Applied Thermal Engineering 24 (2004) 1745–1753

www.elsevier.com/locate/apthermeng

ALLBATROS advanced long life blade turbine

coating systems
M.-P. Bacos a,*, P. Josso a, N. Vialas b, D. Poquillon b, B. Pieraggi b,
D. Monceau b, J.R. Nicholls c, N. Simms c, A. Encinas-Oropesa c, T. Ericsson d,
S. Stekovic d
a
Office National d’Etudes et de Recherches A
erospatiales, 29 Avde la Div, Leclerc, B.P. 72,
92322 Chatillon Cedex, France
b
CIRIMAT––ENSIACET-INPT 118 route de Narbonne, 31077 Toulouse, France
c
Cranfield University, Bedford MK43 0AL, United Kingdom
d
University of Link€oping, S-58183 Link€oping, Sweden
Received 12 July 2003; accepted 8 November 2003
Available online 15 January 2004

Abstract
The scientific and technological objectives of this program are to increase the efficiency, reliability and
maintainability of industrial gas turbine blades and vanes by

• developing coatings that can warrant a 50 000 h life, i.e. twice that of the usual life, of the hot compo-
nents (800–1100 C) even with the use of renewable fuels such as biomass gas or recovery incinerator gas
i.e. low-grade fuels with high pollutant levels,
• characterising advanced existing coatings to assess lifetime and performance of coatings and coated
materials,
• providing material coating data and design criteria to use coating as a design element,
• increasing the fundamental understanding of the behaviour of coated materials, their degradation, fracture
mechanisms and engineering because of the strong need for a mechanism-based modelling of durability.

These programmes permitted the selection of two reference coatings and the development of two
innovative coatings. Concurrently work has been done in order to develop corrosion, oxidation and
thermo-mechanical property models. Correlations between coatings development, experimental results and
calculations will be discussed.
 European Communities, 2004. Published by Elsevier Ltd. All rights reserved.

*
Corresponding author. Tel.: +33-1-46734513; fax: +33-1-46734164.
E-mail address: bacos@onera.fr (M.-P. Bacos).

1359-4311/$ - see front matter  European Communities, 2004. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.applthermaleng.2003.11.018
1746 M.-P. Bacos et al. / Applied Thermal Engineering 24 (2004) 1745–1753

Keywords: MCrAlY; Aluminium; Oxidation; Corrosion; Thermo-mechanics; Turbine

1. Introduction

The objective of this project, ALLBATROS, is to increase the efficiency, reliability and
maintainability of industrial gas turbine blades and vanes by developing new high-resistant
coatings and by increasing fundamental understanding of the behaviour of these coatings. The
innovative coatings will lead to an increase of turbine efficiency and to a decrease of emission
levels (through increased efficiency and by the possibility of using recovery gas as combustion gas
in the turbine). The aim is also to use predictive life models to design long life turbines in order to
lower maintenance and energy operating costs. These models will be based on experimental data
gained on innovative coatings as well as reference coatings (RT22-NiAlPt; MCrAlY AM-
DRY997) deposited on industrial nickel-based superalloys (CMSX-4, SC2 and IN792). The
partners of this project are ONERA (France), TURBOMECA (France), NUOVO PIGNONE
(Italy), ALSTOM POWER UK (UK), ALSTOM POWER Sweden (Sweden), CHROMALLOY
France (France), INPT/CNRS (France), CRANFIELD UNIVERSITY (UK), UNIVERSITY
OF LINKOPING€ (Sweden).

2. Innovative coating development

For both conventional aluminide and MCrAlY coatings, the life of the coatings is controlled by
maintaining a reservoir of aluminium that forms a protective alumina scale on the surface. Loss of
aluminium occurs by spallation of the alumina scale due to thermal cycling and by interdiffusion
into the substrate. To warrant a high durability life, even with the use of low-grade fuels with high
pollutant levels, innovative coatings must ensure the aluminium concentration and activity in the
coating is as high as possible, together with a high chromium concentration. Such coatings
are usually of MCrAlY type where M is equal to nickel, cobalt or a nickel–cobalt alloy. ONERA
has developed a new MCrAlY coating via an innovative electroless-like process [1,2] and the
aim of the work was to improve it in order to reach ALLBATROS coatings specifications.
Indeed the aluminium concentration of this type of electroless-like coating has been modi-
fied with the use of a modified aluminization and/or by interposing a diffusion barrier and
the aluminium activity has also been changed by use of platinum coating. Concerning chro-
mium, its solubility has been altered by using a modified aluminide, such as platinum modified
aluminide.

2.1. Diffusion barrier

A Ni–W diffusion barrier has been developed by modifying an old bath designed by Vaaler and
Holt [3] and by developing a new procedure route. This process leads to a very adherent layer,
 M.-P. Bacos et al. / Applied Thermal Engineering 24 (2004) 1745–1753 1747

enriched in tungsten (W) up to 50% mass. Its role as a diffusion barrier––preventing aluminium to
diffuse from coating to the substrate––has been checked after aluminization and ageing.

2.2. Whole innovative coating

The whole innovative coating is composed of three deposits:

(1) a NiW under layer (barrier diffusion),

(2) a MCrAlY electroless-like coating,
(3) a platinum modified coating as described in Fig. 1.

The non-directionality of the process, even in the case where specimens are coated with the use
of gravity assistance, allows a very good uniformity for the coatings produced.
Corrosion behaviour of these coated specimens (SC2 (superalloy)/MCrAlY electroless-like
coating/platinum modified aluminides) compared to typical coatings (SC2 (superalloy)/LPPS
MCrAlY coatings) in classical corrosion tests (Na2 SO4 salt) is very good (see Fig. 2). During the
first 1000 h, the innovative coating gains mass (alumina formation) while the typical coating looses
mass (corrosion phenomenon). And after these 1000 h of corrosion the innovative coating keeps all
its integrity. Its upper layer shows some chromium precipitates (in black in Fig. 2) and a very low
aluminium depletion leading to c0 phase (in grey in Fig. 2). More aggressive tests are in progress.

Fig. 1. Innovative coating: details of deposits. (a) 5 lm thick NiW layer; (b) 75 lm thick composite Ni–CrAlYTa; (c) 75
lm thick composite Ni–CrAlYTa + 7 lm thick platinum + inward pack aluminization.
1748 M.-P. Bacos et al. / Applied Thermal Engineering 24 (2004) 1745–1753

Fig. 2. Innovative coating after exposure at 850 C in a hot corrosion test (a) mass gain per cm2 versus time of
exposure. Hot corrosion at 850 C, Na2 SO4 contamination, exposed in air (b) general aspect of innovative coating after
1000 h at 850 C, Na2 SO4 contamination, hot corrosion test (c) outer zone: black spots are Cr enriched phases, grey
lines are c0 phases and clear zone is b-NiAl(Pt) phase.

3. Models development

In parallel with innovative coating experimental development, some models are under devel-
opment concerning oxidation, corrosion and thermo-mechanical fatigue behaviour.

3.1. Oxidation model

At the CIRIMAT laboratory (INPT-CNRS), the high temperature oxidation and interdiffusion
of the coating/superalloy systems is studied. Reference and innovative coatings are tested.
Experiments combine isothermal (TGA) and cyclic oxidation conditions in air or air + 2 vol%
H2 O, between 900 and 1150 C. Cyclic oxidation tests are realised on samples allowing gravi-
metric measurements. These tests are either fast cycles (typically 1000 cycles of 1 h at high tem-
perature) under controlled atmosphere, or long cycles (50 cycles of 300 h) under laboratory air.
Oxidised samples are analysed using SEM–EDX and XRD to determine the nature of the
oxides present in the oxide scale. SEM with EDX elementary maps realised on cross-sections
 M.-P. Bacos et al. / Applied Thermal Engineering 24 (2004) 1745–1753 1749

Fig. 3. Electron back scattered image and concentration profiles measured by SEM–EDS for the system RT22 on
CMSX-4, after heat treatment (2 h at 1140 C and 20 h at 870 C).

permit the microstructural evolution of the oxide/coating/superalloy systems to be followed, as a

function of time at 900 and 1050 C. Concentration profiles are measured from the oxide layer to
the centre of the samples for nine elements (see Fig. 3).
Resulting data are used to characterise transient and steady state oxidation kinetics using the
local parabolic rate constant fitting procedure [4] and eventually to determine the occurrence of
breakaway oxidation. Microstructural investigations permit system evolution to be followed,
correlations with oxidation kinetics to be drawn, and the discussion of the various degradation
criteria such as: the critical aluminium content under the oxide scale, the extent of the beta-NiAl
phase depleted zone in the coating, the occurrence of spinel phase in the oxide, the remaining
critical thickness of coating and the occurrence of internal oxidation.
Parallel to this experimental work, numerical models are being developed and tested. All
models combine elemental diffusion in the coating/superalloy system with an outward flux of
aluminium for isothermal and cyclic oxidation. The most complete model (Fig. 4) is a finite
element code (under CASTEM [5]) treating diffusion of the nine species in two dimensions, with
moving boundaries and the possibility of cross-terms in the flux equations (when data are
available). A cyclic oxidation model is used as the boundary condition of the diffusion model. In
its simplified form, this model has an analytical solution and allows easy fitting of experimental
cyclic oxidation data [6]. The implementation of phase transformations in the coating/superalloy
system, and a connection with Thermocalc is currently under study. Most simple models, such as
the one-dimensional diffusion of aluminium in a single phase medium, are also compared with
experimental data in order to access the range of possible application of each model.
1750 M.-P. Bacos et al. / Applied Thermal Engineering 24 (2004) 1745–1753

Fig. 4. Coated Ni-base superalloy oxidation/interdiffusion model.

3.2. Corrosion model

Cranfield UniversityÕs main activity within the ALLBATROS programme is the development
of stochastic hot corrosion models. These models are targeted at predicting the hot corrosion life
of a range of commercial and model coatings over a range of expected high temperature corrosion
environments including both types I and II hot corrosion. Statistically based corrosion models are
required due to the localised nature of hot corrosion damage. The key parameters that influence
the progress of the hot corrosion reactions have been identified as deposition flux, gas compo-
sition, temperature, deposit composition, incubation time, substrate composition, coating type
and coating composition.
A matrix of 15 laboratory hot corrosion tests is being carried out to investigate quantitatively
the role of deposition rate, temperature and gas composition on the hot corrosion of coated and
uncoated high temperature alloys. The tests are being carried out using the Ôdeposit recoatÕ test
procedure which has proved to be a most effective way of simulating in service deposition con-
ditions within a laboratory test [7–11]. The test variables are listed in Table 1––note that 360 of
the possible combinations of these variables will be investigated during the course of these tests.
Table 1
Summary of test variables for the laboratory hot corrosion testing
Test variable Range
Substrate material CMSX-4, SC2 -B and IN792
Coatings RT22, AMDRY997, innovative coating composition/structures
Deposition flux 1.5, 5.0 and 15 lg/cm2 /h
Deposit composition 80/20 mol% (Na/K)2 SO4
Gas composition: air + 50 or 500 vpm SO2
0 or 500 vpm HCl
0 or 5% H2 O
Temperature 650, 700, 750, 850 and 900 C
Duration 500 h
 M.-P. Bacos et al. / Applied Thermal Engineering 24 (2004) 1745–1753 1751

Fig. 5. Effect of deposition flux on corrosion damage to RT22 coated SC2 -B (exposed for 500 h at 700 C in air-500
vpm SOx ).

The performance of materials during these tests is being monitored using mass change mea-
surements. However, the materials performance data required for the development of the hot
corrosion models is being produced using dimensional metrology: pre-exposure contact mea-
surements and post-exposure measurements of features on polished cross-sections [7–9]. These
dimensional metrology methods allow distributions of damage data to be determined which can
then be readily used in the development of statistically based hot corrosion models. Micro-
structural observations of samples are being used to confirm that the data in each model is
associated with particular degradation mechanisms. Fig. 5 illustrates the sensitivity of type II hot
corrosion damage to changes in deposition flux, when exposed at 700 C in an air-500 vpm SOx
atmosphere for 500 h.
The models developed during the laboratory hot corrosion tests will be validated under selected
conditions using burner rig exposures. Details of this test rig and its operation are available
elsewhere [9]. Samples will be assessed using the same dimensional metrology methods as for the
laboratory tests to ensure that fully compatible datasets are produced in order to permit good
model validation.

3.3. Methodology of model development regarding thermo-mechanical properties

A model for thermo-mechanical properties of coated superalloy under varying conditions of

temperature and stress must have as its starting point careful studies of cycles to failure under
1752 M.-P. Bacos et al. / Applied Thermal Engineering 24 (2004) 1745–1753

these different conditions and of crack initiation and propagation. Metallographic examinations
of coated CMSX-4 specimens tested under LCF conditions indicate that crack initiation in most
cases start at the surface of the coating. The microcracks grow from their initiation sites through
the coating towards the coating–substrate interface. Some cracks are arrested at the interface and
other penetrate the substrate and lead to failure. Therefore, it seems that the fatigue endurance of
a coating–substrate system is determined mainly by the fatigue properties of the coating itself.
Pores and microcracks in the surface oxide layer are potential initiation sites. Obviously the
ductile-to-brittle transition temperature of the coating is an important property. If in an out-of-
phase thermo-mechanical cycle the temperature goes below the transition temperature the risk for
failure is much increased.
In Link€ oping University the first step in the modelling work will be to establish damage
equations or parametric life equations to predict number of cycles to crack initiation from the
stress and strain obtained. The first choice is to use frequency-modified strain life or stress life
approaches. It is important to include the interaction stresses that can be generated between the
coating and the substrate due to different thermal expansions. Another factor to consider is that
alloy element depletion of the coating due to selective oxidation and also due to interdiffusion
between coating and substrate will change the thermo-mechanical properties of the coating. This
means that a certain coating will behave differently together with different substrates. After crack
initiation, crack growth life can be taken into account by the use of a fracture mechanics ap-
proach. The crack growth does not need to go much below the coating–substrate interface before
one can consider the component life as exhausted.
It is well known that the crack growth can occur by combined oxidation and mechanical ac-
tions. A model in the literature for acceleration of the growth rate due to simultaneous oxidation,
or rather the formation of oxide spikes will be tested. In the model the local stress–strain field in
the vicinity of a spike is calculated and used to define model constants. As is pointed out above
crack initiation sites can be pores and microcracks in the oxide layer. This opens the possibility to
combine a statistical treatment of oxidation attack with fatigue life calculations. Such a general
model would be of great value.

4. Conclusion

In the framework of this program an innovative coating has been developed. With the proposed
process a three-layer protective coating composed of a modified beta nickel aluminide, a two
phase b=c coating and an NiW diffusion barrier layer can be obtained. Experimental results
showed that this coating has good corrosion resistance in a typical corrosion test.
Predictive models into oxidation, corrosion and fatigue mechanisms fields are under develop-
ment in order to build up the predicted lives of reference and innovative coating systems. The
oxidation model would permit the simulation of long-term oxidation and the development of new
experimental procedures for an accurate determination of oxidation kinetics for very long-term
exposures. The corrosion model provides a statistical model for extreme rates of corrosion attack
as a function of deposit chemistry, deposition rate, gas chemistry and temperature would permit
the prediction of hot corrosion life for a large range of high temperature corrosion environments.
The model for thermo-mechanical properties of coated superalloy will take into account accel-
 M.-P. Bacos et al. / Applied Thermal Engineering 24 (2004) 1745–1753 1753

eration of cracks growth rate due to simultaneous oxidation and will be therefore closer to real
engine conditions than simple thermo-mechanical models.
These models, based on experimental data and gathering many parameters, would permit the
estimation of long life turbine durability and the development of new coatings developments.

Acknowledgements

The authors would like to thank the European Commission for part funding of this work. The
authors would also like to thank all the partners of the project for their fruitful discussions.

References

[1] B. Girard, M.-P. Bacos, E. Berger, P. Josso, Proc
ed
e pour former sur un substrat m
etallique un rev^etement
m
etallique protecteur exempt de soufre, French patent, 2 807 073.
[2] M.-P. Bacos, B. Girard, P. Josso, C. Rio, MCrAlY coating developed via a new electroless-like route: influence of
deposition parameters, Surf. Coat. Technol. 162 (2003) 248–260.
[3] L.E. Vaaler, M.L. Holt, Codeposition of tungsten and nickel from an aqueous ammoniacal citrate bath, Trans.
Electrochem. Soc. 90 (1946) 43–53.
[4] D. Monceau, B. Pieraggi, Determination of parabolic rate constants from a local analysis of mass–gain curves,
Oxidat. Metals 50 (1998) 477–493.
[5] Castem 2000 Finite element Code: <http://www.castem.org:8001>.
[6] D. Poquillon, D. Monceau:, Application of a simple statistical spalling model for the analysis of high temperature
cyclic oxidation kinetics data, Oxidat. Metals 59 (2003) 409–431.
[7] N.J. Simms, J.E. Oakey, J.R. Nicholls, A methodology for the quantification of corrosion and erosion damage
in laboratory, burner rig and plant environments, Proc. Electrochem. Soc. 99-38 (2000) 305–316.
[8] N.J. Simms, J.E. Oakey, J.R. Nicholls, Development and application of a methodology for the measurement of
corrosion and erosion damage in laboratory, burner rig and plant environments, Mater. High Temp. 17 (2) (2000)
355–362.
[9] N.J. Simms, J.R. Nicholls, J.E. Oakey, Materials for solid fuel fired gas turbines: burner rig and laboratory studies,
Mater. Sci. Forum 369–372 (2001) 833–840.
[10] N.J. Simms, P.J. Smith, A. Encinas-Oropesa, S. Ryder, J.R. Nicholls, J.E. Oakey, The development of type II hot
corrosion in solid fuel fired gas turbines, in: M. Sch€utze et al. (Eds.), Lifetime Modelling of High Temperature
Corrosion Processes, EFC No. 34, Maney Publishing, London, 2001, pp. 246–260.
[11] Draft Code of Practice for Discontinuous Corrosion Testing in High Temperature Gaseous Atmospheres, EC
Project SMT4-CT95-2001, ERA Technology, UK, 2000.