.

Wear 225229 1999 789798

Abrasive wear behaviour of conventional and nanocomposite
HVOF-sprayed WCCo coatings
D.A. Stewart, P.H. Shipway
)
, D.G. McCartney
Diision of Materials, School of Mechanical, Materials, Manufacturing Engineering and Management, Uniersity of Nottingham, Uniersity Park,
Nottingham NG7 2RD, UK
Abstract
WCCo cermets have been used traditionally as wear-resistant materials. Recent work has shown that nanostructured cermets offer
improved properties over their conventional counterparts. This work examines the performance of such conventional and nanostructured
. materials in the form of coatings deposited by high velocity oxy-fuel HVOF thermal spraying. WCCo coatings were deposited under
identical conditions using both conventional sintered and crushed and nanocomposite powder feedstocks. Both powders consisted of
. tungsten carbide WC grains in a cobalt binder. Characterisation of the coatings by a range of techniques showed that both coatings not
. only contained WC but also reaction products such as tungsten hemicarbide W C and W and an amorphous Co-rich binder phase
2
containing W and C. Due to differences in the morphology of the powder feedstock and the WC grain size, the nanocomposite coating
contained a smaller fraction of unreacted WC than the conventional coating. Three body abrasive wear tests were performed using a
modified dry sand rubber wheel apparatus with alumina and silica abrasives. A range of abrasive particle sizes and loads were used to
assess the wear resistance of both coatings. It was found that the nanocomposite had a poorer wear resistance than the conventional
coating under all the conditions examined. Wear was dominated by the loss of ductility in the Co-rich binder phase due to its
amorphisation. The differences in the wear behaviour of the coatings could, thus, be explained in terms of differences in powder
characteristics, the extent of reaction and decarburisation during spraying, and the subsequent development of the microstructure in the
coating during splat solidification at high cooling rates. q1999 Published by Elsevier Science S.A. All rights reserved.
Keywords: HVOF; WC; Co
1. Introduction
WCCo cermets are well-established as materials highly
resistant to wear in a wide variety of situations; the main
parameters influencing their properties are carbide grain
size and volume fraction and binder mean free path. The
abrasive wear resistance of sintered WCCo cermets has
been shown to increase dramatically as the carbide grain
w x
size is reduced 1 . Recently, sintered nanoscale WCCo

cermets, i.e., materials which have nanoscale approxi-

. .
mately 70 nm tungsten carbide WC grains in a cobalt
matrix, have been reported to exhibit enhanced perfor-
w x
mance in both sliding and abrasive wear 25 . They also
benefit from substantially higher hardness than their con-

ventional counterparts i.e., those which have carbide grain

. w x
sizes around the micron size upwards 6 . These property
improvements stem from the fact that as the carbide grain
)
Corresponding author. Fax: q44-115-951-3764; e-mail:
philip.shipway@nottingham.ac.uk
.
size is decreased for a given cobalt content , the mean
free path of the matrix is reduced, resulting in greater
constraint and increased hardness. This results in less
indentation of the cermet by the abrasive and less exposure
of the soft and ductile matrix to the abrasive particles and
hence, a generally more homogeneous, wear-resistant com-
posite.
Thermally sprayed WCCo coatings, of the order of
200400 mm thick, are widely used in many industries as
they offer an effective and economic method of conferring
wear resistance without compromising other attributes of
.
the component. High velocity oxy-fuel HVOF thermal
spraying has shown itself to be one of the better methods
for depositing conventional WCCo feedstock powders
w x
79 because the higher velocities and lower temperatures

experienced by the powder particles as compared to plasma

.
based routes result in less decomposition of the WC
w x
during spraying 10 . Consequently, this results in higher
quality, more wear-resistant coatings, with higher levels of
retained WC and less porosity. However, the effects of
0043-1648r99r$ - see front matter q 1999 Published by Elsevier Science S.A. All rights reserved.
. PII: S0043- 1648 99 00032- 0
( ) D.A. Stewart et al.rWear 225229 1999 789798 790
powder morphology, type of HVOF spray system and
spray parameters have all been shown to affect the coating
w x
microstructure and, in turn, the wear resistance 1013 .
With the wide use of thermally sprayed WCCo coat-
ings, it is inevitable that nanocomposite powders will be
used in an attempt to realise their potential benefits over
their conventional sprayed counterparts. This work will,
therefore, study whether the benefits of increased hardness
and wear resistance, observed in sintered nanocomposite
WCCo cermets, can be readily realised when they are
sprayed as coatings by the HVOF method.
2. Experimental procedure
2.1. Materials
Two types of WCCo feedstock powders were used in
this work, namely a conventional sintered and crushed

powder 17 wt.% cobalt, 83 wt.% WC with carbide grain

size of approximately 2 mm; Praxair Surface Technolo-
.
gies, Indianapolis, Code 128.8 and a 15 wt.% cobalt, 85

wt.% WC nanocomposite Nanocarb, Nanodyne, New

.
Brunswick, NJ produced from a spray dry and conversion
.
process carbide grain size approximately 75 nm .
2.2. HVOF spraying
A Miller ThermalrUTP Top Gun HVOF spray system
was used to deposit coatings from both cermet powders
using the spray parameters listed in Table 1. The ratio of
oxygen:hydrogen flow rates was chosen to be approxi-
mately 75% of stoichiometry. The substrates were bright
.
drawn mild steel 57 mm=12 mm=5 mm and prior to
coating, were grit-blasted on one side to clean and roughen
the surface. They were then placed on to a turntable
and rotated to give an effective horizontal traverse rate of
1 m s
y1
whilst the gun traversed vertically at a rate of
0.005 m s
y1
. The powder carrier gas was nitrogen and the
substrates were cooled with compressed air jets during and
after spraying.
2.3. Microstructural characterization
.
X-ray diffraction XRD of powder feedstocks and as-
sprayed coatings was performed on a Siemens Krys-
Table 1
Spray parameters employed during HVOF spraying
y1
Oxygen flow rate 240 l min
y1
. Fuel gas hydrogen flow rate 640 l min
y1
. Carrier gas nitrogen flow rate 16.5 l min
Spray distance 300 mm
y1
. Substrate velocity horizontal plane 1 m s
y1
. Gun traverse speed vertical plane 5 mm s
Number of passes 30
. Fig. 1. SEM micrographs showing the morphology of the a 500600
. mm silica and b 500600 mm alumina abrasives.

talloflex 810 diffractometer with Cu-K radiation 1.5406

a
.
A using a 0.058 step size and a 2 s dwell time. Powder
morphologies were investigated using a Jeol 6400 scan-
.
ning electron microscope SEM utilizing secondary and
.
backscattered electron imaging SEI and BEI, respectively .
Cross-sections of the powders and coatings were obtained
by embedding in cold mounting resin followed by grinding
and polishing to a 1 mm finish and then sputter-coating
with gold. Coating cross-sections were cut from the bulk
using a spark wire cutter. Microhardness tests were per-
formed using a Leco M-400 machine with a 300 gf load
and a dwell time of 15 s. Hardness quoted are an average

of 10 indents with the quoted range being the standard

.
error in the mean which were placed in the middle of the
coatings on cross-sectioned and polished samples parallel
to the coatingrsubstrate interface. Surface roughness mea-
surements were performed with a Surfcom profilometer
.
Advanced Metrology Systems, Leicester, England using
a cut-off of 0.8 mm.
2.4. Wear testing
The samples were tested using a modified dry sand
.
rubber wheel DSRW technique; the details of the experi-
w x
mental set-up are presented elsewhere 14 . The abrasives
( ) D.A. Stewart et al.rWear 225229 1999 789798 791

used were fused alumina Abrasive Developments, Soli-

. .
hull, UK and silica David Ball., Bar Hill, UK . The
abrasives were sieved into three distinct size distributions
.
prior to testing, namely fine 125150 mm , medium
. .
355425 mm and coarse 500600 mm . The alumina
has a sharp, angular morphology whilst the silica is a more
.
rounded abrasive see Fig. 1 , although the smaller silica
particles tended to be slightly more angular than their
larger counterparts. The rubber wheel consisted of a cast

polyurethane elastomer tyre Monothane A60, CIL, Pre-

.
ston, UK around an inner wheel of Tufnol 128 mm
.
diameter , giving an overall diameter of 148 mm. The tyre
had a width of 12 mm and an International Rubber Hard-
.
ness of 63"3 8 as measured with a Wallace Hardness
Meter. Wear tests were performed under three applied
.
loads 23 N, 54 N and 75 N , with the rubber wheel
peripheral speed being 0.62 m s
y1
. No recycling of the
abrasive took place and all tests were performed dry. The
tests were performed for a set number of revolutions of the
.
rubber wheel depending on the abrasive media and load ,
with the coatings being weighed before and then after each
set of revolutions. The tests were continued until the
coating wore through to the substrate or until steady state
conditions were obtained. The wear rates for all materials
were calculated from the gradients of the linear sections on
the plots of cumulative coating mass loss against sliding
distance. The worn coatings were examined by SEM on
the top surface and also on cross-sections through the
middle of the wear scars along the direction of flow of the
abrading medium.
3. Results
3.1. Microstructure of powders
The SEM and XRD analysis of both starting powders
w x
15 showed that they consist solely of WC grains in a
cobalt matrix. However, the production routes give two
morphologically very different powders; the sintered and
. Fig. 2. XRD traces of both the conventional top and nanocomposite
. bottom coatings in the as-sprayed condition.
. Fig. 3. SEM BEI images of both the a conventional and
. b nanocomposite coatings in the as-sprayed condition.
crushed powder is angular with low porosity whilst the
nanocomposite is in the form of hollow spheres, ; 60
mm diameter but with shells -10 mm thick.
3.2. Microstructure of coatings
Since a full description of the coating microstructure
w x
and its mechanism of formation is given elsewhere 15 ,
Fig. 4. Plot of cumulative coating mass loss against sliding distance for
the conventional coating 500600 mm alumina abradant, 75 N applied
. load .
( ) D.A. Stewart et al.rWear 225229 1999 789798 792
. . Fig. 5. Plots of steady state wear rates against applied load for the coating-abrasive combinations tested: a nanocomposite with silica abrasive, b
. . nanocomposite with alumina abrasive, c conventional with silica abrasive, d conventional with alumina abrasive.
only a concise description pertinent to the wear behaviour
will be given here.
Although XRD of both powders demonstrated that they
were composed solely of WC and Co, both coatings
contain a number of secondary phases. In the XRD trace of
.
the conventional coating Fig. 2 , peaks indexed to WC
.
and tungsten hemicarbide W C are evident along with
2

two amorphous diffraction haloes between 2us348508

.
and 2us628808 . However, in the nanocomposite coat-
ing, the W C peaks are of greater intensity and peaks
2
.
indexed to elemental tungsten are also observed Fig. 2 .
The SEM investigation using BEI and energy-dispersive
.
X-ray EDX confirmed that the coatings are made up of
grains of WC, W C and W within a matrix of varying
2
.
composition Fig. 3 . It has been demonstrated by trans-
. w x
mission electron microscopy TEM 15 that the matrix
material is predominantly amorphous. Under BEI, the ma-

trix exhibits distinct contrast levels indicating composi-

.
tionally distinct regions ; both the dark and bright regions
contain dissolved W and C in addition to Co but the bright
matrix contains higher levels of W due to greater degrees
of dissolution of WC particles in these regions. SEM
investigations of both coating types revealed that the

nanocomposite coating has a higher degree of bright high

.
mean atomic number , reacted layers in the matrix when
.
viewed in BEI mode , thus, indicating that more dissolu-
tion of WC into the liquid Co has occurred during spraying
.
Fig. 3 . Angular WC grains can be seen in both coatings,
.
but in the conventional coating, two-phase WCrW C
2
rounded carbides are visible in the bright binder phase. In
the nanocomposite coating, rounded, monolithic particles

which appear very bright in BEI mode are observed W C

2
.
and W . TEM-selected area diffraction confirmed the na-
w x
ture of the phases for both coatings 15 .
Fig. 6. Plot of abrasive wear coefficient, k, against abrading media size
for all coating-abrasive combinations.
( ) D.A. Stewart et al.rWear 225229 1999 789798 793
. Fig. 7. SEM SEI plan view images of wear scars showing a conven-
. tional coating abraded with 500600 mm alumina and b nanocomposite
coating abraded with 500600 mm alumina both under a 23 N load.
Microhardness measurements on both coatings gave a
y2
.
value of 1136"17 kg mm HV for the conven-
300 g
tional coating as opposed to 1211 "43 kg mm
y2
.
HV for the nanocomposite coating. Hardness values
300 g
for the abrasives were determined as 955"30 kg mm
y2
.
y2
.
HV for the silica and 1969"66 kg mm HV
200 g 200 g
Fig. 8. SEM SEI plan view image of nanocomposite coating abraded with
500600 mm silica under a 75 N load.
Fig. 9. SEM BEI cross-sectional view of wear scars in nanocomposite
. . coatings with 125150 mm alumina abrasive under a 23 N and b 75 N
load showing crack propagation through tungsten-rich binder phase.
for the alumina. Profilometry of the top surfaces of both
sprayed coatings gave similar surface roughness values,
namely R f5 mm.
a
3.3. Wear tests
Fig. 4 shows an example of the raw data for one of the
abrasive wear tests performed; the wear rate has been
Fig. 10. SEM BEI cross-sectional view of wear scar in conventional
coating with 125150 mm alumina abrasive under 23 N load showing
vertical cracks within the coating.
( ) D.A. Stewart et al.rWear 225229 1999 789798 794
. Fig. 11. SEM BEI cross-sectional view of wear scars in a conventional
. coating with 125150 mm silica and b nanocomposite coating with
500600 mm silica, both under a 75 N load showing crack propagation
through tungsten-rich binder phase.
determined from a least squares fit of the data that is in the
.
linear steady state regime in this case, a sliding distance
.
of greater than 35 m . Fig. 5a to d show the steady state
wear rates for the abrasiverloadrcoating combinations
tested. Best fit lines have been plotted in each case accord-
ing to the Archard wear equation:
QskW, 1 .
where W is the applied load, Q the wear rate and k the
wear coefficient. The gradients of these lines represent the
wear coefficient, k. Fig. 6 shows the wear coefficient for
the coatings for both sets of abrasive media as a function
of abrasive size. Figs. 711 show examples of the wear
.
scars, in both plan view Figs. 7 and 8 and cross-section
.
Figs. 911 .
4. Discussion
4.1. Coating microstructures
A detailed description of the microstructural develop-
w x
ment of both coatings is given elsewhere 15 , so only a
few salient points, directly relating to the physical proper-
ties and wear resistance, will be highlighted here. It has
w x
been proposed 15 that during spraying, the cobalt melts,
followed by dissolution of some of the WC grains into the
liquid metal. Close to the edges of the powder particles,
more of the WC grains dissolve, promoted by carbon
removal from the melt by oxidation in the hot gas jet. On

impact and subsequent cooling, W C and W in addition to

2
.
WC may precipitate from the liquid with any remaining
liquid forming an amorphous matrix containing W, C and
Co. The differences in W and C concentrations in the
binder phase can be qualitatively observed in backscattered
imaging in the SEM. All areas of the binder phase are
amorphous with W and C dissolved in it, but the bright
.
regions W rich of the binder phase are believed to
originate from the outer edges of the powder particles and,
as such, the splat boundaries are surrounded on either side
by this phase.
.
From the XRD traces Fig. 2 , it can be seen that the
nanocomposite has undergone more decomposition during
spraying. This has resulted in higher W C peaks than in
2
the conventional coating, as well as the appearance of
elemental tungsten peaks. This consequently results in less
retained WC, and greater amounts of the amorphous binder
phase. The greater decomposition in the nanocomposite
coating can be directly related to, amongst other factors,
the higher surface area to volume ratio of the WC phase in
w x
the starting powder 15,16 . Chemical analysis revealed
differences in the carbon levels of the starting powders and
as-sprayed coatings. In the nanocomposite material, the C
level decreased by 41%, whereas in the conventional mate-
rial, the reduction was only 24%. This greater degree of
decarburisation of the nanocomposite coating is attributed
to the more rapid dissolution of the fine-scale WC grains
into the liquid metal during spraying.
The greater degree of decomposition experienced by the
nanocomposite powder particles during spraying thus re-
sults in a larger tungsten concentration in the amorphous
binder phase than in the conventional coating. This differ-
.
ence can be qualitatively observed Fig. 3 where the
bright binder phase is much more evident in the nanocom-
posite. It is also notable that, due to dissolution of carbide
into the binder, the volume fraction of the carbide phase
has significantly decreased. Volume fraction analyses of
w x
the conventional coating and powder feedstock 15 showed
a considerable increase in the quantity of the amorphous
binder in the coating as compared to metallic cobalt in the

powder powder: 35 vol.% Co binder; coating: 73 vol.%

.
binder phase . It was also found that the carbide volume

fraction in the tungsten-rich binder phase where the

.
rounded WCrW C carbides were found was considerably
2

less than in the darker binder phase where the original,

.
blocky WC grains were found , namely 9 vol.% in the
former and 38 vol.% in the latter. Whilst microstructural
measurements for the nanocomposite coating are difficult
to make due to its fine scale, XRD reveals that the
( ) D.A. Stewart et al.rWear 225229 1999 789798 795
w x
crystallinity index, I 17 , for the nanocomposite coating is
lower than for the conventional coating, namely 44% for
the former and 56% for the latter. This indicates that the
nanocomposite coating has a higher fraction of amorphous
binder as well as a lower fraction of carbides.
4.2. Wear behaiour
WCCo cermets are used as wear-resistant materials
due to their favourable combination of toughness and
w x
hardness. Wayne et al. 18 have shown that the abrasive
wear resistance of a range of sintered WCCo cermets is
given by the following:
K
3r8
H
1r2
1C
RA , 2 .
D
WC

where R is the abrasive wear resistance, K and H are

1C
the cermet fracture toughness and hardness, respectively,
.
and D is the carbide grain size which indicates the
WC
advantages in abrasive wear resistance to be gained from
using a fine-grained or even nanocomposite material. It has
w x
also been demonstrated 19,20 that the abrasion resistance
of ceramics, where there is no ductile phase to prevent
large-scale brittle fracture, showed a higher dependence on
fracture toughness and correspondingly less on hardness
according to the following equation:
RAK
3r4
H
1r2
. 3 .
1C
However, HVOF-sprayed cermet coatings have com-
plex, multiphase microstructures, and treating them in the
same way as their sintered counterparts may not be valid,
since the ductile binder in the sintered material has been
replaced by a relatively brittle, amorphous binder phase in
the HVOF-sprayed coating.
Both coatings exhibited increases in wear rate with
applied load when abraded with both silica and alumina as
. .
predicted by Eq. 1 Fig. 5 and thus, a wear coefficient
could be evaluated for each system. Under all the test
conditions examined, the nanocomposite coating had a

lower wear resistance than the conventional coating Fig.

.
6 . In general, steady state wear rates for the nanocompos-
ite are between 1.4 and 3.1 times higher than for the
conventional coating under the same conditions. The actual
values depend on the coatingabradantload combination,
with the differences being greatest when the abradant was
alumina. The wear rates for abrasion with silica are very
similar to those observed during abrasion of WC17 wt.%
w x
Co HVOF-sprayed coatings in other work 21 . As re-
w x
ported by many other workers 22,23 , we observe that the
wear resistance does not necessarily increase with coating
hardness, with, in this case, the harder nanocomposite
coating wearing more rapidly.
With abrasion by alumina, there is rapid material re-
.
moval shown by the high mass loss rates and significant
groove formation on the surface of both coating types.
This is as expected since the abradant is harder than either
coating. SEM cross-sectional analysis of the wear scars
along the direction of abrasive flow reveal that sub-surface
cracks propagate parallel to the coating top surface, pre-
dominantly through the tungsten-rich binder phase or along
. w x
splat boundaries in both coatings Fig. 9 . Kim et al. 24
have argued that extension of sub-surface transverse cracks
is the controlling factor for material removal in abrasive
wear of plasma sprayed WCCo coatings. A number of
vertical cracks within the conventional coating could also
.
be observed Fig. 10 . It is believed that formation of these
vertical cracks is the initial stage of the material loss
procedure and is caused by the indentation of the abradant
into the coating. These cracks propagate down through the
coating until they reach either tungsten-rich binder phase
.
or splat boundaries see Fig. 10 , whereupon they propa-
gate parallel to the coating surface until they find a path
that leads back to the surface, thus, causing material
removal.
With silica, abrasion mass loss rates were, in general,
.
around an order of magnitude lower Fig. 6 and less

coarse grooving on the wear surface has taken place Fig.

.
8 . The hardness of the silica is less than that of both of the
coatings and it has a far more rounded morphology, and so
elasticplastic indentation of the abradant into the coating
is less likely. Significant reduction in wear rates of materi-
als are often observed as the hardness of the abrasive
w x
decreases below that of the material being abraded 25,26
and as the abradant morphology becomes more rounded
w x
27 . Localised polishing of the top surface can be seen for
both coatings. In the conventional material, there were
areas devoid of carbides which did show some grooving
.
Fig. 8 but generally, this was insignificant when com-
pared to that induced during abrasion with alumina. De-
spite the lack of severe particle ploughing and the associ-

ated elasticplastic indentation, cross-sectional SEM Fig.

.
11 showed sub-surface cracking, induced primarily by
elastic contact, indicating a similar mechanism of material
loss as for abrasion with alumina. However, as with the
grooving, the sub-surface cracking was generally less com-
mon than in the coatings abraded with alumina. As is often
w x
observed in both ductile and brittle materials 25,27,28 ,
the abrasion rate increased with increasing particle size
.
Fig. 6 . However, the nanocomposite always wore more
rapidly than the conventional coating across the range of
particle sizes for both abrading media.
Thus, it has been observed that wear of both coating
types occurred predominantly by sub-surface cracking dur-
ing abrasion with both hard angular alumina and also with
the soft, rounded silica; the brittle, tungsten-rich areas of
.
the binder phase and possibly splat boundaries were the
favoured routes for crack propagation in all cases. Differ-
ences in the wear scars produced by the two abrading
media could be observed under plan view SEM investiga-
tions. The scars on both coatings produced by alumina
abrasion were relatively flat with large amounts of groov-
( ) D.A. Stewart et al.rWear 225229 1999 789798 796
.
ing and pitting Fig. 7 , whereas the scars produced by
silica abrasion exhibited only limited grooving in areas
which were devoid of carbides, and original splat outlines
.
could still be discerned Fig. 8 . The areas devoid of
carbide are most likely the bright binder phases seen in the

cross-sections. Despite these differences which mirror the

.
differences in rate of wear , the main mechanism of wear
of both of the coating types with both abrading media was
that of indentation-induced sub-surface cracking.
It has often been reported that the wear resistance of
thermally sprayed WCCo coatings decrease as the levels
of WC reactionrdecomposition during spraying increase.
Abrasion resistance of D-gun-sprayed WCCo coatings
has been observed not to scale with hardness, but more
with amount of retained primary carbide in the coating
w x w x
29 . Usmani et al. 16 observed that fracture toughness
and abrasion resistance of HVOF-sprayed coatings de-
creased with decreasing WC grain size in the initial
..
powder contrary to the trend expected from Eq. 2 and
attributed this to greater degrees of decomposition of the
smaller WC grains to W C during spraying. Harvey et al.
2
w x
30 have suggested that there is a direct correlation be-
tween high wear rate and high levels of amorphous WC

Co phase in the ribbon-like structures tungsten-rich binder

.
phase seen in the SEM. They conclude that high levels of
retained WC are indicative of a coating with good wear
resistance. Similar trends have been observed by Khan and
w x
Clyne 31 in air plasma- sprayed WCCo coatings where

increased plasma power and thus, increased decomposi-

.
tion of the WC grains during spraying led to significant
decreases in coating abrasive wear resistance.
Whilst this is the commonly held view, Schwetzke and
w x
Kreye 32 have shown that WC decomposition and carbon
loss during spraying was not detrimental until a certain
level was reached; it was noted that in a two-body abrasive
wear test, the wear resistance of HVOF-sprayed WCCo
coatings was not impaired until the carbon loss exceeded

60% carbon loss in both our conventional and nanocom-

.
posite coatings was below this value . They suggested that
hardening of the amorphous cobalt matrix by solution of
W and C and the formation of W C both compensate for
2
the loss of primary WC. Moreover, it has been argued that
some decomposition of WC during spraying is beneficial.
w x
Verdon et al. 33 propose that for erosion resistance of
HVOF-sprayed WCCo coatings, there is an optimum
amount of reaction of the WC during spraying; too little
reaction leads to material removal by fracture along brittle
island boundaries whilst too much reaction significantly
reduces the WC content, leaving the binder phase exposed
to erosion.
It has been observed in this work that the hardness of
the coatings are relatively high, and are far higher than
would be expected for cermets with the volume fractions
of carbides that are actually observed in the coatings. The
dissolution of W and C into the Co binder has resulted in a
hard, amorphous binder phase. However, the fact that the

tungsten-rich regions of the binder phase that formed near

.
the periphery of the powder particle is a preferential path
for crack propagation indicates that it is also a brittle
phase; its tendency to crack may also be enhanced by the
splat boundary which is sandwiched within this phase.
Thus, we may conclude that increased decomposition of
WC and subsequent decarburisation in the hot gas jet
produces a coating with decreased resistance to wear; the
decomposition reactions are more pronounced in the
nanocomposite coating due to the small size of the carbide
.
particles which aids their dissolution and the open porous
powder morphology.
It should be noted that the mechanisms of wear pro-
posed for the HVOF-sprayed cermet coatings are quite
different from those proposed for sintered cermets, where
cobalt extrusion followed by carbide removal, or carbide
w x
fracture dominate 18,34 . Thus, methods of increasing

wear resistance in the latter e.g., reduction in carbide

.
grain size may not be useful for thermally sprayed coat-
ings. Indeed, in this work, we have demonstrated that the
reduction in grain size to nanocomposite WC results in a
significant decrease in wear resistance for identical spray
conditions.
With the present spraying parameters, significant car-
bide dissolution and decarburisation occurs during spray-
ing which is deleterious in terms of abrasive wear resis-
tance. The nanocomposite coating suffers greater levels of
reaction and thus, is less wear-resistant than its conven-
tional counterpart. It can be envisioned, however, that
optimization of spray parameters could reduce nanocom-
posite degradation. Alternatively, with the emergence of
new HVOF systems and technology utilizing different
.
fuels especially liquid fuel systems and powder injection
points, it may be possible to spray nanocomposite coatings
with lower levels of decomposition, resulting in mi-
crostructures and wear rates similar to that, or better than
their conventional counterparts.
5. Conclusions
Sintered nanocomposite WCCo cermets have been
reported to have wear resistance superior to that of their
conventional counterparts. However, under a wide range of
abrasive test conditions, wear rates of an HVOF-sprayed
WCCo nanocomposite coating were between 1.4 and 3.1
times higher than a coating sprayed from conventional
powders. This increase in wear rate is attributed to the
greater degree of decomposition suffered by the nanocom-
posite powder particles during spraying which leads to a
reduction in the volume fraction of the wear-resistant
primary WC phase and the formation of brittle amorphous
binder phases within the coating. Wear of the coatings
occurs predominantly by subsurface cracking along the
preferential crack paths provided by the tungsten-rich
binder phase and wear is thus, exacerbated by decomposi-
( ) D.A. Stewart et al.rWear 225229 1999 789798 797
tion during flight. For both the conventional and nanocom-
posite coatings, the wear rate with alumina abrasive was
about an order of magnitude greater than that with silica
abrasive. This was attributed to the softer and more rounded
morphology of the silica abrasive, causing less sub-surface
cracking and hence, subsequent material removal.
It is noted that there is little similarity between the
material microstructures and mechanisms of wear of sin-
tered and thermally sprayed cermets, and thus, strategies
that have been used to increase wear resistance in sintered
.
materials e.g., reduction in grain size may not necessarily
be expected to confer the same benefits in thermal- sprayed
coatings. However, if the microstructure of the thermally
sprayed material may be made to more closely approach

that of the sintered material e.g., by altering the spraying

.
conditions , the potential benefits offered by the nanocom-
posite material may be realised.
Acknowledgements
The authors wish to thank Mr. A. Horlock for perform-
ing the spray runs, Prof. J.V. Wood for use of the laborato-
ries within the department and the EPSRC for funding
through the award of a studentship to DAS.
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