Materials Characterization 135 (2018) 265–269

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Materials Characterization
journal homepage: www.elsevier.com/locate/matchar

Microstructure detection of Mg-Zi-Ti-Si amorphous composite coating T

prepared by SMAT
⁎
Ke Chena, , Hemei Yanga, Junshan Gaob, Yong Yanga
a
College of Engineering, Nanjing Agricultural University, Nanjing 210031, China
b
College of Materials Science and Engineering, Anhui University of Science and Technology, Huainan, Anhui 232001, China

A R T I C L E I N F O A B S T R A C T

Keywords: The Mg-Zn-Ti-Si coating was prepared on Mg alloy through surface mechanical attrition treatment (SMAT)
Amorphous coating which was simple and low-cost. The microstructure and phase composition of coating were detected through a
SMAT scanning electron microscope (SEM), an X-ray diffractometer (XRD) and a high resolution transmission electron
Microstructure microscope (HRTEM). The results demonstrated that the layer thickness, which depended on the rotation speed,
Phase structure
was 20–80 μm. Although the coating was rough, it was well combined with the matrix. The XRD pattern and
HRTEM image analysis demonstrated that the coating contained both amorphous and crystalline phases (Zn,
Mg7Zn3 and Si). The process also led to matrix surface strengthening; the mechanisms are solid solution and
grain refinement.

1. Introduction example, Romankov et al. [14] prepared amorphous/crystalline layer

The magnesium alloy is especially known for its corresponding low
density and recyclability. In contrast, the corresponding wide utiliza-
tion is inhibited due to the low hardness, poor wear-resistance and
weak corrosion-resistance. The surface treatments are considered effi-
cient approaches to the improvement of Mg alloy properties. A high
number of specific methods were developed and resulted in various
coatings [1–3], among which the amorphous coatings were proved to
be novel and attractive. The metal glass display high strength, high
rigidity along with anti-corrosion and anti-abrasion. Therefore, the
amorphous alloy coating is also regarded as an effective surface im-
provement for metals [4–7]. For instance, Fe-based amorphous coating
(FeCrMnWMoSi) was verified to be suitable protective layer of in-
dustrial components served in marine environment for its excellent
resistance to pit corrosion [6]. Analogously, the Mg alloys with metal
glass coatings is expected to be enhanced in the surface properties and
become widely utilized for key parts in industries such as vehicles,
small machinery and biomaterials [8–11].
The surface mechanical attrition treatment (SMAT) is a relatively
new surface processing method. The initial form of SMAT is the shot
peening which was utilized in the nanocrystalline layer preparation
[12,13]. In recent years, a series of coatings or layers, such as alloy
coatings, composite layers and amorphous coatings were prepared by
the SMAT on the Ti/Cu/Al/Fe alloy matrix [14–20]. Various specific
ways for surface attrition treatment were also developed. As an
on Cu plates through ball collision caused by mechanical vibration,
constituting a form of SMAT. The amorphous Ti-Cu-Al coating was
produced on a Ti alloy substrate by Chen et al. [17] through high-en-
ergy mechanical alloying, another form of SMAT. Reference [20] also
reported the gradient structure Mg-Cu-Y amorphous alloy coating was
prepared on Mg alloy via similar processing. All these studies reflected
that the amorphous coatings could evidently improve the properties of
metal substrate, such as the rigidity and the corrosion resistance.
Consequently, the SMAT is a novel way for glass metal coating pre-
paration; it was expected to be applied on a high number of metal
matrices due to the corresponding convenience and efficiency.
At present, there are few amorphous coatings on magnesium alloy
surface were prepared by SMAT; relative research is rare and necessary.
Therefore, in this study, an amorphous composite layer on the AZ91D
alloys was prepared by high-energy ball milling, a way of SMAT. The
equipment utilized was inexpensive and the process cost was low. In
this article, the preparation, microstructure and phase structure of Mg-
Zi-Ti-Si coatings produced by this method are mainly reported.
2. Experimental Procedures
The commercially available AZ91D Mg plate was selected as sub-
strate. The Mg powder (> 99.9 wt%), the Zn powder (> 98 wt%), the
Ti powder (> 99.8 wt%) and the Si powder (> 99.9 wt%) were uti-
lized in the coating preparation. Firstly, the metal powders of Mg, Zn, Ti

⁎
Corresponding author.
E-mail address: ckyf@njau.edu.cn (K. Chen).

https://doi.org/10.1016/j.matchar.2017.11.051
Received 18 February 2017; Received in revised form 22 October 2017; Accepted 24 November 2017
Available online 26 November 2017
1044-5803/ © 2017 Elsevier Inc. All rights reserved.
K. Chen et al.
Table 1
SMAT parameters and roughness of samples.
No. 1 2 3
Duration/h 4 4 4 (such as Zn) adhered to the matrix at first and the initial coating was
Rotation speed/(r/min) 350 400 450
Roughness (Rα)/μm 1.703 2.356 2.214
and Si were entirely mixed in the atom ratio of 60:30:5:5, respectively.
This ratio was proved suitable for the easy amorphous alloy formation
from these elements in our preliminary experiments. Subsequently, the
AZ91D alloy plate of 30 × 30 × 2 mm was fixed onto the inner wall of
the stainless steel milling tank. 10 g of the mix powder and the stainless
steel milling balls (Φ = 20 mm, 10 mm) were also added into tank. The
ball to powder ratio (BPR) was 15:1 by weight. The experimental ap-
paratus was similar to that in reference [21]. The difference was that
the matrix plate was fixed near the bottom of milling tank to enhance
coating efficiency. Then, the tank was vacuumized and filled with Ar
gas (> 99.9%) for three times to prevent oxidation. Finally, the sealed
tank was set in a XQM-4L planetary ball mill and SMATed for 4 h. Three
samples were prepared at various rotation speeds which showed in
Table 1.
After surface treatment, the plates were dipped in acetone and
washed by an ultrasonic cleaner. The sample surface roughness was
detected by a JB-4C roughometer. The microstructure of the surface and
cross-section was observed by the Hitachi S4800 scanning electron
microscope (SEM); the coating chemical composition was analyzed by
an energy dispersive spectrometer (EDS) mounted on the SEM. The
phase composition and crystal structure were identified through the
Panalytical Xpert powder X-ray diffractometer (XRD) and the FEI
Tecnai G2 F30 high resolution transmission electron microscope
(HRTEM). The adhesion force between coating and substrate was tested
through WS-2006 acoustic emission scratch tester. The scratch loading
was increased with a rate of 20 N/min; when the loading reached the
max value of 100 N, the test was terminated. The standard diamond
Rockwell indenter scratched on the sample with a speed of 2 mm/min,
and the move length was 10 mm.
3. Results and Discussion
3.1. Microstructure and Composition
Due to the coatings lack of smoothness, the roughness test was re-
quired. The test was executed on the linear area (length of 10 mm) of
the sample surface. The results, listed in Table 1, demonstrated that the
Rα1 value of sample 1 was 1.703 μm, whereas the Rα2 and Rα3 values
were 2.356 μm and 2.214 μm. As the rotation speed increased, the
coating's roughness also increased and then slightly decreased. These
(a)
Fig. 1. SEM images of coating surface on sample 2.
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Materials Characterization 135 (2018) 265–269
values were close and they were higher than that of the coatings pre-
pared by other methods, such as electroless plating [22]. The cause of
rough coating was that the raw materials were powders with various
rigidity and plasticity values. In the former stage of SMAT, plastic metal
not uniform. Certain areas containing plastic metal tended to adhere
higher amounts of powder during following processing; and these cold-
welded powders could resist the peel off. Subsequently, this area be-
came bulge and the final coating was coarse. Also, when the RS was
extremely high, the grinding effect increased and a higher amount of
powder on the bulged coating area was removed. Therefore, the coating
roughness slightly decreased when the RS exceeded 400 r/min.
The surface and the cross-section of the coatings are presented in
Figs. 1 and 2. As presented in Fig. 1, the coating surface on sample 2
was not smooth and was formed by the laminated adhesion of the de-
formed powders. No apparent pores or crevices appeared in the surface
of coating. Fig. 2 shows that the coatings on all three samples were
combined with the corresponding matrix. When the rotation speed (RS)
was 350 r/min, the coating thickness on sample 2 was 20–40 μm. A few
apertures appeared in the cross-section of layer, so that the coating was
not dense. But the apertures reduced with increasing RS. The corre-
sponding coating thickness also changed to 50–70 μm and 60–80 μm
when the RS was 400 r/min and 450 r/min, respectively. Therefore, the
coating became thicker and denser as the rotation speed increased, in
the range of this research. These phenomena occurred, because the
impact frequency of the milling balls increased along with the rotation
speed and, as a result, the adhesion efficiency was improved.
Fig. 3 presents the test results of linear scanning by the EDS. The
coating composition from the surface to the matrix was demonstrated.
Evidently, the coating was mainly composed by Mg and Zn and also
contained low amounts of Ti and Si. This element composition coin-
cided with the element atom ratio in the raw materials. The Zn content
at the area adjacent to the matrix was higher compared to the surface.
This occurred because the pure Zn had high viscoplasticity which
caused Zn conglutinate onto the matrix at the SMAT initiation. This Zn
portion was not alloyed with other metal powders during further mil-
ling. It just plays the role of the agglomerant.
3.2. Phase Analysis Through XRD
Firstly, the X-ray diffraction patterns of the matrix alloy and sample
2 were conducted and are compared in Fig. 4. The main phases of the
AZ91D alloy were α-Mg and Mg17Al12, as shown in Fig. 4(a). Subse-
quently to SMAT, the α-Mg diffraction peaks, which were caused by the
matrix, were also detected. The Zn, Mg7Zn3 and Si phases were ob-
served in the coating. Despite the crystallized phase peaks, the base line
of the pattern was noticeable. On the base line, a wide hump (red dotted
line) appeared during the arrangement, which was at 2θ ≈ 30–50°. The
relatively low broad hump corresponded to the amorphous phase in the
(b)
K. Chen et al. Materials Characterization 135 (2018) 265–269

(a) (b) (c)

Fig. 2. Cross section of coatings (a) sample 1, (b) sample 2, (c) sample 3.

120
Mg
100 Zn
Ti
80
Si

Atom %
60

40

20

0
0 20 40 60 80 100 120 140 160

distance / m
Fig. 3. The EDS linear scanning test result of the cross-section of sample 2.

Fig. 4. The XRD patterns: (a) AZ91D alloy and

sample 2, (b) diffraction peaks of α-Mg (1 0 4).

sample. In the former analysis of the EDS test result, the Zn was ob-
served to be located, adjacent to the interface boundary. This Zn por-
tion was not finely alloyed with the other elements. Therefore, dif-
fraction peaks of pure Zn crystals appeared in the XRD pattern.
As demonstrated from the patterns, the α-Mg diffraction peaks,
which came from the matrix alloy, shifted subsequently to the SMAT.
The α-Mg (1 0 4) plane peak (Fig. 4(b)), displayed a 2θ equal to 81.8°
prior to processing, where the 2θ value changed to 82.3° for sample 2.
This was interpreted as the interplanar spacing and the lattice constant
slightly decreased. The calculated interplanar spacing of α-Mg (1 0 4)
plane changed from 1.177 Å to 1.171 Å. This phenomenon is often
caused by the solid solution. During SMAT, the powders adhered onto
the matrix and consequently certain other atoms solute into the matrix
crystal under a high stress and elevated temperature. When the Si and
Zn atoms entered the α-Mg crystal, they tended to comprise a substitute
Fig. 5. Williamson-Hall plots of α-Mg in raw AZ91D plate and sample 2.
solid solution, because the atomic size differences between these

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K. Chen et al. Materials Characterization 135 (2018) 265–269

Fig. 6. The bright field HRTEM images of sample 2.

(a) (a1) (a) The coating and the matrix, (b) the crystalline in coating, (c)
the amorphous area in coating.

d= 2.41 Å

2
1 (a2
d= 2.79 Å

Mg alloy matrix
d= 2.41

(b) (b1) d= 2.41 Å

d= 2. 1 Å
=45º

(c) (c1)

(c2)

elements were low. Additionally, because the Zn atomic radius is 1.53 Å the surface rigidity and wear resistance enhancement of the material.
and Si atomic radius is 1.46 Å, being lower than the Mg atomic radius Another variation of the matrix was in the corresponding crystal
(1.72 Å), the lattice constants decreased subsequently to SMAT. This size. As an example, as presented in Fig. 4, the peak width of α-Mg (1 0
phenomenon led to solid solution strengthening, which contributes to 4) increased following the SMAT, which indicated the grain size

268
K. Chen et al.
60
49.2 N
46.7 N
Adhesion force / N
40 35.3 N
20
0 formation) image of atomic arrangement in this area (Fig. 6(c1)) pre-
350 400 450
Rotation speed / (r/min)
Fig. 7. The adhesion force of coatings prepared with different rotation speed.
decrease. According to the Williamson–Hall Eq. (1) [23] and the main
diffraction peaks of α-Mg, the crystal sizes and the lattice strain prior to
and following the SMAT were calculated.
Kλ
Bcosθ = + ηsinθ
D (1)
where D is the grain size, B is the full width at half maximum intensity
(FWHM), θ is the Bragg angle, K is the Scherrer constant (0.89), η = 2ε
is the strain, and λ is the X-ray diffraction wavelength utilized (1.54 Å).
Fig. 5 presents the Williamson-Hall plot of the α-Mg in both the raw
AZ91D plate and sample 2, which was decided by the Bcosθ/λ and
sinθ/λ values. The grain size (D) and the microstrain (ε) were derived
from the intercepts and slopes of the fitting lines. As it could be ob-
served, the α-Mg grain size in the surface of the AZ91D plate was
259.5 nm, whereas it changed to 59.2 nm subsequently to SMAT. The
grain refinement could cause both higher rigidity and strength. On the
other hand, the α-Mg microstrain following the SMAT is 0.428%, lower
than the corresponding microstrain prior to SMAT. This was the result
of solid solution, which was also observed by the lattice contents de-
crease. Therefore, effects of SMAT to the matrix included the solid so-
lution and the grain refinement. Both of these effects enhanced the alloy
matrix performance.
3.3. Phase and Interface Analysis Through HRTEM
Further analysis to sample 2 was executed through HRTEM and the
results are listed in Fig. 6. Fig. 6(a) presents the crystal lattice of the
matrix alloy. The magnified picture of area 1 (Fig. 6(a1)) displays the
clear crystal lattice, with the interplanar spacing of ~2.79 Å. Two
planes existed in Fig. 6(a2) and the corresponding interplanar spacings
were ~2.79 Å and ~ 2.48 Å, respectively. These were (1 0 0) and (1 0
1) of the α-Mg crystal. No apparent interface between the coating and
the AZ91D alloy was exhibited. Also, no apparent pores and crevices
appeared on the boundary. Therefore, the coating was firmly combined
with the matrix.
Additionally, adhesion test result (Fig. 7) provided another support
for the combination of the coating and the matrix. The adhesion forces
of three samples were 35.3 N, 46.7 N and 49.2 N. The value increases
with the rotation speed. When RS was low, small amount of apertures
still remained in the coating and at the interface, which mentioned in
previous section. During loading, the cracks initiated and expanded
from the pores, resulting in the peeling of the coating. When RS in-
creased, reinforced cold welding effect led to the denser coating and the
firmer combination to Mg alloy.
269
Materials Characterization 135 (2018) 265–269
In order to find out more detailed information about the crystal
structure, additional analysis was based on Fig. 6(b) and (c). Fig. 6(b)
presents the crystalline portion in the coating of sample 2. In Fig. 6(b1),
two planes appeared in this magnified picture of the red square area in
Fig. 6(b). The interplanar spacings were ~2.10 Å and ~2.35 Å, re-
spectively. With consideration to the analysis result of the XRD, these
planes were the (1 0 1) and the (1 0 0) of Zn crystal. The angle between
the two planes (β) was 45° which coincided with the theoretical plane
angle between planes (1 0 1) and (1 0 0).
No crystal lattice was observed in Fig. 6(c), because this area was
atom-disordered (the magnified picture of the red square area was
Fig. 6(c1)), being the amorphous part. The FFT (Fast Fourier Trans-
sents the amorphous phase feature (Fig. 6(c2)). It was similar to the
selected area diffraction pattern of the amorphous solid.
Therefore, according to the test results of both XRD and HRTEM, the
coating was a composite layer composed by amorphous and crystalline
phases.
4. Conclusions
An amorphous composite coating containing elements of Mg, Zn, Ti
and Si was deposited on AZ91D alloys through the convenient SMAT
process. The coating was mainly composed of the Zn and the amor-
phous phase, along with low amounts of Mg7Zn3 and Si. Both the
thickness and roughness of the coating were relatively high; also, the
values were firmly related to the processing parameters, such as the
rotation speed of milling. Although the coating was rough, it was well
combined with the matrix. The coating was expected to have excellent
properties due to the corresponding amorphous structure, whereas the
matrix surface was also strengthened by solid solution and grain re-
finement.
Acknowledgements
This research is supported by the Fundamental Research Funds for
the Central Universities of China (No. KYZ201657).
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