J. Mater. Sci. Technol., Vol.25 No.

6, 2009

853

Friction Stir Welding of Zr55 Al10 Ni5 Cu30 Bulk Metallic Glass
to Crystalline Aluminum
Zuoxiang Qin1) , Cuihong Li1) , Haifeng Zhang1) , Zhongguang Wang1) , Zhuangqi Hu1) and
Zhiqiang Liu2)
1) Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academic of Sciences,
Shenyang 110016, China
2) School of Materials Science and Engineering, Dalian Jiaotong University, Dalian 116028, China
[Manuscript received March 20, 2008, in revised form June 3, 2008]

The Zr55 Al10 Ni5 Cu30 bulk metallic glass plate were successfully welded to crystalline aluminum plates by
using a friction stir welding (FSW) method. The welded zone was examined. No defects, cracks or pores were
observed and no other crystalline phases except for aluminum were found in the welded joint. The strength
of the joint is higher than that of aluminum. The glassy phase in the stir zone keeps the amorphous state,
showing a successful welding. The storage modulus softens over the glass transition. And the weldability was
discussed according to this phenomena.
KEY WORDS: Bulk metallic glass; Zr-based alloy; Friction stir welding

1. Introduction
Bulk metallic glasses (BMGs) exhibit many unique
characteristics such as high strength, high elastic
limit, superplasticity, special physical properties and
unique chemical properties associated with the atomic
structure. The development of new BMGs has allowed BMGs to begin to emerge as a useful material, which can outperform traditional metal in many
areas[15] . Although large size BMGs of 30 mm in
diameter had been fabricated by copper mold casting,
the size limitations had relegated the use of BMGs to
a narrow area. It is very important to enlarge the
product size of BMGs, especially enlarge the plate
size for applications. The BMGs exhibit high-strainrate superplasticity[68] and excellent workability[9] in
the supercooled liquid state above the glass transition temperature. These give an inspiration of BMGs
welding. Many researchers have reported that BMGs
were successfully welded together by explosion[10] ,
spark[11] , electron-beam[1214] , laser-beam[15,16] and
friction[1721] welding methods. However, most of
these welding methods are fusion welding. Although
the friction welding is considered as solid-state joining
process, it is only appropriates for rotated pieces and
can not be used to weld plates. Compared with these
methods, friction stir welding (FSW) is a relatively
new solid-state joining process that uses a cylindrical
pin or nib inserted along the weld seam, and this joining technique is energy ecient, environment friendly
and versatile[22,23] . Welding of the bulk metallic glass
to crystalline metal or alloy is expected to expand the
application elds of the bulk metallic glasses. In this
paper, the FSW of the BMG Zr55 Al10 Ni5 Cu30 plate
to the crystalline aluminum plate was reported.
2. Experimental
The Zr55 Al10 Ni5 Cu30 ingot was prepared by arc
melting of pure zirconium, aluminum, nickel and cop Corresponding author. Prof. Ph.D.; Tel.: + 86 24 23971785;
E-mail address: hfzhang@imr.ac.cn (H.F. Zhang).

per in puried argon atmosphere. Bulk metallic glass

plates of 2.0 mm in thickness, 15 mm in width and
60 mm in length were fabricated by copper mold casting method. X-ray diraction (XRD) result shows
the formation of a single glassy phase. The crystalline 1100 aluminum plates with the same size as the
BMG plates were used in welding process. The welding experiments were performed by using FSW machine. The rotating speed and the welding speed were
9001445 r/min and 14.636.3 mm/min, respectively.
Optical microscopy (OM) and scanning electron microscopy (SEM) observations of each FSW joint were
carried out. The polished cross-sections and top surface were etched with an aqueous solution containing
150 ml H2 O, 3 ml HNO3 , 6 ml HCl and 6 ml HF. The
energy dispersive X-ray spectroscopy (EDS) analyses
were conducted by using Oxford INCA. The glassy
structure of the welded zone was detected by D/maxrA X-ray diractometer using CuK radiation. The
thermal properties of the welded zone and the parent
amorphous alloy were examined with a NETZSCH
DSC 204 purged with puried argon gas. The dynamic mechanical response of the sample was measured using a DMA Q800 (TA Instruments) in a bending mode. The tensile test was carried out at room
temperature using an Instron 8810 testing machine
with strain rate of 5103 s1 .
3. Results and Discussion
The BMG Zr55 Al10 Ni5 Cu30 plate and crystalline
aluminum plate were welded by FSW in the conditions with pin rotating speed of 9001445 r/min and
the welding speed 14.636.3 mm/min. Figure 1 shows
the outer appearance of the BMG-aluminum welded
sample under the rotating speed 1445 r/min and the
welding speed 22.1 mm/min. The rough top surface
and the at bottom side can be seen. In the stir zone
of the joint, the plastic ow pattern is clearly seen,
and the BMG Zr55 Al10 Ni5 Cu30 is mixed with crystalline aluminum. The BMG Zr55 Al10 Ni5 Cu30 and
crystalline aluminum have been successfully welded

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J. Mater. Sci. Technol., Vol.25 No.6, 2009

Fig. 1 Outer appearance of friction stir welded BMG-aluminum sample: (a) top surface, (b) bottom side

120

(b)

Fig. 2 Microstructure of the stir zone: (a) optical micrograph of etched cross-section in stir zone, (b)
SEM image of etched top surface

by FSW. It was found that the locations of two dissimilar alloys exerted a signicant eect on the welded
joint forming and the resultant weld quality. The
BMG that has a high strength should be placed on the
advancing side to produce better welded joint, which
is dierent from the crystalline aluminum alloys[24] .
As the workpiece temperature at advancing side is
higher than that at the retreating side[25] , the higher
temperature promotes the BMG reducing its strength
and the BMG becomes soft when it is heated to the
temperature above Tg (glass transition temperature).
Figure 2 (a) and (b) show the optical micrograph
of the etched cross-section and SEM image of the
etched top surface around the interface between the
BMG Zr55 Al10 Ni5 Cu30 and crystalline aluminum. No
visible defects, cracks or pores were observed in the interface, suggesting the successful metallurgical bonding. In FSW, material is moved around the probe by
two processes. (1) Material on the advancing front
side of a weld enters into a rotational zone that rotates and advances with the probe. This material
is very highly deformed and sloughs o behind the
probe in arc-shaped features. (2) Material on the
retreating front side of the probe is entrained (but
never rotates around the probe) and lls in material on the retreating side of the probe wake[22] . In
our experiment, with the rotation of the probe, the
BMG Zr55 Al10 Ni5 Cu30 was stirred into the crystalline
aluminum and the material around the interface is a

Stress / MPa

100

80

60

40

20

0
0.00

0.02

0.04

0.06

0.08

0.10

0.12

Strain

Fig. 3 Photograph of the broken specimen and the

stress-strain curve of welded joint: (a) photograph
of the broken specimen, (b) stress-strain curve of
the welded joint

mixture of BMG Zr55 Al10 Ni5 Cu30 and crystalline aluminum, forming the arc-shaped ow patterns.
The compositions of stir zone were analyzed by
EDS. The result veries that the stir zone is a mixture of BMG Zr55 Al10 Ni5 Cu30 and aluminum with
high content of Zr and Al.
The welded joint was examined by tensile test.
The photograph of the broken specimen and the
stress-strain curve of welded joint are given in Fig. 3.
The breaking position is located at the brim of
stir zone adjoined aluminum. The ultimate tensile
strength is 110 MPa, which is equal to the strength
of aluminum plate. These tensile results indicate that
the strength of the joint is higher than that of the aluminum plate and the Zr55 Al10 Ni5 Cu30 bulk metallic
glass plate was successfully welded to crystalline aluminum plates by FSW.
Figure 4 shows the XRD pattern taken from the
cross-section around the interface between the crys-

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J. Mater. Sci. Technol., Vol.25 No.6, 2009

3
60000

Al(2

00)
0

Al(22 )

Al(3

11)

50000
40000

60
2

80

1
20000
10000

Exothermic heat flow / a.u.

(b)

(a)

100

200

300
Temp. /

400
o

200

500

600

Fig. 5 DSC curves for the bulk metallic glass before

welding (a) and for the stir zone after friction stir
welding (b)

talline Al and the BMG Zr55 Al10 Ni5 Cu30 of the stir
zone. There was a halo pattern of the amorphous
structure, and the diraction peaks of crystalline aluminum FCC phase are superposed, but no other detectable crystalline phases were observed. The result
reveals that the interface was devoid of the diversication and the BMG Zr55 Al10 Ni5 Cu30 still keeps amorphous state in friction stir processing. The dierential
scanning calorimeter was also used to conrm the existence of amorphous phase. Figure 5 shows the comparison of the DSC traces between the stir zone and
the parent BMG with the heating rate of 20 C/min.
Compared with the parent BMG, the result of the stir
zone (the mixture of BMG and aluminum) (Fig. 5(b))
exhibits similar characteristics of the glass transition
followed by one exothermic peak. The measured glass
transition temperature (Tg ) and the onset crystallized
temperature (Tx ) of the welded zone were 409 and
492 C, respectively, and were essentially the same as
those of the BMG Zr55 Al10 Ni5 Cu30 ; the supercooled
liquid region, T =Tx Tg , is 83 C. It is reasonable to
conclude that the welding temperature did not exceed
the onset temperature of crystallization.
Figure 6 shows the dynamic mechanical behavior
of BMG Zr55 Al10 Ni5 Cu30 measured at a heating rate
of 5 C/min and a frequency of 1 Hz as a function
of temperature. The sample is in an amorphous state
with a high storage modulus in the order of 56.7 GPa,

250

300

350

Temp. /

100

Fig. 4 X-ray diraction pattern of etched cross-section

in stir zone

/ deg.

418.8 C
o

Storage modulus
tan

30000

150

40

Al(222)

20

464.4 C

tan

111)

Storage modulus / MPa

Intnensity / a.u.

Al(

400
o

450

500

550

Fig. 6 Curves of storage modulus and tan with temperature at frequency of 1 Hz

which is almost constant at the temperature below

Tg . During heating, the storage modulus E exhibited
a drastic change from a high value to a low one in the
order of 2.0 GPa over the glass transition. The sample undergoes softening and gives rise to internal
friction as the loss factor tan displays a maximum
at 464 C. The abrupt dropdown in storage modulus
and the peak in loss factor are associated with atomic
motion. The sample changes from an amorphous solid
state to a viscous liquid in the supercooled liquid region.
As the BMG becomes soft when it is heated to
the temperature above Tg , superplasticity occurs in
the supercooled liquid region. In the FSW a rotating
cylindrical tool with probe is plunged into the abutting edge of BMG and aluminum plate and traversed
along the joint to be welded. Although the BMG is
so hard that plastic deformation cannot be produced
at room temperature, the heating is accomplished by
friction between the tool and the work-piece; the local heating softens the BMG around the probe and
the crystalline aluminum has a good plasticity. The
combination of tool rotation and translation leads to
movement of BMG or aluminum from the front of the
probe to the back of the probe, thereby forming the
welded joint.
4. Conclusion
Using an FSW method, the joining of the BMG
Zr55 Al10 Ni5 Cu30 plate to crystalline aluminum plate
of 2.0 mm in thickness, 15 mm in width and 60 mm in
length has succeeded. In the welded zone, no visible
defects, cracks or pores were observed and no crystalline phases except for aluminum phase were found.
The strength of the joint is higher than that of aluminum. The glassy phase in the stir zone retained the
amorphous state, showing the successful welding. The
BMG softens abruptly and shows an internal friction
peak when it is heated to the temperature above Tg .
Acknowledgements
This work was supported nancially by the Ministry of Science and Technology of China (Grant No.
2006CB605201), and the National Natural Science Foundation of China (Grant Nos. 50825402 and 50731005).
REFERENCES
[1 ] W.L. Johnson: Curr. Opin. Solid State Mat. Sci.,

856

J. Mater. Sci. Technol., Vol.25 No.6, 2009

1996, 3, 383.
[2 ] A. Inoue: Bulk Amorphous Alloys Preparation and
Fundamental Characteristics, Trans. Tech. Publications, Zrich, 1998, Ch. 1.
u
[3 ] A. Inoue: Acta Mater., 2000, 48, 279.
[4 ] W.H. Wang, C. Dong and C.H. Shek: Mater. Sci.
Eng. R, 2004, 44, 45.
[5 ] A. Inoue, B. Shen and N. Nishiyama: Bulk Metallic Glasses, eds M. Miller and P. Liaw, Springer, New
York, 2007, Ch. 1.
[6 ] Y. Kawamura, T. Nakamura, A. Inoue and T. Masumoto: Mater. Trans., JIM, 1999, 40, 794.
[7 ] Y. Kawamura, T. Shibata, A. Inoue and T. Masumoto:
Scripta Mater., 1997, 37, 431.
[8 ] Y. Kawamura, T. Nakamura and A. Inoue: Scripta
Mater., 1998, 39, 301.
[9 ] Y. Kawamura, T. Shibata, A. Inoue and T. Masumoto:
Acta Mater., 1998, 37, 253.
[10] Y. Kawamura, Y. Ohno and A. Chiba: Mater. Sci.
Forum, 2002, 386-388, 553.
[11] Y. Kawamura and Y. Ohno: Scripta Mater., 2001, 45,
127.
[12] Y. Kawamura and Y. Ohno: Mater. Trans., 2001, 42,
2476.
[13] S. Kagao, Y. Kawamura and Y. Ohno: Mater. Sci.

Eng. A, 2004, 375-377, 312.

[14] J. Kim and Y. Kawamura: Scripta Mater., 2007, 56,
709.
[15] B. Li, Z.Y. Li, J.G. Xiong, L. Xing and Y. Li: J. Alloy.
Compd., 2006, 413, 118.
[16] J.H. Kim, C. Lee, D.M. Lee, J.H. Sun, S.Y. Shin and
J.C. Bae: Mater. Sci. Eng. A, 2007, 449, 872.
[17] Y. Kawamura and Y. Ohno: Scripta Mater., 2001, 45,
279.
[18] T. Shoji, Y. Kawamura and Y. Ohno: Mater. Trans.,
2003, 44, 1809.
[19] C.H. Wong and C.H. Shek: Scripta Mater., 2003, 49,
393.
[20] T. Shoji, Y. Kawamura and Y. Ohno: Mater. Sci.
Eng. A, 2004, 375, 394.
[21] Y. Kawamura: Mater. Sci. Eng. A, 2004, 375-377,
112.
[22] M. Guerra, C. Schmidt, J.C. McClure, L.E. Murr and
A.C. Nunes: Mater. Trans., 2003, 49, 95.
[23] R.S. Mishra and Z.Y. Ma: Mater. Sci. Eng. R, 2005,
50, 1.
[24] L.E. Murr, Y. Li, R.D. Flores, E.A. Trillo and J.C.
McClure: Mater. Res. Innov., 1998, 2, 150
[25] X.L. Su, K.S. Wang and J.J. Zhou: Weld. Technol.,
2006, 35(1), 12. (in Chinese)