Acta Materialia 51 (2003) 42674277

www.actamat-journals.com
Microhardness variation in relation to carbide development
in heat treated Cr
3
C
2
NiCr thermal spray coatings
S. Matthews, M. Hyland

, B. James
The Department of Chemical and Materials Engineering, The University of Auckland, Private Bag 92019, Auckland, New Zealand
Received 22 January 2003; received in revised form 30 April 2003; accepted 5 May 2003
Abstract
Cr
3
C
2
NiCr thermal spray coatings have been extensively used to mitigate high temperature wear. During deposition
compositional degradation occurs through dissolution of the carbide phase into the matrix. High temperature exposure
leads to transformations in the microstructure, which inuences the coating microhardness. While such developments
have been investigated in short-term trials, no systematic long-term investigations of the microhardness variation as a
function of microstructural development have been presented. In this work, high velocity sprayed Cr
3
C
2
NiCr coatings
were heat treated at 900 C for up to 60 days in air and argon. With treatment, matrix phase supersaturation was
reduced, while widespread carbide nucleation and growth generated an expansive carbide skeletal network. An initial
softening of the coatings occurred through matrix phase renement, the subsequent hardness recovery was a function
of carbide development. Treatment in air generated further hardness increases as a result of internal oxidation.
2003 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.
Keywords: Ageing; Isothermal heat treatment; Cermets; Hardness; Thermal spray coatings
1. Introduction
Thermally sprayed Cr
3
C
2
NiCr cermets have
been used extensively to mitigate wear and erosion
at high temperatures where WC based composites
are not suitable [1,2]. During thermal spraying,
substantial variations in the cermet composition
and microstructure are possible due to exposure to
the high temperature accelerating gas [37]. Dis-
solution of the carbide phase into the alloy matrix

Corresponding author. Tel.: +64-9-3737999; fax: +64-9-

3737463.
E-mail address: m.hyland@auckland.ac.nz (M. Hyland).
1359-6454/03/$30.00 2003 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.
doi:10.1016/S1359-6454(03)00254-4
occurs, reducing the carbide concentration and
generating marked variability in the matrix phase
composition. As a result carbon may be lost as CO
or CO
2
, altering the composition of the carbide
phase, while the matrix composition may vary
from regions dominated by Cr through to the Ni
rich starting composition [6,7]. Formation of
oxides can occur on the outer particle surface and
may potentially be distributed within the body of
the particle should widespread melting of the
matrix occur [8]. This widespread compositional
disorder is trapped within the metastable structure
as a result of rapid solidication upon deposition.
In addition, the microstructure of the supersatu-
rated matrix phase varies with the spray conditions,
4268 S. Matthews et al. / Acta Materialia 51 (2003) 42674277
potentially ranging from zones of amorphous
material [6,9,10] through to nano-crystaline [9,10]
and microcrystalline phases [7].
The complex metastable state of the as-sprayed
coating means that there is a large driving force for
microstructural and compositional transformations
when exposed to elevated temperatures. The most
notable change is the precipitation of ne carbides
[7,11,12] or possibly oxides [1,10] accompanied by
recrystalisation of the matrix. The mechanical
properties also change, in particular the microhard-
ness which is commonly related to the performance
of carbide coatings under wear conditions [13].
There is no consistent trend with heat treatment;
reports of plasma coatings generally indicate an
increase in hardness, while HVOF coatings may
soften or harden depending on treatment tempera-
ture and atmosphere, or gun or powder type used
for deposition [35,9,10,14]. It is not surprising
then, that several different mechanisms have been
proposed correlating the variation in coating
microhardness with changes in microstructure.
Industrially, it is the long-term performance of
Cr
3
C
2
NiCr coatings at elevated temperature that
is signicant. This has not been widely addressed
[1,2,15], particularly for high velocity thermal
spray coatings where no long-term (24 h) sys-
tematic studies of microstructural evolution at high
temperature have been presented. The purpose of
this study was to look at the long-term evolution
in microstructure and hardness and to better under-
stand the relationship between the observed
changes in microstructure and hardness. The
response of high velocity air fuel (HVAF) and high
velocity oxygen fuel (HVOF) Cr
3
C
2
NiCr coatings
was assessed after exposure at 900 C for periods
of up to 60 days in air and argon. The variation
in microstructure was characterised and correlated
with the variation in microhardness, the response
varying in a manner unexpected from previously
presented work.
2. Experimental procedure
A cermet powder of nominal composition
75%Cr
3
C
2
25%NiCr (WOKA 2075-NiCr) was
sprayed on to mild steel substrates using Aerospray
HVAF and GMA Microjet HVOF thermal spray
systems. Coating-only samples were prepared by
cutting away the substrate with a metallographic
cutting machine. The thin layer of remaining sub-
strate material was removed from the samples
using a hot 10% nitric acid solution. Copper plates
in contact with the samples were used to accelerate
the steel dissolution. The samples were then
ground and polished. Analysis by X-ray diffraction
(XRD) and energy dispersive X-ray analysis (EDS)
indicated no detectable variation in composition as
a result of acid treatment. The sample dimensions
after polishing were 15 mm 7 mm, the thickness
of the HVAF samples ranging from 650850 m,
while those of the HVOF samples were 200300
m.
Heat treatment was conducted at 900 C in air
and under a positive pressure of argon. Samples
were removed after 2, 5, 10, 20, 30, 40 and 60
days. This temperature was used to accelerate the
microstructural development that occurs at lower
operating temperatures with long-term exposure,
without signicantly altering the mechanism of
development. In all cases a tarnish layer had for-
med and was removed by grinding. This was to
expose the underlying heat treated material that
was not inuenced by oxidation. Compositional
analysis was performed using XRD (Bruker D8
Advance, Cu source at 40 mA and 40 kV). Analy-
sis on mounted and polished cross-sections was
carried out using back scattered electron (BSE)
scanning electron microscopy (SEM) (Philips
XL30S FEG). Vickers microhardness measure-
ments (LECO M-400 Hardness tester) were con-
ducted on the coating cross sections under a load
of 300 g for 5 s. An average hardness was calcu-
lated from 10 indents per specimen.
3. Results and discussion
3.1. Powder characterisation
The agglomerated and sintered WOKA

2075-
NiCr powder showed clear contrast between the
carbide and NiCr matrix phases (Fig. 1) indicative
of negligible carbide dissolution. This was
reected in the XRD analysis (Fig. 2) where only
4269 S. Matthews et al. / Acta Materialia 51 (2003) 42674277
Fig. 1. BSE cross sections of a WOKA

2075-NiCr powder
particle and the as-sprayed HVOF and HVAF coatings.
Cr
3
C
2
and NiCr were identied. The carbide grains
were evenly distributed, forming interconnecting
networks within each powder particle.
3.2. As-sprayed coatings
HVOF sprayed Cr
3
C
2
NiCr coatings have been
extensively investigated, the properties and appear-
ance of the coatings in this work within the ranges
reported by others. BSE micrographs showed that
extensive carbide dissolution in the matrix
Fig. 2. XRD spectra of the Cr
3
C
2
NiCr WOKA

2075-NiCr
powder and the as-sprayed HVOF and HVAF coatings.
occurred, reducing the concentration of carbides
and generating widespread greyscale variation
indicative of marked variation in the matrix com-
position (Fig. 1). Retained carbide grains were
found predominantly in the centre of the larger
splats. Dissolution of carbide into the matrix and
the consequent super saturation of the matrix with
Cr and C gave rise to a large amorphous back-
ground on the low angle side of the NiCr peak in
the XRD scan (Fig. 2). The only detectable crystal-
line phases were Cr
3
C
2
and NiCr: while small
amounts of Cr
7
C
3
may have formed, its concen-
tration was to low be distinguished from other
overlapping peaks. The splats were long and thin,
and often bounded by oxide stringers, indicating
that the majority of the powder particles were
molten at impact.
In marked contrast to the HVOF coating, a high
4270 S. Matthews et al. / Acta Materialia 51 (2003) 42674277
carbide content was retained in the HVAF coat-
ings, the isolated carbide grains being homo-
geneously distributed. The alloy phase showed sig-
nicantly lower degrees of greyscale variation than
in the HVOF coating (Fig. 1). The lower degree
of carbide dissolution is also apparent in the XRD
spectra (Fig. 2). Only Cr
3
C
2
and NiCr were
detected, the spectra of the latter dominated by nar-
row crystalline peaks with smaller amorphous
background. A striking feature of this coating was
the lack of visible splat structure. No inter-splat
oxides were evident and the lack of wide spread
carbide dissolution eliminated the matrix phase
contrast of the previous coating. There are few
published studies of HVAF Cr
3
C
2
NiCr coatings
for comparison, but the general features described
herelow degree of carbide degradation and
homogeneous nature of the coating, mirror features
seen in WCCo and WCCoCr coatings sprayed
by HVAF [1618].
3.3. Heat treatment of the coating samples
It is evident from the XRD spectra of the heat
treated HVAF and HVOF coatings (Fig. 3) that
microstructural transformations were well
advanced after 2 days of exposure. The amorphous
regions of the as-sprayed coating spectra had dis-
appeared, with narrow, intense NiCr peaks domin-
ating the matrix phase spectra. The carbide peaks
were also more dened, and BSE images showed
that ne precipitates had formed. Similar changes
have been documented by others [35,7] and can
take place within 1 h at 800 C [3]. Image analysis
of the BSE images indicated that the carbide vol-
ume fraction rapidly increased from approximately
36% and 67% in the HVOF and HVAF as-sprayed
coatings, respectively, to a value of approximately
75 vol.% (Fig. 4). This remained stable over the 60
days of treatment for both the HVAF and HVOF
coatings under air and argon. The carbide itself
was not signicantly oxidised. Quantitative analy-
sis of the carbide XRD spectra in terms of the peak
area, FWHM, and centre of gravity of the primary
peaks indicated that Cr
3
C
2
remained the dominant
carbide phase and was not oxidised to Cr
7
C
3
in the
HVAF coatings, although a small amount may
have formed in the HVOF coatings. Cr
2
O
3
was
Fig. 3. XRD spectra of the HVOF and HVAF coatings heat
treated for 2 days at 900 C.
Fig. 4. Volume percent carbide in the HVAF and HVOF coat-
ings as a function of heat treatment under argon.
4271 S. Matthews et al. / Acta Materialia 51 (2003) 42674277
detected in some of the XRD spectra, the low
intensity, noisy peaks indicating that this phase
was present in very low concentrations. This evi-
dence indicates that the ne precipitates which for-
med during heat treatment were most likely Cr
3
C
2
and not Cr
2
O
3
as suggested by others [1,2,9,10].
3.4. Carbide precipitation and growth during
heat treatment
For the HVAF coating, precipitation of ne car-
bides occurred throughout the coating during the
initial 2 days of exposure, primarily in regions of
high carbide density (Fig. 5). This reected the low
degree of particle heating in-ight as the dissolved
Cr and C only diffused short distances from the
parent carbides. Preferential nucleation occurred
on those carbides retained during spraying. Where
isolated precipitates occurred they tended to
coalesce and form larger carbides of complex mor-
phologies ranging from blocky agglomerates
through to thin spidery networks.
Continued carbide growth occurred out to 5 days
with the average nucleated carbide size substan-
tially larger than at the shorter exposure time. The
reduction in the number of such grains, and their
more rounded appearance suggested growth via
Ostwald ripening [19]. Widespread coalescence
and bridging occurred with an evident macroscopic
carbide skeletal network beginning to form.
Beyond 5 days development of the carbide struc-
ture began to slow. Growth occurred primarily
through strengthening of the inter-carbide bridging
networks and continued carbide coalescence, gen-
erating large single phase regions of complex mor-
phology. Within this network the grains themselves
appeared more spherical. Beyond 30 days no sig-
nicant changes were evident. The development of
the carbide skeletal network had occurred to the
extent where the carbide phase was largely con-
tinuous, surrounding pockets of matrix phase.
Treatment in air led to the same carbide phase
transformation with time as were noted in argon.
Oxides phases were evident in higher concen-
trations. Somewhat unexpectedly they did not form
inter-splat oxide stringers but were noted to occur
as small isolated pockets.
In the HVOF coatings, after 2 days treatment
Fig. 5. BSE images of the HVAF microstructure in the as-
sprayed condition and after 2, 20 and 60 days of treatment under
argon at 900 C.
4272 S. Matthews et al. / Acta Materialia 51 (2003) 42674277
under argon the extensive variation in the as-
sprayed matrix phase greyscale contrast was sig-
nicantly reduced (Fig. 6). Widespread carbide
precipitation occurred, the average size smaller
than in the HVAF coatings. Unlike the HVAF
coatings, carbide nucleation occurred primarily in
the carbide free zones where the greatest degree
of dissolution had occurred during spraying. The
variation in the magnitude of dissolution generated
a variety of carbide distributions and morphologies
with heat treatment. Three generalised regions
were evident (Fig. 7). Region 1 occurred in the
centre of the largest splats in pools of relatively
unaffected material. Carbide dissolution was mini-
mal and the subsequent carbide nucleation mir-
rored that of the HVAF coating. Region 2 occurred
midway between the core and periphery of the
largest splats, or within those splats where wide-
spread carbide dissolution had occurred. Sponge-
like agglomerates formed via coalescence of large
numbers of nucleated carbides. These were
expansive in nature, occupying signicant regions
of the splat, but at the edges of the splat followed
the splat contour. At the splat boundary, Region 3,
the carbides formed long thin stringers that in three
dimensions may have formed plate-like morpho-
logies.
Growth of the individual carbide grains led to
coarsening of the sponge-like agglomerates, gen-
erating a more porous appearance to these features.
This occurred most rapidly away from the splat
peripheries leading to widespread coalescence and
bridging. While the peripheral plate-like carbides
were still evident after 5 days they were beginning
to break up into more isolated grains. After 1020
days the structure developed to a similar state as
the HVAF coating. Growth and spheriodisation of
the individual grains occurred, while coalescence
and bridging between the grains led to the develop-
ment of a widespread skeletal network. Such devel-
opment of the carbide phase began to overshadow
the preferential orientation of the carbides in
relation to the splat shape. Beyond 30 days, growth
slowed in a similar manner to the HVAF coating.
After 60 days both the HVOF and HVAF coatings
were comparable, the HVOF carbides having a
slightly wider size distribution and more distorted
morphologies. It was evident, however, that despite
Fig. 6. BSE images of the HVOF microstructure in the as-
sprayed condition and after 2, 20 and 60 days of treatment in
air at 900 C.
4273 S. Matthews et al. / Acta Materialia 51 (2003) 42674277
Fig. 7. Schematic illustration of the three generalised regions
of carbide development within a splat during heat treatment of
the HVOF coating.
the marked variation in the as-sprayed condition,
both coating systems tended towards the same
microstructure with heat treatment.
Treatment in air had no obvious inuence on the
carbide nucleation or growth processes. The pres-
ence of oxide in the as-sprayed HVOF coatings
complicated the analysis of oxide ingress, how-
ever, the pockets of oxide and thickening of the
oxide stringers appeared more frequent in the air
treated samples.
3.5. Microhardness of Cr
3
C
2
NiCr coatings as a
function of heat treatment
The same general trend in microhardness
occurred for both the HVAF and HVOF coatings
in air and argon (Fig. 8). A rapid reduction in hard-
ness occurred over the initial period of heat treat-
ment. With continued exposure the hardness
quickly increased, reaching stable values after 20
30 days of treatment. In all instances the HVOF
Fig. 8. Vickers microhardness values of the HVAF and HVOF
coatings treated in air and argon at 900 C.
coatings had higher hardness values, although the
initial period of softening was more dramatic and
took longer to recover in these coatings. Treatment
in air generated consistently harder coatings than
those treated in argon for both coating systems.
Because of the microstructural complexity of
thermal spray coatings, a number of hardness
mechanisms are likely to be responsible for the
changes in hardness with heat treatment and the
hardness differences between coatings sprayed by
HVAF and HVOF as shown in Fig. 8. For carbide
cermets, WC in particular, the model of Lee and
Gurland [20,21] has commonly been applied, Eq.
(1),
H
C
H
WC
V
WC
C H
M
(1V
WC
C) (1)
In this model the cermet hardness (H
C
) is based on
the hardness and volume fraction of the hard phase
(H
WC
and V
WC
) and the hardness of the matrix
phase (H
M
). The contiguity (C), dened by Gur-
land [20,21], describes the percentage surface area
of a carbide grain in contact with other carbide
grains and accounts for the microstructural inu-
ence of the carbide morphology. The hardness of
the two phases is microstructure dependent. Car-
bide hardness is a function of grain size, smaller
grains giving higher hardness values [21,22]. Con-
straint of the matrix between the carbides elevates
the effective hardness value of this phase, higher
hardness values achieved with smaller inter-car-
bide spacing [21,22]. With regard to the overall
cermet hardness, higher degrees of contiguity gen-
erates harder material [20]. In addition, for ther-
mally sprayed cermet coatings, splat-splat bonding,
porosity and oxide formation will also affect the
overall hardness.
The as-sprayed HVAF and HVOF coatings dem-
onstrate this complexity. Despite the signicantly
higher carbide content of the HVAF as-sprayed
coating, its hardness is lower than the HVOF as-
sprayed coating. This is in contrast to the results
of Zimmermann and Kreye [3] who showed a cor-
relation between higher retained carbide content
(as measured by C content of the coating) and
higher hardness in Cr
3
C
2
NiCr coatings sprayed by
three HVOF techniques. However, in their work
other inuencing factors such as porosity were not
taken into account. In the present study, the coat-
4274 S. Matthews et al. / Acta Materialia 51 (2003) 42674277
ings have similar levels of porosity (3%), the dif-
ference in hardness in the as-sprayed coatings is
likely to be due to differences in matrix hardness
the matrix of the HVOF coating will be signi-
cantly harder due to solid solution strengthening
generated by more extensive carbide dissolution
during spraying. When Cr
3
C
2
dissolves into the
matrix the dissolved Cr and C distort the Ni lattice,
inhibiting dislocations motion [23]. The structural
disorder caused by greater amounts of dissolved Cr
and C is shown in the larger XRD peak widths for
the matrix phase in the HVOF compared to the
HVAF (Fig. 2). The extent of binder phase
strengthening is dependent on the deposition para-
meters, being more inuential in the higher tem-
perature techniques where extensive carbide dissol-
ution means that the coatings act more as
dispersion strengthened alloys than carbide based
composites. The higher oxide content of the HVOF
coating could also affect its hardness, however, the
role of oxides is ambiguous. On the one hand, their
higher hardness will increase the overall hardness,
on the other, their presence as stringers may reduce
splat/splat bonding, lowering the measured hard-
ness [4].
Following heat treatment in argon, both the
HVAF and HVOF coatings experience a decrease
in hardness with gradual recovery and strengthen-
ing after 2 or 5 days, respectively. Other
researchers have also recorded decreases in hard-
ness for HVOF coatings using similar powder
types and similar treatment regimesin vacuum at
temperatures between 800 and 900 C, 2 days
[35]. In these studies the treatments were short-
term, so the recovery in hardness was not docu-
mented.
The changes in hardness with heat treatment
were accompanied by concurrent changes in
microstructurenamely the precipitation of ne
carbides and their subsequent growth; and the
recrystalisation of the matrix. Recrystalisation of
the matrix was evident in the reduced matrix con-
trast in the BSE images and in the decrease in d-
spacing of the Ni peak due to a reduction in the
amount of dissolved Cr and C. As indicated by the
narrowing of the matrix phase XRD peaks, recov-
ery, recrystalisation and grain growth occur rap-
idly, reducing the dislocation density, increasing
the grain size and relieving any internal stresses
within the splats. These transformations lead to
matrix phase softening and are thought to account
for the initial reduction in coating hardness over
the rst 25 days of exposure.
At the same time, nucleation of the carbide
phase takes place, which was shown to recover to
a stable concentration within the rst 2 days of
treatment. The increase in carbide content is
thought to contribute to the recovery in hardness
with extended exposure, a mechanism favoured by
several authors [3,5]. Zimmermann and Kreye [3]
heat treated JP5000, Top Gun and Jet Kote HVOF
Cr
3
C
2
NiCr coatings at temperatures up to 800 C
for 1 h. The JP5000 coating showed the highest
hardness which slowly decreased at temperatures
approaching 800 C. The other coatings exhibited
peaks in hardness at 500 and 600 C, respectively,
also before softening. A similar treatment by
Otsubo et al. [5] observed stable hardness values
for JP5000 Cr
3
C
2
NiCr coatings but increasing
hardness values for a PlazJet III250 plasma coat-
ing. Both research groups attributed the increase in
hardness to carbide precipitation. Peaks in hardness
were proposed to result from an optimum carbide
size being achieved, while over-aging of the pre-
cipitates accounted for the softening in the higher
temperature trials [5]. The stable response of the
JP5000 coating was attributed to the minimal
degree of carbide dissolution in-ight and hence
the limited degree of carbide precipitation.
Carbide nucleation is also thought to increase
the coating hardness in the current work, but the
mechanism is different. Initially, carbide precipi-
tation results in isolated or agglomerated groups of
grains. While these are small they effectively act
as dispersion strengthening particulates to harden
the matrix phase. Signicant hardening of the over-
all cermet, however, only occurs with further
development of the carbide phase. The volume
fraction of the matrix and carbide phases were
shown to be constant after 2 days and hence,
according to Eq. (1), it is the variation in micro-
structure and contiguity that control the hardness
with extended exposure. In the HVAF coating this
occurs through bridging and coalescence of the
carbide grains resulting from localised nucleation
of carbides within the regions of high retained car-
4275 S. Matthews et al. / Acta Materialia 51 (2003) 42674277
bide density. Even where carbide interaction was
yet to develop signicantly, the close proximity of
the hard particles generated high localised matrix
hardness. The homogeneous carbide distribution
ensured that such development occurred evenly
throughout the coating. In contrast carbide
nucleation in the HVOF coating occurred in car-
bide free zones, generating expansive sponge-like
agglomerates. Within such features the small car-
bide size and small matrix mean free path between
the carbides suggests that, as an entity, such clus-
ters act effectively as larger reinforcing particles
with a hardness tending towards that of the larger
carbide grains. After 1020 days exposure, there
was a transition in both coatings from the growth
of individual grains to the development of a wide-
spread carbide network. The larger carbides for-
med through agglomeration and coalescence
increase the volume of material over which the
load is applied, thereby increasing the resistance to
penetration. The earlier time at which widespread
carbide interaction occurs is thought to account in
part for the more rapid hardening response of the
HVAF coatings during the early stages of
exposure. With long-term exposure the rate of car-
bide development decreased, a trend reected in
the stable hardness achieved after 30 days.
In addition to the microstructural changes the
physical splat structure of the coating also changes
with heat treatment. Diffusion results in solid state
sintering and the formation of physical bonds
between the mechanically interlocked splats. Such
growth was believed to account for the reduction
in porosity and splat boundaries of thermal spray
coatings with extended heat treatment at 800 and
900 C by Tobe et al. [15]. The resulting increase
in homogeneity of the coating structure also con-
tributes to higher hardness values with long-term
exposure.
3.6. Inuence of the treatment environment
Heat treatment of the coatings in air generated
higher average hardness values in both the HVAF
and HVOF coatings, but otherwise mirrored the
argon heat treatments. This differs from previous
studies, which showed an increase in hardness at
treatment times where the present coatings are still
softening. It is likely that the overall increase in
hardness compared to argon treated samples is due
to oxides in the matrix. Oxidative hardening was
also suggested by Sahoo and Raghuraman [1,2],
He et al. [9,10] and Fagoaga et al. [14] in heat
treatment of Cr
3
C
2
based coatings from blended
powders. The rise in hardness within the rst 24 h
of exposure was attributed to oxidation of the car-
bides Cr
3
C
2
and Cr
7
C
3
directly to Cr
2
O
3
without
any decarburisation steps. While in the work of
Sahoo and Raghuraman [1,2] this applied to large
carbide splats, a different mechanism was high-
lighted by He et al. [9,10] for nano-structured coat-
ings. To some degree these responses may be
dependent upon the use of blended powders, parti-
cularly in regard to the coating structure.
In the present study using sintered and agglom-
erated powders, it is more likely that the matrix,
rather than the carbide is preferentially oxidised.
The higher degree of carbide dissolution generated
with the use of agglomerated and sintered powder
and the ner carbide size means that the binder is
more susceptible to oxidation. Hardening by this
mechanism would be more inuential in the HVOF
coatings of this work due to the thinner sample
thickness and the greater splat surface area per
depth of coating resulting from the thinner nature
of the splats. As highlighted in the results of Sahoo
and Raghuraman [2] the inuence of oxide forma-
tion occurs within the rst 24 h as a protective
oxide layer forms with longer periods of exposure
[24]. As such this suggests that the inuence of
internal oxidation occurred prior to the 2 day data
values, its effect remaining as a xed increment of
higher hardness over the remaining trials.
4. Conclusions
In this work, the microhardness response of
HVAF and HVOF Cr
3
C
2
NiCr coatings was
assessed following treatment at 900 C for periods
of up to 60 days in air and argon. Initially, all
samples showed a drop in hardness. This was attri-
buted to the reduction in strengthening mech-
anisms of the matrix phase with heat treatment. Of
those considered solid solution strengthening gen-
erated by carbide dissolution was thought to be the
most dominant.
4276 S. Matthews et al. / Acta Materialia 51 (2003) 42674277
Hardness recovery and achievement of stable
hardness values after 30 days resulted from the pre-
cipitation and development of the carbide phase.
The air treated samples of both the HVAF and
HVOF coatings were consistently harder than
those treated in argon as a result of internal oxi-
dation.
The HVOF coatings were harder than the HVAF
coatings, possibly as a result of the matrix strength-
ening through carbide dissolution or higher as-
sprayed oxide content.
Acknowledgements
The authors gratefully acknowledge the assist-
ance of WOKA, Metal Spray Suppliers (NZ) Ltd,
and Holster Engineering (NZ) Ltd for supplying
the powder and coatings for this work. The nan-
cial assistance provided by Material Performance
Technologies (NZ) and The University of Auck-
land is greatly appreciated.
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