Oxid Met (2014) 81:95104

DOI 10.1007/s11085-013-9426-7
ORIGINAL PAPER

Early Stages of High Temperature Cyclic Oxidation

of an Electrodeposited Ceria Coating on Nickel
Superalloys Under Water-drop Tests
Maxime Brossard Baptiste Bouchaud
Gilles Bonnet Benoit Rannou Fernando Pedraza

Received: 3 June 2012 / Published online: 14 August 2013

Springer Science+Business Media New York 2013

Abstract Ceria coatings having a well-defined cracks network were electrodeposited

onto Ni-based Rene N5 superalloys. After a subsequent annealing under argon for promoting the formation of a stable alpha alumina scale at the ceria layer/substrate interface,
the samples were isothermally oxidized at 1,100 C for 50 h to thicken the oxide scale.
They were then subjected to cyclic oxidation at 1,100 C for 1-h cycles. 10 lL water drops
were put down onto the surface of the samples during the cold stages to study the influence
of water onto the mechanical integrity of the pre-oxidized system. The multi-cracked ceria
microstructure exhibited a widening of the cracks as well as refinement of the oxide grains.
However, no spallation was observed and the composition remained stable for both ceria
and alumina. It was demonstrated that the crystallization of ceria into the CeO2 fluorite
structure conferred to the coating chemical inertness towards water.
Keywords

Ceria
Superalloy
Water drop test
Cyclic oxidation

M. Brossard
B. Bouchaud
G. Bonnet
B. Rannou
F. Pedraza (&)

Laboratoire des Sciences de lIngenieur pour lEnvironnement LaSIE FRE-CNRS 3474,
Universite de La Rochelle, Avenue Michel Crepeau, 17042 La Rochelle, Cedex 1, France
e-mail: fpedraza@univ-lr.fr
M. Brossard
e-mail: mbrossar@univ-lr.fr
B. Bouchaud
e-mail: bbouch01@univ-lr.fr
G. Bonnet
e-mail: gbonnet@univ-lr.fr
B. Rannou
e-mail: brannou@univ-lr.fr

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Introduction
In aero-engine turbine components, nickel superalloys are protected against hightemperature oxidation by aluminium-containing coatings, which allow the formation of a continuous, adherent and protective alpha stable form of alumina. In the
hottest sections of the aero-engines, a thermal barrier coating is added onto the
oxidation protective coating to diminish the temperature at the metal surface. These
systems can be exposed to varying water contents upon operation due to the
surrounding environment (relative humidity, droplets from clouds) and to the
combustion regime (take-off, cruise, landing). Therefore, an increasing interest has
grown over the last decade to investigate the effect of water vapor on the high
temperature oxidation of metallic alloys and coatings [1].
Water vapour was for instance added to flowing air during oxidation of both raw
and aluminized superalloys [26]. No significant effect on the isothermal oxidation
behavior above 900 C was reported, whereas detrimental consequences were
noticed upon cyclic conditions [3]. Apart from the evaporation of the formed
aluminum hydroxide [7], which should not concern the conditions at which Nibased superalloys operate, water molecules may alter the mechanical properties of
the oxide scale, through a mechanism close to stress corrosion cracking induced by
hydrogen embrittlement [8]. The oxide scale exhibits spallation and cracks [5],
whereas the toughness at the oxide scale/metal interface weakens, hence resulting in
a loss of adherence that can be enhanced by segregated sulphur impurities [9].
Whether most of these phenomena were studied at high temperature, few authors
focused on the water (liquid or vapor) effect at room temperature [1014]. It has
however been reported that water affects the mechanical integrity of the oxide
scales formed at high temperature, thus resulting in failure of the TBC systems. This
degradation mode, firstly observed during contact of mature scales with humidity of
laboratory air, is known as Moisture Induced Delayed Spallation (MIDS) [10] or
Desktop Spallation (DTS) [11].
The addition of water drops was shown to enhance this phenomenon and also to
trigger the early breakaway of a TBC system made of EB-PVD top-coat [12].
Spallation arose from the delamination at the bond coat/TGO interface when the
alumina scale thickness was greater than 5 lm, as recently reported by Deneux et al.
[13] on a comparable TBC system cyclically oxidized at 1,150 C. Micro-cracking
of the alumina scale was also recorded by acoustic emission measurements on EBPVD TBC coatings isothermally pre-oxidized near to failure [14].
In what the thermal barrier concerns exposed to water vapor containing
atmospheres, YSZ has been predicted to be stable from ambient to 1,650 C [15] but
its porous and columnar structure obviously permits water to readily diffuse and
reach the bond coat/TGO interface.
As rare-earth oxide coatings seem to be appropriate candidates for their chemical
inertness against water containing environments, and since they are known to
improve the adherence of alumina scales [1618], electrolytic ceria coatings that
significantly improved the high temperature oxidation behavior of Ni-based
superalloys in dry air in both isothermal [19] and cyclic conditions [20] were
proposed. They indeed conferred a protection similar to that provided by

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97

conventional aluminide coatings. The specifically tailored multi-cracked coating

morphology was in particular shown to favor the accommodation of thermal stresses
upon cycling while limiting spallation at the substrate/TGO interface [20].
These isothermally oxidized coated samples were recently tested by adding water
drops at room temperature and their porous nature and cracked morphology were
shown to promote an easy absorption and release of water [21], while keeping a
stable interfacial alumina layer. It is thus believed that these coatings may increase
the resistance of alumina scales to desktop spallation, by strain accommodation of
the ceria top coat, compared to conventional aluminides and TBCs.
The present study aims at investigating the effects of water drops on the oxidation
resistance of cyclically oxidized coatings during the cooling (T \ 80 C) stage, to
simulate condensed water or relative humidity of air after engine operation. For this, a
pre-oxidation treatment was realized in dry air to develop a continuous and thick alpha
alumina layer. The chemical stability of ceria and alumina towards water at room
temperature as well as microstructural changes of the systems will be discussed.

Experimental Procedures
Coupons of a Ni-based single crystal Rene N5 superalloy were grit blasted with
Al2O3 particles and then cleaned with ethanol under ultrasonic agitation.
9.5 1.2 lm thick cerium oxy-hydroxide coatings were obtained via cathodic
electrodeposition using a three-electrode cell. The deposition parameters were
optimized to obtain a tailored multi-cracked morphology [22]. A subsequent
thermal treatment was carried out to promote a network of fine cracks and the
crystallization of nanocrystalline ceria with a fluorine structure. This treatment also
provoked the pre-oxidation of the substrate and led to the formation of an a-Al2O3
scale at the coating/substrate interface by a mixed diffusion mechanism [23] (see
Fig. 1).

Fig. 1 SEM morphologies of CeO2 coating on a N5 single crystal superalloy, after 1 h thermal treatment
at 1,050 C under Ar atmosphere and before oxidation a top surface (secondary electrons) and b crosssection (back scattered electrons)

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Preliminary isothermal oxidation of coated samples was performed at 1,100 C

for 50 h using a 10-6 g accurate Setaram Setsys Evolution 1,750 thermobalance
upon flowing dry air (heating rate 10 C min-1). The aim of this step was to
develop a continuous, stable and thick alpha alumina scale before cyclic oxidation.
The samples were then cyclically oxidized at 1,100 C for 10 cycles (45 min at
1,100 C, 15 min at ambient temperature). The effect of water was then studied by
systematically depositing five drops of ultrapure water (each drop is 10 lL) before
every high temperature stage, once the samples temperature was lower than 80 C,
to avoid a too rapid evaporation. Non-wetted samples were also cyclically oxidized
under the same experimental conditions for comparison purposes. The specimens
were weighed before and after every cycle using a 10-5 g accurate balance.
The microstructural characterization of the coatings was performed by X-ray
diffraction (XRD) (Bruker D8 Advance, kCu), and Scanning Electron Microscopy
coupled to Energy-Dispersive Spectrometry (SEM/EDS, FEI Quanta 200F/EDAX).
Local surface analyses were carried out with non-destructive Raman spectrometry
(JobinYvon Horibat LabRam HR, kHeNe), as it allows to differentiate hydrated
compounds (hydroxides, oxides) as well as metastable phases. TGA-DSC
measurements (Setaram Labsys Evo) were carried out on scratched powders of
either as-deposited oxi-hydroxide coatings, or thermally treated or isothermally
oxidized ones, by heating up to 1,100 C at 10 C.min-1 under argon to prevent
oxidation. In order to determine whether water can react with the powders and to
study the likely chemical inertness of ceria towards water, similar tests were
performed by also adding the five drops of water to the powders.

Results and Discussion

Pre-Isothermal Oxidation in Dry Air
The ceria-coated samples were pre-oxidized at 1,100 C during 50 h in flowing dry
air. The thermogravimetric curves (Fig. 2) show a behavior similar to that of a
conventional aluminide coating. Both systems undergo a significant mass gain
during the first 5 h, attributed to the growth of remaining transient and nonprotective oxide scales, such as metastable alumina (h) and NiAl2O4 spinel. This
step is rapidly superseded by a stabilized mass gain, revealing the establishment of a
more protective oxide scale (a-Al2O3) at the ceria-substrate interface [23],
corresponding to a parabolic kinetic regime, with a rate constant of 9.3.10-14
g2 cm-4 s-1. However, the stabilization of the regime is more pronounced in the
case of the aluminide coating, with a lower parabolic rate constant of
2.4.10-14 g2 cm-4 s-1 The transformation of transient aluminas into a-alumina is
known to be quick for T [ 1,000 C, thus explaining the rapid regime change into
parabolic. XRD analysis and Raman spectrometry confirmed the presence of the
stable a-alumina phase, of ceria and the contribution of NiAl2O4 spinel, which
increases the oxidation rate as already reported by Bouchaud et al. [21].
The top surface morphology of CeO2-coated sample has evolved after the shortterm isothermal oxidation in dry air. Indeed, the CeO2 layer exhibits wider cracks

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99

0.20
N5 + NiAl - 1100C
N5 + CeO2 - 1100C

-2

m/S (mg.cm )

0.15

0.10

0.05

0.00
0

10

20

30

40

50

Oxidation time (h)

Fig. 2 Oxidation kinetics of pre-oxidized ceria-coated samples compared to conventional aluminide

coatings at 1,100 C under synthetic air

Fig. 3 Top surface morphology

(secondary electrons) of CeO2
coating after isothermal
oxidation at 1,100 C during
50 h in dry air

(4 lm, Fig. 3b) than the ones observed after the annealing step (Fig. 3a) (i.e. about
1 lm), resulting from the shrinkage of the coating and the relaxation of internal
stresses. Nevertheless, the coatings remain homogeneous and adherent to the oxide
scale developed underneath. No spallation was observed.
Cyclic Oxidation with Water Drops
After isothermal oxidation, the composition and morphology of the ceria-coated
samples could be considered as stable. Ultrapure water drops (5 9 10 lL) were

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then deposited on the sample surfaces. A quick and full soaking of water was
observed on the entire surface, until saturation of the cerium oxide layer with water,
revealed by the appearance of a meniscus. Bouchaud et al. [21] related this behavior
to the porous morphology of their annealed ceria coated superalloy systems.
The mass variations with the number of oxidation cycles were all similar, with
and without water drops, and showed no sign of spallation. Indeed, when the
samples were introduced into the furnace at 1,100 C, a very rapid evaporation of
water was assumed to occur. However, the water drops modified the morphology of
the ceria (Fig. 4b) compared to that obtained when no water was added to similar
thick ceria coatings (Fig. 4a). The cracks width increased with the number of cycles
as well as the average size of ceria islands. A statistic distribution of the mean crack
size was calculated by image analysis and confirmed that shrinkage occurred with
oxidation (Fig. 5). In addition, refinement of the ceria grains was observed, evolving
from about 1 lm (Fig. 6a) to 0.7 lm when water drops had been deposited
(Fig. 6b). This can be related to rehydration of the porous structure at room
temperature, hence allowing water molecules to be adsorbed at the surface of the
CeO2 grains [24]. Indeed, repeated evaporation, rehydration and accommodations of
thermal stresses therefore induced an increased size of cracks probably by
shrinkage. This phenomenon is more marked under cyclic conditions (this study)
than under isothermal conditions [21].
The XRD analyses performed after 10 cycles revealed the presence of both ceria
and alpha alumina, with and without water drops. More detailed analyses were
performed by Raman microspectrometry by rastering the very top surface (depth
probe about 1 lm) from the edge to the center of the samples. On wetted samples
(Fig. 7), the spectra showed the CeO vibration mode, associated with CeO2, as
well as NiAl2O4 and a-Al2O3 doublet, irrespective of the cycle considered. The
same signals were obtained without water drops. These results hence demonstrated

(a)

(b)

Fig. 4 Top surface morphology (secondary electrons) of CeO2 coatings after 10 cycles at 1,100 C:
a with water drops b without water drops

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101

Average islands size (m)

Isothermal oxidation
in dry air

35

Cyclic oxidation

18

with water drop

without water drop

16

30

14

25

12
10

20

8
15
6
10

Average crack thickness (m)

20
40

2
0

0
0

50 51 52 53 54 55 56 57 58 59 60

Oxidation Time (h)

Fig. 5 Average width of CeO2 coating cracks upon dry isothermal and cyclic oxidation, with and
without water drop

Fig. 6 SEM cross-sections (BSE) of CeO2 coatings after 10 cycles: a without water drops, b with water
drops

the chemical inertness of both ceria and alumina scales to water drops during the
early cyclic oxidation stages at 1,100 C.
The thermal treatment applied to the electrodeposited cerium oxy-hydroxide
layers seems to be an important step for stabilizing cerium oxide. Indeed, different
studies concerning the surface of as-deposited cerium-based coatings onto zinc
substrate showed the complex nature of the coating, that comprises cerium ions with
mixed valences (Ce3? and Ce4?) and the presence of hydroxides, due to an
incomplete transformation into the oxide form [24]. Overall, the cathodic

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1.2
-Al2O3 doublet

Ce-O

Normalized Intensity

1.0
0.8

Isothermal oxidation 1100C/50h

1 cycle with water drop
5 cycles with water drop
10cycles with water drop

0.6
0.4

NiAl2O4
0.2
0.0
300 400 500 600 700 800 900 1300

1400

1500

1600

-1

Raman shift (cm )

Fig. 7 Raman spectra of CeO2-coated Rene N5 after 50h oxidation in dry air at 1,100C and cycles at
1,100C with water drops

electrodeposition technique results in the growth of oxygen-defective coatings

according to Raman analysis, showing two vibration bands related to oxygen
vacancies [25]. On the contrary, the disappearance of these bands after thermal
treatment at 1,050 C demonstrated the crystallization of stoichiometric ceria under
the CeO2 fluorite form [23].
The calculations [26] and temperature programmed desorption (TPD) measurements [27] performed in oxidized surfaces between 500 and 700 K confirmed the
need of oxygen vacancies for water to dissociate, hence for H2 to desorb. Indeed,
photoelectron spectroscopic studies proposed that the reduction of Ce4? into Ce3?
by Ar? bombardment introduced oxygen vacancies where partial dissociation of
water into OH-groups occurred [28].
These observations have been confirmed by TGA-DSC measurements carried out
with ceria powders scratched from the coating after isothermal oxidation at
1,100 C/50 h (Fig. 8). Indeed, when a water drop is added to the oxidized CeO2
sample, only one endothermic peak is observed from 50 to 140 C, corresponding to
the desorption of free water. Despite the coatings demonstrated an easy capability to
soak water, the rapid weight loss recorded in TGA also suggests the ready release of
water without the establishment of bonds according to the temperature range. On the
opposite, the as-electrodeposited coatings studied in their as-deposited condition
revealed not only the presence of free water but also the appearance of an additional
endothermic peak in the temperature range 135170 C likely arising from linked
water molecules. This second peak was also noticed after the addition of a water
drop. This suggests that the dissociation of water yields hydroxides or hydrated
oxides, and that the as-deposited coatings exhibit a slower desorption of water.

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103

1.0

Normalized TGA

0.8

0.6

0.4

0.2

0.0

1.0

50

100

150

200

250

300

350

400

450

500

0.6

Endo

Normalized Heat Flow

0.8

0.4

As-deposited
As-deposited + H2O
Oxidized at 1100C/50h + H2O

0.2

Free H2O

0.0
0

50

100

Bonded H2O
150

200

250

300

350

400

450

500

Temperature (C)
Fig. 8 TGA and DSC spectra of as-deposited and oxidized CeO2 coatings, with and without water drops

Conclusion
Electrodeposited cerium-based coatings were deposited onto Ni superalloys,
annealed and isothermally oxidized at 1,100 C during 50 h. The ceria-superalloy
system exhibited a multicracked morphology with a stable a-Al2O3 scale. Water
drops were added during the cooling stage of cyclic oxidation at 1,100 C for the
first 10 cycles and no spallation was observed. The porous nature of the coating
allowed water molecules to be absorbed. Microstructural strain accommodations
were observed at the top-surface, with a wider crack thickness and ceria grains
refinement. Nevertheless, the chemical stability of the system was evidenced in the
presence of water. It appeared that the fully oxidized CeO2 coatings only absorb

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water onto the surface whereas the as-deposited oxygen defective CeO2-x layers
can dissociate water and bond OH-groups.
Acknowledgments Dr. J. Balmain from the LaSIE laboratory at the University of La Rochelle is
gratefully acknowledged for fruitful discussions.

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