Pre-Oxidation Treatment For Mcraly Bond Coating

Design of a pre-oxidation treatment for a
NiCoCrAlY bond coating in view of enhancing the

lifetime of high temperature coatings systems
Carlos Serrano Vergel
Master Project Report
Supervisors: Thijs Nijdam
Wim Sloof
Surface and Interfaces
Materials Science and Engineering
Delft University of Technology
Netherlands 2000
CONTENTS
ABSTRACT ...........................................................................................................................i
1. INTRODUCTION .......................................................................................................ii
2. BACKGROUND ........................................................................................................ 1
2.1. HIGH TEMPERATURE OXIDATION ....................................................................... 1
2.1.1. THERMODYNAMICS ............................................................................................... 1
2.1.2. KINETICS ................................................................................................................. 7
2.2. HIGH TEMPERATURE COATINGS ...................................................................... 11
2.2.1. HIGH TEMPERATURE ENVIRONMENT .............................................................. 11
2.2.2. THE HTC SYSTEM ................................................................................................ 12
2.2.3. SUPERALLOY........................................................................................................ 12
2.2.5. THERMALLY GROWN OXIDE .............................................................................. 15
2.2.6. FAILLURE OF THE SYSTEM ................................................................................ 17
3. EXPERIMENTAL .................................................................................................... 24
3.1. MATERIALS............................................................................................................ 24
3.2. FURNACE............................................................................................................... 24
3.3. REACTION CHAMBER .......................................................................................... 24
3.4. XPS ......................................................................................................................... 24
3.5. XRD......................................................................................................................... 24
3.6. SEM ........................................................................................................................ 25
3.7. EPMA ...................................................................................................................... 25
3.8. EXPERIMENT FLOW CHART ............................................................................... 25
4. RESULTS ............................................................................................................... 28
4.1. INITIAL CONDITIONS............................................................................................ 28
4.2. 10 MINUTES ISOTHERMAL HEATING IN Ar-H2 .................................................. 30
4.3. ISOTHERMAL HEATING UNDER VACUUM ........................................................ 31
4.4. 10 MINUTES ISOTHERMAL OXIDATION............................................................. 32
4.5. 60 MINUTES ISOTHERMAL OXIDATION............................................................. 39
4.6. ISOTHERMAL OXIDATION AT 800°C .................................................................. 41
4.7. ISOTHERMAL OXIDATION AT 1100°C ................................................................ 44
4.8. SUMMARY OF RESULTS...................................................................................... 53
5. DISCUSSION.......................................................................................................... 55
5.1. STRUCTURE OF THE LPPS NiCoCrAlY BONDCOATING.................................. 55
5.2. EXTERNAL OXIDATION OF ALUMINUM ............................................................. 55
5.2.1. THEMODYNAMICS................................................................................................ 55
5.2.2. KINETICS ............................................................................................................... 57
5.3. NICKEL, COBALT AND CHROMIUM .................................................................... 60
5.3.1. THERMODYNAMICS ............................................................................................. 60
5.3.2. KINETICS ............................................................................................................... 62
5.4. YTTRIUM ................................................................................................................ 63
5.4.1. THERMODYNAMICS ............................................................................................. 63
5.4.2. INTERNAL YTTRIUM OXIDATION........................................................................ 64
5.5. SUMMARY.............................................................................................................. 69
5.5.1. THERMODYNAMICS ............................................................................................. 69
5.5.2. KINETICS ............................................................................................................... 70
5.6. TGO CRITERIA FOR AN IMPROVED LIFETIME ................................................. 72
5.7. TGO FORMATION ................................................................................................. 73
6. CONCLUSION: Proposed pre-oxidation treatment ............................................... 79
7. RECOMMENTDATIONS ........................................................................................ 80
REFERENCES ................................................................................................................. 81
ABSTRACT
High temperature coating (HTC) systems frequently fail when the thermally grown
oxide (TGO) reach a critical thickness. Pre-oxidation treatments can modify the
mature TGO structure and therefore its growth rate. Structural modifications induced
by isothermal oxidation of a NiCoCrAlY bond coating were studied, in order to define
the pre-oxidation conditions that can lead to an extended HTC lifetime.
The initial structure of a NiCoCrAlY bond coating deposited by low pressure plasma
spray (LPPS) is fined grained and meta-stable. Y is evenly distributed among in the
three initial metallic phases present in the BC (e.g. γ-(Ni,Co)/γ’-(Ni,Co)3(Al,Cr), β-
(Ni,Co)(Al,Cr) and σ-(Co)) . As a consequence of the meta-stable nature of the bond
coating structure and the high density of grain/phase boundaries, closed alumina
layers of uniform thickness can be formed and the initial state of Y (i.e. distribution
and bonding) can be swiftly modified upon short periods of isothermal oxidation. The
modification of the state of Y on the oxidation behaviour is two-fold. On the one hand,
the oxide scale growth kinetics is reduced when Y is bonded to oxygen inside the
coating, because a smaller amount of Y-rich oxides (pegs) are included in the scale.
On the other hand, the oxide scale adhesion may be reduced If Y is internally
oxidized, because then Y is not available for the scavenging of impurities in the
coating (e.g. S, C, Ca). Therefore the state of yttrium in the bond coating has a major
effect in the lifetime.
Based on the oxide layer structures formed by isothermal oxidation upon variation of
the oxidation parameters, such as temperature, time and oxygen partial pressure, a
short pre-oxidation treatment is proposed in view of enhancing the lifetime of the high
temperature coating system.
i
1. INTRODUCTION
1. INTRODUCTION
In gas turbines cycles the exergy of the fuel is converted into shaft work (land based)
or trust power (aero). The open gas turbine cycle has three main steps compression,
combustion and expansion. The three main turbine components are shown in Figure
1. The losses associated with combustion can be reduced by burning the fuel closer
to its adiabatic flame temperature, this implies higher inlet temperature for the turbine
engine. Furthermore, if the ratio between the inlet and outlet temperature of the
expansion cycle is increased, the expansion losses are reduced. Reduction of these
losses means that fuel can be saved [1, 3, 4].
Figure 1: Aeroderivative landbased turbine designed by General Electric
The hot flue gas contains oxygen tied to hydrogen, carbon, sulfur, and nitrogen, plus
solid silicates containing Ca, Mg and Al oxides (CMAS) in the case of aero engines.
This highly aggressive work environment demands: high strength, creep, wear and
oxidation resistance of turbine components [1, 23].
For example, the rotor/stator blades are nowadays made of Ni/Co based superalloys.
After manufacturing these components, the superalloy is heat treated to create the
required strength. This treatment comprises: (i) solution treatment at 1150°C for 2
hours and (ii) precipitation hardening at 850°C for 24 hours. The microstructure
developed after the heat treatment is consists of γ-Ni phase (matrix) and γ´-Ni3Al
phase (precipitates).
ii
1. INTRODUCTION
To maintain the structural integrity of the Ni/Co based superalloy under the described
environmental conditions, turbine blades are isolated by a ceramic layer and cooled
by air or steam. Figure 2 show the air cooling channels of a turbine blade. The
ceramic layer (TBC) is commonly made up of zirconium oxide stabilized with 7-8 wt%
of yttrium oxide. This material has low thermal conductivity, high strain compliance
and toughness, besides an excellent erosion resistance. However, this layer allows
the penetration corrosive species (e.g. O and S). Hence the superalloy needs to be
protected against corrosion. This is accomplished by forming an oxide layer between
the ceramic coating and the metallic blade.
Figure 2: Turbine blade drawing showing internal cooling channels
Alumina (Al2O3), chromia (Cr2O3) and silica (SiO2) are used as protective oxides.
Chromia scales have the highest growth rate, and tend to from volatile oxy-
hydroxides at temperatures above 800°C [3]. Silica layers have the lowest growth
rate in dry oxygen. However, when water vapor is present in the atmosphere, Si
forms volatile hydroxides [34]. Therefore, under the conditions that occur in gas
turbines, alumina is the best option to from a protective oxide layer eventhough it
offers lower protection against hot corrosion (i.e. attack by sulfur [4]) compared to
chromia or silica [1, 4].
Based on their composition, superalloys have the capability to form a protective

alumina layer, but their ability to maintain it will be the limiting factor, compromising
the mechanical strength of the superalloy in a reduced time span. Hence, to expand
the lifetime of the expensive superalloys used to make the turbine rotor/stator blades,
iii
1. INTRODUCTION
bond coatings (BC) are used. A BC is basically an alloy designed to form a protective
alumina scale by the selective oxidation of Al. Two different types of bond coatings
are employed: diffusion and overlay. Overlay bond coatings are usually composed of
MCrAlRE, where the M stands for Fe, Ni, Co or a combination of Ni and Co and RE
is a reactive element such as: Y, Hf, Ce or Zr. The advantages of overlay over
diffusion coatings are: (i) MCrAlRE bond coating can easily be replace while keeping
the coated component undamaged; (ii) MCrAlRE bond coating composition can be
tailored to specific environmental requirements [3, 15].
The protective Al2O3 layer forms during superalloy precipitation hardening and TBC
deposition and grows during operation. This protective oxide layer is commonly
referred to as the thermally grown oxide (TGO).
The growth of the TGO eventually cause the failure of the high temperature coating
system (HTC=BC+TGO+TBC). When the strain energy (function of the scale
thickness) stored in the oxide layer upon cooling (due to the different thermal
expansion coefficients of the BC and the oxide layer) is larger than the fracture
thoughness of the TGO/BC interface, the oxide layer detaches from the BC.
Therefore, the failure of a high temperature coating system (HTC) is influenced by
the growth rate of the oxide layer and the fracture toughness of the TGO/BC interface
[1, 4].
The reactive elements (RE´s) such as Y and Hf interact with impurities such as S and
C in the BC. Parameters such as: temperature, time and partial oxygen pressure can
be used to modify RE’s and impurities state (bonding and distribution) in the BC. This
modifies the TGO structure and can influence the fracture strength of the TGO/BC
interface.
The aim of the present project is to design a pre-oxidation treatment for a LPPS
NiCoCrAlY BC in view of enhancing the life time of complete high temperature
coating system. Different pre-oxidation treatments were performed on a free standing
as-deposited BC in order to understand the influence of oxidation parameters (e.g.
oxidation time, oxidation temperature and oxygen partial pressure) on the initial TGO
structure. Afterwards, isothermal oxidation experiments were performed for a long
oxidation time in order to study the consequences of the pre-oxidation treatments on
the mature TGO structure. The obtained results were used to design the proposed
pre-oxidation treatment.
iv
1. INTRODUCTION
Pre-oxidation treatments performed on an as-deposited BC prior to the super-alloy

precipitation hardening that effectively increased the high temperature coating
system lifetime give a dual advantage: (i) the increase in lifetime reduces overhaul
expenses for the turbine user and (ii) short pre-oxidation times and the possibility to
use a higher pressure set up can reduce the manufacturing cost for the coating
producer.
This document is structured as follows: First, in Section 2, the relevant theoretical

background is presented. Then, in Section 3, a description is given of the
experiments performed and the characterization techniques used. Next, in Section 4,
the obtained results are presented and in Section 5 these results are discussed.
Finally, in Section 6, a pre-oxidation treatment is proposed as a conclusion.
v
2. BACKGROUND
2. BACKGROUND
2.1. HIGH TEMPERATURE OXIDATION
In order to understand how the thermally grown oxide (TGO) is formed during the
turbine operation, it is necessary to mention some fundamental concepts related to
the high temperature oxidation of metals. The fundamental aspects that will be
discussed are: the thermodynamical basis of oxide formation, the kinetics of external
and internal oxidation, and the principle of selective oxidation.
In order to form a metal-oxide molecule two reactions have to take place,
O2 reduction (consumption of electrons):
b
O2 + 2be − ↔ bO 2 − (1a)
2
M oxidation (generation of electrons):
aM + bO 2 − ↔ MaOb + 2be − (1b)
The total reaction is shown in equation 1c.
2.1.1. THERMODYNAMICS
Thermodynamical calculations predict whether the reaction can occur in the given
direction. Eq. 1c is an oxidation reaction describing the formation of a pure oxide. a
and b are the number of metal and oxygen atoms involved in the formation of one
metal-oxide (MaOb) molecule, respectively, i.e.:
b
aM + O2 ↔ MaOb (1c)
2
The change in standard free energy of formation ( ∆G O ) is a function of temperature,

if the composition of the metallic phase is constant, the oxide is stoichiometric and
the process occurs at a constant pressure [1]. The standard free energy for the
elements and compounds of interest as function of temperature used in Eq. 2 can be
found in references 36 and 37. Taking into account the previous assumptions, Eq. 2
gives the standard free energy of formation for a metallic oxide [1 and 4].
1
2. BACKGROUND
A plot of the change in standard free energy as a function of temperature aids in the
analysis of pure and mixed oxide formation. Reactions with a large negative standard
free energy of formation, compared to those with a small negative standard free
energy of formation, are energetically favorable since the magnitude of their driving
force is larger (Graphs 1-4).
 b 
∆GO (T ) = GMOaOb (T ) −  aGMO (T ) + GOO2 (T ) (2)
 2 
Graph 1 shows the standard free energy of formation of the relevant oxides, it can be
seen that Y and Al are the more reactive components of the NiCoCrAlY coating,
while Ni and Co are the more noble ones. In Graph 2, it can be seen that formation of
NiAl2O4 (spinel) by solid state reaction has a much less negative standard energy of
formation than formation by solute incorporation to a pure oxide or by the reaction
between pure elements. Graphs 3 and 4 show the same comparison for YAlO3 and
Y3Al5O12, respectively.
-500
2Cr+1.5O2=Cr2O3
∆G (kJmol )
-1
2Al+1.5O2=Al2O3
Ni+0.5O2=NiO
Co+0.5O2=CoO
O
2Y+1.5O2=Y2O3
-1000
-1500
500 1000 1500
o
Temperature ( C)
Graph 1: Plot of the standard free energy of formation as a function of temperature for pure metals. Data
taken from references 36 and 37.
2
2. BACKGROUND
Ni+2Al+2O2=NiAl2O4 NiO+2Al+1.5O2=NiAl2O4 NiO+Al2O3=NiAl2O4
0 0
-10
-500
∆G (kJmol )
∆G (kJmol )
-20
-1
-1
O
O
-30
-1000
-40
-1500 -50
500 1000 1500
Temperature (°C)
Graph 2: Plot of the standard free energy of formation as a function of temperature for NiAl2O4. The right
side axis applies to the solid state reaction only. Data taken from references 36 and 37.
Y+Al+1.5O2=YAlO3 0.5Y2O3+Al+0.75O2=YAlO3 0.5Al2O3+0.5Y2O3=YAlO3
-500 -25
-30
∆G (kJmol )
∆G (kJmol )
-1
-1
-35
-1000
O
-40
-45
-1500 -50
500 700 900 1100 1300 1500
Temperature (°C)
Graph 3: Plot of the standard free energy of formation as a function of temperature for YAlO3. The right
side axis applies to the solid state reaction only. Data taken from references 36 and 37.
3
2. BACKGROUND
3Y+5Al+6O2=Y3Al5O12 1.5Y2O3+5Al+3.75O2=Y3Al5O12
2.5Al2O3+1.5Y2O3=Y3Al5O12 Al2O3+3YAlO3=Y3Al5O12
0 0
-50
-500
∆G (kJmol )
∆G (kJmol )
-1
-1
-100
O
O
-150
-1000
-200
-1500 -250
500 1000 1500
Temperature (°C)
Graph 4: Plot of the standard free energy of formation as a function of temperature for Y3Al5O12. The
right side axis applies to the solid state reaction(s) only. Data taken from references 36 and 37.
The thermodynamical analysis for a mixed-oxide is analogous to the one explained

for pure oxides and follows the same assumptions. For mixed-oxides Eq. 1 is then
modified by simply adding a second reactant, which can either be a metal or a metal-
oxide.
Three different formation routes are plotted for the formation of mixed oxides (cf.
Graphs 2, 3 and 4): (i) solid state reaction between pure oxides, (ii) reaction between
pure metals and oxygen and (iii) solute incorporation into a pure oxide.
The change in the standard free energy can also be written as follows [4]:
∆G O (T ) = −RT ln(K ) (3)
where R is the ideal gas constant kJmol-1K-1, T is the temperature in Kelvin and K is
the reaction constant, which in this case equals:
aM aOb 1
K= b
= b
(4)
aMa pO22 pO22
4
2. BACKGROUND
An oxidation reaction can occur if the standard free energy of formation is negative
and the oxygen pressure is above the equilibrium oxygen partial pressure [4]. If the
thermodynamic activities are assumed to be unity, the reaction constant K is
inversely proportional to the equilibrium oxygen partial pressure ( pO2 ). Then the
oxygen partial pressure equals:
 2∆GO (T ) 
pO2 = exp  (5)
 bRT 
If the equilibrium oxygen partial pressure is plotted versus 1/T the slope of the line is
proportional to 2∆GO/bR. For the relevant oxidation reactions, these relations are
plotted in Graph 5. In this graph it can be seen that the oxidation of metals with less
negative standard free energy of formation have a higher equilibrium pressure.
Furthermore, the equilibrium oxygen partial pressure increases as temperature
increases. Thus, in general, a metal-oxide is less stable at higher temperature
(Graphs 5-8).
1.E+00
1.E-50 2Cr+1.5O2=Cr2O3
2Al+1.5O2=Al2O3
log (pO2)
Ni+0.5O2=NiO
Co+0.5O2=CoO
2Y+1.5O2=Y2O3
1.E-100
1.E-150
0.5 1 1.5 2
3
1x10 /Temperature (K)
Graph 5: Plot of the oxygen partial pressure of equilibrium as a function of temperature for pure oxides.
Data taken from references 36 and 37.
For the specific case of NiCoCrAlY alloy oxidation, Graph 5 indicates that if a close
aluminum oxide layer is formed, underneath this layer only Y can be oxidized.
Graphs 6, 7 and 8 show that less oxygen is required to from a mixed oxide by solute
5
2. BACKGROUND
incorporation into a pure oxide compared with the reaction of pure metals with
oxygen.
Ni+2Al+2O2=NiAl2O4 NiO+2Al+1.5O2=NiAl2O4
1
log(pO2)
1E-50
1E-100
0.5 1 1.5 2
3
Graph 6: Plot of the oxygen partial pressure of equilibrium as a function of temperature for NiAl2O4. Data
Y+Al+1.5O2=YAlO3 0.5Y2O3+Al+0.75O2=YAlO3
1
log(pO2)
1E-50
1E-100
0.5 1 1.5 2
3
1X10 /Temperature (K)
Graph 7: Plot of the oxygen partial pressure of equilibrium as a function of temperature for YAlO3. Data
6
2. BACKGROUND
3Y+5Al+6O2=Y3Al5O12 1.5Y2O3+5Al+3.75O2=Y3Al5O12
log(pO2)
1E-50
1E-100
0.5 1 1.5 2
1x103/Temperature (K)
Graph 8: Plot of the oxygen partial pressure of equilibrium as a function of temperature for Y3Al5O12.
Data taken from references 36 and 37.
2.1.2. KINETICS
EXTERNAL OXIDATION
Figure 3: Stages of external alloy oxidation.
7
2. BACKGROUND
The kinetics of oxide scale growth by external oxidation of a metallic component is

usually displayed as the oxide scale thickness versus oxidation time. Figure 3 shows
the three stages identify in the external oxidation of alloys.
Initially the oxide layer is thin and contains a high density of grain boundaries [4].
Then, the diffusion through the oxide layer is fast and the kinetics is determined by
the absorption and dissociation of oxygen. The growth of the oxide layer at this stage
is usually linear with oxidation time t [4] :
T
x MO = kLt (6)
T
where x MO is the oxide layer thickness (transient stage) and kL is the linear growth
rate.
The following analysis applies (steady state) to an external oxide layer growing by
inward diffusion of atomic oxygen through grain boundaries (cf. Scheme 1).
Scheme1: Growth of an external oxide layer
The flux of oxygen atoms through the MO/M interface can be written in two
analogous ways. (i) Einstein’s general approach to describe forced diffusion. In this
case the flux of oxygen atoms is the product between the average migration velocity
MO
O
of the oxygen atoms U O m/s through the MO/M interface and the oxygen
MO
M
concentration at the same interface CO in at% and (ii) Fick’s first law in terms of
the chemical potential gradient [4, 59]:
MO
MO CO DOMO dµ O
M MO MO
JO M
=− = CO M U O M (7)
RT dx
In Equation 7, DOMO is the diffusion coefficient of oxygen ions through the oxide layer
in m 2/s. If the existing oxide layer has a thickness equal to xMO and local
thermodynamic equilibrium is assumed at the MO/O2 and the MO/M interfaces, then:
8
2. BACKGROUND
 MOO2 MO 
MO
MO  µO − µO M 
  = C MO M U MO M
M
MO
M
CO D O
JO =− O O (8)
RT x MO
The average migration velocity of the oxygen atoms through the MO/M interface
MO
O
UO equals the growth rate of the oxide layer dxMO/dt. Because, once an oxygen
atom crosses this interface it reacts to form MO becoming part of the oxide layer,
then:
MO MO
O2
MO dx D MO µ O − µO M
UO M
= MO = O (9)
dt RT x MO
If the initial conditions state that at t=0 the oxide layer thickness is zero, then:
2
xMO DOMO  MOO2 MO 
=  µO − µO M t = kP t (10)
2 RT  
The coefficient for oxygen diffusion through the scale can be related to the coefficient
for oxygen diffusion along the oxide layer grain boundaries by considering the grain
boundary width δ and the grain size r :
2
x MO 2δ DOGB  MOO2 MO 
=  µO − µO M t = k P t (11)
2 r RT  
Equation11 states that for thermodynamic equilibrium at the interfaces and if the
oxide growth is controlled by inward oxygen diffusion, the oxide layer thickness is
proportional to the square root of time.
The parabolic constant kP can be determined from measurements of the oxide layer
thickness for a given oxidation time using Eq. 11 and has units of m2s-1. Alternatively,
the mass increment ∆m can be measured upon oxidation and a parabolic growth
constant is deduced from Equation 12, according to the mass change:
 ∆m 
  = kp t
m
(12)
 A 
where A is the area over which the reaction occurs. Then, the parabolic rate constant
calculated from mass gain has units of g2cm-4s-1. The relation between the two
constants in given by Equation 13:
9
2. BACKGROUND
1 (v MO nO )2
kp = 2 2
k Pm (13)
wO
where vMO is the molar volume of the oxide, nO is the oxygen valence and wO is the
atomic mass of oxygen.
After the element forming the protective oxide layer is consumed, the oxide layer is
no longer self-healing, this leads to a rapid degradation of the bond coating which is
known as breakaway oxidation [1, 4 and 55].
INTERNAL OXIDATION
The internal formation of oxides in an alloy occur, when the oxygen partial pressure
in the alloy is high enough to oxidize one or more alloy components that are present
in concentrations below the limit for the transition to external oxidation [4]. Internal
oxidation form oxide precipitates (see Scheme 2), in contrast with the continuous
layer formation by external oxidation.
Scheme 2: Internal oxidation of metal Z bellow an external MO layer
The following analysis of internal oxidation can be found in appendix B of Ref. 4. If

the oxidation front is said to be controlled by atomic oxygen diffusion, then the
penetration depth of the internal oxidation front (i.e. distance between the MO/M
interface and the I.O.F.) xIOF can be written as:
x IOF = 2γ DOM t (14)
10
2. BACKGROUND
where DOM is the effective oxygen diffusion coefficient in the metal and γ is an
undetermined factor that gives the proportionality between xIOF and the characteristic
diffusion length DOM t . Fick’s second law applies if
dJ (x ) dC
=− ≠0 (15)
dx dt
hence, Fick’s second law is the first derivate of the first law with respect to position x,
assuming that the diffusion coefficient is constant with respect to x. For oxygen
diffusion:
∂CO ∂ 2 CO
= DO (16)
∂t ∂x 2
where CO is the concentration of oxygen.
Initial conditions at=0:
MO
x=0 CO = CO M
concentration of oxygen at the MO/M interface
x>0 CO = 0 No oxygen is dissolved in the metal
Boundary conditions at t=t:
MO
x=0 CO = CO M
x=xIOF CO = 0
The solution of Fick’s second law under the mention conditions is:
  x 
 erf  
MO 
 2 DM t 
CO (x ) = CO M 1 −  O 
 (17)
 erf (γ ) 
 
 
Next, Fick’s second law is applied to the solute Z that is being internally oxidized.
Initial conditions at t=0:
11
2. BACKGROUND
x<0 C Z = 0 no metallic Z above the MO/M interface
x>0 C Z = C Z∞ concentration of Z away from the I.O.F.
Boundary conditions at t=t:
x=0 C Z = 0 no metallic Z at the MO/M interface
x= ∞ C Z = C Z∞
Then the solution of Fick’s second law is
  x 
C M∞ 1 − erf  
  2 DM t 
  Z 
C Z (x ) = C Z −
∞
(18)
erfc  Θ 2 γ 
1
 
Where Θ = DOM / DZM . The internal oxidation kinetics (i.e., γ) are obtaining from writing
the flux balance at the internal oxidation front (i.e. x=xIOF). At this interface the flux of
oxygen equals ν (i.e. ν is the ratio between oxygen and Z atoms in one molecule of
the formed oxide) times the flux of Z atoms, since it is assumed that at the I.O.F. the
concentration of metallic Z and oxygen atoms drop to zero. The flux balance yields
to:
MO
CO M
=
ν erf (γ ) exp γ 2 ( ) (19)
CM∞ Θ 2 erfc  Θ 2γ  exp Θγ
1 1 2
( )
 
An analytical solution of Eq. 19 can be obtain for significant counter diffusion of metal
1
Z using the following approximations γ << 1 and γ Θ 2
<< 1. Since
2
erf (γ ) = γ (20)
π
erfc  γ Θ 2  ≈ 1
1
(21)
 
( ) (
exp γ 2 ≈ exp Θ γ 2 ≈ 1 ) (22)
12
2. BACKGROUND
Substituting Equations 20, 21 and 22 into 19 leads to Eq. 23:
1
 M  2 MO
π  DO M  CO M
γ =  DZ 
(23)
2νC Z∞
2
πD CO M 
MO
2
2
x IOF
=
O
  t = k int t (24)
2 2
( )
2ν DZ C Z∞ 2
p
Eq. 24 is obtain by substituting Eq. 23 into Eq. 14 and states that the penetration
depth of the internal oxidation front xIOF is proportional to the square root of time.
SELECTIVE OXIDATION
As was shown in Section 2.1.1, the driving force for oxidation of metallic elements
depends on the standard free energy of formation. Thus, the selective oxidation
depends on the oxygen partial pressure, the temperature and the thermodynamic
activity of the metal in the alloy. Furthermore, the diffusitivity of the elements in the
alloy, which in turn depend on aspects of the alloy microstructure and composition,
have a strong influence on the kinetics.
All these parameters allow to control the selective oxidation of an alloy component in
order to form a protective oxide layer. However, this process is complicated
(impaired) by, formation of transient and mixed oxides and internal oxidation; cf.
Sections 2.1.1 and 2.2.5.
Selective oxidation of elements that form a slowly growing stable oxide layer is the
basis for corrosion/oxidation protection of alloys used at high temperature [4]. Three
elements are considered to form protective scales, Si, Al and Cr. From these three,
the best protection is provided by Al when the temperature exceeds 800°C and water
vapor is present [1].
2.2. HIGH TEMPERATURE COATINGS
The conditions under which high temperature coating (HTC) operate, the
components comprising the HTC system and aspects related to the failure of the
HTC system, will be discussed in this section.
13
2. BACKGROUND
2.2.1. HIGH TEMPERATURE ENVIRONMENT
The operation environment of turbine engines is characterized by: high temperature

and pressure, plus the presence of oxidizing species and solid particles (aero) in the
atmosphere [1, 2].
Due to these operation conditions, materials used in turbine components need to

withstand: thermally induced fatigue, creep damage, oxidative/corrosive degradation
and erosive wear. These degradation processes limit the operation temperature, and
hence have an impact on the power generation efficiency of the turbine [3].
The enhancement of high temperature strength of super-alloys has lead to a

reduction in their oxidation/corrosion resistance [1]. In order to produce components
that can withstand more severe conditions for longer times, coating systems that
provide thermal insulation and enhanced oxidation/corrosion resistance are required.
2.2.2. THE HTC SYSTEM
The function of the HTC system is to provide protection to the super-alloy against the
operation environment. There have bean three fundamental developments
concerning the materials used in high temperature environments [23,4]:
(I) Optimization of superalloy high temperature strength and the coating

corrosion/oxidation resistance.
(II) Improve casting technologies that have lead to the production higher creep
resistance components.
(III) Development of technologies that allowed coating of complex geometry

components.
The high temperature coating is composed by a series of layers of different materials

with different functions see Figure 4.
The top layer is the thermal barrier coating (TBC). This is a ceramic layer made of
Zr2O3 stabilized with Y2O3. The function of the TBC is to thermally insulate the
underlying layers and the substrate from the environment.
The second layer is also a ceramic and is composed mainly of Al oxide. This layer is
not deposited, but it is formed and grows during the deposition of the TBC and during
14
2. BACKGROUND
operation. The function of the thermally grown oxide (TGO) is to prevent the
oxidation of the underlying substrate.
Figure 4: Schematic illustration of the High temperature coating (HTC).
The third layer shown in Figure 4 is the bond coating (BC). This metallic alloy, is
corrosion/oxidation resistant due to its ability to (re)form the TGO under operation
conditions. The two main functions of the BC are to maintain together the TBC and
the superalloy and to serve as a reservoir of Al.
2.2.3. SUPERALLOY
Figure 5: Nickel aluminum phase diagram. Taken from Ref. 1
15
2. BACKGROUND
Superalloys have evolved over the years to optimize high temperature strength,
creep and fatigue resistance at the expense of corrosion/oxidation resistance. This
has led to the development of nickel based superalloys that are able to operate at
80% of their melting point [1].
Superalloys are essentially a γ-Ni matrix hardened by γ’-Ni3Al precipitates. As

indicated in Figure 5, both phases have face centered cubic structure. The slow
growing cubic (coherent) γ’-Ni3Al precipitates are formed by thermal treatment of the
superalloy, commonly after bond coating deposition. This heat treatment comprises:
(i) solution at 1150°C for 2 hours and (ii) precipitation at 850°C for 24 hours [1].
2.2.4. THE BOND COATING
The bond coating (BC) connects the ceramic TBC to the superalloy and serves as an
aluminum reservoir. In order for an alloy to be used as a bond coating, it must be
able to: (i) form a thermodynamically stable, protective and slow growing oxide scale,
(ii) avoid phase transformations in the BC during operation, (iii) accommodate the
strains experience by the TBC and the superalloy upon thermal cycling, (iv) endure
creep damage and thermal fatigue.
In order to comply with the first requirement, sufficient Al has to be supplied to the
TGO. Oxide maps such as the one shown in Figure 6, have been constructed for
different temperatures and alloy systems, in order to aid the design of alloys that form
protective TGO’s.
There are two types of bond coatings: diffusion and overlay. In both cases the idea is
to increase the aluminum concentration at the component surface.
Diffusion coatings can either be formed by inward aluminum diffusion into the super-
alloy or by outward nickel diffusion. Ni-Al compounds have poor solubility of other
elements. Hence, there is a strong interdependence between the bond coating and
the super-alloy composition. This limits both oxidation/corrosion resistance and the
mechanical properties of diffusion bond coatings [1,3].
Overlay coatings give the possibility of tailoring the properties of the BC to the
environmental conditions with much less restrictions as compared to diffusion
coatings. Overlay coatings are comprised of a γ-Ni and/or β-NiAl phase(s), and their
chemical components are: MCrAl-RE, where M can be iron, nickel, cobalt or a
combination of Ni and Co and RE is a reactive element such as Y, Hf, Ce or Zr [1].
16
2. BACKGROUND
Figure 6: External and internal oxides formed after isothermal oxidation of NiCrAl alloys. Taken from
Ref. 1.
There are two widely used techniques for the deposition of overlay BC’s: spraying
and evaporation. Plasma spray can be carried out with high or low pressure. When
the process takes place at low pressure (LPPS) some technical advantages can be
obtained, such as:
(I) The amount of Al loss by oxidation is reduced.
(II) Since the residence time is longer, powders attain higher temperatures. In
addition there is no convective cooling, hence the surface temperature of the
substrate is higher. Both these conditions aid to reduce BC porosity.
(III) Bond strength is enhanced due to higher particle velocity.
ROLE OF DIFFERENT ALLOYING CONSTITUENTS IN THE BC
Every element of an NiCoCrAlY alloy has an specific function. Ni provides the

strength. Co provides strength plus thermal stability, i.e. a NiCrAl alloy has a β-NiAl/γ-
Ni structure at the operating temperature, but upon cooling β−NiAl transforms into
α−NiCr and γ−Ni transforms into γ’-Ni3Al. Adding Co to the alloy prevents these
transformations [1].
17
2. BACKGROUND
Cr improves hot corrosion resistance and promotes the selective oxidation of Al by

reducing the oxygen diffusivity in the BC. A drawback is that Cr has a negative effect
on the alloy creep resistance [1, 4].
Low additions of Y, improve the adhesion between the alloy and the oxide scale.
These elements prevent segregation of impurities such as S and C to the BC/TGO
interface. The mechanism is not well understood. However, it has been observed,
that Y-oxides dissolve at high temperature and metallic Y segregates to the surface,
implying that Y-sulfides should dissolve also [2, 14, 29]. Another relevant observation
is that Y-pegs can mechanically enhance BC/TGO fracture toughness [1, 30].
Finally, the function of Al is to improve oxidation resistance, by forming a protective

and slow growing alumina layer. In addition, it increases the coating toughness and
refines the coating microstructure. Microstructure refinement increases the number of
Al diffusion paths to the surface, enhancing the formation of the alumina scale. A
drawback is that, with increasing aluminum content the melting point of the alloy
decreases [1, 6, 31].
2.2.5. THERMALLY GROWN OXIDE
Generally, the thermally grown oxide forms while other steps on the component
manufacturing process are in progress [1]. Since the growth rate of the TGO controls
the HTC durability [3, 20-22, 30], more attention is now paid to the initial structure of
the TGO and pre-treatments are design to alter the mature TGO structure.
TGO FORMATION
The structure of the TGO depends on the oxidation temperature, oxidation time and
the oxygen partial pressure. As the temperature increases process kinetics are
enhanced and the stability of oxides is reduced (increased oxygen equilibrium
pressure), allowing selective oxidation of the more reactive elements to take place in
a controlled manner. Diffusion of metal cations and oxygen anions takes time, hence
longer oxidation time leads to thicker oxide layer. At lower partial oxygen pressure,
oxide formation is hindered allowing Cr evaporation and Y migration to the surface
[21].
18
2. BACKGROUND
Figure 7: Oxide phase present in the TGO.
The presence of a native oxide lowers the oxygen partial pressure underneath this
layer. Hence, its presence can reduce Cr evaporation and Y migration towards the
surface [21]. Figure 7 shows a schematic representation of the TGO structure.
TRANSITION ALUMINAS
Transition aluminas (γ and θ) form epitaxial films on β-NiAl. The orientation relation
makes their nucleation energetically favorable over the randomly oriented alpha
alumina at temperatures below 1100°C [9]. The precise temperature depends on the
alloy composition.
It has been observed that the orientation relation between the transition aluminas and
the substrate is lost, after the transformation to α-alumina [7]. The θ−alumina to
α−alumina transformation is enhanced as temperature increases [17]. Also, as
oxidation time increases, θ-alumina transforms into α-alumina. Then, the presence of
transition aluminas (γ, δ and θ) is only reported at the early oxidation stages for
temperatures bellow 1100°C [7-9].
The transformation sequence γ-δ-θ-α occurs for pure alumina and is studied by
differential scanning calorimetry [35]. However, this transformation sequence does
not occur upon isothermal oxidation of NiAl as shown by Pint et al. [27].
There are two basic structural differences between the α-alumina and the transition
aluminas: (i) α-alumina has an hcp oxygen sublattice, while transition phases exhibit
a slightly disordered fcc sublattice, (ii) In α-alumina, the Al cations occupy only
19
2. BACKGROUND
octahedral sites, while in transition aluminas, they are distributed between octahedral
and tetrahedral sites.
The ratio between octahedral to tetrahedral occupied sites (i.e. a spinel oxide has a
ratio of 2) in transition aluminas is as follows: for γ and δ aluminas this ratio is
between 1 and 2, and in θ-alumina is exactly one. The occurrence of tetrahedrally
coordinated Al cations is the reason for the stabilization of the fcc oxygen sublattice
[10, 12].
Grabke et al. concluded that transition aluminas have a large component of outward
growth due to the high diffusivity of Al cations, while the α-alumina grow by inward
diffusion of oxygen in NiAl and NiFeAl alloys [9]. Due to the outward growth of
transition aluminas the oxide exhibits a needle like surface morphology. This does
not mean that the surface morphology of the transitional phase can be used as an
indicator of its presence, but it can be considered as evidence of past existence. It
also has been seen that the alumina transformation from θ to α is fast when it grows
on top of the γ’-Ni3Al phase and slow when it grows on top the β-NiAl phase. This is
said to be due to the larger amount of Al, which gives the β phase the ability to
sustain outward growth for longer times [20].
De Wit et al. [32] observed that the addition of Y to β-NiAl delays the transformation
from θ−alumina to α−alumina, since it retards oxygen diffusion and at the same time
it enhances Al diffusion through the oxide layer, although this theory is not proven as
discussed by Pint [33]. Grabke showed that the presence of Cr enhances the growth
rate of α-alumina, but has little effect on the growth of θ. He also observed that as the
content of Cr increases, the transition time from θ to α decreases [8].
Rhüle et al. [27] formed a γ-alumina layer by isothermal oxidation at 800°C and
observed the transformation to α-alumina without formation of θ-alumina, while
Doychak formed oxide layers exclusively composed of θ-alumina on top of the same
substrate after ten hours of isothermal oxidation at 800°C. The difference between
the experiments is attributed to what can be called a ‘nucleation step’; Rhüle oxidized
his samples for ten minutes at 870°C, while Doychak oxidized his samples at 1100°C
[28].
The presence of transitional aluminas (γ, δ, θ) can promote the formation larger
alumina grains as observed by Nijdam et al. [30]. This can reduce the mature TGO
20
2. BACKGROUND
growth rate, since diffusion of atomic oxygen through grain boundaries is considered
the main transport mechanism.
SPINEL OXIDES
(Ni,Co)(Al,Cr)2O4 spinel forms on top of the α-Al2O3 layer, due to the lack of
aluminum to sustain the exclusive formation of alumina. Initially, pure oxides are
formed and is commonly argued that, the following formation of mixed oxides occur
by solid state reactions between NiO or CoO and Al2O3 or Cr2O3 [40].
Spinel formation has been studied by Pettit [43] at 1200-1500°C in diffusion couples
of polycrystalline samples of pure NiO and Al2O3. The kinetics of the transformation is
described by a parabolic relation.
Hence, spinel formation by solid state reaction is a diffusion controlled process. The
parabolic growth constant is largely dependent on temperature at which the reaction
takes place, but independent from oxygen partial pressure. The growth constant
increases by three orders of magnitude from 1200 to 1400°C and is controlled by
aluminum diffusion in this range [43].
YTTRIUM ALUMINATES
Y2O3 is the first oxide to form since Y is the most reactive element. After Y, Al is
oxidized and a closed alumina layer forms. As the process continues both of
elements (Al and Y) are driven towards the surface by the change in free energy
associated to oxide formation. The formation of Y-aluminates at the BC/TGO
interface is commonly explained by the solid state reaction between Y and Al oxides.
When the driving force decreases or the kinetics are reduced (i.e. by reducing the
temperature), less segregation of Y to the surface takes place and consequently the
density of Y-aluminates at the BC/TGO interface decreases. When the formation of
the protective alumina layer is hindered at low oxygen pressure, high Y migration to
the surface is observed.
Impurities such as S and C may segregate to the BC/TGO interface, internal pores
surfaces and grain boundaries. The idea is that, by segregation to these locations,
the impurities have the opportunity to reduce their surface energy. Y prevents the
detrimental effects of the impurities by preventing their migration to the BC/TGO
interface. If S segregates to the BC/TGO interface, it decreases the TGO adhesion,
21
2. BACKGROUND
because the interfacial covalent-ionic Ni-O bonds are replaced by weaker ionic-
covalent S-Al bonds [21, 22, 30 and 49].
2.2.6. FAILLURE OF THE SYSTEM
Lifetime is determined by intrinsic and extrinsic processes. Extrinsic degradation

processes are related to particle impact and high temperature corrosion. Intrinsic
degradation processes arise from misfit strains between the different layers.
The misfit strains develop due to differences in the thermal expansion coefficient as
well as from phase transformations and interdiffusion.
The TBC can easily accommodate misfit strains because of its porosity. This strategy
can not be used for the BC or the TGO because to serve their function they need to
be dense [49]. No large difference exists between the thermal expansion coefficients
of the BC and the substrate. Only between the TGO and the BC an important
difference between thermal expansion coefficients exists. Therefore, failure is most
probable to occur along the TGO/BC interface.
The oxide layer grows at high temperature and at the oxidation temperature only
growth stresses are present. The growth stresses in an oxide layer are related to: (i)
volume differences between the oxide layer and the alloy from which it forms, (ii)
epitaxial relations between oxide layer and alloy, (iii) compositional changes in the
alloy or oxide layer, (iv) recrystallization and (v) mixed-oxide formation within the
oxide layer.
If the volume difference is assumed to be the main source of stress, then the sign of
the stress is given by the ratio between the molar volume of the oxide and the molar
volume of the metal vMO/vM. If this ratio, the so called Pilling-Bedworth ratio is larger
than 1, then compressive stresses develop in the oxide scale. This applies when the
oxide layer grows by inward oxygen diffusion. When the oxide layer grows by
outward diffusion no growth stresses result from this mechanism [4].
Upon cooling the thermal contraction of the metallic BC is larger than the thermal
contraction of the oxide layer. Hence, the thin oxide layer is forced to match the BC
reduction. Forced contraction of the oxide generates inplane compressive stresses.
The Young´s modulus EMO and the Poison´s ratio νMO of alumina are 340 GPa and
0.28, respectively and the difference between the thermal expansion coefficient of
22
2. BACKGROUND
the BC (αM) and the TGO (αMO) equals -8x10-6. The stress in the oxide layer follows
from:
E MO
σ MO = (α MO − α M )(∆T ) (25)
1 − ν MO
This inplane stress is around -4 GPa for the relevant temperature change
( ∆T ≈ 1000°C). Consequently, although the oxide layer may be relatively thin at the
crit
end of the life cycle ( x MO = 5-7 µm), the energy store in it is large.
As the oxide layer grows, the elastic strain energy per unit of interface area G stored
in this layer increases, since it is a function of the oxide layer thickness [49]:
G=
(1 − ν MO ) σ 2 x MO (26)
MO
E MO
In Eq. 26 x MO is the scale thickness. Delamination of the TGO occurs when the
strain energy per unit of interface area (Jm-2) exceeds the TGO/BC interface
toughness. At a thickness of 6 µm the stored energy is in the order of 200 Jm-2 [49
and 55].
crit
Intrinsic failure mechanisms have a characteristic critical TGO thickness x MO , which
depends on BC composition and microstructure as well as on thermal cycling history.
23
3. EXPERIMENTAL
3. EXPERIMENTAL
A description of the experiments performed and the characterization techniques used

to study the changes that had taken place upon oxidation of the bond coating are
described in the following sections.
3.1. MATERIALS
A Ni-23Co-17Cr-12.5Al-0.3Y (wt %) bond coating was plasma sprayed at low

pressure (LPPS) on top of stainless steel substrate. The bond coating with a
thickness of 0.7 mm was removed from the substrate and cut into disks with a
diameter of 10 mm using spark erosion.
Samples were grinded using every SiC paper until P4000 roughness, cleaned
ultrasonically in ethanol and dried with compressed nitrogen prior to the oxidation
treatments.
3.2. FURNACE
The samples were isothermally oxidized in a horizontal alumina tube furnace (Lenton
PTF 16/75/610). The oxidation treatment was carried out at a constant oxygen partial
pressure of 101 kPa, obtained by blowing pure oxygen (99.998 vol% O2) with a flow
rate of 100 ml/min through an alumina tube with an inner diameter of 100 mm. A heat
treatment was also performed under Ar with 5 vol.% H2. The gas mixture flow rate
was again 100 ml/min.
3.3. REACTION CHAMBER
Low oxygen partial pressure experiments were performed in a Ultra High Vacuum
chamber with a base pressure below 1x10-7 Pa, coupled to an instrument for XPS
analysis (base pressure below 1x10-8 Pa), cf. Section 3.4.
The samples were prepared as described for the high pressure experiments (cf.
Section 3.1.). A thermocouple was spot welded to the bottom of the sample in order
to monitor the specimen temperature. The segregation experiments were carried out
at the reaction chamber base pressure.
24
3. EXPERIMENTAL
3.4. XPS
The elements present at the oxide surface were identified by X-Ray Photoelectron
Spectroscopy (XPS), using non-monochromated Mg Kα radiation (1253.6 eV).
Spectra were recorded with a PHI 5400 ESCA instrument. The pass energy of the
spherical capacitor analyzer was set as 35.75 eV for, Al, Cr, Ni, Co, C and O and to
71.55 eV for, Y and S. the energy was incremented in 0.2 eV steps and the detection
angle was set to 45° with respect to the sample surface.
From the recorded spectra, the positions of the peaks were determined after satellite
subtraction and charge correction by repositioning the carbon peak at 284.80 eV [57].
Photoelectron peak positions were determined by curve fitting to a Gauss-Lorentz
distribution and using an iterated Shirley background subtraction [58]. Auger
electrons peak positions were determined from the second derivate of the recorded
spectra [58].
3.5. XRD
X-Ray Diffraction (XRD) measurements were performed using a BRUKER AXS D8,
diffractometer equipped with a Co anode. These measurements were used to identify
the crystalline phases present.
The divergent beam emitted by the X-ray source was converted into a parallel beam
(laminar) by using a polycap. The angle of incidence θ was fixed to 5° while the gas
field detector 2θ range was rotated from 10 to 110° at 0.034° 2θ steps.
The recorded diffractogram was plotted as total counts versus the inter-planar
distance d and analyzed using the ICDD database [PDF2].
3.6. SEM
The morphology, structure and thickness of the oxide layers were studied using a
JEOL JSM 6500F Scanning Electron Microscope (SEM), equipped with an Autrara
backscatter electron detector and a Noran-Pionner 30 mm2 Si(Li) detector for Energy
Dispersive X-Ray Spectroscopy (EDS).
The cross-sections of the samples were prepared by coating the oxide layer surface
with a sputtered thin film of gold. Then, the sample was embedded in a epoxy resin
and cut perpendicular to the scale surface with a diamond saw. The cross-section
surface was grinded with every SiC paper until P4000 roughness. After grinding, the
25
3. EXPERIMENTAL
samples were cleaned ultrasonically in ethanol and dried with compressed nitrogen.
To obtain high resolution images, a second thin film of gold was sputter onto the
cross-sections, next the cross sections were polished with a JEOL precision ion
polishing system for 16 hours, using a 5 keV Ar+ beam. The error in the microscope
magnification was less than 3% as determined with a calibration sample.
3.7. EPMA
Electron Probe X-Ray Micro-Analysis (EPMA) was carried out in regions of 100x50
µm containing the oxide layer and the under laying substrate using a 2x2 µm grid.
The measurements were performed with a JEOL JXA 8900R microprobe using an
electron beam with energy of 15 keV and a beam current of 50 nA employing
Wavelength Dispersive Spectrometry (WDS) for Ni, Co, Al, Cr, Y, Fe and Si.
Carbon and oxygen were measured separately by recording the full spectra of the C-
Kα and O-Kα peaks using multi-layered analysing crystals (LDEC or LDE1). The
electron beam had an energy of 15 keV and a beam current of 500 nA.
The composition at each analysis point of the selected area was determined using
the X-Ray intensities of the constituent elements after background correction relative
to the corresponding intensities of reference materials. The obtained intensity ratios
were processed with a matrix correction program CITZAF [39]. For C and O the last
procedure was performed by determining the area of the spectra recorded. As
standard materials Fe3C and YAlO3 were used for calibration of the C-Kα and O-Kα
intensities, respectively.
The data from the quantitative measurement and the spectroscopy were recalculated
with the PROZA96 algorithm of Bastin and Heijligers [39] taking the experimental
intensity ratios as input.
3.8. EXPERIMENT FLOW CHART
A summary of the oxidation experiments performed with the free standing as-spayed
NiCoCrAlY bondcoating (cf. Section 3.1.) is presented in Flow chart 1.
The experiments were performed at low pressure inside a high vacuum chamber and
at atmospheric pressure in the tube furnace. Low pressure experiments were
performed for the oxidation times listed in the flow chart. After reaching the oxidation
time, the surface was analysed using XPS.
26
3. EXPERIMENTAL
Atmospheric pressure experiments were performed in oxidizing and in reductive

atmospheres, cf. Section 3.3. The treatment in the reductive atmosphere was
intended to reveal the changes induced by heating without sample oxidation.
Experiments at high oxygen partial pressure were performed at four different

temperatures for ten minutes. All sample were then oxidized for 16 hours at 800°C
and then for 96 hours at 1100°C. By performing the described oxidation treatments,
the effects that short term pre-oxidation treatments have on the mature oxide scales
can be studied.
Flow chart 1: Oxidation experiments performed with a free standing as sprayed NiCoCrAlY bond coating
alloy.
27
4. RESULTS
4. RESULTS
The experimental results will be presented as follows: first, the initial conditions of the
NiCoCrAlY bond coating. Next, the changes of the BC microstructure induced by
heating in a non-oxidizing atmosphere. Finally, the oxide formation and
microstructure development upon isothermal oxidation in order of increasing
oxidation time.
4.1. INITIAL CONDITIONS
The composition of the NiCoCrAlY alloy is given in mass fractions in Table 1. The
tabulated composition was determined from the EPMA results, cf. Section 3.7. The
distribution of elements in the BC is displayed in Graphs 9a and 9b. The average of
the metallic elements include every measured spot (i.e. 1250 spots) while in the case
of oxygen spots above 0.5 wt% where left out (pores).
Table 1: Mass fractions of the NiCoCrAlY alloy components (wt%) as determined with EPMA.
Al Y Cr Co Ni
Average 12.6 0.4 17.4 24.9 44.6
3σ 0.8 0.1 0.8 2.6 2.3
Al Cr Co Ni
50
40
Mass Fraction (wt%)
30
20
10
0
0 10 20 30 40 50
Depth (µm)
Graph 9a: Cr, Al, Ni and Co depth profile determined with EPMA.
28
4. RESULTS
Y O #
1 5
0.8 4
Number of Y-oxide spots

Mass Fraction (wt%)
0.6 3
0.4 2
0.2 1
0 0
0 10 20 30 40 50
Depth (µm)
Graph 9b: Yttrium and oxygen depth profile determined with EPMA. The x signs denote the number of
Y-oxide rich spots (right side axis).
The Y distribution in the bond coating as a function of depth is constant as evidenced

in the profile shown in Graph 9b. Y-oxide rich zones where not observed in EPMA
measurements. An Y-oxide rich zone was defined as a zone that contain Y in excess
of 1 wt% and enough oxygen after subtracting oxygen adsorbed at the sample
surface (0.24 wt%) to oxidize all the Y present.
The amount of oxygen adsorbed at the sample surface was determined from the
measurements of the as-sprayed BC, since in this sample the least internal oxidation
is expected. The average oxygen concentration in the as-sprayed BC equals 0.24
wt%, if the points containing more than 0.5 wt% (pores) are not taken into account
which is about20% of the measured spots.
The structure of the as deposited BC can be observed in Figure 8. Al-poor

precipitates are present as needles inside Al-rich zones as well as small grains.
According to the XPS analysis the samples at the beginning of every treatment are
covered with an oxide layer of less than 10 nm, which consists of: Al, Cr, Co and Ni
oxides. The composition of this native oxide is given in Table 2. Y is below the
detection limit and C was identified as the main surface contaminant. C is not taken
into account for composition analysis, but its photoelectron peak is used for charge
correction (cf. Section 3.4).
29
4. RESULTS
Figure 8: Backscatter image of the of the sample surface prior to heat treatment.
Table 2: Composition of the sample surface prior to heat treatment determined with XPS and binding
energy (BE) of the observed photoelectrons.
PEAK Al2p C1s O1s Cr2p Co2p Ni2p Y3d

STATE Al Al-O C O-M Cr-O Co-O Ni-O Y-O
BE (eV) 72.0 73.9 284.8 530.3 576.7 780.8 855.9 -
AS
C (at.%) 10.4 19.7 - 57.8 4.2 2.6 3.1 -
4.2. 10 MINUTES ISOTHERMAL HEATING IN Ar-H2
Upon heating the BC in Ar with 5 vol.% H2 at 1100°C for ten minutes, the γ-(Ni,Co)
phase initially present dissolves (Fig. 9). This observation is an indication of the
meta-stable nature of the as-deposited structure. The occurrence of an initial meta-
stable structure is caused by the high cooling rate associated with deposition method
(i.e. Low Pressure Plasma Spray). During sample introduction ingress of air into the
furnace caused the oxidation of Y and Al.
From backscatter electron images it can be seen that upon heating the initial needle
like precipitates dissolved (cf. Figs 8 and 10). Two main phases made up the
structure: the dark gray phase is β-(Ni,Co)(Al,Cr) and the light gray is γ’-
(Ni,Co)3(Al,Cr)/γ-(Ni,Co).
30
4. RESULTS
Figure 9: X-ray diffractogram of the NiCoCrAlY alloy prior to heat treatment (bottom) and after 10
minutes of isothermal heating at 1100°C under an Ar-H2 atmosphere (top).
Figure 10: Backscatter image of the of the sample surface (grinded) after heating for 10 minutes at
1100°C in an Ar-H2 atmosphere, showing the resulting structure. The light gray is γ’-(Al/Cr)(Ni/Co)3 and
dark gray is β-(Al/Cr)(Ni/Co).
31
4. RESULTS
4.3. ISOTHERMAL HEATING UNDER VACUUM
After heating the samples to 1000°C at low oxygen partial pressure, XPS analysis
(see table 3) indicate that the TGO growth is hindered and Y is observed in the
surface after 10 minutes. As a function of time the amount Y and S at the surface
remain constant. Furthermore, from the sulfur 2s binding energy it can be said that it
is present as a Metal-S compound. Al in the surface is partially oxidized while the
other less reactive elements remain in the metallic state. The summary of these
observations can be found in Table 3.
Table 3: Composition of the sample surface determined with XPS and binding energy (BE) of the
-7
observed photoelectrons. Sample isothermally heated at an oxygen partial pressure below 1x10 Pa.
PEAK Al2p S2s C1s O1s Cr2p Co2p Ni2p Y3d

STATE Al Al-O S-M C O-M Cr Co Ni Y-O
BE (eV) 71.9 73.8 225.3 284.8 530.2 573.6 777.6 852.2 157.9
10 min
C (at.%) 10.7 5.8 0.5 - 35.9 2.4 3.0 11.7 30.1
BE (eV) 71.7 - 225.3 0* 530.2 573.5 777.6 852.3 157.7
30 min
C (at.%) 19.2 - 0.6 - 24.0 1.7 3.9 17.2 33.4
BE (eV) 71.9 - 225.4 0* 530.3 573.4 777.6 852.3 157.7
60 min
C (at.%) 18.2 - 0.6 - 25.0 1.4 4.2 19.7 31.0
BE (eV) 71.6 73.0 225.4 284.8 530.0 573.2 777.3 852.0 157.4
240 min
C (at.%) 15.0 3.1 0.5 - 32.5 1.1 3.6 15.9 28.4
*Substraction of 0.5 [eV] for charge correction
4.4. 10 MINUTES ISOTHERMAL OXIDATION
The BC was isothermally oxidized for ten minutes at 900, 1000, 1100 and 1200°C.
The surface changes were studied using XPS, bulk changes were study with XRD
and the TGO structure was analyzed using electron backscatter images in
combination with EDS. Table 4 shows the surface composition at the four different
temperatures. The highest amount of Y at the surface is observed at the highest
temperature (i.e. 1200°C); the same holds for the other less reactive non-protective
elements (i.e. Cr, Ni, Co). The least amount of non-protective elements is observed
in the surface of the TGO grown at 1000°C.
Table 4: Composition of the samples surface isothermally oxidized for 10 minutes at an oxygen partial
5
pressure of 1x10 Pa determine from XPS.

STATE Al-O S C O-M Cr-O Co-O Ni-O Y-O
900°C C (at%) 40.1 0.0 - 59.4 0.0 0.4 0.1 0.0
1000°C C (at%) 46.3 0.1 - 53.4 0.0 0.3 0.0 0.0
1100°C C (at%) 41.2 0.0 - 57.9 0.2 0.5 0.2 0.1
1200°C C (at%) 38.9 0.0 - 57.2 0.4 0.4 0.3 2.9
32
4. RESULTS
On the basis of the diffractograms recorded of the oxidized BC (Figure 11), The TGO
grown at 900 and 1000°C consist of metastable (γ,θ)-Al2O3. No inclusions were
observed in the backscatter electron images of cross-sections, Figs. 12 and 13.
However Y2O3 is formed internally in the BC.
Figure 11: Diffractogram of the NiCoCrAlY alloy prior to heat treatment (bottom), after 10 minutes of
isothermal oxidation at 900°C (middle), after 10 min of isothermal oxidation at 1000°C (top).
The TGO grown at 900°C has an average thickness of 180 nm (Fig. 12a) while the
average thickness for the TGO growth at 1000°C is 330 nm (Fig. 13). The reported
average thickness was calculated from backscatter electron images using image
analysis software (photoshop).
Micron 1 for every EPMA depth profile is the first measured line with an overall mass
fraction above 80 wt%. In Graph 10a it can be seen that only the first micron of BC
the composition is altered, compared to the as-deposited state. This observation can
be related to NiO nodules at the sample surface. In Graph 10b it can be seen. Y-
oxide can be found at a depth of 20 µm.
After ten minutes of isothermal oxidation at 1100°C a dense TGO consisting of α-

Alumina (Figs 14 and 15) is formed. Internal oxidation of Y is also observed. The
average thickness of the scale determine from Figure 8 is 330 nm.
33
4. RESULTS
Figure 12: Backscatter electron image of the cross section of the bond coating isothermally oxidized for
10 min at 900°C. (a) oxide layer composed of alumina and (b) actual oxide layer formed. Further
characterization of the composition of the top layer is required.
34
4. RESULTS
10 min at 1000°C.
Al Cr Co Ni
50
40
Mass Fraction (wt%)
30
20
10
0
0 10 20 30 40 50
Depth (µm)
Graph 10a: Ni, Co, Cr and Al depth profiles of the cross section of the NiCoCrAlY alloy isothermally
oxidized for 10 minutes at 1000°C.
35
4. RESULTS
O Y #
1 10
0.8 8
Number Y-oxide spots

Mass Fraction (wt%)
0.6 6
0.4 4
0.2 2
0 0
0 10 20 30 40 50
Depth (µm)
Graph 10b: Y and oxygen depth profiles of the cross section of the NiCoCrAlY alloy isothermally
oxidized for 10 min at 1000°C. x signs indicate the number of Y-oxide rich spots at a given depth.
Figure 14: X-ray diffractogram of the NiCoCrAlY alloy prior to heat treatment (bottom), after 10 minutes
of isothermal oxidation at 1100°C under an O2 atmosphere (middle), after 10 min of isothermal oxidation
at 1200°C (top).
36
4. RESULTS
10 min at 1100°C.
10 min at 1200°C.
37
4. RESULTS
Al Cr Co Ni
50
40
Mass Fraction (wt%)
30
20
10
0
0 10 20 30 40 50
Depth (µm)
oxidized for 10 minutes at 1200°C.
Y O #
5 25
4 20
Mass Fraction (wt%)
3 15
2 10
1 5
0 0
0 10 20 30 40 50
Depth (µm)
Graph 11b: Y and oxygen depth profiles of the cross section of the NiCoCrAlY alloy isothermally
oxidized for 10 min at 1200°C. x signs indicate the number of Y-oxide rich spots at a given depth.
38
4. RESULTS
For the highest temperature (i.e. 1200°C) the TGO consists mainly of stable α-Al2O3,
but is porus and non-protective spinel (Ni,Co)(Al,Cr)2O4 oxides are present at the top.
YAP (YAlO3) and YAG (Y3Al5O12) oxides identified by XRD (Figure 14) are observed
at the BC/TGO interface along with large Y2O3 particles bellow the scale (Fig. 16).
The average thickness of this TGO is 620 nm.
In Graph 11a it can be seen that the depletion region extends around 3 µm into the
BC for every element. The depletion is related to the formation of non-protective
(Ni,Co)(Al,Cr)2O4 spinel oxides at the sample surface. At 1200°C Y-oxides are found
until 3 µm underneath the surface. The penetration depth of oxygen is defined as the
depth at which the mass fraction of oxygen drops below 1 wt%, in this case this is
observed to occur at 3 µm also (cf. Figure 11b). This criterion is adopted to determine
the penetration depth of oxygen.
4.5. 60 MINUTES ISOTHERMAL OXIDATION
The surface composition of samples oxidized for one hour at 1000 and 1100°C is
shown in Table 5. Y is observed only at 1100°C. Taking into account the surface
composition after 10 minutes at 1100°C, it can be said that Y can diffuse through this
TGO and reach the surface (compare Y concentration at 1100°C for 10 and 60 min).
The TGO after one hour of oxidation at 1000°C has an average thickness of 660 nm
and is composed of α and (γ,θ) transition aluminas, Y2O3 is formed internally (Figs 17
and 18). After 60 min oxidation at 1100°C the TGO consists of α-Al2O3 and
(Ni,Co)(Al,Cr)2O4 spinel oxides in the top part. YAP oxides are found at the TGO/BC
interface and large Y2O3 particles can be seen below the TGO (Figs 19 and 20). The
average thickness of the TGO growth at 1100°C is 1570 nm after one hour (Fig. 20).
Table 5: Composition of the sample surface determined with XPS and binding energy of the observed
photoelectrons. Sample isothermally oxidized for 60 minutes at an oxygen partial pressure of 101 kPa.

BE (eV) 74.4 - 284.8 531.3 577.2 780.6 855.7 -
1000°C
C (at.%) 42.7 - - 56.7 0.1 0.3 0.1 -
BE (eV) 74.0 - 284.8 530.8 576.6 780.2 856.0 157.9
1100°C
C (at.%) 41.5 - - 56.3 0.5 0.3 0.2 1.3
39
4. RESULTS
at 1000°C (top).
Figure 18: Backscatter electron image of the cross-section of the bond coating isothermally oxidized for
60 min at 1000°C (top).
40
4. RESULTS
at 1100°C (top).
60 min at 1100°C.
41
4. RESULTS
4.6. ISOTHERMAL OXIDATION AT 800°C
After the 10 minutes of isothermal oxidation at the four selected temperatures (i.e.
900, 1000, 1100, 1200°C) the samples were subjected to a second oxidation period
of 16 hours at 800°C. The follow-up of the changes have been investigated only for
the sample initially oxidized at 1000°C.
After the 16 hours oxidation at 800°C, no further surface enrichment of either Y, Cr,
Co or Ni is observed as can be seen from the XPS results in Table 6.
Table 6: Composition of the sample surface determined with XPS and the binding energy of the
observed photoelectrons. Sample isothermally oxidized at 800°C for 16 hours after 10 minutes of
isothermal oxidation at 1000°C.

BE (eV) 74.7 - 284.8 531.8 576.9 781.0 0.0 0.0
800°C
C (at.%) 40.9 - - 58.5 0.3 0.2 0.0 0.0
Figure 21: X-ray diffractogram of the NiCoCrAlY alloy. Sample isothermally oxidized for 10 minutes at
1000°C (bottom). Sample oxidized for 16 hours at 800°C after 10 minutes of isothermal oxidation at
1000°C (top).
42
4. RESULTS
Figure22: Backscatter electron image of the cross section of the NiCoCrAlY alloy isothermally oxidized
for 16 hours at 800°C after a 10 minutes oxidation at 1000°C.
Al Cr Co Ni
50
40
Mass Fraction (wt%)
30
20
10
0
0 10 20 30 40 50
Depth (µm)
oxidized for 10 minutes at 1000°C initially and then oxidized for 16 hours at 800°C.
43
4. RESULTS
Y O #
10 5
8 4

Mass Fraction (wt%)
6 3
4 2
2 1
0 0
0 10 20 30 40 50
Depth (µm)
Graph 12b: Y and oxygen depth profile of the cross section of the NiCoCrAlY alloy isothermally oxidized
for 10 min at 1000°C initially and then oxidized for 16 hours at 800°C. x signs indicate the number of Y-
oxide rich spots.
The TGO average thickness calculated from Fig. 22 is 345 nm, which is slightly
thicker than after the initial ten minutes of isothermal oxidation at 1000°C. From the
XRD diffractogram and the backscatter electron image of cross-section (Figs 21 and
22), it can be seen that the TGO still consists of metastable (γ,θ)-Al2O3. Y2O3 is
present internally in the BC (Fig. 21).
Graph 12a shows no nickel depletion, although (NiO,CoO) nodules are present at the
surface. Y-oxides are observed until 11 µm bellow the surface as can be seen in
Graph 12b. Oxygen concentration above 1 wt% was measured only in the first
micron.
Hence, it can be said that no changes are observed in the TGO structure after 16
hours of isothermal oxidation at 800°C. However, slow growth of the oxide layer and
some increase of the internal Y oxidation occur.
4.7. ISOTHERMAL OXIDATION AT 1100°C
In order to study the effect of the initial 10 minutes oxidation on the structure of the
mature TGO, the following oxidation treatments were executed. After the two
oxidation treatments, i.e. (i) Isothermal oxidation at the four selected temperatures for
44
4. RESULTS
10 minutes, (ii) Isothermal oxidation for 16 hours at 800°C, the NiCoCrAlY alloy was
oxidized for 96 hours at 1100°C (cf. Section 3.8).
Figure 23: Backscatter electron images of the cross section of the NiCoCrAlY alloy isothermally oxidized
for 96 hours at 1100°C with an initial oxidation of 10 minutes at 900°C.
45
4. RESULTS
Al Y O Cr Co Ni
50
40
Mass Fraction (wt%)
30
20
10
0
0 10 20 30 40 50
Depth (µm)
Graph 13a: Elemental depth profile of the cross section of the NiCoCrAlY alloy isothermally oxidized for
96 hours at 1100°C with an initial 10 minutes oxidation at 900°C. Right side axis applies only for Y. The
dotted lined indicate the approximate position of the TGO/BC interface.
O Y #
5 50
4 40
Mass Fraction (wt%)
3 30
2 20
1 10
0 0
0 10 20 30 40 50
Depth (mm)
Graph 13b: Yttrium and oxygen depth profiles of the cross section of the NiCoCrAlY alloy isothermally
oxidized for 96 hours at 1100°C with an initial 10 minutes oxidation at 900°C. x signs indicate the
number of Y-oxide spots.
46
4. RESULTS
Figure 24: Backscatter electron images of the surface (a) and cross section (b and c) of the NiCoCrAlY
alloy isothermally oxidized for 96 hours at 1100°C with an initial oxidation of 10 minutes at 1000°C. In
24a, dark gray is alumina and light gray are mixed oxides.
47
4. RESULTS
Al Y O Cr Co Ni
50
40
Mass Fraction (wt%)
30
20
10
0
0 10 20 30 40 50
Depth (µm)
Graph 14a: Elemental depth profiles in the NiCoCrAlY alloy isothermally oxidized for 96 hours at 1100°C
with an initial oxidation of 10 minutes at 1000°C. The dotted lined indicate the approximate position of
the TGO/BC interface.
O Y #
5 50
4 40
Mass Fraction (wt%)
3 30
2 20
1 10
0 0
0 10 20 30 40 50
Depth (µm)
Graph 14b: Yttrium and Oxygen depth profile in the NiCoCrAlY alloy isothermally oxidized for 96 hours
at 1100°C with an initial oxidation of 10 minutes at 1000°C. x signs indicate the number of Y-oxide spots
at a given depth.
48
4. RESULTS
The TGO formed on the BC that was initially oxidized at 900°C, achieved an average
thickness of 5.35 µm with a fraction of inclusions ((Ni,Co)(Al,Cr)2O4, pores and Y-
aluminates) of 22%. Both the average thickness and the percentage of inclusions
were determined from Figure 23 using image analysis software.
In Graph 13a the TGO/BC interface can be located at 5 µm. At which point the
oxygen concentration is around 30 wt% (~40 at.%). Oxygen concentration drops
bellow 1 wt% at a depth of 21 µm. This is the oxygen penetration depth (as defined
previously). Y-oxides still can be found until 35 µm bellow the surface; see Graph
13b.
The TGO formed on the BC that was initially oxidized at 1000°C, achieved an
average thickness of 5.33 µm with a fraction of inclusion of 27%. A large amount of
non-protective oxides are observed at the sample surface (cf. Figure 14).
oxygen concentration is around 25 wt% (~30 at.%). The oxygen penetration depth is
19 µm. Although Y-oxides still can be found until 35 µm bellow the surface; see
Graph 14b.
49
4. RESULTS
Figure 25: Backscatter electron images of the cross section of the NiCoCrAlY alloy isothermally oxidized
for 96 hours at 1100°C with an initial oxidation of 10 minutes at 1100°C.
Al Y O Cr Co Ni
50
40
Mass Fraction (wt%)
30
20
10
0
0 10 20 30 40 50
Depth (µm)
Graph 15a: Elemental depth profiles in the NiCoCrAlY alloy isothermally oxidized for 96 hours at 1100°C
with an initial oxidation of 10 minutes at 1100°C. The dotted lined indicates the position of the TGO/BC
interface.
50
4. RESULTS
Y O #
5 50
4 40

Mass Fraction (wt%)
3 30
2 20
1 10
0 0
0 10 20 30 40 50 60
Depth (µm)
Graph 15b: Yttrium and Oxygen depth profile in the NiCoCrAlY alloy isothermally oxidized for 96 hours
at a given depth.
The TGO formed in the sample that was initially oxidized at 1100°C achieved an
average thickness of 5.30 µm with a fraction of inclusion of 30% (Figure 25).
In Graph 15a the TGO/BC interface can be located at 5 µm. At this point the oxygen
concentration is around 20 wt% (~25 at.%). The oxygen penetration depth is 19 µm.
Although yttrium oxides still can be found until 25 µm bellow the surface; see Graph
15b.
The TGO formed in the sample that was initially oxidized at 1200°C achieved an
average thickness of 7.17 µm with a calculated fraction of inclusion of 40%. A large
amount of non-protective oxides are observed at the sample surface (Figure 26).
oxygen concentration is around 25 wt% (~30 at.%). The oxygen penetration depth is
19 µm. Although Y-oxides still can be found until 25 µm bellow the surface; see
Graph 16b.
51
4. RESULTS
Figure 26: Backscatter electron images of the sample surface (a) and cross section (b and c) of the
NiCoCrAlY alloy isothermally oxidized for 96 hours at 1100°C with an initial oxidation of 10 minutes at
1200°C. In 26a, dark gray is alumina, light gray are mixed oxides and lighter regions are Y-oxides.
52
4. RESULTS
Al Y O Cr Co Ni
50
40
Mass Fraction (wt%)
30
20
10
0
0 10 20 30 40 50
Depth (mm)
Graph 16a: Composition depth profiles in the MCrAlY alloy isothermally oxidized for 96 hours at 1100°C
with an initial oxidation of 10 minutes at 1200°C. The dotted lined indicates the approximate position of
the TGO/BC interface.
O Y #
5 60
50
4
Mass Fraction (wt%)
40
3
30
2
20
1
10
0 0
0 10 20 30 40 50
Depth (µm)
Graph 16b: Yttrium and Oxygen depth profiles in the NiCoCrAlY alloy isothermally oxidized for 96 hours
at a given depth.
53
4. RESULTS
4.8. SUMMARY OF RESULTS
The results obtain from the performed experiments are summarized in Tables 7-10.
The tabulated observations are: (i) atomic fraction of Y at the samples surface
determined from XPS measurements, (ii) oxide layer thickness and fraction of
inclusions determined from low magnification backscatter electron images, (iii)
phases identified by XRD and EDS and (iv) oxygen penetration determined from the
EPMA data analysis.
Table 7: Summary of the results for the 10 minutes isothermal oxidation
T (°C) Ext. Oxidation Oxygen

10 min Y-Surface (at.%) Tickness (nm) Phases Penetration (µm)
900 - 185 (γ−θ)-Al2O3
1000 - 330 (γ−θ)-Al2O3 <1
1100 0.1 365 α-Al2O3
α-Al2O3
(Ni, Co)(Al, Cr)2O4
1200 2.9 640 3
YAlO3
Y3Al5O12
Table 8: Summary of the results for the 60 minutes isothermal oxidation

60 min Y-Surface (at.%) Tickness (nm) Phases Penetration (µm)
1000 - 670 (γ−θ)-Al2O3
α-Al2O3
1100 1.3 1520 (Ni, Co)(Al, Cr)2O4
YAlO3
Table 9: Summary of the results for the 16 hours isothermal oxidation

10 min 16 h Y-Surface (at.%) Tickness (nm) Phases Penetration (µm)
1000 800 - 345 (γ−θ)-Al2O3 3
Table 10: Summary of the results for the 96 hours isothermal oxidation

10 min 16 h 96 h Tickness (nm) Phases* Inclusions (vol.%) Penetration (µm)
900 5350 α-Al2O3 22 21
1000 5330 (Ni, Co)(Al, Cr)2O4 27 19
800 1100
1100 5300 YAlO3 30 19
1200 7170 Y3Al5O12 40 19
* The forth phases are present in the four different temperatures
54
5. DISCUSSION
5. DISCUSSION
Pre-oxidation treatments have proved to be and effective way to improve the lifetime
of high temperature coating systems [50]. Commonly, such a thermal treatment is
performed after a vacuum annealing which besides strengthening the substrate,
modifies the as deposited structure of the BC [16 and 17]. The aim of this discussion
will be to propose a pre-oxidation treatment before vacuum annealing of the BC, in
view of enhancing the lifetime of high temperature coating systems.
The discussion of the obtained results will be organized as follows: (i) structure of the
LPPS MCrAlY bond coating, (ii) external oxidation of Al, (iii) formation of
(Ni,Co)(Al,Cr)2O4 spinel oxides, (iv) Internal oxidation of Y, (v) summary of the
NiCoCrAlY alloy oxidation, (vi) TGO criteria in view of achieving an improved lifetime
of the high temperature coating system (cf. Section 2.2.6) and (vii) TGO formation.
5.1. STRUCTURE OF THE LPPS NiCoCrAlY BONDCOATING
Three phases where identified in the as sprayed bond coating, γ-Ni/γ’-Ni3Al which
have a face centered cubic structure, simple cubic β-NiAl and a hexagonal σ-Co
phase which is meta-stable and dissolves readily upon heating for ten minutes at
1100°C in an Ar-H2 atmosphere.
Different authors report the presence of σ-(Co, Cr) tetragonal phase and intermetallic
yttrium compounds (M5Y) located at phase boundaries, besides the γ/γ’ and β phases
[16-18]. The mentioned structures belong to samples that have been deposited by
LPPS but heat treated. The heat treatment is performed to simulate precipitation
hardening of the Ni-based super-alloy. During the thermal treatment the sample is
heated at 1150°C for 2 hours and later at 850°C for 24 hours, under vacuum.
5.2. EXTERNAL OXIDATION OF ALUMINUM
5.2.1.THEMODYNAMICS
At the beginning of the oxidation treatment a 10 nm thick native oxide (NO) layer is
present. The amorphous native oxide transforms to crystalline alumina upon thermal
oxidation [48].
A closed (γ,θ) transition alumina layer is formed after ten minutes of isothermal
oxidation, at 900 and 1000°C [cf. Figures 11-13]. Differentiation between α-Al2O3 and
55
5. DISCUSSION
meta-stable aluminas at the surface was attempted by determination of the Auger

parameter from XPS data [24-26]. Differences were observed only in the Auger
parameter of oxygen for the lowest kinetic energy line (i.e.
O
aKL1L1
( )
= BE O1s + hν − BE KL1L1 . However, the observed differences are too small for
reliable identification.
Low angle XRD measurements were performed to reduce the depth of analysis. This
technique aids in the differentiation of the transition phases (reduction of the BC
signal), but the results did not correlate with the backscatter electron images or
XRD measurements performed at a higher incidence angle.
2Al+1.5O2=a-Al2O3 2Al+1.5O2=g-Al2O3
-750
-800
∆G (kJmol )
-1
-850
-900
800 1000 1200 1400
Temperature (°C)
Graph 17: Standard free energy plot as a function of temperature for α-Al2O3 and γ-Al2O3.
The change in the standard free energy of formation is more negative for α-Al2O3 at
every temperature compared to γ-Al2O3, as shown in Graph 17.
It has been shown that (γ,θ)-Al2O3 has excellent lattice matching with β-NiAl at given
relative orientations, this follows from the studies carried out by Doychack on θ-Al2O3
[12] and by Rhüle on γ-Al2O3 [40]. Good lattice matching decreases the strain energy
at the TGO/BC interface and results in a reduction of the total standard free energy of
formation of transition aluminas to levels bellow that of α-alumina. This makes the
56
5. DISCUSSION
nucleation of transition aluminas thermodynamically possible. The reason for

nucleation of transition aluminas on NiCoCrAlY alloys is assumed to be analogous to
nucleation on β-NiAl.
The transition alumina(s) grows mainly by outward cation diffusion [9]. Alumina
growth by outward aluminum diffusion generates a needle like morphology at the
sample surface and a flat TGO/BC interface (cf. Figures 12 and 13 where the
alumina layer is composed of transition alumina(s)).
At the two higher temperatures (1100 and 1200°C) an α-Al2O3 layer was formed after
ten minutes of isothermal oxidation. This indicates that lattice matching no longer
provides the required reduction of the total standard free energy of formation. It is
also mentioned in the literature that the presence of Y-oxides aids in the nucleation of
α-Al2O3 [22]. The XPS measurements performed show the presence of Y-oxides at
the sample surface if the oxide layer consists of α-Al2O3.
It has been argued by several authors [2-4] that the growth of α-Al2O3 occurs
principally by inward oxygen diffusion. However, some dissident work is also found,
in the article written by K. Messaudi [45] important Al diffusion is suggested. It has
also been shown that as the alumina layer grows, the grain size increases. Hence,
the density of grain boundaries as well as the growth rate decreases [41].
Roughening of the TGO/BC interface can also be attributed to inward growth of the
oxide layer [cf. Figures 15 and 16].
5.2.2. KINETICS
Closed alumina layers of homogeneous thickness at the surface of an as-sprayed BC

can be formed after 10 minutes of oxidation (see Figs 12, 13 and 15). At 900 and
1000°C the oxide layer is made up of transition aluminas (cf. Section 4.4.), the
alumina structure is maintained after 16 hours of oxidation at 800°C (i.e. alumina
remains meta-stable), the oxide layer grows from 330 to 345 nm (cf. Section 4.6). If
the oxidation time is increased to 60 minutes at 1000°C, then the scale is composed
of stable α-Al2O3 and (γ,θ)-Al2O3 (cf. Figs 17 and 18) At higher temperatures only α-
Al2O3 is identified after ten minutes of oxidation (cf. Section 4.4.). Hence, during the
96 hours oxidation at 1100°C only α-Al2O3 should be formed.
Assuming that α-Al2O3 grows exclusively by inward oxygen diffusion, the oxide
growth constant can be related to the oxygen diffusion coefficient through alumina
57
5. DISCUSSION
grain boundaries. Several authors have studied the diffusion of oxygen through alpha
alumina. Most of these experiments where performed with bulk aluminas. These
results, when extrapolated to low temperatures, give diffusion coefficients that are
several orders of magnitude lower than those deduced from isothermal oxidation
experiments [44-46].
From backscatter electron images (see Figs 23-26), the oxide thickness can be
determined and the oxide growth constant can be estimated. Using the diffusion
model presented in section 2.1.2 for external oxidation, the oxygen diffusion
coefficient through the grain boundaries of the alumina layer can be determined, if
the change in oxygen potential is known.
The fraction of inclusions f after 96 hours of oxidation at 1100°C is presented in Table

9, for samples initially oxidized for 10 minutes at 900-1200°C. The thickness of a
clean α-alumina layer x Al 2O3 can be calculated using:
x Al 2O3 = x MO (1 − f ) (27)
where x MO is the determined oxide layer thickness.
Oxide Al2O3
7.5E-17
5E-17
kP (m s )
2 -1
2.5E-17
0
900 1000 1100 1200
Temperature (°C)
Graph 18: Determined parabolic growth constants for imaginary pure alumina layers and for the
determined oxide layer thickness for the different pre-oxidation temperatures (initial 10 minutes).
58
5. DISCUSSION
A common thickness increase of 3.5 µm is observed for samples initially oxidized at

1000 and 1100°C. For samples initially oxidized for ten minutes at 900 and 1200°C
the thickness increase was 4.0 µm, upon oxidation at 1100°C for 96 hours.
Using the determined oxide layer thickness increase upon 96 hours of oxidation at
1100°C, a parabolic growth constant can be calculated (Eq. 10). This constant is in
the order of 2.5x10-17 m2s-1 (4x10-14 gr2cm-4s-1), see Graph 18. This value is 1 order of
magnitude less than the growth constant of α-alumina reported by Grabke [9] at
1100°C on a β-NiAl substrate, e.g. 2.5x10-16 m2s-1 (5x10-13 gr2cm -4s-1). This reduction
can be associated with Y doping of the alumina grain boundaries. As can be seen in
Graph 19, Y reduces the diffusion coefficient of oxygen through alumina grain
boundaries.
Nakagaw a Nakagaw a (Y) Prot (Y) Prot
1E-14
1E-17
D02 (m2s -1)
1E-20
1E-23
1E-26
1000 1100 1200 1300 1400 1500
Temperature (°C)
Graph 19: Diffusion coefficients of oxygen along α-Al2O3 grain boundaries. Data taken from reference
43.
Using Eq. 11 in section 2.1.2 and the change in oxygen chemical potential gradient
given in Refs. 53 and 54, i.e. 75 and 750 kJmol-1, the effective diffusion coefficient of
oxygen through α-Al2O3 can be determined.
59
5. DISCUSSION
The oxygen chemical potential gradient can be approximate as follows based on

local thermodynamic equilibrium at the G/MO interface and the MO/M interface:
 aGas MO 
 O 
∆µ = RT ln MO  (28)
 aO M 
 
Gas Gas
MO MO
aO CO
MO
= MO
(29)
M M
aO CO
The change in oxygen chemical potential ( reduction from 750 to 75 kJmol-1) can be
directly related to the increase in oxidation time, i.e. reduced Al activity and increased
MO
M
oxygen penetration, both lead to a higher CO . The reduction of the driving force
for oxygen diffusion and the decrease in the density of grain boundaries in the oxide
layer (cf. images in Ref. 38), reduce the oxide layer growth rate as oxidation time
increases.
Using the growth constant determined for a pure alumina layer (e.g. 2.5x10-17 m2s-1),
an average grain size of 5x10-7 m and a grain boundary width equal to 1x10-9 nm [56]
δDOGB at 1100°C would be between 7x10-26and 7x10-25 m3s-1, the difference is due to
the different chemical potential gradient of oxygen used. The determined values
enclosed the δDOGB value calculated by Clemens in reference 46, i.e. δDO=1x10-25
m3s-1. Then α-Al2O3 growth at 1100°C can be assumed be controlled by oxygen

inward diffusion through alumina grain boundaries, and Y doping of the alumina grain
boundaries reduce the oxygen inward diffusion (cf. graph 19).
This calculation procedure gives results of the right order of magnitude. Hence,
δDOGB can be calculated for the oxide layer formed on the BC.
After an initial oxidation of 10 minutes at 1000°C the oxide thickness is 0.33 µm (cf.
Table 7), this thickness is not significantly modified by the 800°C oxidation for 16
hours ( cf. Table 9). The scale growth after the complete treatment (see Flow chart in
Section 3.8) is 5.33 µm. Hence, the growth during 96 hours of oxidation at 1100°C is
5 µm (the same growth is observed for the samples initially oxidized at 900 and
1100°C). Applying the same analysis to the sample initially oxidized at 1200°C the
estimated growth at 1100°C after 96 hours of oxidation equals 6.5 µm.
60
5. DISCUSSION
This difference in thickness is due to the density of inclusions in the scale, and
doubles the growth constant. The growth constants are: 3.5x10-17 m2s-1 (7x10-14
gr2cm-4s-1) and 6x10-17 m2s-1 (1x10-13 gr2cm-4s-1) for samples initially oxidized for 10
minutes at 900-1100°C and 1200°C respectively, see Graph 18. The growth
constants were calculated using Eqs. 13 and 15, the values used in Eq. 15 are those
Al O3 Al 2O3
of α-Al2O3, i.e. v MO2 = 25.6 cm3mol-1 and w MO = 16 grmol-1. The determined
values agree with the growth constant calculated from gravimetric experiments
performed by D. Toma [17] on VPS NiCoCrAlY coatings (e.g. 7.8x10-14 gr2cm-4s-1
after 260 hours at 1050°C).
The δDOGB values for the samples initially oxidized for ten minutes at 900-1100°C are:
1.4x10-25 m3s-1 (∆µ=750 kJmol-1) and1.4x10-24 m3s-1 (∆µ=75 kJmol-1).
The δDOGB values for the sample initially oxidized for 10 minutes at 1200°C are:
2.3x10-25 m3s-1 (∆µ=750 kJmol-1) and 2.3x10-24 m3s-1 (∆µ=75 kJmol-1). The presence
of oxide inclusions in the scale can be related to an increase of the oxygen diffusion
coefficient through grain boundaries by one order of magnitude.
5.3. NICKEL, COBALT AND CHROMIUM
Ni (Co) oxide nodules are observed at the sample surface after ten minutes of
isothermal oxidation at every temperature, except at 1200°C (Ni,Co)(Al,Cr)2O4 spinel
oxides are found after ten minutes of oxidation (Figure 27).
Growth of these nodules is a common transient phenomenon of alloy oxidation, if

large differences exist in diffusion and thermodynamic properties of the oxides. For
example, nodules of less stable less protective oxides, have been observed in films
of more stable oxides formed on: β-NiAl, Ni-Cr, Co-Cr, Fe-Cr, Fe-Al, and Fe-Si alloys
[41]. As evidenced by Hindam and Smeltzer [41], NiO nodules grew in the early
exposure periods, these nodules grew preferentially at alloy grain boundaries.
However, as oxidation time was increased these nodules transformed into NiAl2O4
spinel oxides. They proposed that the transformation takes place by solid state
reaction between NiO and Al2O3 [41].
61
5. DISCUSSION
Figure 27: Backscatter electrons image of MCrAlY BC oxidized for ten minutes at 1100 nickel oxide
nodule (27a) and 1200°C spinel oxide formation (27b)
62
5. DISCUSSION
Ni+2Al+2O2=NiAl2O4 NiO+2Al+1.5O2=NiAl2O4
2Al+1.5O2=a-Al2O3 NiO+Al2O3=NiAl2O4
0 0
-10
-250
∆G (kJ/molO2)
∆G (kJ/molO2)
-20
-500
-30
-750
-40
-1000 -50
800 1000 1200 1400
Temperature (°C)
Graph 20: Plot of the standard free energy of formation Versus temperature for spinel oxides.
The following thermodynamic considerations should be taken into account to explain

the formation of the observed oxide structures:
(i) the change in the standard energy of formation for a solid state reaction is
negative but closed to zero (cf. Graph 20) (ii) after short oxidation periods NiO
nodules are present at the surface for oxidation temperatures as high as 1100°C (cf.
Figure 27), (iii) the change in standard free energy is slightly more negative for
spinel formation by doping of NiO than for formation of Al2O3 per mole of O2
consumed in the reaction (cf. Graph 20), (iv) α-Al2O3 formation is preferred over
spinel if it takes place at the TGO/BC interface, because the oxygen partial pressure
is too low to form NiO, (v) (γ,θ)-Al2O3 formation is preferred at the gas phase/TGO
interface over spinel formation due to the reduction in the standard free energy of
formation related to good lattice matching.
These considerations and the formation of voids in the upper part of the oxide layer,
lead to the conclusion that (Ni,Co)(Cr,Al)2O4 spinel oxides are formed by solid state
reactions.
63
5. DISCUSSION
5.3.2. KINETICS
The surface concentration of non-protective oxides (Ni, Co and Cr) is below 1 at.%
for every temperature after 10 minutes of isothermal oxidation. By increasing the
oxidation time to 60 minutes no increase of the surface concentration of Ni, Co or Cr
(cf. Tables 4 and 5) was detected. The same can be said for a long oxidation at
800°C. After heating at low oxygen partial pressure for ten minutes, the concentration
of non-protective elements at the surface rises over 15 at.% (cf. Tables 3 and 4).
From the EPMA measurements (cf. Graph 10) it can be seen that after ten minutes of
oxidation at 1000°C Ni is depleted from the first micron bellow the surface , this
depletion is believed to be related with the presence of NiO nodules at the sample
surface ( analogous to Figure 27). No Al depletion is observed since oxide layer in
included in the measured region. The same is observed for the sample oxidized at
1200°C, in this case depletion of Ni, Co and Cr is observed (cf. Graph 11b), which is
congruent with the presence of (Ni,Co)(Al,Cr)2O4 spinel oxides in the top part of the
oxides layer.
The increase in the amount of non-protective oxides (specially NiAl2O4) at the top of
the oxide layer, correlates with the depletion of Ni observed after 96 hours of
oxidation at 1100°C in the region bellow the scale (cf. Graphs 13a-16a)..
As determined by Pettit [43], the NiAl2O4 spinel oxide growth constant by solid state
reaction is around 7x10-17 m2s-1 at 1200°C. Then, after 96 hours of isothermal
oxidation the penetration of Al into NiO would be close to 7 µm. The size of the
observed (Ni,Co)(Al,Cr)2O4 spinel oxide inclusions is well below this limit (cf. Figures
23-26). It is also worth nothing that pores in the scale are located in the top part of
the TGO, next to (Ni,Co)(Al,Cr)2O4 spinel oxides (cf. Figs 23-26). These pores may
be due to condensation of vacancies plus volume changes. This is congruent with
spinel formation by a solid state reaction, taking place mainly by Al diffusion from
Al2O3 into NiO [43].
Although, after the pre-oxidation treatment the concentration of non-protective oxides

is very low (cf. Table 4), their concentration increases after 96 hours of isothermal
oxidation at 1100°C (cf. figs 23-26). Then, the presence of a protective oxide layer
reduce the diffusion Ni, Co and Cr towards the surface, but do not prevent it form
happening after prolonged oxidation periods.
64
5. DISCUSSION
5.4. YTTRIUM
Y is found as Y-aluminates and as pure Y2O3. The location of the different types of
oxide depends on the oxygen partial pressure below the TGO.
At the TGO/BC interface, initially the oxygen partial pressure can be assumed to be
equilibrium pressure of alumina at the oxidation temperature, but as oxidation time
increases the oxygen partial pressure increases. Oxide formation below the close
alumina layer occurs, if the oxide being formed has a lower equilibrium pressure than
that at the TGO/BC interface or if it is formed by a solid state reaction. Since solid
state reactions are independent of oxygen partial pressure.
Y aluminates are observed at the TGO/BC interface and grow deep into the BC
(Figure 16). The standard free energy of formation of YAlO3 (YAP) and Y3Al5O12
(YAG) by solid state reactions is close to zero (Graphs 3 and 4). Also it is relevant to
point out that the solid state reaction between Al2O3 and Y2O3 powders start at
temperatures above 1200°C [42].
0.5Y2O3+Al+0.75O2=YAlO3 1.5Y2O3+5Al+3.75O2=Y3Al5O12
2Al+1.5O2=Al2O3 2Y+1.5O2=Y2O3
1E-25
log(pO2)
1E-50
1E-75
0.7 0.8 0.9 1 1.1 1.2
-3
Graph 21: Plot of the equilibrium oxygen pressure of Y-Al oxides versus inverse of temperature (700-
1400°C).
65
5. DISCUSSION
Al incorporation into Y2O3 posses a standard free energy of formation in between the
pure oxides (i.e. Al2O3 and Y2O3). Hence, the equilibrium oxygen pressure for the
reaction is below that of alumina, and the reaction can take place underneath the
oxide layer after short oxidation periods (cf. Graph 21).
YAP was identified as the only Y-aluminate after 1 hour of oxidation at 1100°C (cf.
Figure 19), while YAP and YAG are both present after ten minutes of oxidation at
1200°C (cf. Figure 14). This is due to the fact that the formation YAG requires higher
Y concentrations and Al incorporation. The Y concentration at the surface increases
at higher temperature (cf. Table 4 and 5) as the diffusivity of Al.
Further away from the TGO/BC interface the amount of available oxygen drops, and
only Y2O3 is formed (see Figures 14 and 19).
5.4.2. INTERNAL YTTRIUM OXIDATION
Y segregation to grain/phase boundaries relaxes the lattice of the BC [21]. Once Y is

at the grain/phase boundaries, it diffuses towards the surface regardless of the
oxygen partial pressure magnitude at the surface. Size Y-oxide precipitates and
penetration of the internal oxidation front depends mainly on the diffusion of Y along
grain boundaries towards the surface.
Temperature has a large influence in the movement of Y towards the surface. After
ten minute of oxidation at 1100°C the surface concentration is only 0.1 at.%, but
when the temperature is raised to 1200°C the concentration increases to 3 at.% (cf.
Table 4). The same effect is observed if the oxidation time is increased from 10 to 60
minutes at 1100°C. In this case the concentration changes from 0.1 to 1.3 at.%.
However, after 16 hours at 800°C no Y is detected at the surface.
The enhancement of the kinetics due to oxidation temperature can also be realized
by comparing the backscatter electron images of the sample oxidized for ten
minutes at 1200°C (Fig. 16) with the ones oxidized at lower temperatures 1100-
900°C (Figs 12, 13 and 15). At 1200°C the surface highly enriched with Y containing
oxides, while in the samples oxidized at lower temperatures no Y-aluminates or large
Y2O3 particles can be observed, or by comparing the backscatter electron image of
the sample oxidized for ten minutes at 1200°C and the sample oxidized for 1 hour at
1100°C (Figure 20), i.e. at that point the structures observed are equivalent, i.e.
presence of (Ni,Co)(Al,Cr)2O4 spinel oxides at the top part of the scale, an α-Al2O3
66
5. DISCUSSION
oxide layer, Y-aluminates at the TGO/BC interface and pure Y2O3 deeper into the
BC.
At low oxygen pressure conditions the amount of Y segregation is striking. Low

oxygen pressure hinders the formation of an external alumina layer and the internal
oxidation of Y. This allows Y enrichment of the BC surface. After ten minutes at
1000°C the atomic fraction measured was 30 at.%, while at high oxygen pressure (1
bar) no Y was detected at the surface for the same temperature (Tables 3 and 4).
Hence, it can be said that oxidation temperature and oxygen partial pressure have a
much stronger effect than oxidation time in the Y distribution and that internal Y
oxidation hinders Y segregation.
1200-10M 1000-10M
5 1
4 0.8
Mass Fraction 1200°C (wt%)
Mass Fraction 1000°C (wt%)

3 0.6
2 0.4
1 0.2
0 0
0 10 20 30
Depth (µm)
Graph 22: Y distribution after ten minutes of isothermal oxidation at 1200°C (left side axis) compared
with the Y distribution of the sample oxidized for 10 minutes at 1000°C (right side axis).
From the EPMA measurements of the BC oxidized at 1000 and 1200°C the
characteristic diffusion length of Y can be determined. :
lY = 2DY t (30)
The characteristic Y diffusion length lY after 600 seconds is around 7.5 µm at 1000°C
and 15 µm at 1200°C (Graph 21).This leads to effective diffusion coefficients in the
order of 4.72.3x10-144 m2s-1 and 1.9x10-13 m2s-1 for 1000 and 1200°C, respectively.
67
5. DISCUSSION
Since D=Doexp(-E/RT) the diffusion coefficient at 1100°C can be estimated from:
 T1 
R ln DY T2 
E=  DY 
= 108 kJmol-1 (31)
1 1
 − 
 T1 T2 
then, DO = 1.5x10-9 m2s-1 and DYEff (T = 1100 °C ) = 9.8x10-14 m2s-1.
The diffusion coefficient of yttrium through grain boundaries equals DYGB = rDY / 2δ .
The average grain size can be taken as 1x10-7 m (as-deposited BC). The grain
boundary width is usually set as 1x10-9 m [56]. This leads to effective diffusion
coefficients in the order of 5x10-12 m2s-1. The Y diffusion coefficient in NiCoAlCrY
alloys has not been thoroughly investigated and the only value found in literature was
reported by T. Nijdam [47] 5x10-12 m2s-1 for a EB-PVD NiCoCrAlY bond coating
where Y was present as an intermetallic compound at grain/phase boundaries.
Table 11: Penetration of the internal oxidation front xIOF for the different pre-oxidation temperatures after
the complete oxidation treatment.
Tpre-o (°C) PO-pre (µm) PMO/M (µm) PO (µm) xIOF (µm)

900 3 5 21 13
1000 3 3 19 13
1100 3 5 19 11
1200 3 7 19 9
The penetration of the internal oxidation front xIOF after 96 hours of oxidation can be
determined by subtracting the position of the MO/M interface PMO/M , and the oxygen
penetration after the 2 previous pre-oxidation treatments (cf. Section 3.8) PO-pre , from
the oxygen penetration depth after the complete oxidation treatment PO (cf. Table
11). In order to analyze the internal oxidation of Y the model presented in Section
2.1.2 can be used (solute Z=Y). In this model inward diffusing oxygen atoms react
with the outward diffusion Y atoms at the I.O.F., at this plane the concentration of
both atomic oxygen and metallic Y drops to zero. The concentration of oxygen does
not drop to zero but it is assumed that this plane is located at PO (oxygen
concentration is bellow 1%). The oxygen diffusion coefficient in the BC can be
estimated from Eq. 32 using the experimentally determined data. :
68
5. DISCUSSION
2
πDO2  CO 
MO
2
M

xIOF
=   t = k int t (32)
2 2ν DY CY∞
2
( ) 2 p
where, DO and DY are the oxygen and Y diffusion coefficients in m2s-1 respectively
and ν is the ratio of oxygen to Y atoms and equals 1.5 for Y2O3. The relevant
MO
M
concentrations are determined with EPMA: CO =30-40 at.% (atomic fraction of
oxygen at the TGO/BC interface) and CY∞ = 0.25 at.% (atomic fraction of yttrium in as
deposited BC). Kofstad et. al. has assumed an oxygen concentration in the metal at
the MO/M interface of 30 at.% for the oxygen dissolution analysis in Ti, Zr and Hf
[59]. The calculated effective diffusion coefficient for oxygen in the BC is presented in
Table 12.
Table 12: Estimated Y and O effective diffusion coefficients in the BC. Minimum value of DO is in red.
2 -1
ν CO (at.%) Initial T (°C) x (µm) DO (m s ) DY/DO
1000 13 6.8E-17 1434
30
1200 9 4.7E-17 2071
1.5
1000 13 5.1E-17 1912
40
1200 9 3.5E-17 2761
The DY/DO ratio is expected to be larger than 1. Eq. 30 indicates that the
characteristic diffusion length l and the diffusion coefficient D can be related as
follows:
D ∝ l2 (33)
for a given temperature and oxidation time. Thus the ratio between the diffusion
coefficients is given by:
2
DYBC  l Y 
=  (34)
DOBC  l O 
The characteristic diffusion length of Y is observed to be 15 µm and the oxygen

penetration into the BC is observed to be around 3 µm for 10 minutes of oxidation at
1200°C, this values give a ratio equal to 25. No reference was found of this ratio. The
calculated oxygen diffusion coefficients can be used to determined an oxygen
distribution as a function of depth x and compare this with the oxygen penetration
curves as determined from EPMA measurements (underneath the oxide layer).
69
5. DISCUSSION
The oxygen penetration profiles are assumed to be of the following form:
 x 
C (x ) = A + Berf   (35)
 2 tD 
The boundary conditions are:
 C(x=0)= COMO / M =25 wt%
 C(x=xIOF)= CO∞ <1 wt%
For these conditions the oxygen diffusion profile is:
 x 
erf  
 2 tD BC 
MO
CO (x ) = CO M
−  CO
MO
M ∞
− CO   O  (36) (39)
   x 
erf  IOF 
 2 tD BC 
 O 
EPMA O-Profile Calculated O-Profile
25
20
Mass Fraction (wt%)
15
10
0
0 10 20 30 40 50
Depth (µm)
Graph 23: Oxygen penetration profile of the sample initially oxidized for ten minutes at 1200°C. The
dotted red line indicates the approximate position of the TGO/BC interface.
70
5. DISCUSSION
EPMA O-Profile Calc O-Profile
30
Mass Fraction (wt%) 25
20
15
10
0
0 10 20 30 40 50
Depth (µm)
Graph 24: Oxygen penetration profile of the sample initially oxidized for ten minutes at 1000°C. The
dotted red line indicates the approximate position of the TGO/BC interface.
The diffusion coefficients DO used were the ones presented in Table 12 (Written is
red). The calculated oxygen concentration profile resembles those measured by

EPMA (Graphs 21-24). This means that diffusion of Y through the BC is faster than
the oxygen penetration by three orders of magnitude.
An analytical solution can also be found for the internal oxidation model presented in
Section 2.1.2 neglecting the counter diffusion of Y. In such a case the relevant
solution would be Eq. 37 [appendix B Ref. 4]. The effective oxygen diffusion
coefficient through the BC in such a case would be in the order of 5x10-13 m2s-1. This
magnitude of the oxygen diffusion coefficient is closer to that observed in non-
protective Ni-Al alloys [56]
MO
2
x IOF 2CO M DO
= (37)
2 ν CY∞
There are three main reasons for the difference: (i) Fast counter diffusion of Y tied up
the penetrating oxygen closer to the surface, (ii) NiCoAlCrY alloys formed a
protective external Al2O3 layer and (iii) oxide particles formed in the NiCoCrAlY alloy
are larger in size and present in lower density, compared to the oxide particles
71
5. DISCUSSION
formed in non protective Ni-Al alloys. The reduced density of fast diffusion paths for
oxygen (i.e. MO/M interfaces) in the NiCoCrAlY alloy reduces the effective oxygen
diffusion coefficient [56].
The difference in the oxygen penetration observed between the sample oxidized at
1000°C and the one oxidized at 1200°C, can be attributed to the difference in Y
distribution after the initial 10 minutes oxidation. The large Y surface enrichment at
the higher temperature prevents oxygen penetration due to oxide formation. This
effect has also been observed in internal oxidation experiments [56], where the
penetration of the internal oxidation front decreases as the solute concentration
increases.
5.5. SUMMARY
The alumina layer consists of meta-stable or α-alumina depending on oxidation

temperature. A high oxidation temperature reduces the strain energy due to lattice
mismatch. Hence, it reduces the effect that good lattice matching have on the
standard free energy of formation for transition aluminas and allows direct nucleation
of α-Al2O3. Nucleation of α-Al2O3 correlates with the presence of yttrium at the
sample surface (cf. Tables 4 and 5).
The closed alumina layer reduces the oxygen partial pressure below the TGO. The
conditions to from Y-aluminates by solute incorporation are: (i) outward diffusion of
aluminum (depletion), (ii) inward oxygen diffusion (α-Al2O3 is present when Y-
aluminates are present), (iii) previous existence of pure Y2O3 and (iv) high enough
oxygen partial pressure. All the mentioned conditions are met, if Y-aluminates are
identified. It is proposed that their formation takes place by Al and O incorporation
into pure yttrium oxide. Further away from the TGO/BC interface only pure Y2O3 is
present.
The thermodynamic considerations to explain the observed oxide layer structure

have been discussed (cf. Sections 5.2.1, 5.3.1 and 5.4.1). Spinel oxides are formed
at the upper part of oxide layer (cf. Figures 23-26). These oxides are formed by solid
state reaction between NiO/CoO and Al2O3/Cr2O3. This is concluded from the
presence of voids in the oxide layer when (Ni,Co)(Al,Cr)2O4 spinel oxides are
present (cf. Figures 16, 20, 23-26). If the formation occurs by solute incorporation no
72
5. DISCUSSION
voids should form in the oxide layer, since the doping elements (Al, Cr) would diffuse
from the BC.
5.5.2. KINETICS
As the alumina layer thickens and Y-aluminates are formed Al is depleted from the
region underneath the oxide layer. Al is incorporated into the protective alumina layer
and into the Y2O3 particles to form Y-aluminates.
The region where the β-NiAl phase is dissolved below the oxide layer formed after 10
minutes of oxidation at 1200°C (cf. Figure 29) is considerably larger than bellow the
oxide layer formed after 10 minutes of oxidation at 1000°C (cf. Figure 28). From
Graph 18 it can be seen that the amount of Al2O3 formed is the same in every
sample. However, by plotting the Al depth profile underneath the TGO/BC interface it
can be observed that depletion region is larger at the higher temperature. Upon
oxidation at 1200°C the segregation of Y to the TGO/BC interface is higher as
compared with oxidation at 1000°C, this caused formation of a larger amount of Y-
aluminates (cf. Figures 13 and 16). This attributes to a higher growth rate of the oxide
layer and also to the larger Al depletion of the BC oxidized at 1200°C.
Figure 28: Backscatter electron image of the sample oxidized for 10 minutes at 1000°C. The bright
areas correspond to γ-(Ni)/γ´-(Ni3Al) and the dark areas correspond to β-(NiAl).
73
5. DISCUSSION
Figure 29: Backscatter electron image of the sample oxidized for 10 minutes at 1000°C. The bright
areas correspond to γ-(Ni)/γ´-(Ni3Al) and the dark areas correspond to β-(NiAl). In the β-phase depleted
region Y-oxides are observed.
Al-1200°C Al-1000°C ASD
40
30
Mass Fracction (wt%)
20
10
0
0 10 20 30 40 50
Depth (mm)
Graph 26: Al depletion underneath the TGO/BC interface of the samples initially oxidized for 10 minutes
at 1000 and 1200°C.
74
5. DISCUSSION
The oxide layer growth can be approximate by assuming that it grows exclusively by
inward oxygen diffusion. In the case of internal Y oxidation, both inward oxygen and
outward Y diffusion are relevant. Y diffuses three orders of magnitude faster than
oxygen in the BC (cf. Table 11). The oxidation temperature has a strong influence on
the Y diffusion, but not on the oxygen penetration (cf. Table 7).
The oxygen penetration depth is approximately the same after 96 hours of oxidation
regardless the pre-oxidation treatment (cf. Graphs 23 and 24). Since the segregation
of Y increases with the oxidation temperature (see Graph 22), the amount of Y-
oxides is larger at higher temperature.
5.6. TGO CRITERIA FOR AN IMPROVED LIFETIME
In the performed experiments only intrinsic failure mechanisms are operative and
crit
since all intrinsic mechanisms have a characteristic TGO thickness x MO , the life( )
time analysis will be based on this feature, see Section 2.2.6. Failure along the
TGO/BC interface can be considered as an upper limit for the lifetime of the high
temperature coating system. If failure occurs within the TGO, then the lifetime of the
high temperature coating system is shorter and the TGO thickness after failure is
crit
smaller than x MO [50].
Figure 30: Backscatter electron image of Y-Aluminates formed at phase/grain boundaries and inside
grains.
75
5. DISCUSSION
Failure within the TGO is associated with progressive damage build up in the vicinity
of defects such as voids and micro-cracks which are commonly observed in the
upper part of the oxide layer where (Ni.Co)(Al,Cr)2O4 spinel oxides are formed (cf
Figures 23-26). Thus, the formation of these oxides should be minimized.
As discuss in Section 5.2.2 and 5.5.2, the growth of the oxide is faster and the β-NiAl
phase depletion is enhanced, if the amount of Y-rich oxide inclusions in the oxide
layer increases. Thus, to reduce the growth of the scale, the segregation of Y to the
surface (top 5 µm of the BC) must be minimized.
As mentioned in section 4.4., Y2O3 forms after short oxidation times when the BC
microstructure is fine. During extended periods of high temperature (1100°C)
oxidation, recrystalization and grain growth in the BC occurs [52]. Then, a fraction of
the initially formed Y2O3 particles become part of the growing β or γ/γ’ grains. The
oxidation lifetime of ODS alloys is usually 2-3 time lower than that of FeCrAlY alloys
of similar composition [51]. This difference is linked to the benefit of stress relaxation
in the weaker wrought material. If internal oxidation of Y occurs, and the formed
oxides become part of the new grains, the elastic modulus of the BC in the internal
oxidation zone (IOZ) may increase. Consequently, the BC deformation is hindered
and hence relive of the stresses generated in the scale upon cooling is impaired. The
reduction of stress release capability causes an increase of the strain energy in the
oxide layer. This can be directly related to a reduction in the oxidation lifetime of the
alloy (i.e. smaller critical thickness).
Also internal Y oxidation hinders the formation of Y-sulfides since more stable Y-
oxides are being formed (reactive element effect, cf. Section 2.2.5.). If S segregates
to the TGO/BC interface its fracture toughness will be reduced. Thus, to increase the
lifetime, oxygen penetration should be minimized.
Failure along the TGO/BC interface is promoted upon increasing oxidation time
since: (i) as the TGO thickens the strain energy stored increases, (ii) the fracture
toughness of the TGO/BC interface may decrease due to segregation impurities from
the BC, (iii) the density of Y-rich oxide inclusions in the oxide layer increases, and (iv)
the amount of (Ni,Co)(Al,Cr)2O4 spinel oxides at the top of the oxide layer increases.
So, to extend the lifetime of the high temperature coating the following four points
should be addressed: (i) the TGO should have the lowest growth rate at the
temperature of interest (900-1200°C), (ii) the BC/TGO interface must be as strong as
76
5. DISCUSSION
possible in order to increase the critical TGO thickness, (iii) large Y enrichment of the
surface and extended oxygen penetration should be avoided and (iv) the density of
defects within the TGO should be small in order to suppress the number of crack
initiation sites for premature failure.
5.7. TGO FORMATION
To from an oxide layer on the TGO that grows as slowly as possible during
isothermal oxidation, the presence of other oxides besides Al2O3 in the initial
oxidation stage should be minimized.
Closed oxide layers that exclusively consist of alumina can be formed after short
oxidation times, cf. Table 7 and Figures 12, 13 and15. Then, it is an advantage to
have a fine BC structure with a high density fast diffusion paths for Al and oxygen.
This is the case directly after BC deposition (see Figure 8). However, Y segregation
towards the surface is also facilitated.
Extending the oxidation time to 1 hour and still form a pure alumina layer is possible
at 1000°C (cf. Figure 18). The formation of closed oxide layers of transition aluminas
may be of advantage (formed at T = 1000  C ), because of two reasons: (i) the
transition alumina will transform to coarse grained [30] stable α-Al2O3 upon solution
treatment (first part of the precipitation hardening) of the substrate precipitation and
(ii) metastable aluminas grow mainly by outward Al diffusion, which reduces the
mass fraction of oxygen underneath the TGO after the pre-oxidation treatment.
The formation of (Co, Ni) oxide nodules can not be avoided by shortening the
oxidation time or by decreasing the oxidation temperature (Figure 27). However, their
density is minimal after the 10 minutes oxidation treatments (cf. Table 4). Although,
the alumina layer is closed and (Co, Ni) oxide concentration at the surface is low, a
significant amount of (Ni,Co)(Al,Cr)2O4 spinel oxides are formed at the sample
surface after 96h hours of isothermal oxidation (cf. Figures 23-26). This means that
metallic elements (e.g. Ni and Co) diffuse through the closed alumina layer towards
the surface. A possible solution can be to increase the thickness of the outer alumina
layer.
Thickening of the external alumina layer is considerably slow at low oxidation

temperature (800°C). Long oxidation periods at low temperature will form pure
alumina scales. Since Y diffuses slower at lower temperatures, the density of Y-rich
inclusions in the scale, the size of the Y-oxides (cf. Figures 16 and 20) and the
77
5. DISCUSSION
growth rate of the scale decreases. But, since oxidation time is longer the oxygen
diffusion into the BC will increase (cf. Table 10) as well as β-NiAl depletion.
This approach was initially considered (cf. Figures 13 and 22). Instead, thickening of
the external scale is better achieved by increasing oxidation time at temperatures
below 1100°C to minimize Y segregation towards the surface (cf. Table 5), but above
900°C in order to enhance the oxide layer growth kinetics.
Pre-oxidation treatments above 1100°C are not recommended, massive Y

segregation and rapid formation fast growing oxides takes place even after a very
short time plus large depletion of the β-NiAl phase, which is the main Al source for
the formation of the protective alumina layer (c.f. Figure 16). After just 10 minutes,
heating at 1000°C in the vacuum chamber large amounts of Y can be found at the
sample surface. The Y concentration at the surface remains constant with time
during the low pressure heating. At high oxygen partial pressure and the same
temperature no Y at the sample surface is observed. Then, pre-oxidation treatments
(with native oxide on BC with fined grained structure) at very low partial oxygen
pressures should be avoid, since they cause rapid Y diffusion towards the surface.
After long time oxidation periods, the oxide structure show the same features for any
pre-oxidation treatment: i.e. a thin layer with a high density of (Ni,Co)(Al,Cr)2O4 spinel
oxides on top of thick layer of alumina with Y-rich oxide inclusions (Figures 23-26).
The initial treatment has proved to be able to change the density of inclusions
present in the mature scale and thereby its growth rate.
78
6. CONCLUSION
6. CONCLUSION: Proposed pre-oxidation treatment
As the main conclusion of the research executed, a pre-oxidation treatment is

proposed:
Perform the pre-oxidation before precipitation hardening of the super alloy substrate.
In this way the fined grained structure of the as deposited BC helps in forming a
closed alumina layer of uniform thickness. Furthermore, the effects of the substrate
strengthening on the oxide layer formed after pre-oxidation may be of advantage for
the lifetime of the high temperature coating system. Because upon solution heat
treatment of the super alloy substrate, the metastable oxides formed after pre-
oxidation transform into stable α-Al2O3 with relatively large grains.
After very short oxidation times the Y distribution is effectively modified. Since Y
movement towards the surface should be minimized, the oxygen partial pressure
should be high and the temperature should not exceed 1100°C during the pre-
oxidation treatment. To reduce oxygen penetration and β-NiAl phase depletion, the
pre-oxidation time should short.
The oxidation treatment should be carried out between 1000 and 1100°C at an
oxygen pressure of about 1 bar. A lower temperature will reduce Y diffusion towards
the surface. The oxidation time can be varied between 15 and 25 minutes depending
on the temperature. In this way the formed oxide layer will be composed of pure
alumina and thick enough to minimize the formation of non-protective oxides at the
top part of the oxide layer.
Thermal cycle oxidation experiments are necessary to determine the effect of the
proposed pre-oxidation treatment on the lifetime of the high temperature coating.
79
7. RECOMENDATIONS
7. RECOMMENTDATIONS
After the pre-oxidation treatment, the heat treatment of the super-alloy should be
simulated. Since the initial two hours at 1150°C of heating in argon/vacuum may
modify the Y distribution and the structure of alumina. The second part of the super-
alloy strengthening treatment, will not affect the Y distribution but, can modify the
nickel distribution as was evidenced after the 16 hours of isothermal oxidation at
800°C (cf. Graphs 10a and 12a), the Ni depletion region observed after ten minutes
is not present after the second 16 hours oxidation period.
The next step should be to compare the lifetime in a cyclic oxidation experiment for
samples pre-oxidized before strengthening of the substrate at 1000°C (low density Y-
rich oxides in the oxide layer) and 1200°C (high density of Y-rich oxides in the oxide
layer). Also the ability of the BC, after precipitation hardening of the substrate, to form
closed alumina scales after short oxidation time should be investigated, and a
comparative analysis of the TGO performance when the pre-oxidation is done before
and after precipitation hardening of the substrate.
80
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Pre-Oxidation Treatment For Mcraly Bond Coating

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Design of a pre-oxidation treatment for a

NiCoCrAlY bond coating in view of enhancing the

Carlos Serrano Vergel

Master Project Report

Supervisors: Thijs Nijdam

Surface and Interfaces

Materials Science and Engineering

Delft University of Technology

Figure 1: Aeroderivative landbased turbine designed by General Electric

Figure 2: Turbine blade drawing showing internal cooling channels

Based on their composition, superalloys have the capability to form a protective

Pre-oxidation treatments performed on an as-deposited BC prior to the super-alloy

This document is structured as follows: First, in Section 2, the relevant theoretical

2.1. HIGH TEMPERATURE OXIDATION

In order to form a metal-oxide molecule two reactions have to take place,

O2 reduction (consumption of electrons):

M oxidation (generation of electrons):

aM + bO 2 − ↔ MaOb + 2be − (1b)

The total reaction is shown in equation 1c.

The change in standard free energy of formation ( ∆G O ) is a function of temperature,

Ni+2Al+2O2=NiAl2O4 NiO+2Al+1.5O2=NiAl2O4 NiO+Al2O3=NiAl2O4

Y+Al+1.5O2=YAlO3 0.5Y2O3+Al+0.75O2=YAlO3 0.5Al2O3+0.5Y2O3=YAlO3

The thermodynamical analysis for a mixed-oxide is analogous to the one explained

∆G O (T ) = −RT ln(K ) (3)

oxygen partial pressure equals:

Figure 3: Stages of external alloy oxidation.

The kinetics of oxide scale growth by external oxidation of a metallic component is

Scheme1: Growth of an external oxide layer

the chemical potential gradient [4, 59]:

Scheme 2: Internal oxidation of metal Z bellow an external MO layer

The following analysis of internal oxidation can be found in appendix B of Ref. 4. If

x IOF = 2γ DOM t (14)

diffusion length DOM t . Fick’s second law applies if

where CO is the concentration of oxygen.

Initial conditions at=0:

x>0 CO = 0 No oxygen is dissolved in the metal

Boundary conditions at t=t:

Initial conditions at t=0:

x<0 C Z = 0 no metallic Z above the MO/M interface

x>0 C Z = C Z∞ concentration of Z away from the I.O.F.

Boundary conditions at t=t:

x=0 C Z = 0 no metallic Z at the MO/M interface

Then the solution of Fick’s second law is

Substituting Equations 20, 21 and 22 into 19 leads to Eq. 23:

2.2. HIGH TEMPERATURE COATINGS

2.2.1. HIGH TEMPERATURE ENVIRONMENT

The operation environment of turbine engines is characterized by: high temperature

Due to these operation conditions, materials used in turbine components need to

The enhancement of high temperature strength of super-alloys has lead to a

2.2.2. THE HTC SYSTEM

(I) Optimization of superalloy high temperature strength and the coating

(III) Development of technologies that allowed coating of complex geometry

The high temperature coating is composed by a series of layers of different materials

Figure 4: Schematic illustration of the High temperature coating (HTC).

Figure 5: Nickel aluminum phase diagram. Taken from Ref. 1

Superalloys are essentially a γ-Ni matrix hardened by γ’-Ni3Al precipitates. As

2.2.4. THE BOND COATING

(I) The amount of Al loss by oxidation is reduced.

(III) Bond strength is enhanced due to higher particle velocity.

ROLE OF DIFFERENT ALLOYING CONSTITUENTS IN THE BC

Every element of an NiCoCrAlY alloy has an specific function. Ni provides the

Cr improves hot corrosion resistance and promotes the selective oxidation of Al by