation of China (Grant no. 50961008, 51061008) and the
then leads to a larger plastic strain, as shown in Fig. 3. ‘973’ Special Preliminary Program (Grant no. 2011CB612203).

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