J OURNAL OF MATERI ALS SCI ENCE LETTERS 20, 2001, 2225 2229

Effect of aluminum on hot corrosion resistance of MCrAIY-

based bond coatings
I . GURRAPPA
Defence Metallurgical Research Laboratory, Kanchanbagh PO, Hyderabad-500 058, India
E-mail: igp@dmrl.ernet.in
A major concern associated with the improvement of
land based gas turbines efciencies is a signicant in-
crease of gas inlet temperatures. This results in an in-
creased service temperature of the blading materials
and consequently to an enhanced oxidation and hot
corrosion attack if deposited salts can penetrate into
the blade coatings, which are usually of MCrAlY type
where M is Ni or NiCo. These coatings can provide
protection against oxidation and hot corrosion and act
as bond coats for zirconia based thermal barrier coat-
ing systems. In both the cases, slow growth rates and
optimum adherence of the alumina scales forming on
the MCrAlY coatings during high temperature expo-
sure are of signicant for component life. These re-
quirements can be fullled only by using coatings with
sufciently high aluminum contents to ensure protec-
tive alumina scale formation and re-healing after oxide
spallation/reaction with the environment. The lifetimes
of the coatings are mainly limited by aluminum deple-
tion occurring upon aluminum consumption as a result
of alumina scale growth and repeated spallation and re-
healing of the alumina scale during oxidation process.
If a point is reached where the aluminum level in the
bond coatings falls below the level at which alumina
scale can not be formed preferentially, faster growing
oxides of other constituents of the bond coating will
form and thereby affect the coatings life.
The MCrAlYbased bond coatings acts as a bond coat
between the superalloys and the ceramic thermal barrier
topcoat. This ceramic topcoat, usually based on yttria
stabilized zirconia acts as a thermal barrier, reducing
the substrate and bond coating temperature by about
150

C. The principle involved in protection of the al-

loy from corrosion and/or oxidation is to control both
the diffusion of alloying elements from the base alloy
towards the outer surface and diffusion of the corrosive
species into the substrate by developing a chemically
and thermodynamically stable and well adherent alu-
mina/chromia/silica layer whenexposedtoanoxidizing
environment. Spallation of the YSZ layer induced by
oxidation of the bond coating is considered to be the
ultimate failure mode of electron beam physical vapor
deposition (EB-PVD) thermal barrier coatings. Failures
usually occur at the interface between the bond coating
and its oxide scale, whether the bond coating is diffu-
sion aluminide or overlaid MCrAlY. This observation
suggests that the life of these TBCs is largely controlled
by the factors that govern the bonding at the scale/bond-
coating interface. For air plasma sprayed TBCs, spal-
lation usually occurs within the ceramic layer, but very
close to the bond coating/YSZ interface. The major
sources of stress leading to degradation of TBCs are
thermal mismatch with the bond-coating, temperature
gradient through the TBC, stress at the YSZ/bond coat-
ing interface from oxide growth and transformation in
the YSZ-especially tetragonal to monoclinic, which re-
sults in a 3 to 5% volume changes [1]
MCrAlYcoatings play a signicant role in providing
suitable surface for the application of thermal barrier
coatings and helps in protection of the alloy from oxi-
dation and/or hot corrosion. Due to proven performance
of these coatings for a variety of superalloys for over
two decades in different applications, MCrAlY coat-
ings have studied extensively [26] and proposed var-
ious degradation mechanisms [79]. Recently, a novel
electrochemical mechanism was proposed and showed
that the degradation of protective coatings takes place
through an electrochemical route [10].
In the present paper, the results on the hot corrosion
properties of a variety of MCrAlY type model alloys
containing different amounts of aluminum and cobalt
are presented explaining the effect of aluminum on the
life of coatings in the presence of vanadium contain-
ing environments. Based on the results, the optimum
content of aluminum required in association with other
alloying elements to form a thermodynamically stable
alumina scale on MCrAlY based bond coatings un-
der hot corrosion conditions has been suggested. This
study will be extremely useful to manufacture the coat-
ing compositions with optimum amounts of key alloy-
ing elements and thereby enhance the operational life
of gas turbine engines. Finally, the degradation mech-
anism of MCrAlY based model alloys has been dis-
cussed.
Different model alloys with varying composition
(Table I) were prepared by high frequency induction
melting technique under argon atmosphere.
Hot corrosion experiments were conducted in sil-
ica crucibles containing a mixture of 90% Na
2
SO
4
+
5% NaCl +5% V
2
O
5
environments. The Analar grade
Na
2
SO
4
, NaCl and V
2
O
5
were used in the present study.
The experiments were conducted at 800

C for 25 h.
The performance of the alloys was estimated by ob-
serving weight loss after cleaning in the hot distilled
water. The corroded samples were examined by opti-
cal microscopy with a viewto understand the structural
changes after exposure to the corrosive environments
at the selected elevated temperature. The corrosion
02618028 C
2002 Kluwer Academic Publishers 2225
TABLE I Nominal composition of tested MCrAlY based model
alloys (wt%)
Model alloy Nickel Chromium Cobalt Aluminum Yttrium
IGA Balance 20 20 6 0.4
IGB Balance 20 20 9 0.4
IGC Balance 20 20 12 0.4
IGD Balance 20 10 6 0.4
IGE Balance 20 10 9 0.4
IGF Balance 20 10 12 0.4
products of typical alloys were identied by X-ray
diffraction (XRD) technique.
Fig. 1 provides weight loss measurements for differ-
ent model alloys tested at 800

C in 90% Na
2
SO
4
+
5% NaCl +5% V
2
O
5
environments. As can be seen,
the model alloy, IGF containing 12% aluminum, 10%
cobalt, 20% chromium and 0.4% yttrium exhibits min-
imum weight loss. While the model alloy, IGD con-
taining 6%aluminum, 10%cobalt, 20%chromiumand
0.4%yttriumexhibits maximumweight loss. The com-
bination of 6% aluminum and high amount of cobalt
could lead to moderate weight loss as observed with the
model alloy, IGA, though good amount of chromium is
present. Whereas, the model alloys, IGBand IGEwhich
contain 9% aluminum, 20% chromium, 0.4% yttrium
and 20% and 10% cobalt respectively, improves hot
corrosion resistance when compared to the model al-
loys, IGA and IGD, which contain only 6% aluminum.
It indicates that 20% cobalt addition appears to be not
helpful in reducing the weight loss and therefore, the
optimumamount of cobalt is found to be 10%to exhibit
good hot corrosion resistance. It is conrmed by ob-
serving excellent hot corrosion resistance for the model
alloy, IGF, which contains only 10% cobalt. In the case
of model alloy, IGC, which contains maximum amount
Figure 1 Weight loss measurements for different MCrAlY based model alloys at 800

C in 90% Na
2
SO
4
+5% NaCl + 5% V
2
O
5
environments.
of cobalt does not help in improving the hot corrosion
resistance as that of model alloy, IGF, which contains
only 10% cobalt, though both the model alloys ap-
pears equally good (Fig. 1). In essence, the amount
of cobalt required in MCrAlY based bond coatings for
obtaining good hot corrosion resistance is 10%. More
amounts of cobalt addition i.e. 20% is detrimental as
observed in the case of model alloy, IGA, particularly
when aluminum content is less. Therefore, the combi-
nation of 10%cobalt and 12%aluminumcontents along
with 20% chromium and 0.4% yttrium makes the alloy
highly hot corrosion resistant (IGF).
Fig. 2 illustrates the inuence of aluminumon weight
loss in the MCrAlY based model alloys. It is very clear
that aluminum plays a major role in affecting the hot
corrosion resistance of MCrAlYalloys though the con-
centration of other alloying elements remains constant.
The weight loss is maximum for the model alloy con-
taining 6% aluminum, decreases with increase in alu-
minum content to 9% and minimum weight loss is ob-
served for the alloy containing 12% aluminum. The
behavior is same for all the model alloys whether the
cobalt content is 10% or 20%. As can be seen from
Fig. 2, the weight loss drastically reduces after increas-
ing the aluminum content from 6 to 9%. The effect of
further addition of aluminum does not help in reduc-
ing the weight loss signicantly. Therefore, the min-
imum amount of aluminum required to be present in
the MCrAlY based bond coatings is 9%. It is very
important to mention that the optimum content of alu-
minum required providing good hot corrosion resis-
tance is 12%, though its effect is marginal when com-
pared 9% aluminum containing alloys.
It is worthwhile to mention that the combination of
cobalt and aluminum contents is a must to exhibit good
hot corrosion resistance. From the present results, it
2226
Figure 2 The effect of aluminum on the weight loss of MCrAlY based model alloys illustrating its importance and optimum amount required in bond
coatings.
is also very clear that cobalt plays a signicant role
in supporting aluminum to form a chemically and ther-
modynamically stable oxide scale. Recent results on the
hot corrosion of MCrAlYbased bond-coatings revealed
that the life of the coating improves only when the
coating contains the combination of nickel and cobalt
but not either one is present in the coating [10]. Of
course, the other alloying elements addition is a must.
The present results clearly reveals the combination of
cobalt and aluminum in providing good hot corrosion
resistance. In addition, optimum amounts of aluminum
and cobalt to be present in the MCrAlY bond coatings
decide the life of the coating, which exhibits minimum
weight loss. The best combination is 10% cobalt and
12% aluminum along with 20% chromium and 0.4%
yttrium.
Fig. 3 shows the cross sections of optical micro-
graphs of typical model alloys, IGD, IGF and IGA.
As can be seen, the alloy, IGD has corroded severely
and formed extensive corrosion products in the matrix.
In fact, this model alloy was completely corroded after
exposure of 25 h. The corrosion-affected zone is more
for the model alloy, IGA, which contains 20% cobalt
and 6% aluminum, indicating the detrimental effect of
higher concentration of cobalt with low amount of alu-
minum. The main products in the matrix are sulphides
of chromium and nickel as sulphur diffuses readily
into the superalloys and forms metal sulphides [1114].
The corrosion-affected zone is minimum for the model
alloy, IGF for the same exposure time and tempera-
ture indicating good hot corrosion resistance. These re-
sults are in excellent agreement with the weight loss
data.
From the present studies, it is very clear that high
aluminum content is essential for the alloy/coating to
become hot corrosion resistant as the chemically and
thermodynamically stable alumina scale that forms on
the surface of the alloy/coating decides their life. As
mentioned earlier [2], the life of any alloy or coating
under hot corrosion conditions depends on the abil-
ity of the oxide scale to ux in the corrosive salts
at elevated temperatures. In the present studies, the
model alloy, IGF, which contains 12% aluminum is
capable of forming a stable and continuous alumina
scale even after reaction with the corrosive environ-
ment. Here, the aluminum is consumed as a result
of alumina scale growth and repeated uxing reac-
tion with the corrosive salts during the hot corrosion
process. The degradation of alloy/coating takes place
when the aluminum level falls below, which it can no
longer form the alumina scale preferentially and un-
der such circumstances faster growing oxides of other
elements of the alloy/coating form, which uxes eas-
ily in the environment and thereby affects the life of
coatings. This mechanism is clearly explained by ob-
serving higher susceptibility of the model alloys, which
contain only 6% aluminum. These alloys corrode at a
faster rate and hence the reason for observing maxi-
mumweight loss. This study also clearly reveals the ef-
fect of cobalt along with aluminumcontent in MCrAlY
model alloys. When the aluminum content is 6%, the
addition of cobalt proved to be detrimental. However,
when the aluminum addition increased to 9%, its detri-
mental effect was nullied. It indicates that the ox-
ides of cobalt in association with nickel appear to be
formed preferentially if the aluminum content is 6%,
and thereby uxes easily in the corrosive salts at el-
evated temperatures. This is the reason for observing
maximum weight loss for the model alloys contain-
ing 6% aluminum. However, when aluminum content
2227
Figure 3 Cross sections of model alloys, IGF, IGDand IGAafter hot corrosion studies at 800

Cin 90%Na
2
SO
4
+5%NaCl +5%V
2
O
5
environments
showing excellent hot corrosion resistance for IGF model alloy.
is increased to 9%, alumina formation takes place pre-
dominantly and thereby improves the hot corrosion
resistance by reducing weight loss signicantly. The
presence of 12% aluminum in the model alloy makes
them highly hot corrosion resistant by preferentially
forming chemically and thermodynamically stable alu-
mina scale. The results of model alloys, IGF and IGC
clearly support the above mechanism. Further conr-
mation of the above mechanism can be given based
on the maximum life observed for the Ni-22Co-18Cr
12AI-0.5Y bond coating when compared to other bond
coating compositions under same hot corrosion condi-
tions [10]. The present results are in excellent agree-
ment with the ndings of recent studies on the life of
2228
MCrAlY based bond coatings suggesting the optimum
amount aluminum to be present in the future MCrAlY
coatings.
The life of the coating depends not only on its chem-
ical composition as mentioned above but also the tech-
nique by which the coating is being applied. Then,
the microstructure of the coating is a complex func-
tion of many variables: material, deposition rate, and
pressure, part rotation rate, geometric altitude, temper-
ature and so on. The substrate temperature is one of
the most important parameters affecting the coating
microstructure and life, and the temperature must be
maintained within a dened envelope during coating
deposition. Therefore, the operating parameters have
to be optimized in order to get maximum life for the
coatings.
Several mechanisms were proposed for degradation
of coatings. In aggressive environments the protective
oxide either reacts with the corrosive species or dissolu-
tion of protective oxide in the aggressive environments
which ultimately results in reducing the coating life.
Recently, it has been established that the degradation
of superalloys and protective coatings under hot corro-
sion environments takes place through an electrochem-
ical route [2, 1014]. It was also stressed the need of
applying electrochemical techniques for assessing the
performance of a variety of alloys and coatings for gas
turbine engine applications.
Acknowledgments
Defence Research and Development Organisation is
gratefully acknowledged for providing nancial assis-
tance.
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Received 11 April
and accepted 18 October 2001
2229