Comparative tribological study of air plasma sprayed WC12%Co coating

versus conventional hard chromium electrodeposit

M. Heydarzadeh Sohi

, F. Ghadami
School of Metallurgy and Materials, College of Engineering, University of Tehran, Tehran, Iran
a r t i c l e i n f o
Available online 21 December 2009
Keywords:
Coating
Structure
Wear
a b s t r a c t
In this work, the properties of air plasma sprayed WC12%Co coating before and after heat treatment
were compared with the properties of the hard chromium electrodeposit. WC12%Co coatings were
heat treated at 650, 900 and 1150 1C for 1h in an argon atmosphere. XRD patterns conrmed the
formation of an amorphous phase in the as-sprayed coating. This amorphous phase gradually
transformed to Z-carbides in the course of heat treatment of the coating. This transformation was
conrmed by the XRD analysis of the coatings heat treated above 900 1C. Pin-on-disc wear test results
showed that WC12%Co coatings had a signicantly better tribological performance as compared with
that of the hard chromium electrodeposits. The results also indicated that heat treatment of the WC
12%Co coatings at 900 1C gave the highest wear resistance among the coatings, which was due to the
formation of hard Z-carbides at this temperature.
& 2009 Elsevier Ltd. All rights reserved.
1. Introduction
Hard chromium electrodeposits are used to restore the original
dimensions of worn surfaces of several industrial components.
However, their usage is decreasing due to some intrinsic
limitations of these deposits and the toxic and carcinogenic
characteristic of the hexavalent chromium (Cr
6+
) [1]. Thermal
sprayed carbide coatings especially WCCo coating are being used
as a replacement for hard chromium electrodeposits [2,3].
In recent years, several studies have been carried out on the
effect of heat treatment on physical and mechanical properties of
these coatings. Heat treatment increases the effective carbides
content of these coatings due to the recrystallisation of the
amorphous phases in the coatings to Z-carbides [2,3]. The
Z-carbides are commonly formed in W
x
Co
y
C ternary system
which consists of one or a combination of W
3
Co
3
C, W
4
Co
2
C and
W
6
Co
6
C carbides [48]. Tribological properties of these coatings
have also been studied by a number of researchers [69].
In this paper the effects of the heat treatment on structure, and
wear behavior of air plasma sprayed WC12%Co coatings were
investigated and compared with those of the hard chromium
electrodeposits.
2. Experimental
Agglomerated and sintered WC12%Co powder obtained from
TAFA-Praxair with particle size about 45715mm was used as the
feedstock. The morphology of this type of powder is spherical
and semi-spherical. Air plasma spraying (APS) equipment
(Plasma-Technik) was used to deposit about 200mm thickness
of WC12%Co coatings on grit blasted mild steel (0.23wt%C). APS
process was carried out in a mixture of argon/hydrogen plasma
gases. Table 1 lists the main spray parameters employed for
WC12%Co deposits. In addition, for comparison, conventional
hard chromium electrodeposits were applied on the same steel
substrates with a thickness of 100mm using standard acidic bath
(250gr/l chromic acid and 2.5gr/l sulfuric acid) and a current
density of 40A/dm
2
.
WC12%Co coated samples were placed in a furnace, which
was purged with argon before being heated at a rate of
201Cmin
1
up to the treatment temperature. They were then
held for 1h before being allowed to cool to room temperature in
the furnace. The heat treatment temperatures were chosen to be
650, 900 and 11501C.
The Vickers microhardness test was performed using a 200gf
load. The distance between indentations was large enough to
avoid interaction between the work hardened regions and any
micro-cracks caused by the indentations. The crystalline phases of
as-sprayed and heat treated coatings were identied using X-ray
diffraction (XRD) and measurements were made on an xpert
Phillips difractometer with Cu-Ka (l=0.15406nm) radiation at
40kV and 30 mA. A low scanning rate of 0.21/min was used to
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Tribology International
0301-679X/$ - see front matter & 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.triboint.2009.12.049

Corresponding author. Tel.: +982182084077; fax: +982188006076.

E-mail address: mhsohi@ut.ac.ir (M. Heydarzadeh Sohi).
Tribology International 43 (2010) 882886
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achieve the desired precision. The diffraction patterns were
indexed according to International Centre for Diffraction Data
(ICDD).
Wear rates and friction coefcient of the as-sprayed and heat
treated WC12%Co coatings as well as hard chromium electro-
deposits were measured using a conventional pin-on-disc appa-
ratus. The coated specimens with rectangular cross-section with
the dimensions of 510mm
2
were prepared as pins for wear
testing and a sintered alumina disc of 50mm diameter was used
as counter face. The tests were performed under 30N load
with a sliding distance of up to 1000m, sliding speed of 0.5m/s
and a wear track diameter of 30mm at room temperature. The
wear rates were then calculated by dividing total weight loss
(in milligrams) with total sliding distance of 1000m.
3. Results and discussion
3.1. Characterization of the coatings
Figs. 1a and b show typical microstructure of the cross-section
of an as-sprayed WC12%Co coating at two different
magnications. According to Fig. 1a, this coating has a lamellar
structure and is consisted of two major phases, i.e. carbide and
cobalt rich matrix phase, together with interlamellar pores and
microporosities. Fig. 1b also shows the formation of W
2
C in the
boundaries of WC particles with cobalt which could be an
indication of decarburization of the carbides during plasma
spray process, according to Liao et al. [7] and Nerz et al. [8].
Figs. 2a, b, c, and d show the backscatter images of WC12%Co
coating before and after heat treatment at 650, 900 and 11501C,
respectively. The white areas in these gures which are rich in
tungsten are reduced as the heat treatment temperature is
increased. Comparison of the x-ray diffraction patterns of the
feedstock powder, as-sprayed and heat treated specimens (Fig. 3)
explains this phenomenon. The XRD pattern for the feedstock
powder shows peaks indexed to WC and Co. The XRD pattern
of the as-sprayed coating exhibit WC and W
2
C peaks along
with broad diffuse peaks (humps) between 2y=37461 and
2y=73811 representing amorphous or nanocrystalline material.
These results also support with those observed by Nerz et al. [8]
and Stewart et al. [9].
Owing to decarburization and dissolution of the WC in liquid
cobalt at high temperatures during spraying [3], as well as
thermal and kinetic history of melted particles, the phases present
in the coatings differ from those in the powder. Diffraction
patterns from the heat treated coatings at 900 and 11501C show
peaks indexed to Z-carbides (W
3
Co
3
C, W
4
Co
2
C and W
6
Co
6
C). The
XRD pattern for the samples heat treated above 9001C clearly
showed Z-carbide peaks along with WC and W
2
C peaks.
Diffraction patterns of the heat treated coatings did not show
any amorphous phase especially at 11501C.
Microhardness proles of the as-sprayed and heat treated WC
12%Co coatings together with conventional hard chromium
electrodeposit are shown in Fig. 4. It is clear that heat treatment
of WC12%Co coating at 6501C causes slight decrease in
microhardness because of the relaxation of residual stresses in
the coating. But by increasing heat treatment temperature to 900
and 11501C, the average microhardness of the coatings is
increased. This is related to the formation of Z-carbides in
coating during heat treatment at high temperatures. Increase in
hardness at relatively high treatment temperatures has also been
reported for WC17wt%Co coatings, where increases in hardness
up to 1400kg mm
2
were observed after heat treatment at 7001C
[9]. This was attributed to a decrease in the void content of the
coating. However, the measured hardness is known to be a
function of the amount of Z-carbide formed during heat treatment
[1012].
According to Fig. 4, it is clear that the hardness of conventional
hard chromium coating is relatively lower than those of the WC
12%Co coatings both before and after heat treatment.
Table 1
Thermal spray parameters employed during deposition of WC12%Co coatings.
Nozzle diameter (mm) 6
Plasma gas ow Ar (l/min) 65
Secondary gas ow H
2
(l/min) 3
Carrier gas Ar (l/min) 2
Arc current (Amp) 700
Arc voltage (V) 58
Spraying angle 901
Number of passes 8
Powder feed rate (g/min) 36
Stand off distance (mm) 140
Digital setting 40
Fig. 1. Backscattered electron micrograph of the as-sprayed WC12%Co coating
showing (a) lamellar microstructure, (b) WC and W
2
C.
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3.2. Wear behavior of the coatings
Fig. 5 shows the wear rates of hard chromium and WCCo
coated specimens before and after heat treatment. In addition,
Fig. 6 shows the friction coefcient of all coated specimens.
According to these results, chromium coated samples showed
relatively higher wear rate and coefcient of friction in
comparison with those of WC12%Co coatings. These differences
are mainly related to the hardness values of the coatings.
For the as-sprayed and heat treated WC12%Co specimens,
after a transition period of relatively high wear, a steady state
wear behavior was established. According to the results, except
for the coating which was heat treated at 6501C, the wear rates of
heat treated coatings were lower than the wear rate of the as-
sprayed coating. The best wear resistance was obtained after heat
treating of the coated materials at 9001C. Despite its higher
hardness, the wear rate of the coating that had been heat treated
at 11501C was slightly higher than the sample that had been heat
treated at 9001C. This might be related to more brittle nature of
the sample that had been treated at 11501C.
Figs. 7a, b, c and d show micrographs of the worn surfaces of
the WC12%Co and hard chromium coated specimens. For the
case of the WC12%Co coated specimens, the light contrasts in the
backscatter images are regions that are rich in tungsten carbide,
whereas the darker regions are cobalt rich matrix, which had been
worn preferentially (Figs. 7a, b and c). According to Figs. 7a, b and
c, it is suggested that during the wear process, the carbide
particles are progressively exposed until they become vulnerable
to removal by fracture as complete detached particles from the
matrix [10].
With regard to the effect of the heat treatment on the wear
behavior of the WCCo coating, except for the coating that was
heat treated at 6501C, the wear rates of heat treated coatings
were lower than that of the as-sprayed coating. The best wear
resistance was obtained after heat treating of the coated materials
at 9001C. Nerz et al. [8] also observed an increase in abrasive wear
resistance after heat treatment of HVOF sprayed WCCo coatings
at 9001C. They concluded that this was due to the increased
carbide content, as the amorphous phase recrystallised to form
the Z-carbides. Stewart et al. [9] also demonstrated that the role
of such recrystallisation on the wear behavior of the coating is
Fig. 2. Microstructure of APS WC12%Co coatings: (a) as-sprayed, and after heat treatment at (b) 6501C, (c) 9001C and (d) 11501C for 1h.
Fig. 3. XRD patterns of WC12%Co powders and sprayed coatings before and after
heat treatment at 6501C, 9001C and 11501C.
M. Heydarzadeh Sohi, F. Ghadami / Tribology International 43 (2010) 882886 884
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difcult to ascertain owing to other changes that accompany heat
treatment, such as cracking of the coatings and change in the state
of the residual stress.
For the case of hard chromium, according to Fig. 7d, wear me-
chanism is probably based on fatigue wear because of the
generation of structural cracks grown during wear of hard
chromium deposit.
4. Conclusions
WC12wt%Co powders were deposited onto steel sub-
strates to form coatings by the air plasma spraying
(APS) method. The coatings were consisted of WC, W
2
C and
an amorphous phase consisting of cobalt, tungsten and
carbon.
Heat treatment of the coatings in an inert atmosphere above
9001C promoted the formation of Z-carbides from the
amorphous phase.
Microhardness of WC12%Co coatings for different heat
treating conditions was relatively higher than that of the
conventional hard chromium electrodeposit.
The hardness and wear resistance of WC12%Co coatings after
being heat treated at 9001C increased due to formation of
Z-carbides.
Steady state wear rate of the conventional hard chromium
deposit was relatively higher than those of as-sprayed and
heat treated WC12%Co coatings.
Fig. 4. Microhardness proles of the as-sprayed and heat treated WC12%Co coatings as well as conventional hard chromium electrodeposit.
Fig. 5. Variation of the wear rates for WCCo before and after heat treatment and
hard chromium electrodeposit, at an applied load of 30N and a sliding distance
of 1000m.
Fig. 6. Variation of friction of coefcient for as-sprayed and heat treated coatings.
M. Heydarzadeh Sohi, F. Ghadami / Tribology International 43 (2010) 882886 885
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References
[1] Sartwell BD. HVOF thermal spray coatings replace hard chrome. Advanced
Materials and Processes 1999;156(2):258.
[2] Ko PL, Robertson MF. Wear characteristics of electrolytic hard chrome
thermal sprayed WC10Co4Cr coatings sliding against AlNibronze in air
at 211C, at 401C. Wear 2002;252:88093.
[3] Nestler M, Prenzel CG and Seitz T. HVOF spraying vs. hard chrome plating
coating characteristics and aircraft applications. In: Proceedings of the 15th
International Thermal Spray Conference, ASM International; 1998. p. 11625.
[4] Dullin B and Nicoll AR. Plasma sprayed tungsten carbide cobalt coatings. In:
Proceedings of the 2nd International Thermal Spray Conference, Metals Park,
OH, USA; 1987. p. 34551.
[5] Subrahmanyam J, Spivanstava MP, Sivakumar R. Characterization of plasma
sprayed WCCo coatings. Material Science and Engineering 1986;84:20914.
[6] Chen H, Hutchings IM. Abrasive wear resistance of plasma sprayed tungsten
carbidecobalt coatings. Surface and Coatings Technology 1998;58:1069.
[7] Liao H, Normand B, Coddet C. Inuence of coating microstructure on the
abrasive wear resistance WC/Co cermet coatings. Surface and Coatings
Technology 2000;124(2):23542.
[8] Nerz J, Kushner B, Rotolico A. Microstructure evaluation of tungsten
carbidecobalt coatings. Journal of Thermal Spray Technology 1992;1:
14752.
[9] Stewart DA, Shipway PH, McCartney DG. Inuence of heat treatment on the
abrasive wear behavior of HVOF sprayed WCCo coatings. Surface Coating
and Technology 1998;105:1324.
[10] Li C, Ohmori J, Harada AY. Formation of an amorphous phase in
thermally sprayed WCCo. Journal of Thermal Spray Technology 1996;5(1):
6973.
[11] Ghadami F, Heydarzadeh Sohi M. The effect of heat treatment on wear
properties of air plasma sprayed WC12Co coatings. In: Proceedings of
the 5th Recent Advances in Mechanical and Metallurgical Engineering; 2005.
p. 5607.
[12] Zhang FL, Wang CY, Zhu M. Nanostructured WC/Co composite powder
prepared by high energy ball milling. Scripta Materialia 2003;49(11):11238.
Fig. 7. SEM images of worn surfaces of (a) as-sprayed WC12%Co coating, (b) WC12%Co coating heat treated at 650 1C, (c) WC12%Co coating heat treated at 9001C and
(d) hard chromium electrodeposit.
M. Heydarzadeh Sohi, F. Ghadami / Tribology International 43 (2010) 882886 886