Novel bond coat for High Performance

Thermal Barrier Coatings

F. Z. Mohammad
Mechanical Engineering Workshop
Plot No 174 I-10/3 Islamabad

Abstract

Oxidation and exfoliation of the bond coat is a primary failure mechanism in

thermal barrier coatings. Rare earth elements such as Y, Hf, La are very well known
for their effect in improving the oxidation performance of the overlay bond coats. The
current research is focused on incorporating Yttrium into the diffusion bond coats and
to study its effect on the oxidation performance of the diffusion bond coats. As a
result during this research Yttrium was successfully incorporated into the aluminide
and Pt-modified aluminide bond coats through a one step process. High temperature
testing of these bond coats indicate that Yttrium does has a positive effect in
improving the adhesion of the alumina scale, formed during thermal cycling.

Introduction
TBCs are composite coatings having two or three layered structure. A typical
two layered structure consists of a metallic bond coat and a ceramic top coat. The
bond coat protects the substrate from oxidation, as the top ceramic coat is transparent
to oxygen, and the top coat is meant to minimise the thermal flow to the substrate.
Oxidation and exfoliation of the bond coat is a primary failure mechanism and
determines the life of TBCs. Many efforts have been made to improve the oxidation
performance of the bond coat, such as Pt-modified bond coats [1, 2] and rare earth
reactive elements modified bond coat [3].
All high temperature coating systems rely on the formation of stable oxide
scale that protects the substrate from high temperature oxidation and hot corrosion.
Ideally this oxide scale should be continuous, adherent, chemically inert and have a
slow growth rate.
In aluminide bond coats Al2O3 scale has the reputation of exfoliation when
exposed to high temperature thermal cycling conditions. Such exfoliation results in
spallation of the ceramic top coat and depletion of Al in the bond coat. Once this
happened less noble and fast growing oxides are formed leading to relatively rapid
degradation of the component. Therefore avoidance or delay in the exfoliation of
Al2O3 scale must result in improvement of the oxidation performance of the bond
coat. Rare earth elements such as Y, Hf, La are very well known for their effect in
improving the oxidation performance of overlay bond coats, because these elements
are sulphur getters, and have the property to form non- stoicheometric oxide that
improve the adhesion of the protective scale[4,9,11,13]. However up until now very
little efforts have been made to incorporate these elements into the diffusion bond
coats [1], while diffusion bond coats are being used in 80% of all the airfoils [11], and
have an edge over the overlay bond coats in two respects. First these are less
expensive to produce and second, unlike overlay bond coats, they do not have the
problem of formation of intermettalic layer at the coating- substrate interface [11]
rather form a layer which is gradient in nature.
Present work is aimed at incorporating yttrium into the diffusion bond coats;
both simple aluminides and Pt-modified aluminides, by pack cementation method.
Then to note the micro structural changes caused by the incorporation of these
elements and study their effect on the oxidation performance of aluminide and Pt-
modified aluminide bond coats.

Experimental work
The substrate material used in this work was CMSX4; a single crystal
superalloy, commonly used for the making of aero-engine turbine blades. The
nominal chemical composition of this alloy is given in table1. Specimens were disc
shape, 16mm in diameter and 1.5mm thick. Both sides of all the specimens were
finely ground with SiC 1200 grit paper using water as lubricant and coolant, followed
by ultrasonic cleaning and vapour degreasing.

Element Ni Al Co Cr Ta Re Mo W Ti
Wt% 61.8 5.6 9.0 6.5 6.5 3.0 0.6 6.0 1.0
At% 63.8 12.6 9.2 7.6 2.2 1.0 0.4 2.0 1.3
Table1 chemical composition of CMSX4

As aim of this study was to note the effect of reactive elements on the
oxidation performance of both aluminide and Pt-modified aluminide bond coats,
therefore half of the samples were deposited with a platinum layer. The thickness of
this layer was kept 7µm thick [5, 12], and it was deposited by magnetron sputtering
technique using a Nordiko magnetron sputter coater.
All the Pt sputter coated samples were heat-treated, before aluminising, at
1050oC for 10 minutes in a Vacuum furnace. The purpose of this heat treatment was
to remove any Ar entrapped in the coating during the sputtering process and to
partially diffuse the coated Pt into the substrate.
The aluminide bond coats were produced both on the Pt sputter coated and
uncoated CMSX4 samples by using the pack cementation technique; the pack cement
was provided by Tilcon ltd. The composition of the pack cement is given in the Table
2.
Al NaF KFHF NH4Cl H2O Al2O3
1.38 0.90 0.08 0.17 0.1 Bal
Table 2 Pack composition.

To get the optimum processing time and temperature conditions a series of

experiments were conducted. The relation between coating thickness and processing
time at different temperatures is shown in Fig. 1. From Fig. 1 the optimum time
decided for the final coatings was 25-30 minutes at 1050oC.

85

Fig. 1 Standard aluminization at 900oC, 980oC, and 1050oC.

75
All the samples were packed in the aluminising powder in a circular coating box.
In order to produce similar coating conditions for all the specimens, a 10mm thick
layer of the aluminising powder was packed in the box and specimens were placed
over it. After that another layer of 10mm thick powder was packed on the top of the
specimens.
The assembly was placed in the retort and a metallic bell dome was placed over it.
Then the retort was pulled to soft vacuum of approximately ~0.25 bar using a rotary
pump.
After that, the hot furnace; that has already been heated to 1000oC, merely to
shorten the time of the coating process and ensure a rapid heat up rate, was lowered
over the dome. During this procedure the temperature of the furnace dropped to about
700oC, and it took several minutes to reach to 1000oC again. When the temperature of
the furnace was at 1000oC the process time started, that was in this case 25 minutes.
After about fifteen minutes the temperature of the furnace reached 1050oC, therefore
the samples stayed at the 1050oC for only 10minutes in the aluminising cycle. Then
the furnace was switched off and lifted up to allow the dome cool in the natural
atmosphere of the lab.
For co-deposition of Yttrium and Aluminium the composition of the pack cement
is given in table3. This composition was optimised to get the desired level of yttrium
in the bond coat; which should be 0.5%wt [14].

YCl3 Al NH4Cl Y2O3

5% 2% 0.2 Bal
Table 3. Pack composition.
The aluminised coatings after pack aluminising process are very brittle due to
the formation of Ni2Al3, and there can be high Al concentration gradient in the coating
during the service. For these reasons a diffusion and ductilising recovery heat
treatment is generally given [10,12]. All the specimens were given a recovery heat
treatment in vacuum furnace for 2 hours at 1120oC followed by 24 hours at 845oC. It
is a standard post aluminising heat treatment, and was not changed in our case even
for the reactive element modified aluminide coating.

After the post aluminising heat treatment two samples from each variation were
taken to be coated with a ZrO2-8wt%Y2O3 ceramic top-coat using electron beam
physical vapour deposition. The topcoat was deposited to a thickness of
about170µ m, as shown in Fig. 2. During the EBPVD the electron beam impinges on
the ceramic rod and creates the depositing species that are then transported to the
substrate in the line of sight in an atmosphere of 90%oxygen and 10% argon.

Fig. 2 EBPVD coated top coat.

Four different types of bond coats were developed during this study. These
bond coats were aluminide, Pt-modified aluminide, aluminide co-deposited with
yttrium, Pt-modified aluminide co-deposited with yttrium. All the four samples were
cut in cross section and were studied on scanning electron microscope. During SEM
study Digi-Point analysis was carried out at regular interval from surface of the
coating into the substrate.
The samples coated during this experimentation were tested for their oxidation
performance in a rapid cyclic oxidation rig. The temperature for the test was 1180oC,
and the dwelling time at this temperature was 1 hour followed by 15 minutes cooling
in the still laboratory air. The rapid cyclic oxidation test was used to study the growth
of the protective oxide during the high temperature exposure; this growth is measured
by weighing the samples after suitable number of cycles. The temperature of the test
was selected to finish the experiment in a given time span.

Results and Discussion

Microstructures
 Legend
B
C
D
100 E
F

Percentage present
90
G
80
H
70 I
YL
60

50

40

30

20

10

0 10 20 30 40 50 60
XB
DepthinM icrons[A-1/C]
B=Ni, C=Al, D=Co, E=Cr, F=Ta, G=M o, H=W
I=Ti

Fig.3. Aluminide bond coat Fig.3a. Compositional profile of aluminide bond

coat
B
C
D
1
00 E

Percentage present
F
9
0 G
8
0 H
I
7
0
J
6
0

5
0

4
0

3
0

2
0

1
0

0 1
0 2
0 3
0 4
0
DepthinMicrons[A Y-1/C]
B=N
i,C=Al,D=Co,E=C r,F=T a,G=M o,H =W ,
I=Ti,J=Y

Fig.4. Aluminide + yttrised bond coat Fig. 4a. Compositional profile of aluminide +
yttrised bond coat
Legend
B
C
D
100 E
Percentage present

90 F
G
80
H
YL
70 I
60 J

50

40

30

20

10

0 20 40 60 80
XB
DepthinM icrons[AP-!/C]
B=Ni, C=Al, DCo, E=Cr, F=Ta, G =Mo, H=W
I=Ti, J=Pt

Fig. 5. Pt-modified aluminide bond coat Fig. 5a. Compositional profile of Pt-modified
aluminide bond coat.
B
C
D
E
1
00 F
Percentage present

G
H
8
0 I
J
K
6
0

4
0

2
0

0 1
0 2
0 3
0 4
0
De
pthinmic
ro ns[A
P Y-1/C
]
B
=Ni,C
=Al,D
=Co
,E=Cr,F=T a
,G =Mo,H =W
I=T i,J=Pt,K=Y

Fig. 6. Pt-modified aluminide+ yttrised bond coat Fig. 6a. Compositional profile of Pt-modified
aluminide + yttrised bond coat
 The simple alumnide bond coat shown in Fig.3 has all the features of an
inward grown coating. In the inward grown diffusion coatings Al is forced to diffuse
into the substrate γ-Ni/ γ’- Ni3Al matrix which is transformed to δ-Ni2Al 3. In δ-Ni2Al3
the diffusivity of the Ni is nearly zero compare to Al at 600oC. [6]. As a consequence
of inward growth, slowly diffusing alloying elements from the substrate are entrapped
in the coating. That is why the concentration of the slow diffusing elements in the
outer zone of the coating in the simple aluminide case is usually higher.
Another important difference between the inward and outward grown
coatings, in as deposited form, is their Al content in the β-NiAl. In inward growth
Al/Ni >1 and in outgrown coating Al/Ni <1. [7]. However this ratio may reverse after
the post aluminising heat-treatment.
From the micrograph of aluminide bond coat, Fig. 3, three distinct zones of
the coating can easily be identified. These are: outer zone, inter-diffusion zone and the
zone between them. In the outer zone there is homogenous distribution of fine
precipitates. In the intermediate zone there exists a network of fine white precipitates
coming out from the inter-diffusion zone. The inter-diffusion zone is characterized by
the presence of equiaxed precipitates in the outer portion and acicular precipitates
near the substrate. The acicular precipitates near the substrate and the equiaxed
precipitates in the inter-diffusion zone can be explained as that in the initial phase of
the coating when the concentration difference of Ni between the coating and the
substrate was high, and when β-NiAl was not yet transformed to γ’, Ni diffuses away
very rapidly towards the outer zone which results in massive inward growth of the
inter-diffusion zone. Heavy outflow of Ni leaves behind a region that is rich in heavy
elements, which tends to precipitates in this region, due to their higher percentage
their precipitates are energetically able to nucleate at many sites which results in the
formation of equiaxed precipitates. When in the later stage of the coating growth, Ni
diffusion is relatively slow, only occasional precipitates are nucleated due to a low
driving force for their formation. Now they tend to grow from the already nucleated
precipitates and these results in the formation of acicular precipitates that lead into the
substrate.
From the micrograph and compositional profile of the aluminide and yttrised
bond coat shown in the Fig. 4 and Fig. 4a, it appears that there exist β -NiAl phase
near the surface of the outer zone mixed with uniformly distributed heavy metal
intemetallic phases. The thickness of this zone is approximately 12µ m, and is
followed by a Ni rich β -NiAl phase, containing probably σ precipitates [8].
Then there is an inter-diffusion zone of equiaxed heavy metal precipitates
ended with acicular precipitates embedded into the substrate. The explanation of this
particular morphology of the inter-diffusion zone has already been given in the
preceding paragraphs. The thickness of this coating is almost half of that for the
aluminide coating under the same processing conditions. This may be due the lower
Al activity within the pack in the presence of YCl3.
In the Pt-modified bond coat, shown in Fig. 5, the growth pattern was a
mixture of both inward and outward growth. The outgrown portion is characterized by
uneven outer surface and the presence of some trapped internal oxide marks that
indicate the original substrate surface.
When the coating is grown outwardly the Al activity at the surface is lower, Ni
diffuses outward from the substrate and a β-NiAl layer built up near the surface. The
diffusivity of Ni in sub-stochiometric β-NiAl is much larger than that of Al. This
result in a zone that is cleaner with respect to the slowly diffusing elements from the
substrate.
The back scattered image of the Pt-modified bond coat, shown in Fig
5,indicates that coating has an outer zone that is about 40μm thick with some
precipitates homogeneously distributed throughout the zone. This outer zone is
divided into two regions, the outgrown outer zone and ingrown outer zone. It is
supposed that beneath the brighter zone there lies some where the original surface of
the substrate. However from the digi point analysis (Fig. 5a) it appears that for up to
20μm, where Al/Ni+Pt <1and heavy elements are present in very low percentage, the
growth pattern was outgrown and after that it was ingrown. The matrix in the outer
zone of the coating is Pt rich which give it brighter contrast in the back scattered
image. Between the outer zone and the inter-diffusion zone there is a zone where the
density of the precipitate is comparatively less. This comparatively less precipitate
zone can be explained simply because of the unavailability of the precipitate forming
elements in this region. Many of the precipitate forming elements are pushed ahead by
the inward diffusing Al that means that Al diffusion clears and sweep the precipitate
out of this zone. Digi point analysis of the sample also shows very low percentage of
 refractory elements in this region. From the chemical composition results of the
region it looks that it is Ni rich β-NiAl phase.
The inter-diffusion zone of this coating is very much similar to the inter-
diffusion zone of the aluminide coating except that the precipitates penetrating into
the substrates are relatively finer. The reason for their finer morphology is probably
higher concentration of the refractory elements in this region compared to the
aluminide coating. In case of Pt-modified coating it is generally believed that Pt
impedes the outward movement of the refractory elements from the substrate.
In the Pt-modified aluminised and yttrised bond coat, shown in Fig. 6 and Fig.
6a, the presence of outgrown and ingrown coating regions in the outer zone was again
witnessed. Like Aluminide+Yittrised bond coat, the presence of YCl3 in the cement
reduced the Al-activity and the result is reduced thickness of bond coat.

Oxidation performance
Oxidation performance data of all the four bond coats is given in the Table 4.
Rapid thermal cycling rig was used for this testing. In each thermal cycle samples
stayed at the test temperature, 1180oC, for one hour and then were kept at room
temperature for 15 minutes.
Weight gained per unit area (mg/cm2)
Number of
Cycles AP APY A AY
4 0.37 0.92 Spalled off 0.72
10 0.52 1.12 - 1.07
18 0.67 1.37 - Spalled off
28 0.77 1.47 - -
47 0.89 1.44 - -
67 0.85 1.74 - -
Spalled
86 off Spalled off - -
o
Oxidation performance data at 1180 C for CMSX4 Samples with bond coat and
ceramic top coat ( Test Cycle- one hour at test temperature followed by 15
minutes at room temperature)
Table 4: AP= Pt-modified aluminide, APY= Pt-modified Aluminide+ yttrised,
A= Aluminide, AY= Aluminide+yttrised,
 2

1.8
Fig. 7 Oxidation performance of different bond coats.

1.6
The oxidation performance of all the Pt-modified bond coats was much better
than the bond coats without Pt. Why Pt has improved the oxidation performance is
still to be explored, however two things are clear from the present findings: one that
Pt changed the coating growth pattern and the other it retarded the diffusion of slow
diffusing elements from the substrate to the coating. These may be the reasons for
improved oxidation performance.

1.4
By changing the growth mechanism from totally inward growth in case of
aluminide coating to mixture of outgrown and ingrown coatings in the Pt-modified
coatings, it provides more pure coatings in the outer zone. As the outgrowth is the
result of Ni diffusion from the substrate to the coating surface rather than Al diffusion
into the substrate it has less probability of having impurities from the substrate,
particularly refractory elements. As Ta, Mo, W are known to have destabilizing effect
on the β-NiAl., thus their absence stabilize β-NiAl phase, the more stable the β-NiAl
g/cm2)

1.2
phase the longer will be the coating life. This fact is also supported by the digi-point
analysis of all the bond coats samples studied.
 From the oxidation performance data of all the samples, given in the Table 4.it
is clear that Pt-modified aluminide and Pt-modified aluminide and yttrised samples
outclass all the other bond coats. Both spalled after 86 thermal cycles.
However when the oxidation performance of these two samples was seen in
detail two marked differences were quite evident. First the thickness of the two
coatings developed under the same time and temperature conditions was different: the
thickness of Pt-modified aluminised and yttrised bond coat was near 35µ m, while for
Pt-modified aluminide coating it was about 65µ m. Both the micrographs are shown
in fig 5 and 4. This reduced thickness of the coating may be due to the lower Al
activity in the pack in the presence of YCl3. The second difference was the presence of
comparatively Ni-rich β -phase in case of Pt-modified aluminised and yttrised coating
compared to Pt-modified aluminide coating.
Both of these features are not conducive for the oxidation performance of the
coating. Less thickness of the coating; with the assumption that coating is β-NiAl,
which is always a desirable case, means that the coating has the smaller Al content
that can form protective Alumina scale. The presence of Ni-rich β -phase means that
this coating will degrade more quickly than the coating that has less Ni in the β -
phase. As with the increase in Ni content in the β -phase; that usually happens during
the degradation of the coating due to the depletion of the Al content, β -phase tends to
transform to γ ’ phase.
Although both the samples were spalled off after equal number of thermal
cycles but the important thing to note is the net weight gain before the spallation.
From the oxidation performance test results, shown in the Table 4, the weight gained
by the Pt-modified aluminised and yttrised sample before spallation was 1.74mg/cm2,
while the weight gained by the Pt-modified aluminide coating before spallation was
only 0.85mg/cm2. It means that Pt-modified aluminised and yttrised coating had
critical mass; needed before spallation, double that of for the Pt-modified coating.
And it is well known fact that weight gain during the oxidation is due the formation of
metal oxides, these oxides are volumetrically quite bigger than the metal atoms, and
therefore oxide formation exerts stress on the Alumina scale -coating interface. The
more the oxide forms the more will be the stress on the interface and greater will be
the chances for spallation of Alumina scale. In this case despite the fact there is larger
stress on the interface in Pt-modified aluminised and yttrised sample due to the more
oxide formation, the spallation of the coating occurred after the same number of
cycles as in the case of simple Pt-modified coating. It means that yttrium has played
some role in enhancing the adhesion of alumina scale and thus delaying the spallation
of the coating.
Theses arguments get further support from the oxidation performance of the
bond coats without Pt modification. While the aluminide coated sample could not
even survive 4 thermal cycles, the aluminised and yttrised sample began to spall off
after 18 thermal cycles. Weight gain comparison of these samples could not be noted
because of the quite earlier failure of the aluminide bond coat sample.
It can be positively said that yttrium did improve the adhesion of Al2O3. In
case of TBC’s the critical mass gain of the bond coat is more important than the
depletion of the coating of its protective scale forming elements. However in coatings
without ceramic top-coat the depletion is more important and from the findings of the
present study it can be said that if equal thickness of the aluminised and yttrised
coating and aluminide coatings are exposed to the same high temperature conditions
aluminised and yttrised coating will last longer than the aluminide coating.

References

1. Reactive Elements Modified Chemical Vapour Deposition Low Activity

Platinum Aluminide Coating by Bruce Michael Warnes. Surface and coating
technology 146-147(2001) pages 7-12.
2. Substrate and Bond Coat Composition: Factors Affecting Alumina Scale
Adhesion by B. A Pint. Material Science And Engineering A, V 245, issue
2(1998) page 201-211
3. Comparative Performance of Selected Bond Coats in Advanced Thermal
Barrier Coating Systems by Twancy, H. M. Journal of Materials Science. V
35, Issue 14 (2000) page 3615-3629
4. Oxidation Mechanism of HfC and Hafnium Diboride in the Temperature
Range 1400-2100oc by C. B. Bargeron. John Hopkins APL Technical Digest.
V 14, n 1(1993) pages 29-35
5. Effects of Micro Structural Morphology on the Performance of Platinum
Aluminide Coatings. By P. Deb, D. H. Broone, and R. Strieff. Surface
modifications and coatings (1986)
6. Reactive Diffusion and Kirkenall Effect in the Nickel -Aluminium System.
By M. M. P. Janssen and G. D. Rieck. Transactions of the metallurgical
society of AIME. V 239(1967) pages 1372-1385
7. Aluminide Diffusion Coatings for Ni-Based Superalloys Ph.D thesis by
Johan ANGENETE Goteborg University Sweedon.
8. Comparison of Inward and Outward Grown Pt-Modified Aluminide
Diffusion Coating on Ni-Based Single Crystal Superalloy by C Pollak.
Surface coating and technology. V 150, Issue 2-3(2002) pages 107-118.
9. The influence of implanted Yttrium on the Oxidation Behaviour of β-NiAl
by J. Jedlinski, Material Science and Engineering, 87 (1987) 281-287.
10. Progress in coating for gas turbine airfoils by G.W. Goward, Surface &
Coatings Technology, 108-109 (1998) 73-79.
11. Mechanism of spallation of electron beam physical vapor deposited
thermal barrier coatings with and without platinum aluminide bond coat
ridges by Krishnakumar Vaidyanathan, Surface & Coatings Technology, 133-134
(2000) 28-34.
12. The effects of active elements addition on the oxidation performance of a
platinum aluminide coating at 1100 oC by G. Fisher, Surface & Coatings
Technology, 110 (1998) 24-30.
13. Smart overlay coatings ______ concept and practice by J.R. Nicholls, Surface
& Coatings Technology, 149 (2002) 236-244.