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‘Development of a tool for MCrAlY coatings oxidation resistance assessment

and thermal barrier coating life prediction

Conference Paper · April 2015

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Title: ‘Development of a tool for MCrAlY coatings oxidation resistance assessment and thermal
barrier coating life prediction’

B.G.Gallo, A.Bonadei, G.Vercelli and P.Villari

Ansaldo Sviluppo Energia, Via Lorenzi 8, 16152 Genova

R.A. Huls and A.B. Kloosterman

National Aerospace Laboratory, Anthony Fokkerweg 2, 1059 CM Amsterdam

Introduction
The turbine inlet temperatures (TIT) have been increased over the last decades to improve the gas turbine
efficiency. The consequent increase of the metal temperature in the components could influence their
mechanical integrity. To withstand these extreme gas temperatures, turbine blade design has been developed
from solid via internally cooled to both internally and externally cooled. In order to reduce the heat flow
through cooled components a low thermal conductivity ceramic coating (Thermal Barrier Coating TBC made of
Yttria Partially Stabilized Zirconia YPSZ) is applied on the surface of the components operating in most severe
environmental conditions. A major concern is the limited service life of the TBC. As the TBC fails the blade
material gets exposed to extremely high gas temperatures. Therefore it is of the utmost importance to
understand the degradation behavior in correlation with the TBC life. A life prediction model is therefore
needed to predict the thermal barrier failure. The model has been developed including two basic damage
mechanisms combined in a Manson-Coffin like life criterion. The two damage mechanisms are the induced
thermal strains and the oxidation of the metallic coating that involves the formation of a compact Alumina
scale (also called Thermally Grown Oxide TGO) at the interface with the TBC. The TGO growth rate depends on
the metallic coating compositions (basically it is dependent on the Aluminum content of the bond coat), so
specimens with two different NiCoCrAlY + Rhenium type coatings have been tested. Cyclic and isothermal
oxidation tests at different temperatures have been performed in order to understand the correlation between
the two phenomena and to determine the model parameters for the prediction of the TBC failure. Life model
can be used to predict the TBC expected life in the different zones of gas turbine components and especially to
determine the areas where TBC spallation is most likely to happen.

The protection of the component base material against the high temperature oxidation and corrosion, is widely
assured by the metallic coating, also called bond coat in a system with the TBC. On the AEN gas turbine
blades/vanes external surfaces coatings belonging to the MCrAlY-material group are used. The as-deposited
coating is characterized by the presence of the β phase, which is finely dispersed in the γ matrix and uniformly
distributed within the whole coating thickness. The β phase is an intermetallic phase with a BCC (Body
Centered Cubic) crystallographic structure, NiAl nominal composition and it is considered the main Aluminum
reservoir of the coating. During the exposure to high temperature there is a progressive dissolution of the β
phase due to the Aluminum diffusion towards both the base material and the interface with the TBC. The
lifetime of the coating can be predicted by modeling the time to total β depletion through the measurement of
the residual portion of the coating rich in β phase. To evaluate the performance of these coatings a model for
the calculation of the consumption rate of the β phase has been developed. The oxidation behavior of four
different bond coats applied on three different base materials has been investigated in isothermal conditions.
Microstructural evolution and chemical composition changing in the coating have been observed and detected
by optical microscope and EDS technique respectively. Finally a simulation model for the diffusion phenomena
and lifetime prediction of MCrAlY coatings has been developed and implemented in a MatLab routine. The
model is able to predict the lifetime of bond coat as function of time, temperature and thickness and moreover
it represents a valid tool for coating design of the gas turbine components.

Experimental
The experimental tests performed to determine the TBC life prediction model parameters and consumption
rate of the β phase in the metallic coating are presented.

TBC life prediction model tests

Two different types of tests have been performed at
the same time in the Ansaldo Energia and National
Aerospace laboratories. Firstly oxidation tests have
been performed to determine the weight gain of the
bond coats as a function of temperature and time.
Then cyclic furnace tests have been performed to
determine the TBC life at different temperatures and
for different cycle lengths.

Isothermal oxidations test

Figure 1 [Optical Microscope, 100x] Micrograph of a
Disc shaped buttons of 25 mm diameter and 4mm coating/substrate system.
thickness have been used. Coated buttons have been
coated only with VPS NiCoCrAlY(Re type I) and NiCoCrAlY(Re type II) metallic coating, without the presence of
a TBC. Some uncoated buttons have been used to compensate the measured weight gain of the coated button
for the weight gain of the substrate. The oxidations tests were carried out at four temperatures: 900, 950, 1050
and 1100°C. For all temperatures coated and uncoated specimens were tested simultaneously. The weight of
each button has been measured at fixed durations up to 1000 hours to determine the weight gain of the
buttons. Based on these results the weight gain due to the coating oxidation and the TGO thickness evolution
has been calculated as a function of time and temperature.

Cycling oxidation test

Disc shaped buttons of 25 mm diameter and 4mm thickness have been used. Four different coating/substrate
systems have been tested, with two different base materials: IN792Sx and René80. The specimens have been
coated with VPS NiCoCrAlY(Re type I) and NiCoCrAlY(Re type II) bond coat and APS YPSZ topcoat; the total
thickness of the coating systems was approx. 500μm (250μm for the metallic and the same for the TBC). The
TBC life tests have been carried out at 1050°C and 1100°C. For each temperature four thermal cycles have been
used: 1, 2, 8 and 24 hours. The cycle consists of heating the test buttons to the prescribed test temperature,
performing a dwell time and cooling down to 50°C by natural cooling. Thermocouples have been used to
monitor the button temperature during the oxidation test. Cycling continued until delamination of the TBC and
the achieved results are just the number of cycles to failure (at least 3 specimens have been tested per each
test condition, in order to achieve statistically relevant result).
Metallic coating diffusion model tests
To evaluate the consumption rate of the β phase in the coating, experimental tests have been performed in
conditions comparable to the ones that the blades and vanes experience during the engine run. The oxidation
tests performed in Ansaldo Energia Materials Laboratory have been planned from 750°C to 1000°C for test
durations up to 30000 hours. All tested specimens were disc shaped of 25 mm diameter and 4mm thickness,
with different combinations of metallic coating and base material in order to characterize all metallic
coating/substrate systems used for Ansaldo Energia gas turbines. The tested systems are reported in the
Table1:

Table 1 Coating/substrate systems characterized in Ansaldo Energia laboratory. All specimens are coated with APS TBC.

The metallographic inspection of specimens allows determining the residual thickness of the β phase-rich layer
to quantify the coating degradation. The evolution of the coating microstructure during the exposure at high
temperatures is depicted in Figure 2.

Figure 3 Microstructure metallic coating evolution at two different temperatures for four different time durations.

Results and discussion

This section describes how the experimental data have been
elaborated to obtain a model for the prediction of the TBC failure
I phase
as a function of the temperature cycle length, and a diffusion
model to calculate the consumption rate of the β phase as a time,
temperature and coating thickness function.

The TBC failure can be described into three phases as presented in

Figure 3. In Phase-1 micro cracks form at the TGO/TBC interface II phase
and inside the TBC. As the TGO scale thickness reaches a critical
value due to the exposure to high temperature, cracks within the
alumina oxide grow. The driving force for the crack propagation
through the interface between ceramic and metallic coating is the
III phase
Figure 2 The three phases that lead to TBC
failure.
normal stress. Further thermal cycling and longer exposure at high temperature lead to growth and
coalescence of several micro cracks. Such a continuous degradation of APS TBC together with the bond coat
oxidation produce the spallation of the ceramic top coating. For this reason, a life prediction model taking into
account the TGO growth and the normal stress range value at the BC-TBC interface has been identified.

To model the diffusion phenomena that take place in the metallic coating during the exposure to high
temperature an analytical approach has been used. A kinetic model based on the Fick diffusion laws has been
developed. It’s able to predict the consumption of the β phase inside the coating. This phenomenon is due to
the aluminum diffusion towards the external surface forming the TGO and the inter-diffusion between the
coating and the substrate, generally less rich in aluminum. These phenomena, as illustrated in Figure 4, involve
the formation of an area of mixed composition in the base material called interdiffusion zone (IZ) and two
depleted layer of β phase in the coating called ODZ at the interface with the TBC and IDZ at the interface with
the base material. The diffusion model permits to evaluate the evolution of the two β phase depleted layers
and so to predict the β phase complete consumption as a function of temperature and time.

Figure 4 Representative sketch of a typical Hot Gas Path component coating/substrate system.

TBC life prediction model

To obtain the TBC life prediction model, the normal stress for different coating/substrate systems has been
calculated using a Finite Element Model (FEM) developed in Ansys. Important input parameters of this model
are the properties of the two selected base materials, the two metallic coatings and APS YPSZ top coat. The
FEM analyses calculated eight different values (one for each coating/substrate systems and each tested
temperature) of normal stress range (Δσ) between the bond coat and the TBC. Based on these results, a life
prediction algorithm has been developed. The static oxidation tests data have been used as an input for the
prediction of the TGO thickness depending on time and temperature for the two metallic coatings.
Subsequently, the cyclic furnace tests have been used to evaluate the parameters model predicting the life of
the TBC depending on the temperature, number of cycles and the Δσ calculated in Ansys.

To evaluate the TGO-weight gain a classic Arrhenius relation has been used. Furthermore, to evaluate the
influence of the initial oxidation process, which forms other oxides beside those from aluminum and is
generally different and faster than the steady state oxidation, an initial oxide weight, as a constant, has been
added. These result in Equation 1:
  Q 
w(t , T ) = w0 + A0 t n exp −  Equation 1
 RT 

where A0 and n are constants, Q is the activation energy of the oxidation process, R the universal gas constant
and T is the absolute temperature. Using the obtained activation energy a MatLab routine to evaluate the
corresponding parameter of the TGO increase thickness law has been developed. The oxide scale thickness can
be estimated from the weight gain measurement taking into account the mass of the oxide, its density and the
medium roughness value of the metallic coating surface. The TGO thickness data have been fitted with an
equation similar to [Equation1]:

 Q 
h(t ) = h0 + B0t n exp −  Equation 2
 RT 

Equation 2 and the normal stress range values in the coating/substrate system have been used to develop the
life prediction algorithm for the TBC failure. The model is then described by Equation 3:

N f = C1 (h f + C2 ∆σ ) m Equation 3

where Nf is the number of cycles to failure, C1, C2 and m are constants, hf(tf) is the thickness of the TGO at
failure and Δσ is the normal stress range. The Equation 3 cannot be solved analytically since the life time tf and
the numbers of cycles Nf are related by tf=Nfteq, with teq. the equivalent length of the cycle. Therefore an
iterative algorithm has been implemented in MatLab to solve the equation numerically.

Figure 5 TGO thickness growth as a function of time and Figure 6 Number of cycles to failure depending on the
temperature in case of NiCoCrAlY (Re type II) coating. thermal cycle for René80 and IN792SX in case of
Solid symbols refer to experimental data while dotted NiCoCrAlY (Re type II) coating (experimental data).
lines refer to model.
Metallic coating diffusion model
The overall diffusion phenomena that take place in the metallic coating is also determined by the behavior of
the several secondary phases that characterize the coating. The diffusion of the different phases is regulated by
different parameters. Not all chemical elements are active in the whole investigated temperature range (750-
1000°C) and not all phases reach the thermodynamic equilibrium at the same time and temperature. The
analytical and complete resolution of a multi-diffusion system is derivable from a very complex system of
differential equations as in Equation 4.

 ∂n1 ( x, t )   ∂ 2 n1   ∂ 2n ∂ 2 n2 ∂ 2 nα 
   2   D11 21 + D12 + ... + D α 
 ∂t  ∂x ∂x ∂x 2 ∂x 2
1
   
 ...  = Ddiffusion ×  2... = ...  Equation 4
 ∂nα ( x, t )   ∂ nα   ∂ 2 n1 ∂ 2 nα −1 ∂ 2 nα 
 ∂t   ∂x 2   Dα 1 ∂x 2 + ... + Dαα −1 ∂x 2 + ... + Dαα ∂x 2 
     

Where ni is the concentration of the element i, Ddiffusion is the diffusion coefficient matrix and Dij are the
diffusion coefficients of the chemical element i in a binary system with j. This approach is very complex and in
theory shall be solved taking into consideration each thermodynamic equilibrium states. Equation 4 can be
reduced to Equation 5 considering that only the diffusion of Aluminum determine the β phase consumption
rate and taking into account those temperature ranges for which the thermodynamic equilibrium state remain
almost constant as calculated with Thermo-Calc.

∂nAl ( β − phase ) ∂ 2 n Al ( β − phase )

= φ Al ( β − phase ) ( Dij ) × Equation 5
∂t ∂x 2

where φ is a complex function of the diffusion coefficients of all chemical elements present in the coating
taking into account also the microstructure-induced diffusion blocking phenomenon. The experimental data
show generally two different trends for the interdiffusion phenomenon according to literature. At “low”
temperatures (up to 850 °C), the interaction between the coating and the substrate is limited and the time-
evolution of the two β-depletion layers are very similar. For higher temperatures the Aluminum diffusion rate
towards the base material is considerably higher than towards the external surface. Thus two different β
consumption trends have been evaluated for every coating/substrate systems.

The time and temperature evolution of the inner depletion and outer depletion layers is derivable from
Equation 5 and a good approximation of the β phase consumption with a simpler formula is achievable:

 β (t , T ) = x0 − ( f ODZ + f IDZ )

 i −
F i 2 ( Eij ) Equation 6
 f (t ) = l 0 + F 1 ( Dij )e RT t n
i i

in which fODZ and fIDZ are the function that describe the evolution of the ODZ and IDZ layers respectively, l0 is a
constant, F1 is a parameter depending on the diffusion coefficients Dij and F2 is a function of activation energy
of the different diffusion phenomena. Experimental data of the inner and outer depletion layers using Equation
6 have been fitted separately. Dij in the case of the interdiffusion phenomenon is depending on the
composition of the substrate, so for each type of coating/substrate system (see Table 1) a different series of
parameter has been calculated. Furthermore experimental tests showed a great dependence of the dissolution
rate of the β phase by the coating thickness, so an appropriate correction coefficient has been calculated by
homemade software.

Figure 7 Residual percentage of β phase in case of Figure 8 Residual percentage of β phase for different
NiCoCrAlY (Re type I) coating on René80 base material. combination of coatings and base materials. Solid
Solid symbols refer to experimental data while dotted symbols refer to experimental data while dotted lines
lines refer to model. refer to model.

Conclusions and models applications

Today’s gas turbine market requires to operate at more and more extreme conditions, often at the design limit
of the hot gas path components, so having confidence in their ability to remain structurally undamaged is
paramount. In this context the models described in this paper represent a very important tool for the design
and life assessment of the gas turbine blades/vanes.

The model for the metallic coating high temperature oxidation resistance allows:

• Evaluation of the oxidation resistance of the thermally sprayed coated gas turbine components as a
function of the operating condition;
• Material selection and coating design;
• Check and re-design of the metallic coating of the gas turbine components in case of TIT increase or
maintenance interval extension.

The model for TBC life prediction is a significant tool in the design of improved or completely new components
and it is an important advantage in supporting gas turbine safe operation and maintenance. The identification
of the most critical areas of a component for the TBC failure is a great achievement in the component know-
how and to limit failure risks as well as to reduce the medium scrap rate during the refurbishment process.
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