Journal of Alloys and Compounds 544 (2012) 4649

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Journal of Alloys and Compounds

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

Effects of ultrasonic treatment on the structure and properties of Zr-based

bulk metallic glasses
Yongyong Wang, Wei Zhao, Gong Li , Riping Liu
State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, China

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

Article history: The effects of ultrasonic treatment on the structure and properties of Zr-based bulk metallic glasses
Received 23 May 2012 (BMG) at room temperature were investigated by nanoindentation, in situ high-pressure synchrotron dif-
Received in revised form 28 July 2012 fraction and differential scanning calorimetry (DSC). Results show that the glassy characteristics of the
Accepted 30 July 2012
samples were stable up to 31 GPa. Furthermore, the hardness, elastic modulus, and distribution of
Available online 11 August 2012
reduced hardness improved after ultrasonic treatment. The DSC results indicate that ultrasonic treatment
increased the thermal stability of the BMG. This study reveals that ultrasonic treatment can be used as an
Keywords:
effective way to design BMG-based materials with selective properties.
Ultrasonic treatment
Nanoindentation
2012 Elsevier B.V. All rights reserved.
Free volume
Bulk metallic glasses

1. Introduction 2. Experiments

Master alloy with a nominal composition of Zr55Al10Ni5Cu3 was prepared by arc

Metallic glasses are relative newcomers in the glassy family
[16], and are of fundamental interest and technological importance
worldwide because they offer attractive benets, combining some of
the desirable mechanical, magnetic, and chemical properties of
crystalline alloys and the formability of oxide glasses. Among the
various kinds of bulk metallic glasses, Zr-based [79] alloys
extensively used in commercial applications because they contain
less rare and less noble metals. Additionally, Zr-based alloys also
have excellent mechanical properties and high glass formability.
However, the structure and properties of BMG are very sensitive to
external elds. Ultrasonic treatment (UST) has been used to
investigate the structural evolution and properties of various BMGs.
Ichitsubo et al. [1013] studied the Zr- and Pd-based BMGs under
ultrasonic vibrations and found that crystallization can be acceler-
ated; Wang et al. [14] and Keryvin et al. [15] studied the equation
of state and thermal stability of BMGs by the ultrasonic method.
In this work, the Zr55Al10Ni5Cu30 [16] bulk metallic glass (BMG)
was subjected to ultrasonic waves at room temperature using an
ultrasonic device, and the spatial nanohardness distribution of
the samples were measured by nanoindentation. The compression
behavior of the samples was investigated by in situ high-pressure
synchrotron diffraction. The effects of UST on the thermodynamic
properties of Zr55Al10Ni5Cu30 BMG were also analyzed by differen-
tial scanning calorimetry (DSC). This study provides valuable
information about the structure and properties of the samples.
Corresponding author.
E-mail address: gongli@ysu.edu.cn (G. Li).
melting a mixture of pure Zr, Al, Ni, and Cu (purity higher than 99.9%) under a Ti-
gettered high-purity argon atmosphere. The ingots were remelted in a quartz tube
by induction heating followed by injection into copper molds. The amorphous nat-
ure as well as the homogeneity of the samples was ascertained by D/MAX-RB X-ray
diffraction (Fig. 1(a)). UST was conducted on a JXD-02 system at a frequency of
20 kHz for 48 h. The sample was identied by X-ray diffraction to be at fully glass
phase after UST, as shown in Fig. 1(b).
The sample for nanoindentation was cut into dimensions of 10  10  3 mm3
and carefully polished to smoothen the surface. The indentations were carried
out over a square area of 40  40 lm2 for the samples in a nanoindenter Hysitron
TriboIndenter with a diamond Berkovich tip having a 260 nm radius of curvature.
The constant contact force and the amplitude of the sinusoidal force were 0.2 and
0.25 lN, respectively. All the indentations were programmed to penetrate the same
depth, viz., 100 nm, and the spacing between adjacent indentations was 2 lm. The
applied loading/unloading rate was 200 lN/s.
Powder was prepared for the pressure experiments. Samples were loaded into
the 150 lm hole of a T301 stainless steel gasket in a membrane-type DAC with dia-
mond-culet sizes of 400 lm. Ruby grains were loaded with the samples for pressure
determination. A 16:3:1 methanolethanolwater mixture was used as a pressure-
transmitting medium. The monochromatic X-ray had a spot beam of 80  80 lm
and a wavelength of k = 0.6199 . More experimental details can be found in Refs.
[17,18].
DSC measurements were conducted under a high-purity argon atmosphere on a
STA449C/DSC (NETZSCH Instruments Co., Ltd.) at different heating rates.
3. Results
The surface smoothness was examined by scanning electron
microscopy. Only indistinct scratches that had minimal inuence
on the result of nanoindentation results were found on the sample
surface. Given the geometry and dimension of the probe tip, an
indentation impression of 800 nm remained. Although the shear

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 Y. Wang et al. / Journal of Alloys and Compounds 544 (2012) 4649 47

Fig. 1. The X-ray diffraction patterns of the Zr55Al10Ni5Cu30 BMGs; (a) before and
(b) after UST.

bands usually develop around indentations, they rarely extended

the strain to an outer area as large as the impression itself
[19,20]. Thus, the size of the entire strained zone of an indentation
observed in this study was 1.6 lm in this study. Therefore, a
distance of 2 lm between two neighboring indentations was
chosen to prevent the overlapping of neighboring strained zones.
The hardness and the elastic modulus can be obtained via the
nanoindentation. The average nanohardness of the specimens
increase from 7.22 GPa to 8.26 GPa. The average elastic modu-
lus increase from 113.78 GPa to 123.5 GPa after UST. Ratios of
nanohardness to elastic modulus (H/E) were 0.0634 and 0.0669
for the alloys untreated and treated respectively. These results
indicated that the hardness, elastic modulus, and mechanical prop-
erties of the BMGs signicantly improved after UST.
To gain a better understanding of the variation in hardness of
the Zr55Al10Ni5Cu30 BMGs, contour maps of the spatial distribution
of the nanohardness of Zr55Al10Ni5Cu30 BMGs over a 40  40 lm2
square area before and after UST were obtained, as shown in
[Fig. 2(a) and (b), respectively]. The average hardness of the mate-
rial is evidently increased after UST. To a certain extent, these maps
also demonstrated that the amorphous alloy was inhomogeneous
at the microscale. Fig. 2. Spatial distribution of the hardness values of the Zr55Al10Ni5Cu30 BMGs; (a)
The relative nanohardness was introduced to minimize the before and (b) after UST.
effect of scratches on the absolute value. To compare the spatial
hardness distributions of the specimens before and after UST, re- activation energy for various processes in the present amorphous
P alloy can be estimated by the following Kissinger equation [22]:
duced hardness hri was determined as hri hi =HH 1=n i hi ,
where hi is ith nanohardness value. Histograms (a), and (b), in !
T 2h Eh
Fig. 3 characterize the nanohardness distribution of the ln const
Zr55Al10Ni5Cu30 BMGs before and after ultrasonic treatment, b RT h
respectively. hri was distributed mainly between 0.9 and 1.115
where b is the heating rate; Th represents the characteristic temper-
for Zr55Al10Ni5Cu30 BMG, and between 0.85 and 1.125 for
atures such as Tg, Tx, and Tp (crystallization peak temperature); and
ultrasonically treated sample. The results indicate that the
R denotes the gas constant. By plotting lnT 2 =b versus 1/T for the
distribution of the reduced nanoindentation hardness for Zr55
samples, (Fig. 5), the related effective activation energies were
Al10Ni5Cu30 BMGs expanded after UST compared with the sample
obtained. These energies are summarized in Table 1.The effective
that was not subjected to UST.
activation energy of BMG signicantly increased after UST, which
The stability of Zr55Al10Ni5Cu30 BMG under high pressure was
indicates the thermal stability of Zr55Al10Ni5Cu30 BMG was
investigated by in situ high-pressure synchrotron diffraction.
enhanced.
Fig. 4 shows the selected synchrotron radiation X-ray diffraction
spectra of Zr55Al10Ni5Cu30 BMG under different pressures. With
increased pressure, the broad diffusive amorphous halo visibly 4. Discussion
shifted to a high angle, which shows the compression behavior of
bulk amorphous alloys [21]. No new diffraction peaks were The defects of amorphous alloy are often described by the free
detected from the curves up to 31.19 GPa, indicating that the struc- volume model, in which the inhomogeneity of the local distribution
ture of the Zr55Al10Ni5Cu30 BMG was stable at room temperature. of excess free volume together with density uctuation in
The effects of UST on the thermal stability of Zr55Al10Ni5Cu30 amorphous materials results in inhomogeneous nanohardness.
BMG were investigated by DSC measurements at different heating According to Turnbull and Cohens theory [23], the increase in the
rates (10, 20, 30, 40 K/min). Subsequently, the characteristic peak free volume in BMGs can increase the interatomic distance and
temperatures were derived from the DSC measurements. The weakens the atomic bonding energy. Thus, the low concentration
48 Y. Wang et al. / Journal of Alloys and Compounds 544 (2012) 4649
Fig. 3. Distributions of the reduced nanoindentation hardness for Zr55Al10Ni5Cu30
BMGs; (a) before and (b) after UST.
Fig. 4. Angle-dispersion X-ray diffraction patterns of Zr55Al10Ni5Cu30 BMGs; (a)
before and (b) after UST.
in the free volume after UST can results in a shorter interatomic dis-
tance and more closed packed structure, leading to higher hardness
and elastic modulus [24]. When the samples were treated with
ultrasonic waves, the atoms in the partially softened region of the
amorphous alloy exhibited diffusions and rearrangements. The free
volumes were annihilated and nanohardness increased. In the very
few regions, the free volumes gathered with the diffusions and
rearrangements of the atoms, thereby decreasing nanohardness.
The annihilation and coalescence of free volumes induced a broader
distribution of reduced hardness, indicating that UST enhanced the
plasticity of the samples to a certain extent. Furthermore,
Ruitenberg [25] pointed out that the effective activation energy
obtained from Kissinger plots was approximately equal to
T 0h
Q 0 Q kB B 2
T h  T 0
Fig. 5. Kissingers plot of Tg, Tp and Tx for Zr55Al10Ni5Cu30 BMGs; (a) before and (b)
after UST.
Table 1
Activation energy of different characteristic temperatures for Zr55Al10Ni5Cu30 BMGs
before and after UST.
UST Eg (kJ/mol) Ex (kJ/mol) Ep (kJ/mol)
Before 189.78 371.09 356.28
After 202.07 388.56 406.41
The rst contribution (Q) is equal to the activation energy for
the migration of a structural defect. The second contribution is
related to the equilibrium defect concentration. Although the for-
mer does not change because of the ultrasonic process, the latter
increases as defect concentration decreases, whereas the free
volume concentration decreased and approached the equilibrium
value with the annihilation of free volumes in the ultrasonic
process. Thus, the hardness and the thermal stability have
improved after UST.
5. Conclusions
In this study, the effects of UST on the structure and properties
of Zr-based BMG were investigated. The Zr55Al10Ni5Cu30 BMGs re-
mained stable up to 31 GPa after UST. The nanoindentation and
in situ high-pressure synchrotron diffraction reveals that the hard-
ness and elastic modulus increased, and that the distribution of re-
duced hardness expanded. The non-isothermal crystallization
kinetic behaviors were also discussed and UST signicantly im-
proved thermal stability. The results demonstrate that UST can
cause the rearrangement of atoms, resulting in the annihilation
of free volume and the structural relaxation of BMGs. The mechan-
ical and thermal properties were considered related to the changes
in free volume and structure.
Acknowledgments
This work was supported by the National Basical Reseach Pro-
gram of China (Grant No. 2010CB731600) and National Science
Foundation of China (Grant No. 50731005/50821001).
 Y. Wang et al. / Journal of Alloys and Compounds 544 (2012) 4649 49

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