Intermetallics 26 (2012) 36e39

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Intermetallics
journal homepage: www.elsevier.com/locate/intermet

Isothermal oxidation behaviour of TiAleCreNbeB alloys produced by induction

melting
Daniela Pilone*, Ferdinando Felli
Dipartimento ICMA, Sapienza Università di Roma, Via Eudossiana 18, 00184 Roma, Italy

a r t i c l e i n f o a b s t r a c t

Article history: The oxidation behaviour of Ti-48Al-2Cr-1.5Nb-0.04B, Ti-48Al-2Cr-3Nb-0.04B, Ti-48Al-2Cr-6Nb-0.04B

Received 29 December 2011 alloys were investigated by thermogravimetric method. Isothermal experiments were carried out at
Received in revised form 900
C and 1000
C in air.
7 March 2012
The work focused on the synergistic effect of Cr and Nb on the oxidation resistance of the considered
Accepted 9 March 2012
alloys when Nb content was increased from 1.5% at. to 6% at. The alloy’s microstructure and composition
Available online 28 April 2012
as well as the composition distribution of the oxide scale were analysed by Scanning Electron Microscopy
(SEM), Energy Dispersive Spectroscopy (EDS) and X-Ray Diffractometry (XRD). The results showed that
Keywords:
A. Titanium aluminides, based on TiAl
the scale composition changes with the Nb content in the alloy and that, by increasing the Nb
B. Oxidation percentage, the mass gain decreases and the scale adherence increases, with a consequent overall
G. Aero-engine components improvement of the oxidation resistance.
G. Automotive uses, including engines (and Ó 2012 Elsevier Ltd. All rights reserved.
other transportation uses)

1. Introduction alloys [3e5]. Non-metallic elements such as C and N are effective in

The emerging success of gamma TieAl alloys is due to their
properties which allow weight reduction in high temperature
aerospace industry. For aircraft engine applications, small and
efficient turbines are envisaged. Weight savings in private trans-
portation and automotive engines with a consequent improvement
in fuel consumption is also attractive. In fact the high specific
mechanical properties of titanium aluminide alloys push the
development of these materials.
Because of their ordered structure, intermetallics have high
mechanical strength both at room and at high temperature [1,2].
Despite that, TiAl-based alloys cannot be used as single phase alloys
since they have a very low ductility at room temperature. The most
interesting alloys are called near gamma. The presence of a second
a2 phase allows control of the microstructure. As far as mechanical
properties are concerned, the addition of ternary elements such as
Cr, V and Mn reduces the grain size with consequent ductility
improvement.
To date, various TiAl-based alloys have been developed. Adding
transition metals with high melting temperatures is generally
beneficial to increasing the high temperature strength of these
* Corresponding author. Tel.: þ39 0644585879; fax: þ39 0644585641.
E-mail address: daniela.pilone@uniroma1.it (D. Pilone).
increasing their strength because of both solid solution and
precipitation hardening effects.
Titanium aluminide alloys, interesting as lightweight structural
materials [6] because of their excellent mechanical properties, are
limited to low temperature applications due to insufficient oxida-
tion resistance. Poor oxidation resistance currently limits the use of
TiAl above 800
C. When these alloys are subjected to oxidation in
air the scale is not a protective Al2O3 layer, but a mixture of Al2O3
and TiO2. The oxidation resistance of TiAl intermetallics is known to
be significantly affected by the addition of ternary elements [7e11].
Improvements in the oxidation resistance of gamma alloys have
been achieved by modifying the alloy compositions, particularly by
the addition of Mo, W and Nb [4,7]. There have been various
theories proposed to account for these improvements, but there is
considerable support for the suggestion that the “doping effect”
[10] determines the suppression of TiO2 growth. Many authors have
postulated that in TiO2 formed during oxidation, vacancies play
a role in inward oxygen diffusion [12].
When ions with valence þ5 or þ6, such as Nb and W, are
incorporated in the scale, oxygen vacancies should be reduced and
this presumably results in the suppression of TiO2 growth. Recent
research [14] on high Nb intermetallics highlighted that a dopant
element with a higher valence than that of titanium is expected to
decrease the oxygen vacancy concentration owing to the elec-
troneutrality in the oxide, and thus to suppress TiO2 growth. In
addition, the (Ti,Nb)O2-rich layer is a dense and chemically

0966-9795/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.intermet.2012.03.008
 D. Pilone, F. Felli / Intermetallics 26 (2012) 36e39
Table 1
Chemical composition (% at.) of the three tested alloys.
Ti Al Cr Nb
Alloy 1 48.46 48 2 1.5
Alloy 2 46.96 48 2 3
Alloy 3 45.46 48 2 6
uniform scale. Hence, it is more protective than the TiO2 layer
[13,14].
2. Experimental procedure
The alloys used in this work (Table 1) were produced by
induction melting under an Ar atmosphere from pure Ti, Al, Cr, Nb,
while B was added as TiBAl master alloy. The molten metal was cast
directly into the rotating mould. The ingots were homogenized at
1100
C.
Isothermal TGA was carried out at 900 and 1000
C under
laboratory air. The specimens used in the oxidation tests were
polished up to 600 grit SiC papers and cleaned with acetone before
oxidation. The weight of the specimen being oxidized was measured
by using a Cahan microbalance in conjunction with a computer.
In order to perform metallographic examinations, test speci-
mens prior to and after oxidation tests were ground to a mirror-like
surface by SiC papers up to 1200 followed by 0.3 mm alumina.
Metallographic structure, scale morphology and specimen cross
sections were inspected by scanning electron microscope (SEM) and
microanalyses were carried out by energy dispersion spectroscopy
(EDS). Reaction products formed during the oxidation were exam-
ined by X-ray diffraction (XRD) and SEM equipped with EDS.
3. Results and discussion
Fig. 1 presents SEM micrographs of the alloys containing 1.5%
and 6% Nb. Although Al-concentration in both alloys IS the same,
the as-cast structures differ. In the two tested alloys, there are
grains composed of alternating lamellae of a2-Ti3Al and g-TiAl.
Lamellar structure of TiAl intermetallics is generally considered as
beneficial in relation to mechanical properties. However, Fig. 1
shows that for all the considered compositions there are also
regions composed of massive g phase. The diffusionless massive
Fig. 1. SEM micrographs showing the microstructure of (a) Ti-48Al-2Cr-1.5Nb-0.04B and (b) Ti-48Al-2Cr-6Nb-0.04B.
37
B
0.04
0.04
0.04
Fig. 2. Isothermal oxidation kinetics at 900
C of (a) Ti-48Al-2Cr-1.5Nb-0.04B, (b) Ti-
48Al-2Cr-3Nb-0.04B and (c) Ti-48Al-2Cr-6Nb-0.04B.
transformation of high-temperature a to highly faulted g phase
commonly occurs on rapid cooling which suppresses diffusion, i.e.
decomposition of a to a mixture of a and g. It is well known that
some ternary additives to TiAl-based alloys support the massive
transformation even at relatively low cooling rates [14]. Therefore,
the slower the diffusivity of an additive, the lower the critical
cooling rate for massive transformation to occur. For the Nb alloy,
the massive g is not observed, because niobium is believed to
possess a high diffusion coefficient in TieAl phases [15,16]. SEM
observation of the cast alloys showed that the amount of g phase
decreases with increasing the Nb concentration in the alloy.
Specimens of the 3 considered alloys were subjected to
isothermal oxidation tests. Fig. 2 shows thermogravimetric oxida-
tion curves obtained at 900
C in air. The results reported in Fig. 2
clearly show that at 900
C the mean oxidation kinetics are much
higher for the alloy containing 1.5% Nb in comparison with the
alloys containing 3% and 6% Nb. The weight gain after 100 h reaches
7.8 mg cm2 for the 1.5% Nb containing alloy, 1.8 mg cm2 for the 3%
Nb alloy and 1.0 mg cm2 for the 6%Nb alloy. Thermogravimetric
oxidation curves obtained at 1000
C showed again that oxidation
kinetics increase with decreasing the Nb content and that 6% of Nb
38 D. Pilone, F. Felli / Intermetallics 26 (2012) 36e39

Fig. 3. Isothermal oxidation kinetics at 1000
C of (a) Ti-48Al-2Cr-1.5Nb-0.04B,

(b) Ti-48Al-2Cr-3Nb-0.04B and (c) Ti-48Al-2Cr-6Nb-0.04B.

in the alloy allow to have a weight gain after 100 h that is rather
limited and reaches 2.1 mg cm2 at 1000
C (Fig. 3).
The knowledge of overall oxidation kinetics is crucial in
studying the high temperature oxidation commonly controlled by
the diffusion of reactive species through the oxide scale and/or in
the subjacent alloy. Diffusion-driven oxidation usually produces
parabolic kinetics described through the parabolic law Dm2 ¼ kpt,
where Dm is the mass gain per unit area at time t and kp is the
parabolic rate constant. In the lower temperature range, the
experimental curves obey the parabolic law and the kp value is
about 1.43$104 mg2 cm4 s1 for the alloy containing 1.5% Nb. It
decreases by increasing the Nb content of the alloy reaching a value
of about 3.3$106 mg2 cm4 s1 when the Nb content is 6%. At
1000
C the parabolic law for the alloys containing 3 and 6% Nb is
Fig. 5. X-ray diffractograms of (a) Ti-48Al-2Cr-1.5Nb-0.04B, (b) Ti-48Al-2Cr-3Nb-0.04B
obeyed only in the early stages since after a few hours the oxide
and (c) Ti-48Al-2Cr-6Nb-0.04B after isothermal oxidation at 900
C for 100 h: C Al2O3,
layer becomes very protective. At 1000
C, the alloy with 6% Nb has TiO2, + AlTi, A TiO2, NbO, : AlTi3.
a kp value of about 1.76$105 mg2 cm4 s1. The kinetics were
reasonably reproducible and represented at every temperature,
a very protective behaviour. Breakaway oxidation kinetics were 900
C revealed that all the scales are compact and adherent to the
never observed during isothermal oxidation. subscale, but their thickness decreases with increasing the Nb
After 100 h samples were cut to inspect by SEM the transverse content reaching a value of about 5 mm when 6% Nb is added to the
section in order to study oxide composition and metal-oxide alloy. Fig. 4 shows the cross-section of the 3 alloys after isothermal
interface. Examination in cross section of specimens treated at oxidation at 900
C. EDS analyses revealed that the primary scale

Fig. 4. Back scattered SEM imaging showing the transverse section of (a) Ti-48Al-2Cr-1.5Nb-0.04B, (b) Ti-48Al-2Cr-3Nb-0.04B, (c) Ti-48Al-2Cr-6Nb-0.04B after isothermal oxidation
tests at 900
C.
 D. Pilone, F. Felli / Intermetallics 26 (2012) 36e39
Fig. 6. SEM micrographs showing the morphology of the oxide formed on (a) Ti-48Al-2Cr-1.5Nb-0.04B, (b) Ti-48Al-2Cr-3Nb-0.04B, (c) Ti-48Al-2Cr-6Nb-0.04B samples after
isothermal oxidation at 900
C for 100 h.
constituents are alumina and titanium oxide. X-ray maps showed
also that in the alloy containing 1.5% Nb a chromium rich layer was
formed just below the oxide scale (light grey phase in Fig. 4(a)), but
it was not able to promote formation and stabilization of a protec-
tive Al2O3 layer. The back scattered SEM image reported in Fig. 4(a)
highlights also that 1.5% Nb is not able to avoid the formation of
a scale constituted by alternating layers of Al2O3 and TiO2 that
produce a non protective behaviour.
XRD analyses, carried out on the oxide external surface, iden-
tified as primary phases aAl2O3 and TiO2 (Fig.5) in the specimens
containing 1.5% Nb. As the Nb content increases the oxide
composition changes: the TiO2 content decreases while the Al2O3
content increases. Moreover the scales grown on the alloys con-
taining 3% and 6% Nb contain also Nb oxide.
A close examination of SEM micrographs of the oxide
morphologies highlights that when the Nb content is low and the
titanium oxide percentage in the scale is high the oxide shows the
presence of prismatic shaped particles, while when the Nb content
reaches 6% the oxide scale morphology appears really different. As it
can be observed in Fig. 6(c) thermal treatment at 900
C and 1000
C
determines the growth of a high number of alumina nuclei. In this
case, because of the multinucleated structure, the compressive
stresses are still present in the oxide layer favouring the resistance
to scale cracking. It is well established that when the alumina scale
grows almost exclusively by inward oxygen transport, it appears flat
and adherent since the new oxide is formed nearly exclusively at the
metal/oxide interface [17]. In contrast, a mixed transport mode of
aluminium and oxygen determines the formation of new oxide
within the scale and then the formation of convolutions. It seems
that in the studied alloys the scale always grows by inward oxygen
transport and that, as stressed by other authors, the Nb determines
a significant reduction of the oxide growth at high temperatures in
air, an improved adherence of the oxide scale to the substrate, the
absence of an aluminium-depleted zone below the oxide scale. A
lower oxide growth can be explained by the fact that niobium affects
the diffusion processes in such a way that metal and/or oxygen
transport through the oxide scale is decreased.
4. Conclusions
The effect of Nb addition up to 6%at on the oxidation behaviour of
Ti-48Al-0.04B alloys was investigated at 900 and 1000
C. The results
highlighted that when the Nb content is higher than 1.5% at Nb oxide
39
is detected by XRD analyses in the oxide scale. Moreover by
increasing the Nb content the quantity of TiO2 in the oxide layer is
considerably reduced. 6% at. of Nb in the tested alloys allows to obtain
a flat, thin and adherent oxide layer characterised by a multinucle-
ated structure. This suggests that the Nb in the oxide, even at rela-
tively low concentrations, reduces the oxygen diffusion rate,
suppresses the rutile growth and enhances the alumina formation.
References
[1] Djanarthany S, Viala JC, Bouix J. An Overview of monolithic titanium aluminides
based on Ti3Al and TiAl. Materials Chemistry and Physics 2001;72:301e19.
[2] Dimiduk DM. Gamma titanium aluminide alloys e an assessment within the
competition of aerospace structural materials. Materials Science and Engi-
neering 1999;A263:281e8.
[3] Ye HQ. Recent developments in Ti3Al and TiAl intermetallics research in China.
Materials Science and Engineering 1999;A263:289e95.
[4] Yamaguchi M, Inui H, Ito K. High-temperature structural intermetallics. Acta
Materialia 2000;48:307e22.
[5] Lin JP, Xu XJ, Wang YL, He SF, Zhang Y, Song XP, et al. High temperature
deformation behaviors of a high Nb containing TiAl alloy. Intermetallics 2007;
15:668e74.
[6] Westbrook JH, Fleischer RL. Structural application of intermetallic compounds.
Chichester (UK): John Wiley & Sons; 2000. 75.
[7] Kim BG, Kim GM, Kim CJ. Oxidation behaviour of TiAleX (X¼Cr, V, Si, Mo or
Nb) intermetallics at elevated temperature. Scripta Metallurgica et Materialia
1995;33:1117e25.
[8] Narita T, Izumi T, Yatagai M, Yoshioka T. Sulfidation processing and Cr addi-
tion to improve oxidation resistance of TiAl intermetallics in air at 1173 K.
Intermetallics 2000;8:371e9.
[9] Jung HG, Kim KY. Effect of ternary elements on the oxidation behavior of
Aluminized TiAl alloys. Oxidation of Metals 2002;58:197e216.
[10] Yoshihara M, Kim YW. Oxidation behavior of gamma alloys designed for high
temperature applications. Intermetallics 2005;13:952e8.
[11] Brady MP, Brindley WJ, Smialek JL, Locci IE. The oxidation and protection of
gamma titanium aluminides. JOM 1996;48:46e50.
[12] Kofstad P. Note on the defect structure of rutile (TiO2). Journal of Less
Common Metals 1967;13:635e8.
[13] Lin JP, Zhao LL, Li GY, Zhang LQ, Song XP, Ye F, et al. Effect of Nb on oxidation
behavior of high Nb containing TiAl alloys. Intermetallics 2011;19:131e6.
[14] Saage H, Huang AJ, Hu D, Loretto MH, Wu X. Microstructures and tensile
properties of massively transformed and aged Ti46Al8Nb and Ti46Al8Ta alloys.
Intermetallics 2009;17:32e8.
[15] Vojtech D, Popela T, Kubásek J, Maixner J, Novák P. Comparison of Nb- and Ta-
effectiveness for improvement of the cyclic oxidation resistance of TiAl-based
intermetallics. Intermetallics 2011;19:493e501.
[16] Wang YH, Lin JP, Xu XJ, He YH, Wang YL, Chen GL. Effect of fabrication process
on microstructure of high Nb containing TiAl alloy. Journal of Alloys and
Compounds 2008;458:313e7.
[17] Quadakkers WJ, Nicholls J, Naumenko D, Wilber J, Singheiser L. Factors
affecting oxide growth rates and lifetime of FeCrAl alloys. In: Bode H, editor.
Materials aspects in automotive catalytic converters. Weinheim, Germany:
Wiley-VCH; 2002. p. 93e105.