Thin Solid Films 561 (2014) 28–32

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Thin Solid Films

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

Fatigue properties improvement of high-strength aluminum alloy by

using a ZrCu-based metallic glass thin film coating
P.H. Tsai a, J.B. Li b, Y.Z. Chang b, H.C. Lin a, J.S.C. Jang a,b,⁎, J.P. Chu c, J.W. Lee d,e, P.K. Liaw f
a
Institute of Material Science and Engineering, National Central University, Chung-Li, 32001 Taiwan, ROC
b
Department of Mechanical Engineering, National Central University, Chung-Li, 32001 Taiwan, ROC
c
Department of Materials Science and Engineering, National Taiwan University of Science and Technology, Taipei 10607, Taiwan
d
Department of Materials Engineering, Ming Chi University of Technology, Taipei, Taiwan
e
Center for Thin Film Technologies and Applications, Ming Chi University of Technology, Taipei, Taiwan
f
Department of Materials Science and Engineering, The University of Tennessee, Knoxville, TN 37996, USA

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

Available online 8 July 2013 For further enhancing the fatigue properties of high-strength aluminum alloy, the coating, which was com-
bined with a layer of 200 nm ZrCu-based metallic glass thin film (MGTF) coupled with 50 nm titanium
Keywords: thin film buffer layer, was applied to coat on the surface of 7075-T6 aluminum alloy by the DC sputtering
Metallic glass method. The results show that the fatigue limit could be significantly improved from 150 MPa for the
Thin film uncoated sample to 250 MPa (66.7% increase) for the samples coated with ZrCu-based MGTF. In parallel,
Sputtering
the fatigue life of 7075-T6 aluminum alloy with ZrCu-based MGTF could be drastically improved 45 times
Fatigue property
at a stress level of 250 MPa than the bare one. The outstanding mechanical properties of ZrCu-based MGTF,
such as high strength and good adhesion between the film and the substrate, are the key factors to enhance
the fatigue resistance of the coated aluminum alloy.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction alloy substrates have been reported to be an effective way to improve

Because of the high specific ratio of strength to density for the
high-strength aluminum alloys, they are favorable applied in the air-
craft, automotive and bicycle industries. For example, the strength of
7xxx series aluminum alloys can reach over 500 MPa by precipitate
strengthening. However, one major drawback on aluminum alloys is
their relatively poor fatigue strength in contrast to steels. The typical
fatigue limit of 7xxx series high-strength aluminum alloys in the
high-cycle fatigue regime (N5 million cycles) is only about 140–
160 MPa [1]. Since most of the fatigue cracks initiate on the surface
where it suffers tension stress, the conditioning of the surface to resist
crack initiation and earlier crack growth becomes a major approach of
improving fatigue performance. Accordingly, high-strength alumi-
num alloys are usually modified by the surface treatments, such as
shot peening [2–5] and hard coating [6]. The major part of improving
fatigue endurance has been attributed to the introduction of com-
pressive residual stresses in the surface. However, the effect of shot
peening was found often overcompensates the worsening of surface
morphology and microstructure caused by shot impacts [4–7]. In
the meantime, the Zr-based metallic glass thin films (MGTFs) as a
hard coating on the surface of 316 L stainless steel and Ni-based
⁎ Corresponding author at: Institute of Material Science and Engineering, National Central
University, Chung-Li, 32001 Taiwan, ROC. Tel.: +886 3 4267379; fax: +886 4254501.
E-mail address: jscjang@ncu.edu.tw (J.S.C. Jang).
their fatigue properties significantly [8–10]. The Zr-based MGTFs pos-
sess unique properties owing to their amorphous natures such as
grain-boundary free, no segregation, isotropy, high strength and
toughness [11,12], great flexibility and good corrosion resistance
[13–16]. Some earlier reports showed that several MGTFs can be pre-
pared by electroless plating as well as sputtering with an alloy target
or elemental targets [17,18]. In this study, in order to improve the fa-
tigue behavior of high-strength aluminum alloy and to avoid the side
effect of shot peening, the improved fatigue behavior of 7075-T6 alu-
minum alloy coated by ZrCu-based MGTF by sputtering is under
investigated.
2. Experimental procedures
The specimen substrates of fatigue testing with dimensions of
4 mm H × 3 mm W × 45 mm L were machined from the as-extruded
commercial-grade 7075 aluminum alloys with T6 heat treatment
(solutionizing at 466 °C for 30 min and aging at 120 °C for 24 h
[19]). A 50-nm-thick Ti buffer layer coupled with a 200-nm-thick
Zr48Cu35.5Al8Ag8Si0.5 (ZrCuAlAgSi) films were, respectively, depos-
ited onto one surface of the heat-treated aluminum alloy substrates
by a DC sputtering system (MDX1000). The operating conditions of
DC sputtering system were set as follows: the base pressure of
1 × 10− 3 Pa, working pressure at 400 Pa, Ar flow of 5.4 sccm. No
bias voltage, 20 W sputtering power and 5-min sputtering time

0040-6090/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.tsf.2013.06.085
 P.H. Tsai et al. / Thin Solid Films 561 (2014) 28–32 29

were set for preparing the Ti buffer layer coating. A 50-V bias volt-
age, a 30-W sputtering power and a 30-min sputtering time were
set for preparing the MGTF coating. The Ti target is a 2-inch diam-
eter plate with purity of 99.99%, and the target for coating the
MGTF is one assembled rapidly quenched Zr-based alloy with the
composition the same as that of the films. X-ray diffraction (XRD)
measurements were performed in a 2θ scan configuration in the
range of 20°–80° at a fixed incident angle of 0.05°. Atomic force mi-
croscopy (Bruker DI3100 AFM, operated by contact mode with a
Si3N4 probe and a load less than 100 nN) is used to determine
the surface roughness of the thin film as well as the aluminum
alloy substrate. A MTS testing machine (MTS 858 Mini Bionix II)
is employed to carry out the four-point-bending fatigue test. The
samples are loaded so that the coated surface is under tension. De-
tails of the fatigue test are described elsewhere [10,11]. Various
stress levels are applied with an R value (minimum/maximum ap-
plied stress) of 0.1 by the load-control mode using a 10-Hz sinusoi-
dal waveform. The MTS testing results are used to plot the curves
of stress versus number of cycles to failure (S–N curves) for all
samples. The hardness of the as-deposited film is measured by
nanoindentation within one-tenth of the film thickness to avoid
the substrate effect. The adhesion of the as-deposited films on the
substrates was detected by the Scratch Tester (J&L, JLST022T) with a
200-μm-sized diamond probe. The initial load is set to 0.2 N, and the
maximum load is 100 N under indent speed of 0.08 mm/s. The fatigued
samples are examined by scanning electron microscopy (SEM, Hitachi
S4700, operated at 30 kV) to study fatigue and fracture mechanisms. To
further study the fracture mechanism, selected coated samples are also
examined by cross-sectional transmission electron microscopy (TEM,
FEI Tecni G2, operated at 200 kV). These TEM samples were prepared
from the offset areas of the MGTF-coated samples after fatigue testing
by using the focused ion beam system (FEI Quanta 3D FEG FIB, operated
at 30 kV) with special care to minimize the ion damage to samples. Fig. 2. AFM surface-roughness results of (a) as-polished Al alloy substrate and (b) Al
alloy substrate coated with ZrCuAlAgSi MGTF. (Img. Rms(Rq): root mean square
value of surface roughness; Img. Ra: arithmetic average surface roughness).
3. Results and discussion

Fig. 1 shows that in the XRD pattern of the fatigue specimen,
which was coated with ZrCuAlAgSi thin film that presents a typical
diffraction pattern of amorphous state, a diffuse hump was found be-
tween 30° and 50°. No apparent crystalline peak could be resolved ex-
cept three high-intensity crystalline peaks from the face centered
cubic-structured aluminum substrate, which is in a good agreement
with the data of JCPDS file no. 85-1327. Note that the Zr-based
MGTF is only 200-nm-thick, which makes the incident beam XRD de-
tect the microstructure of aluminum substrate. This indicates that the
ZrCuAlAgSi thin film coating would form an amorphous phase after
sputtering [9,20,21].
It is accepted that rough surfaces with defects such as polished
marks are prone to the crack initiation and propagation during fatigue
cycles. Nevertheless, a smooth surface could be obtained by coating
with the Zr-based MGTF [12,20]. As the AFM results shown in Fig. 2,
the surface roughness decreased from 7.87 nm as-polished to
3.5 nm after the ZrCu-based MGTF coating, respectively, due to the
defects on the surface being covered by the coatings. In addition,
the result of scratch test reveals that the detached load was found
to be around 90 N. This implies the adhesion between ZrCu-based

400 As-polished 7075-T6

Max. alternating stress (MPa)

With ZrCu-based MGTF

350

300

250

200

150

10000 100000 1000000 1E7 1E8

2θ (Degree) Number of cycles to failure

Fig. 1. XRD patterns of the fatigue test specimen with ZrCuAlAgSi MGTF coating and Fig. 3. S–N curves for 7075-T6 aluminum alloys without and with ZrCuAlAgSi MGTF
the ZrCuAlAgSi bulk metallic glass. coating. Arrows indicate the run-out data after 1 × 107 cycles without failure.
30 P.H. Tsai et al. / Thin Solid Films 561 (2014) 28–32

Fig. 4. SEM fractographs of (a) uncoated and (b) ZrCu-based MGTF coated 7075-T6 Al alloy specimens fractured at 300 MPa and 350 MPa, respectively. (I), (II) and (III) in (a) and
(b) are denoted as crack-initiation, crack-propagation and final-fast-fracture regions, respectively.

MGTF and aluminum alloy substrate is comparable to the level of in-
dustrial requirement.
The S–N fatigue curves of 7075-T6 Al alloy substrates with and
without ZrCu-based MGTF coating are shown in Fig. 3. Arrows in
the curves indicate the run-out data that the test is interrupted
when the samples survive for more than 107 fatigue cycles without
failure. At the stress level of 300 MPa, the fatigue life is enhanced
16 times from 7.5 × 104 cycles for the bare substrate to 1.2 × 106 cy-
cles for the as-deposited one. When the stress reduces to 250 MPa,
the fatigue life is further improved to more than 45 times from
2.2 × 105 cycles for the uncoated sample to N 107 cycles for the as-
deposited one. On the other hand, the fatigue limit is improved
from 150 MPa for the uncoated sample to 250 MPa for the as-deposited
samples. Obviously, the as-deposited samples perform much better fa-
tigue resistance than the bare substrates. Nevertheless, the fatigue life of
the as-deposited sample decreases to 4.0 × 105 cycles at the stress level
of 400 MPa (near the yield stress of the substrate—455 MPa for the
7075-T6 Al alloy). This is due to yield of the substrate which determines
the fatigue life. In other words, the ZrCu-based MGTF coating could pro-
tect the substrate at the early stage of fatigue life but could not sustain
the large deformation at high stress level. The result is catastrophic film
peeling-off and subsequent substrate fracture.
In literature, several previous reports [9,22,23] proposed that the
improvement of fatigue properties in the thin film coated sample
can be attributed to several major factors: (1) the surface roughness
of the coating, (2) the mechanical properties of the coating, (3) the
adhesion capability between the coating and the substrate and
(4) the existence of compressive residual stresses of the coatings. In
the present case, the substantial improvement of the fatigue proper-
ties might be attributed to the good adhesion of MGTF/Ti coating to
substrate which benefited from the Ti buffer layer coating, high
strength and good flexibility of the coated MGTF, as reported in the
Pt- and Zr-based bulk-metallic glass [11,24,25]. Fig. 5 illustrates the
SEM fractographs of typical fracture surfaces of uncoated and coated
samples tested at σmax = 300 MPa and σmax = 350 MPa, respectively.
The whole fatigue–fracture surface consists of three distinct regions:
(I) crack initiation on the surface with tension stress, (II) crack propaga-
tion and (III) final-fast-fracture areas. Fig. 4(a) and (b) show that the
fractures are likely initiated at the surface cracks for both coated and
uncoated samples. The crack propagation and final-fast-fracture are sim-
ilar in both cases. Although some local film delamination is found to be
associated with cracks as shown in Fig. 5(a), the overall MGTF coating
still remains intact with the substrate, and no obvious macroscopic film
delamination is found even after severe plastically deformed as shown
in Fig. 5(b). Additionally, the good film adhesion with the substrate
after the high-stress fatigue test suggests the excellent flexibility of the
ZrCu-based MGTF could accommodate the fatigue deformation.
Moreover, the compressive residual stress of the Zr-based MGTF has
been estimated about 2.0 GPa by Stoney's equation in our previous re-
port [9], and the high strength of the ZrCu-based MGTF (hardness of
4.9 GPa relative to 1.7 GPa of the 7075-T6 Al alloy) have made the film
strong enough to protect the substrate surface from the crack initiation.

a b

10 μm

Fig. 5. SEM fractographs of 7075-T6 Al alloy coated with ZrCu-based MGTF fractured at 350 MPa with ~2 × 105 fatigue cycles; (a) top view image and (b) enlarged tilt-view image
of the fracture area on the tension surface.
 P.H. Tsai et al. / Thin Solid Films 561 (2014) 28–32
During the fatigue test, the defects generated inside the substrates
and resulted in forming slip bands or cracks, which propagated to-
ward the surface and a pile-up layer between film and substrate, as
shown in Fig. 6. Nevertheless, cracks starting from the interface
were also observed in Fig. 6(a). However, the strong adhesion with
the substrate even on the offset area, a pimple-like appearance on
the film surface, would protuberate from the substrate, as illustrated
in Fig. 6(b). This suggests that the ZrCu-based MGTF with their
great flexibility would retard the defects to appear on the surface.
Consequently, our ZrCu-based MGTF coating can restrict the surface
offset because of its good adhesion, high strength and great flexibility,
thus yielding an improved fatigue property. Once the results were
categorized, there were found to be two failure modes of the defect
propagation. One is that the cracks open up on the substrate surface,
especially the free edge, propagating through the sample. The other is
that the slip system of the substrate, as the illustration shown in
Fig. 7(a), generated a slip band and formed an extrusion defect offset
on the surface that cracked, which led to the film breaking in Fig. 7(b).
In Fig. 7(c), the crack growth with loading cycles resulted in the sam-
ple failing.
Fig. 6. Cross-sectional TEM images taken from the sample coated with ZrCu-based
MGTF after fatigue test at 350 MPa and 2 × 105 cycles. (a) One crack initiated at the in-
terface between the substrate and MGTF; insert is the enlarged image of the dashed
circle in Fig. 7(a). (b) One pimple-like appearance on the film surface, which
protuberate from the substrate, shows the high density of slip bands; insert is the en-
larged image of the dashed circle in Fig. 7(b).
31
Fig. 7. Schematics of different stages showing a slip system resulted in sample failure at
fatigue test. (a) Initiation state: offset formation. (b) Dislocation pile up resulting in
crack formation at the offset. (c) Crack opened up on surface led to film peeling off.
ZrCu-based MGTF has demonstrated to be as a protective layer to
enhance the fatigue life of 7075-T6 Al alloy. The MGTF provides a
smooth surface than the bare substrate to reduce the crack initiation
area. The outstanding mechanical property of ZrCu-based MGTF, in-
cluding higher strength than the substrate, when accompanied by
flexibility, certainly restricted the crack formation on the substrate
surface.
4. Conclusions
This study revealed that the smooth surface, the excellent adhe-
sion and the high strength of MGTF have a significant effect on im-
proving the fatigue properties of 7075-T6 Al alloy. By means of a
thin-layer ZrCu-based MGTF coating, the fatigue life of the 7075-T6
Al alloy could be increased by 45 times at the maximum applied
stress of 250 MPa, and the fatigue limit could be increased by 66.7%,
from 150 MPa to 250 MPa. The superior mechanical properties of
the ZrCu-based MGTF, such as the high strength, great flexibility
and good adhesion to the substrate are the major factors to improve
the fatigue endurance of the crystalline substrate. Therefore, the
ZrCu-based MGTF is believed to be a promising coating material for
enhancing the fatigue properties of high-strength aluminum alloys
with many industrial applications.
Acknowledgments
The present work was supported by the National Science Council
of Republic of China in Taiwan (grant nos. NSC101- 2120-M-110-
007 and NSC101-2221-E-008-043-MY3). PKL appreciates the support
of the National Science Foundation (grant nos. DMR-0909037 and
CMMI-0900271).
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