12

Life Time Analysis of MCrAlY Coatings for

Industrial Gas Turbine Blades
(calculational and experimental approach)
Pavel Krukovsky
1
, Konstantin Tadlya
1
, Alexander Rybnikov
2
,
Natalya Mozhajskaya
2
, Iosif Krukov
2
and Vladislav Kolarik
3

1
Institute of Engineering Thermophysics, 2a, Zhelyabov Str., 03057 Kiev
2
Polzunov Central Boiler and Turbine Institute, 24, Politechnicheskaya Str.
194021 St. Petersburg
3
Fraunhofer-Institut fr Chemische Technologie, 7, Joseph-von-Fraunhofer Str.,
76327 Pfinztal
1
Ukraine
2
Russia
3
Germany
1. Introduction
Modern power gas turbine blades are subject to high-temperature oxidation and are
protected by metal coatings of MCrALY type. The major element retarding oxidation of a
coating is aluminium (Al) whose percentage in a coating amounts to 6-12%.
A blade coatings lifetime of 25000 h is required in stationary gas turbines at operating
temperatures from 900 to 1000 making experimental lifetime assessment a very expensive
and often a not practicable procedure. A feasible and low-cost method of coating lifetime
assessment is the calculation analysis (modeling) of mass transfer processes of basic oxide-
forming elements (in our case Al) over a long period of time. Oxidation (Al
2
O
3
oxide film
forming on the external coating surface) and Al diffusion both towards the oxide film
border and into the basic alloy of a blade are the mass transfer processes which determine
coating lifetime at the usual operating temperatures.
The existing models describing high-temperature oxidation and diffusion processes in
MCrALY coatings use simple approximated empirical dependences (of power-or other type)
[1-4] for oxide film mass or thickness variation with time, and differential equations describing
the oxide-forming element diffusion in the oxide-coating-basic alloy system [5, 6].
However the practical application of these models for long-time prediction is often difficult
or impossible because of the lack of reliable model input parameter values, such as diffusion
factors of an oxide-forming element. Some data on element diffusion factors can be found in
literature only for simple alloy compositions (two- or three-component alloys), while the
alloys used in practice are more complex. In the present case a coating alloy containing 5
elements-nickel, cobalt, chromium, aluminium, yttrium is to be investigated. Data on Al
diffusion factor can be found in literature studying similar element composition, but only
for three-component NiCrAl alloy [7].
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It should be noted that the models, which have been described in [5, 6] disregard the
importance of a number of alloys peculiarities of Al transport from the coating to the base
alloy, which is, the formation of a so-called interdiffusion zone between the coating and the
base alloy. In that case mass transfer from the coating to the base alloy occurs through the
interdiffusion zone and the Al accumulation here begins to play an important role. The
factors of its mathematical description become all the more uncertain.
This work offers to define model factors (effective Al diffusion factor, the intensity factor of
aluminum segregation in the interdiffusion and other zones) using the solution of inverse
problems of diffusion based on the experimental data on Al concentration distributions at
different coated sample exposure times and temperatures in furnaces. The approach based
on the use of short-term experimental data for model factor determination followed by the
application of this model for long-term predictive calculations is called here as a calculation-
experimental approach.
This approach was used for the analysis of chromium mass transfer in a coating with the
formation of chromium oxide and chromium diffusion into a basic alloy [8] except for the
coating life analysis.
The purpose of this work is to improve the existing model of mass transfer processes in
MCrAlY-type metal coatings as well as the development and application of the calculation-
experimental approach to coating life assessment based on the proposed models and the
solution of inverse problems of diffusion.
2. Calculational and experimental approach
The essence of the present approach is the choice of such a mass transfer model and a set of
data which, when combined, enable one to obtain a more equivalent model based on the
solution of inverse problems of diffusion (IPD). The use of the model will allow for a more
accurate long-term prediction of mass transfer processes and metal coating life at given
lifetime criterion.
The diagram of the approach (Fig.1) to mass transfer prediction is as follows:
1. The construction (selection) of a mathematical model which gives the adequate
description of major physical processes occurring in the system under consideration
and determining coating life. This model makes it possible to find the calculated Cm
concentration (profiles) for Al in the coating-basic alloy system.
2. The performance of short-term experimental studies in order to find regular trends of
the oxide film and interdiffusion zone formation and determine Al concentration
distributions in a coating and a basic metal (CE) at different times and temperatures
(coated sample exposures in furnaces).
3. The identification of the unknown Pn(T) model parameters from experiments based on
the IPD solution, which gives the proximity of C
M
and C
E
profiles by minimizing the F
value.
4. Long-term prediction of mass transfer processes and coating life with the use of the
proposed model in p.1 together with the unknown model parameters determined in p.3.
A simpler diagram of prediction is usually used (Fig.1): model + literature P
0
(T) model
parameters = prediction.
Generally the diagram can be applied for simple alloy compositions, for instance, for a
three-component alloy [5, 6]. As for more complex compositions, it may lead to
insufficiently accurate predictions due to the uncertain P
0
(T) model parameters. So the use
of a full calculation-experimental approach diagram based on the identified Pn(T) model
parameters provides more accurate predictions.
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Life Time Analysis of MCrAlY Coatings for Industrial Gas Turbine Blades
(calculational and experimental approach)

327

1 Experiment, 2 Model, 3 Inverse Problem Solution, 4 Prediction
Fig. 1. Diagram of the calculation and experimental approach to mass transfer and life
predictive of gas turbine blade coatings.
The calculation-experimental approach under consideration suggests a search (identification)
for model parameters (p.3) by means of IPD solution based on the available short-term
experimental data. The IPD solution amounts to searching for such Pu (T) parameter values
for which the quantity
( ) ( )
0.5
2
,
,
1
/ min
m
j E
j
j
F C P T C m
M
=



=

(1)
This method of IPD solution is given in more detail in [8, 9]. Thus the calculation-
experimental approach manifests itself as a way of improving the accuracy of the results of
calculations and prediction of the processes at hand by identifying the mathematical model
parameters based on the experimental data on the process being studied. The construction
of the mathematical model required the performance of special works concerned with the
study of the regularities of high-temperature material and coating behaviour during long-
term exposures at high temperatures and the development of a physically valid model for
coating life prediction.
3. Experiment
In this connection the purpose of short-term researches was a study of kinetics of the oxide
film formation on a coating surface, structural changes in surfaces layers of coated heat-
resistant alloys, and the modeling of structural-phase changes in coatings and at isothermal
ageing the duration of which was sufficient for model parameter identification. Then the
experiment was continued till coating life expiration in order to confirm the validity of the
proposed method.
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328
The work investigated the degradation of two coatings with different aluminum content.
The coatings were applied on IN 738LC alloy samples by LPPS (Low Pressure Plasma
Spray) method. The isothermal exposure times and temperatures are given in Table 1.

Coating
Coating
thickness, m
Base
material
Exposure
temperature,

Exposure time, hr
100
Ni30Co28Cr8AlY
200
IN 738 LC 900, 950, 1000
100, 300, 700, 1000, 5000,
10000, 15000, 20000
Ni30Co28Cr10AlY
100
200
IN 738 LC 900, 950, 1000
100, 300, 700, 1000, 5000,
10000, 15000, 20000
Table 1. The program of coated sample tests.
The samples of the same thickness and composition were obtained by cutting cylindrical bar
(10 mm in diameter and 100 mm long) into pieces. The isothermal oxidation in air was
carried out in laboratory muffle furnaces (LINN HIGH TERM LK 312-type) equipped with
parameter control system (PID-controls) allowing to put the furnace into a specified mode
and maintain the required temperature. Initial samples and those after isothermal exposure
were subjected to metallographic examination by optical microscopy, X-ray spectrum
microanalysis and X-ray diffraction analysis for studying the changes which had occurred in
coatings. The samples were electropolated with Cu before preparation (cutting, mechanical
grinding and polishing) in order to preserve the oxide film which had formed on a coating
surface after exposure in the furnace.
3.1 Metallographic examination
The inverted microscope Neophot 32 (Karl Zeiss Jena) with the Baumer Coptronic video
camera was used for the micrographic examination. The obtained images were processed by
means of VideoTest Structure software (Video Test, St. Petersburg, Russia). The
following parameters were measured on each sample with the use of digital metallography:
- thickness of an oxide film and all layers formed in a coating and adjacent basic metal
layer as a result of isothermal exposure in air;
- the volume fraction of phases existing in an initial coating and formed during
isothermal exposure.
3.2 X-ray spectrum microanalysis
The X-ray spectrum microanalysis was carried out using MS46 Camera X-ray
spectroscope analyzer. Samples before etching and poorly etched were used for study.
The standards of both pure metals and compounds and known-composition alloys have
been used for quantitative concentration evaluations of elements under consideration. The
corrections for absorption, atomic number and characteristic radiant fluorescence effects
were introduced by using special computer program. The curve for aluminium
concentration variation across the depth of a coating and basic metal layer was built after
each exposure. To this end, the X-ray spectrum microanalysis of coating and basic metal
layers was carried out every 2 to 10 m and up to 250 m deep. The window size for the
element analysis was 100 m parallel and 3 m perpendicular to the coating surface (100
3 m).
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Life Time Analysis of MCrAlY Coatings for Industrial Gas Turbine Blades
(calculational and experimental approach)

329
3.3 X-ray diffraction analysis
The oxide film formation in the first 100 hours was studied in situ by high-temperature X-
ray diffraction by Fraunhofer Institute for Chemical Technology, Germany.
The experimental set-up consists of an X-ray diffractometer and a high-temperature device
with a programmable thermal controler. A set of X-ray diffraction patterns with a defined time
interval or temperature step was recorded in situ allowing for the identification of structural
changes in the sample as a function of time or temperature. This method makes it possible
- to identify in-situ the following oxide phases,
- To follow the formation of each phase in time or as a function of temperature;
- To evaluate kinetic data on each of the reactions involved;
- To detect the thermal expansion of all phases simultaneously;
- To determine residual stresses in the oxide film or basic metal.
In order to identify the oxide phase structures ex situ after long term exposures, the X-ray
diffraction analysis was performed using a DRON-3M diffract meter in Cu K radiation
with corresponding filters. Methods of polycrystalline sample structure examination were
standard.
3.4 Experimental results
3.4.1 Protective oxide film formation mechanism
The mechanism of oxide film formation and growth on coating surfaces after long exposures
at high temperatures in air or pure fuel combustion products was studied (Fig.2).
Oxidation measurements were carried out on coating under isothermal conditions (900C,
950C and 1000C) up to 20000 hours.

300 h 1000 h 5000 h 15000 h

3,4 m 4,4 m 7,1m 12,3 m
Fig. 2. Oxide film thickness on a coating surface depending on time of isothermal oxidation
The measurement of oxide film thickness after different exposure times show that the
change in oxide film thickness at the initial stage of formation does not fit to the power-type
dependence at longer exposures.
The studies of oxide film phase composition were performed by high-temperature X-ray
diffraction method in order to find out the causes of the accelerated oxide film thickness
growth at short exposures. The in-situ observation of the oxide film formation during the
first 100 hours at 900 and 950 showed the formation of -Al
2
O
3
and -Al
2
O
3
oxides on the
surface (see Table 2).
The growth of -Al
2
O
3
and -Al
2
O
3
at 950 as a function of time is given in Fig.3 as
intensity curves iz(t). Both alumina phases on polished samples grow simultaneously in the
first 50 hours and then the rate of -Al
2
O
3
growth decreases and -Al
2
O
3
increases. The
amount of -Al
2
O
3
reaches maximum after 100 hours and with further exposure the oxide
starts to disappear as a result of its transformation into -Al
2
O
3
.
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Time, hr
Temperature,

100 700 5000 10000 20000
900 - + -Al
2
O
3
-Al
2
O
3
-Al
2
O
3
-Al
2
O
3

-Al
2
O
3

(Me
3
O
4
)
950 - + -Al
2
O
3
-Al
2
O
3
-Al
2
O
3

-Al 2O
3

(Me
3
O
4
)
-Al
2
O
3
,
Me
3
O
4

1000 -Al
2
O
3
-Al
2
O
3
-Al
2
O
3

-Al
2
O
3

(Me
3
O
4
)
-Al
2
O
3
,
Me
3
O
4

Table 2. Oxide film phase composition on Ni30Co28Cr10AlY and Ni30Co28Cr8AlY 200 m
thick protective coatings (the phase indications in brackets mean, that their amount did not
exceed 5 %).

0
500
1000
1500
2000
2500
3000
0 10 20 30 40 50 60 70 80 90 100 110 120
I
n
t
e
n
s
i
t
y

i
z
(
t
)

[
c
p
s
]

Time t, [hr]
-Al
2
O
3
950 C
-Al
2
O
3
900 C
-Al
2
O
3
900 C
-Al
2
O
3
950 C

Fig. 3. Diffraction peak intensities of -Al
2
O
3
and -Al
2
O
3
on polished coatings with 8% Al at
900
o
C and 900
o
C.
Hereinafter, these data were corrected in the developed model by splitting the oxide film
growth curve into two parts (the first one refers to the period of simultaneous existence of -
Al
2
O
3
and - Al
2
O
3
oxides and the second to period of only - Al
2
O
3
).
Investigations using standard X-ray diffraction methods were performed in order to find
out the oxide film growth mechanism in the range of 310
2
210
4
hours. It has been
established that the oxide film phase composition in this range depends on aluminum
content.
As is seen from Table2, the oxide phase composition on coating with aluminum content over
8% (NiCoCr8alY (for instance) after exposures in this time interval presents mainly - Al
2
O
3
.
At long exposures (210
4
hours), an oxide of complex composition of a spinel type
(Co,Ni)(Cr,Al)
2
O
3
forms on the coating surface simultaneously with - Al
2
O
3
. The results of
the investigations performed enabled to plot the variation of the oxide film phase
composition with time and temperature (Fig.4).
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Life Time Analysis of MCrAlY Coatings for Industrial Gas Turbine Blades
(calculational and experimental approach)

331

Fig. 4. Diagram of phase transformations in protective oxide film on Ni30Co28Cr8AlY and
Ni30Co28Cr10AlY coating
Three areas can be seen on the diagram:
- - Al
2
O
3
+ - Al
2
O
3
corresponding to exposure time to 200 hours at all temperatures;
- - Al
2
O
3
corresponding to exposure time to 210
4
hours at all temperatures;
- - Al
2
O
3
+ complex-composition oxide of a spinel type (Co,Ni)(Cr,Al)
2
O
3
corresponding
to exposure time over 210
4
at temperatures 950 and above.
The basis for the development of methods of corrosion life modeling for these coatings was
the existence of constant phase composition oxide (- Al
2
O
3
) in a wide time range of
exposures of Ni30Co28Cr8AlY and Ni30Co28 Cr10AlY coatings for the temperature interval
from 900 to 1000.
3.4.2 Kinetics of changes in coating structures
The coating structural changes and the redistribution of elements between a coating and a
basic metal can be observed during long isothermal exposures of the coated basic metal.
These changes depend on both boundary conditions including environment composition
and the thickness and composition of an oxide film forming during long exposures and the
thickness of a coating layer. Both the coating and basic metal compositions and the exposure
times and temperatures will naturally determine the structural changes.
The work investigated the coating depth-variation of the chemical composition and
structure and the changes in the surface layer of a basic metal during long exposures in air
simulating service conditions in the medium of pure fuel combustion products. The
structural changes in coating and surface layers of a basic metal and the thickness of the
depleted layer were studied by optical metallography and the distribution of elements in the
coating and basic metal layers by X-ray spectrum analysis. The investigations have
shown that all the coatings in their initial phase composition represent a matrix with a face-
centered cubic lattice -solid solution (Ni,Co)-Cr-based and a -phase (Ni,Co)Al which is
uniformly distributed across the coating layer. As is known, the -phase presents a
compensation reservoir for aluminum which is spent on the protective oxide film formation
on a coating surface (Brady et al., 2001).
0 500 100010000 20000 30000
900
950
1000
Ni30Co28Cr8AlY
Ni30Co28Cr10AlY
Al
2
O
3
+ Al
2
O
3
-Al
2
O
3

+ Me
3
O
4
Al
2
O
3
T
e
m
p
e
r
a
t
u
r
e
,

Time, hr
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After applying a coating and performing heat-treatments a diffusion zone is formed in the
alloy. The zone width, phase composition and structure depend on coating and basic metal
compositions, coating application technique and subsequent heat-treatment conditions.
The diffusion zone for all the coatings had about the same width (a. 15 m) and the phase
composition a significantly different from that for basic metal + +carbides.
The characteristic structure of this coating after high temperature exposures is given in Fig.5.

Al
2
O
3
(initial)

Al
2
O
3
(protection
scale)
M
23
C
6
Interdiffusion
zone

Base In738

Fig. 5. Microstructure of Ni30Co28Cr8AlY coating on IN738LC alloy after exposure for 1000
hours at 950
o
C (300)
During long-term exposures to high temperatures the coating structure changes due to the
phase composition variation in its different zones followed by the formation of the
characteristic layers.
It has been established that each of the coatings investigated after long-term exposures
shows a specific character of structural changes.
The phase composition of the layers is mainly retained and their thickness changes with
exposure time and temperature variation.
The changes in coating structure and phase composition depending on exposure time and
temperature can be traced from the structures given in Fig.6.
It should be noted that the -phase stabilization is observed in coatings of this composition.
In relation to this, the phase transformation in a coating during its degradation at high-
temperature exposure occurs in the direction (+).
The kinetics of a change in the volume fraction of the -phase and aluminium concentration
depending on exposure time and temperature can be seen from the curves in Fig.7 and 8.
The X-ray spectroscopy microanalysis of aluminium distribution in the surface layers of
coatings in the initial state and after long exposure at 900 to 1000 was performed. This
microanalysis allowed to identify phases which had been found during metallographic
study. The sizes of dealloyed and diffusion zones and special features of element
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Life Time Analysis of MCrAlY Coatings for Industrial Gas Turbine Blades
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333

900

100 hr 700 hr 1000 hr 5000 hr 20000 hr

950

100 hr 300 hr 1000 hr 5000 hr 10000 hr

1000

100 hr 1000 hr 5000 hr 10000 hr 20000 hr

Fig. 6. The change in Ni30Co28Cr8AlY coating on IN738LC alloy after different exposures at
900C, 950C and 1000C
distribution in these zones can be seen from the curves built in Fig.7. Thus, for the external
dealloyed zone characteristic for all types of coatings, a sharp decrease in aluminium
content is observed under the oxide film Al
2
O
3
(51.78%) up to 2.5 to 3.2%, which
corresponds to its content in the -phase. In coatings of this composition, the volume
fraction of the initial -phase amount to 45% for the Ni30Co28 Cr8AlY coating and 62% for
NiCo28Cr10AlY. During the exposures this phase amount decreases according to the curves
shown in Fig.8, the decrease being less intensive for the coating with greater aluminium
content (and |or larger thickness) determining the coating aluminum life.
The diagrams of phase transformation proposed by Tamarin Jr. (Tamarin, 2002) are very
convenient for presentation of data on the coating phase composition variation with
exposure time and temperature. The external coating surface is taken as the onset of
counting and considered to be constant in these phase transformation diagrams.
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334

Fig. 7. The Al concentration profile across a coating after isothermal oxidation at high
temperatures for up to 10 000 hour

Ni30Co28Cr8AlY(200 ) Ni30Co28Cr10AlY(200 )
0 20 40 60 80 100 120 140 160 180 200 220 240
0
10
20
30
40
50
60
70
V
o
l
u
m
e

f
r
a
c
t
i
o
n

,

%
Distance, mkm

300
700
10000
0 20 40 60 80 100 120 140 160 180 200 220 240
0
10
20
30
40
50
60
70
V
o
l
u
m
e

f
r
a
c
t
i
o
n

,

%
Distance,

300
700
1000
10000

Fig. 8. The -NiAl volume fraction in the + region after different duration of exposure at
950 C
As is seen from Fig.9 and 10 the phase changes in external layers at high-temperature
exposures are observed only due to the formation of an external depleted zone the width of
which increases with increasing exposure time and temperature.
This zone is formed as a result of -phase solution and aluminium consumption for the
protective oxide film Al
2
O
3
formation. At the same time, significant temperature-dependent
structural changes of a diffusion zone are observed at the interface coating - basic metal.
The studies performed have found out particular features of the diffusion zone formation
0 50 100 150 200 250 300 350 400
0
2
4
6
8
10
12
14
40
50
60
A
l

c
o
n
c
e
n
t
r
a
t
i
o
n
,
%
Distance,
300 hr
1000 hr
5000 hr
10000 hr
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Life Time Analysis of MCrAlY Coatings for Industrial Gas Turbine Blades
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335




Fig. 9. Diagram of phase transformations in Ni30Co28Cr10AlY coating on IN738LC
superalloy after exposure at 900 C and 950

C
between a metal and a coating depending on the aluminum content in the zone: with the
aluminum content 10% the diffusion processes develop at the interface on a basic metal side
(in this case a + structure is formed), while with the aluminum content 8% in a coating the
diffusion processes develop on both sides of the interface (the + structure is first formed
and then it transforms to a single -phase -zone).
It is self-evident that the common model of the diffusion element redistribution in an oxide
film, a coating and a basic metal requires accounting for the diffusion processes of all
coating and alloy components. The practical handling the problem is however labour
intensive, ambiguous, and requires a great number of experimental data.
That is why there is a good reason to make a choice of the best concept of diffusion which
could be used as the basis of a coating corrosion life prediction according to one or another
dominant process depending on the temperature interval.
In the temperature range 900 to 1000 it is advisable to use aluminum redistribution
processes whose characteristics have been studied as dominant diffusion processes for
building a model.

1000 10000
-350
-300
-250
-200
-150
-100
-50
0
+ '
+ '
+ '+carbides

1
+
900
o
C
D
i
s
t
a
n
c
e
,

1000 10000
-350
-300
-250
-200
-150
-100
-50
0

2
+
A
l
l
o
y
C
o
a
t
i
n
g
+ '
+ '+carbides

1
+
950
o
C
900
o
C, 10% Al, 100 mkm
950
o
C, 10% Al, 100 mkm
1000 10000 20000
-350
-300
-250
-200
-150
-100
-50
0
+
+ '
+ '+carbides

1
+
900
o
C
D
i
s
t
a
n
c
e
,

Time, hr
1000 10000
-350
-300
-250
-200
-150
-100
-50
0
+
A
l
l
o
y
C
o
a
t
i
n
g
+ '
+ '+carbides

1
+
950
o
C
Time, hr
900
o
C, 10% Al, 200 mkm 950
o
C, 10% Al, 200 mkm
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336

Fig. 10. The phase composition transformations in Ni30Co28Cr8AlY coating (100m and 200
m on IN738LC superalloy after exposures at different temperatures (900 C, 950 C and
1000 C).
4. Physical and mathematical models
The physical model for aluminium diffusion redistribution in the oxide-coating-basic
metalsystem obtained from the analysis of experimental studies of oxidation and diffusion
processes in coatings of NiCoCrAlY-type is described as follows (Fig.11).
An oxide is formed by combining aluminuim and oxygen which is absorbed from the gaseous
medium and by means of diffusion through the oxide layer x
1
x
0
it reaches the interface

800 1000 2000 4000 6000 800010000
-350
-300
-250
-200
-150
-100
-50
0
+ '

1
+
1000
o
C
D
i
s
t
a
n
c
e
,

Time, hr
800 1000 2000 4000 6000 800010000
-350
-300
-250
-200
-150
-100
-50
0
+ '

1
+
950
o
C
D
i
s
t
a
n
c
e
,

Time, hr
800 1000 2000 4000 6000 800010000
-350
-300
-250
-200
-150
-100
-50
0
+ '

1
+
1000
o
C
D
i
s
t
a
n
c
e
,

Time, hr
1000 10000 20000
-350
-300
-250
-200
-150
-100
-50
0

2
+
A
l
l
o
y
C
o
a
t
i
n
g
+ '

1
900
o
C
D
i
s
t
a
n
c
e
,

Time, hr
1000 10000
-350
-300
-250
-200
-150
-100
-50
0
+
2
+
A
l
l
o
y
C
o
a
t
i
n
g
+ '

1
950
o
C
D
i
s
t
a
n
c
e
,

Time, hr
1000 10000
-350
-300
-250
-200
-150
-100
-50
0

3
+
A
l
l
o
y
C
o
a
t
i
n
g
+ '

1
+
1000
o
C
D
i
s
t
a
n
c
e
,

Time, hr
100 200
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337

1. coating, 2. basic alloy, 3. -region, + region, 4. depletion zone, 5. interdiffusion zone
Fig. 11. Typical aluminium concentration distribution in an oxide, coating, and basic alloy.
x
1
oxide - coating. The aluminuim diffusion from the coating proceeds in two directions:
- to the interface x
1
oxide - coating where it enters into reaction with the arrived oxygen.
- to the interface x
4
coating - basic alloy where it is accumulated in the interdiffusion
zone and then diffuses to the basic alloy.
The formation of aluminium-depleted single-phase zones with a decreased Al (-phase) content
on both the oxide and basic metal side (depletion zones I and II, Fig.11) occurs at the cost of the
aluminium departure from the coating (+ two phase zone. All aluminium leaving the coating
departs from the coating (+ two phase zone owing to the -phase disappearance. The
aluminium concentration profile has the form of a stepwise curve in the region of NiCoCrAlY
coating and a curve with maximum in the interdiffusion zone within the basic alloy.
Six major zones can be distinguished:
-
x
0
< x < x
1
oxide;

-
aluminium-depleted x
1
< x < x
2
zone where only one -phase is present;

-
two-phase x
2
< x < x
3
zone

where - and -phases exist simultaneously;

-
x
3
< x < x
4
zone in the coating, also aluminium-depleted with -phase:

- interdiffusion aluminium-rich zone x
4
< x < x
5
in the basic alloy.
-
x
5
< x Zone in the basic metal where aluminium diffuses from the interdiffusion zone.

The aluminium accumulation in the interdiffusion zone with time occurs at the cost of the
formation of different phases (+ and + -phases, for instance) due to the different
quantitative compositions and the corresponding thermodynamical equilibrium of elements
in a coating and a basic alloy. The accumulated in the interdiffusion zone aluminium
diffuses partly to the basic alloy and back to the coating. In the model under consideration,
all the borders apart from the border x
4
(the interface between a coating and a basic alloy)
are movable. The borders x
2
and x
3
move toward each other because of the -phase content
decrease in the + - two-phase coating zone x
2
< x < x
3
from which the aluminium diffusion
occurs. The concentrations of total aluminium amount of C and -phase C

in the

+ two-
phase x
2
< x < x
3
decrease with time.
A mathematical model presented in [6] was taken as the basis of the above-described model.
The model from [6] was improved by adding the capabilities of accounting for special
features of border x
2
and x
3
moving as well as the formation and growth of the
interdiffusion zone which has a great effect on the aluminium mass transfer processes in the
coating-basic alloy system.
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Below is given this improved model according to which aluminium mass transfer processes
in the region of solution x
1
< x < x

can be described by the main diffusion equation

W

ef
C C
D
x x



= +


(2)
0, > ,
1
x x x

< < , ( , ) C C x = , ( , ) W W x = , ( )
ef ef
D D x = ,
1 1
( ) x x = ,
2 2
( ) x x = ,
3 3
( ) x x = ,
5 5
( ) x x = ,
at the initial condition

( ) ( )
0
4
0
4
0
, 0

C x x
C x C x
C x x

< <

= =

(3)
at the boundary condition on border x

( ) ,
0
C x
x

(4)
and boundary condition on the movable border x
1
describing the aluminium diffusion flow
from the coating to the left to form the oxide (Fig.11) at the cost of Al concentration gradient

( )
1
1
,
( , )
x ef
C x
J x D
x

+
=
(5)
Flow (5) together with the mass (flow) ( )
1
1
,
dx
C x
d

that was formed owing to the border

movement to the right make up a total oxide film mass of x thickness which can be
described by two parabolic equation [5,6].

0.5 *
1 0
0 *
, 0
( ) x ( ) x ( )
,
x
x
k
x
k

< <

= =

< <

(6), (7)
where
x
k

,
x
k

- intensity factors of oxide film thickness growth, in literature often called

oxidation constants,
*
- time prior to which the oxidation law (6) is valid and after which the
oxidation law(6) is valid
0
-time prior to which the oxidation law (7) is in force.
At the moment of time
*
the curves from equations (6) and (7) cross;
0
-the time (negative
value) of crossing law (7) and the time axis . The necessity of describing the law of Al oxide
growth by the two parabolic equations (6) and (7) is due to a more rapid growth of oxide -
phase prior to the moment of time
*
and a slower growth of - phase of the oxide film Al
2
O
3
at >
*
. The factors
x
k

,
x
k

,
0
and the
*
value in (6) and (7) are determined from the
experimental data on the oxide film thickness growth with time.
The border x
1
movement is described by the equation
2 3 2 3 1
1
0.5
1
1
Al O Al O

k
dx
d
s

=

+



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339
derived with regard to the stoichiometric relationship between Al and oxygen masses
consumed to form an aluminium oxide. The relationship is used in the model of parabolic
law of oxide film thickness growth (6.7).
According to the accepted model prototype [6]

the following concentration values are set on
movable borders x
2
and x
3
:

2 3
( , ) ( , ) C x C x C

+
= = ,
2 3
( , ) ( , ) C x C x C


+ +
= = . (8)
Then by analogy with the boundary condition (5) for a movable border x
4
we can write the
aluminium diffusion flow from a coating to the right to form the interdiffusion zone y= x
5
-
x
4
and aluminium diffusion to a basic metal as

( )
4
4
,
( , )

b ef
C x
J x D
x

= (9)
In compliance with the physical model (Fig.2) the aluminium flow (9) arrived from the
coating takes part in the formation of new phases in the interdiffusion zone y= x
5
- x
4
thick
and uniformly segregates in this zone , that is

4
( , ) ( , ) ( )
b
J x W x y

= (10)
where the interdiffusion zone width y= x
5
- x
4
increase with time due to the border x
5

movement to the right and the parabolic law of its growth, as for the oxide film, is taken in
the form of

0
5 4
( ) ( )
iz iz
y x x k = = (11)
iz
k factors and
0
iz
value in (11) are determined from the experimental data on the
interdiffusion zone growth with time. The expression for Al W mass arrived from the
coating and uniformly segregated in the interdiffusion zone x
4
< x < x
5
is taken as dependent
on C C
+
. (in power m) and has the form

4 5
1 4 5
( ) , x x x
( , )
0, x x x , x x
m
w
k C C
W W x

< <

= =

< < >

(12)
where k
w
-intensity factor of aluminium segregation in the interdiffusion zone. Since the
balance of masses must be met in the coating-oxide film-basic alloy system the expression
for the total aluminium flow departed from the coating two-phase zone, in accord with (5)
and (9), will take the form

1 4
( ) ( , ) ( , )
ox b
J J x J x
+
= + (13)
In accord with the accepted physical model all aluminium flowing from the coating departs
the coating + two-phase zone at the cost of -phase consumption. Then the movement of
borders x
2
and x
3
as well as the aluminium concentration decrease in the + two-phase zone
can be described by the equation of mass balance between aluminium mass flows on these
borders and the flows resulted from the aluminium concentration difference in + - and -
phases C C C
+
=
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340
( )
3 2
2 3 3 2
( , ) ( , )
dC
dx dx
J J x J x C C x x
d d
d

+
+
= + = + + (14)
where
2
2
( , )
( , ) -
x
ef
dC x
J x D
d

= and
3
3
C( , )
( , ) -
x
ef
d x
J x D
d

+
+
=
are diffusion flows to the oxide and basic alloy due to the aluminium concentration
gradients to the left and to the right of borders x
2
and x
3
respectively.
After division of all the terms by J

the expression (14) has form

( )
3 2
3 2 2 3 2,3
1 / / /
dC
dx dx
C J C J x x J g g g
d d
d

+

= = + + + + (15)
where
g
2
and g
3
total aluminium mass fractions gone from the coating due to the movement of
borders x
2
and x
3
respectively, g
2,3
= (1- g
2
- g
3
) a fraction of aluminium mass gone from
the coating due to the Al -phase amount decrease in the x
2
< x < x
3
zone.
The g
2
and g
3
quantities having a direct effect on the rate of borders x
2
and x
3
. movement are
also taken as dependent on the concentration difference C C C
+
=

2 2
0

C
g k
C

= ,
3 3
0

C
g k
C

= (16)
The laws of borders x
2
and x
3
movement and Al C
+
amount decrease in a two-phase zone
can be derived from expressions (15) and (16)

2 2
0

k dx
J
d C

= ,
3 3
0

k dx
J
d C

= , ( ) ( )
3 2 2 3
1
dC
J x x g g
d

= (17)
The k
2
and k
3
coefficients of proportionality in (16) are determined from expressions (16)
and (17) based on the experimental data on the dynamics of borders x
2
and x
3
movement
and the value of platform C
+
in the region x
2
< x < x
3
for different sample exposure times.
The association of total Al C
+
content with the -phase ( ) C

amount in the coating is

described by the expression
( ) ( ) 1 ( )
Al
C C C C C


+
= +

(18)
where
Al
C const

= is Al amount in -phase.
The diffusion factor D
ef
, k
w
factor and the index of power m in the mathematical model (2) -
(18) are determined from the experimental data by solving the inverse problem of diffusion.
The diffusion factor D
ef
in (2) is valid for all the region of solution except for the subregion
x
2
< x < x
3
where it was taken to be equal to a large value because of the lack of a space
aluminium concentration gradient. The accumulated in the interdiffusion zone aluminium
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341
diffuses partly back to the coating as a result of the aluminium concentration gradient to the
right of the borders x
4

The appearing here diffusion flow
( )
4
4
,
( , )

iz ef
C x
J x D
x

+
+
=
returns to the interdiffusion zone by adding to the main flow (9).
The distinction of the above model from that in [6] is not only in the account for the
interdiffusion zone but also in the introduction of total aluminium mass fractions g
2
and g
3

in (15) which departed the coating due to the movement of borders x
2
and x
3
This allow for a wider application of the model (2) -(18) to different coating compositions for
which the rate of movement in not defined on the whole by concentration gradients on
borders x
2
, x
3
and x
4
. In term of the thermodynamic theory of diffusion, these borders can be
determined by complex processes of the and phase formation dissolution in a solid
solution, but the practical application of this theory for complex systems under
consideration is rather conjectural. Following assumptions are accepted in this model:
- the character of main physical-chemical processes occurring in the coating-substrate
system does not change with time;
- only one element (Al) takes part in the formation of an oxide. This assumption for the
coating type at hand is conformed by experimental investigations for up to 20000 hours
- the oxide forms on the border x
1
only;
- aluminium comes to the interdiffusion zone only from a coating ;
- the diffusion factor D
ef
derived by the IPD solution is an effective characteristic
independent of time;
- the formation of new phases at the interface coating-basic alloy is not accounted for;
- no oxide film spallation takes place.
The above formulated mathematical model of diffusion and oxidation processes is
integrated by means of the numerical method of finite differences using the inexplicit
diagram and iterative method of nonlinearity accounting.
5. Calculation results
The application of calculation and experimental approach to the analysis of aluminium,
oxidation and diffusion processes in a coating 100 m thick is considered. The coating
contains Ni35%, Co30%, Cr24% and Al8.4% (here and below the concentration is given in
weight percents unless otherwise specified).
The mathematical model (2) -(18) was used in calculations. The above described calculation-
experimental approach was used for experimental conditions at 950 and exposures for
700, 10000 and 20000 hours. The model parameter identification was performed with the use
of exposure for 700 and 10000 hours (Fig.12a, 12b). The results of Al and -phase
concentration distribution prediction were compared to the results of experimental exposure
for 20000 hours (Fig.12b).
The main input parameters in the model (2) -(18) were diffusion factors D
ef
, intensity factor
of aluminium segregation in the interdiffusion zone k
w
, the index of power m, weight
coefficients k
2
, k
3
and coefficients
x
k

,
x
k

, and
0
. The coefficients
x
k

,
x
k

, and
0
in the
parabolic equations(6,7) were found by the approximation of experimental data ( )
ex
x f =

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342

Fig. 12. Comparison of calculated and measured concentration profiles
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343
for exposures 7000 and 10000 hours. In our case for the temperature 950
x
k

= 2.8810
-9
m/s
0.5
,
x
k

= 7.4410
-10
m/s
0.5
,
0
=-3.3107 s.
The weight coefficients were preestimated from the analysis of experimental data k
2
=0.24,
k
3
=0.16.
The diffusion factor D
ef
, the intensity factor of aluminium segregation in the interdiffusion
zone

k
w
and the index of power m

were found by IPD solution. The initial values of these
factors were taken as follows: D
ef
=1.010
-15
.m
2
/s, k
w
=1.010
-8
s
-1
, m = 0.5.
The IPD solution was performed by the method described in more detail in [10]. The
parameter values found by using the IPD solution were D
ef
=710
-16
.m
2
/s, k
w
=1.3710
-7
s
-1
,
m = 0.65.
The index of power appeared to be constant m = 0.65 for all three temperatures in the
experiments. The C

value was taken from the experiment as equaling 3.0%.

It is commonly assumed that the time of a complete - phase dissolution is a NiCoCrAlY-
type coating life. This criterion is determined by the fact that after the - phase
disappearance the aluminium concentration in a coating is not sufficient for maintaining the
protective oxide film formation. Further operation of the coating with the dissolved - phase
brings to the rapid oxidation of blade coating and basic alloy layers, which is impermissible.
The calculation results of the time of - phase disappearance in the coating for three
temperatures 900, 950 and 1000 are given in Fig.13.
Thus with the above criterion of coating lifetime in mind a lifetime of NiCoCrAlY-type
coating with the initial Al amount 8.4% and 20m thick is considered to be 50 thousand
hours at 900, 22 thousand hours at 950 and 12.5 thousand hours at 1000.
By using defined model parameters the corrosion lifetime of different coatings was assessed
in comparison with the obtained experimental data (Fig.14, Table3).



Fig. 13. -phase C (volume %) concentrations in a coating depending on time .. 1- at
T=1000, 2- at T=950, 3 - at T=900
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a- Ni30Co28Cr8AlY 200m thickness on In738LC alloy,
b- Ni30Co28Cr10AlY 200m thickness on IN738LC alloy.

Fig. 14. The life of different coatings determined from the -phase amount (volume %)
versus time curves for coatings

Calculated coating life time (h) at temperature,
0
Coating
(base alloy)
900 950 980 1000
Co29Cr6AlY
(GS6K)
11400 5000 - 1000
Ni30Co28Cr8AlY (100 m)
(IN738 LC)
- 12500 - -
Ni30Co28Cr8AlY (200 m)
(IN738 LC)
49000 21000 - 12000
Ni30Co28Cr10AlY (100 m) - - - -
Ni30Co28Cr10AlY (200 m)
(IN738 LC)
55000 28000 - -
Ni25Cr5Al2SiTaY
( CM 247 LC)
46000 26000 - 8000
Ni25Co17Cr10AlYRe
(Rene80)
58000 34000 - 11500
Ni25Co17Cr10AlYRe (LPPS)
(PWA1483 SX)
- 51400 - 22800
Ni25Co17Cr10AlYRe (VPS)
(PWA1483 SX)
52700 - 20000 -
1 -coating (on alloy), 2 - Calculated coating life (hour at temperature., 3 -on
Table 3. The results of different coating life calculations
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Life Time Analysis of MCrAlY Coatings for Industrial Gas Turbine Blades
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345
6. Conclusions
The proposed calculation and experimental approach has shown its efficiency in lifetime
assessments of gas turbine blade coatings. The model taken from [6]

was significantly
improved.
The existence of the interdiffusion zone was modeled and calculated and a more flexible
approach to the calculation for two-phase border movement was introduced in the
mathematic model as a result of model improvement.
There is a good agreement between experimental and calculated aluminium concentration
profiles and - phase amount in a coating.
The application of the approach made it possible to evaluate model input parameters, in
particular, to determine aluminium diffusion factor and perform rotating blade life
predictions.
The authors express their acknowledgement to the NATO Scientific Program, Ministry of
Education and Science and the Institute of Engineering Thermal Physical, Ukraine for the
financial support of the researches; to Alperine S. (SNECMA, France), Stamm W. (SIEMENS,
Germany) for their participation in discussing the results of the work.
7. References
P. Kolomyteev, Gaseous corrosion and strength of nickel alloys|| M.: Metallurgy, 1984,
p.216.
N. Nikitin, Metal heat-resistance calculation. M.: Metallurgy, 1989, p.207.
Superalloys II, edited by Ch. Sims, N. Stoloff, W. Hagel. Book 2. M.: Metallurgy, 1995,
p.384.
Meirer S. M., Nissleu D. M. , Sheffer K. D. , Cruse T. A., Thermal Barrier Coating Life
Prediction Model Developed|| Trans. of ASME. J. of Eng. For Gas Turbines and
Power, 1992, v116, 4.p. p. 250-257.
J. Nesbitt, Numerical Modelling of High-Temperature Corrosion Processes/|| Oxidation of
metals, 1996, 44, p. p. 309-338.
E.Y. Lee, D. M. Chartier, R. R. Biederman and K. D. Sisson, Modelling the microstructural
evolution of M-Cr-Al-Y coatings during high-temperature oxidation.|| Surface
and coatings technology, 1987, 32. p.p. 19-39.
J. Nesbitt, R. Heckel, Interdiffusion in Ni-rich, Ni-Cr-Al Alloys at 1100 and 1200: Part II.
Diffusion coefficients and Predicted Concentration Profiles|| Met.Trans., 1987,
18A,December, p.p. 2087-2094.
E. Kartavova, P. Krukovsky, Modelling of Heat Transfer Processes in protective coatings of
GT blades:|| Industrial Heat Engineering,1996.6, p.p. 23-30.
P. Krukovsky, V. Kolarik, K. Tadlya, A. Rybnikov, I. Kryukov, M. Jues-Lorento, Lifetime
Modelling of High Temperature Corrosion Processes.|| Proceedings of an EFC
Workshop, 201, p.p. 231-245.
P. Krukovsky, Inverse Problems of Heat Transfer (general engineering approach) Kiev,
Institute of Engineering Thermal Physics NaN Ukraine, 1998. p.218.
K. Borggreen, P. Auerkari, Assesment of the thermal damage in the superalloy GTD
Baltika V. , Condition and Life Management for Power Plants, vol. 1, 2001, p.p. 125-
137.
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Brady M. P. , Pint B. A., Tortorelli P. F., Whright, Hanrahan R. J. High-temperature
oxidation and corrosion of intermetallic || Corrosion and environmental
degradation, edited by M. Schutze|| v. II, Ch. 6, 2001 p.p. 229-311.
Tamarin Y. Protective coating for turbine blades|| ASM International, Materials Park, ON,
2002, p.247.
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Gas Turbines
Edited by Gurrappa Injeti
ISBN 978-953-307-146-6
Hard cover, 364 pages
Publisher Sciyo
Published online 27, September, 2010
Published in print edition September, 2010
InTech Europe
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This book is intended to provide valuable information for the analysis and design of various gas turbine
engines for different applications. The target audience for this book is design, maintenance, materials,
aerospace and mechanical engineers. The design and maintenance engineers in the gas turbine and aircraft
industry will benefit immensely from the integration and system discussions in the book. The chapters are of
high relevance and interest to manufacturers, researchers and academicians as well.
How to reference
In order to correctly reference this scholarly work, feel free to copy and paste the following:
P. Krukovskyi, K. Tadlya, A. Rybnikov, N. Mozhajskaja, I. Krukov and V. Kolarik (2010). Life Time Analysis of
MCrAlY Coatings for Industrial Gas Turbine Blades (Calculational and Experimental Approach), Gas Turbines,
Gurrappa Injeti (Ed.), ISBN: 978-953-307-146-6, InTech, Available from:
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