International Journal of Refractory Metals & Hard Materials 25 (2007) 1115

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0263-4368/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijrmhm.2005.10.009
Characterization of WCVCCo thermal spray
powders and coatings

S. Luyckx

, C.N. Machio
School of Chemical and Metallurgical Engineering, University of the Witwatersrand,
DST/NRF Center of Excellence in Strong Materials, Johannesburg, South Africa
Received 13 July 2005; accepted 28 October 2005
Abstract
The composition and microstructure of agglomerated and sintered WCVCCo thermal spray powders and of the high pressure/high
velocity oxy-fuel (HP/HVOF) coatings produced from the powders were analysed and compared to those of agglomerated and sintered
commercial WCCo thermal spray powders of equal Co mass fraction and of the commercial WCCo coatings that were deposited under
the same conditions as the WCVCCo coatings. The results of the analyses helped to explain the abrasion resistance of WCVCCo
coatings being superior to that of WCCo coatings.
2005 Elsevier Ltd. All rights reserved.
Keywords: WCVCCo HP/HVOF coatings; WCCo HP/HVOF coatings
1. Introduction
WC10VC12Co and WC10VC17Co thermal spray
HP/HVOF coatings have proved to be more abrasion resis-
tant than WCCo coatings with the same cobalt mass frac-
tion and deposited under the same conditions. In order to
determine the reasons for the improved performance, the
starting WCVCCo powders and the Wnal coatings have
been characterized in detail. This paper reports the results
of the abrasive wear tests and of the characterization which
provided some quantitative insight into the processes
occurring during coating deposition.
2. Method
WC10VC12Co and WC10VC17Co powders were
produced from WC, VC and Co powders and were agglom-
erated by spray drying and sintered, similarly to commer-
cial WC12Co and WC17Co thermal spray powders
which were used for comparison purposes. The powders
were characterized as follows:
(a) size and morphology were determined using a Mal-
vern Mastersizer model MS 1002 and a Jeol 840 scan-
ning electron microscope;
(b) phase composition was determined by XRD using a
Philips DiVractometer with a CuK

radiation source
and the Rietveld proWle reWnement method;
(c) carbide grain size and distribution were determined
by lineal analysis on scanning electron micrographs in
SE and BSE mode as well as X-ray dot mapping using
a Leo FESEM;
(d) Xowability was measured by means of a Hall Flow-
meter.
The coatings were deposited on AISI 304 stainless steel
substrates using a 6-axis robotic HP/HVOF Tafa JP 5000

gun. The deposition parameters, which had been optimized

for the WCCo coatings, were the same for the WCVC
Co and the WCCo coatings, and were as follows: 4 in. gun
barrel; 380mm spray distance; 0.0227 m
3
/h fuel (kerosene)
Xow rate; and 56.6 m
3
/h oxygen Xow rate.

Presented at the 16th Plansee Seminar, Reutte, Austria, May 2005.

*
Corresponding author.
E-mail address: nluyckx@icon.co.za (S. Luyckx).
12 S. Luyckx, C.N. Machio / International Journal of Refractory Metals & Hard Materials 25 (2007) 1115
The coatings were characterized as follows:
(a) porosity and microstructure were examined on cross
sections by optical and scanning electron microscopy;
(b) phase composition, carbide grain size and carbide dis-
tribution were determined using the same techniques
as for the powders;
(c) hardness and wear resistance were measured as
reported in References 1 and 2.
3. Results and discussion
3.1. Morphology and size of the powders
All the powders (i.e. WCVCCo and WCCo powders)
were spherical. Particles with a hollow core were observed
in both the experimental (WCVCCo) and the commer-
cial powders (WCCo) [3]. Fig. 1 shows the general mor-
phology of the powders. The mean size of the powders
particles and the Xowability of the powders are given in
Table 1. Table 1 shows that the experimental powders were
Wner and had a narrower particle size distribution than the
commercial powders. The lower scatter in the Xowability of
the commercial powders is likely to be due to the coarser
particle size as well as the lower volume of powder tested
(since the density of WC is higher than the density of VC
[4]).
3.2. Amount of phases and phase properties of the powders
XRD analyses showed that the WCVCCo powders
consisted of WC, (W, V)C and Co, without any VC present,
in agreement with results from sintered WCVCCo alloys
produced from WC, VC, and Co powders [5].
Table 2 gives the amount of phases in the powders as
obtained using the Rietveld proWle reWnement method. In
these calculations the composition of the (W, V)C phase
was assumed to be approximately (W
0.3
, V
0.7
)C
x
(with x<1)
because this was found to be the equilibrium composition
of (W, V)C from Thermo-Calc calculations [6] and from
experiments [7].
The powders were found to be all stoichiometric, i.e.
without free carbon or eta phase, in agreement with the
analyses carried out by the suppliers [8]. Table 2 shows that
the fcc Co/hcp Co ratio appeared to be unrelated to the
presence of vanadium. The latter result is in contrast with
results obtained from WCVCCo and WCCo sintered to
full density [9], where (at equal cobalt mass fraction) the fcc
Co/hcp Co was higher in materials containing vanadium,
suggesting that vanadium in solution in Co stabilizes the
fcc structure. A possible explanation of the present result is
that the powders were porous and that the internal stresses
that control the fcc !hcp transformation were diVerent in
magnitude and distribution from those in a fully dense
structure.
The cobalt content of the powders in Table 2 as derived
from Rietveld analysis does not agree with the nominal
Fig. 1. Morphology of powder WC10VC12Co. This morphology was
similar for all the powders.
Table 1
Mean particle size and Xowability of the thermal spray powders used in
this investigation
Powders Particle size (m) Flowability (s/50 g)
WC12Co 43.4 25.7 32 0
WC10VC12Co 26.9 16.1 29 2
WC17Co 40.1 24.9 28 0
WC10VC17Co 31.6 18.3 29 5
Table 2
Phase composition (in wt.%) of the powders used in this investigation and of the coatings produced from the powders, from X-ray diVraction and Rietveld
calculations
WC (W, V)C fcc Co hcp Co Amorphous Co W
2
C Co
6
W
6
C
Powders
WC12Co 89.5 2 8.7 1.5 2 1.8
WC10VC12Co 78.5 2 13.3 2 7.5 1.5 1 1.3
WC17Co 89.6 2 10.4 1.5
WC10VC17Co 77.1 2 12.1 2 9.2 1.5 1.5 1.3
Coatings
WC12Co t74.8 t9.8 t7.2 t8.2
WC10VC17Co t60.3 t17.5 t10.3 t5.3 t6.6
WC17Co t75.7 t14.5 t0.8 t9.1
WC10VC17Co t63.4 t10.8 t14.4 t1.9 t9.5
S. Luyckx, C.N. Machio / International Journal of Refractory Metals & Hard Materials 25 (2007) 1115 13
composition given by the suppliers and reported in Table 1.
This is also inconsistent with the large diVerences in wear
behaviour of the coatings produced from these powders
(see Figs. 35). It is not clear if the incorrect results of the
Rietveld calculations are due to the porosity of the powders
or to the high adsorption coeYcient of Co for CuK

radia-
tion. The results of the phase analyses of the coatings
included in Table 2 are discussed in Section 3.4.
The WC and (W, V)C grain size is given in Table 3. Table
3 shows that the WC grain size was similar in all powders,
except the WC17Co powder, and that the grain size of the
(W, V)C grains in the two WCVCCo powders was similar
and signiWcantly larger than the mean grain size of the WC
grains. Table 3 includes the results from the measurements
of grain size in the coatings, which are discussed in Section
3.4.
From X-ray dot maps it was possible to establish that
the (W, V)C phase was distributed uniformly both in the
WCVCCo powders and in the WCVCCo coatings
[2,3].
3.3. Porosity and general microstructure of the coatings
The porosity of the coatings was measured on cross sec-
tions, by dot counting. The results are given in Table 4
together with the thickness of the coatings.
As has been observed by other researchers [10] in WC
Co-based thermal spray coatings, the Co composition and
distribution in the coatings was less uniform and the WC
grains less angular than in sintered WCCo-based alloys
(including WCVCCo alloys [5]). The higher porosity of
the WCVCCo coatings is due to the deposition condi-
tions having been those used industrially for WCCo coat-
ings and not having been optimized for the new
experimental coatings. Fig. 2 is an example of the micro-
structure of a WC10VC12Co and a WC10VC17Co
coating. The microstructures of the WCCo coatings were
similar, apart from the absence of (W, V)C grains [2,3].
3.4. Amount of phases and phase properties of the coatings
Table 2 shows that neither fcc Co nor hcp Co were pres-
ent in the coatings, in agreement with previous investiga-
tions, according to which Co in WCCo-based thermal
Table 3
WC and (W, V)C grain size in the powders and coatings
WC grain size (m) (W, V)C grain size (m) % decrease in WC grain size % decrease in (W, V)C grain size
Powders
WC12Co 0.8 0.2
WC10VC12Co 0.8 0.1 1.8 0.4
WC17Co 1.2 0.3
WC10VC17Co 0.8 0.1 1.9 0.4
Coatings
WC12Co 0.5 0.2 37
WC10VC12Co 0.4 0.1 1.0 0.4 50 44
WC17Co 0.8 0.3 33
WC10VC17Co 0.5 0.2 1.1 0.4 37 42
Table 4
Porosity and thickness of the coatings
Coating Average porosity (%) Average thickness (m)
WC10Co 3.6 0.3 200 4
WC10VC12Co 4.4 0.6 200 5
WC17Co 0.5 0.2 186 5
WC10VC17Co 6.3 1.8 214 7
Fig. 2. Characteristic microstructures of (a) WC-10VC-12Co and (b) WC
10VC17Co. For both coatings: light round shapes are WC grains; con-
tinuous grey/dark matrix is solution of V and W in Co; dark irregular
shapes (W, V)C, one of which is marked. Arrow 1 shows grains that are
brighter than WC and were probably W
2
C.
14 S. Luyckx, C.N. Machio / International Journal of Refractory Metals & Hard Materials 25 (2007) 1115
spray coatings is amorphous [10]. Therefore the Co content
in the coatings could not be determined by X-ray diVrac-
tion. The Co contents given in Table 2 are approximate
since they were calculated from the XRD results for the
crystalline phases, assuming that the Co mass percent was
the nominal one, except for the mass percent of Co in
Co
6
W
6
C (the Co mass fraction in Co
6
W
6
C being 0.24). The
calculations neglected the amounts of W, V and C in solu-
tion in the Co and possible other phases (such as W) which
may have been present in amounts not detectable by XRD.
Of the phases not present in the powders but present in
the coatings, i.e. W
2
C and Co
6
W
6
C, the W
2
C grains were
prominent in BSE micrographs because they appeared
lighter than any other phase, on account of their high mean
atomic number. They occurred predominantly as clusters of
very Wne grains and their occurrence was visibly less fre-
quent in the 17%Co coatings, which conWrms the results of
the analyses reported in Table 2. The C-deWcient phases
W
2
C and Co
6
W
6
C formed as a result of oxidation and
decarburization during the coating deposition process, in
agreement with the literature [10].
Table 3 shows that the mean grain size of both WC and
(W, V)C coatings decreased substantially during coating
deposition. The decrease in mean grain size of the carbides
is due to the solubility of the carbides in Co at the deposi-
tion temperatures. The W, V and C in solution in the Co
did not re-precipitate on the existing grains, contrary to
what happens during the slow cooling of sintered WCCo-
based alloys, because of the high cooling rate of the coat-
ings. Although it would be interesting to investigate in
detail the development of the microstructure of the coat-
ings by simulations of the solidiWcation process, such an
investigation was beyond the scope of the present project.
3.5. Abrasion test results
Figs. 35 summarize the results of the dry and wet abra-
sion tests carried out on the four types of coatings under
identical conditions. The wear of the coatings is given per
unit load and per unit time. The graphs show that the wear
resistance of the VCcontaining coatings was consistently
higher than the wear resistance of the commercial coatings.
More details on these abrasion tests are given in References
1 and 2.
4. Conclusions
The characterization of WCVCCo and WCCo ther-
mal spray powders and coatings of equal Co mass fractions
has led to new quantitative insight into some of the pro-
cesses occurring during coating deposition and to an expla-
nation of the diVerence in abrasion resistance between
WCVCCo and WCCo coatings.
In both materials, during coating deposition the WC
grains acquire a less angular morphology and a Wner mean
size than in the powders and a signiWcant fraction of WC
grains are decarburized, with the formation of W
2
C and
Co
6
W
6
C. Changes in the morphology of the (W, V)C grains
could not be detected on account of their typical irregular
shape [5], but their mean size also decreased. The outer sur-
faces of the carbide grains, therefore, dissolve in the Co at
the high deposition temperatures and no re-precipitation
on the un-dissolved grains occurs during cooling because of
Fig. 3. Plots of rates of mass loss per unit load (in g/N/min) for test load
25 N in dry abrasion.
WC - 12Co
WC - 17Co
WC-10VC-12Co
WC-10VC-17Co
30
45
60
75
90
105
120
0 5 10 15 20 25 30 35
Time (min)
R
a
t
e

o
f

m
a
s
s

l
o
s
s
/
u
n
i
t
l
o
a
d

(
u
g
/
N
/
m
i
n
)
Fig. 4. Plots of rates of mass loss per unit load (in g/N/min) for test load
50 N in dry abrasion.
WC-12Co
WC-10VC-12Co
WC-17Co
WC-10VC-17Co
10
20
30
40
50
60
70
0 5 10 15 20 25 30 35
Time (min)
R
a
t
e

o
f

m
a
s
s

l
o
s
s
/
u
n
i
t
l
o
a
d

(
u
g
/
N
/
m
i
n
)
Fig. 5. Plots of rate of mass loss per unit load (in g/N/min) for wet abra-
sion. The abrasive was replaced after 30 min.
WC-17Co
WC-12Co
WC-10VC-12Co
WC-10VC-17Co
0
50
100
150
200
250
300
350
400
450
0 10 20 30 40 50 60 70 8
Time (min)
R
a
t
e

o
f

m
a
s
s

l
o
s
s
/
u
n
i
t
l
o
a
d

(
u
g
/
N
/
m
i
n
)
0
S. Luyckx, C.N. Machio / International Journal of Refractory Metals & Hard Materials 25 (2007) 1115 15
the very high cooling rate. As a result, a fraction of W, V
and C remains in solution in the Co, although it could not
be measured by EDS, for example, because of the small size
of the Co areas.
The higher dry abrasion resistance of the WCVCCo
coatings relative to WCCo coatings of equal Co mass frac-
tion [1] is attributed mainly to the Wner WC grain size in the
coatings (even when starting from equal grain size in the
powders), and to the presence of the (W, V)C grains, which,
on account of their hardness and Wne size, are not only
resistant to abrasion but also to fracture. The higher wet
abrasion resistance of the WCVCCo coatings compared
to the WCCo coatings is, in addition to the above factors,
due to the lower volume fraction of the Co binder phase at
equal mass fraction. In wet abrasion, the binder phase is
lost via both corrosion and abrasion leading to more car-
bide grain fall-out, thus the wear resistance is higher when
the Co fraction on the wearing surfaces is lower.
Acknowledgements
The authors wish to acknowledge the sponsorship of
Vanitec, DAAD, the Department of Science and Technol-
ogy and the Department of Trade and Industry (as
THRIP) and the National Research Foundation of South
Africa. The thermal spray powders were supplied by Starck,
Germany. XRD and Rietveld analysis on powders and
coatings were carried out by Dr M. Herrmann of the Fra-
unhofer Institute, Dresden, Germany.
References
[1] Machio CN, Akdogan G, Witcomb MJ, Luyckx S. Performance of
WCVCCo thermal spray coatings in abrasion and slurry erosion
tests. Wear 2005;258(14):43442.
[2] Machio CN. Ph.D. Thesis, University of the Witwatersrand; 2005.
[3] Machio CN, Luyckx S, Zimmermann S, Keller H. New thermal spray
coatings from WCVCCo powders. In: Proc. ITSC2005 int. thermal
spray conf, Basel, Switzerland, May 24; 2005. p. 145055.
[4] Luyckx S. (V, W)Cbased hardmetal and its resistance to wear and
erosion. In: Proc. powder metallurgical world congress, Paris, France,
June 69; 1994, vol. 1. p. 16971.
[5] Luyckx S, Osborne C, Cornish L, WhiteWeld D. Fine grained WC
VCCo hardmetal. J Powder Metall 1996;39(3):2102.
[6] Jansson B. Seco Tools, Sweden, Private Communication.
[7] Obbard EG, Luyckx S, Hamar-Thibault S, Allibert CH. Determina-
tion of the composition range suitable to the formation of WC
(V, W)C
x
Co materials. Int J Refract Metals Hard Mater 2001;
19:34957.
[8] Zimmermann S. Starck, Germany, Private Communication.
[9] Sebeya T. M.Sc. Dissertation, University of the Witwatersrand; 2005.
[10] de Villiers-Lovelock HL, Luyckx S. Preliminary investigation of the
potential of VCWCCo HP/HVOF powders and coatings. In: Ther-
mal spray: surface engineering via applied research, Proc. 1st ITSC
int. thermal spray conference, Montreal, Canada, May 811; 2000. p.
64756.