Journal of Non-Crystalline Solids 506 (2019) 1–5

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Journal of Non-Crystalline Solids

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

Ultrasonic additive manufacturing of bulk Ni-based metallic glass T

a a a,b,⁎ b a a
Wenzheng Wu , Jili Jiang , Guiwei Li , Jerry Ying Hsi Fuh , Hao Jiang , Pengwei Gou ,
Longjian Zhanga, Wei Liua, Ji Zhaoa
a
School of Mechanical and Aerospace Engineering, Jilin University, Changchun, Jilin 130025, China
b
Department of Mechanical Engineering, National University of Singapore, Singapore 117576, Singapore

A R T I C LE I N FO A B S T R A C T

Keywords: It is difficult to produce bulk blanks directly from metallic glass, which limits its application. Ni-based metallic-
Metallic glass glass thin strips that can be manufactured easily were used to manufacture bulk metallic glass additively by
Additive manufacturing ultrasonic bonding. The effects of ultrasonic vibration energy on the quality of the additive manufacturing of
Ultrasonic bonding bulk Ni-based metallic glass were studied. The experimental results showed that a fully amorphous structure of
Mechanical properties
bulk Ni-based metallic glass can be obtained with an appropriate ultrasonic vibration energy. The thermal
3D printing
properties were almost unchanged, and the hardness and elastic modulus of the Ni-based metallic glass were
improved compared with the original material. Additive manufacturing of bulk metallic glass by ultrasonic
bonding can broaden the application field of metallic glass.

1. Introduction
Metallic glass, which is also termed an amorphous alloy, has metal
and glass advantages. Bulk metallic glass has a strength of two to three
times that of its corresponding crystalline state, a high elastic strain and
elastic limit, a low elastic modulus and a superplastic deformation be-
havior in the supercooled liquid-phase region [1–4]. Metallic glass is a
high-performance metal material that was developed at the end of the
twentieth century and it has been used widely in industry, in sports
equipment, biomedicine and consumer electronics fields [5,6]. How-
ever, it is difficult to produce bulk metallic glass directly because of the
critical size of metal-glass forming, which makes it difficult for the
metallic glass to become a new generation of structural materials [7,8].
Therefore, the research focus in the field of metallic glass has been on
the production of metal-glass powder or metal-glass strip material into
bulk metallic glass, while maintaining its excellent physical and me-
chanical properties.
Many researchers have studied the manufacture of bulk metallic
glass additively. Pauly, S. et al. used selective laser melting (SLM)
technology to manufacture bulk Zr-based metallic glass additively with
powder, and elucidated the relationship between the process para-
meters, phase formation, relative density and mechanical properties of
the alloy [9]. Li, X.P. et al. studied the SLM formation of Zr-based and
Al-based metallic glass, and the experimental results showed that the
internal stress and amount of crystallized grains can decrease by
choosing the appropriate laser power [10,11]. Wang, G. et al. produced
bulk Ti-based metallic glass by friction joining, and the influence of
interfacial friction temperature distribution on the interface joining
quality was studied [12,13]. Shao, L. et al. adopted a pulsed laser beam
to weld Pb-based bulk metallic glass, and the mechanical properties of
the welded sample were studied [14]. Wang D.J. et al. used spark
plasma sintering technology to manufacture Ti-based bulk metallic
glassy composites, and the investigated results illustrated that bulk
metallic glass prepared by this method had potential for engineering
applications [15].
The above researches have focused on the manufacture of bulk
metallic glass with a high-energy beam or a larger bulk original mate-
rial. High-energy-beam additive manufacturing technology is complex
and the manufacturing costs are high. Larger bulk original materials are
not readily available. Based on the principle of ultrasonic bonding, the
additive manufacturing of metallic glass has advantages of a simple
formation process, a low requirement for original materials and direct
solid-state cumulative forming. We used a 35-kHz ultrasonic spot-
bonding machine to explore the mechanism of ultrasonic bonding
technology during ultrasonic layer-by-layer additive manufacturing.
2. Materials and methods
2.1. Ultrasonic additive manufacturing of bulk Ni-based metallic glass
Ni82.2Cr7B3Si4.8Fe3 metallic glass strips (1.7 mm × 0.04 mm) pre-
pared with rapid quenching via the melt spinning technique were used.

⁎
Corresponding author at: School of Mechanical and Aerospace Engineering, Jilin University, Changchun, Jilin 130025, China.
E-mail address: ligw15@mails.jlu.edu.cn (G. Li).

https://doi.org/10.1016/j.jnoncrysol.2018.12.008
Received 7 September 2018; Received in revised form 27 December 2018; Accepted 29 December 2018
0022-3093/ © 2019 Elsevier B.V. All rights reserved.
W. Wu et al. Journal of Non-Crystalline Solids 506 (2019) 1–5

Fig. 1. Schematic diagram.

A customized ultrasonic spot-bonding machine (Dongguan Jieshi Table 1

Ultrasonic Automation Co., Ltd. Dongguan, China) was used to make Experimental parameters.
bulk metallic glass at 35 kHz and 800 W, as shown in Fig. 1. Two-layer Fixed factors Control factors
Ni-based metallic glass strips were placed on the fixture, the ultrasonic
bonding parameters were set, and the ultrasonic bonding system was Factor Level Unit Factor Value Unit
initiated. The ultrasonic bonding horn contacted the metallic glass strip,
Pressure 0.22 MPa Bonding time 0.03 s
and placed pressure on the metallic glass strips to achieve ultrasonic Delay time 0.4 s 0.05
bonding. The horn continued to compact the sample after ultrasonic Hold time 0.5 s 0.09
bonding to prevent the specimen from warping.
Fig. 2(a) and (b) showed three-layers bulk metallic glass with one
bonding point and four bonding points respectively, and Fig. 2(c) transverse appearance of the bonded parts. X-ray diffractometry (XRD,
showed five-layers bonded bulk metallic glass. Fig. 2 illustrated that X' Pert PRO MPD, PANalytical BV, Netherlands) was used to test and
bulk metallic glass can be additively manufactured through the ultra- analyze the phase composition of the bonded parts with Cu Kα of
sonic bonding process of point-by-point and layer-by-layer. The effects λ = 1.54 Å operated at 40 kV and 40 mA. Differential scanning calori-
of ultrasonic bonding time on the quality of the three-layers Ni-based metry (DSC, LABSYS EVO, Setaram Labsys, France) was used to test and
metallic glass were studied. Since the initial strips were prepared analyze the thermal properties of the bonded parts. The detection at-
through melt spinning, the surface which was in contact with a wheel mosphere was nitrogen and the heating rate was 10 °C/min. The
usually had some defects, and the other free surface was smooth. While hardness and modulus of the samples were measured by using a nano-
the three-layers bulk metallic glass was manufactured, the first inter- indentation instrument (Nano Indenter G200, Agilent, USA). The sur-
face was bonded by two smooth surfaces contacted, and the second face approach velocity was 10 nm/s and the peak holding time was 3 s.
interface was bonded by rough surface and smooth surface. The ex-
perimental scheme is shown in Table 1. Six samples were manufactured
for each group of processing parameters to characterize the perfor- 3. Results and discussion
mance.
3.1. SEM of the cross-sectional morphology

2.2. Characterization of sample performance
In order to analyze the characterization of sample performance
accurately, the cross section of sample was firstly polished with 8000
mesh sandpaper, and then the polishing machine was used to further
polish with 50 nm SiO2 polishing liquid. Scanning electron microscopy
(SEM, ZEISS-EVO18, Carl Zeiss NTS, Germany) was used to observe the
Fig. 3 shows the cross-sectional morphology of the bulk Ni-based
metallic glass at different bonding times. There are no apparent dif-
ferences between the two bonded interfaces, which illustrate that the
initial surface has no effects on the ultrasonic bonding process. As
shown in Fig. 3(a), when the bonding time is 0.03 s, a short dis-
continuous gap exists in the interface of the bonded bulk Ni-based
metallic glass sample. As illustrated in Fig. 3(b), when the bonding time

Fig. 2. Three-layers bulk metallic glass with one bonding point (a), four bonding points (b), and five-layers bonded bulk metallic glass (c).

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W. Wu et al. Journal of Non-Crystalline Solids 506 (2019) 1–5

Fig. 3. Cross-sectional morphology of bulk Ni-based metallic glass at 0.03 s, 0.05 s and 0.09 s welding time.

is 0.05 s, the interface of the bulk Ni-based metallic glass sample shows
no void, and the interface between the three layers of Ni-based metallic
glass is almost indistinguishable. As shown in Fig. 3(d), even the part
that contacts the edge of the horn has a good bonding effect. As shown
in Fig. 3(c), when the bonding time is 0.09 s, the bonded bulk Ni-based
metallic glass is well bonded between the layers, but cracks and chips
exist on the bonded surfaces in contact with the horn.
During the ultrasonic bonding process, the energy input from the
ultrasonic bonding system to the bonding sample is: Q = Pt, where P is
the power, Q is the input energy, and t is the ultrasonic bonding time.
With an increase in ultrasonic bonding time, the energy input of the
bonding system into the bonding sample is greater. At a bonding time of
0.03 s, the lack of input energy from the bonding system to the bonding
sample may lead to an intermittent weld in the sample. When the
bonding time is 0.05 s, the bonding-system input energy into the sample
is moderate, and so the bonding effect is better. Ichitsubo et al. found
that ultrasonic vibration could cause metallic-glass crystallization and
changed the mechanical properties of the metallic glass [16]. When the
Fig. 4. XRD diagram of bulk Ni-based metallic glass with the original material
bonding time is 0.09 s, excessive input energy from the ultrasonic
and bonding time of 0.03 s, 0.05 s and 0.09 s.
bonding system into the bonding sample may result in partial crystal-
lization of the bulk Ni-based metallic glass, which made the bonded
parts brittle. Under ultrasonic vibration, the surface of the bonded parts diffraction peak between 40° and 50° was significantly higher than that
crack, and exfoliation debris appeared. of the original material, and a diffraction peak at around 2θ = 44°
corresponded to the Cr (110) plane that coincided with the second
diffuse scattering peak was detected. This result indicates that a crys-
3.2. XRD of the original material and the bonded bulk metallic glass
tallizing phenomenon of the bonded Ni-based bulk metallic glass is
observed when the bonding time is 0.09 s. Excessive input energy from
To study the effect of ultrasonic bonding on the phase composition
the ultrasonic bonding system may cause the atoms inside the metallic
of bulk Ni-based metallic glass after bonding, XRD was used to sweep
glass to become more ordered. The increased volume fraction of the
the surface of the original material and the samples at different bonding
short or medium range ordered structure enhanced the second diffuse
times. As shown in Fig. 4, when the bonding times are 0.03 s and 0.05 s,
peaks. Therefore, for a bonding time of 0.09 s, the SEM image shows
the XRD curves exhibit no sharp diffraction peaks, and the first diffuse
that the crack and exfoliation debris on the sample surface are caused
diffraction peaks between 15° and 40° are almost the same as the ori-
by crystallization of the metallic glass.
ginal material. The second diffuse diffraction peaks between 40° and
50° are significantly lower than those of the original material. Since the
diffuse diffraction peak value corresponds to a common distance ex- 3.3. DSC of the original material and the bonded bulk metallic glass
isting between particles in the metallic glass. The moderate ultrasonic
vibrations might make atoms more disorderly inside the metallic glass, To analyze the effects of ultrasonic vibration on the thermal prop-
and decreased one of the common distances. The reduced volume erties of bonded bulk Ni-based metallic glass, the original material and
fraction of the short or medium range ordered structure weakened the the sample at bonding time of 0.03 s and 0.09 s were studied by using
second diffuse peaks. When the bonding time was 0.09 s, the second DSC. As shown in Fig. 5, the endothermic phenomenon is hardly

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W. Wu et al. Journal of Non-Crystalline Solids 506 (2019) 1–5

ultrasonic vibrations might change the amorphous form of metallic

glass, while the excessive ultrasonic vibrations might make the metallic
glass crystalized, which might cause the different peaks at the same
temperature. The melting endothermic peaks of the bulk metallic glass
produced by ultrasonic additive manufacturing appeared near 973 °C,
which is slightly lower than the original melting temperature of 982 °C.
And there is a fluctuation of the DSC signal at 973 °C for the bonded
bulk metallic glass, which may be caused by the changed phase at
852 °C. The bonded bulk metallic glass samples might contain more
kinds of crystal phases than the original material with the increased
temperature, which result in the melting peaks appeared earlier and a
fluctuation appeared at 973 °C. Fig. 5 indicates that ultrasonic vibration
hardly changes the thermal properties of Ni-based metallic glasses.
However, the composition of an amorphous phase of bulk metallic glass
made by ultrasonic additive manufacturing may be changed.

3.4. Internal hardness and modulus of the bonded sample

Fig. 5. DSC diagram of original material and bulk Ni-based metallic glass with
bonding time of 0.03 s and 0.09 s. The hardness and elastic modulus of the cross section of the sample
with a bonding time of 0.03 s and the original material were measured
by nano-indentation to analyze the effect of ultrasonic vibration on the
observed before the exothermic peak of crystallization, so it is difficult
mechanical properties of the bulk metallic glass that was manufactured
to determine the glass transition temperature of the sample, which
by ultrasonic bonding. Each sample was measured at five points, and
should be determined by the properties of the Ni-based metallic glass.
the sampling-point position and indentation test curves are shown in
The crystallization exothermic peaks of bulk Ni-based metallic glass and
Fig. 6. The indentation test curves showed a good repeatability. In
the original materials began to appear near 440 °C. The initial crystal-
particular, the indentation curves of the sample points inside the bulk
lization temperature of bulk Ni-based metallic glasses was unaffected
metallic glass made by ultrasonic additive manufacturing were almost
by ultrasonic vibration. When the bonding time is 0.03 s, an en-
completely coincident. The unloading curves of the original material
dothermic peak appeared near 852 °C. However, there is an exothermic
show an obvious pop-out phenomenon, which is related closely to the
peak existed near 852 °C for a bonding time of 0.09 s. The moderate
phase transition of metallic glass in the region of the indenter action

Fig. 6. Nanoindentation test results of original material and bulk Ni-based metallic glass with bonding time of 0.03 s.

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W. Wu et al.
during unloading [17,18]. The unloading curves of the bulk metallic
glass made by ultrasonic bonding were relatively smooth, and the pop-
out phenomenon was not obvious, which indicates that the bulk me-
tallic glass manufactured by ultrasonic additive manufacturing is more
stable under pressure.
The hardness of the bulk metallic glass by ultrasonic bonding and
that of the original material were 8.55 ± 0.96 GPa and
8.21 ± 0.62 GPa, respectively, and the elastic moduli were
134.10 ± 11.69 GPa and 81.74 ± 1.62 GPa, respectively. The con-
trast between the hardness and modulus of the bulk metallic glass and
the original material by ultrasonic additive manufacturing is shown in
Fig. 6. The average hardness and modulus of the bulk metallic glass
manufactured by ultrasonic bonding was higher than that of the ori-
ginal material. The modulus of elasticity of the ultrasonic bonding
samples was significantly different from that of the original materials
revealed by the Tukey's test (p < 0.01), which indicates that the bulk
Ni-based metallic glass manufactured by ultrasonic bonding can bear
more pressure when unit deformation occurs. As shown by Fig. 4, the
diffraction peak between 40° and 50° for the sample with a bonding
time of 0.03 s is significantly lower than that of the original material in
the XRD diagram. The strength of the metallic glass diffraction peak is
correlated with the amorphous-phase content, so ultrasonic vibration
may change the content of a certain amorphous phase in the metallic
glass, and increase the hardness and elastic modulus of the bulk Ni-
based metallic glass formed by ultrasonic bonding.
4. Conclusions
Ultrasonic vibration was used to manufacture Ni-based bulk metal
glass additively. With appropriate manufacturing parameters, the bulk
Ni-based metallic glass formed by layer-by-layer accumulation did not
crystallize, its thermal properties were almost unchanged, and it was
almost impossible to separate the interlayer bonding interface. When
the input energy of the ultrasonic bonding system to the sample was too
large, the nanocrystalline phase precipitated. The internal hardness and
modulus of the bulk metallic glass parts made by ultrasonic additive
manufacturing are higher than that of the original materials. The
combination of ultrasonic bonding and traditional machining or laser-
cutting technology is expected to form large and complex metallic glass
parts rapidly, and widen the application field of metallic glass.
Funding
This research is supported by National Natural Science Foundation
of China (No. 51675226), Key Scientific and Technological Research
Project of Jilin Province (No. 20180201055GX), Project of International
Science and Technology Cooperation of Jilin Province (No.
Journal of Non-Crystalline Solids 506 (2019) 1–5
20170414043GH) and China Scholarship Council (CSC).
Declaration of interest statement
The authors declare no competing financial interests.
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