Surface & Coatings Technology 205 (2011) 2806–2812

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Surface & Coatings Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s u r f c o a t

Influence of nano-Al2O3 particles on the microstructure and wear resistance of the

nickel-based alloy coating deposited by plasma transferred arc overlay welding
Qing Yu Hou a,b,⁎, Zhenyi Huang a, Jing Tao Wang b
a
School of Materials Science and Engineering, Anhui University of Technology, Maanshan, Anhui 243002, PR China
b
School of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing, Jiangsu 210094, PR China

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

Article history: Nickel-based alloys powders with and without nano-Al2O3 (α-Al2O3) addition (Al2O3-free and Al2O3-added,
Received 21 May 2010 respectively) were deposited on Q235A low carbon steel using plasma transferred arc (PTA) welding
Accepted in revised form 21 October 2010 machine. Microstructures of the two deposited coatings were studied by optical microscopy, scanning
Available online 28 October 2010
electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscope (TEM). More
details about the phase compositions and their mass fractions in the deposited coatings were obtained with
Keywords:
Plasma transferred arc (PTA)
applying the Rietveld refinement method to analyze XRD patterns. Wear resistance experiment was
Nickel-based alloy conducted on one sliding wear machine to value the deposited coatings. The results show that the typical
Nano-Al2O3 hypoeutectic microstructure and the component segregation exist in the Al2O3-free coating where consists of
Rietveld refinement method γ (Ni, Fe), (Fe, Cr)7C3, and (Fe, Cr)2B phases. Adding 0.8 wt.% nano-Al2O3 particles does not change the
hypoeutectic microstructure characteristics of the Al2O3-free coating, though refines its microstructure and
decreases its component segregation. The nano-Al2O3 particles being mainly tetragonal lattice (γ-Al2O3)
which is different to that the added α-Al2O3 particles being rhombohedral lattice exist in the Al2O3-added
coating. Adding nano-Al2O3 particles increases the mass fraction of the (Fe, Cr)2B phase and decreases that of
the (Fe, Cr)7C3 phase, though such adding has little effect on the mass fraction of the total (Fe, Cr)-rich phases.
The substructure of the Al2O3-free coating is mainly dislocations. Adding nano-Al2O3 particles promotes to
form stacking faults and dislocation cell wall. The sliding wear resistance of the Al2O3-added coating is higher
than that of the Al2O3-free coating.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction
It was commonly recognized that the nickel-based alloy coatings
deposited by thermal spray or overlay welding techniques showed
good surface finish, high hardness, and excellent wear resistance [1–
5]. However, the coarser microstructures of the nickel-based alloy
coatings might result in more weight loss [6]. Therefore, several ways
were used to refine their microstructures to increase their wear
resistance, especially by adding Al2O3 particles in those coatings [7–
10]. Ding et al. [7] studied the effect of the Al2O3 particles with
different sizes on the microstructure and wear resistance of the
nickel-based alloy coating deposited by oxy-acetylene surfacing
welding. They proposed that adding Al2O3 particles could refine its
microstructure and increase its wear resistance. Zhou et al. [10] later
carried out a more detailed study about the influence of Al2O3
particles on the microstructure and wear resistance of the nickel-
⁎ Corresponding author. School of Materials Science and Engineering, Anhui
University of Technology, Maanshan, Anhui 243002, PR China. Tel./fax: + 86 555
2311570.
E-mail address: qingyuhou@hotmail.com (Q.Y. Hou).
based alloy coating. They found that adding Al2O3 particles could not
only refine its microstructure but also change its phase characteristics,
leading to increase its wear resistance.
The reasons of adding Al2O3 particles in the nickel-based alloy
coating could refine its microstructure had been intensively studied
[7–10]. Nevertheless, the reasons of adding Al2O3 particles affecting
the phase compositions and their mass fractions in the nickel-based
alloy coating had not been fully clarified. Especially, there were little
works using Rietveld refinement method to study the effect of Al2O3
particles on the phase compositions and their mass fractions,
especially to the mass fractions of the borides and the carbides, in
the nickel-based alloy coating by now. It is obvious that the relative
change in the mass fractions of the borides and the carbides might
have important effect on the wear resistance of the deposited
coatings. Moreover, it was reported that the wear resistance of the
nickel-based alloy coating with nano-Al2O3 addition was higher than
that of the nickel-based alloy coatings with micro or submicron Al2O3
addition [7]. However, little attention has so far been paid to study the
effects of nano-Al2O3 particles on the substructure of the nickel-based
alloy coating. It is obvious that the substructure including dislocations
and stacking faults have important effect on the wear resistance of the
deposited coatings.

0257-8972/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2010.10.047
 Q.Y. Hou et al. / Surface & Coatings Technology 205 (2011) 2806–2812
Besides, it can be found from the reported data [1–10] that several
thermal spray or overlay welding techniques were employed to
prepare nickel-based alloy coatings. However, a lower bonding
strength existed between the coating obtained by thermal spray
technique and the substrate [2,5,9] because the porosity and
mechanical bonding that were bad to the wear resistance [6]. Though
a good metallurgical bonding and lower porosity could be obtained by
thermal spray welding and laser cladding techniques [1,4,7,8,10], the
low deposition rate for the two techniques restricted their potential
application [6]. Comparing with those techniques, plasma transferred
arc (PTA) overlay welding has attracted more attention for improving
the wear resistance of materials surface because of its high deposition
rate, lower porosity, and a good metallurgical bonding [3,6].
Unfortunately, little attention has so far been paid to study the
influence of nano-Al2O3 particles on the microstructure and wear
resistance of the nickel-based alloy coating deposited by PTA
surfacing welding.
Therefore, in this work, the nickel-based alloy coating with nano-
Al2O3 addition was prepared using PTA overlay welding technique.
Considering the experimental results obtained by the reported data
[7,8], the most suitable content of nano-Al2O3 added in the nickel-
based alloy was between 0.5 and 1.0 wt.%. The excessive addition of
nano-Al2O in the nickel-based alloy will reduce the improvement of
nano-Al2O3 on microstructure and certainly bad to the wear
resistance [7,8]. Due the fact that the wear resistance of the nickel-
based alloy coating increases with increasing the nano-Al2O3 content
within an appropriate range [7,8], therefore, based on the homoge-
nization of the microstructure, 0.8 wt.% nano-Al2O3 particles were
added into the nickel-based alloy powders and then deposited on
Q235A low carbon steel to increases the wear resistance of the nickel-
based alloy coating to a great extent. Then the influences of 0.8 wt.%
nano-Al2O3 particles on the microstructure, substructure and sliding
wear resistance properties of the nickel-based alloy coating were
examined. Besides, Rietveld refinement method was conducted to
analyze the obtained XRD patterns to study the influence of adding 0.8
wt.% nano-Al2O3 on the phase compositions and their mass fractions
of the nickel-based alloy coating.
2. Experimental procedures
2.1. Coatings deposition
The PTA treatment was performed using an L4-400PC equipment.
The commercial atomized nickel-based alloy powder (Al2O3-free)
used in this experiment was spherical in shape with 75–185 μm in
diameter whose nominal compositions are given in Table 1.
The substrate was 200 × 32 × 20 mm3 annealed low carbon steel
(Q235A) plate whose composition is listed in Table 1 and has not been
preheated before PTA treatment. The substrates were rinsed with
ethyl alcohol just before the PTA treatment. The 0.8 wt.% α-Al2O3
powder with average size of ~20 nm in diameter having a purity of
over 99.8% was added into the nickel-based alloy powder (Al2O3-
added). Detailed PTA treatment conditions, as listed in Table 2, were
optimized by dilution, formability, surface hardness and deposition
thickness after several experiments. Therefore, the coatings with low
dilution (7.8% for Al2O3-free and 8.1% for Al2O3-added coatings), good
formability, high surface hardness (~500HV0.1) and ~3.0 mm thick-
ness were prepared on the surface of the Q235A low carbon steel.
Table 1
Chemical compositions for the nickel-based alloy powder and the substrate (wt.%).
Materials C Si B Mn Cr Fe
Nickel-based alloy powder 0.75 4.43 4.81 18.25 21.17
Substrate 0.12 0.30 0.45 Balance
2807
Table 2
Experimental conditions for PTA overlay welding.
Transferred Transferred Ion gas Powder Oscillation Travel Torch
arc current arc voltage flow supply rate speed gap
185–195 A 33-35 V 0.5 m3/ 65 g/ 21 times/ 105 mm/ 7 mm
h min min min
2.2. Microstructure analysis
The deposited specimens for metallographic examination were
first cut vertical to the coating surface with an electrospark wire
electrode-cutting machine. The cross sections of the deposited
samples were polished by mechanical procedures and were etched
using a solution of HCl and HNO3 in a volume ration of 3:1 for
microstructure studies. Then the microstructures of the deposited
specimens were studied by optical microscope and JSM-6490LV
scanning electron microscopy equipped with X-ray energy spectrom-
eter (EDS). Besides, two samples were obtained by removing the
Al2O3-free and Al2O3-added coatings from the substrates respectively
using an electrospark wire electrode-cutting machine and cleaned
using acetone and ethanol followed by drying with a hairdryer. Then
the received samples were crushed into chippings using diamond file
whose hardness was ~HRC70. The obtained chippings were then
mashed and grinded manually into powers using steel mortar whose
hardness was ~ HRC60. Finally, the obtained powers were meshed into
less than 48 μm in diameter using mesh screen. XRD data were
collected from these milled powders. The XRD measurements were
performed using a Rigaku D/MAX-3C diffractometer with Cu Kα
target radiated at 45 kV and 150 mA. The step time and step size used
in the XRD analysis were set at 1 s and 0.02°. The XRD profiles were
then analyzed using the Rietveld refinement method program
Rietan2000TM [11]. The Rietveld refinement method has been
successfully used by the authors to study the phase compositions
and their mass fractions in some deposited coatings [12–14]. Such an
approach allows a calculated XRD profile for each phase in the alloys
to be generated from its known crystal structure. Subsequently, all
calculated patterns are fitted to the observed XRD profile of a
multiphase sample by nonlinear iterative least-squares analysis to
find the optimum individual phase scales. The phase scales are then
used to determine the mass fractions of different phases in the
samples. One software to study the XRD profile in this way is
Rietan2000 TM initially described by Izumi and Ikeda [11]. In the
calculation using Rietan2000 TM software, the Rietveld parameters for
each phase can be adjusted simply and interactively within the
program to allow for variation in the standard patterns because of
zero drift, substitution, preferred orientation and other factors. The
quality of a Rietvled refinement result can be decided mainly by
viewing the deviation between the observed and calculated patterns
graphically [15].
Finally, more details about identifying the substructure, Al2O3, (Fe,
Cr)7C3, and (Fe, Cr)2B in the deposited coatings were investigated by
TEM technique using thin-film samples. Techniques for preparing the
TEM samples are same to our previous investigation [14]. TEM
examination was carried out using an JEM2000EX transmission
electron microscope.
2.3. Wear resistance
Sliding wear test was conducted on the deposited coatings using a
ring-block wear testing machine (MM200, P.R. China). The specimens
with 30 × 6.5 × 6.5 mm3 dimensions were ground using mesh 230–
800 emery paper before wear test. Then the obtained specimens were
Ni
fixed on one metal fixture as the upper sample (block specimens).
Balance One 35 wt.% WC-strengthen nickel-based alloy coating (~950HV0.5)
obtained by laser cladding was used as a ring (counterpart material,
2808 Q.Y. Hou et al. / Surface & Coatings Technology 205 (2011) 2806–2812
inner bore is 16 mm and external diameter 40 mm). The coated block
specimens were worn by the ring as the rotation axis running. The test
was performed under a 5 kgf load at room temperature for 1800 s
without a lubricant. It should be pointed out that the grindings caused
by the emery paper existed on the block specimens. Those grindings
might affect the wear resistance results. Therefore, in the present
work, those grindings were removed by prewear tests for 300 s then
the weights of the samples worn by prewear were measured. Then the
normal wear tests were performed on the samples worn by prewear.
Weight losses of the deposited coatings were measured to within
0.01 mg and the average value for each specimen was calculated using
three data.
3. Results and discussion
3.1. Microstructure characteristics
Fig. 1a shows the typical optical micrograph of the Al2O3-free
coating, where the typical hypoeutectic microstructure can be found
clearly. Therefore, the first phase precipitating from the molten bath is
the primary Ni-rich solid solution and the remaining liquid eventually
solidifies by a eutectic reaction into a mixture of Ni-rich solid solution
and (Fe, Cr)-rich phases. Besides, it can also be seen the obvious
component segregation (dark in Fig. 1a) exists in the Al2O3-free
coating because the cooling rate of the PTA overlay welding is so quick
that the alloy elements have no time to distribute homogenously [13].
Comparing with the Al2O3-free coating, adding 0.8 wt.% nano-Al2O3
particles changes its microstructure characteristics, as shown in
Fig. 1b, where the primary Ni-rich solid solution existing in the Al2O3-
free coating gets little and the microstructure is refined. Besides, it can
Fig. 1. Typical microstructures for the nickel-based alloy coatings: (a) Al2O3-free and
(b) Al2O3-added.
also be found from Fig. 1 that the degree of the component
segregation in the Al2O3-added coating is lower than that in the
Al2O3-free coating. It was proposed that some of the Al2O3 particles
would preserve in the deposited coating even though those particles
were treated by high-energy beam [7–10]. Those preserved particles
might become particles of heterogeneous nucleation, which was
helpful to increase the nucleation rate and promote heterogeneous
nucleation. At present, it is reasonable to speculate some of the Al2O3
particles should preserve in the Al2O3-added coating deposited by PTA
overlay welding. Those preserved Al2O3 particles refined the micro-
structure of the nickel-based alloy coating. Therefore, the volume and
surface area of the grain boundary were increased, increasing the
diffusion velocity of the alloy elements in the Ni-rich solid solution. So,
the homogeneous microstructure can be received and the degree of
the component segregation decreases after adding 0.8 wt.% nano-
Al2O3 in the nickel-based alloy coating.
More details about the typical microstructure characteristics of the
Al2O3-free and Al2O3-added coatings can be obtained by the SEM
technique, as shown in Fig. 2. It can be found clearly that both
microstructures can be divided into solid solution (region A), region
B1 in the morphology of continuous plate-like, region B2 in the
morphology of discontinuous short-bar, and region C in the morphology
of island. Comparing the microstructure in the Al2O3-free coating
(Fig. 2a) with that in the Al2O3-added coating (Fig. 2b), it can be seen
that adding nano-Al2O3 has little effect on the relative of the Ni-rich solid
solution and the total (Fe, Cr)-rich compounds.
Table 3 shows the EDS results for different microstructures shown
in Fig. 2. It can be seen that there is no obvious difference in the
compositions for regions B1 and B2, in which Fe and Cr are the major
elements. From the following XRD analysis (Fig. 3) and the TEM
Fig. 2. SEM morphology of the nickel-based alloy coatings: (a) Al2O3-free and (b) Al2O3-
added.
 Q.Y. Hou et al. / Surface & Coatings Technology 205 (2011) 2806–2812 2809

Table 3 the molten bath, changing the morphology of the eutectic carbide
EDS results of the nickel-based alloy coatings deposited by PTA overlay welding, wt.%. from continuous plate-like into discontinuous short-bar [17]. So, the
Coatings Regions Ni Fe Cr Si Al volume fraction of region B2 being discontinuous short-bar increases
and that of region B1 being continuous plate-like decreases after
Al2O3-free A 64.42 27.33 4.85 3.40 –
B1 10.65 56.41 32.45 0.49 – adding 0.8 wt.% nano-Al2O3 particles in the deposited coating. Besides,
B2 11.06 56.45 32.06 0.43 it can also be seen from Table 3 that the relative content of Al element
C 48.12 41.85 7.27 2.76 – in the Ni-rich solid solution is higher than that in the (Fe, Cr)-rich
Al2O3-added A 64.12 27.46 4.89 2.71 0.82
carbide. This result is good agreement with the reported data [18] that
B1 10.31 55.35 33.86 0.27 0.21
B2 11.17 54.17 34.15 0.32 0.19 Al element mainly distributed in the solid solution.
C 44.97 43.72 7.56 2.90 0.85 As discussed before, the component segregation existed in the Ni-
rich solid solution. This can be verified by the EDS analysis shown in
Table 3. It can be seen that the major elements in region A and region
observations (Figs. 6 and 7), it is reasonable to concluded that regions C are all Ni and Fe. From microstructure observation and our previous
B1 and B2 are all consisted of the (Fe, Cr)7C3 phase because the size of studies on one similar coating [13], it can be received that the two
the (Fe, Cr)2B phase is so small (~ 75 nm in Fig. 7a) that it cannot be regions are all Ni-rich solid solution. The difference between the two
detected in present magnification shown in Fig. 2. Nevertheless, the regions is the relative mass fractions of Ni and Fe elements. Therefore,
volume fraction of region B2 in the Al2O3-added coating (Fig. 2b) is the component segregation exists in the Ni-rich solid solution [13].
higher than that in the Al2O3-free coating (Fig. 2a) though the relative
content of the total (Fe, Cr)-carbides (including region B1 and region 3.2. X-ray Rietveld refinement
B2) change a little. From Table 3, it can also be seen that Al element
not only exists in the Ni-rich solid solution, but also in the (Fe, Cr)-rich Fig. 3a shows the result of the Rietveld refinement for the Al2O3-
carbide. The result shows that the Al atom could be received in the free coating. It can be seen that γ(Ni, Fe), (Fe, Cr)7C3, and (Fe, Cr)2B
Al2O3-added molten bath under the effect of the high energy plasma phases are present. Comparing with the Al2O3-free coating, adding 0.8
beam. The result is good agreement with the reported data [16] that wt.% nano-Al2O3 has little effect on the XRD patterns, as shown in
the added Al2O3 particles would be decomposed into Al atom though Fig. 3b. The phase compositions and their mass fractions refined by
some of the Al2O3 particles would be preserved in the Al2O3-added the Rietveld refinement method are listed in Table 4. It can be received
coating under the effect of high energy beam. Those Al atoms existing that the matrix phase is γ(Ni, Fe) solid solution because its mass
in the molten bath decreased the diffusion rate of the C atom [17]. fraction is higher than that of the total (Fe, Cr)-rich compounds. The
Therefore, the carbides were difficult to precipitate aggregatively from result also verifies previous discussion that the hypoeutectic micro-
structure can be obtained in the nickel-based alloy coatings deposited
by PTA overlay welding. Comparing the mass fractions of the different
phases in the two coatings, it can also be found that adding 0.8 wt.%
nano-Al2O3 does not change the mass fraction of the γ (Ni, Fe) solid
solution and that of the total (Fe, Cr)-rich compounds. This result
verifies the result shown in Fig. 2 that adding 0.8 wt.% nano-Al2O3 has
little effect on the mass fraction of the Ni-rich solid solution and that
of the total (Fe,Cr)-rich compounds. However, adding 0.8 wt.% nano-
Al2O3 decreases the mass fraction of the (Fe, Cr)7C3 phase but
increases that of the (Fe, Cr)2B phase. As proposed above, some of the
Al2O3 particles would be decomposed then the single Al atom could be
obtained during the PTA overlay welding. Those Al atoms existing in
the molten bath decreased the diffusion rate of the C atoms [17].
Therfore, the precipatation rate of the (Fe, Cr)7C3 phase decreased
during the solidification. Accordingly, more Fe and Cr atoms would
combine with B atoms to form the (Fe, Cr)2B phase, increasing its
mass fraction in the Al2O3-added coating comparing with that in the
Al2O3-free coating. The changing result leads to the relative mass
fraction of the γ (Ni, Fe) solid solution and that of the total (Fe, Cr)-
rich compounds in the two kinds of coatings change a little.

3.3. TEM observation

As discussed before, some of the Al2O3 particles should preserve in

the Al2O3-added coating. However, the peaks corresponding to Al2O3

Table 4
Structural parameters and phases mass fractions of the nickel-based alloy coatings
deposited by PTA overlay welding refined by the X-ray Rietveld refinement method.

Coatings Phase Space Lattice parameters (nm) Mass fraction

group (wt.%)
a b c


Al2O3-free γ(Ni,Fe) Fm 3m 0.357407(4) 57
Rwp = 8.31 % (Fe,Cr)7C3 P63MC 0.696863(7) 0.450083(5) 16
S = 1.7145 (Fe,Cr)2B I4/mcm 0.514522(5) 0.421618(6) 27


Al2O3-added γ(Ni,Fe) Fm 3m 0.357795(2) 57
Rwp = 8.07 % (Fe,Cr)7C3 P63MC 0.698595(9) 0.449495(7) 10
Fig. 3. Observed (points), calculated (line) and difference (bottom line) X-ray
S = 1.7011 (Fe,Cr)2B I4/mcm 0.514048(4) 0.421851(4) 33
diffraction patterns of the deposited coatings: (a) Al2O3-free and (b) Al2O3-added.
2810 Q.Y. Hou et al. / Surface & Coatings Technology 205 (2011) 2806–2812

phase could not be indexed clearly in the obtained XRD patterns being ~250 ergs/cm2 for pure nickel [25]). Therefore, the stacking
(Fig. 3b), which might because the content of Al2O3 particles in the faults could not be formed easily in these alloys, and the substructure
coating was so little that it could not be detected by XRD technique. This of these alloys might be mainly dislocations [25]. Present work shows
can be verified by TEM observation, as shown in Fig. 4a. The that the dislocations are the major substructure of the Al2O3-free
corresponding selected area diffraction (SAD) patterns of the spherical coating, as shown in Fig. 5a. However, the stacking faults can be easily
phase
 in Fig. 4a give evidence of the γ-Al2O3 being tetragonal lattice found in the Al2O3-added coating except for the existence of the
S:G:P4m2ð115Þ with a zone axis [100] existing in the Al2O3-added dislocations (Fig. 4a), as shown in Fig. 5b. As reported in the reference
coating (Fig. 4b). Obviously, the result is not good  agreement with
 the [26] that the existence of nanometer materials could lower the SFE of
added α-Al2O3 being rhombohedral lattice S:G:R3c ð167Þ . The the nickel-based alloy. In this work, the Al2O3 particles with
reasons for such phase transformation from rhombohedral α-Al2O3 to nanometer were obtained in the Al2O3-added coating (Fig. 4a),
tetragonal γ-Al2O3 in the Al2O3-added coating deposited by PTA overlay resulting in decreasing the SFE of the coating. Therefore, the stacking
welding might be similar to the phase transformation of the Al2O3 phase faults might be easily formed in the Al2O3-added coating. Besides, as
in the plasma or thermal spray coatings [19–24]. Nevertheless, the real proposed by the reported data [27] that the SFE affected forming
reasons for such phase transformation should be investigated further relatively strain free dislocation walls. In this work, the SFE of the
because there are differences between PTA overlay welding and the
plasma or thermal spary.
From Fig. 4a, it can also be seen that the Al2O3 particles distributing
on the γ(Ni, Fe) solid solution pin the dislocations, resulting in
increasing the properties of the deposited coating. Besides, the Al2O3
particles might become particles of heterogeneous nucleation, which
was helpful to increase the nucleation rate and promote nonsponta-
neous nucleation [7–10], leading to refine the microstructure of the
nickel-based alloy coating (Fig. 1b).
Comparing with the employed Al2O3 particles, it is noticeable from
Fig. 4a that the size of the Al2O3 particles being ~40 nm whose size is
larger than that of the employed particles being ~20 nm distribute on
the γ(Ni, Fe) solid solution and pin the dislocations. Such particles are
helpful to refine the microstructure and increase the wear resistance of
the Al2O3-added coating.
Besides, it was reported that the stacking fault energy (SFE) for
most of the pure nickel or nickel-based alloys was high (commonly

Fig. 5. Substructure of the nickel-based alloy coatings: (a) dislocations in Al2O3-free;

Fig. 4. TEM observation of Al2O3 particles (a) and its SAD patterns (b). (b) stacking fault in Al2O3-added; and (c) dislocation cell wall in Al2O3-added.
 Q.Y. Hou et al. / Surface & Coatings Technology 205 (2011) 2806–2812
nickel-based alloy coating decreased because some of the Al2O3
particles with nanometer preserved in the Al2O3-added coating. The
decreasing SFE of the nickel-based alloy coating promoted to form
dislocation cell wall which was obstacled by eutectic, as shown in
Fig. 5c, increasing the shear stress and the wear resistance of the
Al2O3-strengthen coating [27].
Further, as received in the Rietveld refinement, the (Fe, Cr)7C3 and
(Fe, Cr)2B phases existed in the deposited coatings. These can be
verified using TEM technique. Fig. 6a and b show the morphology of
the (Fe, Cr)7C3 phase and the substructure within it, respectively.
From the SAD patterns shown in Fig. 6c for the (Fe, Cr)7C3 shown in
Fig. 6a and b, it can be obtained that the hexagonal (Fe, Cr)7C3 phase in
the morphology of lath with a zone axis [101] exists in the deposited
coatings. Besides, it can also been found from Fig. 6b that high density
Fig. 6. TEM observation of the (Fe, Cr)7C3: (a) morphology, (b) stacking faults within the
(Fe, Cr)7C3 and (c) SAD patterns for the (Fe, Cr)7C3.
2811
streaks exist in the (Fe, Cr)7C3 phase. The result indicates that a high
density of planar faults might exist within the (Fe, Cr)7C3 phase. From
the elongated diffraction fringes shown in Fig. 6c, it can be concluded
that the planar faults within the (Fe, Cr)7C3 phase are stacking faults
[28,29]. This is due to the fact that the stacking fault energy of the (Fe,
Cr)7C3 phase is very weak, hence the frequent occurrence of the
staking faults in the phase [28,29].
Besides, from Fig. 7, it can be seen that the tetragonal (Fe, Cr)2B
phase in the morphology of blocky being ~80 nm (Fig. 7a) with a zone
axis [111] (Fig. 7b) exists in the deposited coatings. These results are
good agreement with the Rietveld refinement results.
3.4. Wear characteristic
Fig. 8 shows the sliding wear resistance of the deposited coatings.
It can be seen that the sliding wear resistance of the Al2O3-added
coating increases by 1.57 times comparing to that of the Al2O3-free
coating. The reasons for that might be corresponded mainly to the
following. First, adding 0.8 wt.% nano-Al2O3 particles refines the
microstructure of the nickel-based alloy coating, which results in
grain refinement strengthening. Second, adding 0.8 wt.% nano-Al2O3
increases the mass fraction of the (Fe, Cr)2B phase and decreases that
of the (Fe, Cr)7C3 phase, though such adding has little effect on the
relative mass fractions of the γ (Ni, Fe) and the total (Fe, Cr)-rich
phases. Therefore, the sliding wear resistance of the Al2O3-added
coating increases because the wear resistance of the borides is higher
than that of the carbides under the total (Fe, Cr)-rich compounds have
not been changed [30]. Third, the Al2O3 particles with nanometer
distribute on the γ(Ni, Fe) solid solution, and then the dispersion
strengthening can be received. Fourth, the hard Al2O3 particles
distributing in the Al2O3-added coating reduce the friction between
Fig. 7. TEM observation of the (Fe, Cr)2B (a) and its SAD patterns (b).
2812 Q.Y. Hou et al. / Surface & Coatings Technology 205 (2011) 2806–2812
Fig. 8. Sliding wear resistance of the nickel-based alloy coatings.
the soft γ(Ni, Fe) matrix and the wearing ring [31]. Besides, as
obtained in Fig. 5b, it can be seen that the stacking faults exist in the
Al2O3-added coating. The appearance of stacking faults in the Al2O3-
modified coating may increase the feasibly or lower the difficulty of
deformation of this coating (softening effect), reducing the wear
resistance. However, it should be noted that the additional strain
hardening [32] can be obtained because the additional deformation
can be obtained in the Al2O3-added coating comparing with the
Al2O3-free coating, increasing the wear resistance. Under the effect of
the two reasons, the wear resistance of the deposited coating
increased because the softening effect is lower than the hardening
effect [32]. Finally, as obtained in Fig. 5c, the dislocation cell wall was
formed in the Al2O3-added coating, helping to increase its wear
resistance. As a result, the sliding wear resistance of the Al2O3-added
coating is higher than that of the Al2O3-free coating.
4. Conclusions
(1) The typical hypoeutectic microstructure and component segre-
gation exist in the Al2O3-free nickel-based alloy coating where
consists of γ (Ni, Fe), (Fe, Cr)7C3, and (Fe, Cr)2B phases. Adding
0.8 wt.% nano-Al2O3 particles does not change the hypoeutectic
microstructure of the nickel-based alloy coating, though refines
its microstructure and decreases the degree of the component
segregation. Adding 0.8 wt.% nano-Al2O3 particles leads to the
existence of the nano-Al2O3 particles being mainly tetragonal
crystal structure (γ-Al2O3) which is different to that added
particles being rhombohedral crystal structure (α-Al2O3) except
for those phases existed in the Al2O3-free coating.
(2) Adding 0.8 wt.% nano-Al2O3 increases the mass fraction of the
(Fe, Cr)2B phase and decreases that of the (Fe, Cr)7C3 phase,
though such adding has little effect on the relative mass
fractions of the γ (Ni, Fe) and the (Fe, Cr)-rich phases.
(3) The substructure of the Al2O3-free nickel-based alloy coating is
mainly dislocations. Adding 0.8 wt.% nano-Al2O3 promotes to
form stacking faults and dislocation cell wall.
(4) Adding 0.8 wt.% nano-Al2O3 particles increases the sliding wear
resistance of the nickel-based alloy coating by 1.57 times in
comparison to that of the Al2O3-free nickel-based alloy coating.
Acknowledgements
This work was supported by the Natural Science Foundation of
China under grant 51071001.
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