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Microstructure evolution of vacuum plasma sprayed CoNiCrAlY coatings

after heat treatment and isothermal oxidation
P. Poza
a,

, P.S. Grant
b
a
Departamento de Ciencia e Ingeniería de los Materiales, Universidad Rey Juan Carlos, Escuela Superior de Ciencias Experimentales y Tecnología,
C/ Tulipán s.n. 28933 Móstoles (Madrid), Spain
b
Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH, United Kingdom
Received 8 February 2006; accepted in revised form 1 June 2006
Available online 13 July 2006
Abstract
The microstructure of a CoNiCrAlY coating vacuum plasma sprayed onto an aluminized MARM002 Ni-base superalloy was investigated in the
as-deposited condition, after heat treatment to promote adhesion, and after oxidation in air for 100 h at 1100 °C. The as-sprayed coating comprised
three main phases: the solid solution γ-(Ni, Co), the intermetallic compound β-(Ni, Co)Al and the intermetallic compound γ′-(Ni, Co)
3
Al that grew
as small precipitates inside γ grains. γ′ phase was present even in the as-sprayed condition because of Al diffusion into the coating from the
aluminized substrate during manufacture at temperatures of 800–1000 °C. The microstructure was fine-scale and complex with β phase within γ
grains, at γ grain boundaries and large βgrains surrounded by γ matrix. After heat treatment, the microstructure comprised βgrains typically of 3-μm
diameter randomly distributed throughout the γ matrix. There was little or no Al depletion of the coating because of Al diffusion from the substrate
aluminized layer. Diffusion of C from the substrate induced the formation of Cr
23
C
6
and M
5
Y (where M was predominantly Ni and Co) in the as-
sprayed coating; with M
5
Y transforming to Y
2
O
3
during heat treatment due to internal oxidation. After oxidation, there was a loss of Al despite the
aluminized layer, because of the formation of a thermally grown oxide (TGO) layer on the upper surface of the coating, mainly comprising Al
2
O
3
with
some Cr
2
O
3
. There was a corresponding reduction in β phase fraction and a substantial reduction in the substrate aluminized layer thickness. Some β
grains persisted close to the TGO at grain boundaries, together with Y
2
O
3
and Cr
23
C
6
particles.
© 2006 Elsevier B.V. All rights reserved.
Keywords: B: Phase transitions; B: Scanning electron microscopy (SEM); B: Transmission electron microscopy (TEM); B: X-ray diffraction; B: Plasma spraying;
X: MCrAlY coatings
1. Introduction
The continuing development of modern gas turbine aero-
engines requires materials capable of withstanding increasing
operating temperatures, mechanical loads and chemical degra-
dation. Ni-base superalloys are widely used in the severest
operating conditions in the high pressure compressor, combus-
tor and turbine sections because of their creep, toughness and
low cycle fatigue properties. However, Ni base superalloys may
suffer from chemical attack resulting from the high temperature
and highly oxidising atmosphere, which may contain aggressive
sulphates, chlorides and sulphurous gas species. Furthermore,
combustor and turbine gas temperatures may exceed the melting
point of the Ni superalloy, leading to structural failure by
melting. To overcome these limitations, Ni superalloy compo-
nents in combustor and turbine sections are cooled by a
combination of internal and surface boundary layer air cooling,
and the application of an insulating surface thermal barrier
coating (TBC). In general, TBCs are preferred to air-cooling
where possible because increasing the use of TBCs reduces the
need to use compressor discharge air for the cooling and
dilution of the flame entering the turbine first stage. This is
desirable to maximise thermodynamic efficiency and recovery
of maximum compressor work in the turbine section. TBCs may
also allow turbine components to withstand increased turbine
entry gas temperatures, which also promotes overall engine
efficiency [1–7].
ZrO
2
coatings, in which the high temperature cubic phase is
partially stabilised relative to the lower temperature monoclinic
Surface & Coatings Technology 201 (2006) 2887–2896
www.elsevier.com/locate/surfcoat

Corresponding author. Tel.: +34 914 887 179; fax: +34 914 888 150.
E-mail address: pedro.poza@urjc.es (P. Poza).
0257-8972/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2006.06.001
phase by the addition of typically 8-wt.% Y
2
O
3
are used widely
in TBCs. Partially stabilised zirconia (PSZ) coatings also have
the required low thermal conductivity (0.8–1.5 W m
−1
K
−1
)
together with a relatively high coefficient of thermal expansion
(CTE) of 7–10×10
−6
K
−1
in an attempt to provide mechanical
compatibility with metallic components with a CTE typically of
15×10
−6
K
−1
. However, the direct use of a PSZ layer on a Ni
superalloy component is problematical because the CTE mis-
match between PSZ and Ni superalloys generates high inter-
facial shear stresses during coating manufacture and in-service
thermal cycling that leads to PSZ failure by spalling. Problems
of CTE mismatch and the need to protect the load carrying Ni
superalloy component from chemical attack (ZrO
2
is permeable
to oxygen and other species at high temperature) has led to the use
of an intermediate metallic “bond coat”. This coat: (i) increases
the adhesion of PSZ “top coat” providing a three-dimensionally
rough surface into which the PSZ can attach by mechanical
keying; (ii) creeps at high temperature in-service to accommodate
thermally induced strains and so reduces interfacial shear stresses;
and (iii) provides enhanced oxidation and corrosion resistance. To
this end, these coatings should develop a surface oxide layer that is
thermodynamically stable, slow growing and adherent. MCrAlY
type (M=Co, Ni or Co+Ni) coatings are currently used in systems
processed by thermal spraying. During oxidation at high tem-
perature, a thermally grown oxide (TGO) layer is formed between
the MCrAlY bond coat and the ceramic top coat. The main con-
stituent of this TGO layer is a protective Al
2
O
3
scale that inhibits
continued ingress of active oxygen and other species. The presence
of an active element such as Yin the coating inhibits Al
2
O
3
growth
and improves its adherence [4,6–8]. Further improvements in
component oxidation resistance may be achieved by the formation
of a β-NiAl phase rich layer directly onto the Ni superalloy [9,10]
prior to the application of the bond coat. These diffusion coatings
are processed by exposure of the Ni base superalloy to a solid
vapour Al source at high temperature in an inert atmosphere
[4,6,11–15], which provides extra aluminium content to form a
protective Al
2
O
3
scale. Consequently, TBCs may comprise three
layers: a diffusion coating, an overlay bond coat, and a ceramic top
coat. This arrangement is shown schematically in Fig. 1.
The mechanisms controlling the durability of TBCs [16–18]
and the TGO layer development [18–22] are being studied
extensively. The microstructure of MCrAlY coatings has been
studied in several papers [23–29], however detailed microstruc-
tural investigations of the commercially important arrangement
comprising a Ni superalloy substrate with both an aluminised and
MCrAlYcoating are rare. This paper describes the microstructural
investigation of a MCrAlY coating vacuum plasma sprayed onto
an aluminised MARM002 Ni-base superalloy substrate.
MARM002 is used in nozzle guide vanes that experience some
of the severest combinations of environment andhigh temperature.
The coating microstructure was studied as-sprayed, after a heat
treatment to promote adhesion, and after high temperature oxida-
tion using a combination of scanning and transmission electron
microscopy, electron probe microanalysis and X-ray diffraction.
2. Materials and experimental techniques
CoNiCrAlY coatings were manufactured by vacuum plasma
spraying onto flat, circular, aluminized MARM002 Ni-base
superalloy substrates using a Sulzer Metco A2000 unit. The
chemical composition of the CoNiCrAlY coating and substrate
are shown in Table 1. The aluminized substrates were prepared
by grit blasting with 60-mesh Al
2
O
3
, blowing with compressed
air, cleaning with ethanol, and then placing in the VPS chamber.
The VPS chamber was evacuated to less than 10
−1
mbar to
exclude oxygen and then back filled with Ar to a preset pressure
typically in the range 20–80 mbar. Substrates were then sputter
Table 1
Chemical composition (wt.%) of CoNiCrAlY coating and MAR-M002 substrate
Ni Co Cr Al Y W Ta Hf B C Zr
CoNiCrAlY 32 38.5 21 8 0.5 – – – – – –
MAR-M002 Balance 10 9 5.5 – 10 2.5 1.5 0.15 0.15 0.03
Fig. 1. Schematic of a typical TBC arrangement.
Fig. 2. BEI of the as-sprayed CoNiCrAlY coating microstructure.
2888 P. Poza, P.S. Grant / Surface & Coatings Technology 201 (2006) 2887–2896
cleaned using the transferred arc system in the VPS, and
preheated to a temperature typically in the range 400–800 °C.
The CoNiCrAlY coatings where then sprayed to an even
thickness of 100–200 μm using robot manipulation of the
plasma gun. The precise VPS parameters were previously
optimised to provide minimum porosity, high deposit efficiency
and good adherence to the substrate and are proprietary.
Substrate temperature was monitored at 1 Hz using a K-type
thermocouple embedded 0.25 mm below the substrate surface.
During the manufacture of the coatings, the temperature at this
point was typically 750 °C, rising to ∼1000 °C over a
deposition period of 50 s, and then cooling in the chamber such
that temperatures of >700 °C were experienced for >120 s.
Several as-sprayed coatings were then vacuum heat treated at
1080 °C for at least 1 h. Finally, several heat-treated specimens
were oxidised in air for 100 h at 1100 °C.
Metallographic samples from the as-sprayed, heat-treated
and oxidised coatings were prepared in the longitudinal section,
parallel to the spraying direction. The samples were cut with a
diamond saw and polished using 1200 grit SiC paper. This was
followed by polishing in a diamond slurry to a 1-μm finish. Care
was taken to minimise polishing times and pressures to minimise
enlarging any surface porosity or the excessive removal any
poorly bonded regions of the coating (commonly referred to as
“pull-out”). Polished surfaces were cleaned in deionized water,
and afterwards by ultrasound in acetone and ethanol. The
microstructure was observed in an Hitachi 520 scanning electron
microscope (SEM) equipped with energy dispersive X-ray
microanalysis (EDX). Secondary electron images (SEI) and
backscattered electron images (BEI), were obtained. Substrate/
aluminized layer/CoNiCrAlY coating inter-diffusion was ana-
lysed using electron probe microanalysis (EPMA) on a Cameca
Su30.
As-sprayed CoNiCrAlY coatings were removed from the
substrate by mechanical leverage, and heat-treated and oxidised
coatings by progressive grinding of the substrate. X-ray
diffraction (XRD) analysis was then performed on both the
under-side (adjacent to the aluminised substrate) and the top-
side of the coating in a Philips PW1710 diffractometer using
Cu–Kα, and an X-ray current and voltage of 50 mA and 35 kV
respectively.
CoNiCrAlY foils for transmission electron microscopy
(TEM) examination were prepared by cutting 3-mm diameter
discs fromremoved coatings followed by mechanical thinning to
approximately 50 μm, and finally by ion milling using argon
ions with a voltage of 5 kV, current of 1 mA and using 14° as
angle of incidence. Specimens were examined using a JEOL-
200-CX transmission electron microscope (TEM) employing a
combination of bright field (BF) and centre dark field (CDF)
imaging, as well as selected area diffraction pattern (SADP)
Fig. 3. XRD profiles of the as-sprayed CoNiCrAlY coating near (a) and far away (b) from the substrate.
2889 P. Poza, P.S. Grant / Surface & Coatings Technology 201 (2006) 2887–2896
analysis. A JEOL-2010-FX TEM was also used for nano-beam-
diffraction (NBDP), EDX analysis and high-resolution electron
microscopy (HREM).
3. Results and discussion
3.1. As-sprayed microstructure
The as-sprayed SEM microstructure in Fig. 2 was inhomo-
geneous containing thin splats seen in cross-section associated
with the deposition of individual molten droplets, with porosity
between splats and ≈ 50-μm diameter un-melted particles.
Contrast in Fig. 2 derived from the expected two-phase mixture
of β-(Ni, Co)Al and solid solution γ-(Ni, Co), as well as inter-
splat porosity.
Fig. 3 shows XRD traces from (a) the coating under-side,
adjacent to the aluminized substrate, and (b) the coating top side.
Fig. 3a showed peaks, as expected, associated with the γ-(Ni,
Co) (fcc structure, a=0.354 nm) and β-(Ni, Co) Al (ordered B2
structure, a=0.288 nm) phases, as well as the intermetallic
compound γ′-(Ni, Co)
3
Al, (ordered L1
2
structure coherent with
γ). The low angle γ′-(100) peak disappeared at the coating
surface, as shown in Fig. 3b. Comparison of Fig. 3a and b also
showed that there was a strong reduction in the intensity of β-
(110) and other β peaks relative to γ/γ′ peaks away from the
substrate, suggesting a reduction in βvolume fraction because of
Al diffusion from the aluminized layer into the CoNiCrAlY
coating during plasma spraying.
TEM investigations showed that γ′ phase grew as small
precipitates inside γ grains, and was readily identified by the
weak reflections from the L1
2
structure, as shown in the lower
inset SADP in Fig. 4a. γ′ was previously observed in coatings
deposited by plasma spraying onto non-aluminized Ni base
superalloys [23,24] and stainless steels [28], and by electron
beam physical vapour deposition (EB-PVD) onto a non-alu-
minized Ni base superalloy [29]. γ′ phase has generally been
reported after heat treatment, near the coating–substrate interface
because the diffusion of Co and Cr to the substrate and the
replacement of Co by Ni stabilised the γ′ phase at the expense of
γ. In addition, the loss of Cr also facilitated the formation of γ′
because Cr favours the formation of disordered γ over the ordered
γ′. However, γ′ phase in this study was present in the as-sprayed
CoNiCrAlY microstructure because the combination of both a
pre-heated and aluminized substrate promoted significant Al
diffusion during plasma spraying and the formation of both γ′
and β over γ in the as-sprayed coating.
The β phase occurred in different morphologies, which have
been previously related to the different cooling rates associated
with different sized powder particles during plasma spraying
[24]. Elongated laths of β phase inside γ grains (Fig. 4a) and
small grains of β located in the boundary between γ grains (Fig.
4b) were associated with rapid cooling of small droplets on
deposition or in the plasma spray. Larger grains of β (Fig. 4c)
were more common and were associated with larger, slower
cooling particles.
Several minor phases were also present in the as-sprayed
microstructure. Rapid diffusion of carbon from the MAR-M002
substrate leaded to the formation of Cr
23
C
6
(fcc structure,
a=1.066 nm). Occasionally, there were Cr
23
C
6
particles at grain
boundaries, such as the ∼150 nm Cr
23
C
6
particle shown in Fig.
5a, which was identified by NBDP analysis and by the
corresponding EDX spectrum shown in Fig. 5b. Fig. 5a also
Fig. 4. Distribution of β phase over the as-sprayed coating microstructure. a)
Elongated laths of β phase inside a γ grain. NBDP from the laths of β
(B≈<111>) and the γ grain (B≈<112>) are also provided. The weak reflections
corresponding to the L1
2
structure characteristic of γ′ are present in the NBDP.
b) Small grains of β located in the γ grain boundaries. c) Large grain of β
surrounded by the γ matrix, B≈<111>.
2890 P. Poza, P.S. Grant / Surface & Coatings Technology 201 (2006) 2887–2896
shows an Y-rich particle assigned as M
5
Y (hcp structure,
a=0.496 nm and c=0.397 nm) in which M was predominantly
Ni and Co, on the basis of the corresponding EDX spectrum
shown in Fig. 5c.
3.2. Heat-treated microstructure
Aheat treatment is routinely applied to as-sprayed coatings in
order to enhance coating adhesion by inter-diffusion with the
substrate and to homogenise the as-sprayed microstructure. The
coated substrate comprised a ∼70-μm wide aluminized layer as
shown in Fig. 6a formed directly onto the substrate with a
structure characterised by β phase, as normally observed in
aluminized coatings [11–15]. Brighter particles near the
substrate/aluminized layer interface decreased in volume
fraction in the vicinity of the CoNiCrAlY coating. These
particles were formed by the diffusion of heavy elements from
the substrate during heat treatment. The CoNiCrAlY coating
Fig. 5. a) Cr
23
C
6
and M
5
Yparticles observed in the as-sprayed coating. b) EDX profile corresponding to the Cr
23
C
6
particle. c) EDX profile corresponding to the M
5
Y
particle.
2891 P. Poza, P.S. Grant / Surface & Coatings Technology 201 (2006) 2887–2896
microstructure is shown in Fig. 6b. Once again, the coating
comprised primarily of a duplex γ/β microstructure, but now
with β grains significantly coarsened to typically ∼3 μm in
diameter, surrounded by the γ matrix. In addition, there were
occasionally Y-rich inclusions of ∼0.5 μm in diameter, usually
between β and γ grains as shown in Fig. 6b. These inclusions
were subsequently identified as Y
2
O
3
particles by TEM as
described later.
Fig. 7a and b show XRD traces taken from the underside of
the CoNiCrAlY coating (near the substrate) and top-side res-
pectively after heat treatment. Similarly to the traces for the as-
sprayed condition in Fig. 3, γ′ formed readily in the γ/β mi-
crostructure close to the substrate, but was not detected at the
coating top-side where there was now an even more marked
decrease in the intensity of β peaks relative to γ/γ′ peaks,
suggesting a further reduction in β volume fraction.
Fig. 8 shows a 125-μm long line trace obtained by EPMA for
elements Al, Ta, Y, Ti, Cr, Co and Ni, taken across the
MARM002/aluminized/CoNiCrAlY region every 2 μm. The
majority phase in the aluminized layer shown in Fig. 6a was β-
(Ni,Co,Cr)Al. Fig. 8 suggested that the particles close to the
aluminized-CoNiCrAlYinterface were Ta rich, and probably Ta
carbides. Closer to the aluminized-CoNiCrAlYinterface, Co and
Cr diffused significantly into the aluminized layer where they
substituted for Ni. A small amount of Y diffusion also occurred.
Al diffused from the aluminized layer into the CoNiCrAlY
coating and it was this Al diffusion that promoted the formation
of the relatively Al-rich phases γ′-(Ni, Co)Al
3
and β-(Ni, Co)Al
at the expense of relatively Al-deficient γ-(Ni, Co) in regions
close to the aluminized layer, and previously shown in Fig. 7.
This effect is beneficial for the corrosion behaviour of the
coating, due to the relatively good oxidation properties of the
intermetallic compound β. Depletion of aluminium from the
CoNiCrAlY coating has been observed after heat treatment in
non-aluminized substrates with pernicious effects during
oxidation at high temperature [24], including the formation of
a β depletion zone near the coating–substrate interface due to
interdiffusion with substrate. However, this is not the case in the
present study because of the “reservoir” of Al available at the
surface of the MARM002. Elemental profiles from within the
CoNiCrAlY coating were consistent with the two phase γ/β
microstructure, with high Co and Cr concentrations associated
with a low Al concentration suggesting Co and Cr had a
preference for dissolution in γ rather than β.
Higher magnification investigations of the microstructure by
TEM showed β grains often exhibited the “tweed contrast”
shown in Fig. 9 and commonly observed in NiAl, especially
when this phase is Ni-rich [11,12,23]. Fig. 9 also shows that γ
phase was twinned as a result of the depression of the stacking
fault energy of γ by Co [23]. γ′ phase grew as small precipitates
in the γ grains favoured by the Al diffusion from the aluminized
layer, and were easily detected by the weak reflections corre-
sponding to the L1
2
structure as shown in the inset diffraction
pattern in Fig. 9. Fig. 10a shows a dark field TEM image
obtained using the γ′-(100) reflection with γ′ particles up to
10 nm in size that were further investigated using HREM as
shown in Fig. 10b. The blocky ∼10-nm γ′ particle in Fig. 10b
was coherent with the γ parent matrix.
Fig. 11a shows an HREM image of an Y
2
O
3
particle, about
50 nm in diameter, in a γ matrix containing fine scale γ′
precipitates. Fig. 11b shows a corresponding TEM image from a
similar ∼200-nm Y
2
O
3
particle, this time at a γ/β grain bound-
ary, and described in Fig. 6b. The NBDP inset in Fig. 11b
confirmed the particle as Y
2
O
3
(BCC structure, a≈1.060 nm).
These Y
2
O
3
particles have been proposed to form by the internal
oxidation of M
5
Yparticles [24] previously shown in Fig. 5. The
TEM investigations in this study support the disappearance of
M
5
Y particles on heat treatment and the corresponding
appearance of Y
2
O
3
. The formation of yttria through oxidation
Fig. 6. a) BEI of the heat-treated coated structure showing the aluminized layer
over the substrate and the CoNiCrAlY coating. b) γ/β microstructure observed
in the CoNiCrAlY coating, dark areas correspond to β phase, grey areas to γ
phase and white particles to an yttrium rich phase.
2892 P. Poza, P.S. Grant / Surface & Coatings Technology 201 (2006) 2887–2896
is expected to be beneficial for the coating oxidation behaviour
since several authors have suggested that yttria particles “peg” the
Al
2
O
3
scale and improve its adherence [4,6,8]. Chromium
carbides, such as Cr
23
C
6
, were found homogeneously throughout
the coating with greater frequency than in the as-sprayed
conditions. A pair of characteristic blocky Cr
23
C
6
particles
approximately 500 nm in length and 200 nm in width are shown
in Fig. 12. These particles were located inside the γ grains and not
at the grain boundaries, as in the case of the as-deposited coating.
Fig. 7. XRD profiles of the heat-treated CoNiCrAlY coating near (a) and far away (b) from the substrate.
Fig. 8. EPMA line scan across the coating arrangement: substrate/aluminized
layer/CoNiCrAlY coating.
Fig. 9. Twined γ grain, B≈<011>, and β grain exhibiting a marked tweed
contrast. The SADP corresponding to the γ grain shows weak reflections
corresponding to the L1
2
structure characteristic of γ′.
2893 P. Poza, P.S. Grant / Surface & Coatings Technology 201 (2006) 2887–2896
This change was probably due to grain coarsening that occurred
during heat treatment.
3.3. Oxidised microstructure
Fig. 13a and b show SEM images of the CoNiCrAlY coating
and MARM002-aluminized CoNiCrAlY regions respectively,
following high temperature oxidation. Fig. 13a shows there was
a progressive reduction in the volume fraction of darker β phase
towards the CoNiCrAlYuppermost surface, resulting in a ∼70-μm
wide β depletion zone. Fig. 13b shows that the aluminized layer
was consumed substantially during high temperature oxidation,
reducing from a width of ∼70 μm to less than 50 μm. This
reduction occurred because of the growth of TGO, in which Al
2
O
3
was the main constituent [18–22]. There was extensive reaction at
the aluminized layer–MARM002 interface resulting in the
formation of β grains within the γ phase of MARM002. In ad-
dition, there was coarsening of the particles previously ascribed as
primarily Ta-based carbides.
Fig. 14 shows a 375-μm long EPMA line trace for elements
Al, Ta, Y, Ti, Cr, Co and Ni, taken perpendicularly across the
MARM002/aluminized/CoNiCrAlY region every 10 μm. Sig-
nificant Al diffusion from the aluminized layer into both the
MAR-M002 substrate and the CoNiCrAlY coating occurred.
This process induced the formation of β phase inclusions in the
MARM002 near to the interface as shown in Fig. 13b. Co and Cr
from the CoNiCrAlY coating diffused across the aluminized
Fig. 10. a) Dark field image of γ′ precipitates grown within γ matrix in the heat-
treated CoNiCrAlY coating. b) HREM of γ′ phase coherent with γ, B=<011>. Fig. 11. Y
2
O
3
particles observed in the heat-treated CoNiCrAlY coating. a)
Particles grown inside γ grain. b) Particles observed in a boundary between β
and γ grains and corresponding NBDP, B≈<011>.
Fig. 12. Blocky Cr
23
C
6
particles observed in the heat-treated CoNiCrAlY coating.
2894 P. Poza, P.S. Grant / Surface & Coatings Technology 201 (2006) 2887–2896
layer and into the MAR-M002 substrate. Variations in the Co,
Cr, Ni and Al concentrations along the trace, associated with the
CoNiCrAlY two phase γ/β structure, were no longer clearly
defined. The uppermost free surface of the CoNiCrAlY coating
was clearly enriched in Al and depleted in Ni and Co. Depending
on the Al and Oactivities, other oxides such as Cr
2
O
3
or (Ni, Co)
Al
2
O
4
spinels have been reported [20,22]. In these previous
studies, the TGO was initially Al
2
O
3
but as Al activity
decreased, Ni or Co diffused to the surface of the Al
2
O
3
scale
to form (Ni,Co)Al
2
O
4
. The formation of spinels may compro-
mise TBC durability by promoting spalling because of their
relatively fast growth rate and associated volume changes
[4,5,16]. The bond coat analysed in this study comprised both
aluminised and CoNiCrAlY coatings that increased the Al
activity and may delay the formation of spinels. The profiles
presented in Fig. 14 show a dramatic decrease in Ni and Co
concentration from∼30%in the middle of the coating to ∼5%in
the uppermost surface. Cr concentration decreased from∼20%to
∼10% whereas Al concentration increased from ∼10% to
∼20%. Characterisation of the TGO itself was beyond the scope
of this study but larger scale diffusion profiles suggest that spinel
formation was delayed by the reservoir of diffused Al in the
aluminized coating. The Cr concentration in the uppermost
surface of the CoNiCrAlY coating was still significant and
suggested that the TGO layer may include some Cr
2
O
3
, along
with potentially beneficial minor amounts of Y
2
O
3
.
TEM investigations of the oxidised coating confirmed β
phase volume fraction was reduced with β grains primarily at γ
grain boundaries, such as that shown in Fig. 15.
Fig. 15. Small β grain in a γ grain boundary. Probably formed from a β grain
partially oxidised during the treatment at 1100 °C.
Fig. 13. BEI of the oxidised coating structure showing depletion in β phase (a)
and the substrate–aluminised layer interface (b).
Fig. 14. EPMA line scan across the coating arrangement: substrate/aluminized
layer/CoNiCrAlY coating after the oxidising treatment.
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4. Conclusions
The microstructure of a CoNiCrAlY coating vacuum plasma
sprayed onto a pre-heated aluminized MARM002 Ni-base super-
alloy comprised three main phases: γ, β and γ′. The γ′ phase
formed as small precipitates inside γ grains and is not usually
reported in the as-sprayed condition, but occurred here as a
consequence of significant Al diffusion fromthe aluminized layer
during spraying because of high substrate pre-heat temperatures
of 800–1000 °Cto promote as-sprayed adhesion and the presence
of an aluminized layer on the substrate surface.
The solidification of CoNiCrAlY droplets took place at dif-
ferent cooling rates during deposition in plasma spraying and led
to an inhomogeneous microstructure in which the β phase oc-
curred in three different microstructures. The highest cooling rates
resulted in elongated laths of βinside γ grains. Where the cooling
rate was reduced, small grains of β were located at the γ grain
boundaries, and large grains of β surrounded by γ matrix were
associated with the lowest cooling rates. Further diffusion from
the substrate, especially of Al, also occurred during spraying and
Cr carbide particles formed occasionally at γ grain boundaries.
Finally, M
5
Y particles formed during spraying and deposition
particularly at γ grain boundaries.
Diffusion fromthe substrate and within the coating took place
during heat treatment. As a consequence, the coating adherence
was improved and the grains coarsened leading to a more
homogenous microstructure. β grains coarsened to typically
3 μm in diameter, surrounded by the γ matrix. No depletion of β
phase was observed near to the substrate–coating interface be-
cause of Al diffusion from the aluminized layer. As a conse-
quence, the improved in-service behaviour of coating systems
making use of an aluminized layer prior to CoNiCrAlY bond or
overlay coating application can be attributed to the aluminized
layer acting as a reservoir of Al to promote Al activity and
preserve optimum coating phase fractions, rather than by simply
promoting the formation of Al
2
O
3
in the TGO alone. Internal
oxidation transformed the M
5
Yparticles into Y
2
O
3
.
During oxidation in air at 1100 °C, a TGO layer comprising
Al
2
O
3
and Cr
2
O
3
was formed at the uppermost free surface of
the CoNiCrAlY coating. The associated loss of Al resulted in a
large depletion zone of β phase near the free uppermost surface
and a substantial reduction in the aluminized layer thickness.
However, the aluminized layer provided a higher local Al con-
centration than in non-aluminized systems that increased Al
activity, potentially delaying or restricting the formation of
spinels that could compromise coating durability. The original
γ/β dual microstructure remained in the centre of the coating
with a significant reduction of β. Aluminium also diffused to
the MAR-M002 substrate and promoted the formation and
growth of β.
Acknowledgements
The authors would like to thank Rolls-Royce plc. for the
supply of substrates, and the Spanish government MCYTthrough
grant MAT 2001-1123-C03-03 for financial support.
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