Materials Science and Engineering A356 (2003) 372
/380

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Protection of titanium alloy components against high temperature

corrosion
I. Gurappa *
Defence Metallurgical Research Laboratory, Kanchanbagh PO, Hyderabad 500 058, India

Received 9 July 2002; received in revised form 20 February 2003

Abstract

The current paper presents the oxidation characteristics of titanium alloy, Ti
/5.8Al
/4.06Sn
/3.61Zr
/0.7Nb
/0.54 Mo at different
elevated temperatures. The degradation of the alloy under oxidizing conditions is described in detail. The behaviour of the titanium
alloy under various hot corrosion conditions and the mechanism involved in degrading the alloy are explained. It is stressed that the
application of a high performance coating is extremely necessary in order to use the titanium alloy safely for gas turbine engine
applications. Efforts were made to develop high performance coatings for titanium alloy, Ti
/5.8Al
/4.06Sn
/3.61Zr
/0.7Nb
/0.54
Mo to protect from high temperature corrosion as well as a-case formation. The developed coating exhibited outstanding
performance with negligible weight gain and absence of a-case formation during the entire exposure period. It was shown that the
formation of a continuous, protective and adherent alumina scale on the surface of coating upon exposure to elevated temperatures
is the reason for exhibiting excellent performance.
# 2003 Elsevier Science B.V. All rights reserved.

Keywords: Titanium alloy; Oxidation; Hot corrosion; Protective coatings

1. Introduction hot corrosion) and a-case formation and thereby helps

In view of excellent combination of high temperature
strength and lightweight properties, titanium-based
alloys are more attractive for manufacture of gas turbine
engine compressor section components [1]. These com-
ponents expose to elevated temperatures and corrosive
environments. The titanium alloys posses good affinity
towards oxygen at elevated temperatures in air and
thereby leading to oxidation and a-case formation [2
/4].
Further, the components experience hot corrosion
problem when aircraft flies at low altitudes across the
sea [5]. These factors severely limit the high temperature
capability of alloys in terms of mechanical properties. It
is therefore, desirable to understand the characteristics
of titanium alloys under simulated gas turbine engine
conditions and then apply appropriate coatings, which
can prevent high temperature corrosion (oxidation and
* Tel.: /91-40-458-6515; fax: /91-40-444-0683.
E-mail address: igpl@rediffmail.com (I. Gurappa).
0921-5093/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0921-5093(03)00150-3
in enhancing the life of gas turbine engines significantly.
In the present paper, an attempt was made to under-
stand the oxidation and hot corrosion characteristics of
the titanium alloy, Ti
/5.8Al
/4.06Sn
/3.61Zr
/0.7Nb
/
0.54 Mo. Then, the degradation mechanism under two
different environmental conditions was explained. Sub-
sequently, the development of high performance coat-
ing, which enhances the life of titanium alloy
significantly, has been explained in detail. Finally, the
degradation mechanism of the developed coating has
been discussed based on the extensive studies since the
coating is bound to fail after prolonged exposure.
2. Experimental
The chemical composition of the titanium alloy is Ti
/
5.8Al
/4.06Sn
/3.61Zr
/0.7Nb
/0.54 Mo
/0.05C
/
0.009Fe
/0.105O
/0.002N.
The cyclic isothermal oxidation studies were carried
out in air for the bare titanium alloy at 600, 700 and
800 8C for a period of 100 h. The weight gain was
 I. Gurappa / Materials Science and Engineering A356 (2003) 372
/380
monitored initially every 3 h i.e. holding the specimens
at the required temperature (example 800 8C) for 3 h
and then allowed to cool at room temperature in air for
1 h with a view to observe any rapid weight gain and
subsequently every 10 h i.e. holding the specimens at
800 8C for 10 h and then cooling to room temperature in
air for 1 h. The hot corrosion studies were carried out by
weight loss method in crucibles containing pure Na2SO4,
90% Na2SO4/10% NaCl and 90% Na2SO4/5%
NaCl/5% V2O5 at 500, 600 and 700 8C. Subsequently,
the corrosion rate constants were calculated. Weight loss
measurements were carried out after washing the
samples in hot distilled water.
The platinum aluminide coating was produced on the
titanium alloy samples by depositing platinum of about
5 mm thickness electrochemically, followed by a diffu-
sion treatment at 700 8C for 2 h under an argon
atmosphere in order to obtain good metallic bonding
between the substrate and platinum. Then aluminium
was deposited over platinum by a high activity pack
aluminizing route for 2 h at 700 8C under an argon
atmosphere. Subsequently, a diffusion treatment was
given at 700 8C for a period of 4 h under an argon
atmosphere, with a view to obtain good bonding
between the substrate and intermetallic layer. The plain
aluminide coated samples were prepared by depositing
aluminium over titanium alloy (without platinum coat-
ing) by following the procedure mentioned above. Later,
the oxidation studies for coated specimens were carried
out for 400 h at 800 8C. Scanning Electron Microscopy
(SEM) was used to observe cross sections of oxidized
specimens and the effect of chloride on stability of
titanium alloy oxide scales. Energy Dispersive X-ray
Spectroscopy (EDS) was used to determine the compo-
sitions of oxide scales. Electron probe microanalysis
(EPMA) was used to determine elemental distribution
for oxidized coated specimens. X-ray line scans were
taken for bare titanium alloy specimens oxidized at
800 8C for 100 h with a view to show the oxygen
dissolved region (a-case) in the titanium alloy. Micro
hardness measurements were taken in order to deter-
mine the depth of the oxygen dissolved region or a-case
in the titanium alloy.
3. Oxidation characteristics
Fig. 1 shows the weight gain as a function of time for
the titanium alloy oxidized at 600, 700 and 800 8C. The
weight gain is smallest for the specimen exposed at
600 8C, slightly more at 700 8C and higher yet at 800 8C.
The rate of oxide growth is higher at 800 8C (Kp /3.2 /
102) and lower at 600 8C (Kp /3.1 /10 4). On all the
specimens, initially rutile is formed followed by alumina
scale. The alumina scale thickness is not uniform and at
the same time rutile also is not protective at high
373
temperatures [2,3]. After reaching a certain thickness,
the oxide scale started spalling due to adherence
problem. This behaviour is observed only for the
specimens exposed at 800 8C. As the rate constant value
is higher at 8008, the oxide scale formation takes place at
a faster rate and started to spall after reaching a certain
thickness [3].
Elemental distribution of oxygen as well as alloying
elements of titanium alloy, which was exposed for 100 h
at 800 8C, is illustrated in Fig. 2. The results clearly show
the presence of all alloying elements of titanium in the
oxide scale. Zirconium and tin, the alloying elements of
titanium have diffused outwardly and concentrated
beneath the oxide scale. A very important and interest-
ing observation is the presence of dissolved oxygen just
below the oxide scale. The high intensity peak represents
the oxygen present in the oxide scale and lower intensity
one represents the oxygen dissolved in the subsurface
zone of titanium alloy. The dip observed between the
two oxygen peaks is due to the detachment of oxide
scale during the preparation of specimens. As reported
recently [3], the oxide scale does not have good
adherence because of higher thickness of the oxide scale.
Therefore, it can be detached easily during the sample
preparation. The micro hardness measurements made as
a function of depth for the specimens exposed at 800 8C
for a period of 100 h, clearly indicated that the hardened
zone due to dissolution of oxygen, exhibits a hardness of
about 700 HV and the depth of a-case is about 140 mm
which is consistent with the SEM results [6].
The more weight gain observed for the specimen
exposed at 800 8C when compared to the specimens
exposed at 600 and 700 8C, is due to the fact that weight
gain is not only due to the formation of oxide scale but
also for the dissolution of oxygen in the subsurface zone
of the titanium alloy. An excellent correlation has been
observed between the weight gain and the depth of a-
case at 800 8C which is high. It indicates that a-case
formation or the dissolution of oxygen in the titanium
alloy causes significant weight gain at 800 8C. Due to
poor adherence of the thermally grown surface scale, the
oxide scale spalls easily. As a result, it is very easy for
oxygen to react with fresh metallic surface and thereby
increasing re-formation of oxide scale on the unpro-
tected/fresh surface. This process continues as long as
the exposure continues and the depth of attack of the
alloy increases gradually by a-case formation as well as
oxide scale growth and thus affecting the mechanical
properties of the alloy drastically. The same mechanism
is true at lower temperatures but the time required for
reactions to take place is more. Finally, it is concluded
that both the formation of oxide scale as well as a-case
formation due to dissolution of oxygen affects the
mechanical properties of the titanium alloy at elevated
temperatures. Therefore, appropriate protective coat-
ings for the titanium alloy are a must in order to use the
374 I. Gurappa / Materials Science and Engineering A356 (2003) 372
/380
Fig. 1. Weight gain as a function of time for the titanium alloy at different elevated temperatures.
alloy safely at the desired elevated temperatures, which
improve the efficiency of gas turbine compressor sec-
tions significantly.
4. Hot corrosion characteristics
Typical weight loss data as a function of time for the
titanium alloy, IMI 834 exposed at 600 8C in different
environments such as pure Na2SO4, 90% Na2SO4/10%
NaCl and 90% Na2SO4/5% NaCl/5% V2O5 environ-
ments is shown in Fig. 3. The alloy obeyed parabolic
kinetics at all the temperatures and at various environ-
ments studied. The rate constant increases by about six
times in chloride-containing environment and about
seven times in vanadium-containing environment. It
indicates that the rate of reaction is high in chloride-
containing environments and higher in vanadium-con-
taining environments and lower in pure Na2SO4 envir-
onments. The Scanning Electron Micrograph (SEM) for
the specimen corroded at 600 8C in chloride-containing
environment is shown in Fig. 4. It is clear that the oxide
scale that formed on the surface of the alloy was cracked
due to the presence of NaCl in the environment. The
cracks were not observed for the specimens corroded in
pure Na2SO4. It indicates that the chloride ions present
in the environment causes the oxide scale to crack and
facilitates the species present in the environment to react
with the alloy, which is the reason for observing
significant increase in weight loss. It is known that
chloride leads to pitting type of attack, which generally
initiates at imperfections in the oxide scale. The micro
hardness measurements as a function of depth for the
specimens exposed at 600 8C for a period of 65 h,
revealed the presence of about 500 mm hardened zone
due to dissolution of oxygen, which is sufficient for
affecting the mechanical properties of the alloy by
forming a highly brittle zone from which crack initiates
during service conditions [5]. The depth of oxygen
dissolved region is observed to vary with the tempera-
ture and the environment at which the specimens were
exposed. The results show that the depth of a-case
increases from Na2SO4 to 90% Na2SO4/10% NaCl and
then in 90% Na2SO4/5% NaCl/5% V2O5. The total
depth of the titanium alloy affected that corroded in
90% Na2SO4/10% NaCl environment at 600 8C for 65
h is about 500 mm which is about 100 times more than
that of the specimens oxidized in air for 100 h at the
same temperature [5]. It clearly indicates the greater
aggressiveness of hot corrosion environments compared
to oxidized conditions. The above observations clearly
stress the need to protect the titanium alloy components
from hot corrosion and thereby enhance their life by
avoiding failures during service. The results also focus
on the development of suitable coatings, which can
enhance the life of titanium alloy components by
protecting it both from oxidation and hot corrosion.
Both these processes are experienced practically by gas
turbine engine compressor section components.
 I. Gurappa / Materials Science and Engineering A356 (2003) 372
/380 375

Fig. 2. X-ray intensity variations for oxygen, zirconium, aluminium and tin across the cross section of oxidized titanium alloy after oxidation at
800 8C for 100 h showing the formation of a-case.

5. Development of high performance protective coatings resistance while maintaining excellent bulk properties of
the substrate. Recent approaches in this direction
Surface engineering plays a major role in tailoring the include a variety of surface modification techniques,
surface properties of alloys to suit the environmental such as pack cementation, electro-deposition, plasma
376 I. Gurappa / Materials Science and Engineering A356 (2003) 372
/380
Fig. 3. Weight loss as a function of time1/2 for the titanium alloy in various environments at 600 8C showing the detrimental effect of the presence of
NaCl and V2O5.
spraying, ion plating and sputtering techniques [7
/13].
A patent has been produced on the production of high
melting point intermetallic layer of PtAl2 from the
reaction of sequentially applied platinum and alumi-
nium layers using an R.F. biased DC sputtering route,
which can protect titanium alloys effectively against
oxidation [14]. An attempt has been made to deposit an
iron
/chromium-based alloy to prevent the formation of
a-case in titanium alloys [15]. However, successful
results have not been reported till recently. The author
has successfully developed high performance as well as
economically viable coatings for titanium alloy compo-
nents used in gas turbine engines recently [6,16
/18].
Fig. 4. SEM of hot corroded titanium alloy in NaCl environment at
600 8C showing the cracking of oxide scale.
Fig. 5 illustrates the weight gain as a function of
oxidation time in air for the specimens with plain
aluminide and platinum aluminide coatings. In order
to understand the effect of the coatings, the oxidation
data have been compared with those for the uncoated
alloys. The weight gains for the plain aluminide coated
specimens decrease by almost half when compared with
those for the uncoated alloys. Further reductions in
weight gains for the specimens coated with platinum
aluminide are observed. The platinum aluminide coated
alloy had a weight gain of only 0.1 mg cm 2 after 100 h
of exposure and about 0.4 mg cm2 after 400 h of
oxidation at 800 8C. This weight gain is extremely low
and is /34 times less than that of the uncoated alloy.
This indicates that the platinum aluminide coating
provides excellent oxidation resistance to the titanium
alloy and thereby enhances its life significantly. It is
important to mention that the platinum in the coating
promotes selective alumina formation (Fig. 6) in addi-
tion to better scale adhesion properties [6,17,18]. This
aspect is confirmed by reduction in weight gain to only
half that for the plain aluminide coatings in which there
is no platinum content. This type of behaviour was
observed when nickel-based super alloys were coated
with platinum aluminide coatings for protection from
oxidation [19]. In essence, the platinum aluminide coat-
ing shows a remarkable improvement in oxidation
resistance over plain aluminide coating and thereby
increases the life of titanium alloy considerably.
The micro hardness measurements of the platinum
/
aluminide-coated specimens showed no detectable har-
dened zone even after 400 h of exposure. This indicates
 I. Gurappa / Materials Science and Engineering A356 (2003) 372
/380
Fig. 5. Oxidation kinetics of uncoated and with different coatings of titanium alloy showing the superior performance of platinum aluminide
coating.
that the platinum aluminide coating effectively pre-
vented the formation of a-case, even during the pro-
longed exposure of 400 h at 800 8C. SEM results
indicate the presence of a continuous, adherent and
protective alumina scale on the surface of platinum
aluminide coating after exposure for 400 h at 800 8C.
Analysis of the oxide scale by EDS confirms the
presence of a protective aluminium-rich scale in associa-
tion with smaller amounts of platinum on the surface of
the coating. EPMA results further confirm the presence
of a continuous, adherent and protective alumina scale
on the surface of the coating (Fig. 7). This protective
layer, which forms during exposure of the coating to the
Fig. 6. Scanning electron micrograph showing the presence of
protective alumina scale on the surface of platinum aluminide coating.
377
oxidising environment, is a major contributing factor to
excellent oxidation resistance and very low weight gain
during oxidation.
One of the limitations of plain aluminide coatings is
that during the formation process, large amounts of
elements from the substrate are introduced into the
coating. Even small amounts of elements, such as
zirconium, tin or titanium from the substrate can
decrease the oxidation resistance of the coatings sig-
nificantly at high temperatures. Therefore, there is a
need to obtain coatings free of those detrimental
elements by forming coatings whose composition is
not influenced by the diffusion of elements from the
substrate. This requirement necessitates the develop-
ment of platinum aluminide coatings where the Pt
/Al
layer acts as a barrier to diffusion of alloying elements
from the substrate to the coating.
The platinum aluminide coating was deposited onto
the titanium alloy by a combination of electro-deposi-
tion and pack aluminising techniques, and subsequently
protected the alloy surface from oxidation which is a
major limitation to using these materials at temperatures
of 600 8C and higher. The platinum aluminide coating
effectively eliminates a-case formation and also provides
excellent oxidation resistance to the titanium alloy, even
at 800 8C, which is a temperature generally considered
being highly aggressive and not commonly experienced
during service. The normal maximum operating tem-
perature of the modern compressor components is about
590 8C, at which the platinum aluminide coating pro-
tects the titanium alloy in an excellent fashion from
oxidation. Therefore, it is one of the promising coatings,
378 I. Gurappa / Materials Science and Engineering A356 (2003) 372
/380

Fig. 7. Elemental distribution of platinum aluminide coated titanium alloy after oxidation at 800 8C for 400 h showing the formation of continuous,
adherent and protective alumina scale.

Fig. 8. A schematic representation of degradation of platinum aluminide coated titanium alloy showing the sequences of steps that cause
degradation of the coating after prolonged exposure. (a) Formation of protective alumina scale; (b) Initial formation of titania; (c) Formation of
alumina/titania; (d) Final stage.
 I. Gurappa / Materials Science and Engineering A356 (2003) 372
/380
which could be applied to titanium alloy components
intended for use in gas turbine engine compressor
components. Platinum aluminide coatings were origin-
ally developed to protect nickel-based super alloys
against oxidation up to temperatures of 1100 8C and
higher, and are regarded to be stable and as able to
prolong significantly the life of the components [20,21].
The results demonstrate that these coatings are useful
for titanium alloys and for protection against high
temperature oxidation. The main factor contributing
to this behaviour is the presence of platinum, which
effectively promotes continuous alumina scale forma-
tion during high temperature exposure [20]. It is
desirable that any coating developed should have
sufficient hot corrosion resistance under the aircraft
operating conditions, to enhance component durability
against both oxidation and hot corrosion. Hot corrosion
tests on platinum aluminide coatings applied on nickel-
based super alloys have reported good performance
under aggressive environments. Recently, the good
performance of platinum aluminide coatings in combat-
ing both oxidation and hot corrosion for nickel-based
super alloys was confirmed [20]. The high performance
platinum aluminide coatings therefore appear to be a
promising coating material to protect titanium alloy
components from oxidation, hot corrosion as well as a-
case formation (though the application of coatings on
the compressor components fabricated from titanium
alloys has not been done so far) and thereby enhance the
life of modern gas turbine engines significantly.
6. Degradation mechanism of protective coating
The durability of any coating depends on its composi-
tion and method of application. Among the coatings,
alumina formers prolong the life of components con-
siderably when compared to chromia formers, particu-
larly at elevated temperatures. This requires the presence
of an aluminium reservoir in the coating that is useful
for the formation and rehealing of the oxide scale after
spallation. If the coating contains an appropriate
amount of aluminium, it provides the maximum life to
the component [22,23]. The degradation of the platinum
aluminide coating takes place as follows: Initially, a
protective alumina scale forms on the surface of the
coating on exposure to high temperatures. After reach-
ing a certain thickness, it naturally spalls and again
forms a protective scale. This process continues as long
as the aluminium reservoir in the coating can supply
aluminium. After reaching a critical concentration of
aluminium, the alumina scale is unable to reform. Up to
the critical level of aluminium in the reservoir, platinum
can effectively prevent the diffusion of titanium and
other elements through it. Once alumina scale is unable
to reform, titanium diffuses outwards and forms titania
379
by interacting with oxygen. After prolonged exposure,
titanium and other alloying elements start to diffuse out
very fast through platinum and form less protective
oxides of titanium, tin, zirconium etc. It is important to
mention that, as titanium has the highest affinity
towards oxygen, it is the first element to diffuse out
and form titania by interacting with oxygen. Prolonged
exposure causes the coating to fail completely and only
oxides of the alloying elements in the substrate, which
are not protective, form. Practical observation of titania
on the surface of the coating after exposure for 400 h
provides evidence of the present proposed mechanism
for platinum aluminide coatings. A schematic represen-
tation of degradation of platinum aluminide coating is
shown in Fig. 8.
7. Conclusions
(1) Titanium alloy, IMI 834 is susceptible to oxidation
and a-case formation when exposed to elevated tem-
peratures.
(2) Hot corrosion has a greater detrimental effect on
the degradation of the titanium alloy.
(3) Application of protective coatings on the titanium
alloys is essential in order to improve their life.
(4) A high performance platinum aluminide coating
has been successfully developed to enhance the life of
titanium alloy components significantly by effectively
protecting them from oxidation, a-case formation as
well as hot corrosion.
(5) The degradation mechanism of developed plati-
num aluminide coating has been established. The coat-
ing fails after prolonged exposure by forming non-
protective oxides.
Acknowledgements
Defence Research and Development Organisation is
gratefully acknowledged for financial assistance.
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