Surface & Coatings Technology 206 (2012) 40004010

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Surface & Coatings Technology

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Inuence of heat treatment on the microstructure and performance of high-velocity

oxy-fuel sprayed WC12Co coatings
Qun Wang a,, Luoxing Li a, Guibin Yang b, Xinqi Zhao a, Zhangxiong Ding c
a
College of Materials Science and Engineering, Hunan University, Changsha, Hunan 410082, PR China
b
Ganzhou Zhangyuan Tungsten New Materials Co.,Ltd, Ganzhou, Jiangxi 341300,PR China
c
College of Energy & Engineering, Wuhan University of Technology, Wuhan, Hubei 430063, PR China

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

Article history: In this study, a high-velocity oxy-fuel sprayed WC12Co coating was heat treated at 550, 750, 900 and
Received 14 December 2011 1150 C for 1 h in an argon atmosphere. Various properties of these coatings such as hardness, fracture
Accepted in revised form 27 March 2012 toughness, abrasive wear resistance, phase composition and microstructure were investigated before and
Available online 4 April 2012
after heat treatment. We can conclude from X-ray diffraction patterns that the phase of the as-sprayed coating
is composed mainly of WC, an amorphous phase, a small amount of W2C and trace metal W. However, with an
Keywords:
High velocity oxy-fuel spraying
increase in the heat-treatment temperature, the amorphous phase was found to be gradually transformed to
Heat treatment eta phases such as Co3W3C, Co6W6C and Co2W4C, coupled with the decrease of W2C and WC phases. Element
Phase transformation diffusion and new phase generation processes at the coatingsubstrate interface and within the coating were
Abrasive wear studied via energy dispersive X-ray spectrometry, scanning electron microscopy and transmission electron
WCCo microscopy. The results indicated that the coating hardness increased at rst with an increase in the heat-
treatment temperature, followed by a decrease, whereas the fracture toughness shows almost the reverse
tendency. In addition, wet sand rubber wheel abrasive wear testing results indicate that heat treatment of
the WC12Co coatings at 950 C resulted in the highest wear resistance among all the coatings due to the
formation of the hard, unbrittle, crystalline Co6W6C phase and the tough Co phase without consuming much of
the WC phase.
2012 Elsevier B.V. All rights reserved.

1. Introduction reported that annealing as-sprayed WC12Co coatings at temperatures

High velocity oxy-fuel thermal spraying WC/Co coatings have
been used widely in many elds which are subjected to severe abra-
sive wear, such as metallurgy, energy sources, and in the construction
industry as a result of their excellent resistance to abrasive wear [1,2].
High velocity oxy-fuel spraying is a favorable method for depositing
WCCo cermet powders compared with air plasma spray processes
due to its higher velocity and lower ame temperatures [24]; how-
ever, one or several phases of W2C, metal W and even other CoWC
amorphous phases can inevitably be generated in the as-sprayed
coatings as a result of the decarburization of WC during spraying
[5,6]. This extra phase formation is detrimental to the performance
of the WCCo coating, limiting its applications [7]. It has been found
that heat treatments can signicantly improve the hardness and wear
performance of WCCo coatings coupled with a transformation in
the phase composition by some researchers [810]. Nerz, et al. [11]
Corresponding author. Tel.: + 86 13787113453; fax: + 86 731 88821950.
E-mail address: wangqun72@163.com (Q. Wang).
of 875 C and 1100 C for 560 min in argon gas recrystallized the
matrix phase to form Co6W6C and Co2W4C carbides. The wear
resistance of high-velocity oxy-fuel sprayed WC12Co coatings was
increased by heat treatment at temperatures of 900 C for 560 min as a
result of the precipitation of eta carbides. The best abrasive wear
resistance occurred after a 50 minute heat treatment, after which the
wear resistance gradually decreased. Similar phase changes have been
observed by Sohi et al. [12], who also found that the best slide wear
resistance of the WC12Co coating occurred after a 1 h heat treatment
at 900 C, which is increased by about 27.6%. Li et al.[13] reported that
crystalline Co6W6C and Co were transformed from an amorphous
matrix by annealing high-velocity oxy-fuel sprayed WC18Co coatings
at 600 C for 6 h in an ambient atmosphere and 900 C for 0.5 h under
vacuum. Stewart et al. [10] reported similar phase changes within the
coating with a heat treatment temperature above 600 C, Also, they
found that the increase in wear resistance after heat treatment even at
250 C is substantial (between 21% and 35% depending on the applied
load). Asl et al. [14] have found the WC, crystal Co and eta phases
coexisting in WC17Co coating heat treated at 1100 C in a vacuum
chamber by using transmission electron microscopy without examining
their mechanical performance.

0257-8972/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2012.03.080
 Q. Wang et al. / Surface & Coatings Technology 206 (2012) 40004010 4001

In light of the above literature, it can be seen that the phase
transition temperature is approximately 600 C and that the wear
resistance is improved for high-velocity oxy-fuel sprayed WCCo
coatings under the inert or vacuum heat treatment. However, at
this time, most papers just emphasized one side of the mechanical
performance variation [710,12] or microstructural evolution [11,14]
for the WC/Co coatings under the condition of heat treatment. In this
paper, a more comprehensive study, such as toughness on the wear
performance, the microstructural evolution of the coatings as well as
the element diffusion at the interface of the coatingsubstrate during
the heat-treatment process will be investigated in detail.
2. Experiment
2.1. Coating preparation and heat treatment
A conventional WC12Co coating was deposited with optimal
spray parameters by a Praxair Surface Technologies JP-8000 high-
velocity oxy-fuel spraying system, the optimal processes can be found
in our previous studies [15]. The WC12Co powder feedstock used
was spray dried and agglomerated, and then sintered into spherical
shape sprayable particles in the range of 545 m. The coated samples
were placed in the furnace, which was evacuated of air, lled with
argon and heated at a rate of 5 C/min. The coatings were held after
1 h at 550 C, 750 C, 950 C and 1150 C, and then cooled to room
temperature in the furnace. In subsequent paragraphs, the coatings
heat treated at 550 C, 750 C, 950 C and 1150 C are abbreviated as
HT550, HT750, HT950 and HT1150, respectively.
2.2. Characterization
X-ray diffraction analysis of the coatings was carried out using a
Rigaku D/max-2550 diffractometer with Cu-Ka radiation. Scanning
electron microscopy of cross sections of the coatings and their en-
ergy dispersive spectrometer line scans were obtained using an FEI-
Quanta200 with an energy dispersive X-ray spectrometer. A JSM-
3010 transmission electron microscope was used to observe the new
phase formed in the coating after heat treatment. Hardness measure-
ments were performed on the transverse section of the coatings with
a Vickers indenter at loads of 0.3 kg, 1 kg and 5 kg, with a 10 s dwell
time. The average of ten readings is reported. Measureable cracks
parallel to the substrates appeared on the cross section of the coating,
and the fracture toughness of the coatings was calculated using the
length of the indentions and cracks measured according to the Evans
and Wilshaw equation [16].
2.3. Abrasion wear
The coated specimens, with dimensions of 57 25 ~ 5.35 mm 3,
were tested using a well-known wet sand rubber wheel abrasion
tester [5]. Steel wheels covered with vulcanized rubber whose
shore hardness is 72 turn against the test specimen under a load of
100 N. The rotational speed of the rubber wheel was 240 rpm. The
tribological pair was submerged in a mixture of 2040 mesh quartz
sand and fresh water; the weight of the quartz sand was 1.5 kg, and
the weight of the water was 1 kg; the abrasive slurries used were not
recycled. The coating mass loss was measured every 3000 rounds; the
total duration of the test was 9500 rounds. The rst 500 rounds were
performed to acclimatize the system and were not considered in the
wear measurements. Before and after testing, all of the samples were
measured by ultrasonic cleaning for 5 min in acetone, then dried in a
stream of hot air. The weight loss of the samples was measured using
an FA1004 electric balance with an accuracy of 0.1 mg. The mass loss
obtained was normalized with the coating density, leading to the
wear loss per unit volume.
3. Results and discussion
3.1. Phase composition
The X-ray diffraction patterns of the powder, as-sprayed and heat
treated WC12Co coatings are shown in Fig. 1.
The sprayed powder is composed of WC and Co without other
phases. The X-ray diffraction pattern of the as-sprayed coating shows a
broad maximum between 38 and 48 of 2, which is the characteristic
peak of microcrystalline or amorphous materials [11,13,15], conrming
the formation of an amorphous phase in the as-sprayed coating. This
amorphous phase gradually transforms to eta phases such as Co3W3C,
Co6W6C and Co2W4C over the course of heat treatment of the coating
with an increase in the heat-treatment temperature. No signicant
phase transformations are caused when the heat treatment temperature
is below 550 C [10]. With high-temperature heat treatments (950 C),
the amorphous phases are completely transformed to crystalline eta
phases (Co6W6C), and even a Co phase and Co2W4C appear at tem-
peratures of 1150 C.

7000
1 1:WC
2:W2C
6000 1 3:W
4:Co6W6C
5000 5:Co
4 6:Co2W4C
Intensity/a.u.

1
4000 4 5 4 7:Co3W3C
4 14
6 6 65 6
4 1 1 1 1 1
H1150 4 4
3000 4
4 5
4 4 4
5 H950 4 4
2000 273 574 5 H750
2 27
2 2 H550
2
1000 2 2 3 2 As sprayed 2
5 Powder
5
0
30 40 50 60 70 80 90
2/degree

Fig. 1. X-ray diffraction patterns of the powder, as-sprayed and heat-treated WC12Co coatings.
4002 Q. Wang et al. / Surface & Coatings Technology 206 (2012) 40004010

3.2. Microstructure and evolution of WC12Co coatings after heat
treatment
3.2.1. BSE images of cross-sectional micrographs of coatings
Cross-sectional BSE images of as-sprayed and heat-treated coatings
are shown in Fig. 2.
Fig. 2(ae) shows a decrease in the white phase that is W2C, W
or the binder rich in W[1719] (marked by the arrow), whereas the
continuous gray binder phase that is associated with the crystalline
eta or Co phases, later identied by transmission electron micros-
copy analysis, increases with increasing temperature of the heat
treatment. It was found in the X-ray diffraction results shown in

Fig. 2. BSE images of (a) as-sprayed, (b) HT550, (c) HT750, (d) HT950 and (e) HT1150, (f) high magnication of the rectangular region marked in Fig. 2d, (g) energy dispersive X-ray
spectrometry of the point marked 1 in Fig. 2f,(h) energy dispersive spectrometry of the point marked 2 in Fig. 2f.
 Q. Wang et al. / Surface & Coatings Technology 206 (2012) 40004010 4003

Fig. 3. Energy dispersive X-ray spectrometer line scan analysis of the elemental distribution across the coatingsubstrate interface (a) HT550, (b) HT750, (c) HT950, (d) HT1150.

Fig. 1 that the white phase completely disappears at a temperature [20]. In addition, the atom radius of C element is small and the
of 950 C. concentration gradient of C element is high in coating which can
Typical cross-sectional images and their energy dispersive X-ray also result in a lot of C element diffusing into substrate, but it can't be
spectrometer line scans with elemental distribution across the coating precisely detected by energy dispersive spectrometer line scan
substrate interfaces of the coatings under the different heat treatment because of its light element mass. Some new phases are generated
temperatures are shown in Fig. 3 (ad). within the coating at the high temperature, which is briey sketched
From Fig. 3 (a) and (b), it can be seen that there is little element in Fig. 4b and will be discussed later by the transmission electron
diffusion between the coatingsubstrate interface under tempera- microscope analysis.
tures of 550 C and 750 C. When the heat treatment temperature was
increased to 950 C (Fig. 3c) and 1150 C (Fig. 3d), apparent element
diffusion takes place across the interface of the coating and substrate.
There are some Kirkendall pores and an apparent diffusion band
generated at the interface of the coating and substrate, respectively,
when the temperature of the heat treatment was 1150 C.
In Fig. 4, we illustrate a schematic of the element diffusion process at
the substratecoating interface under high-temperature heat treatments.
Fig. 4a shows the atom diffusion direction at interface of the
coatingsubstrate during heat treatment and Fig. 4b shows the nal
microstructure state of substratecoating interface after the high
temperate heat treatment. Considering element diffusions have taken
place at the substratecoating interface under the high temperate
heat treatment, which is illustrated by Fig. 4a. Because the substrate
riches in Fe and the coating riches in W, Co and C, when the
temperature of heat treatment is high up to 1150 C, a lot of Fe
elements diffuse into coating and a large number of Co elements also
diffuse into substrate, but the W shows little diffusion at the interface
according to the results of the energy dispersive spectrometer line
scan (Fig. 3d). Both Fe and Co are transition elements which have
similar atom radius and electronegativity, which are responsible for
their reciprocal diffusion. The Kirkendall pores only appear in the
substrate near the interface (Fig. 3d), due to the higher concentration
gradient of Fe element in substrate compared with the Co element in Fig. 4. The schematic of (a) the diffusion directions of different atoms at the coating
coating [20,21]. The atom radius of W is large and the content of W in substrate interface in the heat treatment process, (b) nal microstructure state at the
binder is low, leading to little diffusion of W element into substrate interface of substratecoating after the heat treatment of 1150 C.
4004 Q. Wang et al. / Surface & Coatings Technology 206 (2012) 40004010
3.2.2. Transmission electron microscopy images of coatings
Typical transmission electron microscopy image and the corre-
sponding selected area X-ray diffraction patterns of as-sprayed coatings
are shown in Fig. 5.
It can be seen that, W2C phase generates at the interface between
WC and amorphous cobalt binder. Some literatures [10,11] have also
reported the similar phenomenon, they attributed the amorphous
binder to the rapid cooling of molten and semi-molten and attributed
the W2C to the oxidization of WC generated by using molten liquid
cobalt as a media.
Typical transmission electron microscopy images including WC
and Co phases and the corresponding selected area electron diffraction
patterns of a coating after the heat treatment at 1150 C are shown in
Fig. 6.
It can be seen that crystalline Co has been generated among the
sharp WC particles according to the transmission electron microscope
image and the corresponding energy dispersive X-ray spectrometer
response and the selected area electron diffraction patterns (Fig. 6).
Compared with the as-sprayed coating, the amorphous CoWC has
transformed into crystalline Co, and dislocations in the WC still exist.
A typical transmission electron microscope image including WC
and eta phases and the corresponding selected area X-ray diffraction
patterns of a WC12Co coating after the heat treatment at 1150 C are
shown in Fig. 7.
It can be seen from Fig. 7 that a new eta phase (Co6W6C) has been
generated around the rim of the rounding WC particle according
to the transmission electron microscope image, the corresponding
energy dispersive X-ray spectrometer response and the selected area
electron diffraction pattern. Compared with the as-sprayed coating,
Fig. 5. TEM image and corresponding selected area X-ray diffraction patterns of as-sprayed WC12Co coating (a) Transmission electron microscope image,(b, c, d) the selected area
electron diffraction pattern of the region marked by 1, 2,3" in (a), respectively.
the amorphous CoWC has transformed into crystalline Co6W6C.
However, we do not observe the other eta phase (Co2W4C) by trans-
mission electron microscopy, which may be attributed to its trace
content and similar crystalline structure to the Co6W6C. In addition,
the shape of the WC particles has shifted from sharp into round,
which can be attributed to their decarburization in the previous
thermal spraying process. The sharp corners of the WC grains pref-
erentially melted into molten Co and rounded out with a rim of
W2C when they were deposited in the coating (the detailed phase
transition process during the heat treatment will be proposed later).
The coatings under the heat treatments of 550 and 750 C were
unable to be processed into suitable transmission electron micro-
scope samples due to their high brittleness.
A schematic of the WC12Co coating microstructure evolution
during the heat treatment is shown in Fig. 8 in accord with the results
and analysis of X-ray diffraction, scanning electron microscopy and
transmission electron microscopy of the WC12Co coatings.
From Fig. 8, it can be seen that with an increase in heat treatment
temperature, new phases began to nucleate in the different regions
of the coating, and grew gradually into crystalline Co and eta phases
such as Co3W3C, Co6W6C and Co2W4C, coupled with the gradual
disappearance of the amorphous CoWC, W2C and W phases. In
addition, an edge zone of WC was dissolved into the binder under
conditions of high-temperature heat treatment. According to the
vertical section of the ternary phase diagram of WCoC[22,23],
if the carbon content of WC10Co material is less than 5.4 wt.%,
the eta phase would be generated in equilibrium state. The carbon
content in the sprayed WC12Co powder is about 5.38wt.%, so the
carbon content in the WC12Co coating must be less than 5.38wt.%
 Q. Wang et al. / Surface & Coatings Technology 206 (2012) 40004010 4005

Fig. 6. Transmission electron microscopy images (including WC and Co) and selected area electron diffraction patterns of a coating after the heat treatment at 1150 C.
(a) Transmission electron microscope image, (b) the selected area electron diffraction pattern and (c) energy dispersive X-ray spectrometer response of the region marked by 1 in
Fig. 6a; (d) the selected area electron diffraction pattern and (e) energy dispersive X-ray spectrometer response of the region marked by 2 in Fig. 6a; (f) the selected area electron
diffraction pattern and (g) energy dispersive X-ray spectrometer response of the region marked by 3 in Fig. 6a.

as a result of some extent decarburization has taken place during
the HVOF spray process according to the X-ray diffraction patterns
of as-sprayed WC12Co coatings (Fig. 1).The presence of a con-
centration gradient and less total carbon content in the coating
as well as the dissolution process in case of binder cobalt in WC
12Co coating enabled the diffusion process, which result in gen-
erating some eta phases in coating after high temperature heat
treatment.
According to the classication of temperature, the microstructure
evolution processes of the coatings are presented as follows:
1) Room temperature ~ 550 C (Fig. 8a)
550 C is the highest temperature for using the WC/Co coating,
the microstructure of the coating shows little change except for
strain when the heat treatment temperature is below 550 C, as
proposed by Stewart et al. [10].
4006 Q. Wang et al. / Surface & Coatings Technology 206 (2012) 40004010

Fig. 7. Transmission electron microscope images (including WC and eta phases) and selected area X-ray diffraction patterns of a coating after the heat treatment at 1150 C.
(a) Transmission electron microscope image, (b) selected area electron diffraction pattern of the region marked with the arrow in Fig. 7a, (c) energy dispersive X-ray spectrometer
response of the region marked by 1 in Fig. 7a; (d) the selected area electron diffraction pattern and (e) energy dispersive X-ray spectrometer response of the region marked by 2
in Fig. 7a.

2) 550 C750 C (Fig. 8b)
The amorphous CoWC is recrystallized, and new phases are
generated when the coating undergoes the heat treatment at
750 C. The new phases formed are controlled by means of the C
and W content in the amorphous CoWC, and their generation
mechanisms may be one or all of the following three situations.
i The Co recrystallized in the region marked by I in Fig. 8a, the
crystalline Co might be generated and a small amount of excess W
and C elements diffused outside in the region where WC particles
usually experienced little decarburization and exhibited multi-
angular shape (Fig. 6a)during thermal spraying.
ii The Co6W6C might be generated at the interface between W2C
and the amorphous CoWC where WC experienced moderate
decarburization (marked by II in Fig. 8a) and particles usually
exhibited round shape (Fig. 5a and Fig. 7a), meanwhile, the
content of W and C in the amorphous CoWC binder is higher
compared with that in the rst situation during thermal spraying.
The C content was lower in contrast to W in the CoWC binder
due to the oxidation of part of the C and the generation of gas
during thermal spraying. The Co6W6C with a relatively low C
content experienced nucleation and growth and coupled with the
decrease of W2C and even WC according to the chemical reaction
equation shown in Eq. (1-1)[24].
CoWC W2 C WCCo6 W6 C: 1  1
Little WC will also participate in the reaction according to Eq. (1-1)
compared with the W2C at relatively low heat treatment temper-
atures because the W2C phase is a metastable phase and is more
likely to decompose relative to WC.
 Q. Wang et al. / Surface & Coatings Technology 206 (2012) 40004010
Fig. 8. A schematic of the WC12Co coating microstructure evolution during the heat treatment (a) Room temperature ~ 550 C, (b) 550 C750 C, (c) 750 C950 C, (d) 950 C
1150 C.
iii The Co3W3C generated at the interface between WC, W2C and the
amorphous CoWC (marked by II in Fig. 8a) where W and C are
present in the amorphous CoWC binder in amounts between
those present in the rst and the second situation. Asl et al.[14]
found that Co3W3C phase has a non-uniform crystalline structure
with a lot of defects like dislocations and stacking faults in a WC
17Co coating after a vacuum heat treatment, they also deduced the
Co3W3C generating from the high carbon phases like WC or W2C
particles by mixing with cobalt at high temperature. The Co3W3C
is generated by the chemical reaction shown in Eq. (1-2) [24].
CoWC W2 C WCCo3 W3 C 1  2
All of the new phases (such as crystallized Co, Co3W3C and
Co6W6C) are generated after an hour of heat treatment at 750 C
and are limited due to the slow diffusion velocity of elements
such as W, C and Co in the solid coating at the relatively low heat-
treatment temperatures.
3) 750 C950 C (Fig. 8c)
The amount of new phases (such as Co and Co6W6C) will
gradually increase by way of nucleation and growth at 950 C by
consuming W2C and even WC because the content of the W and C
in the Co binder is insufcient for the formation of Co6W6C. The
W2C and amorphous phase can barely be detected in the coating
after an hour of heat treatment at 950 C according to the X-ray
diffraction results shown in Fig. 1. The metastable Co3W3C phase
begins to be generated at a heat-treatment temperature of 750 C
and eventually disappears at 950 C according to the chemical
reaction shown in Eq. (1-3) [24].
Co3 W3 CCo Co6 W6 C WC
This equation indicates that the Co3W3C phase experiences
nucleation and growth and then decomposes and disappears, so
the Co3W3C phase cannot be detected in the HT950 coating.
4007
4) 950 C1150 C (Fig. 8d)
The new phases generated early on continue to grow larger.
Meanwhile, another new phase, Co2W4C, is generated in the region
where the W content is highest and is present in the form of metal W
in the as-sprayed coating (as shown in Eq. 1-4) [24].
CoWC W WCCo2 W4 C 1  4
This W precipitates from the supersaturated molten Co binder
(the region marked by III) when impacting and cools down on the
substrate due to the overheating of WC in the plume during the
spraying process. The consumed WC increases with the increasing
temperature of heat treatment, and C and W diffuse into the binder
and generate various eta phases such as Co3W3C, Co6W6C and
Co2W4C.
3.3. The effects of heat treatment on the hardness of the coatings
The effects of heat treatment on the hardness of the coatings are
shown in Fig. 9.
It can be seen from Fig. 9 that for each coating, both the Vickers
hardness and its standard deviations decreased with an increase in
the applied load, and the changes in the hardness for all the coatings
have a nearly uniform tendency. As the thermal-spray coating has
a lamellar structure with some defects such as pores and oxides,
the hardness values are scattered when the indenter presses on the
different micro-regions that have different amounts of defects under
a small load. The area of indentation produced by the Vickers indenter
usually exceeds the localized area of the intensively distributed
pores when the applied load is larger, leading to smaller standard
deviations in the coating hardness.
1  3
3.4. The effect of heat treatment on the fracture toughness of the coatings
The effects of heat treatment on the fracture toughness of the
coatings are shown in Fig. 10.
4008 Q. Wang et al. / Surface & Coatings Technology 206 (2012) 40004010

were then concurrently distributed in the coating, thereby causing

the coating that was heat treated at 750 C to exhibit a similar high
hardness but lower fracture toughness. When the heat-treatment
temperature was increased to 950 C or even 1150 C, the amount of
brittle phases in the coating decreased gradually and only one eta
phase (Co6W6C) was left in the coating. Yao et al. [25] reported that
Co6W6C precipitated from the solid state of the coating during the
cooling process with ne crystalline grains and a uniform distribution,
which resulted in it being less brittle compared with Co3W3C; thus,
the fracture toughness increased greatly after the heat treatment at
950 C. The fracture toughness attained the maximum possible value
when the temperature of the heat treatment was increased to 1150 C,
which can be attributed to a decrease of WC and an increase in
crystalline Co in the HT1150 coating.

3.5. The effect of heat treatment on the abrasive wear resistance of the
coatings

The effects of heat treatment on the abrasive wear resistance of

Fig. 9. The effects of heat treatment on the hardness of as-sprayed and heat-treated
coatings.
To study the relationship between fracture toughness and hard-
ness, the hardness of the coatings is also given in Fig. 10. It can
be seen that the hardness of the coatings initially increased with
increasing temperature of the heat treatment, attaining a maximum
at 550 C, and then decreasing. Likewise, the fracture toughness of
the coatings shows nearly the reverse tendency compared with the
hardness, but the lowest fracture toughness of the coating is located
at the heat treatment temperature of 750 C instead of 550 C.
Little phase transformation took place after the heat treatment
of 550 C, but the hardness and fracture toughness varied greatly.
This phenomenon was also shown in a previous publication [10] and
is attributed to variations in the stress state and integrity of the
coating, as well as the difference in expansion coefcients between
the coating and substrate. When the heat-treatment temperature was
increased to 750 C, a partial phase transformation occurred and the
original brittle phase (amorphous CoWC and W2C) decreased, and
a new brittle phase (Co3W3C) was generated. Many brittle phases
the coatings are given in Fig. 11.
It can be seen from Fig. 11 that except for the coating that was heat
treated at 950 C, the wear rates of the heat treated coatings were all
higher than those of the as-sprayed coatings.
Fig. 12 shows the abrasive worn micrograph surfaces of the coatings
before and after heat treatment.
According to Fig. 12, different patterns of abrasive wear are observed
in the coatings treated at various temperatures. The micrograph of
the HT550 coating showed that less binder phase is found among the
WC particles in the worn surface (see Fig. 12d), resulting from highly
brittle binders, such as CoWC, W2C and W. The HT750 coating
exhibited many large pits on the low-magnication micrograph of the
worn surface (see Fig. 12e) due to its lowest fracture toughness. Various
brittle binder phases exhibited poor bonding ability, which made the
WC particles and splats easily removed from the coating and generated
many deep pits on the surface of the coating, resulting in the worst wear
resistance among the samples.
The micrographs of the worn surfaces of HT950 and HT1150
coatings exhibited similar smooth wear as that of the as-sprayed
coating. However, the mean free binder in the HT1150 coating is
larger than that in the HT950 coating, and one possible reason for this
nding is that many more WC particles in the HT1150 coating were

1600 10
1.0
1500
Fracture toughness(MPam(1/2))

8
1400 0.8
Wear Loss(10-3mm3/m)
Hardness(HV5)

1300
6
0.6
1200

1100 4 0.4
1000

900 2 0.2

800
0 0.0
As-sprayed HT550 HT750 HT950 HT1150 As-sprayed HT550 HT750 HT950 HT1150
Coating NO. Coating No.

Fig. 10. The effects of heat treatment on the fracture toughness of as-sprayed and heat- Fig. 11. The effects of heat treatment on the abrasive wear rate of as-sprayed and heat
treated coatings. treated coatings.
 Q. Wang et al. / Surface & Coatings Technology 206 (2012) 40004010 4009

consumed, and the W and C were allowed to diffuse into the binder,
generating eta phases such as Co2W4C and Co6W6C. The formation of
smaller amounts of new phases such as Co6W6C and tough crystalline
Co without consuming a great deal of hard WC phase made the
HT950 coating exhibits higher hardness and abrasive wear resistance
relative to the HT1150 coating.
4. Conclusions
WC12Co coatings were heat treated at 550 C, 750 C, 950 C and
1150 C for 1 h in an argon atmosphere. The phase composition,
microstructure evolution and the coating properties of the as-sprayed
and heat treated coatings were studied, and the results are summarized
as follows.
(2) Signicant diffusion at the interface between the coating and
substrate occurred when the temperature of the heat treat-
ment was at or above 950 C. Interactive diffusion mostly
involved cobalt and iron with trace amounts of tungsten, and
the degree of interfacial diffusion increased with the temper-
ature of the heat treatment.
(3) The hardness of the coatings initially increased with the heat
treatment temperature and then decreased, whereas the fracture
toughness showed almost the reverse tendency. WC12Co
coatings heat treated at 950 C exhibited the highest wear
resistance among all the coatings as a result of the formation of
hard crystalline Co6W6C and tough crystalline Co without the
consumption of a great deal of the WC phase.

(1) The amorphous phase gradually transformed to crystalline Co Acknowledgments

and eta phases such as Co3W3C, Co6W6C and Co2W4C coupled
with the solution of W2C and WC phases in the coating with an This research was supported by the Fundamental Research Funds
increase in the heat-treatment temperature. for the Central University.

a b

c d

e f

Fig. 12. The worn surfaces of coatings at low and high magnications (a, b) as-sprayed, (c, d) HT550, (e, f) HT750, (g, h) HT950 and (i, j) HT1150.
4010 Q. Wang et al. / Surface & Coatings Technology 206 (2012) 40004010

g h

i j

Fig. 12 (continued).

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