RR3000和CMSX-4单晶高温合金的高温氧化行为

High temperature oxidation behaviour of

single crystal superalloys RR3000 and CMSX-4
C. M. Younes, G. C. Allen and J. A. Nicholson
This paper describes the oxidation behaviour of two technologically important nickel based
superalloys, RR3000 and CMSX-4, used extensively in gas turbine blade applications. Oxidation
tests were conducted in air at 1100uC for equal and extended periods of time, up to 100 h to
compare the superalloys characteristic properties. The morphology of oxide growth in the test
samples was investigated using metallography, SEM, EDX, X-ray diffraction (XRD) and Cr3z
photoluminescence spectroscopy. The results indicated that irrespective of the duration of
exposure, alloy RR3000 develops a much thicker oxide scale than alloy CMSX-4. Examination of
cross-sections revealed that the scale grown on the alloy RR3000 is porous and has a three
layered structure consisting of an outer layer of (Ni,Co)O; a sublayer of CrTaO4 rich oxide with
different spinels; and an inner layer of a-Al2O3 . By contrast, the scale that forms on alloy CMSX-4
is compact and consists of two layers. The upper layer is primarily composed of spinels
(Ni,Co)Al2O4 and (Ni,Cr)2O4, and the inner layer of a-Al2O3. Residual stress measurements using
luminescence spectroscopy point to a weak adhesion of the oxide scale to the substrate for alloy
RR3000 and a strong adhesion for alloy CMSX-4.
Keywords: Superalloys, Single crystals, Oxidation, Oxide structure, Characterisation

Introduction used to manufacture the blades and vanes of turbines for

Gas turbines have benefited from considerable techno-
logical advances in the last four decades to become
the most efficient engineering systems available for the
power generation and aerospace industries. As the
turbine engine has evolved, efficiency has increased
through improvements in the engine design, material
castings and coating technologies, which allowed the
temperature of fuel combustion to be raised.1–4 The
materials used to manufacture the components of
the turbine engine have evolved alongside, enabling
them to function safely at the highest temperatures
possible.2 In particular, nickel based superalloys, which
are used for blades and vanes in the hottest section of
the engine, have been developed from conventionally
cast superalloys to single crystals to withstand higher
thermal and mechanical loads as well as to resist harsh
corrosive and oxidative environments to which they are
exposed in service. The development of these superalloys
was a costly process, but very successful since, between
1940 and 1970 alone, thrust to weight ratios were tripled,
overhaul times improved from 100 to 12 000 h, and
operating temperatures were increased by y300uC.1,2
Single crystal nickel based alloys, such as those
belonging to the so called second and third generations
of superalloys, are currently the materials most widely
Interface Analysis Centre, University of Bristol, Oldbury House, 121 St
Michael’s Hill Bristol, BS2 8BS, UK
*Corresponding author, email c.m.younes@bris.ac.uk
aircraft engines, owing to their superior performance.2,5
However, the need for greater fuel economy means that
efficiency and, hence, engine temperature must increase.
These alloys are already working in conditions in excess
of 80% of their melting temperature, so for higher
operating temperatures (.1200uC), and/or increased
lifespan, thermal barrier coatings (TBCs) are applied
onto the blade external surface. Thermal barrier coat-
ings are ceramic coatings often made from zirconia
stabilised with 6–8% yttria.4 They can raise the
temperature of operation by up to 150uC relative to
that possible without the coating, because their low
thermal conductivity, aided by component internal
cooling, enable the substrate surface to be kept at a
safe operating temperature.
In order to facilitate the adherence of the TBC to the
superalloy and to protect this from corrosion and
oxidation, a bond coat is first applied to the substrate
surface followed by the TBC. The bond coat chosen is
preferably an alumina forming material either of the
type NiCoCrAlY or (Ni,Pt)Al. At the high temperatures
needed for combustion, oxygen travels through the
porous TBC and reaches the underlying bond coat.
Aluminium diffuses readily from the aluminium rich
phase of the coating and reacts with oxygen to form an
aluminium rich oxide at the bond coat surface. Thus a
layer of a-Al2O3, the thermally grown oxide (TGO),
forms at the interface between the bond coat and the
TBC. While this layer tends to protect the component by
reducing the amount of oxygen reaching the substrate, it

ß 2007 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 6 July 2006; accepted 11 Ocotber 2006
80 Corrosion Engineering, Science and Technology 2007 VOL 42 NO 1 DOI 10.1179/174327807X159925
 Younes et al.
is this layer which will eventually become a major cause
of TBC system failure.3,6 Upon thermal exposure and
cycling, stresses develop within the TGO, and it is
thought that when the stored elastic strain energy
reaches a critical value, exceeding the TGO fracture
toughness, scale failure occurs. In such events, the bond
coat and ultimately the base metal will be directly
exposed to the hot gas stream where the oxidation
behaviour of the latter becomes the main influencing
factor for component integrity and durability.
Therefore, data on the oxidation resistance of the coated
and uncoated blade materials are needed to help in
assessments of the safety and reliability of the turbine
engines.
In this study, the high temperature oxidation beha-
viour of two single crystal nickel based superalloys
RR3000 and CMSX-4 has been investigated to under-
stand and compare their characteristic properties. For
this purpose, isothermal oxidation experiments were
performed by exposing these materials to air at the same
temperature and for equal durations. Post-oxidation
investigations were carried out to characterise the
microstructures, compositions and residual stresses in
the oxide scales as well as the development of these with
oxidation time at the test temperature. The results of
these investigations are presented first and then dis-
cussed with emphasis placed on the resistance of the
alloys studied to oxidation in gas turbine environments.
Experimental
The chemical compositions of the single crystal super-
alloys investigated are listed in Table 1. Both materials
were supplied by Rolls-Royce plc. Alloy RR3000 was in
the form of 60630650 mm bar and alloy CMSX-4
as a rod y12 mm in diameter. A series of duplicate
test samples, y3 mm thick, were cut from each alloy
and then prepared with surfaces perpendicular to
the solidification direction of the single crystal. After
polishing to a 1 mm finish followed by rinsing in alcohol,
they were separately placed in alumina boats inside a
tube furnace and oxidised in air at 1100uC. All oxidation
experiments were conducted in the following way:
(i) heat the sample to 1100uC within 30 min
(ii) hold at this temperature for a fixed length of
time
(iii) cool to 300uC at a rate of 5 K min21
(iv) retrieve the sample from the furnace and cool to
room temperature in ambient air. The periods
of oxidation at 1100uC are given in Table 2.
Following the oxidation experiments, the microstruc-
ture, morphology of surface scales and cross-sections
through the metal/oxide interfaces were examined using
a Hitachi S-2300 scanning electron microscope equipped
with an energy dispersive X-ray (EDX) analysis system.
Development of the surface scale with oxidation time
was monitored for each alloy by taking low magnifica-
tion photographs of the test samples on an Olympus
Table 1 Nominal compositions of alloys CMSX-4 and
RR3000, wt-%
Element Al Co Cr Mo Ti Re Ta W Hf Ni
CMSX-4 5.8 9.5 6.5 0.4 1.0 3.0 6.5 6.5 0.1 Bal.
RR3000 5.7 3.0 2.2 0.4 0.2 6.0 8.5 5.5 0.03 Bal.
Corrosion Engineering, Science and Technology
High temperature oxidation behaviour of superalloys RR 3 000 and CMSX- 4
SZ11 optical microscope. Higher spatial resolution
investigations were also carried out on metallographic
cross-sections in a JEOL JSM 840A SEM and on
microsections produced with an FEI focused ion beam
(FIB) 201 system. The microsections were milled
perpendicular to the metal/oxide interface following a
procedure described elsewhere.7
An automated X-ray diffractometer, Philips X’Pert,
was used with Cu Ka radiation at 40 kV and 20 mA to
identify the phases present in the oxidised samples. X-
ray analysis was performed at a scan rate of 2u min21
over a 2h range of 20–100u. Phase identification from the
XRD spectra was made using the JCPDS-ICDD
database (International Centre for Diffraction Data,
Newton Square, PA)
Shortly after each oxidation experiment, the residual
stress in the oxide scale was measured at room
temperature using photostimulated Cr3z luminescence
piezospectroscopy.6,8 This technique was implemented
in a laser Raman microprobe, Renishaw 2000, to
determine the residual stress from scale regions identi-
fied in an optical microscope attached to the Raman
system. For each alloy condition, a series of 15 measure-
ments were made on randomly selected areas of the
sample surface. All areas were probed using a 633 nm
He–Ne laser beam 5 mm in diameter. Stress values were
derived from the spectral data according to a procedure
described in Ref. 8 and by using the equation6
Dn(cm{1 )~5:07s(GPa) (1)
where Dn represents the shift in frequency of the
characteristic R2 luminescence line of a-Al2O3 and s
the biaxial stress.
Results
Initial microstructure of alloys
Figures 1 and 2 show the microstructures of the alloys
studied in the as received condition. The optical and
electron optical images were taken after etching
mechanically polished samples of each alloy in a
1 : 1 : 1 vol.-% solution of acetic, nitric and hydrochloric
acids for 10 s. The microstructure of alloy RR3000 was
similar to that of alloy CMSX-4, though it looked finer.
In each case, the alloy exhibited a dendritic structure
(Fig. 1) consisting of a mixture of c matrix and c9 phase
(Fig. 2). The c9 phase stood out from the c matrix as
cube like particles with a mean edge length of y300 nm.
In addition to these main features, a small amount of
c/c9 eutectic phase, exhibiting a ‘fan-like’ structure, was
found in alloy RR3000.
Oxidation behaviour
Surface scale development
The development of the surface scale was monitored by
taking a series of macrographs of the test samples for
each alloy. Figure 3 shows examples of the macrographs
recorded after test durations of 3, 30 and 100 h. The
scale formed on alloy RR3000 was initially light green
and contained numerous crater like features randomly
Table 2 Oxidation times (hours) used for testing alloys
RR3000 and CSMX-4
RR3000 0.25 0.5 1.0 1.5 2.0 3.0 5.0 20 30 50 100
CSMX-4 0.25 0.5 1.0 1.5 2.0 3.0 5.0 10 30 … 100
2007 VOL 42 NO 1 81
Younes et al. High temperature oxidation behaviour of superalloys RR 3 000 and CMSX- 4

1 Optical macrographs of transverse dendritic structures of alloys RR3000 and CMSX-4

distributed across the sample surface. These features were
of various sizes ranging between 10 and 250 mm in
diameter and exhibited, in general, a distinct blue
coloration. After exposure for 3 h, the surface of the
scale darkened significantly and developed a pattern
resembling that of the dendrites in the base alloy, though
at a larger scale. This pattern was visible for up to y30 h
of exposure and then became undiscernable as the
oxidation progressed. In the early stages of oxidation,
0.25–5 h, the scale appeared to adhere quite well to the
substrate. However, spallation of the scale, during cool-
ing, subsequently occurred. The extent of spallation was
found to increase gradually over 20 h of oxidation and
then intensified to a point where only small portions of the
scale remained adherent to the underlying metal (Fig. 3).
In contrast to alloy RR3000, a different develop-
ment of the scale was observed with alloy CMSX-4.
In the early stages of oxidation, 0.25–1 hour, the
scale appeared to grow preferentially on dendritic
areas of the metal surface. After few hours of expo-
sure, its general appearance evolved into a distinct ‘criss-
cross’ structure comprised of alternated dendritic and
interdendritic regions, as shown in Fig. 4. After longer
exposures, this structure tended to fade slightly but
remained visible under a light microscope. All the
test samples were found to exhibit good adhesion of
the scale to the substrate. Spallation of the scale upon
cooling did not occur on any of these samples other than
near the sample edge following the 100 hour test
(Fig. 3).

2 Images (SEM) of c/c9 microstructure in alloys RR3000 and CMSX-4

82 Corrosion Engineering, Science and Technology 2007 VOL 42 NO 1

 Younes et al.
a RR3000 for 3 h; b CMSX-4 for 3 h; c RR3000 for 30 h;
d CMSX-4 for 30 h; e RR3000 for 100 h; f CMSX-4 for
100 h
3 Optical macrographs of representative samples of
alloys RR3000 and CMSX-4 following oxidation for dif-
ferent periods
Scale morphology and composition
Alloy RR3000
The structure and composition of the scale formed on
this alloy during air exposure at the test temperature of
1100uC were investigated using SEM/EDX and XRD.
X-ray diffraction data obtained for the alloy samples
oxidised for 3, 30 and 50 h are listed in Table 3. They
show identical oxidation products for the three samples.
However, the proportions of individual oxide phases
present changed with oxidation time, owing to solid
phase reaction, intermixing between the various oxides
and possible loss by evaporation of some oxides, when
formed, such as CrO3 and WO3. It was noteworthy that
no rhenium containing oxide(s) was apparent in the
XRD spectra, despite the fact that this element is highly
concentrated in the base metal (Table 1).
Scanning electron microscopy examination of the
oxidised samples revealed a scale structure consisting of
three distinct layers. This structure was seen after few
hours of oxidation and was basically retained in the
alloy throughout its oxidation life. Cross-sections
showed that the top layer of the scale was porous and
composed mainly of NiO with a small amount of CoO in
Table 3 Oxide phases detected by XRD on test samples of alloy RR3000
Sample oxidised 3 h Sample oxidised 30 h
NiO (S) NiO (S)
NiCoTa2O6 (VW) NiCoTa2O6 (W)
CrTaO4 (W) CrTaO4 (S)
AlTaO4 (W) AlTaO4 (M)
NiCoAl2O4 (VW) NiCoAl2O4 (W)
Cr2O3 (W) Not detected
W20O58 (VW) Not detected
NiCr2O4 (VW) NiCr2O4 (W)
Al2O3 (VW) Al2O3 (W)
NiAl2O4 (VW) NiAl2O4 (W)
S – strong; M – medium; W – weak; VW – very weak.
Corrosion Engineering, Science and Technology
High temperature oxidation behaviour of superalloys RR 3 000 and CMSX- 4
4 Image (SEM) of surface of alloy CMSX-4 after 3 h of
oxidation at 1100uC
solution (Fig. 5a and b). The middle layer also contained
considerable fine porosity, particularly in the zone
beside the innermost layer (Fig. 5a). Energy dispersion
X-ray analysis showed that the middle layer contained
oxygen, chromium, tantalum, tungsten and aluminium
together with small amounts of nickel, cobalt and
titanium. X-ray elemental mapping revealed a high
concentration of Al throughout this layer. High levels of
Cr and Ta were also detected in a zone situated beneath
the NiO top layer (Fig. 5b). The bottom layer in contact
with the alloy appeared relatively compact and was
composed of aluminium and oxygen with traces of
nickel. The major constituent of this layer, as suggested
by the XRD data, was Al2O3 with a small amount of a
nickel–aluminium spinel phase, probably NiAl2O4. The
cross-section obtained after 5 h of oxidation showed
that the NiO top layer was ,4 mm thick and the
intermediate layer ,7 mm thick. The lower Al2O3 rich
layer was very thin, less than 0.2 mm, irregular and
pegged in at some places on the alloy surface. After 30 h,
the inner layer became ,1.2 mm in thickness though
pegging of the oxide (localised thickening) seemed to
persist. At this stage of oxidation, it appeared that the
innermost layer had failed to protect the base metal,
since the top and intermediate layers were found to be
increasingly thickened, reaching on average a thickness
of 12 and 15 mm respectively. The samples oxidised for
50 and 100 h, were observed to develop coarse and
convoluted NiO scales (Fig. 6a). In the spalled areas on
these samples, rutting of the exposed metal surface was
apparent (Fig. 6b). Moreover, porosity, oxide particles
Sample oxidised 50 h
NiO (S)
NiCoTa2O6 (W)
CrTaO4 (S)
AlTaO4 (M)
NiCoAl2O4 (M)
Not detected
Not detected
NiCr2O4 (W)
Al2O3 (W)
NiAl2O4 (M)
2007 VOL 42 NO 1 83
Younes et al. High temperature oxidation behaviour of superalloys RR 3 000 and CMSX- 4

5 a cross-sectional view of oxide scale formed on alloy RR3000 after oxidation for 30 h and b corresponding X-ray
images

6 a close up view of NiO top layer and b spalled area of surface oxide on alloy RR3000 after 50 h of oxidation

and remnants of the inner layers of the scale were

commonly found in the exposed areas. Cross-sectioning
through the unspalled parts of the scale formed on the
100 h sample, revealed that the thickness of the inner
layer was on average y2.7 mm, that of the middle layer
,19 mm and that of the NiO top layer ,15 mm. This
moderate increase in thickness of the scale, when
compared with that found after the first 30 h of
exposure, indicates that the inner layer was somewhat
protective. However, the extent of scale spallation
witnessed in the sample treated for 100 h (Fig. 3),
indicated poor adhesion of the scale to the base metal.
Further examination of the cross-sections after
chemical etching revealed the development of a c9
denuded zone near the alloy/scale interface (Fig. 7).
The width of this zone, measured after 30 and 100 h of 7 Cross-sectional view of oxidised sample of alloy
oxidation, was about 6 and 9 mm respectively. At greater RR3000 chemically etched to reveal subsurface c9
depths in the alloy matrix, it was evident that the size of denuded zone
c9 precipitates had increased following exposure to the
test temperature. After 100 h, the size of these pre- the other oxides increased as the oxidation time
cipitates averaged 1.3 mm. increased. Small amounts of TiO2 and CrTaO4 were
also detected. The amount of TiO2 correlated with the
Alloy CMSX-4 concentration of Ti in the alloy while that of Ta in the
After oxidation for 3, 30 and 100 h, XRD analysis of oxide was less than that might have been expected.
this alloy showed that the scale comprised mainly NiO, Energy dispersion X-ray analysis revealed that the
NiCoAl2O4, Al2O3 and NiCoCr2O4 (Table 4). The oxide formed initially on the dendritic areas (Fig. 4)
amount of NiO was found to decrease while those of contained mainly Ni, Cr and Co with small amounts of

84 Corrosion Engineering, Science and Technology 2007 VOL 42 NO 1

 Younes et al.
a dendritic area; b interdendritic area
8 Morphology of surface scale formed on alloy CMSX-4 after 3 h of oxidation
Al, Ti, W and Ta. By contrast, the oxide that developed
on the interdendritic areas was found to contain a large
amount of Al with traces of Ni, Cr, Co, Ti and Ta.
Figure 8 shows the morphology of the scale in these
areas after oxidation for 3 h. It can be seen that even
after such a short exposure period, the scale was
compact and exhibited smaller grain sizes in the
interdendritic areas than in the dendritic areas. This
scale morphology was observed to change gradually as
the oxidation progressed. After 30 h, there was no
significant difference in the appearance of the oxide in
these areas. The EDX spectra obtained from several
locations on the scale surface of the samples treated for
30 and 100 h were practically identical, showing a
particularly high signal for Al.
Cross-sectioning of these samples, revealed a scale
consisting of two layers (Fig. 9). These showed little
porosity and adhered well to each other and to the
alloy–substrate. Elemental mapping with EDX revealed
that the top layer of the scale contained high level of Al.
Other elements including Ni, Co and Cr were also
detected but at lower concentrations (Fig. 10). This,
together with the XRD results, suggested that the
outermost layer of the scale was composed mainly of
NiCoAl2O4, Al2O3 and probably (Ni,Cr)Al2O4 oxide
phases. The X-ray maps for Ti and Ta, displayed in
Fig. 10, indicated that these elements are mostly
concentrated in isolated oxide patches within the top
layer, probably forming TaCrO4 and TiO2. The X-ray
image for Al, when compared for example with that of
Ni, clearly showed that Al was the major constituent of
the innermost oxide layer, which is presumably Al2O3.
Initially, this layer was regular and y0.4 mm in
thickness after 5 h of exposure. After 30 h, its thickness
increased to y1 mm. After 100 h, the thickness of the
inner and outer layer nearly doubled. As in the case of
Table 4 Oxide phases detected by XRD in test samples
of alloy CMSX-4
Sample oxidised Sample oxidised Sample oxidised
3h 30 h 100 h
NiO (S) NiO (W) NiO (VW)
Al2O3 (W) Al2O3 (S) Al2O3 (VS)
NiCoAl2O4 (VW) NiCoAl2O4 (M) NiCoAl2O4 (M)
NiCoCr2O4 (VW) NiCr2O4 (W) NiCr2O4 (M)
TaCrO4 (VW) TaCrO4 (VW) TaCrO4 (W)
TiO2 (VW) TiO2 (VW) TiO2 (VW)
S – strong; VS – very strong; M – medium; W – weak; VW – very
weak.
Corrosion Engineering, Science and Technology
High temperature oxidation behaviour of superalloys RR 3 000 and CMSX- 4
9 Cross-section, produced using focused ion beam (FIB)
technique, of oxide scale formed on alloy CSMX-4 after
30 h of oxidation
alloy RR3000, exposure of CMSX-4 to the test
temperature led to the creation in the base metal of a
c9 denuded zone and to coarsening of the c9 particles.
The width of the denuded zone and the size of the c9
particles measured after 100 h of exposure, were on
average 6 and 1.3 mm respectively.
Stress measurements
Figure 11 shows the change of residual stress in the
scales of the alloys studied as a function of oxidation
time at 1100uC. Each data point in this figure represents
the average stress value derived from 15 luminescence
measurements made on a single sample. The standard
deviation associated with the data points is of the order
of ¡1 GPa for the samples oxidised for ,10 h and
¡0.4 GPa for the samples oxidised for longer times. It
mainly derives from the variation from location to
location in the stress level in the scale across the probed
areas on the sample. All the luminescence measurements
were made on the surface of intact/unspalled scales away
from the sample edge(s). Interestingly, the Cr3z
luminescence of the a-Al2O3 was detectable in alloy
RR3000, despite the fact that this oxide was buried
beneath continuous thick layers of NiO and mixed
oxides.
The results obtained for alloy CMSX-4 show that the
residual stress measured was relatively independent of
the oxidation time after an initial transient period lasting
y2 h. This time coincided with the completion of the
transformation of the metastable alumina phases to
2007 VOL 42 NO 1 85
Younes et al. High temperature oxidation behaviour of superalloys RR 3 000 and CMSX- 4
10 a cross-sectional view of oxide scale formed on alloy CMSX-4 after 100 h of oxidation and b corresponding EDX
images
a-alumina at 1100uC, as reported in the literature.9,10 It
can be observed from the results shown in Fig. 11 that
over this transient period, the stress in the scale
increased rapidly reaching a peak value of ,4 GPa
after oxidation for only 1.5 h. The stress dropped from
its peak value after 2 h exposure rising again following
the next exposure. This sudden change in the stress level
over a short period of time was also seen with alloy
RR3000. It is believed to be due to the tensile stresses
developed in the scales by the large shrinkage in volume
(,9%) accompanying the transformation of alumina
from the metastable h phase to the stable a phase. In
fact, both of these phases could be identified in the
luminescence spectra from samples oxidised for short
durations between 0.25 and 2 h. The spectra obtained
from samples oxidised for longer periods, indicated that
only the a phase was present in the scale. After
completion of the alumina phase transformation, the
compressive residual stress in the scale of CMSX-4
increased progressively until the last exposure (Fig. 11b).
Such a steady increase was indicative of good adhesion
of the scale to the substrate.
The development of residual stress in the scale of alloy
RR3000 after the transient period differed markedly
from that observed for alloy CMSX-4 (Fig. 11a). For
periods of oxidation over 3–20 h, the residual stress
11 Development of residual stress in oxide scale formed on a alloy RR3300 and b alloy CMSX-4 as function of oxida-
tion time
86 Corrosion Engineering, Science and Technology 2007
appeared, at first, to relax a little and then increase again
to reach a peak at ,4 GPa. The most likely reason for
stress relaxation was believed to be microcracking in the
alumina layer. Subsequently the cracking seemed to heal
leading to a rapid increase in stress for exposures
between 5 and 20 h. After this time, the stress started to
decrease significantly attaining after 100 h a level well
below that measured after the first exposure. The onset
of the sharp decrease in stress coincided with that of the
acceleration in scale spallation observed in the samples
oxidised for periods between 30 and 100 h. The low
stress levels associated with these samples were indica-
tive of the presence of large cracks in the scale, which
ultimately led to buckling and spallation of large
portions of the oxide (Fig. 3).
Discussion
Studies of the oxidation behaviour of Ni–Cr–Al alloys
(often considered as the ternary equivalents of nickel
based superalloys),11 have clearly identified a transient
phase at the commencement of oxidation followed by a
steady state period.12,13 During the transient period,
oxidation of the various alloy constituents takes place,
leading to the nucleation of NiO, complex spinels, Cr2O3
and Al2O3. During the steady state period, different
VOL 42 NO 1
 Younes et al.
oxide scales may form and can be divided into three
distinct types, depending on the concentrations of Cr
and Al in the metal substrate. Type I is an external scale
of NiO and a subscale of chromium and/or aluminium
oxides. Type II is an external layer of Cr2O3 and a
sublayer of Al2O3. Type III is solely an external layer
of Al2O3. According to the free energy of formation
values, for the oxidation of Ni–Cr–Al alloys, a
continuous Al2O3 scale should form if the Al content
exceeds 4 wt-%, provided the Cr/Al concentration ratio
is less than or equal to 4 (Ref. 12). Hence the alloys
investigated here, which contain nearly equal amounts
of Al (,5.8 wt-%) with 2.2 and 6.5 wt-%Cr respectively
(Table 1), would be expected to form an Al2O3 outer
layer during oxidation. However, owing to the addition
of other elements, such as Co, Ti, Ta, W and Re, both of
the alloys under investigation exhibited a more complex
behaviour than simple Ni–Cr–Al alloys.
The results of the XRD and SEM/EDX analyses
presented in the previous section indicated that upon
exposure to air at 1100uC, a mixed oxide scale was
formed on the surface of the single crystal superalloys.
During the initial stage of oxidation, simple oxides of
the alloy elements, such as NiO, CoO, Al2O3, Ta2O5 and
Cr2O3 (although some of them were not detected),
formed simultaneously (Table 3). At 1100uC, the much
higher growth rate of NiO as compared with that of the
other oxides resulted in the overgrowth of NiO crystals.
This was more apparent in the case of alloy RR3000
than in CMSX-4. Meanwhile, solid phase reactions
among the initial simple oxides led to the formation of
more complex oxides, including NiCr2O4, CrTaO4,
AlTaO4 and NiCoAl2O4. As a result, after 3 h of
oxidation the predominant oxide was identified to be
(Ni,Co)O in the scale of alloy RR3000 and (Ni,Co)O,
(Ni,Co)Al2O4 and a-Al2O3 in that of alloy CMSX-4.
The formation of CrTaO4 and AlTaO4 on the single
crystal superalloys Rene N6 and CMSX-10 upon
isothermal and cyclic oxidation at temperatures in the
range 1000–1200uC was reported by other research-
ers.14,15 In the present work, the XRD results indicated
the formation of Cr2O3 and W20O58 during the initial
stage of oxidation and their disappearance from the
scale on longer exposure (Table 3). This could be the
result of the continued oxidation of Cr2O3 (s) to CrO3(g)
and W20O58 (s) to WO3 (g) at temperatures .1000uC.16
Moreover, the XRD data and X-ray images did not
reveal the presence of a Re rich oxide or a Re enriched
layer in the scales formed on the superalloys studied.
This was believed to be due to the loss by vaporisation
of the Re oxide, Re2O7, which has a high vapour
pressure at high temperatures.17
After the formation of a mixed oxide scale, the
activity of oxygen at the metal/oxide interface may
decrease, facilitating the selective oxidation of alumi-
nium. With increasing oxidation time, the inner a-Al2O3
crystals grew laterally and eventually converged to form
a compact inner layer. The formation of this layer on
both alloys was ascertained by cross-sectioning some
samples which appeared to have readily reached steady
state conditions (Figs. 5 and 10). However, comparison
of samples oxidised for equal durations, particularly
those exposed for short times, showed that the a-Al2O3
layer had formed earlier on alloy CMSX-4, because this
layer proved to be thicker and more uniform than that
Corrosion Engineering, Science and Technology
High temperature oxidation behaviour of superalloys RR 3 000 and CMSX- 4
seen in alloy RR3000. The rapid establishment of a
continuous a-Al2O3 inner layer immediately after the
transient stage retarded the oxidation of alloy CMSX-4.
Because of the slow diffusion of reactive species in a-
Al2O3, the growth of CrTaO4 and other oxides was
inhibited. This beneficial effect of the a-Al2O3 layer was
not evident in alloy RR3000 and was substantiated by
the fact that the overall thickness of the scale formed on
the latter was greater than that formed on alloy CMSX-
4. The results and observations of the present study are
in agreement with those of a recent investigation aimed
at elucidating the effect of rhenium on the oxidation
resistance of Ni based alloys.18 For such a purpose, the
Re content was varied in two series of Ni–8Cr–2Ti–
10Al–Re and Ni–8Cr–2Ti–15Al–Re model alloys (the
concentrations expressed in at.-%) and it was found that
the alloys with a Re/Al ratio >0.1 exhibited a much
larger mass change than those with Re/Al ratio (0.1, as
a result of cyclic oxidation at 1100uC. This observation
led to the suggestion that the Re/Al ratio is a good
indicator of the resistance to oxidation. Furthermore,
examination of cross-sections showed that the a-Al2O3
layers that formed on the alloys with Re/Al ratio >0.1
are highly porous owing to increased Re content and
formation of more volatile Re2O7 oxide. Since the alloys
investigated in the present study have similar Al
contents but different Re/Al ratios, it is possible that
the high Re content and the associated high vapour
pressure of its oxide renders the a-Al2O3 layer formed on
alloy RR3000 porous and less protective.
It is obvious from the results obtained from the test
samples (Fig. 3) that spallation of the scale is the major
process impairing the resistance of alloy RR3000 to
oxidation at high temperatures. Under cyclic loading
conditions, such as in gas turbines, alloy CMSX-4 would
be expected to be more resilient to oxidation owing to
the good adherence of its scale and resistance to spalling
upon cooling. This is confirmed by the results of residual
stress measurements shown in Fig. 11, which indicated a
strong bonding of the scale with the substrate in the case
of alloy CMSX-4 and a weak bonding in the case of
alloy RR3000. However, the oxidation of these alloys
leads to the creation of a c9 denuded zone beneath the
scale and coarsening of the c9 precipitates (Fig. 7). The
reduction in the volume fraction of c9 precipitates in the
denuded zone may lead to a local decrease in strength.
This weakening effect may be extensive as the c9 volume
fraction is closely related to the stress to give a
specified creep rate.19 The formation of a weak subsur-
face zone could make the alloy susceptible to cracking
under combined mechanical and thermal loading con-
ditions, of the type encountered in gas turbines. To
alleviate or better suppress the above mentioned
damaging effects owing to oxidation, it still appears
necessary to provide the superalloys studied with a
protective coating.
Conclusions
The following conclusions can be drawn based on the
present isothermal oxidation study of the single crystal
superalloys RR3000 and CMSX-4.
1. On exposure to air at 1100uC, alloy RR3000
develops an oxide scale which is much thicker than that
which forms on alloy CMSX-4.
2007 VOL 42 NO 1 87
Younes et al. High temperature oxidation behaviour of superalloys RR 3 000 and CMSX- 4
2. The oxide scale on alloy RR3000 has a composite
structure consisting of three layers: an upper layer made
of (Ni,Co)O; an intermediate porous layer comprised
primarily of CrTaO4 rich oxide with a mixture of the
spinels (Ni,Co)Al2O4 and (Ni,Cr)2O4; and an inner layer
constituted of a-Al2O3.
3. The scale on alloy CMSX-4 exhibits a two layer
structure. The outer portion of the scale consists mainly
of the spinels (Ni,Co)Al2O4 and (Ni,Cr)2O4 with small
amounts of simple oxides of Ti and Ta. Its inner portion
is made of a-Al2O3.
4. Residual stress measurements indicate that after
20 h of oxidation, the adhesion of the scale to the
substrate deteriorates rapidly in the case of RR3000
whereas in CMSX-4, it remains strong up to at least
100 h of exposure. As a consequence, extensive spalla-
tion of the oxide occurred during cooling in the former
alloy while it was very limited in the latter.
5. Oxidation exposure of the superalloys causes
depletion of aluminium near the surface and dissolu-
tion of c9 precipitates. Consequently, a subsurface
layer of (c9 free) c phase is created whose thickness is
a direct function of exposure time at the applied
temperature. The creation of a c9 denuded zone
decreases the alloy strength locally, which could pose a
cracking problem under severe thermal–mechanical
loading conditions.
88 Corrosion Engineering, Science and Technology 2007
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