Vacuum 191 (2021) 110297

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Vacuum
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Evolution of surface morphology, roughness and texture of tungsten

disilicide coatings on tungsten substrate
Yingyi Zhang a, *, Tao Fu a, Kunkun Cui a, Fuqiang Shen a, Jie Wang a, Laihao Yu a, Haobo Mao b
a
School of Metallurgical Engineering, Anhui University of Technology, Maanshan, 243002, Anhui, China
b
School of Materials Science and Engineering, Jiangsu University, Zhenjiang, 212013, China

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

Keywords: The hot dip silicon-plating method is considered as a promising surface coating technology. However, the cor­
Tungsten disilicide relation between the process parameters and the WSi2 coatings properties is unclear entirely. In this work, the
Microstructure SEM, TEM, AFM combining with EBSD methodology are applied to study the evolution behavior of surface and
Roughness
interface morphologies, roughness and texture of tungsten disilicide coatings. The coating mainly consists of
Tungsten
Texture
WSi2 outer layer and W5Si3 interface layer, HDS coating presents a smooth surface and dense interface. AFM
AFM results show that the particle distribution on the coating surface is homogeneous with a small surface roughness
(Ra = 124.57–422.67 nm). It is observed that at low deposition times, the surface morphologies are more ho­
mogeneous with lower surface roughness and vice versa. EBSD results show that the orientation of the columnar
WSi2 grains in the coating is perpendicular to the W substrate, the grain diameter of WSi2 range from 7.45 to
10.67 μm, and has a significant preference orientation on (100) and (110) crystal planes. This is mainly
attributable to the vigorous bombardment from the high energy Si ions prevents the formation of the lowest
energy (111) crystal plane orientation.

1. Introduction
Refractory metal silicides such as, MoSi2, NbSi2 and WSi2 are of great
research interest owing to high melting point, excellent high-
temperature strength, oxidation resistance and high-temperature
corrosion resistance [1–5]. Among them, tungsten disilicide (WSi2) is
considered to be an important oxidation protection coating material for
W and W-based alloy components [6,7]. Moreover, WSi2 emerges as
high temperature structural material due to its good oxidation resistance
at temperatures over 1300 ◦ C [8]. The oxidation reactions of WSi2 are
expressed as the following equations [9–11]:
5/7WSi2(s) + O2(g) = SiO2(s) + 1/7W5Si3(s)
2/21W5Si3(s) + O2(g) = 2/7 SiO2(s) + 10/21WO3(s)
2/7WSi2(s) + O2 (g) = 4/7 SiO2(s) + 2/7WO3(s)
3WO3(s) = (WO3)3(g)
Unlikely, it is difficult to generate continuous SiO2 protective scale
on the coating surface during the low temperature oxidation [12].
Granular WO3 forms easily because of oxygen diffusing along cracks and
holes etc. defects, which results in a catastrophic failure and pulveri­
zation [13]. Yoon [9] and Niu [14] et al. believe that the oxidation
resistance of WSi2 coating is closely related to the oxidation temperature
and the vapor pressure of WO3. When the oxidation temperature is low
and oxygen is sufficient, the oxidation products consist of WO3 and SiO2.
The formation of WO3 leads to a serious volume expansion, which causes
the WSi2 coating becomes very loose and porous, and promotes the
diffusion of oxygen. Therefore, the “pest oxidation” of tungsten and
tungsten disilicide coating seriously restricts their application in the
high temperature structural materials field [14,15]. The surface
morphology and surface roughness are considered as important indexes
(1)
of coating materials [16–18]. Good surface and interface properties can
(2) significantly improve the intrinsic oxidation resistance of coating ma­
terials [19]. Kim [20], Knotek [21], and Zhang [22,23] et al. have re­
(3) ported the microstructure and phase composition of the WSi2 coating.
Our previous studies show that the silicide coating mainly consists of
(4)
WSi2 and W5Si3 layers with higher surface silicon content (34.90 wt % to
46 wt%), and the decrease of W5Si3 layer thickness is mainly attributed
to the phase transition from W5Si3 to WSi2. Similarly, the high tem­
perature oxidation behavior has also been studied through the

* Corresponding author.
E-mail address: zhangyingyi@cqu.edu.cn (Y. Zhang).

https://doi.org/10.1016/j.vacuum.2021.110297
Received 12 April 2021; Accepted 4 May 2021
Available online 14 May 2021
0042-207X/© 2021 Elsevier Ltd. All rights reserved.
Y. Zhang et al.
Fig. 1. Schematic drawing of WSi2 coating prepared by HDS. Sample preparation (a), Siliconized WSi2 coatings (b), Coating characterization (c).
Fig. 2. The schematic diagram of the contact mode AFM.
characterization of oxide scale [24,25]. When the oxidation temperature
is higher than 1200 ◦ C, WO3 begins to volatilize quickly with a vapor
pressure over 10 Pa, which promotes the formation of the continuous
SiO2 protective layer [26]. Therefore, the volatilization rate of WO3 has
a great influence on the density and continuity of SiO2 layer. In addition,
Zhang et al. also reported MoSi2 coatings on Mo substrate obtained by
hot dip silicon-plating method (HDS), which have excellent high tem­
perature oxidation resistance. These MoSi2 coatings have good coating
surface and interface characteristics. Therefore, the HDS method is
considered as a superior and low-cost surface coating and protection
technology [27,28].
In the present study, the tungsten disilicide coatings are deposited on
the tungsten substrate by HDS method at different deposition times. The
evolution of surface morphology, roughness and texture of tungsten
disilicide coatings are observed. The 3D surface morphology, roughness
parameters, grain size and texture of WSi2 coatings are also identified.
2. Experimental procedures
2.1. Deposition process of WSi2 coatings
Tungsten metal of 99.95% purity was cut into cuboid samples (50 ×
20 × 5 mm3) and then polished by using an automatic polishing machine
with SiC papers of 500–3000 grits. The W samples were ultrasonically
cleaned in alcohol with a purity of 75%, and then dried at 120 ◦ C for 5
min in a drying oven; the ultrasonic cleaning temperature and time were
60 ◦ C and 5 min, respectively. The WSi2 coatings were prepared by HDS
method, and shown in Fig. 1. The molybdenum wires with a diameter of
2 mm were used to hang W samples, then the experiment of liquid phase
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Vacuum 191 (2021) 110297
siliconizing was carried out in a silicon bath with a purity of 99.95% at
1500 ◦ C for different deposition times (10, 15, 20, and 25 min). Finally,
the coated samples were taken out and cooled to room temperature, and
cut into cuboid shapes with a size of 10 × 10 × 5 mm3, and then were
used for morphology, roughness and texture analysis (see Fig. 1 c).
2.2. Characterization of WSi2 coatings
2.2.1. SEM, TEM and EBSD characterization
The typical microstructure of WSi2 coatings was observed by high-
vacuum, field-emission scanning electron microscopes (FE-SEM,
NANO SEM430, 1.0 nm @ 15 kV) under the secondary electron imaging
(SEI) mode. Chemical composition of the WSi2 coatings was identified
using the techniques of energy dispersive spectroscopy (EDS). In order to
observe the cross-section morphology and texture of WSi2 coatings, the
cross-sections of samples were polished by using a metallographic
vibratory polishing machine (LVP-300) with a vibration frequency of
50–400 Hzs. The interface microstructure of the WSi2 coating was
characterized by a high-resolution transmission electron microscope
(Titan ETEM G2 80-300, America FEI). Finally, the microstructure,
morphology and texture of WSi2 coatings were identified by electron
back scattering diffraction analyses (EBSD).
2.2.2. AFM characterization
Atomic force microscope (AFM) technology has become an indis­
pensable surface characterization tool, especially at the nanoscale. A
large number of literature reports show that AFM technology has been
widely used in different fields such as material science, chemical engi­
neering, electronics, medicine, molecular biology and physics [29–31].
AFM uses a cantilever with a nanoprobe to scan the surface and measure
the interaction between the sample surface and the tip to image. AFM
includes a conductive probe cantilever, sample platform connected to a
piezoelectric tube, probe testing system, and computer display system,
as shown in Fig. 2. In principle, the position of AFM probe is fixed, while
the sample platform can be moved in x, y, and z directions by piezo­
electric tubes, the movement accuracy is controlled below 1.0 nm.
A contact mode AFM (Bruker Multimode 8) was used to observe the
surface morphology of the tungsten disilicide coatings, and the scanning
range and scan rate are 80 × 80 μm2 and 0.5 Hz, respectively. In order to
obtain the average surface roughness, three different samples obtained
at the same deposition conditions were observed, and then analyzed by
the NanoScope Analysis 1.7 software (Bruker). In addition, the rough­
ness parameters were used to characterize the evolution of coating
surface morphology. The average roughness (Ra), root-mean-square
roughness (RMS or Rq) and maximum roughness (Rz) parameters
were used to examine the surface of different samples. According to the
height of the (i, j) measuring point (Z (i, j)), the roughness parameters
were defined as follows [32–35].
Y. Zhang et al. Vacuum 191 (2021) 110297

Fig. 3. AFM surface morphology images and cross-section profiles of W substrate. 2D AFM image (a), 3D AFM image (b) and cross-section profiles (c) and (d).

Fig. 4. SEM micrographs of WSi2 coatings prepared at 1500 ◦ C for 25 min, (a) surface SEI image, (b)–(c) cross section SEI images, and the corresponding EDS
spectrums (d)–(h).

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Fig. 5. TEM image (a) of zone 1 in Fig. 4b, HRTEM images of W (b), WSi2 (c), and W5Si3 (d).

1 ∑ Nx ∑Ny structures have a size of 0.5–3 μm and depth of 5–50 nm. In conclusion,
Ra = |z(i, j) − zmean | (5) the tungsten substrate has a relatively smooth surface structure with a
Nx Ny i=1 j=1
low roughness.
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
√ Ny
√ 1 ∑ Nx ∑
Rq = √ (z(i, j) − zmean )2 (6) 3.2. Surface and sectional morphology of WSi2 coating
Nx Ny i=1 j=1
The surface and cross-sectional SEM morphology of WSi2 coatings
Rz = zmax (xi , yi ) − zmin (xi , yi ) (7) prepared at 1500 ◦ C for 25 min are shown in Fig. 4 (a)-(c), and the EDS
spectrum and element composition of the micro-zones are shown in
Ny
Nx ∑
∑ Fig. 4 (d)–(h). SEM image and EDS analysis show that the surface of
where zmean is the mean height of the image, zmean = Nx1Ny z(i, j).
i=1 j=1
WSi2 coating is very homogeneous, dense and present smooth surfaces
where the Nx and Ny are the number of scanning points on the x-axis with no microscopic defects such as micro cracks or holes. SEI image
and y-axis, respectively; and zmean is the mean height of all measuring shows that the WSi2 grains have a granular structure with a diameter of
points. 5–30 μm (Fig. 4c). Cross section SEI image indicates that a good
metallurgical bond is achieved between the WSi2 coating and W sub­
3. Results and discussion strate, the interface layer is consist of W5Si3 with a thickness of 3 μm
(Fig. 4b). The previous GDS results show that the concentrations of W
3.1. Microstructure of tungsten substrate and Si elements present a gradient change law at the interface layer
[20], which greatly eliminates the thermal expansion mismatch between
The surface morphology images and cross-section profiles of W the WSi2 coating (8.5 × 10− 6 K− 1) and W substrate (5.8 × 10− 6 K− 1).
substrate were observed with AFM, and presented in Fig. 3. As shown in Because the thickness of the interface layer is small, it is difficult to
Fig. 3, the surface of tungsten substrate has many micro scratches and clearly determine the structural characteristics of the interface layer
micro-bulges with a small roughness with average roughness and root- from the SEM analysis. A focused ion beam (FIB) is used to cut the micro-
mean-square roughness of 25.1 and 32.5 nm, respectively. In order to zone of interface layer, then the selected region electron diffraction
obtain the cross-sectional profile of micro scratches, AFM line scanning patterns of WSi2 layer, interface layer and tungsten substrate are ob­
were performed along the parallel and direction perpendicular to the tained by TEM, as shown in Fig. 5. It can be seen that the outer coating
micro scratches, respectively. Three major micro scratches were and the interface layer are composed of WSi2 and W5Si3 phases,
observed with a width of 6.3–10.3 μm and depth of 71.8–111.9 nm, as respectively. The cross-sectional microstructure of coating is very dense,
shown in Fig. 3 (a), (b), and (d). On the contrary, the sizes of granular no microscopic defects such as holes and cracks are observed. A good
structures are very small compared to the micro scratches. The granular metallurgical bonding between the coating and the substrate is ach­
ieved, which effectively improves the bonding strength and thermal

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Y. Zhang et al. Vacuum 191 (2021) 110297

Fig. 6. 2D AFM images of WSi2 coatings deposited at different times. Samples: (a) S1–S3 with 10 min; (b) S1–S3 with 15 min; (c) S1–S3 with 20 min; (d) S1–S3 with
25 min.

Table 1
Surface grain sizes of WSi2 coatings deposited at different times.
Labels Sample 1 Sample 2 Sample 3 Average grain size

Min. size Max. size Avg. size Min. size Max. size Avg. size Min. size Max. size Avg. size

HDS-10 0 min 2.80 22.22 6.55 3.06 21.11 7.93 2.76 18.89 6.96 7.15 ± 0.58
HDS-15 min 3.09 21.71 10.13 3.91 27.6 10.29 3.13 22.23 10.67 10.36 ± 0.23
HDS-20 min 4.16 26.67 11.92 3.43 31.12 11.65 3.22 20.76 10.34 11.30 ± 0.69
HDS-25 min 4.21 22.33 12.45 4.47 30.18 13.53 4.26 27.78 13.15 13.04 ± 0.45

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Fig. 7. BSE micrographs of WSi2 coating [23]. (a) 10 min, (b) 15 min, (c) 20 min, (d) 25 min.

Fig. 8. Ra values of HDS WSi2 coatings and compared to other methods including SAPS and HAPC.

Table 2
Surface roughness values of WSi2 coatings measured by AFM.
Labels Sample 1 Sample 2 Sample 3 Average roughness (nm) Max roughness

Ra Rq Rz Ra Rq Rz Ra Rq Rz Ra Rq Rz

10 min 62.7 73.9 398 150 180 613 161 183 589 124.57 ± 43.98 145.63 ± 50.74 533.33 ± 96.20
15 min 189 257 1863 160 208 1566 208 254 1619 185.67 ± 19.74 226.33 ± 14.70 1682.67 ± 129.34
20 min 225 251 2262 187 208 1843 234 262 2203 215.33 ± 20.37 240.33 ± 23.30 2102.67 ± 185.19
25 min 396 478 2676 412 493 3885 460 536 4188 422.67 ± 27.19 502.33 ± 24.58 3583.00 ± 653.17

shock resistance of the coating. Fig. 5 (b) shows that the crystal plane
spacing of the W is 0.129 nm, corresponding to the (211) crystal plane
with a tetragonal structure. The crystal plane spacing of the WSi2 phase
is 0.297 nm, corresponding to the (103) crystal plane, and the electron
diffraction spots of WSi2 correspond to the [042] crystal axis of the body-
centred tetragonal crystal (C11b type). As shown in Fig. 5 (d), the crystal
plane spacing of 0.482 nm correspond to the (200) plane of the W5Si3
phase with a tetragonal structure, and the electron diffraction spots
correspond to the [040] crystal axis. The above phase composition is
consistent with the reports by Yoon [20] and Pan [36] et al. TEM and
SEM-EDS results show that the formation of WSi2 coatings follows the
chemical reaction sequence: 5W + 3Si→W5Si3 + 7Si→5WSi2.

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Y. Zhang et al.
Fig. 9. 3D AFM images of the WSi2 coatings. Samples: (a) S1–S3 with 10 min; (b) S1–S3 with 15 min; (c) S1–S3 with 20 min; (d) S1–S3 with 25 min.
3.3. Evolution of surface morphology and roughness
In order to investigate the evolution of the surface morphology of
WSi2 coating, three different samples obtained at the same deposition
conditions were observed by AFM Particle Analysis. Fig. 6 shows the 2D
AFM images of WSi2 coatings obtained with different deposition times.
The surface grain sizes were summarized in Table 1. The WSi2 grains
have a granular microstructure with a diameter of 2.76–31.12 μm,
which is in agreement with the SEI image (see Fig. 4 a). The grain sizes of
the WSi2 coatings present a gradually increasing trend with the increase
of hot dip time, which can be attributed to the grain coarsening caused
by solid state diffusion. And the average grain sizes are ranges from 7.15
to 13.04 μm. In addition, the surface morphologies have a good
repeatability with a small standard deviation of grain size from 0.23 to
0.69. In addition, the grain boundary size of WSi2 grains is also gradually
increasing, and is filled with silicon element in the green areas. This is
consistent with the previous SEM results, as shown in Fig. 7 [23].
The three-dimensional surface morphology of WSi2 coatings ob­
tained at 1500 ◦ C with various deposition times were observed using
AFM, as shown in Fig. 8. The measurement results of surface roughness
were summarized in Table 2. Images of atomic force microscopy (AFM)
indicated that those WSi2 coatings consist of many fine grains distrib­
uted uniformly throughout the surface. Lower roughness are observed
by AFM when the prepare time are 10–20 min. Although the roughness
values of the WSi2 coatings have not been previously reported. Fu et al.
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Vacuum 191 (2021) 110297
[37] reported a HAPC MoSi2 coating on niobium based alloy with a Ra
values of 8.79–15.53 μm. Li and Shi et al. [38] also reported a
plasma-sprayed LaB6–MoSi2 coating on carbon/carbon (C/C) compos­
ites with a Ra values from 20.3 to 31.5 μm, which are much higher than
our data (Ra = 124.57–422.67 nm). Table 2 shows that the surface
roughness of WSi2 coatings increases with deposition time gradually,
which are mainly due to the growth of WSi2 columnar crystals. When the
hot dip time ranges from 10 to 25 min, both Ra and Rq values are less
than 1 μm, the max roughness (Rz) are 533.33 nm, 1.68 μm, 2.10 μm,
and 3.58 μm, respectively.
The 3D surface morphology images of the WSi2 coatings are shown in
Fig. 9. The change of surface height can be accurately determined by the
cross section profiles of scan lines, and shown in Fig. 10. A smaller grain
diameter, height, grain spacing, and surface roughness are determined
at a deposition temperature of 1500 ◦ C for 10 min (Figs. 9 a & Fig. 10 a).
The corresponding average roughness (Ra) and root-mean-square
roughness (Rq) are 124.57 nm and 145.63 nm, respectively. And the
maximum vertical height or maximum roughness (Rz) is only 533.33
nm. Increasing deposition time to 15 min, the grain size and surface
roughness increases significantly (Figs. 9 b & Fig. 10 b). The corre­
sponding Ra, Rq, and Rz are 185.67 nm, 226.33 nm, and 1.68 μm,
respectively. However, the surface roughness and grain size increases
sightly when the deposition time increases to 20 min (Figs. 9 c & Fig. 10
c). And the corresponding Ra, Rq, and Rz are 215.33 nm, 240.33 nm,
and 2.10 μm, respectively. The maximum surface roughness and grain
Y. Zhang et al. Vacuum 191 (2021) 110297

Fig. 10. 3D images and cross-sectional profiles of WSi2 coatings.

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Y. Zhang et al. Vacuum 191 (2021) 110297

Fig. 11. Surface height distribution histogram of WSi2 coatings deposited at 1500 ◦ C for various hot dip times. Samples: (a) 10 min; (b) 15 min; (c) 20 min; (d)
25 min.

Fig. 12. EBSD maps of the coatings prepared at 1500 ◦ C for different hot dip times. Samples: (a) 10 min; (b) 15 min; (c) 20 min; (d) 25 min.

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Y. Zhang et al.
Fig. 13. The variation curve of grain size and aspect ratio with deposition time.
diameter are observed at deposition temperature of 1500 ◦ C for 25 min
(see Figs. 9 d & Fig. 10 d), which is owing to the contribution of the large
size WSi2 grains scattered on the surface. And the corresponding Ra, Rq,
and Rz are 422.67 nm, 502.33 nm, and 3.58 μm, respectively. Moreover,
the WSi2 grains present a granular structure with a diameter of 5–30 μm.
As shown in Fig. 10 d that the size of WSi2 grains is relatively large and
the particle height reaches the micron scale when the prepare time is 25
min, which is much higher than that of other coatings.
3D-AFM images only give the average roughness (Ra) and the root
mean square roughness (Rq), but do not provide the height distribution
ratio of WSi2 grains. The height distribution histogram just makes up for
this shortage, and the proportion of each height can be observed clearly.
Fig. 11 shows the statistical analysis histogram of surface vertical height
(Z) distribution of WSi2 coatings. It can be seen that the vertical distri­
bution of surface height could be described as a Gaussian distribution.
With the increase of deposition time, the vertical depths of the coating
surface show a trend of increasing gradually. And the corresponding
average vertical heights are 0.26, 0.75, 1.03, and 1.36 μm, respectively.
This is mainly attributing to the change of grain size on the coating
surface. The statistical analysis indicates that the WSi2 grains have low
vertical heights and the height percentages less than 1 μm are 100.00%,
96.03%, 47.35%, and 25.10%, respectively. Therefore, the WSi2 coat­
ings have a very lower surface vertical height when the deposited time
ranges from 10 to 15 min.
3.4. EBSD analysis of WSi2 coatings
The chemical compositions and crystallographic structures of WSi2
coatings were analyzed by EDS and XRD in previous studies [29]. In this
work, the EBSD were used to identify the phase constitution,
cross-section morphology, and texture evolution in silicide layers after
hot-dipping for various times, and shown in Fig. 12. The coating
thickness increases slightly when the hot dip times are 10–20 min, and
presented in Fig. 12 (a), (b) and (c). The corresponding coating thickness
are 12.73, 18.18, 24.85 μm, respectively. However, the coating thick­
ness increases sharply when the deposition time increases to 25 min, and
shown in Fig. 12 (d). The corresponding coating thickness is 36.97 μm.
Furthermore, the WSi2 coatings present a typical columnar grain
structure with a diameter of 7.45–10.67 μm. Statistical analysis of the
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Vacuum 191 (2021) 110297
grain size in cross-section coatings reveals that there is a parabolic
relation between grain size and deposition time, the largest grain
diameter is observed at hot dip time of 20 min, and presented in Fig. 13
a. However, the smallest aspect ratio is observed when the hot dip time
is 20 min, which is mainly due to the larger WSi2 columnar crystals and
the smaller coating thickness. Our previous studies have shown that the
increase of aspect ratio is beneficial to improve the bending strength of
the coating [2]. Because the increase of phase interfaces and grain
boundaries is beneficial to improve the mechanical performance of the
coating [39].
The influence of hot dip time on texture evolution of WSi2 coating is
shown in Fig. 14. The YD and XD are vertical direction and horizontal
direction, respectively. The WSi2 coating have a similar texture when
the deposition time ranges from 10 min to 20 min, and the corre­
sponding texture strengths are 20.85, 20.20 and 22.74, respectively.
When the deposition time increases to 25 min, texture strength de­
creases slightly, and the texture strength is 15.98. The texture analysis
shows that the WSi2 coating has two grains (100) and (111) with
different orientations, which is in good agreement with reported CVD
WSi2 coatings [19]. Moreover, Tortorici [40], Ito [41], and Kawanowa
[42] et al. also reported a (110) tetragonal texture component of MoSi2
on the surface of Mo and Mo–9Si–18B alloys. This is mainly due to the
same crystal structure of WSi2 and MoSi2. Chen [43] et al. found that the
(110)-orientated has lower atomic density along the growth direction,
and the (110) grains grew faster than (111) grains with the same atomic
deposition rate and finally won the competition. Therefore, the
preferred orientation of WSi2 coating could be related to the density of
broken metallic bond and relative surface energy of dominating crystal
faces of crystal structure [39]. During the hot dip siliconizing, the
vigorous bombardment from the high energy Si ions prevents the for­
mation of lowest energy (111) crystal plane orientation.
4. Conclusions
(1) A dense and homogeneous silicide coating was prepared on W
substrate by HDS method. The coating mainly consists of WSi2
outer layer and W5Si3 interface layer. The HDS coatings present
smooth surfaces with no microscopic defects such as micro cracks
or holes, and a good metallurgical bond is achieved between the
WSi2 coating and W substrate.
(2) AFM results indicates that the particle distribution on the coating
surface is very homogeneous with a small surface roughness (Ra
= 124.57–422.67 nm, Rq = 145.63–502.33 nm), the average
surface roughness is only 239.6 nm, and the largest surface
roughness is observed with a maximum average grain size at
1500 ◦ C for 25 min. The Ra, Rq, and Rz of WSi2 coatings increase
with the increase of hot dip time, which is mainly attributed to
the increase of coating thickness and WSi2 grain size.
(3) The WSi2 coatings present a typical columnar grain structure with
a diameter of 7.45–10.67 μm, and the WSi2 coatings present a
significant preference orientation on (100) and (110) crystal
planes. The preferred orientation of WSi2 coating could be related
to the density of broken metallic bond and relative surface energy
of dominating crystal faces of crystal structure. During the hot dip
siliconizing, the vigorous bombardment from the high energy Si
ions prevents the formation of the lowest energy (111) crystal
plane orientation.
Author contributions
The manuscript was written through contributions of all authors. Y.
Y. Zhang performed the Resources, Writing-Review & Editing,
Y. Zhang et al.
Fig. 14. Pole figures of WSi2 coatings on (111), (220), (311) and (331) texture prepared at different hot dip times. (a) 10 min; (b) 15 min; (c) 20 min; (d) 25 min.
Supervision, and Data Curation. Y.Y. Zhang and T. Fu performed the
SEM, EDS, TEM, and AFM measurements; K.K, Cui and T. Fu performed
the surface cleaning, sample cutting, and EBSD measurement; J, Wang,
F.Q. Shen and L.H. Yu performed the polishing of samples; Y.Y. Zhang,
K.K. Cui, and H.B. Mao performed coating depositions and image pro­
cessing. All authors have given approval to the final version of the
manuscript.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
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Vacuum 191 (2021) 110297
Acknowledgments
This work was supported by the National Natural Science Foundation
of China (No.51604049).
References
[1] Y. Pan, E.D. Yu, D.J. Wang, H. Deng, Sulfur vacancy enhances the electronic and
optical properties of FeS2 as the high performance electrode material, J. Alloys
Compd. 858 (2021), 157662.
[2] Y.Y. Zhang, S. Hussain, K.K. Cui, T. Fu, J. Wang, M.S. Javed, Y. Lv, B. Aslam,
Microstructure and mechanical properties of MoSi2 coating deposited on Mo
substrate by hot dipping processes, J. Nanoelectron. Optoelectron. 14 (12) (2019)
1680–1685.
[3] Y. Pan, D.L. Pu, E.D. Yu, Structural, electronic, mechanical and thermodynamic
properties of Cr-Si binary silicides from first-principles investigations, Vacuum 185
(2021), 110024.
Y. Zhang et al.
[4] S.L. Wang, Y. Pan, Y.H. Lin, First-principles study of the effect of Cr and Al on the
oxidation resistance of WSi2, Chem. Phys. Lett. 698 (2018) 211–217.
[5] Y.Y. Zhang, K.K. Cui, T. Fu, J. Wang, F.Q. Shen, X. Zhang, L.H. Yu, Formation of
MoSi2 and Si/MoSi2 coatings on TZM (Mo–0.5Ti–0.1Zr–0.02C) alloy by hot dip
silicon-plating method, Ceram. Int. (2021). In press.
[6] S.O. Akintunde, P.A. Selyshchev, Kinetics of growth of thin-films of Co2Si, Ni2Si,
WSi2 and VSi2 during a reactive diffusion process, Res.. Phys 6 (2016) 43–47.
[7] Y.K. Rao, Chemical vapour deposition of WSi2 thin films: equilibrium
W–Si–H–Cl–Ar system, J. Alloys Compd. 452 (2008) 116–121.
[8] G.F. Shao, X.D. Wu, S. Cui, J. Jiao, X.D. Shen, Design, formation, and property of
high emissivity WSi2-Si-glass hybrid coating on fibrous ZrO2 ceramic for reusable
thermal protection system, Sol. Energ. Mat. Sol. C. 172 (2017) 301–313.
[9] H.S. Kim, J.K. Yoon, G.H. Kim, J.M. Doh, S.I. Kwun, K.T. Hong, Growth behavior
and microstructure of oxide scales grown on WSi2 coating, Intermetallics 16 (2008)
360–372.
[10] M.Z. Alam, S. Saha, B. Sarma, D.K. Das, Formation of WSi2 coating on tungsten and
its short-term cyclic oxidation performance in air, Int. J. Refract. Met. H. 29 (2011)
54–63.
[11] E.A. Gulbransen, K.F. Andrew, Kinetics of the oxidation of pure tungsten from
500◦ C to 1300◦ C, J. Electrochem. Soc. 107 (1960) 619–628.
[12] Y. Pan, J. Wang, D. Wang, H. Deng, Influence of vacancy on the elastic properties,
ductility and electronic properties of hexagonal C40 MoSi2 from first-principles
calculations, Vacuum 179 (2020), 109438.
[13] M. Zarezadeh Mehrizi, M. Shamanian, A. Saidi, R. Shoja Razazvi, R. Beigi,
Evaluation of oxidation behavior of laser clad CoWSi–WSi2 coating on pure Ni
substrate at different temperatures, Ceram. Int. 41 (2015) 9715–9721.
[14] C.H. Zhai, Y.R. Niu, L.P. Huang, H.H. Pan, H. Li, X.B. Zheng, J.L. Sun,
Microstructure characteristics and oxidation behavior of vacuum plasma sprayed
tungsten disilicide coating, Ceram. Int. 42 (2016) 18798–18805.
[15] D.L. Pu, Y. Pan, Influence of high pressure on the structure, hardness and brittle-to-
ductile transition of NbSi2 ceramics, Ceram. Int. 47 (2) (2021) 2311–2318.
[16] G. Ghosh, A. Sidpara, P.P. Bandyopadhyay, Understanding the role of surface
roughness on the tribological performance and corrosion resistance of WC-Co
coating, Surf. Coating. Technol. 378 (2019), 125080.
[17] K. Cui, Y.Y. Zhang, T. Fu, S. Hussain, A.T. Saad, J. Wang, X. Zhang, S. Ali, Effects of
Cr2O3 content on microstructure and mechanical properties of Al2O3 matrix
composites, Coatings 11 (2) (2021) 234.
[18] M. Rahsepar, M.E. Bahrololoom, Study of surface roughness and corrosion
performance of Ni/Zn–Fe and Zn–Fe/Ni compositionally modulated multilayer
coatings, Surf. Coating. Technol. 204 (2009) 580–585.
[19] Y.Y. Zhang, Y.G. Li, C.G. Bai, Microstructure and oxidation behavior of Si–MoSi2
functionally graded coating on Mo substrate, Ceram. Int. 43 (2017) 6250–6256.
[20] K.H. Lee, J.K. Yoon, J.K. Lee, J.M. Doh, K.T. Hong, W.Y. Yoon, Growth kinetics of
W5Si3 layer in WSi2/W system, Surf. Coating. Technol. 187 (2004) 146–153.
[21] O. Knotek, R. Elsing, H.R. Heintz, Corrosion and oxidation resistance of plasma
sprayed WSi2 coatings, Surf. Coating. Technol. 30 (1987) 107–114.
[22] Y.Y. Zhang, J.M. Qie, K.K. Cui, T. Fu, X. Zhang, Effect of hot dip silicon-plating
temperature on microstructure characteristics of silicide coating on tungsten
substrate, Ceram. Int. 46 (2020) 5223–5228.
[23] Y.Y. Zhang, K.K. Cui, T. Fu, J. Wang, J.M. Qie, X. zhang, Synthesis WSi2 coating on
W substrate by HDS method with various deposition times, Appl. Surf. Sci. 511
(2020), 145551.
[24] J.K. Yoon, K.W. Lee, S.J. Chung, I.J. Shon, J.M. Doh, G.H. Kim, Growth kinetics and
oxidation behavior of WSi2 coating formed by chemical vapor deposition of Si on
W substrate, J. Alloys Compd. 420 (2006) 199–206.
12
Vacuum 191 (2021) 110297
[25] T.S.R.C. Murthy, J.K. Sonber, C. Subramanian, R.C. Hubli, A.K. Suri, Densification,
characterization and oxidation studies of TiB2–WSi2 composite, Int. J. Refract.
Metals Hard Mater. 33 (2012) 10–21.
[26] K. Kazuya, S. Akiko, K. Akira, Formation of SiO2 scale in high temperature
oxidation on WSi2, Trans. JWRI 36 (2) (2007) 51–55.
[27] Y.Y. Zhang, J. Zhao, J.H. Li, J. Lei, X.K. Cheng, Effect of hot-dip siliconizing time
on phase composition and microstructure of Mo–MoSi2 high temperature structural
materials, Ceram. Int. 45 (2019) 5588–5593.
[28] Y.Y. Zhang, W. J Ni, Y.G. Li, Effect of siliconizing temperature on microstructure
and phase constitution of Mo–MoSi2 functionally graded materials, Ceram. Int. 44
(2018) 11166–11171.
[29] F. Lofaj, M. Ferdinandy, G. Cempura, J. Dusza, Nanoindentation, AFM and
tribological properties of thin nc-WC/a-C coatings, J. Eur. Ceram. Soc. 32 (2012)
2043–2051.
[30] G. Elia, P.T. Pilar, R.M. Giráldez-Pérez, R. Prado-Gotor, F. Muriel-Delgado, Ethanol
effect on gold nanoparticle aggregation state and its implication in the interaction
mechanism with DNA, J. Colloid Interface Sci. 529 (2018) 65–76.
[31] X.N. Shi, W.H. Qing, T. Marhaba, W. Zhang, Atomic force microscopy-Scanning
electrochemical microscopy (AFM-SECM) for nanoscale topographical and
electrochemical characterization: principles, applications and perspectives,
Electrochim. Acta 332 (2020), 135472.
[32] Y. Li, J.H. Yang, Z.J. Pan, W.S. Tong, Nanoscale pore structure and mechanical
property analysis of coal: an insight combining AFM and SEM images, Fuel 260
(2020), 116352.
[33] E.S. Gadelmawla, M.M. Koura, T.M.A. Maksoud, I.M. Elewa, H.H. Soliman,
Roughness parameters, J. Mater. Process. Technol. 123 (2012) 133–145.
[34] K. Darowicki, M. Szocinski, K. Schaefer, D.J. Mills, Investigation of morphological
and electrical properties of the PMMA coating upon exposure to UV irradiation
based on afm studies, Prog. Org. Coating 71 (2011) 65–71.
[35] Y.Y. Zhang, K.K. Cui, Q.J. Gao, S. Hussain, Y. Lv, Investigation of morphology and
texture properties of WSi2 coatings on W substrate based on contact-mode AFM
and EBSD, Surf. Coating. Technol. 39625 (2020), 125966.
[36] Y. Pan, Y.P. Wu, Insight into the thermodynamic properties of tungsten disilicides,
Vacuum 155 (2018) 361–363.
[37] J. Sun, Q.G. Fu, L.P. Guo, Influence of siliconizing on the oxidation behavior of
plasma sprayed MoSi2 coating for niobium based alloy, Intermetallics 72 (2016)
9–16.
[38] C.C. Wang, K.Z. Li, X.H. Shi, Q.C. He, C.X. Huo, High-temperature oxidation
behavior of plasma-sprayed ZrO2 modified La-Mo-Si composite coatings, Mater.
Des. 128 (2017) 20–33.
[39] K. Yang, J.W. Feng, X.M. Zhou, S.Y. Tao, Microstructural characterization and
strengthening-toughening mechanism of plasma-sprayed Al2O3-Cr2O3 composite
coatings, J. Therm. Spray Technol. 21 (2012) 1011–1024.
[40] P.C. Tortorici, M.A. Dayananda, Growth of silicides and interdiffusion in the Mo-Si
system, Metall. Mater. Trans. 30 (1999) 545–550.
[41] K. Ito, T. Hayashi, M. Yokobayashi, H. Numakura, Evolution kinetics and
microstructure of MoSi2 and Mo5Si3 surface layers on two-phase Mo-9Si-18B alloy
during pack-cementation and high-temperature oxidation, Intermetallics 12 (2004)
407–415.
[42] H. Kawanowa, Y. Gotoh, Crystal growth of WSi2 on a W (110) surface, J. Cryst.
Growth 197 (1999) 163–168.
[43] W.P. Wu, Z.F. Chen, X.W. Cheng, Y.W. Wang, EBSD study of (110) orientation of
iridium (Ir) coating on niobium (Nb) substrate by double glow plasma, Nucl.
Instrum. Methods B. 307 (2013) 315–319.