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1.

27 High Temperature Coatings: Protection and


Breakdown
H. E. Evans
School of Metallurgy and Materials, The University of Birmingham, Birmingham B15 2TT, UK

ß 2010 Elsevier B.V. All rights reserved.

1.27.1 The Need for Coatings 692


1.27.2 Underlying Requirements of Coatings 693
1.27.2.1 The Protective Oxide Layer 693
1.27.2.2 Coating Composition and Solute Supply 694
1.27.3 Examples of Main Coating Types 696
1.27.3.1 Overlay Coatings 696
1.27.3.1.1 MCrAlY coatings 696
1.27.3.1.2 Examples of other metallic coatings 697
1.27.3.1.3 Oxide overlay coatings 698
1.27.3.2 SMART MCrAlY Overlay Coatings 699
1.27.3.3 Diffusion Coatings 700
1.27.3.3.1 Basic types 700
1.27.3.3.2 Aluminide coatings 701
1.27.3.3.3 Platinized coatings 702
1.27.3.3.4 Silicide diffusion coatings 702
1.27.3.4 Thermal Barrier Coatings 704
1.27.4 Case Study I: Oxidation and Lifing of MCrAlY Overlays 705
1.27.4.1 Protective Oxidation 705
1.27.4.2 Spallation and Cracking of the Protective Alumina Layer 706
1.27.4.3 Aluminum Depletion 709
1.27.4.3.1 Uniform depletion 709
1.27.4.3.2 Diffusion cells and chemical failure 710
1.27.5 Case Study II: Oxidation-Induced Failure of TBC Systems 712
1.27.5.1 Failure Times under Oxidizing Conditions 712
1.27.5.2 Failure Characteristics 713
1.27.5.3 Strain Energy Considerations 715
1.27.5.4 Formation of Subcritical Cracks 716
1.27.5.4.1 Transformation strains 716
1.27.5.4.2 Mechanical instabilities 717
1.27.5.4.3 Roughness of the BC surface 718
1.27.5.4.4 Chemical failure 719
1.27.5.5 Surface Roughness: A Common Factor? 720
References 722

Em Young’s modulus of the alloy or metallic coating


Symbols
(Pa or GPa)
a Amplitude of bond coat surface roughness (m)
Eox Young’s modulus of the oxide (Pa or GPa)
b Wavelength of bond coat surface roughness (m)
fB Bulk fractional concentration of solute
C Concentration (at.%)
fl Fractional concentration of solute at oxide–
CAl Concentration of aluminum (m3)
coating interface
Cb Bulk concentration (at.%)
f(x) Fractional concentration at position x
D Interdiffusion coefficient (m2 s1)
h thickess of oxide layer (m)
DAl Interdiffusion coefficient for aluminum (m2 s1)
ho Preexisting oxide thickness (m)

691
692 High Temperature Materials

JAl Flux of aluminum (m2 s1) oxidation/hot-corrosion protection. As a result, the


kn Oxidation rate constant (mn s1) intrinsic protection capability of many superalloys is
kp Parabolic oxidation rate constant (m2 s1) adequate only for short-term exposures and coatings
kp0 Mass gain parabolic rate constant (g2 m4 s1 or are required to permit extended operation under service
mg2 cm4 s1) conditions. This point will be demonstrated in the later
Mo Atomic weight of oxygen (kg) text for the particular case of Ni-based superalloys
Mox Molecular weight of the oxide (kg) under oxidizing conditions.
n Dimensionless number High-strength nickel-based alloys are used exten-
R Radius of decohesion zone (m) sively for components in gas turbines; an excellent
t Exposure time (s) account of their development and properties is
T Temperature (K) provided by Reed.1 Single crystal alloys, for example,
Tox Oxidation temperature (K) CMSX4, are used for high-pressure blades in
DT Amplitude of temperature change (K) aeroengines and in small (10 MW) land-based tur-
DTb Critical temperature change for oxide buckling bines, but, in larger machines, polycrystalline alloys
(K) (e.g., IN738LC) are used. Some compositions of
DTc Critical temperature change for oxide nickel-based alloys are given in Table 1. These are
spallation (K) given in ‘weight percentage’ as is customary, but, in
v Volume of oxide formed per aluminum atom (m3) assessing the ability to form and maintain a protective
w Half the specimen or cell thickness (m) alumina layer at high temperatures, it is the atomic
W* Strain energy (J m3) percentage of available aluminum which is a key
WAl Atomic weight of aluminum (kg) factor. For alloys having high nickel, chromium, and
WAI2O3 Molecular weight of alumina (kg) cobalt contents, the atomic concentration of alumi-
x Spatial coordinate and distance from the oxide– num is roughly twice the weight percentage value. In
metal interface (m) more complex alloys containing appreciable amounts
xh Section loss (m) of heavy elements such as tungsten, rhenium, or
am Linear thermal expansion coefficient of alloy or ruthenium, this factor is nearer 2.5. Thus, even
coating (K1) though in most of the alloys (shown in Table 1) the
aox Linear thermal expansion coefficient of oxide aluminum concentration is 5.6 wt%, its atomic con-
(K1) centration increases from 11 at.% in simpler alloys
« Strain such as RR2000 to 13 at.% in PWA1497. Much of
f Pilling–Bedworth ratio this aluminum is associated with the strengthening g0
gF Effective fracture energy (J m2) phase in these alloys.
n Poisson’s ratio The importance of both aluminum and chromium
rAI2O3 Density of alumina (kg m3) concentrations to the ability of a Ni-based alloy to
rm Density of the alloy (kg m3) form a protective alumina layer is summarized in
rox Density of the oxide (kg m3) Figure 1. This diagram is similar to that given by
sox In-plane oxide stress (Pa or MPa) Evans and Taylor,2 but has been modified to reflect
the low-Cr compositions of the more recent alloys
shown in Table 1 and to include g/g0 coatings. For
convenience in comparing between alloys, concen-
1.27.1 The Need for Coatings trations in weight percentage are used. The experi-
mentally based lines shown in Figure 1 derive from
High temperature superalloys, usually based on iron-, the work of Giggins and Pettit3 on NiCrAl alloys at
cobalt-, or nickel-rich compositions,1 are optimized for temperatures within the range 1000–1200  C. They
mechanical properties, such as creep and fatigue resis- show that in simple Ni–Al binary alloys, at least 6 wt
tance, since they are used for highly-stressed compo- % aluminum is required to form an alumina layer at
nents. In all cases, however, these alloys will be exposed these temperatures. This critical value decreases with
to oxidizing or hot-corrosion environments during ser- increasing alloy chromium content to 3wt% alumi-
vice and will undergo some form of degradation pro- num at chromium contents 10 wt%. At low alumi-
cess resulting from this interaction. The composition num and chromium contents, that is, below
optimization required to achieve good mechanical prop- the downward sloping line to the left-hand side of
erties, however, often conflicts with the requirements for Figure 1, the principal surface oxide is expected to
High Temperature Coatings: Protection and Breakdown 693

Table 1 Compositions (wt%) of some representative nickel-based superalloys

Alloy Ni Co W Cr Al Ta Re Hf Ru Ti Mo Nb

RR2000 Balance 15.0 – 10.0 5.5 2.8 – – – 4.0 3.0 –


IN738LC Balance 8.5 2.6 16.0 3.4 1.7 – – – 3.4 1.7 0.9
CM186 Balance 9.3 8.5 6.0 5.7 3.4 3.0 1.4 – 0.5 0.2 –
CMSX4 Balance 9.8 6.4 6.4 5.6 6.5 3.0 0.1 – 1.0 0.6 0.4
CMSX10 Balance 3.0 5.0 2.0 5.7 8.0 6.0 0.03 – 0.2 2.9 –
PWA1497 Balance 16.5 6.0 2.0 5.6 8.3 6.0 0.15 3.0 – 2.0 –
TMS162 Balance 5.8 5.8 2.9 5.8 5.6 4.9 0.1 6.0 – 3.9 –

30 is exacerbated with recent generations of alloys


in which chromium levels have been decreased to
β-forming
diffusion coatings
2–2.5 wt% (Table 1), making it less favorable for a
25
protective layer of alumina to form (see Figure 1). In
addition, elements such as rhenium and ruthenium
20
have been introduced, which have volatile oxides
Al2O3
that can be released at high temperatures, at least in
wt% Al

15 the absence of a protective surface oxide layer.


γ/γ9-forming Another important consideration when assessing the
diffusion coatings Overlay
10 coatings oxidation resistance of an alloy is its ability to reform
Typical a protective alumina layer should that which formed
superalloys
5 initially spall or crack. This is an arduous requirement
for borderline alloys, since the formation and growth of
NiO + sub-surface Cr2O3 + subsurface the original alumina layer is a process of selective oxida-
0
0 5 10 15 20 25 30 tion and necessarily depletes the alloy of aluminum.
wt% Cr Thus, even though an alumina layer may have formed
100 wt% Ni initially on the superalloy, residual aluminum concen-
Figure 1 A schematic map derived from Evans and trations are unlikely to be able to maintain protective
Taylor,2 based on experimental data3 showing the type of conditions when repeated spallation events occur.
oxide formed in the NiCrAl system over the temperature It is for this combination of reasons that Ni-based
range 1000–1200  C. Superimposed are the composition superalloys operating at elevated temperatures, say
ranges of typical superalloys and coatings.
1000  C, are coated with Al-rich layers. The com-
position ranges of two important classes of such coat-
ings, overlays and diffusion coatings, are shown in
be NiO (in NiCrAl alloys), with internal oxidation of Figure 1. These will be discussed shortly but, clearly,
aluminum and chromium. To the right-hand side of both types are designed to lie within the alumina-
Figure 1, corresponding to alloys of high chromium forming region in the diagram. It is the combination
and lowaluminum content, chromia will be the expected of high-strength superalloy and oxidation-resistant
surface oxide and aluminum will oxidize internally. coating that permits component operation for
Also shown schematically, as the cross-hatched extended periods at high temperatures.
ellipse in Figure 1, is the approximate range of
aluminum and chromium contents often used in
Ni-based superalloys. It is immediately apparent 1.27.2 Underlying Requirements of
that they tend to lie on or near the bounding lines Coatings
for protective alumina formation. In some cases, alu-
1.27.2.1 The Protective Oxide Layer
mina formation can be expected but not in others.
As a group, these Ni-based superalloys can be consid- High temperature coatings rely, for protection, on the
ered to be borderline alumina formers and nonprotec- formation of a dense and adherent surface oxide layer
tive oxidation has been reported in this temperature that is chemically stable, thickens slowly with time at
range for IN738LC4,5 and CMSX10.6 The situation temperature, and has good adherence to the coating.
694 High Temperature Materials

These are, of course, the same requirements as are It must be borne in mind, though, that the formation
needed in the design of oxidation-resistant alloys in of the protective layer is a process of selective oxidation
general, as discussed elsewhere in this book, and, as in in which the solute atom is preferentially removed
that case, the choice is limited to chromia (Cr2O3), from the coating, oxidized, and incorporated into the
silica (SiO2), and alumina (a-Al2O3). oxide layer. This removal necessarily depletes the coat-
Chromia layers are particularly useful in conferring ing of the solute and will generate a concentration
protection against Type-II hot corrosion7 and interme- profile as shown schematically in Figure 2 for the
diate-temperature oxidation, say 600–800  C, but can case of aluminum removal from, nominally, a NiCrAlY
be converted to CrO3 at higher temperatures. The rate overlay coating. This is assumed to have had an initial
of formation of this gaseous oxide can be significant in aluminum concentration of 10 wt% and can be com-
both dry and moist air at temperatures 950  C and pared with the uncoated alloy having an initial concen-
chromia-forming coatings have limited usage at high tration of 5.6 wt%.
temperatures in such environments. Silica layers are The second requirement of a protective coating is
capable of providing protection to very high tempera- that the residual solute concentration after initial for-
tures, for example, via ceramic layers on carbon-based mation of the surface layer is still sufficient to reform a
materials, to 1800  C.8 They also suffer, however, protective layer in the event of cracking or spalling of
from concerns with chemical stability in moist envir- this first-formed layer. As shown in Figure 2, the
onments. Alumina layers do not suffer from such con- coating has sufficient aluminum, and hence even after
cerns and are the favored means of protection under alumina formation, there is still sufficient solute at the
Type-I hot-corrosion and high temperature oxidation oxide–metal interface to reform this layer. By contrast,
conditions. The majority of coatings are now designed because the superalloy had barely sufficient aluminum
to form a continuous alumina layer under these condi- to form the alumina layer initially, the interfacial con-
tions and to have sufficient aluminum content to pro- centration falls below the critical value after formation
vide a healing capability in the event of cracking or of the protective layer. Subsequent spallation of this
spallation of this layer. The majority of this chapter will layer would then mean that rapid oxidation of the alloy
place emphasis on the behavior of such alumina-form- would take place until the local concentration had
ing coatings designed for use under high temperature reached the critical value for reforming the alumina
oxidizing conditions, but interesting exceptions with layer. The quantity of metal consumed is shown by the
commercial relevance are also included. hatched area in Figure 2 as 7 mm but it will be much
larger if spallation occurs later in life when more pro-
nounced depletion has occurred. Typically, the thick-
1.27.2.2 Coating Composition and
ness of this at-risk zone will increase parabolically with
Solute Supply
exposure time up to the first spallation event.
The initial priority of oxidation-resistant coatings is to The shapes of the depletion profiles shown in
form a protective layer that can be achieved simply by Figure 2 are determined by the need to maintain a
incorporating sufficient amount of the relevant ele- mass balance at the oxide–metal interface, such that
ment into the coating composition. However, this the flux of aluminum leaving the metal is equal to
approach can impair physical and mechanical proper- that required to produce the observed thickening rate
ties, for example, by decreasing melting temperatures of the oxide.9 Considering the ideal case that the
or coating fracture toughness and ductility, and a bal- oxide thickness, h, increases parabolically with time,
ance must always be sought. The composition ranges of t, and forms at the start of the exposure period, the
three types of alumina-forming coatings are shown in rate constant, kp, is then defined as
Figure 1, from which it is clear that all lie in the
kp ¼ h2 =t ½1
appropriate composition range for protective oxide
formation. Detailed discussion of the coating types is This means that the flux of aluminum atoms, JAl,
provided later, but it is clear that aluminum concentra- arriving at the oxide–metal interface is
tions of 10 wt% are typical for both the MCrAlY    
@CAl 1 dx 1
overlays and g/g0 diffusion coatings. These compare JAl ¼ DAl ¼ ¼ kp0:5 t 0:5 ½2
@x x¼0 V dt 2
with the minimum requirements for alumina formation
(solid lines) of 3 and 6 wt% aluminum, respectively. where it is assumed, reasonably for protective condi-
The b-forming class of diffusion coating has substan- tions, that the recession of the oxide–metal interface
tially larger amounts of aluminum at 25 wt%. is much smaller than the diffusion distances within
High Temperature Coatings: Protection and Breakdown 695

12

Alumina layer NiCrAlY coating


10

Al concentration (wt%)
8

Al depletion profiles
Bare alloy
6

4
Critical healing concentration of 3 wt% Al

Depth of alloy consumed by oxide if 2


the alumina layer cracks or spalls.

0
0 20 40 60 80 100
Distance from Oxide–metal interface (μm)

Figure 2 Selective oxidation of aluminum from a NiCrAlY coating and superalloy produces depletion profiles in that
element. They result in interfacial aluminum concentrations insufficient to reform the alumina layer on the superalloy without
the prior consumption of some of the underlying metal. The critical interfacial concentration for reforming an alumina layer is
taken as 3 wt%, that is, of similar magnitude to those shown as solid lines in Figure 1.

the coating. In eqn. [2], DAl is the interdiffusion function. The interfacial concentration, fI, is constant
coefficient for aluminum within the coating, CAl is provided that parabolic oxidation and semiinfinite con-
the aluminum concentration (number/unit volume), ditions apply, but its value is directly related to the rate
x is the spatial coordinate measured from the oxide– constant kp and can be determined from the need to
metal interface, and V is the volume of oxide formed conserve the aluminum flux at the oxide–metal inter-
per aluminum atom. The depletion profile within the face. For simplicity, taking f as a weight fraction, the
metal can then be obtained from solution of Fick’s interfacial concentration during the growth of alumina
second law is given as11
@CAl @ 2 CAl "   #
¼ DAl ½3 pkp 1=2 rA12 O3 WA1
@t @x 2 f1 ¼ fB  ½5
DA1 rm WA12 O3
using eqn. [2] as a boundary condition, that is, the
flux of aluminum at the oxide–metal interface varies as
Here, r is density, W is molecular or atomic weight, the
t1/2. At relatively short exposure times, the depletion
suffix ‘m’ is the coating, and Al2O3 the oxide.
distance will be small compared with the thickness of
The concentration in the coating at its interface with
the coating so that the latter can then be considered as
the oxide will be maintained provided that there is
semiinfinite. Under these conditions, the depletion
sufficient aluminum reservoir and thickness of the coat-
profile is obtained as10
! ing to approximate to semiinfinite conditions. Protec-
f ðxÞ  fI x tion should, thus, be provided by these generic coatings
¼ erf ½4 until end-of-life effects, initiated often by aluminum-
fB  fI 2ðDAl t Þ0:5
reservoir depletion, intervene. At this stage, the interfa-
where the fs are consistent concentration parameters, cial concentration will begin to decrease and a level will
for example, weight (mass) fractions, f (x) is the value at eventually be reached where the protective alumina
distance x, fI is the value in the metal at the oxide– layer cannot be maintained. These issues will be dis-
metal interface, fB is the bulk value, and erf is the error cussed in detail in the following sections.
696 High Temperature Materials

1.27.3 Examples of Main Coating relate to the coatings shown in the table. Details of
Types these techniques and the historical development of
protective coatings can be found elsewhere.13–18
1.27.3.1 Overlay Coatings Even though the details of the coating techniques
1.27.3.1.1 MCrAlY coatings will be covered elsewhere in this book, it is important
Overlay coatings consist of a discrete coating layer to note that different application methods will pro-
deposited onto the surface of the component, with little duce different coating structures as can be appre-
interdiffusion and chemical reaction with the alloy ciated from Figure 3. In both of the plasma sprayed
substrate. These overlay coatings are often metallic coatings, (a) and (b), the sequential spray runs are
alloys, 150–300 mm thick, based on MCrAlY composi- evident in the lateral dark stringers of oxide formed
tions where M is Ni, Co, sometimes Fe, or a combina- around individual alloy particles during the deposi-
tion of these. Early development of these overlay tion process. These stringers can be continuous in the
coatings centered on cobalt-based materials containing APS coating in which extensive oxidation in the air
20–40 wt% Cr, 12–20 wt% Al, and 0.5 wt% Y.12 On the environment can result. Some oxide formation is
basis of hot corrosion and mechanical property tests, an inevitable also under LPPS, as can be appreciated
optimal composition of Co25Cr14Al0.5Y (wt%) was from Figure 3(b), but in this case, continuous strin-
selected. This initial composition is similar to those of gers are not usually formed (e.g., see Figure 4). These
the more recent Co-based coatings, ATD 2B and ATD differences affect the longevity of the coatings, even
5B, given in Table 2. Later trends, however, have been for a given nominal composition, as will be discussed
to replace some or all of the cobalt content with nickel later with reference to aluminum reservoir issues. The
in order to improve toughness and to limit interdiffu- EB-PVD coating, by contrast, forms as vertical col-
sion effects when protecting high temperature umns with negligible oxidation. These vertical features
Ni-based superalloys. There has also been a tendency can be seen on closer inspection in Figure 3(c), and
to decrease aluminum content, again to improve coating their presence provides sites of potential mechanical
toughness. A few examples of the composition of current weakness, which can be removed by postprocessing,
MCrAlY overlay coatings are given in Table 2. for example, peening, to improve lateral bonding.
It is sometimes the case, as can be inferred from The MCrAlY coatings (shown in Table 2) have a
Table 2, that overlay coatings of the same or similar nominal b/g structure, where b can be NiAl or CoAl
compositions have different designations, for exam- and g is face-centered cubic Ni- or Co-rich solid solu-
ple, LCO22 and CN122. This reflects the different tion. In practice, however, the actual microstructure will
possible deposition methods in commercial use. depend on cooling rate and temperature as well as on the
These include air plasma spraying (APS), argon- detailed composition. Ni-rich phases, for example, can
shrouded plasma spraying (ASPS), low-pressure undergo the following four-phase reaction at 980  C19:
plasma spraying (LPPS), high-velocity oxy-fuel b þ g ! g0 þ a ½6
(HVOF) spraying, electrodeposition, and physical
0
vapor deposition (PVD) processes such as sputtering where g is the Ni3Al phase and a is the a-Cr solid
and electron beam (EB) PVD. Some of these methods solution. It can be appreciated that a given coating

Table 2 Compositions (wt%) of some MCrAlY overlay coatings

Coating or feedstock Al Cr Ni Co Fe Y Others

ATD 2B 12 23 – Balance – 0.3


ATD 5B 11 18 – Balance – 0.5
LCO 22 8 22 32 Balance – 0.5 –
CN 122 8 22 32 Balance – 0.5 –
LN 34 11 20 Balance – – 0.5 0.5Mo
ATD 8 11 24 – – Balance 0.6 –
Amdry 963 6 25 Balance – – 0.4 –
Amdry 995 8 21 32 Balance – 0.5 –
Amdry 997 8.5 20 Balance 23 – 0.6 4Ta

LN and LCO coatings deposited by argon-shrouded plasma spraying, ATD deposited by EB-PVD, CN deposited by low-pressure plasma
spraying, Amdry are feedstock powders.
High Temperature Coatings: Protection and Breakdown 697

CMSX4
substrate

20 μm

MCrAlY
APS
coating

(a)

Ni plate

Figure 4 The duplex microstructure of a LPPS CoNiCrAlY


overlay coating. Courtesy of Dr. M.P. Taylor.
MCrAlY
LPPS
coating effect, however, possibly because the strains arise at
temperatures where the coating is ductile and stress
Interdiffusion zone relaxation rates are high.21,22 Nevertheless, the con-
cern has been one of the historic factors influencing
CM186 alloy
the incorporation of cobalt into many coating com-
positions in order to decrease the stability of the g0
(b)
phase. Even so, g0 phases have been reported20 in Ni-
MCrAlY based MCrAlY coatings containing 20 wt% Co.
EB-PVD
coating
Minor alloying additions, in addition to yttrium,
have also been made to MCrAlY coatings either in
attempts to improve alumina formation or adherence
IN738LC or to improve mechanical properties. Some examples
alloy include silicon23 and hafnium24 and also tantalum
(Table 2), titanium,23 molybdenum (Table 2), nio-
(c)
bium, rhenium, and zirconium. These are often used
Figure 3 Examples of the structure of MCrAlY coatings in combinations, but detailed compositions of current
deposited by (a) APS,2 (b) LPPS,2 and (c) EB-PVD 13
coatings tend to be proprietary. MCrAlY coatings have
techniques.
also been modified by means of surface enrichment
with silicon25 and aluminum (e.g., GE coatings 29+
composition can have a b/g microstructure at higher and 33+) and, in lower-density air plasma sprayed
temperatures, but at lower temperatures – often structures, by inward percolation of liquid NiAl3.26
corresponding to service conditions – can be g0 /a. In
reality, particularly if fairly rapid temperature 1.27.3.1.2 Examples of other metallic coatings
changes take place, the microstructure may be non- Much effort has been made to deposit metallic coat-
equilibrium and contain a mixture of the various ings other than MCrAlYs in attempts to improve
phases.20 An example of a typical duplex microstruc- substrate properties15; some examples designed to
ture is provided in Figure 4. Further complications confer oxidation resistance are given here.
may arise near the interface with the substrate alloy if Ti–Al alloys have considerable commercial poten-
g0 -stabilizing elements such as tantalum, titanium, tial because of their high specific creep strength, that
and niobium have diffused into the coating; the g0 is, the combination of good creep strength and low
phase can then exist to temperatures above 980  C at density. Their disadvantage lies in their poor oxida-
this location. tion resistance resulting from the competitive growth
Reaction [6] is also accompanied by linear con- of alumina and rutile (TiO2). Both of these oxides are
traction strains of 0.7% and there has been concern very stable, but the latter has a much higher growth
that this could prejudice the integrity of the coating. rate than alumina and the combination makes it
There is no particular evidence for any deleterious difficult to form and sustain protective conditions.
698 High Temperature Materials

The situation can be improved by the application of the formation of silica coatings. An early evaluation of
surface coatings of increased aluminum to titanium silica coatings, produced from silane onto a 9Cr ferritic
ratios having greater propensity to form alumina. steel, has been made by Crouch and Dooley.33 Later
Interesting examples are the use of a sputtered Ti– developments have used plasma-assisted vapor deposi-
51Al–13Cr (at.%) overlay27 to improve oxidation tion (PAVD) resulting from the decomposition of tetra-
performance of a near-a titanium alloy at 750  C in ethoxysilane. Very dense, uncracked, and adherent
air. A similar principle has been adopted28 through amorphous silica coatings up to 10 mm thick have been
the use of either graded or discrete sequential layers produced by this method on, for example, Incoloy
of Ti3Al, TiAl, and TiAl3, again on a near-a alloy. 800H,34 IN 738LC35 and 20Cr25Ni, Nb-stabilized aus-
In an alternative approach,29 it is recognized that tenitic steel.36 The improvements in oxidation resistance
at typical operating temperatures for Ti–Al (say obtained from these coatings have been substantial, for
700–750  C), it is not necessary to use an alumina example, decrease by a factor of 5 in mass gain for IN
layer for oxidation protection, since a chromia layer 738LC after 5000 h exposure in air at 900  C.35
will provide the necessary improvements. As a conse- A striking demonstration of the improvement
quence, it is possible to use Al-free chromia-forming obtained on the 20Cr25Ni austenitic steel at 1300  C
coatings of high fracture toughness and ductility to is given in Figure 5.37 In this figure, the top micro-
confer oxidation protection.29 graph shows how the entire cross-section of the
Overlay coatings may also allow the potential of uncoated specimen has been oxidized after 1h expo-
other reactive alloys with attractive mechanical prop- sure at this temperature in a CO2-based gas. In con-
erties to be realized. Important examples are those trast, the silica-coated specimen (lower micrograph)
alloys based on niobium, which have good creep is largely still intact. This example is particularly
properties at high temperature but poor oxidation interesting, since the 20Cr25Ni, Nb-stabilized
resistance. Alumina-forming FeCrAlY and silica- alloy is used as thin-walled (0.38 mm) tubes to contain
forming SiCrAlY overlays, deposited by APS, can UO2 fuel in the UK’s Advanced Gas-Cooled Reactors
produce oxidation protection to molybdenum for (AGRs). The test time and temperature used relate to
significant periods, 300 and 2000 h, respectively, at postulated fault scenarios with restricted coolant flow.
1200  C.30 An advanced coating architecture for the These substantial improvements in oxidation
protection of a Nb–5Mo–15W alloy has been devel- resistance arise because the silica coating acts as a
oped by Narita and coworkers,31 in which the outer barrier both to the inward diffusion of oxygen and to
Al-rich reservoir within the coating is protected from
interdiffusion by underlying Re–Cr-rich layers.

1.27.3.1.3 Oxide overlay coatings


Directly depositing a surface coating of a protective
oxide layer ought, in principle, to be an attractive
option, since it bypasses the need for the metallic
element to be present in significant quantities in the
underlying alloy. This is particularly the case for alu-
minum and silicon, whose presence in large amounts
can impair the mechanical properties of the alloy. (a)
A low-cost method for the deposition of an oxide
coating is through the use of sol–gels.15,32 In this,
the coating is formed by evaporation of a colloidal
suspension of oxide or hydroxide particles and subse-
quent consolidation of the deposit to form a dense layer.
A common feature, though, is the formation of cracks 225 μm
(b)
during the curing process, which necessitates the use of
multilayers to confer reasonable oxidation protection. Figure 5 Optical micrographs of cross-sections of
Even so, crack-like defects will exist within the layer specimens of a 20Cr25Ni, Nb-stabilized alloy after oxidation
for 1 h at 1300  C in a CO2/1% CO gas.37 (a) Complete
thickness, which will lead to decreased coating ductility. oxidation of the uncoated alloy and (b) relatively intact
A better approach is to produce the oxide layer from the silica-coated specimen. The magnification is the same in
vapor phase and this has had considerable success with each case.
High Temperature Coatings: Protection and Breakdown 699

the outward diffusion of the alloy constituents. and the need to protect against Type-I hot corrosion
A disadvantage, though, is that the coating offers no and high temperature oxidation. In the former case,
self-healing capability in the event that through- high chromium levels and chromia protective layers
thickness cracks or localized spallation occurs. In are optimum whereas, in the latter case, high alumi-
other words, there is no reservoir of silicon available num concentrations and protective alumina layers are
to reform the silica layer. Cracks in the layer will more effective.7,39 These coatings respond reasonably
allow oxygen ingress to the underlying alloy and the but not as well as coatings designed for specific local
continuing formation of nonprotective oxides.32 The conditions of temperature and environment within,
situation is aggravated in the case of amorphous silica say, a large land-based gas turbine. Furthermore,
because of its low linear thermal expansion coeffi- the range of protection afforded by these coatings
cient of 0.5  106 K1. Because the coating layer is is limited and hampers moves to a more flexible
much thinner than the metal thickness, it is reason- operating regime in which various alternative fuels
able to assume that the planar dimensions of could be employed, for example, ranging from natural
the coating will follow those of the underlying alloy gas through kerosene, diesel oils to gaseous fuels made
during a temperature change, DT ¼ (T  Tox), from coal, biomass, or waste.
(where T is the new temperature and Tox is the SMART MCrAlY overlay coatings have been
original oxidation temperature). The in-plane strain, designed40,41 to address this problem of flexibility
e, within the coating is then given as and also the need to increase fuel efficiency by
higher-temperature operation. Under these aggres-
e ¼ DT ðametal  asilica Þ ½7
sive conditions, high temperature oxidation and both
where a is the respective thermal expansion coeffi- Type-I and Type-II hot corrosion may be experi-
cient. A detailed discussion of such mechanical issues enced across a single component. The intention is
has been given elsewhere,38 but it is instructive here for SMART coatings to respond to the local environ-
to calculate the thermal expansion strain in the silica ment and to generate the optimum protective system
coating of Figure 5(b). Assuming that the silica layer to it, that is, either a chromia or an alumina layer. The
was deposited at 800  C, DT ¼ 500  C for the tem- coatings are chemically graded to provide surface
perature rise to the test temperature of 1300  C. layers enriched in aluminum and chromium, respec-
Taking also ametal ¼ 17.5  106 K1 then gives a tively, overlying a MCrAlY overlay coating. The
tensile in-plane strain within the silica coating of structure is shown schematically in Figure 6. The
0.85%. Interestingly, this is much higher than the
fracture strain values at 500  C of 0.27–0.45% found
Alumina layer
by Crouch and Dooley33 for sol–gel-deposited silica.
It can be surmised from Figure 5(b) that the silica
layer formed by PAVD remains uncracked, however, MCrAlY
High
even after the 500  C temperature rise, since there is b-NiAl
temp.
continued oxidation protection. It implies that the a-Cr Substrate
PAVD structure either contains fewer crack-like alloy
MCrAlY
defects and, hence, has higher intrinsic ductility
than the sol–gel equivalent or that creep processes
at the oxidation temperature relax stresses at crack Substrate
alloy Chromia layer
tips and, again, increase ductility.
Eventual degradation of the amorphous silica MCrAlY
layer is associated both with its transformation to
the crystalline state (a-cristobalite) and with reaction Low
Substrate
with cations from the alloy.34 temp.
alloy

1.27.3.2 SMART MCrAlY Overlay Coatings Figure 6 Schematic diagram of the chemically-graded
SMART coating structure showing the outer b-NiAl layer
The compositions of current MCrAlY coatings
and the intermediate Cr-rich zone overlying the base
(Table 2) reflect a compromise between the need to MCrAlY coating. The right-hand figures show the expected
provide protection against low-temperature Type-II response under different oxidation and hot-corrosion
hot corrosion and intermediate-temperature oxidation regimes.
700 High Temperature Materials

outer layer consists of b-NiAl produced by aluminiz- montage of SEM micrographs of cross-sections of
ing but before this treatment, the base MCrAlY coat- corroded specimens shown in Figure 7.40,41 The test
ing had been pretreated to form an intermediate layer duration in all cases was 500 h in an air–400 vpm
rich in chromium. Manufacturing details of this pro- SO2/SO3 environment and were recoated every 20h in
cess are currently proprietary,41 but it is the presence an 80% Na2SO4/20% K2SO4 eutectic mix. Figure 7
of this intermediate Cr-rich layer that distinguishes shows a comparison of a SMART coating variant
SMART coatings from over-aluminized variants, for (SmC 155H) with a Pt-aluminized diffusion coating
example, GT33þ, currently available. (RT22) and an over-aluminized CoNiCrAlY overlay
Under high temperature oxidation or Type-I hot coating in the as-produced condition and after testing
corrosion conditions, the outer layer of the SMART at 700 and 800  C. It can be seen that both commer-
coating reacts to form an alumina layer and provide cial coatings have been severely corroded at both
optimum protection. The Cr-rich intermediate layer temperatures whereas the SMART variant is rela-
acts as a diffusion barrier limiting interdiffusion and, tively unaffected at 800  C and shows penetration
particularly, the loss of aluminum from the outer only through the outer aluminized layer at the
layer into the base coating. Under Type-II hot corro- lower temperature.
sion conditions, say at 600–800  C, the outer region of
the coating forms an alumina layer sluggishly and is
1.27.3.3 Diffusion Coatings
intended to be sacrificed to allow the corrosion front
to encounter the intermediate Cr-rich layer at which 1.27.3.3.1 Basic types
a chromia protective layer will form. The rate of Diffusion coatings are formed by direct interaction of
pitting attack, associated with Type-II corrosion, the substrate alloy with elements, typically chro-
will then be substantially decreased at this stage. mium, aluminum, and silicon, which are capable of
Extensive testing of these coatings40,41 under hot forming protective oxide layers. Typically, coatings
corrosion conditions has demonstrated that these are produced through either immersion in a
concepts do work, as can be appreciated from the cementation-type pack or by vapor transfer of the

As manufactured 500 h at 700 ⬚C 500 h at 800 ⬚C

RT22
platinum
aluminide

100 μm 100 μm 100 μm

Over aluminized
CoNiCrAlY
(amdry 995)

200 μm 200 μm 200 μm

SmC 155H
smartcoat
treated
amdry 995
200 μm 200 μm 200 μm

Figure 7 Comparison of the corrosion morphology of a SMART coating variant with a RT22 (platinum-aluminide) coating
and an over-aluminized MCrAlY coating.41 See text for further details.
High Temperature Coatings: Protection and Breakdown 701

active species to the component remote from the unless formed by vapor deposition above pack) and
pack at temperatures where concurrent diffusion exists over a wide range of stoichiometry47 as shown
in the alloy develops the coating layer. Details can schematically in Figure 1. These coatings provide
be found elsewhere.13–18 Unlike overlays, diffusion good resistance to Type-I hot corrosion and to
coatings produced by these methods have limited high temperature oxidation through the formation
flexibility to vary composition, although it is possi- and maintenance of a protective alumina layer.
ble to codeposit more than one reactive species, Their disadvantage is that they are relatively thin
for example, Al/Cr,42 Al/Si,43 and Cr/Si44 and to and, although having higher aluminum contents
use predeposited layers, for example, platinum, to than the thicker MCrAlY overlay coatings, have a
vary coating structure.45 More flexibility with regard smaller total reservoir of aluminum. Loss of alumi-
to coating composition can be achieved through num through the oxidation process as well as by
the use of a slurry of reactive species, which can be interdiffusion with the substrate alloy limits their
painted or sprayed onto a work piece and sub- effectiveness after extended periods at high tempera-
sequently diffusion annealed. By repetition of this tures, say >1050  C.
process, multilayered coatings can be produced.46 A particularly successful modification to alumi-
Important examples include Cr–Si- and Al–Si- nide coatings has been the incorporation of platinum
rich compositions, for example, Sermaloy J and into the coating by deposition of a thin layer, 10 mm
Sermetel 1515. thick, prior to the aluminizing stage. The b layer
Chromizing can be used with both iron- and which is formed, again 50 mm thick, has the compo-
nickel-based alloys to provide protection at moderate sition (Ni, Pt)Al with platinum contents of 8 at.%.
temperatures (700  C) against Type-II hot corrosion This phase can also exist over a wide range of alumi-
and intermediate-temperature oxidation. The con- num and platinum contents.47 The microstructure of
centration of chromium in the alloy surface can be such a coating is shown in the as-received condition
raised to 40–80 wt% and this is sufficient to form a in Figure 8(a) as a bondcoat (BC) within a thermal
protective chromia layer. Chrome–aluminizing is also
used to improve protection, particularly at slightly
higher temperatures. It has become the case, however,
as temperatures increase in the pursuit of improved 25 μm EB-PVD YSZ topcoat
fuel efficiency, that more attention has been paid
to the production of aluminide layers and the Alumina TGO
subsequent formation of alumina protective layers. β-(Ni,Pt)Al bondcoat

1.27.3.3.2 Aluminide coatings IDZ

Important applications of aluminide coatings arise in


the protection of Co- and, particularly, Ni-based CMSX-4 superalloy
superalloys, since both form aluminide phases
(a)
which fix high concentrations of aluminum as a sur- Grit and
face layer, typically 30–70 mm thick. The coatings can possibly
voids
be produced from packs of either high or low alumi-
num activity. The former is processed at lower tem- β IDZ
peratures and the latter at higher temperatures in the
γ′
typical range 800–1100  C. High-activity aluminizing Pt-aluminide
results in the formation of a Ni2Al3 layer produced 25 μm coating
predominantly by inward diffusion of aluminum.
Constituents of the alloy can become incorporated
within this layer, which has relatively poor toughness. (b)
Improvements result in subsequent heat treatment to Figure 8 Cross-section of Pt-aluminide diffusion coatings.
convert the higher aluminide to NiAl. Low-activity (a) In the as-received condition as a bondcoat (BC) in a TBC
processing results directly in the formation of a NiAl system showing the fully b-(Ni, Pt)Al layer and an extensive
interdiffusion zone (IDZ) and (b) after 100h oxidation at
layer, which forms principally by the outward diffu- 1100  C showing partial transformation of the original b
sion of nickel. This layer is then relatively free of phase to g0 resulting from aluminum depletion. Courtesy of
alloy constituents (but can contain pack residues Miss F. Schenach.
702 High Temperature Materials

barrier coating (TBC) system, which will be flux of aluminum from the alloy into this zone. Con-
described later. It can be seen that there is also an centrations of aluminum in the Ni–Al–Pt coating
extensive interdiffusion zone beneath the b layer. need to be 10 wt%, that is, approximately twice
This contains a dispersion of phases rich in alloy the base alloy concentration, to stabilize the g/g0
constituents such as tantalum and titanium. phase structure at 1100  C.47 The likely range of
The addition of platinum to the b-phase appears aluminum contents within the coating, shown sche-
to improve the oxide spallation resistance of the coat- matically in Figure 1, is similar to that of MCrAlY
ings, possibly by decreasing the segregation of sulfur coatings and will be sufficient both to form an initial
to the oxide–metal interface.48,49 It also decreases the alumina layer and to reheal this in the event of its
chemical activity of aluminum47 and then should be failure (Figure 2). The apparent ‘uphill’ diffusion of
expected to decrease the extent of aluminum loss by aluminum out of the alloy into the coating, that is, its
interdiffusion with the substrate alloy. The experi- diffusion against its concentration gradient, can be
mental evidence is ambiguous, however, because explained again by the strong bonding between plati-
platinum additions also seem to increase the princi- num and aluminum. It must mean that the chemical
pal diffusion coefficient of aluminum.47 Continued activity of aluminum within the coating is lower than
exposures at high temperature will inevitably result that within the alloy so that the enrichment within
in aluminum depletion as a consequence of both the coating is simply a consequence of aluminum
alumina formation and interdiffusion and this will diffusing down its activity gradient. As recognized,47
cause phase transformation within the coating along the coating has a replenishing capability by being
the sequence able to transfer aluminum into itself from the alloy,
as the continued growth of the alumina layer removes
b ! g0 ! g
aluminum from its outer surface.
An example of a Pt-aluminized coating with par-
1.27.3.3.4 Silicide diffusion coatings
tial transformation to the g0 phase after oxidation at
Silicide coatings have the potential of offering signif-
1000  C for 100 h is shown in Figure 8(b). It should
icant improvements in oxidation and hot corrosion
be noted, though, that both phases have adequate
resistance through the formation of a protective layer
aluminum contents to maintain a protective alumina
of silica. Siliconizing of iron and simple carbon steels
layer.
was achieved by Fitzer in 195453 using pack cemen-
tation. These coatings were found to improve resis-
1.27.3.3.3 Platinized coatings tance to both Type-I and Type-II hot corrosion.
An important variation on the conventional Pt- They consist principally of an outer layer of ferrite
aluminized coatings described above is to omit the alu- containing up to 10 wt% Si and are susceptible to
minizing stage in coating manufacture but to retain cracking during mechanical and thermal loading.54
the step of platinum deposition and subsequent Silicon-rich coatings on Ni-based alloys have been
inward diffusion into the Ni-based superalloy. This achieved using chemical vapor deposition (CVD)55
approach was patented in 1999 by Rolls-Royce and but there are concerns with the Ni–Si system over
Chromalloy UK50 and has subsequently been devel- the presence of relatively low melting temperature
oped to the stage of commercial deployment as BCs in eutectics. NiSi, in particular, forms an eutectic with
TBCs – see later text for a description of these. Unfor- Ni2Si which melts at 943  C. More attractive
tunately, few of the results of the underlying research approaches for iron- and nickel-based alloys are
work supporting this development have appeared in likely to involve the incorporation of silicon into
the open literature.51,52 chromized or aluminized layers.36,56
The key requirement of the coating is that it Direct reaction of silicon with the alloy substrate to
should be capable of forming and maintaining a pro- form a high melting-point surface layer is of particular
tective alumina layer. It is not intuitively obvious, interest with molybdenum-,57 niobium-,58 and tita-
however, that this should be so because no aluminum nium-based57,59–62 alloys. The last, in particular, are
is added and, as is recalled from Section 1.27.1 and of current relevance in aeroengines because of their
1.27.2, the Ni-based superalloy has borderline prop- good density-compensated creep properties but are
erties in this respect. Nevertheless, a 50-mm-thick g/ handicapped by poor long-term oxidation resistance.
g0 surface zone of enhanced aluminum concentration A wide range of titanium silicides can be produced
is formed indicating that there must be an outward in sequential layers on the alloy surface by using a
High Temperature Coatings: Protection and Breakdown 703

cementation pack, as shown by Cockeram and The subsequent reaction [9] produces the silicide:
Rapp.57,61 These coatings can be 100 mm thick and
5Tiþ3SiO ! Ti5 Si3 þ1‰O2 ½9
substantially improve oxidation resistance, particu-
larly when doped with germanium when oxidation The overall reaction is
rates in the temperature range 700–1000  C are simi-
5Tiþ3SiO2 ! Ti5 Si3 þ3O2 ½10
lar to those for the growth of silica itself (Figure 9).
Protection is maintained even under thermal cycling This reaction will only proceed in the direction shown
but the layers are brittle and cracking should be at low oxygen partial pressures, calculated by Gray
expected. This is accentuated by the thickness of et al. 62 at 7.7  1022. This seems to have been achieved
the coating which increases the probability of crack- in a sealed silica capsule, evacuated from an argon
like initiating defects being present. atmosphere, without the use of extraneous oxygen
Thinner coatings (1–10 mm) can be produced by getters, such as titanium chips, but by using the
siliconizing, in which the test piece is buried in silicon a2 phase of the alloy as an intrinsic getter. As with the
powder, at temperatures between 800 and 1100  C.59,60 above, a substantial improvement in oxidation resis-
Higher temperatures in this range favor the formation tance, a factor 5 in weight gain in this case, was achieved
of the Ti5Si3 phase rather than TiSi2 as the outermost over the uncoated Ti–Al control over the test duration
layer produced in the cementation pack.57,61 These of 500 h at 900  C. The parabolic rate constants of the
thin Ti5Si3 layers were uncracked and the layers more protective coatings are plotted in Figure 9 and
again conferred significant improvements in oxidation compared with the behavior of unalloyed titanium63
resistance of the underlying Ti-rich alloy, as can be and pure silicon.64 It can be seen that only the Ge-
appreciated from Figure 9. A rather novel approach62 doped coatings actually achieve the level of protection
to producing a thin, 1–2 mm, layer of Ti5Si3 is to use expected of a pure silica layer.
reaction (B) below to transport silicon to a Ti–Al test Broadly similar behavior to the Ti5Si3 coatings
piece via gaseous SiO. has been found by Taniguchi et al.65 for the bulk
phase. In this case, rutile (TiO2) had formed above
3SiO2 ! 3SiO þ 1‰O2 ½8 the silica layer and clearly contributed to the weight

10–2

Unalloyed Ti (Kofstad)
10–3
Gray et al.
Parabolic rate constant (mg2 cm–4 s–1)

Li et al.
10–4
Cockeram and Rapp, B-modified
Cockeram and Rapp, Ge-doped
10–5

10–6

10–7

10–8
Pure Si
(Deal and Grove)
10–9
7.5 8.0 8.5 9.0 9.5 10.0 10.5
104/T (K–1)
Figure 9 Parabolic rate constants for some silicide-coated titanium-rich alloys compared with the behavior of unalloyed
titanium and silicon.
704 High Temperature Materials

gain of the specimen. An implication is that the The most recent development is the use of cast, sin-
beneficial influence of Ge-doping (Figure 9) arises gle-crystal alloys, such as CMSX-4 (see Table 1), for
by limiting the transport of titanium through the blades which remain cooled and also are now coated
silica layer. with TBC systems. The use of these can improve
engine efficiency and can also extend service life-
times.66,67 This same general developmental trend is
1.27.3.4 Thermal Barrier Coatings
mirrored in land-based turbines although TETs in
When discussing the need for high temperature coat- these cases tend to be lower and the moves toward
ings in Section 1.27.1, emphasis on placed solely on TBC usage lag behind those of aeroengines. A cross-
achieving adequate oxidation and corrosion resis- section of a typical TBC system is shown schemati-
tance. However, under modern turbine conditions cally in Figure 11.
and in other applications, such as diesel engines, it A TBC system consists of the outer thermal bar-
can also be necessary to protect the substrate alloys rier topcoat which is attached to the alloy substrate
from combustion temperatures by means of TBCs. by means of a mechanically-compliant, oxidation-
This developmental trend for aeroengines and asso- resistant BC. The topcoat is generally zirconia,
ciated Ni-based superalloys is shown in simplified containing 7–8 wt% yttria. This addition provides
form in Figure 10. partial stabilization of the tetragonal (and cubic) zir-
It can be seen how in the first 20 years or so, blade conia phases and avoids the volume changes asso-
alloys had adequate properties in the wrought and ciated with the formation of the monoclinic phase.
unprotected form to satisfy turbine requirements. In This yttria-stabilized zirconia (YSZ) layer (sometimes
the early 1960s, a significant change in blade design termed yttria partially stabilized zirconia (YPSZ)) has a
permitted the use of some intake air to provide cool- low thermal conductivity, 1 Wm1 K1, which is
ing and this increased the turbine entry temperature approximately an order of magnitude lower than that
(TET) significantly above the inherent capabilities of for alumina. It means that for cooled turbine blades, a
the substrate alloys. During this period from 1940 to temperature drop of perhaps 150  C can be obtained
approximately 1990, successive generations of super- across a 250–300-mm-thick topcoat during service
alloys were developed with improved mechanical which provides considerable benefit to the load-bear-
properties and, hence, higher temperature capabil- ing capability of the Ni-based superalloy. It needs to be
ities. This has been shown simply as a linear trend in emphasized, however, that the YSZ topcoat is perme-
Figure 10 but more details can be found elsewhere.1 able to oxygen and will not provide oxidation protec-
The main change during this period was to move from tion. This is achieved by means of the BC which is
wrought to cast, directionally-solidified structures. intended to be alumina-forming and can be based on

Uncooled Cooled Coated


2100 blades blades blades

1900

Turbine
TET capability k

1700 capability
Superalloy
1500 capability

1300

Cast Cast
1100 single-crystal
polycrystalline
Wrought alloys
alloys
900 alloys

1940 1960 1980 2000


Date
Figure 10 A comparison of the historical increase in turbine entry temperature (TET) for aeroengines and the associated
temperature capability of the alloys used for turbine blades.
High Temperature Coatings: Protection and Breakdown 705

aeroengines, platinized diffusion coatings. A typical


TBC topcoat
cross-section of a system consisting of an EB-PVD
topcoat and a Pt-aluminide diffusion BC is shown in
Figure 8(a). The columnar nature of the EB-PVD
TGO topcoat is evident and can be contrasted with the splat
Bondcoat structure of that produced by APS. A much more
extensive interdiffusion zone than in the MCrAlY
Substrate alloy system is also formed during coating manufacture.
To date, the commercial exploitation of TBC
systems has been dominated by applications using
Ni-based alloys but there is also foreseeable potential
for their use on other high temperature structural
materials such as the Ti–Al series. Significant prog-
Figure 11 Schematic cross-section of a thermal barrier ress has already been made in the production of
coating system. aluminide diffusion coatings on Ti-based alloys69–71
and recently these have been used as a BC under an
APS YSZ topcoat in a TBC system.72

APS YSZ topcoat

MCrAlY bondcoat
1.27.4 Case Study I: Oxidation and
Lifing of MCrAlY Overlays
IN738 superalloy
1.27.4.1 Protective Oxidation
In the initial stages of exposure of a complex alloy
Figure 12 Cross-section of a typical land-based TBC
coating system consisting of an air plasma sprayed (APS) such as the (Ni, Co)CrAlYs, all constituents which
YSZ topcoat with a MCrAlY BC68 on an IN738 Ni-based can oxidize will do so and nonprotective oxides such
superalloy substrate. Note the relatively rough BC surface as NiO together with spinels such as NiCr2O4 are
and the limited interdiffusion zone compared with the TBC likely to form. Eventually, however, a continuous
system shown in Figure 8(a).
a-alumina layer will develop underneath these oxi-
des and oxidation rates will rapidly decrease. The
formation of metastable aluminas, even at the rela-
one of the MCrAlYoverlays discussed previously or on tively low temperature of 950  C, was not found in a
diffusion coatings of the Pt-aluminide or platinized study73 using in situ high temperature XRD on a
variants. The oxidation of these BCs forms a layer of CoNiCrAlY coating. This transitional behavior may
thermally grown oxide (TGO) over time between not be an issue with these systems at relevant operat-
the BC and TBC topcoat as shown schematically in ing temperatures although with FeCrAlY alloys at the
Figure 11. As will be discussed in some depth in slightly lower temperatures of 900 and 925  C, the
Section 1.27.5, the formation of the TGO plays a transition from y- to a-alumina took tens of hours.74
significant role in the failure by spallation of the TBC. The growth kinetics of the a-alumina layer on
TBC systems used in practice on Ni-based super- MCrAlY-type alloys have been variously reported
alloys for turbine applications tend to be of two dis- to be parabolic (eqn. [1])75,76 or subparabolic77 as in
tinct types. For large, land-based units, a system the general eqn. [11] for increase in oxide thickness,
consisting of a MCrAlY BC, deposited by any of the h, with exposure time, t, at a constant temperature.
processes discussed previously, with a YSZ topcoat
h ¼ ho þ kn t 1=n ½11
produced by APS is usually used. An example of this
system is shown in Figure 12. In smaller machines, Here, ho is the preexisting oxide thickness at t ¼ 0, n is a
such as aeroengines or, increasingly, small land-based time-invariant numerical constant, and kn is
turbines, YSZ layers deposited by electron-beam the corresponding rate constant. Ideal parabolic con-
physical vapor deposition (EB-PVD) are favored. ditions exist when ho ¼ 0 and n ¼ 2 (eqn. [1]) but
These TBC systems can use MCrAlY BCs also but subparabolic kinetics obtain when n > 2. The reasons
more typically have Pt-aluminide or, in Rolls-Royce for the differences in kinetics are poorly understood
706 High Temperature Materials

although there are considerable implications for the 10–9


longevity of the coatings. Subparabolic kinetics can CoCrAl Ni3Al
CoCrAlY Ni–25Al
arise, in principle, as a result of an increase with time FeCrAl Ni–32Al
of compressive growth stress within the oxide layer.38,78 FeCrAlSc NiCrAl
They will also arise79 if oxide grain size increases FeCrAlY NiCrAl
10–10 FeCrAl(Y) NiCrAl
during exposure and diffusion of reactive species
occurs principally by grain boundary diffusion. It is FeCrAl(Ce) NiCrAlY
FeCrAlY NiCrAl (Th, Y)
also feasible, particularly with a stoichiometric com- NiAl Pt-6Al
pound such as alumina, that the gradual incorporation
10–11

kp (g2 cm—4 s)
of coating or alloy (minor) constituents affects any
doping of the oxide layer so as to decrease diffusion
rates progressively with time. Apparent subparabolic
kinetics will also occur in those systems and exposure
conditions in which metastable alumina forms and 10–12
transforms over time to the a phase.80 The situation is
unclear and, for present purposes, it will be assumed
that the a-alumina layer grows parabolically with time
with ho ¼ 0 and n ¼ 2 in eqn. [11]. This assumption 10–13
leads to conservative estimates of coating lifetimes.
The temperature dependence of the parabolic
rate constant for the growth of a protective a-alumina
layer on various coating-type alloys is shown in 10–14
1300 1200 1100 1000 900
Figure 13,75,76 but expressed in terms of mass gain, T (⬚C)
Dm, per unit surface area. A reasonable mid-range
expression for the rate constant, kp0, from Figure 13 is Figure 13 Parabolic rate constants for the formation of
  alumina on coating-type alloys.76
275 000
kp0 ¼ 2:68  104 exp  ; mg2 cm4 s1 ½12
8:314T
where T is absolute temperature and the mass gain has h 20
xh    15:6 mm ½15
been expressed in the more common units of mg cm2. f 1:28
This equation can be expressed in terms of the para- where f is the Pilling–Bedworth ratio for alumina
bolic rate constant kp, which uses oxide thickness rather (1.28). This level of loss in an MCrAlY coating some
than mass gain, by means of eqn. [13]. 200 mm thick after this exposure period would be
 
Mox 2 0 excellent behavior but, unfortunately, other degrada-
kp ¼ k ½13 tion processes also occur which limit lifetimes. Princi-
3Mo rox p
pal among these is the loss of aluminum from the
Here, rox is the density of a-alumina (taken as 4000 mg coating and the consequences of this. Depletion will
cm3), Mox is the molecular mass of alumina and Mo is occur as a result of selective oxidation, as described in
that of oxygen; the factor three arises because there are Section 1.27.2.2, and will increase with time at tem-
three oxygen atoms in Al2O3. This conversion equates perature. In addition, it will be exacerbated by spall-
1 mg cm2 mass gain to an 5.3 mm thick layer of ation or cracking (and rehealing) of the protective
a-alumina. Using eqn. [13] to substitute into eqn. [12] oxide layer, geometrical factors, internal oxidation,
then gives: and interdiffusion with the substrate alloy. All of these
 
275 000 factors will be considered in this section.
kp ¼ 7:56  107 exp  m2 s1 ½14
8:314T
1.27.4.2 Spallation and Cracking of the
The protection offered by the alumina layer can be
Protective Alumina Layer
appreciated by using eqn. [14] in eqn. [1] to show that
the oxide thickness after 30000h at 1000  C is still only Spallation and cracking of the protective oxide layer
20 mm. This corresponds to a section loss, xh, of the results from the generation of strains and associated
coating of 38 stresses arising from the oxide growth process,
High Temperature Coatings: Protection and Breakdown 707

from temperature changes or imposed upon the com- relative to the metal substrate, the equation can be
ponent. The issues are particularly complex since simplified to (compare eqn. [7]):
they depend on the nature of the oxidation process
Eox T ðam  aox Þ
(the balance between growth by cation or anion sox ¼ ½17
fluxes), on the curvature of the substrate and on the ð1  uÞ
elastic, plastic and, particularly, creep properties of It is also reasonable to assume that the underlying
the respective layers of the coating system. A back- superalloy is much thicker than the coating and, of
ground review is available38 and phenomenological course, the oxide so that the alloy’s dimensional
approaches to failure which combine strains from changes are imposed upon the oxide. This means
multiple sources have also been developed.81–83 that in eqn. [17], the expansion coefficient, am, should
These predictive approaches have been formulated be that for the superalloy rather than for the coating.
specifically for TBC systems but contain general Using representative values of, u ¼ 0.3, Eox ¼ 387
principles. GPa, aox ¼ 7.9  106 K1, and am ¼ 15.0  106
This chapter emphasizes solely the influence of K1 in eqn. [17] predicts a residual in-plane oxide
thermal strains in producing oxide spallation from a stress of 3.9 GPa after a temperature drop of
MCrAlY substrate in order to establish mechanisms. 1000  C. Values of stress of this magnitude have
Strains deriving from oxide growth will be signifi- been measured in related alloys and coatings.68,85,86
cant only if creep relaxation rates are low or, on Since the values of expansion coefficients and
curved surfaces, if the oxide thickness is of similar Young’s modulus are assumed to be independent
magnitude to the local radius of curvature.38 For of temperature, the elastic oxide stress varies pro-
now they are neglected but, if significant, can sim- portionately with temperature change and will be
ply be introduced as an additive term.82 The impli- tensile for temperature increases above the oxida-
cation is that the alumina–MCrAlY interface is tion temperature.
sensibly flat, that is, there are no locations where Spallation under in-plane compression can
the local radius of curvature is of similar magnitude occur by two nominally distinct routes depending
to the oxide thickness. During cooling there are on the relative strengths of oxide and oxide–coating
then negligible out-of-plane strains, provided the interface,38,39 as shown schematically in Figure 14.
oxide remains adherent, but a substantial biaxial The critical stress for buckling of the oxide layer
compressive in-plane strain can develop within the (Figure 14(a)) can be obtained from standard
oxide layer. If elastic conditions are assumed, this text87 and converted38 to a critical temperature
strain corresponds to an in-plane oxide stress, sox, drop, DTb, of
given by84:  2
1:22 h
Eox T ðam  aox Þ Tb ¼ ½18
sox ¼   ½16 ð1  u2 Þðam  aox Þ R
ð1  uÞ 1 þ EEmoxwh
where the symbols have the same meaning as previ-
Here, DT (¼T  Tox) is the temperature drop, ously and R is the radius of the circular zone of prior
taken as a negative quantity, Eox and Em are the decohesion at the oxide–coating interface. It can be
Young’s moduli of, respectively, oxide and metal; a appreciated that for a given value of R, the tempera-
is the corresponding linear thermal expansion coef- ture drop required to effect buckling increases with
ficient; u is the Poisson’s ratio, assumed to be the oxide thickness. For typical values of the various
same for oxide and metal; h is the oxide thickness, parameters, the zone diameter needs to be approxi-
and w is half the specimen thickness. For thin oxides mately at least 20 the thickness of the oxide layer

Oxide
layer Compression

Metal
(a) substrate (b)
Figure 14 Spallation of the oxide layer under in-plane compression from the metallic MCrAlY substrate can occur by
either (a) a buckling or (b) a wedging process.
708 High Temperature Materials

before the buckle configuration can develop. Thus, 10


for a typical oxide thickness of 5 mm, a circular inter- ΔTc = 397 ⬚C

facial zone of some 100 mm would be required.


8 102 ⬚C h–1
This is a problematic issue since such large areas of 104 ⬚C h–1
decohesion are not seen at the alumina–MCrAlY

Crack length (μm)


interface in these simple overlay coatings. The 6
intrinsically good adherence of the alumina layer is
related to the addition of yttrium into these coatings
which appears to mitigate the potentially harmful 4
effects of sulfur segregation in lowering interface
adhesion.88,89
2
In the presence of good adhesion between oxide
and coating, a thick protective layer can develop but
this, as found on related systems, still contains poros- 0
ity and crack-like defects.90,91 At some critical value
0 100 200 300 400 500 600
of the compressive thermal stress generated during
Temperature drop (⬚C)
the cooling transient, a shear crack can be initiated
from one or more of these defects, as shown schema- Figure 15 Finite-element predictions of the kinetics of
interfacial wedge crack growth for an alumina layer on
tically in Figure 14(b). Continued cooling and con- Haynes 214 cooled from 1100  C at the rates shown. The
traction of the oxide layer will produce further shear dashed line reflects ideal behavior for spallation to occur at
on the crack-like surface and the development of out- a critical value of oxide strain energy.
of-plane tensile stresses at the oxide–coating inter-
face. A consequence is that a wedge crack will grow
along this interface as cooling continues and may oxide–metal interface at a temperature drop DT is
cause spallation of the overlying oxide layer. Exten- given as95:
sive finite-element (FE) modeling of this wedging hW ¼ hEox ð1  uÞðT Þ2 ðam  aox Þ2 ½19
process has now been undertaken for chromia and
alumina layers on various metallic substrates.92–94 Equating this to the fracture energy, gF, of unit area of
A consistent result from this work is that the growth interface gives the critical temperature drop for spall-
rate of the interfacial wedge crack is significantly ation as:
retarded during cooling as a result of the relaxation " #1=2
gF
of crack-tip stresses by creep of the adjoining metal. Tc ¼ ½20
Some results93 for a 5-mm-thick alumina layer on hEox ðam  aox Þ2 ð1  uÞ
Haynes 214 are given in Figure 15. They show that
the wedge crack nucleates quickly but its growth rate This shows that the critical temperature drop
is then stopped until some lower temperature at decreases with oxide thickness, that is, spallation
which rapid propagation occurs over a narrow tem- becomes easier for thicker oxides which is a common
perature range. This period of quiescence corre- observation. It contrasts with the buckling mode (eqn.
sponds to the period of significant stress relaxation [18]) which becomes more difficult with increasing
by alloy creep and its extent decreases with increased oxide thickness.
cooling rate, as shown. In applying eqn. [20] for prediction it should be
The general behavior shown in Figure 15 can be noted that the fracture energy is an effective value
approximated by the dashed horizontal and vertical since most of the strain energy is lost by creep relax-
lines superimposed, for clarity, only on the FE results ation during the cooling transient.92–94 Its value can
for a cooling rate of 104  C h1. They can be inter- be obtained from eqn. [20] using the FE predictions
preted as showing that the oxide remains adherent to of DTc and is always larger than the intrinsic fracture
the alloy or coating until a critical temperature drop, energy of the interface when relaxation processes are
DTc, at which stage the stored strain energy, W*, per present. Thus, for the example shown in Figure 15,
unit volume in the oxide layer is sufficient to produce gF is calculated to be 33 J m2 for the higher cool-
decohesion of the oxide–metal interface. For a thin ing rate and 62 J m2 for the lower. Using a similar
planar biaxially strained oxide layer of thickness h, approach for a free-standing NiCrAlY coating,93 the
the strain energy in the oxide layer per unit area of values of the effective fracture energy shown in
High Temperature Coatings: Protection and Breakdown 709

Table 3 Estimated effective fracture energies, gF, for shown in that section, how the aluminum concentra-
the spallation of a 5-mm-thick alumina layer from a free- tion can be decreased beneath the oxide but that the
standing NiCrAlY coating92
aluminum reservoir within the bulk of the coating
Cooling rate Computed DTc ( C) g F (J m2) could maintain concentrations sufficiently to ensure
( C h1;  C s1) reformation of the alumina layer in the event of its
spallation or cracking. Nevertheless, the depletion of
102 745 40
103 620 28 aluminum by selective oxidation will destabilize Al-
104 550 22 rich phases in the vicinity of the surface oxide. In
105 382 10 particular, dissolution of the b-NiAl phase will occur
106 314 7 in a zone near the alumina layer100,101 and, as
expected for parabolic oxidation kinetics, the depth
of this b-free zone will thicken parabolically with
Table 3 are obtained as a function of cooling rate. time. In addition, loss of aluminum by interdiffusion
This decrease of gF with increasing rate reflects the with the substrate can also result in the formation of a
decreased contribution from creep relaxation and b-free zone at this inner interface. With continued
shows that no unique value of the fracture energy exposure, the entire coating can become free of the
can be assumed. It is possible, however, to interpolate b-phase and this has been used as a failure condition
between these results for any given conditions within for the coating.100 This is a useful pragmatic approach
the range shown. The values of gF given in the table but is conservative since sufficient aluminum will
are typically 10–100 greater than the likely intrinsic usually still be present to provide a rehealing
interfacial fracture energy but are of similar magni- capability.
tude to those measured by blister testing96 and spall- Even so, substantial exposure periods can be
ation93,94,97,98 on other systems. obtained while still retaining some b-phase. Anton
This discussion has highlighted the benefits of et al.,101 for example, find a total b-depletion zone,
stress relaxation within the coating to the spallation from inner and outer coating surfaces, of 160 mm
resistance of the oxide during a simple cooling tran- in a 250-mm-thick LPPS CoNiCrAlY coating after
sient. It should not necessarily be generalized from 10000h at 1000  C. This particular coating contained
this, however, that weak coatings should be preferred only 8 wt% Al but exhibited substantial interdiffu-
over strong. An important consideration is that creep sion with the IN738LC alloy substrate and formation
relaxation during thermal cycling can generate a of Kirkendall voids within the interdiffusion zone
mechanical hysteresis loop94,99 which can place the (IDZ). The extent of b depletion was decreased, as
oxide layer into in-plane tension on the return to expected, by increasing the aluminum content to
temperature. Consequent tensile cracking will, of 12 wt% in a NiCoCrAlY coating but rhenium addi-
course, impair the protective function of the oxide tions also decreased the extent of interdiffusion. In
layer. Strong coatings are also desirable to maintain this case the total b-depletion zone was only 75 mm
mechanical stability in rapidly rotating components. after 10 000 h at 1000  C.101
The balance of creep properties between high and Although the extent of aluminum depletion
low strength will depend on the application, for resulting from selective oxidation can be predicted
example, the magnitude of external stresses, the fre- based on the concepts outlined in Section 1.27.2.2, it
quency of thermal cycling, the rate of change of is much more difficult to model the interdiffusion
temperature, and the presence of hold periods within process. Analytical and numerical attempts have been
the creep regime. made for MCrAlY systems83,102 but it is difficult to
deal with diffusion and concurrent precipitation
without knowing the appropriate interaction terms
1.27.4.3 Aluminum Depletion
for the diffusion coefficients or, equivalently, the
1.27.4.3.1 Uniform depletion chemical activities of the diffusing species. Taylor,
The second main form of coating degradation is et al.,102 for example, report how the diffusion of
through the loss of aluminum and the consequent aluminum from a LPPS CoNiCrAlY coating into a
inability to maintain and reform the protective alu- CM186 substrate alloy, in the early stages of exposure
mina layer. A general discussion of the depletion at 1200  C, is limited by the formation of Al-rich
occurring as a result of the selective oxidation of phases, associated with tantalum, within the IDZ.
aluminum has been given in Section 1.27.2.2. It is With continued exposure and further aluminum
710 High Temperature Materials

25 depletion within the coating, these phases dissociate


and act as a reservoir to resupply aluminum back into
Isolated particle the coating. These counter-flows of diffusive flux
20 reflect the changing aluminum activities within the
Al concentration (at.%)

coating and IDZ. They emphasize that, in such com-


15 Initial concentration plex situations, modeling using single-valued diffu-
No diffusion sion coefficients and chemical potential gradients
cells approximated by gradients in concentration can
10 lead to erroneous results.
Interesting future developments to limit inter-
D = 2.40 ⫻ 10–14 m2 s–1 diffusion are likely to involve the control of aluminum
5 kp = 1.16⫻ 10–16 m2 s–1 chemical activity within the coating103 or the use of
diffusion barriers such as a-Cr or Re-based alloys.104
0
0 5 10 15 20 25 30 35 40 45 50 55 1.27.4.3.2 Diffusion cells and chemical failure
(a) Distance (μm) In practice, exceptions to the ideal condition of
uniform depletion will exist. These include the diffu-
25
sional isolation of volumes of the coating as a result of
internal oxidation or geometric factors. As high-
D = 2.40 ⫻ 10–14 m2 s–1 lighted in Figure 3, MCrAlY coatings deposited by
20 kp = 7.87 ⫻ 10–17 m2 s–1
plasma spraying in air (APS) are of relatively low
Al concentration (at.%)

density as a result of oxidation of the sprayed parti-


15 Initial concentration cles during coating formation. Bonding between the
splats within the coating is impaired and internal
No diffusion cells
oxidation at the splat surfaces can continue during
10 subsequent exposure. ASPS and even HVOF coatings
probably also suffer from this but to a lesser extent.
The alumina layers formed internally in APS
5
MCrAlY coatings have been shown105 to act as diffu-
sion barriers which isolate the splat volume from the
0 reservoir of aluminum in the remainder of the coat-
0 5 10 15 20 25 ing. As a consequence, aluminum depletion within
(b) Distance (μm)
the relatively small splat volume occurs at a much
25 greater rate than would be expected for the coating as
a whole. This is shown in Figure 16 for an APS
D = 2.40 ⫻ 10–14 m2 s–1 CoNiCrAlY coating oxidized in air at 1100  C.105
20 kp = 6.30 ⫻ 10–17 m2 s–1 Here the measurements of aluminum concentration
were obtained across separate diffusion cells which
Al concentration (at.%)

were located at the surface of the coating and


15 Initial concentration bounded around their surface by an alumina layer.
No diffusion cells
The lines in the figures are predictions from eqn. [21]
which considers the cell to be approximated as a long
10
2-dimensional slab, on both flat surfaces on which
alumina grows parabolically.
5

The points are measured using SEM/EDS and the solid line
0 is the best-fit solution to eqn. [21] using the values shown for
0 5 10 15 20 25 30 35 40 45 50 55
D and kp. See text for more details. The dashed line is the
(c) Distance (μm)
expected depletion profile, using the same values of D and
Figure 16 Enhanced aluminum depletion measured in kp, if diffusion cells were absent. Oxidation was performed in
individual diffusion cells in an APS CoNiCrAlY coating. air for (a) 4 h, (b) 4 h, and (c) 100 h.105
High Temperature Coatings: Protection and Breakdown 711

 
50 pkp 1=2 500 20
C ¼ Cb  :
f D 200
" ! !# 10
X1

Exposure time at 1100 ⬚C (h)


2nwþx 2ðnþ1Þw  x 100 Chemical failure
þ erfc ½21

Alumina thickness (μm)


erfc 1 1
n0 2ðDt Þ2 2ðDt Þ2 50 5.0

Here, C is the aluminum concentration in at.%, Cb is 20


3.0
the initial value within the cell, D is the aluminum 10
2.0
interdiffusion coefficient, 2w is the cell width, x is
5
the distance from the oxide–metal interface, and 1.0
t is the exposure time. The predictions were made No chemical failure
2
using a single-valued interdiffusion coefficient 2.4  0.5
1
1014 m2 s1 (N.B. the sites were remote from any 0.3
0.5
interdiffusion effects from the substrate) consistent 7 10 20 30 40 50 70 100 200
with measurements on NiCrAl106 and CoCrAl107 Cell width, 2w (μm)
systems. The corresponding kp values to give the
Figure 17 A chemical failure (CF) map for a MCrAlY
observed fit vary within a factor 2 but lie within the coating (M¼Co,Ni). The left-hand ordinate refers to
data spread of Figure 13 (shown there in terms of exposure times at 1100  C but the oxide thickness of the
mass gain). The expected depletion profile without right-hand ordinate is independent of temperature.
diffusion cells is shown by the dashed line. The
agreement with the data is good and confirms that
oxidation is continuing at similar rates at both the initiating CF is relevant to the MICF condition
external and internal surfaces in these coatings. It can assuming a critical aluminum concentration of 5 at.
be seen that depletion is much more pronounced in %. The exposure times shown as the left-hand verti-
the small cell of Figure 16(b) than in the larger one cal axis refer to 1100  C but the oxide thicknesses
of Figure 16(a) even after 4 h at 1100  C. After 100 h (right-hand axis) apply at other temperatures also.
exposure, aluminum has been essentially consumed Clearly, small cells are susceptible to early MICF
in the 55 mm cell, Figure 16(c). leading to the consumption of the entire cell volume
The decrease in aluminum concentration can with the formation of porous and friable nonprotec-
make these cell volumes susceptible to chemical fail- tive oxides. For dense coatings, however, for example
ure (CF) at which stage fast-growing nonalumina those produced by LPPS, internal oxidation is negli-
oxides will form. A framework theory of CF can be gible and small diffusion cells do not form.110
found elsewhere.108 The cell will be susceptible to MCrAlY coatings produced by spraying tend to
mechanically induced chemical failure (MICF) when have convoluted surfaces consisting of protuberances
the aluminum concentration anywhere within it with dimensions relating to those of the original
(usually, at the center plane) falls below that needed sprayed particles. They may also be postprocessed
to reform the alumina layer should the original crack to change this topography but usually have a signifi-
or spall. Intrinsic chemical failure (InCF), unlike cant residual surface roughness. The significance is
MICF, is a thermodynamic boundary at which the that a surface protuberance will have a surface-to-
aluminum concentration at the oxide–metal interface volume ratio larger than that of a flat coating. Alumi-
falls to that below which alumina can be reduced by num depletion will then occur at an enhanced rate
another of the coating constituents, chromia for and early CF of the protuberance can be expected.
example. This critical concentration is very close to Calculation of the rate of depletion is difficult to
zero for the reduction of alumina by chromium but undertake analytically because the protuberance is
there is experimental evidence for the formation of not isolated from the bulk of the coating, as with the
Cr-rich oxides beneath an alumina layer in NiCrAlY diffusion cells discussed earlier. Some resupply of
coatings.109 aluminum will occur via the neck of the protuber-
A CF map for MCrAlY coatings can be con- ance. Useful progress in prediction can be made,
structed using eqn. [21] as shown in Figure 17. however, using numerical finite-difference methods
The calculations were performed using D ¼ and an example of some results, obtained using the
2.4  1014 m2 s1, as above, and a mid-range value 2-dimensional ODIN (Oxidation and INterdiffusion)
of kp ¼ 9.0  1017 m2 s1. The threshold line for code, is shown in Figure 18. These results apply to a
712 High Temperature Materials

0 10 20 30 40 50 longevity. In order to achieve this and to develop the


0
full potential of TBC systems safely and reliably, it is
Protuberance necessary to understand and predict the degradation
1 at.%
–10 and failure processes within the system leading to
2
4 spallation of the insulating topcoat. As a consequence,
–20 6 a tremendous amount of research activity has been

at.% Al
undertaken worldwide, particularly in the last decade,
8 to try and achieve these goals. At the time of writing,
–30
9
success has been elusive although large amounts of
experimental data have been produced and a plethora
–40 of theoretical models have been suggested. It is beyond
Coating the scope of this present work to provide a detailed and
–50 comprehensive review of this large body of work which
is often contradictory. Rather, a personal view will be
Figure 18 Finite-difference predictions of the Al depletion
presented which will attempt to identify key experi-
produced in a surface protuberance of a MCrAlY coating
after oxidation at 1100  C for 1 h. The left-hand and top mental observations and materials’ properties and favor
axes give distances in microns. The right-hand axis gives theoretical models which are consistent with these.
the aluminum concentration corresponding to the In some applications, for example, on rotating
iso-concentration lines drawn on the figure. Courtesy of blades in gas turbines, TBC systems will experience
Dr. W.M. Pragnell.
mechanically-imposed strains in addition to those
developed by the oxidation process. As discussed in
100 mm thick MCrAlY coating oxidized at 1000  C for relation to MCrAlY overlay coatings (Section
1 h but with, for purposes of illustration, a relatively 1.27.4.2), it may be feasible to sum these various
low initial concentration of 10 at.% Al. It can be strains and define a critical total value at which TBC
appreciated that selective oxidation to form the alu- failure will occur.81–83 The approach is phenomeno-
mina layer causes a significant decrease in aluminum logical in that no detailed mechanisms of failure are
content at the surface of the bulk coating with concen- considered. It is, therefore, difficult to generalize com-
tration increasing with distance from this interface. plex situations where strains may be tensile or com-
More details can be found elsewhere.111 This level of pressive and may act in different directions at different
depletion is similar to the schematic line for an locations within the TBC system. Nevertheless, the
uncoated alloy, of similar aluminum content, shown approach does attempt to address the difficult subject
in Figure 2. In this particular example, there remains of the interaction between applied external stresses
sufficient aluminum at depths of 10 mm to reform and those produced by oxidation. For present pur-
the protective alumina layer. This contrasts with the poses, however, as earlier with MCrAlY overlays, the
situation within the protuberance, however, where intention is to examine only the role of oxidation and
concentrations have dropped everywhere to <1 at.% thermal loading in TBC failure.
after 1 h exposure. Early MICF of this is then likely It was pointed out in Section 1.27.3.4 that oxygen
and, indeed, was observed.111 This failure time is can penetrate the YSZ TBC layer and oxidize the
somewhat less but of similar magnitude to that underlying BC. The TGO, designed to be alumina,
shown for diffusion cells in Figure 17. forms as an interlayer between the topcoat and BC as
shown schematically in Figure 11. The development
of this layer has been implicated in TBC spallation
1.27.5 Case Study II: Oxidation- for many years and a simple failure criterion, used in
Induced Failure of TBC Systems practice, is to assume that spallation will occur at a
critical TGO thickness. As shown in Figure 19, this
1.27.5.1 Failure Times under Oxidizing
can be a useful approach.
Conditions
The time-to-failure data shown in Figure 19
An overview of TBC systems and principal types derive from previous compilations,112,113 but have
has been given in Section 1.27.3.4. They are an been simplified to distinguish only between the
essential part of present-day strategies to operate common types of TBC system in commercial use:
high temperature machinery, particularly aeroengines Pt-aluminide/EB-PVD YSZ, MCrAlY/EB-PVD
and gas turbines, with increased fuel efficiency and YSZ, and MCrAlY/APS YSZ. Results on experimental
High Temperature Coatings: Protection and Breakdown 713

systems, which can show improved behavior to the eqn. [14], assuming an initially bare BC surface. It
above, have been omitted from this graph intentionally should be noted, though, that those systems with an
although they are prominent in current research liter- EB-PVD topcoat will usually have a preformed alu-
ature. These include the use of platinum over- and mina layer, 0.5 mm thick on the BC surface. The
under-layers to MCrAlY BCs,114 preoxidation of agreement with the solid-line prediction is, neverthe-
MCrAlY BCs,115,116 polishing of the BC surface,117 less, quite reasonable and supports the use of this
and platinized BCs51,52 see also Section 1.27.3.3.3). simple criterion as a pragmatic lifing method. It also
This body of work is of interest and may point the way supports the view,118,119 that time and temperature are
to future improvements in TBC systems. The results the principal parameters affecting lifetimes. The scat-
have been omitted from Figure 19 simply because ter can then be thought of as reflecting the underlying
they add other variables which will confuse the trends variability in the oxidation process together with the
present in the failure-life compilation for conventional influence of uncontrolled variables, many of which are
systems. likely to arise from the manufacturing process. These
The data shown in Figure 19 include results from will include BC surface roughness,112,113,117 defects
tests ranging from nominally isothermal exposure to within the topcoat which may initiate interfacial
those using hourly thermal cycles, for which the cracks,120 segregation of elements such as titanium
accumulated time at peak temperature is used in from the substrate alloy,52 and variable sulfur contents,
the figure. A striking feature of the results is the particularly in Y-free BCs and alloys.91,121
very large scatter in lifetime – a factor 10 – at any
given temperature. Within this scatter, there appears
1.27.5.2 Failure Characteristics
to be no systematic difference in behavior between
the coating types or with the frequency of cycling.112 The failure times plotted in Figure 19 refer to the
This is a valuable working premise with which to find loss of typically 20% or more of the area covered by
a path through the diverse competing models of the YSZ topcoat. Often this occurs by the spallation
failure. The solid line in the figure is the expected of the topcoat in sheets measuring some mm across as
behavior if topcoat spallation occurred at a critical shown in Figure 20.117 The morphology of these
TGO thickness of 4 mm. It is calculated from failed regions in terms of the ratio of the diameter

Pt-aluminide BC/EBPVD TBC


MCrAlY BC/EBPVD TBC
3000
MCrAlY BC/APS TBC
Time to failure (h)

2000

4-μm oxide growth


1000 during exposure

0
950 1000 1050 1100 1150 1200 1250
Temperature (°C)
Figure 19 The temperature dependence of the time to spallation of the ceramic topcoat in various TBC systems in
general commercial use.
714 High Temperature Materials

possible to construct a map showing the extent of


these low-stress regions as a function of exposure
time. A particularly satisfying example is shown in
Figure 21129 for a platinized BC system exposed to
repeated thermal cycles from 1150  C.
The darker regions in this figure are those of
relatively low in-plane compressive stress compared
with the lighter regions. The low-stress regions can
be interpreted as damaged, involving cracks at either
the TGO–BC interface or within the TGO itself. For
this particular example, it is clear that the extent of
the damaged regions increases markedly only after
190 h leading to spallation of some of the TBC top-
coat after 225 h.
The attractions of using this nondestructive tech-
nique to evaluate the residual life of TBC systems
in situ within turbines are considerable but there are
Figure 20 Decohesion of large sheets of the YSZ TBC on cautionary factors. The first to note is that although an
a coated 25 mm diameter specimen.117 EB-PVD YSZ topcoat is transparent to the laser light
there is lateral spread of the beam so that return signals
are obtained from an area of 20–60 mm diame-
of the area of decohesion to the thickness of the ter.128,129 It follows that early-stage cracks, perhaps
coating (20) is consistent with buckling occurring 5 mm long, will not readily be detected. This may be
during cooling (Section 1.27.4.2). This is supported why there appears to be an extensive damage-free
by examination of cross-sections of partially failed period in the example shown in Figure 21 whereas, in
coatings122 and by extensive modeling.123 Edge crack- reality, small cracks may already have nucleated. For
ing can also, in principle, produce spallation of large APS topcoats, the applicability of the technique is less
areas of the coating123 but this appears to be a much clear since the lateral splat boundaries now form inter-
more variable event than buckling. It has not occurred, nal interfaces across the path of the impinging laser
for example, in the specimen shown in Figure 20 but beam and significant attenuation of the return signal is
there are other cases of laboratory samples where likely.
coating failure at edges has occurred117 but also The other important consideration is the location
accompanied by failure remote from these sites.124 of the spallation interface. In practice, cracks can form
As discussed in Section 1.27.4.2, catastrophic within the topcoat near the TGO, at the TGO–top-
buckling will occur during cooling only when a delam- coat interface, within the TGO, and at the TGO–BC
ination zone of critical radius has formed under the interface. The luminescence technique relates damage
coating. Preexisting zones of this size are not present to a decrease in stress within the TGO and this will
in the as-manufactured coating and must form during occur only if cracking occurs within the TGO itself or
the high temperature exposure. The relatively slow along its interface with the BC. Fracture damage
growth of these subcritical defects determines the life occurring at the other locations will not be detected
of the TBC system and, understandably, there has been by the luminescence technique. For the example of the
much interest in techniques which can assess the extent platinized BC shown in Figure 21, fracture damage
of this damage nondestructively. Studies of the use of did indeed develop both at the TGO–BC interface
impedance spectroscopy have been made125 but a more and within the TGO. The luminescence technique
developed technique to date is that of laser-activated would detect this, subject to the limits on spatial reso-
luminescence of trace Cr3+ ions within alumina. Appli- lution. There are many examples in the literature of
cation of this to TBC systems has been pioneered by crack formation in TBC systems and a perceived
Clarke and coworkers.126–128 A particularly powerful tendency for the spallation path to be at the TGO–
aspect of the technique is its ability to determine BC interface in Pt-aluminide/EB-PVD YSZ systems.
regions in which the alumina TGO within TBC sys- This is indeed frequently the case but it does not seem
tems has relatively low stress after cooling to room to be an intrinsic feature of this system, however, since
temperature. By laser scanning the specimen, it is fracture along the TGO–topcoat or within the topcoat
High Temperature Coatings: Protection and Breakdown 715

25 h 98 h
900

720

Distance (AT)
540

360

180

132 h 190 h
900

720

Distance (AT)
540

360

180

206 h 225 h
900

720

Distance (AT)
540

360

180

0
0 180 360 540 720 900 0 180 360 540 720 900
Distance (AT) Distance (AT)

Figure 21 Map showing the development of low-stress regions (dark areas) with increasing number of cycles, containing
1 h hold periods at 1150  C, for a TBC system consisting of an EB-PVD YSZ topcoat and platinized BC. Note that a single
specimen was examined sequentially but not the same area.129

has also been observed.117 This cracking is often asso- crack, marked A, is hundreds of microns long and lies
ciated with BC protuberances, that is, with increased at the base of the topcoat. It intersects sites, marked B,
roughness of the BC. An example of the early stages of of porous nonprotective oxides resulting from
cracking within the topcoat of a (rough) Pt-alumi- CF. There is also a crack, marked C, along the
nide/EB-PVD YSZ system is shown in Figure 22. TGO–BC interface which appears to be linked to
By contrast, the perceived tendency with an inclined shear crack traversing the thickness of
MCrAlY/APS YSZ systems is for the fracture path the TGO. This is a similar morphology to that
to lie mainly within the topcoat. Again, this is not an expected for wedge cracking (Section 1.27.4.2).
intrinsic property of the system but is associated with
the generally rough BC surface. An example of mul-
1.27.5.3 Strain Energy Considerations
tiple fracture sites, that is, within the topcoat, within
the TGO and at the TGO–BC interface in such a The driving force for spallation within the TBC
system is shown in Figure 23. Here, the principal system is the release of the stored strain energy
716 High Temperature Materials

vary through the coating thickness and is likely to


reach its highest value at its base. Nevertheless, for
purposes of illustration, consider a topcoat of thick-
ness 200 mm with an average Young’s modulus of
50 GPa, which is representative of literature values.
Using linear thermal expansion coefficients of
12  106 K1 for the topcoat and 15  106 K1
for the superalloy and 0.1 for the Poisson’s ratio of
the topcoat within eqn. [19] yields a value for the
stored strain energy within the topcoat of 81 J m2 on
cooling to 100  C from 1100  C. It is the release of
this energy that will develop cracks at the TGO–
topcoat interface or within the topcoat near the
TGO. It should be noted that this strain energy may
change with time as a result of sintering of the top-
coat and an increase in its Young’s modulus130 or it
30.00 μm
may decrease as a result of thinning due to chemical
⫻750
or physical erosion.131
Figure 22 SEM image of a section through a TBC system The specific strain energy within the TGO will
consisting of a Pt-aluminide bond coat with an EBPVD YSZ increase as the oxide thickens and, in principle,
top coat that has been held at 1200  C for 3 h. Small cracks should be added to that within the topcoat to produce
have developed, arrowed, at the flanks of BC
cracking either within the oxide layer or at the inter-
protuberances. Courtesy of Dr. M.P. Taylor.
face between the TGO and the coating. The strain
energy within the TGO can be calculated from
B eqn. [19]. For an oxide thickness of 4 mm, that is,
Top coat
A corresponding to the failure line drawn in Figure 19,
and using similar parametric values as previously,
TGO gives a specific stored energy within the TGO of
C
Bond coat 53 J m2. The total energy available to produce frac-
100.00 μm ture within the TGO or along the oxide–coating
Substrate
interface is then 134 J m2 for the example used.
Figure 23 Section through a TBC system consisting of an These values of specific strain energy should cer-
electroplated CoNiCrAlY BC and an APS topcoat after tainly be sufficient to produce cracking even with the
oxidation in air at 1100  C for 600 h. Different cracking sites dissipation of energy by creep anticipated for typical
are indicated and described in the text. See text for (MCrAlY) BCs – see, for example, Section 1.27.4.2
discussion. Courtesy of Dr. M.P. Taylor.
and Table 3. Interestingly, the stored energy within
the topcoat is available to produce cracks within the
TBC layer or at its interface with the TGO from the
within the respective layers. It is an analogous situa- onset of exposure. The reason that cracking is
tion to the spallation of the alumina layer from a deferred and that TBC systems survive beyond the
MCrAlY coating discussed in Section 1.27.4.2. As in first thermal cycle is that there must also develop a
that case, eqn. [19] can be used as a first approach but mechanism for producing cracking and releasing this
it needs to be noted that this is a ‘thin-layer’ approxi- energy. This is a product of the high temperature
mation which makes no allowance for any strain exposure and various suggested possibilities will be
energy stored within the coating and alloy substrates. described briefly in the next section.
As pointed out earlier, it also assumes that negligible
stress exists at the exposure temperature and that the
1.27.5.4 Formation of Subcritical Cracks
strain energy derives only from thermal loading.
The stored energy within the topcoat will depend 1.27.5.4.1 Transformation strains
linearly on the in-plane Young’s modulus (eqn. [19]) The removal of aluminum from the BC both by
but this parameter is not well defined, particularly for selective oxidation and interdiffusion will result in
EB-PVD topcoats. Here the in-plane modulus will phase transformation and associated volume changes.
High Temperature Coatings: Protection and Breakdown 717

The most obvious of these, evident in Figure 8(b) for out-of-plane tensile stresses may be produced across
example, is the transformation from b to g0 phases. the TGO–BC interface at the transformation tem-
Tolpygo and Clarke132 have estimated an associated perature of 450–500  C.139 The magnitude of these
volume contraction during this process of 38% and is unclear since the strains may also be accommo-
have suggested that this transformation strain could dated by void formation within the original b grain
induce BC rumpling and decohesion. A difficulty and some thermal or athermal relaxation may still
with the calculation is that, in the vicinity of the be possible at this temperature. There is a strong
TGO, the transformation occurs as a direct result of circumstantial argument, however, that the transfor-
the removal and oxidation of aluminum. The volume mation is not a significantly damaging event. If it
change at this location should then also include the were so, both Pt-aluminide and MCrAlY coatings
expansion arising from formation of alumina. When would tend to fail before b-depletion had occurred.
this is done,133 the transformation (and concurrent In practice, much of the life of MCrAlY coatings, for
oxidation), is found to produce a volume expansion, example, is spent with a b-depleted zone adjacent to
rather than contraction, which is of similar magni- the TGO layer. Platinized g/g0 coatings, of course,
tude to that produced by direct oxidation of alumi- never form the b phase.
num. Little effect of the b to g0 transformation on
TGO adherence and mechanical stability of the BC 1.27.5.4.2 Mechanical instabilities
surface should then be expected and this seems to be The alumina TGO layer is under compression dur-
borne out by observations.134,135 It can also be seen ing cooling and will also be so at temperature if
from Figure 8(b) that there is no marked indentation growth stresses are compressive. The strain energy
of the coating–oxide interface above the large g0 within the layer can be released and contribute to
phase. It is worth noting, though, that at the inner decohesion if the oxide layer can relax and extend to
surface of the BC where interdiffusion is occurring its stress-free dimensions. The linear relaxation strain
with the alloy substrate, the volume change asso- per cooling transient will be no more than 0.5%,
ciated with alumina formation should not be equivalent to an extension of 0.1 mm over a 20 mm
included in the calculation of total volume. The distance. Large dimensional changes of the TGO
transformation may result in contraction strains in layer over these small lengths would then require
this case which could contribute to the cavity devel- multiple thermal cycles.
opment sometimes found at these locations. It is not One suggested mechanism is that of ratchet-
easy to calculate these transformation strains, how- ing.135,141 The initiating event, in this case, is the
ever, since other, often poorly characterized, phases formation of small cracks within the TBC above
will form within the interdiffusion zone and the vol- preexisting undulations of the BC, essentially as
ume changes associated with these should also be shown arrowed in Figure 22. These cracks remove
taken into account. mechanical constraint from the underlying TGO
Another transformation of interest is that of mar- which, as discussed earlier, may be under a compres-
tensite formation of the b phase during cooling. This sive growth stress at the oxidation temperature but
has been recognized for many years for b-NiAl136,137 will certainly experience large in-plane compressive
and has also recently been confirmed in b-(Ni, Pt)Al stresses during cooling. Within the model, it is envi-
coatings.134,138,139 Typical of martensitic transforma- saged that, with increasing number of cycles, these
tions, a critical cooling rate is required but this seems stresses can drive the oxide layer as an indent into the
remarkably low in this case where martensite has BC and, in doing so, enlarge the crack at the base of
been found after air cooling 138 and even after furnace the topcoat. The model seems feasible, in principle,
cooling.139 The former, at least, is consistent with and experimental support has been provided135
earlier observations on b-NiAl.140 These recent although the incidence of failure by this route does
results suggest that martensitic transformation of not seem widespread. It is often observed, for exam-
the b-(Ni, Pt)Al phase should be a common occur- ple, that the main fracture site in TBC systems with
rence during cooling. such diffusion BCs is at the TGO–BC inter-
The formation of martensite will result in a volume face51,52,128 rather than within the TBC topcoat.
change estimated at 2%, that is, a linear contrac- A key aspect is that there needs to be either a certain
tion of 0.7%.138,139 Unlike the b ! g0 transformation roughness to the BC surface so that cracks such as
discussed earlier, the expansion due to alumina forma- those in Figure 22 can form or there needs to be a
tion will not mitigate this transformation strain and defect at the base of the topcoat which offers no
718 High Temperature Materials

constraint to the downward migration of the TGO. 1.27.5.4.3 Roughness of the BC surface
The issue of surface roughness will be addressed in It has been known for some time that the roughness of
later sections. the BC surface will have a significant influence on the
There will probably exist a window of BC strengths development of stresses in the TBC system during
within which the ratcheting process could occur. It is cooling.148,149 Various attemspts have been made to
not possible to quantify this because modeling the evaluate these using FE methods113,130,133,150–153 which
progressive indentation is difficult and has tended to incorporate materials’ behavior of varying degrees of
assume135,141 that the BC deforms by athermal plastic- relevance. Most recently, it has also become clear that
ity characterized by yield behavior. In fact, creep pro- out-of-plane tensile stresses can also develop at the
cesses will dominate,142,143 even during cooling.133 Low oxidation temperature as a consequence of the volume
creep strength is necessary to move the BC away from increase on oxide formation.112,113
the indenting oxide but this deformation occurs at con- The development of these numerical models has
stant volume. There must, thus, also be an upwelling of to some extent mirrored the expansion in computing
the displaced matter against the TBC topcoat adjacent power. Thus, initial approaches tended to assume
to the indent. In this case, the creep strength of the BC entirely elastic behavior of the respective layers but,
must be high enough to displace the topcoat upward and importantly, creep behavior has been subsequently
allow continued penetration of the indenting oxide layer incorporated and recognition made that the TGO
into the BC. These two contradictory requirements of thickens during exposure. The most recent mod-
the BC creep strength may be satisfied only within a els113,130,133 incorporate creep of both BC and
limited temperature and composition range. TGO, allow for growth of the latter together with
Another interesting mechanical instability is rum- the associated volume change at temperature during
pling. This has been recognized for some years the computation. In addition, they permit densifica-
and has been shown to occur in aluminized and Pt- tion of the YSZ topcoat, again during the simulated
aluminized coatings under thermal cycling condi- exposure time, and consider a variation in BC surface
tions132,144,145 but in the absence of a topcoat. It is roughness. Some predicted results for two different
manifested by a roughening of the specimen surface BC-roughness geometries are shown in Figure 24.133
and is clearly associated with thermal cycling because As described in the caption, the stress contours of
isothermally-tested specimens do not show the phe- Figure 24 apply to the situation at the test tempera-
nomenon.144 The basic underlying reasons for the ture of 1100  C. For the case examined, the total
surface instability are well understood146,147 and are thickness of the alumina TGO had increased to
broadly the same as discussed above for the ratchet- 3.3 mm during the simulated 100 h isothermal expo-
ing process. In both cases, deformation of the coating sure at this temperature. The parameters b and a
permits the compressively stressed TGO to increase are the amplitude and half-wavelength, respectively,
its length and, thereby, relax its strain energy. As of the surface undulations shown in Figure 24. For
pointed out earlier, this increase in length per tem- the rougher surface, Figure 24(a), out-of-plane ten-
perature transient is small, 0.5%, and repeated sile stresses of 150 MPa, have developed within the
thermal cycles are needed to produce readily observ- topcoat along the flank of the BC protuberance.
able deformation. For the less-rough surface, however (Figure 24(b)),
The rumpling process has been implicated147 in these stresses are absent, showing the strong sensitiv-
failure of the TBC system because the instability ity of isothermal stress development to BC surface
would develop significant out-of-plane stresses in the roughness. In both cases, tensile stresses also develop
vicinity of the TGO with associated crack initiation. in the valleys of the undulations.
Modeling of the process again assumes plastic yielding The out-of-plane tensile stresses on the flanks of
rather than creep behavior and, although the presence the BC protuberance arise from continuity strains112
of the topcoat is considered, no mechanical constraint which are required if the topcoat is to remain
is attributed to it. This constraint will be present in uncracked. Their origins can be understood by
real cases and, for the reasons given above when dis- recognizing that the outward displacement due to
cussing ratcheting, is likely to limit the applicability of the formation of the TGO is normal to the BC
the process in TBC systems. Again, exceptions will interface and, so, changes direction around the pro-
arise when defects exist in the topcoat such that, tuberance shown in Figure 24. The out-of-plane
locally, mechanical constraint is absent and upward component, the x22 direction, of this displacement
displacement of the TGO and BC becomes feasible. also varies around the protuberance and reaches a
High Temperature Coatings: Protection and Breakdown 719

s22 (MPa)

153
120
YSZ 90
60
30
A 0.0
−134
TGO
(3.3 μm)

BC

X2

X1
(a) b/a − 0.52 (b) b/a − 0.25

Figure 24 FE predictions 133
of the s22 stress contours at 1100 C after 100 h oxidation at the same temperature for an
EB-PVD YSZ TBC system containing a Pt-aluminide BC. Creep of the BC and TGO, sintering of the topcoat and outward
strains due to TGO growth are considered in the stress analysis. The BC creep properties used were those of Taylor et al.,143
The arrowed locations mark the general sites of high stress at the flank (a) and valley (b) regions.

minimum on its flank. To maintain continuity of the These regions of high stress correspond to loca-
topcoat, tensile stresses must then develop to strain tions where cracks form in TBC systems. Examples of
the topcoat in these locations to account for the out- those found at flank and valley locations are arrowed
of-plane deficit in the displacements resulting from in Figure 22 and may well have formed at tempera-
oxide growth. ture. Crack initiation, presumably during cooling, has
The effect, on the s22 stress distribution, of cool- also been reported113 at the TGO–BC interface at
ing the specimen to 25  C after the isothermal the peak of the BC protuberances. These nucleation
exposure for 100 h at 1100  C is shown in Figure 25, processes will occur, however, only with relatively
again for the two BC surface roughnesses.133 The rough BCs. Cracking events should be less easy and
out-of-plane flank stresses in the rougher specimen, TBC lifetimes would be expected to be longer with
Figure 25(a), are largely unaffected by this transient flatter BC surfaces. This has been clearly demon-
and no new stress is developed in these locations strated recently by Yanar et al.117 who found an
in the less-rough specimen, Figure 25(b). There is approximate factor 10 increase in the lifetime of a
a large increase, however, in the tensile stress devel- NiCoCrAlY/EB-PVD YSZ system by hand polishing
oped in the topcoat in the valley regions and across the BC prior to deposition of the topcoat.
the TBC–TGO interface. For the rougher surface,
this is 700 MPa but is appreciably smaller (200 1.27.5.4.4 Chemical failure
MPa) for the smoother surface. Significant tensile A discussion of CF processes in relation to aluminum
stresses are also developed at the TGO–BC inter- depletion and the endurance of overlay coatings has
face during cooling as a result of differential con- been given earlier in Section 1.27.4.3.2. Identical con-
traction strains between oxide and coating (see cepts apply to BCs in TBC systems but, in this case,
Ref. [37] for a general review of such issues). Broadly, spallation of the YSZ topcoat may be induced prior to
the same behavior has also been found with MCrAlY complete CF of the BC.105 This can arise because
BCs where, again, appropriate creep and oxide CF will result in the fast growth of nonalumina, break-
growth kinetics were incorporated into the FE away-type oxides which will produce upward displa-
modeling.113 cements of the topcoat. This is an oxide-jacking
720 High Temperature Materials

σ22 (MPa)
717
500
YSZ 375
250
105
0.0
−407
TGO
(3.3 μm)

BC

X2

X1

(a) b/a = 0.52 (b) b/a = 0.25


Figure 25 FE contour plots of the s22 stress for the same specimen as shown in Figure 24 but after cooling to 25  C
after exposure at 1100  C for 100 h.133 The arrows indicate the general areas in which out-of-plane stresses had developed
prior to cooling.

process which will result in the development of out-of-


Ceramic
plane tensile stresses within the topcoat when the CF topcoat
sites are discrete (Figure 26). Possible localized sites
for enhanced aluminum depletion and the early initi- Tensile stress
at periphery of
ation of CF are diffusion cells (splats) within sprayed oxide mound
MCrAlY BCs,105 protuberances (roughness) at the BC
surface,109,111,153 and locally thin cross-sections.
The jacking associated with the formation of the
mound of fast-growing (Ni, Cr)-rich breakaway oxides,
shown schematically in Figure 26, will tend to nucle- Mound of
Alumina
ate and propagate delamination cracks within the top- breakaway
coat near the TGO. This process will occur at the oxide
oxidation temperature and will not need thermal cycles Bondcoat
to produce this damage. It is likely that this type of
process was responsible for the long crack (marked A) Figure 26 A schematic diagram showing how the growth
in the cross-section shown in Figure 23. This particu- of fast-growing ‘breakaway’ oxides resulting from CF will
lar specimen had been exposed isothermally until the generate out-of-plane tensile stresses within the topcoat.
final cooling transient and several discrete regions of
breakaway oxides (marked B), associated, in this case, importance of others (phase transformation strains,
with BC protuberances, had formed. rumpling) to TBC failure is less clear and awaits
more robust experimental support. Of those mechan-
isms which have been shown to nucleate and propa-
1.27.5.5 Surface Roughness: A Common
gate subcritical cracks, some are either aided by or,
Factor?
indeed, require BC surface roughness (e.g., CF, out-
A number of the degradation mechanisms described of-plane tensile stress development at temperature or
in Section 1.27.5.4 have been observed experi- during cooling, ratcheting) and others (wedging) are
mentally and, consequently, have validity. The likely to operate only on relatively flat interfaces. The
High Temperature Coatings: Protection and Breakdown 721

experiments of Yanar et al.,117 in particular, show very shown schematically in Figure 27 which relates
well that decreasing the surface roughness of a TBC lifetimes to the BC surface roughness.
MCrAlY BC can increase the lifetime of a TBC Relatively flat surfaces (low values of b/a) provide
system by an order of magnitude. The improved the longest lifetimes since opportunities for crack
behavior was similar in their experiments to the behav- nucleation caused by continuity strains and CF will
ior of a Pt-aluminide BC which had similarly flat BC be limited. Studies of failure processes in such ideal
surfaces. As can be appreciated from Figure 22, how- structures are limited although in localized areas of
ever, flat Pt-aluminide BCs with EB-PVD topcoats otherwise rough BCs, wedge-type cracks have been
need not always be the case and will depend on the found (Figure 23 but see also Section 1.27.4.2).
extent of grit blasting performed by the manufacturer. The red line, representing continuity cracking in
The factor 10 improvement in lifetimes found by Figure 27, shows a decrease in lifetimes as BC
Yanar et al. is of the same order of magnitude found roughness increases. It refers to the development of
in the compilation of published lifetime results from subcritical cracks at the flanks of BC protuberances at
commercial systems shown in Figure 19. It is certainly temperature, possible ratcheting nucleation, and the
tempting to suggest that much of this scatter in life- nucleation of cracks at the TGO/BC interface during
times can be attributed to an uncontrolled variation in cooling. The stresses produced increase with oxide
the surface roughness of the BCs. There will be other thickness and, so, time at temperature is an important
sources of scatter, inevitably included within these factor. They will also increase with the roughness
various tests, but the first-order importance of BC factor b/a (Section 1.27.5.4.3)113 and it is expected
surface roughness to the scatter at any given tempera- that TBC lifetimes will decrease as this increases. For
ture can be taken as a working hypothesis.113 large values of b/a, aluminum depletion within BC
The dependence of the various delamination protuberances will be enhanced (e.g., Figure 18) and
mechanisms on surface roughness are only now CF with the formation of breakaway-type oxides will
being assessed quantitatively using realistic numeri- take place. These will increase the stresses produced
cal models which, as described in earlier sections, within the TBC layer at temperature and failure will
allow for creep processes and the volume expansion occur earlier than in the absence of breakaway. This
due to oxide formation. Work in this area is incom- trend is shown as the downward-sloping blue line in
plete but some rather qualitative trend lines are Figure 27. Again, time at temperature will also be an

Wedge
failure
Chemical failure
Wedge cracking along BC interface

Continuity
cracking
Time to failure

Cracking in topcoat due


to continuity strains
and ratcheting
Continuity cracking in
topcoat enhanced by
chemical failure of BC

Increasing roughness, b/a

Figure 27 A schematic map showing how variously proposed mechanisms for the nucleation and growth of subcritical
cracks may depend on the surface roughness of the BC. The colored lines show possible dependences of continuity cracking
and CF on roughness.
722 High Temperature Materials

important parameter since the depletion of alumi- 19. Taylor, A.; Floyd, R. W. J. Inst. Met. 1952–53, 81,
451–464.
num will be directly related to this. 20. Muñoz-Arroyo, R.; Clemens, D.; Tietz, F.; Anton, R.;
As a final note of caution, it should be emphasized Quadakkers, W. J.; Singheiser, L. Mater. Sci. Forum
that the discussion in this section relates to typical 2001, 369–372, 165–172.
21. Brindley, W. J.; Whittenberger, J. D. Mater. Sci. Eng. A
laboratory experience in which the test specimens 1993, 163, 33–41.
have relatively simple shapes. The map of Figure 27 22. Taylor, M. P.; Evans, H. E.; Ponton, C. B.; Nicholls, J. R.
then provides a mechanistic framework for these con- Surf. Coat. Technol. 2000, 124, 13–18.
23. Fritscher, K.; Leyens, C.; Peters, M. Mater. Sci. Eng. A
ditions but the concepts are also expected to be valid 1995, 190, 253–258.
for service conditions although some modification 24. Gupta, D. K.; Duval, D. S. US Patent 1986, 4, 585, 481.
might well be required. There may be thin regions, 25. Goebel, J. A.; Giggins, C. S.; Krasij, M.; Stringer, J. EPRI
Report 2639SR; Palo Alto, CA, 1981.
for example, within the complex geometry of actual 26. Chan, W. Y.; Evans, H. E.; Ponton, C. B.; Nicholls, J. R.;
components in which the local total aluminum reser- Simms, N. J. Mater. High Temp. 2000, 17, 173–178.
voir is insufficient to maintain a protective TGO. Bulk 27. Leyens, C.; van Liere, J.-W.; Peters, M.; Kaysser, W. A.
Surf. Coat. Technol. 1998, 108–109, 30–35.
depletion and breakaway oxidation could then occur 28. Leyens, C.; Peters, M.; Kaysser, W. A. Mater. Sci. Forum
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only weakly dependent on the surface roughness of the 29. Gray, S.; Ponton, C. B.; Jacobs, M. H.; Evans, H. E.
United States Patent 2002, 6, 387, 541 B1, May 14.
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