Microstructure and mechanical properties of friction stir welded joint

of Zr46Cu46Al8 bulk metallic glass with pure aluminum

F.P. Li
a,b
, D.C. Zhang
a,b
, Z.C. Luo
a,b
, C.G. Tan
a,b
, J.G. Lin
a,b,n
a
Key Laboratory of Low Dimensional Materials and Application Technology of Ministry of Education, Xiangtan University, Xiangtan, Hunan 411105, China
b
Faculty of Materials and Optoelectronics Physics, Xiangtan University, Xiangtan, Hunan 411105, China
a r t i c l e i n f o
Article history:
Received 16 April 2013
Received in revised form
4 September 2013
Accepted 7 September 2013
Available online 18 September 2013
Keywords:
Zr-based BMG
Friction stir welding
Aluminum
Fracture
a b s t r a c t
A 2 mm thick Zr
46
Cu
46
A
l8
bulk metallic glass (BMG) plate and 4.5 mm thick pure aluminum plate were
successfully joined by friction stir welding (FSW), and the defect-free BMG/Al joint is produced. Some
BMG particles were stirred into the aluminum side in the stir zone and reacted with the Al to form the
Al-rich phase. The residues of the BMG particles still maintained the amorphous structure. However, no
crystallization and reaction layer are detected at the interface between the BMG and Al. The ultimate
tensile strength of the joint is about 190 MPa, which reaches up to 92% of the pure aluminum matrix.
& 2013 Elsevier B.V. All rights reserved.
1. Introduction
Bulk metallic glasses (BMGs) exhibit high specic strength, high
hardness, superior corrosion resistance, etc., which are attractive for a
lot of applications [1,2]. However, there are some problems, which
are still constraining the widespread use of these materials. One of
the major issues is their low ductility at room temperature due to the
localized shear deformation. In the past decades, extensive
researches have been carried out to understand the deformation
mechanism and to improve the ductility of BMGs at room tempera-
ture, e.g. through alloying and/or introducing ductile crystalline
phases to produce composites, and thus the ductility of BMGs has
been obviously promoted [3]. Another major issue is that most
current homogeneous glassy BMGs are not big enough for structural
applications. To extend the engineering applications of BMGs, weld-
ing technologies need to be developed. Furthermore, in order to
better integrate the metallic glass components into the structure of
machines or other products, the possibility of joining metallic glass
with itself or crystalline materials is desirable. Recently, many
welding methods have been tried to join BMGs with themselves or
crystalline materials, and they can be classied into two kinds
generally. One is liquid phase welding method, such as laser welding,
electron beam, pulse current, etc. [36]. In these methods, the
temperature in the nugget is higher than the melting point of
work-pieces, which will inevitably induce the crystallization from
the amorphous structure or the change of chemical composition in
the metallic glass. Another is performed in a solid state, which
includes friction stir welding [7,8], explosion welding [9] and diffu-
sion welding [10], etc. In these methods, the temperature rise is
relatively low and an excellent metallurgical joining can be obtained
without any crystallization in the BMGs.
Friction stir welding (FSW) is a novel solid-state welding method,
which has found particular applications in the aerospace and auto-
motive industries. During FSW, localized heating due to friction
between the tool and workpieces, and the plastic deformation of
materials is produced, which makes the materials around the pin soft.
By the combination of tool rotation and translation movement of
material from the front to the back of the pin, a welded joint in the
solid state is realized [7]. Comparing with other welding method, FSW
process can be accomplished far below the melting point of the work-
pieces. So, it shows a strong candidate for the joining of BMGs with
themselves or with crystalline materials. For example, Sun et al. [7]
have successfully friction stir welded two Zr-based BMG plates
together without crystallization and defects in the stir zone by using
a rotation tool with large shoulder. Kawamura et al. [11] rst applied
FSW to the joining of Zr
55
Cu
30
Al
10
Ni
5
BMG with AlZnMgCu alloys,
which shows strong bonding and mixed microstructure with BMG
particles in the stir zone reported by Wang et al. [6]. Therefore, it is
worthwhile to investigate welding between BMGs and commercial
light alloys by means of FSW.
In the present work, a Zr
64
Cu
26
Al
8
BMG and commercial pure
aluminum were subjected to FSW process to investigate the weld
ability of these dissimilar materials. Since the aluminum alloys
have a low melting point and the temperature rise during the
FSW process was said to be lower than the onset crystallization
Contents lists available at ScienceDirect
journal homepage: www.elsevier.com/locate/msea
Materials Science & Engineering A
0921-5093/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.msea.2013.09.035
n
Corresponding author at: Faculty of Materials and Optoelectronics Physics,
Xiangtan University, Xiangtan, Hunan 411105, China. Tel./fax: 86 731 58298119.
E-mail addresses: lin_j_g@xtu.edu.cn, lin_j_g@163.com (J.G. Lin).
Materials Science & Engineering A 588 (2013) 196200
temperature (T
x
) of Zr
46
Cu
46
Al
8
BMG. After FSW of Zr
46
Cu
46
Al
8
BMG with pure aluminum, the microstructure evolution at the
interface and the mechanical properties of the welded joint were
investigated.
2. Experimental procedure
A plate of Zr
46
Cu
46
Al
8
BMG with 2 mm in thickness was prepared
by injection cast into water-cooled copper mold in an induction
melting furnace, and it was friction stir but welded with a commercial
pure aluminum plate 4.5 mm thick at a welding speed of 75 mm/min
and the tool rotation speed of 1500 rpm. The tool used is made of the
high temperature high speed steel which has a shoulder of 12 mm in
diameter and a cylindrical pin of 8 mm in diameter and 5 mm in
length. During the FSW process, the BMG was put on the down side,
and the pure aluminum on the up side. The work-piece was hole
drilled the pure aluminum side and slightly touching the BMG side.
Fig. 1 schematically shows the tool and work-piece positions during
the welding.
The joint was cross-sectioned perpendicular to the welding
direction for microstructure observation and hardness measure-
ment. The microstructure observation was conducted on a scan-
ning electron microscope (SEM). The phase constitution at the
BMG/Al interface was detected by X-ray diffraction (XRD). The
micro-hardness prole was measured along the center line of the
cross-section with an applied load of 4.9 N and dwell time of 10 s.
At least two rectangle tensile specimens with a gauge length of
3 mm and width of 2 mm were machined perpendicular to the
welding direction with the stir zone located in the center of the
specimen. The tensile tests were carried out on a CTM6001
machine at a cross-head speed of 0.075 mm/min.
3. Results
Fig. 2 shows a typical XRD pattern obtained from the as-cast
Zr
46
Cu
46
Al
8
plate. It exhibits a broad halo peak, and no crystalline
diffraction peak is detected on the XRD pattern. The result
indicates that the plate used is in fully amorphous structure.
Fig. 3a shows the back scattering SEM image at the cross-section
across the interface of the joint. A clear interface is observed between
the BMG and pure Al, and no defects are detected in the joint
indicating that the sound joining was achieved between the BMG
and pure Al by FSW. Moreover, some bright and gray particles
are detected in the aluminum side near the interface. Energy
dispersive spectroscopy (EDS) analyses were conducted at the
different positions of the joint marked with A, B, C and D, and the
EDS spectra at these positions are shown in Fig. 3b. The EDS analysis
results reveal that the bright particle (marked with B) contains
64.21%Zr, 26.74%Cu and 9.05%Al (in atom percent), which is almost
identical to the composition of BMG matrix. So the bright particles
are the BMG fragments stirred into the aluminum matrix in the FSW
process. The gray particle is an Al-rich phase containing 68.87%Al,
14.02%Cu and 17.11%Zr (in atom percent).
Fig. 4 shows the XRD patterns measured at the BMG/Al interface in
the stir zone. The XRD curve exhibits a superimposition of several
sharp peaks characteristic for crystalline phase on a broad halo peak
from the amorphous phase, indicating the existence of a mixture of
the amorphous and some crystalline phases. After indexing, one can
see that the sharp crystalline peaks come from pure Al and the
unknown crystalline phases. Combining the EDS analysis results
mentioned above, the unknown phase can be identied to be an
Al-rich phase. As a result, during the FSW, the BMG fragments were
stirred into the aluminum matrix, which can react with the Al to form
the Al-rich phase, and the residues still maintained the amorphous
structure.
Fig. 5 shows the hardness prole of the stir zone across the BMG/
Al interface. The zero position denotes the interface between the two
different materials. On the left side to the zero position, the hardness
is about 545 HV, which exhibits the intrinsic high strength of BMGs.
However, the hardness suddenly drops down to 150 HV around the
zero position, the BMG/Al interface, and its value varied within a
wide range depending on the amount of the BMG fragments
involved in the hardness tests. It is clear seen that for the Al matrix
without BMG fragments in the stir zone, the hardness is as low as
about 50 HV, which is slightly higher than that of the base metal
(about 25 HV). In the DSW process, the Al experienced remarkable
deformation, and the rened microstructure in the stir zone due to
the dynamic recrystallization [7] and strain hardening may be
responsible for the increased hardness of the aluminum in the stir
zone. However, when the indent was performed on the region
containing BMG fragments, the hardness value can be signicantly
increased. As for the BMG fragments, the hardness reached a value of
about 500 HV. Obviously, the hardness value in the stir zone is higher
than that of the aluminum metal matrix due to the presence of the
reaction particles and embedded BMG fragments.
The tensile tests were carried out to evaluate the mechanical
properties of the BMG/Al joint. The stress-strain curve of the joint
is shown in Fig. 6, and for comparison, the stressstrain curve of
pure Al is also illustrated in Fig. 6. From the curves, the ultimate
tensile strengths of the joint and pure Al are about 195 MPa and
Fig. 1. Schematic illustration of the positions of the tool and work-piece during
the FSW.
Fig. 2. XRD pattern of the as-cast Zr
46
Cu
46
Al
8
plate.
F.P. Li et al. / Materials Science & Engineering A 588 (2013) 196200 197
210 MPa, respectively. The BMG/Al joint exhibits reduced strength
and ductility with the joining efciency being about 92%.
Fig. 7 shows SEM images of the tensile fracture surfaces of the
BMG/Al joint. From the appearance of the fractured sample, the
tensile specimen usually fractured on the aluminum side in the
stir zone very close to the BMG/Al interface. The location of the
fracture implies that the bonding of the BMG/Al interface is
excellent and stronger than the stir zone. Careful observations
reveal that two distinct regions exist on the fracture surface of the
joint (see Fig. 7a). One region is characterized by large dimples and
tearing ridges (see Fig. 7a and b), implying that the pure Al matrix
underwent a large plastic deformation during tensile test. Another
region of the fracture surface is characterized by the cleavage
plane, which caused by the fracture of the BMG particles or Al-rich
phases in the stir zone (see Fig. 7c). The fracture mode in the stir
zone implies that, during the tensile test, the large hard and brittle
BMG particles or Al-rich phases induced non-uniform deformation
in the stir zone, and these large particles were rstly fractured at
relatively low stress due to the load transfer from the matrix. As a
result, the BMG fragments embedded in the Al matrix will
deteriorate the mechanical properties of the joints, and thus, the
tensile properties of the joint are lower than that of the Al matrix.
4. Discussion
During FSW, the materials for welding undergo a high strain and
high strain rate process. This kind of severe plastic deformation is
Fig. 3. Back scattering SEM image showing the cross-section across the interface of FSW BMG and aluminum (a) and the EDS spectra at the positions marked with A, B, C, D
in Fig. 3(b).
F.P. Li et al. / Materials Science & Engineering A 588 (2013) 196200 198
necessary for the joining of conventional crystalline materials like Al,
Cu, Ti and Mg alloys, etc. However, the plastic deformation or high
temperature will inevitably bring risks of brittle failure or crystal-
lization to the BMGs. As a kind of metastable metallic materials, BMG
may transform to a stable state with the reduction of the total free
energy through crystallization from the amorphous structure if the
BMGs are exposed in the supercooled liquid region for long time or at
temperature higher than T
x
[12,13]. It was reported that, during FSW
of BMG to Al alloys, the temperature rose in both BMG side and Al
side, which may be higher than the onset glass transition tempera-
ture (T
g
) but less than T
x
of the Zr
46
Cu
46
Al
8
BMG report by Pampillo
et al. [14]. Therefore, the BMG was supposed to be deformed in the
supercooled liquid region, and the viscous ow of the BMG would
benet its mixing with Al alloy without the formation of defects and
crystallization fromthe BMG. However, pure aluminumhas a melting
point higher than aluminum alloys, which indicates that higher
temperature is necessary for the FSWof pure aluminum. By using the
same machine, the peak temperature for FSWof pure aluminumwas
measured between 480 and 580 1C, higher than the T
x
of Zr
46
Cu
46
Al
8
BMG. The high temperature provides the thermodynamic preference
for the crystallization of the amorphous structure. However, the
nucleation of a crystalline phase is a time-depended process and an
incubation period is necessary before the occurrence of the crystal-
lization from the amorphous structure. It was reported that the
incubation time for the crystallization of the Zr
46
Cu
46
Al
8
BMG is
about 10 min at 500 1C. Xie et al. [12] reported the conclusion. As a
result, the thermally induced crystallization of the Zr-based BMG can
be avoided due to the short time in the FSW process.
It is interesting to be noted that the BMG particles being stirred
into the aluminum matrix reacted with Al to form an Al-rich phase,
but no reaction layer are not detected between the BMG/Al interface.
It can be seen that, in the stir zone, the Al and the BMG particles
underwent severe plastic deformation in the FSW process, and the
severe plastic deformation may enhance the interfacial diffusivities
[13,15]. Moreover, the curvature of the BMG particles, especially for
the ne particles, at the contact surface between BMG and Al can
drive the owof atoms. So, it is reasonable that the reaction between
BMG particles and Al occurred in the stir zone.
After welding, the mechanical properties of the welded joints can
be affected by either the microstructure renement or the embedded
BMG fragments in the aluminum matrix. However, the microstruc-
ture renement of aluminum in the stir zone is not expected to
improve the mechanical properties. The annealing soft effect of
aluminum will decrease the tensile strength, which shows the same
phenomena as that in the hardness tests. In addition, we found that
blocky BMG fragments would fracture from the BMG plate and
would be mixed with aluminum in the stir zone if the rotations tools
were moved into the BMG side. As a result, voids usually formed
between the BMG blocks and the aluminum matrix due to the
different volume shrinkage when cooled from the high temperature.
The formation of void will decrease the mechanical properties of the
joint and lead to early fracture of the materials. To prevent these
problems, the rotation tool is often moved to the crystalline materials
side during the welding process to reduce the intense interaction
between the tools and the BMG. On the other hand, the possible
formation of the micro-voids around the BMG fragments might split
the continuity of the matrix, which may act as the source of the crack
growth, resulting in the early fracture of the materials. In the present
study, the BMG plate is slightly touched with the rotation tools. Thus,
only small pieces of BMGs are stripped off to stir into the aluminum
side, which greatly reduces the formation of voids around the BMG
fragments. As a result, the tensile strength of the welded joint is high,
which reaches 92% of the aluminum metal matrix.
5. Conclusions
1) A defect-free FSW Zr
46
Cu
46
Al
8
BMG and pure Al joint was
successfully achieved by offsetting the pin to the aluminum
side and slightly touching the BMG side.
Fig. 4. XRD patterns measured at the interface between the BMG and the Al plate.
Fig. 5. Hardness prole in the stir zone across the BMG/Al interface.
Fig. 6. Tensile stressstrain curve of the BMG/Al joint and pure Al.
F.P. Li et al. / Materials Science & Engineering A 588 (2013) 196200 199
2) The sire zone consists of some BMG particles being stirred into
the aluminum matrix and Al-rich phases. The BMG fragments
can react with the Al to form the Al-rich phase, and the
residues still maintained the amorphous structure. However,
no crystallization and reaction layer are detected at the inter-
face between the BMG/Al.
3) The strength of the FSW BMG-pure Al joint reaches up to 92% of
pure aluminum, and the joint fractures in the stir zone close to
the interface of BMG/Al. The presence of the large BMG
particles and Al-rich phase in the stir zone is responsible for
the reduction of the strength of the joint.
Acknowledgments
This work was partially supported by National Natural Science
Foundation (10972190), PCSIRT (IRT1080), Hunan Province Science
and Technology Planned Project (2012GK2024), the Natural
Science Foundation of Hunan (13JJ3063) and the research project
of the Education Department of Hunan Province (12C0376).
References
[1] M.M. Trexler, N.N. Thadhani, Prog. Mater. Sci. 55 (2010) 759839.
[2] S.V. Madge, D.V. Louzguine-Luzgin, J.J. Lewandowski, A.L. Greer, Acta Mater. 60
(2012) 48004809.
[3] S. Pauly, S. Gorantla, G. Wang, U. Khn, J. Eckert, Nat. Mater. 9 (2010) 473477.
[4] G. Wang, Y.J. Huang, M. Shagiev, J. Shen, Mater. Sci. Eng. A 541 (2012) 3337.
[5] J. Kim, Y. Kawamura, Scr. Mater. 56 (2007) 709712.
[6] D. Wang, B.L. Xiao, Z.Y. Ma, H.F. Zhang, Scr. Mater. 60 (2009) 112115.
[7] Y. Sun, Y. Ji, H. Fujii, K. Nakata, K. Nogi, Mater. Sci. Eng. A 527 (2010)
34273432.
[8] K.J. Hodder, H. Izadi, A.G. McDonald, A.P. Gerlich, Mater. Sci. Eng. A 556 (2012)
114121.
[9] B.A. Greenberg, M.A. Ivanov, V.V. Rybin, O.A. Elkina, O.V. Antonova, A.M. Patselov, A.
V. Inozemtsev, A.V. Plotnikov, A.Y. Volkova, Y.P. Besshaposhnikov, Mater. Charact.
75 (2013) 5162.
[10] L. Liming, Z. Meili, P. Longxiu, W. Lin, Mater. Sci. Eng. A 315 (2001) 103107.
[11] Y. Kawamura, Y. Ohno, Scr. Mater. 45 (2001) 127132.
[12] G.M. Xie, Z.Y. Ma, L. Geng, Scr. Mater. 57 (2007) 7376.
[13] H.N.B. Schmidt, T.L. Dickerson, J.H. Hattel, Acta Mater. 54 (2006) 11991209.
[14] C.A. Pampillo, H.S. Chen, Mater. Sci. Eng. 13 (1974) 181188.
[15] Y. Kawamura, Mater. Sci. Eng. A. 375377 (2004) 112119.
Fig. 7. SEM images showing the tensile fracture surfaces of the BMG/Al joint.
F.P. Li et al. / Materials Science & Engineering A 588 (2013) 196200 200