Surface & Coatings Technology 203 (2009) 11441153

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Surface & Coatings Technology

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / s u r f c o a t

High temperature erosion of Cr3C2-NiCr thermal spray coatings The role of

phase microstructure
S. Matthews a,, B. James b, M. Hyland b
a
b

School of Engineering and Advanced Technology, Massey University, Auckland, New Zealand
Department of Chemical and Materials Engineering, University of Auckland, Auckland, New Zealand

a r t i c l e

i n f o

Article history:
Received 6 March 2008
Accepted in revised form 8 October 2008
Available online 17 October 2008
Keywords:
Erosion
Cermets
Thermal spray coating
High temperature deformation
Scanning electron microscopy (SEM)

a b s t r a c t
Cr3C2-NiCr thermal spray coatings are extensively applied to mitigate erosion at temperatures above 450
550 C. The aim of this work was to extend the current comparison based knowledge towards a mechanistic
interpretation of the high temperature erosion of Cr3C2 based thermal spray coatings. Coatings that span the
range of industrial quality were assessed. They were eroded under high temperature (700 C and 800 C),
aggressive (impact velocity 225235 m/s) conditions designed to simulate the high velocity erodent impacts
within a turbine environment. The inuence on the erosion response of high temperature induced changes in
the coating microstructure and composition with extended in-service exposure was assessed by heat treating
selected samples to generate a steady state microstructure prior to testing. In spite of the marked variation in
coating microstructure the erosion rates were comparable across the range of coatings tested. The
signicance of this conclusion is discussed in terms of the erosion mechanism.
2008 Elsevier B.V. All rights reserved.

1. Introduction
Cemented carbide composites are extensively applied by thermal
spraying to resist wear and erosion. WC-Co is the most widely applied
composite [1], however, its corrosion and oxidation performance limit
applications to temperatures below 450550 C [16]. At higher
temperatures the superior oxidation response of Cr3C2 enables Cr3C2NiCr coatings to be applied. This composite has a high melting point and
maintains high hardness, strength and wear resistance up to maximum
operating temperatures approaching 900 C [712]. Such attributes have
seen this coating applied industrially to mitigate the effects of high
temperature erosion in turbine based power generation applications.
Previous works addressing erosion in such applications have
focused primarily on bulk materials. Up to 300400 C mixed erosion
rate results have been observed [13], with the erosion resistance
reported to increase or decrease for different materials. Beyond this
temperature range the erosion rate of most materials tends to increase
with increasing temperature [1320]. Gat and Tabakoff [15] interpreted this response by describing the effect of increasing temperature on the following factors:

Corresponding author. School of Engineering and Advanced Technology, Private Bag

102 904, North Shore Mail Centre, Auckland 0745, New Zealand. Tel.: +64 9
4140800x9872; fax: +64 9 443 9774.
E-mail address: s.matthews@massey.ac.nz (S. Matthews).
0257-8972/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2008.10.008

Type I Factors: Material properties that decrease erosion resistance

with increasing temperature e.g. reduction in mechanical strength,
modulus of elasticity, hardness and resistance to fatigue.
Type II Factors: Material properties that increase erosion resistance
with increasing temperature e.g. increase in ductility and rate of
recovery, decrease in rate of work hardening.
The signicance of each set of factors is dependent upon the material
and test conditions, but serves to highlight the key variations in material
properties with increasing temperature. By way of example, several
authors have noted a reduction in the velocity exponent below 2 in
Equation 1 [21] when correlating erosion rates versus impact velocity at
high temperatures [16,20]. The relationship of the erosion rate (E) to the
erodent impact velocity (V) is expressed as:
E Vn

At ambient temperatures metallic materials typically show an

exponent value of 24 [19,22], with ceramics generating values of up
to 6 [22]. This implies less sensitivity of the erosion rate to this
variable, a factor resulting from a reduction in strength (Type I
variable) and an increase in ductility (Type II variable) [16,19,20].
The reduction in Type I factors and an increase in Type II factors
with temperature do not signicantly inuence the mechanism of
erosion impact deformation, but do increase the magnitude of
deformation. The resulting mass loss resulting from repeated deformation is determined by the interaction between the increased
ductility and decreased resistance to fatigue [15]. The signicance of

S. Matthews et al. / Surface & Coatings Technology 203 (2009) 11441153

brittle erosion mechanisms at high temperature is material property

dependent and has not been widely considered. As the exposure
temperature increases the material brittle-to-ductile transition temperature becomes increasingly important due to the marked change in
the response mechanism that occurs [15]. Laugier [23] observed this
effect experimentally during testing of WC-Co cermets. At 25 C and
400 C the sample exhibited classical brittle behaviour with higher
erosion rates at 90 impact angle than at 45 impact. However, at
750 C the opposite trend occurred, indicative of a transition to a more
ductile erosion response.
Elevated temperature testing of cermet thermal spray coatings has
primarily been of a comparative nature relating to erosion rate as a
function of erosion variables. In testing blended powder based HVOF
Cr3C2-NiCr coatings, Wang and Luer [19] noted an initial reduction in
erosion rate as temperature increased from 25 C to 300 C. Beyond this
the erosion rate increased at a constant rate with increasing
temperature up to 750 C. Under more aggressive erosion conditions
Sue and Tucker [18] noted a gradual increase in erosion rate with
temperature up to 500 C for blended powder based D-Gun chromium
carbide based coatings. Beyond this temperature the erosion rate
increased markedly up to 700 C for all coatings tested, at both 30 and
90 impact angles. Below 500 C erosive mass loss occurred by a
localised erosion mechanism. At 700 C large at features in the eroded
surface indicated that the splat structure played a signicant role in the
mass loss process.
The aim of the work presented was to extend the current
comparison based knowledge of erosion rates, to a mechanistic
interpretation of high temperature erosion of Cr3C2 thermal spray
coatings. Coatings that span the range of industrial quality and starting
powder types were eroded under high temperature aggressive
conditions designed to simulate the high velocity impact of turbine
applications. Short exposure periods and aggressive erosion conditions
prevented oxide scales from playing a signicant role in the erosion
mechanism. Instead this work focused on contrasting the erosion
mechanisms of the different coatings as a function of microstructure in
both the as-sprayed and heat treated condition. Single impact studies
were used to interpret the variation in erosion rate with temperature.
By incorporating heat treated samples with high temperature steady
state microstructures, the variation in erosion response of the coatings
over their service lifetime could be determined.
2. Experimental procedure
Three coating systems were investigated in this work, Table 1. The
HVAF coating consisted of an agglomerated and sintered 75 Cr3C2-25
(Ni(20Cr)) powder (WOKA 2075NiCr) sprayed using a High Velocity Air
Fuel (HVAF) thermal spray system (Browning Aerospray 150). The
HVOF coating used the same powder but was sprayed using a High
Velocity Oxygen Fuel (HVOF) thermal spray system (GMA Microjet). The
Blended coating was produced from a mixture of crushed Cr3C2
powder (WOKA Chromium Carbide) and water atomised Ni20Cr powder
(Sulzer Metco 43VF-NS), with a ratio of 75 wt.% Cr3C2/25 wt.% NiCr. This

Table 1
Coating designation and pretreatment
Designation Powder
HVAF
HVOF
Blended

WOKA 2075NiCr

Deposition
technique

Aerospray
150 HVAF
WOKA 2075NiCr
GMA Microjet
HVOF
GMA Microjet
Blend of WOKA
chromium Carbide/Sulzer HVOF
Metco 43VF-NS

Treatment
As-sprayed, heat treated
2 days and 30 days at 900 C
As-sprayed, heat treated
5 days and 30 days at 900 C
As-sprayed, heat treated
5 days and 30 days at 900 C

1145

Table 2
Thermal spray systems and operating parameters
Spray parameters

HVAF

HVOF

Spray system
Fuel
Fuel consumption
Oxidant
Oxidant consumption
Chamber pressure
Nozzle length
Powder feed rate
Carrier gas
Carrier gas consumption
Spray distance
Traverse speed

Aerospray 150
Kerosene
23 l/h
Air
3.3 m3/min
275-310 kPa
200 mm
35 g/min
Nitrogen
870 l/h at 290 kPa
150 mm
150 mm/s

GMA Microjet
Propane
5 bar supply
Oxygen
7 bar supply

32 mm with 38 mm air-cap
11.7 7 g/min
Nitrogen
870 l/h at 290 kPa
125 mm
55 mm/s

powder was sprayed using the HVOF system using the same spray
parameters as for the agglomerated/sintered powder. Samples were
sprayed on to degreased and grit blasted plates of 3 mm Sandvik 253MA
stainless steel using the parameters of Table 2.
Coatings were sprayed to a thickness of approximately 400 m.
Samples of 15 mm 15 mm were cut from the sprayed plates. Samples
from each coating system were heat treated for various times at 900 C in
still air, Table 1. The duration of heat treatment was based upon the
variation in microhardness as a function of treatment time as presented
in [24]. All samples were ground to remove any surface scale and the top
of the coating polished using 3 m diamond media. Specimens from
each treatment were characterised using XRD (Bruker D8 Advance, Cu
source), with cross sectional analysis performed by SEM (Philips XL30S
FEG). Vickers microhardness analysis was carried out under a 300 g load
(LECO M-400 Hardness tester).
Erosion trials were performed in a custom built test rig, Fig. 1.
Compressed air passed through a recuperator to recover as much heat
as possible from the spent process stream. It then passed through a
primary heating unit and secondary heating unit before mixing with
the erodent in a chamber above the nozzle. The nozzle consisted of a
630 mm long 5 mm ID alumina tube. The erodent was accelerated
down the tube by the expanding gas to impact the sample below. The
sample was maintained at 25 mm from the nozzle exit at a xed
impact angle of 90. By controlling the pressure drop across the nozzle
the erodent impact velocity could be calculated using the model of
Ninham and Hutchings [25]. Crushed alumina of 2025 m nominal
size was used in all trials.
Trials were carried out at 700 C and 800 C. The calculated erodent
velocities were 225 m/s and 235 m/s respectively. Samples were
preheated to the test temperature in a box furnace before being inserted
into the erosion rig.
Two types of erosion test were performed. Single impact trials
eroded the samples for 1 s in order to generate isolated impacts for
analysis. These trials were performed on the HVAF and Blended coatings
at 700 C and 800 C. Erosion rate trials were performed by eroding the
samples for 5 min in the 700 C trials and 4 min in the 800 C trials. The
erodent feed rate was maintained at 10 g/h. The samples were weighed
to an accuracy of 0.01 mg (Mettler Toledo AG245 balance) prior to
preheating and after cooling to ambient temperature following erosion.
While oxidation did occur during the heating and cooling periods, the
magnitude of mass gain was considerably smaller than that lost by
erosion. It was therefore not taken into account in the erosion rate
analysis. All three coating systems were tested to measure the erosion
rate. Two samples of each coating with each different pre-treatment
were tested for each erosion condition.
The eroded samples were analysed using SEM. Where possible a
mixed secondary electron-backscattered imaging process was used to
highlight the relationship between the coating phases and erosion
deformation.

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S. Matthews et al. / Surface & Coatings Technology 203 (2009) 11441153

3. Results and discussion

3.1. Coating characterisation
The three coating systems have been characterised in detail in
previous works [24,2628]. A review of the most signicant microstructural features related to this work is presented below.
The as-sprayed HVAF coating retained the same general microstructure as was present in the starting powder. Minimal carbide
dissolution occurred in-ight resulting in a high retained carbide
content of 67%, Fig. 2. Cr3C2 and NiCr were the only phases detected
with no evidence of any oxide phases or decarburisation phases
present. XRD analysis indicated that the matrix phase contained
substantial amorphous material resulting from rapid solidication.
Heat treatment for 2 days led to an increase in the carbide content
to 75 vol.%. Carbide precipitation occurred primarily on the retained
carbide grains. Cr3C2 was the only carbide phase detected by XRD. The
matrix phase recrystallised with treatment.
Extended heat treatment to 30 days led to coarsening and
agglomeration of the carbide grains to form a three dimensional
skeletal structure. Cr3C2 was the only carbide phase detected, with no
sign of decarburisation occurring over the treatment time.
Signicant in-ight carbide dissolution occurred in the HVOF
coating, reducing the carbide content to 36 vol.%. The NiCr matrix
phase became supersaturated with Cr and C, as highlighted by the
mid-grey zones of Fig. 3. In spite of this Cr3C2 and NiCr were the only
phases detected by XRD. Oxide stringers were occasionally observed
as long thin dark phases at the splat boundaries.
Extensive carbide precipitation occurred with 5 days heat treatment
such that the carbide content reached 75 vol.%. Carbide precipitation
occurred mainly in regions where the greatest dissolution occurred
during spraying. Coalescence and bridging of the large number of ne
grains led to the development of a sponge-like three dimensional

Fig. 2. Cross sections of the HVAF coating in the as-sprayed condition (top) and
following heat treatment at 900 C for 2 days (middle) and 30 days (bottom).

Fig. 1. Schematic of the high temperature, high velocity erosion rig.

structure. Continued exposure for 30 days led to coarsening of the grains

and the formation of a microstructure comparable to that seen in the
HVAF coating. Cr3C2 was the only carbide phase observed over the
duration of heat treatment, with no evidence of Cr7C3 or Cr23C6 formation.
Fig. 4 illustrates the characteristic single phase splat structure of
the Blended coating. The dark Cr3C2 splats and light NiCr splats are
readily identiable. Signicant in-ight oxidation was evident in the
large number of oxide stringers. The carbide phase appeared to be
largely amorphous and of low intensity in the XRD analysis.
Signicant internal oxidation occurred with heat treatment to form
Cr2O3. Recrystallisation of the carbide phase occurred and XRD indicated
a dominant composition of Cr7C3. This formed by in-ight decarburisation rather than through heat treatment. Sintering of the single phase
splats occurred. This allowed diffusion and growth of carbide features
into the matrix splats with extended exposure to 30 days, Fig. 4.
Prior work [24] illustrated that the HVAF and HVOF coatings softened
with initial heat treatment periods of 2 and 5 days respectively, Fig. 5.
Beyond this time the hardness increased before reaching a plateau level.
The development in hardness was correlated with the development in
the carbide structure.

S. Matthews et al. / Surface & Coatings Technology 203 (2009) 11441153

Fig. 3. Cross sections of the HVOF coating in the as-sprayed condition (top) and
following heat treatment at 900 C for 5 days (middle) and 30 days (bottom).

The hardness of the Blended coating increased with heat treatment

time. Internal oxidation and inter-splat sintering were postulated to
account for the initial increase in a similar manner to Fagoaga et al [3].
Such processes were thought to have reached completion within the
rst 5 days of treatment and so it is uncertain what mechanism
accounted for the increase in hardness out to 30 days.
Overall the HVOF coating was harder than the HVAF coating across
all treatment times. HVOF and HVAF coatings, based on the agglomerated/sintered powder, were both signicantly harder than the blended
powder based coating.

1147

Fig. 4. Cross sections of the Blended coating in the as-sprayed condition (top) and
following heat treatment at 900 C for 5 days (middle) and 30 days (bottom).

In the as-sprayed coatings in the region directly outside the

immediate impact zone large akes and mounds of laterally displaced
material were evident. These resulted from the large depth of

3.2. Single impact studies HVAF coating

3.2.1. Erosion at 700 C
The high temperature and impact velocity generated signicantly
greater depths of erodent penetration in the as-sprayed coating
compared to previous ambient temperature trials under milder
conditions [26,28], Fig. 6. Within the impacted zone the erodent readily
cut through the carbide grains. No carbide fracture or inter-phase
cracking was evident within the side of the indents.

Fig. 5. Vickers microhardness variation of the three coatings as a function of heat

treatment time at 900 C in air.

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S. Matthews et al. / Surface & Coatings Technology 203 (2009) 11441153

Fig. 6. Representative erosion impact deformation on the as-sprayed HVAF coating at

700 C.

Fig. 7. Representative erosion impact deformation at 700 C on the HVAF coating heat
treated for 2 days (top) and 30 days (bottom).

penetration of the erodent. Deformation occurred in this area in a largely

brittle manner. Brittle inter-phase cracking was evident as the laterally
loaded carbide grains were displaced relative to each other and out of
the surface. The brittle nature of cracking was evident in the at surfaces
of the NiCr matrix material which did not deform in a ductile manner.
Brittle extrusion of the NiCr matrix between neighbouring carbide
grains was also evident. The brittle response of this phase enabled the
impact to be distributed away from the indent, expanding the volume of
deformation.
The brittle matrix response was localised relatively close to the
indent. Towards the outer periphery of the deformed material more
ductile matrix plastic deformation occurred. Extrusion without brittle
inter-phase cracking was observed. Minimal brittle inter-phase cracking
radiated outwards from the displaced akes and mounds. The brittle
matrix response was attributed to the high loading rate close to the
impact, the limited ductility of the phase at this temperature and the
constraint imposed by the carbide grains. In regions rich in matrix phase
the impact features reected a greater degree of plastic deformation
without brittle fracture.
With short term heat treatment matrix ductility increased relative
to the as-sprayed state, Fig. 7. Peripheral deformation became more
localised around the impact zone. Cracking and fracture in the ake
and mound features occurred primarily through inter-phase cracking.
Outside this zone plastic deformation of the matrix was able to
accommodate carbide grain movement without fracture or interphase cracking. As a result cracking was not observed to propagate
away from the impact zone.
With extended heat treatment the contiguity of the carbide phase
greatly increased. Localised carbide movement became restricted, while
at the same time it allowed erodent impact loading to be distributed
over a greater volume. Both factors contributed to restricting impact
deformation to zones near the impact site, Fig. 7. This phase
development also minimised inter-phase fracture in the deformation
zone. However the inability of the carbides to move made them prone to

degradation under impact. The high velocity particles readily cleaved

through the carbide agglomerates. In spite of this, little cracking or
fracture was observed, indicating an increase in carbide toughness at
this elevated temperature.
3.2.2. Erosion at 800 C
The elevated temperature greatly increased the ductility of the NiCr
matrix phase in the as-sprayed samples, Fig. 8. The low temperature
brittle response induced by supersaturation of the NiCr phase by
dissolved carbide elements and the rapidly solidied structure were no
longer observed. As a result the primary effect of carbide dissolution was
to reduce the cermet to a hard phase content of 67 vol.%. Impact
deformation in cermets of this hard phase concentration is known to be
determined by matrix phase deformation [2931]. Extensive NiCr
matrix phase deformation was evident in the form of ductile mounds,
ductile extrusion between carbide grains and the formation of platelets
around the indent periphery. A measure of the matrix ductility was also

Fig. 8. Representative erosion impact deformation on the as-sprayed HVAF coating at

800 C.

S. Matthews et al. / Surface & Coatings Technology 203 (2009) 11441153

reected in the high concentration of erodent fragments retained within

the impact features. The increased matrix phase ductility limited crack
initiation, propagation and load displacement away from the erodent
indent. Deformation was therefore limited to those features directly
surrounding the impact zone.
The magnitude of erodent penetration meant that a large number
of carbide grains were incorporated within each impact zone. Carbide
deformation occurred via fracture and plastic deformation. Within the
impact zone carbide grains were cleaved without relative motion with
the surrounding substrate and without undergoing brittle cracking.
Outside the impact zone plastically deformed platelets of mixed
phases were found as a result of the deep penetration of the erodent.
However, this rarely led to direct mass loss. The results suggest that
the temperature range 700800 C encompasses a transition from
brittle to ductile impact response of the as-sprayed coatings as a
function of matrix phase ductility.
Carbide development with heat treatment led to constraint on bulk
deformation of the matrix phase. This was in spite of the increase in
matrix ductility with the reduction in carbide element supersaturation.
This effect was more evident at 800 C than at 700 C. Within the impact
zone the carbide grains were readily cleaved and compressed within the
NiCr matrix, Fig. 9. No cracking or inter-phase separation was observed
in this zone. Lateral displacement of material resulting from the depth of
erodent penetration formed peripheral akes and mounds. Carbide
agglomerates were cleaved by the erodent and forced sideways. Such
movement was restricted by the surrounding carbide skeletal network,
forcing the displaced material out of the surface. This resulted in interphase cracking and fracture of the thin bands of matrix material
between the carbide agglomerates. Outside this deformation zone the
carbide network enabled the applied load to be distributed over a large
volume without deformation. The few cracks that did propagate away
from the impact site were blunted by ductile matrix phase deformation.

1149

Fig. 10. Representative erosion impact deformation on the as-sprayed Blended coating
at 800 C.

lateral loads generated by erodent penetration were dissipated through

ductile deformation of the matrix phase in the surrounding material,
rather then being concentrated at the splat boundaries. Bulk separation
of entire splats from the surface was not observed at this temperature
but was common in single impact studies under milder impact velocities
at ambient temperature [26].
Heat treatment led to inter-splat sintering, further reducing the
effect of splat boundaries on the erosion response. The impact of the
subtle development of carbide features was overshadowed by the size
of the impact deformation zone relative to such features, Fig. 11.
3.4. Erosion rate trials

The results for the as-sprayed coatings did not vary signicantly
between 700 C and 800 C. Variations that might have arisen from the
effect of temperature on mechanical properties were overshadowed
by the complex deformation generated at impact, Fig. 10.
The carbide phase exhibited a generally brittle erosion response.
However, the toughness of this phase appeared to increase with
temperature as evident by the increasing degrees of plastic deformation
without fracture. The NiCr matrix ductility signicantly increased with
temperature. This phase exhibited classical ductile erosion deformation
features. The response of mixed phase regions was dominated by matrix
phase deformation up to very high carbide concentrations. Unlike at
ambient temperature the splat boundaries did not dominate the impact
response [26]. The large depth of erodent penetration meant that it
cleaved through multiple splats of varying phase composition. The high

Figs. 12 and 13 present the average erosion mass loss of samples at

700 C and 800 C respectively. Note that it is not possible to directly
compare the data at 700 C and 800 C due to the different impact
velocities and erosion times.
During erosion at 700 C heat treatment did not result in a reduced
erosion rate of the HVAF sample. This is in contrast to previous work at
ambient temperature in which signicant improvements in erosion
resistance occurred following heat treatment [26,28]. The 700 C erosion
rate of the HVOF coating also showed very little variation with heat
treatment. The results were comparable with those of the HVAF coating
in spite of the variation in carbide degradation during spraying. The
Blended coating had a slightly poorer erosion rate response compared to
the agglomerated/sintered powder based coatings. However, the
variation between this and the previous coatings was comparable
with the within-sample variation in some of the duplicate results.
Therefore further trials are required to quantify the relative difference in
erosion rates. Heat treatment had a minimal effect on the erosion rate of
this coating. This was also in contrast to the ambient temperatures trial
results [26].

Fig. 9. Representative erosion impact deformation at 800 C on the HVAF coating heat
treated for 2 days.

Fig. 11. Representative erosion impact deformation at 800 C on the Blended coating
heat treated for 5 days.

3.3. Single impact studies Blended coating

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S. Matthews et al. / Surface & Coatings Technology 203 (2009) 11441153

Fig. 12. Erosion mass loss data for the three coating systems at 700 C.

During erosion at 800 C there was a pronounced effect from heat

treatment. The erosion rate of the HVAF coating increased with
increasing heat treatment time. The largest variation occurred between
the 2 and 30 day treatment specimens. The as-sprayed HVOF coating
had a very low erosion rate, less than 75% of the HVAF result. The erosion
rate increased with heat treatment but remained consistent over the 5
and 30 day treated specimens. These results were comparable with the
2 day treated HVAF samples, but less than the 30 day heat treated HVAF
samples. Heat treatment had a very minor inuence on the Blended
coating results. The results were slightly larger than the heat treated
HVOF coating and surprisingly, lower than the 30 day HVAF coating.
In contrasting the results above with Fig. 5 it is clear that ambient
temperature microhardness measurements on the coating cross section
are a poor indicator of relative erosion resistance under these conditions.
3.5. Steady state topography analysis
The same generalised erosion features were observed on the assprayed HVAF coating eroded at 700 C and 800 C, but were larger at the
higher temperature. Localised mass loss occurred through fracture of
akes and platelets displaced from the periphery of the indents. More
extensive mass loss occurred via a gross chipping mechanism previously described in [26,28]. Essentially this involves lateral displacement of material from one impact into the indentation of a previous

impact. Fracture occurs via a low cycle fatigue mechanism to produce

chips of debris of the same magnitude as the depth of erodent indentation. The effects of this mechanism could be seen in the large fracture
features across the surface, Fig. 14. There were no indications that the
splat structure played a signicant role in erosion at either temperature.
Heat treatment had a negligible effect on the eroded surface
topography at either temperature. The subtle variations in impact
damage with carbide development were overshadowed by the chaotic
nature of the surface.
Deformation of the as-sprayed HVOF coating appeared less ductile
than in the HVAF coating at both temperatures. This was reected in the
limited degree of ductile deformation in some single impact indents
observed around the periphery of the steady state erosion crater, Fig. 15.
The extensive degree of NiCr supersaturation appeared to extend the
brittle to ductile transition of this phase to a higher temperature relative
to the HVAF coating. Localised mass loss occurred via the same
mechanism as highlighted for the HVAF coating. Bulk mass loss was
accentuated by splat based mechanisms. Splat edge chipping, lateral
displacement of splat segments and chip formation through the link up
of through splat cracks and splat boundaries occurred frequently as
indicated by the smooth splat surfaces visible in the steady state eroded
topography, Fig. 16.
It is notable, however, that such features were not as prevalent as
in the ambient temperature trials [26,28]. The increased matrix phase

Fig. 13. Erosion mass loss data for the three coating systems at 800 C.

S. Matthews et al. / Surface & Coatings Technology 203 (2009) 11441153

1151

Fig. 14. Representative image highlighting the gross chipping mass loss mechanism at
800 C.

Fig. 16. Representative steady state erosion impact deformation on the as-sprayed HVOF
coating at 800 C.

ductility at the higher temperature is clearly able to dissipate greater

degrees of impact energy through plastic deformation. This resulted in
an overall transition from splat structure dominated mass loss
mechanisms to more microstructural based erosion mechanisms.
Heat treatment had a signicant inuence on the morphology of the
eroded surface. A greater degree of ductility was evident in the plastically
deformed material. Sintering of the splats signicantly improved the
inter-splat bonding. This was reected in the lack of smooth splat
surfaces in the eroded surface topography. The general morphology
tended to that of the HVAF coating following heat treatment.
The response of the as-sprayed Blended coating appeared similar at
both temperatures, with the size of the deformation features larger at
the higher temperature. The broad spectrum of responses highlighted in
the single impact trials were observed in the steady state eroded surface.
Bulk mass loss was related to splat based erosion mechanisms as
highlighted by the appearance of smooth splat surfaces. These were
notably less common than in the ambient temperature trials [26]. This
results from the greater depth of erodent penetration. The impact load is
distributed over a greater volume of material incorporating multiple
splats instead of being concentrated on a single surface splat.
Heat treatment had a negligible effect on the eroded surface
morphology. The signicance of inter-splat sintering was overshadowed by the increase in the NiCr matrix ductility and the transition
from a splat based to microstructure based erosion response.

brittle response transferring high loads to a greater volume of material

without plastic deformation. With increasing temperature the tendency
for localised brittle fracture reduced, enabling greater degrees of plastic
deformation and effectively toughening the carbide-matrix interface.
The increased ductility enabled the impact energy to be dissipated
through localised plastic deformation restricting erosion damage to the
localised zone around the indent. The increased NiCr matrix ductility
also reduced the impact loading on the splat boundaries, leading to a
generalised transition in erosion response from splat based to microstructure based erosion mechanisms. This was a particularly signicant
transition given the dominance of the splat structure effect at ambient
temperature and the much greater depth of erodent penetration though
multiple splats in these higher velocity erosion trials.
The toughness of the carbide phase increased with temperature.
Brittle fracture and cracking were less evident while crack blunting and
plastic deformation features were observed. However, the drawback of
increased temperature is the reduction in hardness and therefore
resistance to penetration. This hardness effect was accentuated under
the conditions of this work where the carbide was at elevated
temperature while the erodent was essentially at ambient temperature
during impact.
The effect of these temperature induced variations in phase response
was most evident at 800 C. The erosion rate results supported the
microstructural observations in indicating a transition from a splat
based towards a microstructure based response. This was highlighted by
the increase in erosion rate of the heat treated agglomerated/sintered
powder based coatings (HVAF and HVOF), in spite of the improved splat
bonding. A comparable variation in response did not take place in the
Blended powder based coatings where minimal carbide development
occurred with heat treatment. Furthermore the consistency of the assprayed and heat treated blended powder results was in direct contrast
to the ambient temperature trials where sintering of the splats
signicantly reduced the dominance of splat based erosion mechanism
[26].
The microstructural erosion response of the agglomerated/sintered
powder based coatings was a balance between the effect of the
increased ductility of the matrix phase and the increasing constraint
imposed by the developing carbide phase, Fig. 17. In terms of
composition the primary effect of in-ight carbide dissolution was to
reduce the carbide content. The elevated temperature enabled a ductile
response of the matrix phase in spite of it being supersaturated with Cr
and C. This in combination with the reduced effective carbide content
meant the matrix phase dictated the erosion mechanism and resulted in
an overall more ductile response in the as-sprayed coatings. Heat
treatment improved the matrix phase ductility [24,2628] through a
reduction in supersaturation of Cr and C. However, this improvement in
ductility was countered by the developing carbide phase which
increasingly restricted the degree of matrix deformation. While plastic
deformation of the cermet was still determined by matrix phase

3.6. Inuence of temperature on the erosion mechanism

Elevated temperature during erosion signicantly inuenced both
Type I and II factors [15] of the different coating phases. The ductility of
the as-sprayed agglomerated/sintered powder based coatings dramatically increased, in spite of the effects of supersaturation and rapid
solidication. At ambient temperature [26,28] this phase exhibited a

Fig. 15. Representative erosion impact deformation at 800 C on the as-sprayed HVOF
coating.

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S. Matthews et al. / Surface & Coatings Technology 203 (2009) 11441153

Fig. 17. Schematic illustration of the transition in erosion response as a function of heat treatment at 700 C and 800 C for the agglomerated/sintered powder HVAF and HVOF
coatings.

deformation, the overall erosion response of the heat treated coatings

tended towards a more brittle erosion mechanism. This transition in
erosion response was reected in the erosion rate. Brittle materials
erode to the greatest extent at a 90 impact angle. Therefore the transition in erosion mechanism of the HVAF and HVOF cermets with heat
treatment towards a more brittle response was reected in the increased
erosion rate under xed erosion conditions with an impact angle of 90.
At 700 C the variation in the microstructural erosion response was not
as evident as at 800 C. The similarity in the results of the HVAF and
HVOF coatings indicates that carbide development did not inuence the
erosion response to the same degree as at 800 C. This resulted from the
reduced ductility of the NiCr matrix at this temperature which allowed
more brittle erosion mechanisms to occur. The similarity in the assprayed and heat treated Blended powder based coating response
suggested that the splat structure did not dominate the erosion
mechanism to the same extent as at ambient temperature.
3.7. Inuence of deposition technique and starting powder morphology
For the agglomerated/sintered powder based coatings the effect of
deposition technique was most evident at 800 C. This variation is a direct
response of the variation in carbide dissolution in-ight. The HVOF
coating suffered the greatest degree of carbide dissolution leading to a
more ductile erosion response and lower erosion rate at 90 relative to the
more carbide rich HVAF coating. While the extensive degree of supersaturation in the HVOF coating reduced the ductility of the NiCr phase
relative to the HVAF coating, the extensive nature of the matrix meant
that this phase generated a more ductile response of the overall cermet.
The HVAF erosion response appears to correspond with the
increasing constraint imposed by the developing carbide. Short term
heat treatment led to an increase in the carbide content to 75 vol.%.
However, carbide nucleation occurred primarily on the retained
carbide grains. Hence, while the number of carbide particles increased
to inhibit the NiCr deformation, the grains themselves remained
largely independent. In this way the matrix phase still had the ability

to deform in a ductile manner, but not to the same extent as in the assprayed state. Further heat treatment led to the formation of a three
dimensional carbide network, resulting in severe constraint of the
NiCr phase and a more brittle erosion response of the cermet.
The HVOF coating exhibited a consistent erosion rate with heat
treatment. This is caused by the carbide development with heat
treatment [24,27]. Carbide nucleation formed high density networks
of ne carbide grains in the extensive supersaturated NiCr regions of the
coating. The distribution of such grains effectively hardens the NiCr
matrix, restricting the extent of ductile deformation under impact. With
extended heat treatment a coarse three dimensional carbide network
developed to inhibit ductile deformation in the manner described for
the HVAF coating. Of signicance is that in spite of the HVAF and HVOF
coatings tending towards the same microstructures after 30 days of heat
treatment the HVOF coating was notably more erosion resistant. The
cause of this variation is currently unknown.
While the same microstructural changes occurred in the HVAF and
HVOF coatings tested at 700 C, no obvious trend in erosion rate as a
function of heat treatment occurred. This is caused by the low degree of
matrix phase ductility at this temperature which promotes a brittle
erosion response in the cermet. This is particularly evident in the assprayed HVOF coating which showed a comparable erosion rate to the
heat treated samples in marked contrast to the response at 800 C. This
brittle matrix response meant that splat based erosion mechanisms
potentially played a greater role in determining the degree of mass loss
in the as-sprayed coatings relative to at 800 C. The complex relationship
between the degree of matrix ductility and the effect of the developing
carbide microstructure accounts for the consistent erosion rate of the
heat treated samples with that of the as-sprayed samples for both
coating sets.
The Blended coating underwent limited phase development with
heat treatment. Sintering of the splats had the greatest effect at
ambient temperature and contributed to the slightly higher erosion
rate of the as-sprayed samples at 700 C. The 5 day and 30 day samples
generated consistent results since the subtle carbide development

S. Matthews et al. / Surface & Coatings Technology 203 (2009) 11441153

that did occur was dramatically smaller than the degree of deformation induced by erodent impact. At 800 C the results were more
consistent due to the increased degree of matrix phase ductility and
the depth of erodent penetration. The erodent penetrated multiple
splats at this temperature, in contrast to the largely surface based
deformation at ambient temperature. The impact load was therefore
spread over a large volume of material incorporating multiple splats
rather then focusing the impact load on a single surface splat. As a
result splat based erosion mechanisms were no longer as dominant,
thereby minimising the most signicant variation between the assprayed and heat treated coatings.
The depth of erodent penetration also accounts for the similarity in
the magnitude of erosion between the agglomerated/sintered powder
based coatings and the blended powder based coating. In the ambient
temperature trials the erodent impacts were small enough that
deformation was dictated by the localised coating phase. This was
particularly so for the Blended coating with its extensive pools of
materials resulting from the single phase splats [26]. The increase in
erodent induced deformation in these high velocity, high temperature
trials increased the volume of coating material interacting with the
erodent. This had the effect of averaging out the inuence of the cermet
composition within the impact zone. The size of the Blended powder
microstructure was on the same scale as the erodent indentation and as
such provided a similar resistance to indentation as the more
homogeneous microstructure of the HVAF/HVOF coatings. The dramatic
contrast in relative erosion resistance between the two starting powder
types as function of erosion conditions highlights the fact that no broad
generalisations can be made in regard to their performance without
testing under simulated industrial conditions.
This conclusion is reinforced in the lack of correlation between the
trends in microhardness of Fig. 5 with the erosion rate data of Figs. 12
and 13. Many of the mechanisms discussed here, in relation to changes
in mechanical properties with microstructure development, have also
been considered to account for the microhardness development [24].
However, the variation in mechanical properties of the different
phases with temperature combined with the complex variation in the
composition of the phases themselves with heat treatment mean that
trends in microhardness at ambient temperature are a poor indicator
of the relative high temperature erosion response.
4. Conclusions
Cr3C2-NiCr thermal spray coatings are extensively used at elevated
temperature to mitigate erosion. The aim of this work was to investigate
the variation in erosion mechanism and relative erosion rate of
industrially representative coatings as a function of starting powder
morphology, deposition technique and heat treatment induced microstructural development. The key conclusions stemming from this work
were:
The coating microhardness measured at ambient temperature is a
poor indicator of the relative erosion response of these coatings under
aggressive erosion conditions at elevated temperature.
At 700 C the HVAF and HVOF coatings sprayed using the
agglomerated/sintered powder produced comparable erosion rates
in the as-sprayed and heat treated conditions. This consistency was
related to the complex transition in inuence of the brittle matrix
phase in the as-sprayed state through to the impact of the three
dimensional carbide network following heat treatment.
Although the ductility of the NiCr matrix phase signicantly
increased for both coatings at 800 C the erosion rate increased with
heat treatment due to the increasing constraint imposed upon the
matrix by the developing carbide microstructure.
The Blended powder based coating exhibited comparable erosion
rates in the as-sprayed and heat treated conditions. Elevated tempera-

1153

ture increased the ductility of the NiCr matrix phase such that the impact
load could be dissipated through plastic deformation. This reduced the
signicance of the splat based erosion mechanisms which was the main
differentiating factor following heat treatment at ambient temperature.
The Blended coating generated comparable erosion rate results to
the agglomerated/sintered powder based coatings. This resulted from
the large depth of erodent indentation which penetrated multiple
splats. This had the effect of averaging out the microstructural
resistance to indentation over the indentation volume. In this way the
variation in carbide microstructural features was not as signicant as
in the milder ambient temperature trials.
Acknowledgements
The authors gratefully acknowledge the assistance of WOKA
GmbH, Metal Spray Suppliers (NZ) Ltd, and Holster Engineering (NZ)
Ltd for supplying the powder and coatings for this work. The nancial
assistance provided by Material Performance Technologies (NZ) and
The University of Auckland is greatly appreciated.
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