Intermetallics 37 (2013) 7e10

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

Phase transitions assessment on g-TiAl by Thermo Mechanical Analysis

M. Terner a, *, S. Biamino a, D. Ugues a, S. Sabbadini b, P. Fino a, M. Pavese a, C. Badini a
a
Dipartimento di Scienza Applicata e Tecnologia, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129 Torino, Italy
b
Avio SpA, Via I Maggio 56, Rivalta, 10040 Torino, Italy

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

Article history: Phase transition temperatures of g-TiAl alloys were successfully identified by Thermo Mechanical
Received 5 December 2012 Analysis. The derivative curve of the displacement as a function of temperature exhibits well defined
Received in revised form peaks at the temperatures 1100
Teu
1200  C and 1250
Ta
1350  C which correspond to the phase
25 January 2013
transformations (a2 þ g) 4 a and (a þ g) 4 a respectively. The well-known effects of Al and Nb content
Accepted 28 January 2013
Available online 15 February 2013
on transition temperatures were studied for validation.
Ó 2013 Elsevier Ltd. All rights reserved.
Keywords:
A. Titanium aluminides, based on TiAl
B. Phase transformation
C. Powder metallurgy
E. Phase diagram, prediction

1. Introduction an ordered hexagonal D019 structure). These phases combine to

Titanium aluminide alloys have been studied for many years
with the intent to replace the heavier Ni-based alloys currently
used as structural parts in the aeronautic field. g-TiAl based alloys
are intermetallic materials which exhibit promising high temper-
ature specific properties since the density of TiAl is about two times
lower than that of Ni-based superalloys [1e8].
However, the properties of g-TiAl based alloys strongly depend
on their chemical composition and microstructure. Thereby, first
generation g-TiAl with an Al content from 45 to 48 at.% exhibited
acceptable balance of ductility, creep and high temperature oxi-
dation resistance [1,9,10]. Second generation alloys with small
addition (usually from 1 to 3 at.%) of alloying elements were then
developed. Addition of V, Hf, Cr and Mn increases significantly the
ductility, Cr being the most effective. Addition of refractory ele-
ments such as W, Si, Mo, Ta and Nb increases creep and high
temperature oxidation resistance [1,2,11e15]. Finally, third gener-
ation alloys containing higher amount of refractory elements (for
example Nb or Ta up to 8 at.%) are developed nowadays to increase
oxidation resistance and thus the application temperature of g-TiAl
alloys [1,2,13,16e19].
In the range of Al content considered, g-TiAl alloys exhibit a two
phases structure containing a mixture of g-TiAl phase (with an
ordered face-centered tetragonal L10 structure) and a2-Ti3Al (with
* Corresponding author. Tel.: þ39 388 8779967; fax: þ39 011 090 4699.
E-mail address: mathieu.terner@polito.it (M. Terner).
build up different microstructures. The microstructure strongly
determines the mechanical properties of the final material. Basi-
cally, four different microstructures can be obtained: equiaxed,
duplex, nearly lamellar and fully lamellar [1,20]. Depending on the
microstructure, specific sets of mechanical properties can be
obtained [1,21,22]. For instance, the fine duplex microstructure
shows better strength and ductility [1,6,21,22], while a coarser fully
lamellar microstructure exhibits a better toughness and creep
resistance [1,6,23,24]. The different microstructures can be
obtained by careful heat treatment at given temperatures in rela-
tion with the alpha transus temperature Ta of the alloy (i.e. the
transition between the a mono-phase region and the (a þ g) bi-
phase region) which is highly affected by changes in the alloy
chemical composition.
Since g-TiAl alloy performances are strongly microstructure-
dependent, it is of great importance to improve the understand-
ing of fundamental aspects such as phase relations, microstructure
evolution and control. As suggested, the microstructure can be set
up by heat treatment. Fig. 1 shows the central part of the TieAl
phase diagram [20]. For a given composition, heat treatment at
a high temperature in the a phase field (T1 in Fig. 1) leads to a fully
lamellar microstructure. On the other hand, heat treatment at
a temperature in the (a þ g) phase field leads to a duplex micro-
structure with a higher or lower lamellar colonies ratio and size (T2
and T3 respectively in Fig. 1). Finally, heat treatment in the (a2 þ g)
phase field leads to an equiaxed microstructure of g and a2 grains
(T4 in Fig. 1) [20].

0966-9795/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.intermet.2013.01.019
8 M. Terner et al. / Intermetallics 37 (2013) 7e10

oxidation. Specimens were heated from room temperature to

1400  C with different heating rates in the range 5e50  C/min,
hence giving as results dynamic transitions. All measurements
were realized along the height of the sample, i.e. the longest di-
rection. On the other hand, DSC (TGA-DSC 92, Setaram) were per-
formed on 1.5  1.5  3 mm specimens under 20 ml/min argon
flow. Specimens were heated from room temperature to 1400  C
with a heating rates of 5  C/min.
In particular, TMA and DSC were used to identify the phase
transition temperatures of 2nd and 3rd generation g-TiAl produced
by electron beam melting (EBM) [14,38e40]. The process and the
produced materials were described in previous publications by
Biamino et al. [14,38].

3. Results and discussion

3.1. Thermo Mechanical Analysis

Fig. 1. Central portion of the binary TieAl phase diagram as described by Kothari et al. Fig. 2 shows the displacement curve of the studied alloy,
[20].
measured by TMA, as a function of temperature (continuous line)
during heating at 5  C/min from room temperature to 1400  C.
Thereby, the accurate knowledge of the phase diagram and thus Normally, the displacement increases almost linearly when tem-
the phase transition temperatures is very important. The binary Tie perature increases as a result of thermal expansion. However, at
Al phase diagram has been assessed and revised many times but temperatures close to the transitions anticipated from the phase
still remains a matter of debate [1,18,20,25e27]. However, the al- diagram in Fig. 1, rather sudden changes, because of the change in
loys with industrial interests, as pointed out above, always contains lattice parameters, are observed and pointed out by circles in Fig. 2.
allowing elements. For this reason, the effect of alloying elements This behavior becomes even more evident when plotting the de-
on phase transitions of g-TiAl alloys has been widely studied. For rivative curve (dotted line in Fig. 2) of the displacement: two dis-
example, Huang et al. [15] showed that Cr addition decreases both tinct peaks are observed. Such peaks in the derivative curve
the a transus temperature Ta and the eutectoid temperature Teu. In represent the sudden change of microstructural parameters during
addition, the influence of Nb addition was widely studied and phase transitions. One can note that in some alloys, other transi-
found to increase the eutectoid temperature Teu but have little in- tions can take place involving for example the b phase, but are not
fluence on the a-transus temperature [1,6,7,28,29]. Thus, it was studied in this paper.
thus of particular interest for a given alloy composition to find
a way to determine the phase transition temperatures, and in 3.2. TMA versus DSC
particular the alpha transus temperature Ta which sets the heat
treatment temperature for a given microstructure. In addition to In order to confirm and analyze the accuracy of the measure-
the evident scientific interest, it is also industrially convenient to be ments by TMA, results were compared to DSC measurements which
able to quickly set up the proper thermal treatment. in literature is a well-established [6,7,29,31] technique for g-TiAl
The traditional way to assess equilibrium phase diagrams for phase transition evaluation.
complex alloys, determined by annealing heat treatments followed Fig. 3A shows the derivative curve of the displacement as
by metallographic examination of the microstructure [1,7,20,26e a function of temperature obtained by TMA (dotted line) along with
28,30], can be heavy and expensive in alloy screening and devel- the DSC curve (continuous line) of Tie47Ale2Cre2Nb. Both
opment. Conversely, differential scanning calorimetry (DSC)
[4,6,7,29,31] and differential thermal analysis (DTA) [32] usually are
the preferred techniques to identify the transformation by meas-
uring the heat evolution. Also, Thermo-Calc CALPHAD method
showed good agreement with experimental data [7,33e35] as well
as high energy X-ray diffraction [36].
In this paper, Thermo Mechanical Analysis (TMA) is proposed as
alternative method to determine the transition temperatures and
in particular Ta. TMA is generally used to measure the glass tran-
sition in polymers based on changes in thermal expansion [37]. It
was suggested that the microstructural rearrangement that occurs
during phase transitions may be observed by TMA. In particular, the
change in lattice parameter during the transformation between L10
and D019 at Ta.

2. Material and methods

TMA (Setsys Evolution, Setaram: max temperature 1620  C,

resolution 0.2 nm, measuring range  2 mm, max size of sample in
mm length/diameter: 20/10) were performed on 4  4  10 mm Fig. 2. TMA measurement of Tie47Ale2Cre2Nb: displacement vs. temperature (con-
specimens under 20 ml/min argon flow in order to prevent tinuous line) and derivative of the displacement vs. temperature (dotted line).
 M. Terner et al. / Intermetallics 37 (2013) 7e10 9

bigger specimens than DSC which are more representative of real

components.

3.3. Alloying elements effect on transition temperatures

In order to validate the model, in terms of TMA accuracy for g-

TiAl phase transformations evaluation, TMA tests were realized on
materials with different chemical compositions since alloying ele-
ments are known to modify the phase transition temperatures.
Thereby, TMA measurements were performed on three different
materials produced by EBM under equivalent conditions. Fig. 3B
shows the derivative curve of the displacement of Tie47Ale2Cre
2Nb (fine dotted line), Tie46Ale2Cre2Nb (dotted line) and Tie
46Ale2Cre8Nb (continuous line).
Both materials with the same 46 at.% Al content exhibit almost
the same a-transus temperature (1292e1295  C) while Teu in-
creases with the increase of Nb from 1175  C to 1215  C. On the
other hand, both materials with the same 2 at.% Nb content show
that varying the Al content leads to different Ta whereas Teu re-
mains the same (1175e1180  C, as can be seen Fig. 3B). In particular,
higher Ta was found when the aluminum content increases (from
1292  C for 46 at.% Al to 1315  C for 47 at.% Al). This is consistent
with the trend of the a transus line in the TieAl phase diagram
(Fig. 1).

3.4. Dynamic to static results

The transition temperatures determined by either DSC, DTA or

TMA are measured dynamically and vary substantially with dif-
ferent heating rate. However, by extrapolation and linear regres-
sion, as it was realized for DSC analysis [7,31] or DTA [32], it is
possible to correlate dynamic and static conditions according to the
following equation:
Fig. 3. (A) Comparison between DSC curve (continuous line) and the derivative of the
displacement measured by TMA (dotted line) for Tie47Ale2Cre2Nb under argon at- _
mosphere and 5  C/min heating rate. (B) Comparison of the derivative of the dis-
TReu;
_ a ¼ k:R þ T0eu;a (1)
placement measured by TMA between Tie47Ale2Cre2Nb (fine dotted line), Tie46Ale
2Cre2Nb (dotted line) and Tie46Ale2Cre8Nb (continuous line). Where TReu;
_ a is the transition temperature for a given heating rate
_
R,k a coefficient and T0eu;a is the transition temperature for
a theoretical heating rate of 0  C/min or the static transition
measurements in Fig. 3A were realized in argon atmosphere with temperature.
the same heating rate of 5  C/min. TMA were realized on Tie46Ale2Cre8Nb with the different
One can appreciate the similarity between the two curves. heating rates 1, 3, 5, 10, 20, 30  C/min and the values of Teu and Ta
Rather evident peaks are observed and the temperatures at which were identified. The results are plotted Fig. 4. By linear regression,
the variations are identified for both techniques correspond. A the eutectoid temperature Teu and the a-transus temperature Ta
similar comparison between TMA and DSC was carried out to assess could be approach by equation (1).
the glass transition temperature of latex films showing good
results [37].
According to the literature [6,7,29,31], the first peak corresponds
to the eutectoid transformation (a2 þ g) 4 a and is identified at
a temperature Teu ¼ 1180  C (Fig. 3A). The second peak corresponds
to the transformation (a þ g) 4 a at the alpha transus temperature
Ta ¼ 1315  C (Fig. 3A). The position of the two peaks were identified
graphically at the abscissa of the maximums of the displacement
derivative versus temperatures plots.
From Fig. 3A, some conclusions can be drawn. First of all, the
results show that TMA actually allows the identification of phase
transition temperatures. Just like DSC [6], only transition temper-
atures can be determined by TMA and additional measures such as
X-ray Diffraction (XRD) or Energy Dispersive Spectroscopy (EDS)
are needed to identify the actual phase composition. Furthermore,
the derivative curves exhibit well defined peaks that enabling to
accurately determine the transition temperatures while identifying
the precise position of the peaks is more difficult by the analysis of
the DSC results. Finally, TMA allows more freedom with regards to Fig. 4. Linear regression from dynamic transition temperatures TReu;
_ a measured at
the specimen geometry than DSC. In particular, TMA allows to test different heating rates R_ of Tie46Ale2Cre8Nb.
10 M. Terner et al. / Intermetallics 37 (2013) 7e10
4. Conclusions
TMA was thus found reliable to assess the phase transition
temperatures of g-TiAl alloys. When compared to other well
established techniques (such as DSC or DTA), TMA exhibits sharper
well-defined peaks to identify the phase transition temperatures.
Finally this method is obviously quicker than annealing heat
treatments and metallographic observations. When one changes
the composition of the g-TiAl alloy, a rather quick and reliable
method to identify the transition temperature variations is a pow-
erful tool. g-TiAl alloys properties strongly depend on micro-
structure which is very sensitive to the processing temperature or
the heat treatment temperature. When a variation is observed in
the transition temperature, the different heat treatment to obtain
the same microstructure can be quickly assessed saving time and
resources.
Acknowledgments
The authors acknowledge the support of Arcam AB and AvioProp
for the production by electron beam melting of the tested materials.
References
[1] Appel F, Paul JDH, Oehring M. Gamma titanium aluminide alloys. Wiley VCH;
2011. 746 pages.
[2] Tetsui T. Intermetallics 2002;10:239e45.
[3] Voice WE, Henderson M, Shelton EFJ, Wu X. Intermetallics 2005;13:959e64.
[4] Clemens H, Bartels A, Bystrzanowski S, Chladil H, Leitner H, Dehm G, et al.
Intermetallics 2006;14:1380e5.
[5] Cha L, Scheu C, Clemens H, Chladil FF, Dehm G, Gerling R, et al. Intermetallics
2008;16:868e75.
[6] Appel F, Oehring M, Wagner R. Intermetallics 2000;8:1283e312.
[7] Chladil HF, Clemens H, Leitner H, Bartels A, Gerling R, Schimansky FP, et al.
Intermetallics 2006;14:1194e8.
[8] Loria EA. Intermetallics 2000;8:1339e45.
[9] Lasalmonie A. Intermetallics 2006;14:1123e9.
[10] Kim Y-W. Acta Metallurgica Sinica August 1999;12(4):334e9.
[11] Liu ZC, Lin JP, Wang YL, Lin Z, Chen GL, Chang KM. Materials Letters 2004;58:
948e52.
[12] Zhang WJ, Chen GL, Appel F, Nieh TG, Deevi SC. Materials Science and Engi-
neering 2001;A315:250e3.
[13] Haanappel VAC, Clemens H, Stroosnijder MF. Intermetallics 2002;10:
293e305.
[14] Biamino S, Penna A, Ackelid U, Sabbadini S, Tassa O, Fino P, et al. Intermetallics
2011;19:776e81.
[15] Huang SC, Hall EL, Shih DS. ISIJ International 1991;31(10):1100e5.
[16] Chen GL, Zhao LL, Lin JP, Xu XJ. Supplemental proceedings. Materials Fab-
rication, Properties, Characterization, and Modeling, TMS 2011;2:547e55.
[17] Lapin J, Pelachovà P, Domànkovà M. Intermetallics 2011;19:814e9.
[18] Wu X. Review of alloy and process development of TiAl alloys. Intermetallics
2006;14:1114e22.
[19] Hu D, Wu X, Loretto MH. Advances in optimisation of mechanical properties
in cast TiAl alloys. Intermetallics 2005;13:914e9.
[20] Kothari K, Radhakrishnan R, Wereley NM. Progress in Aerospace Science
2012;55:1e16.
[21] Kim Y-W. Intermetallics 1998;6:623e8.
[22] Yan YQ, Zhou L, Wang WS, Zhang YN. Journal of Alloys and Compounds 2003;
361:241e6.
[23] Yamaguchi M, Zhu H, Suzuki M, Maruyama K, Appel F. Materials Science and
Engineering, A 2008;483e484:517e20.
[24] Bystrzanowski S, Bartels A, Clemens H, Gerling R, Schimansky FP, Dehm G,
et al. Intermetallics 2005;13:515e24.
[25] Schuster JC, Palm M. Journal of of Phase Equilibria and Diffusion 2006;27:
255e77.
[26] Okamoto H. Journal of Phase Equilibria 1993;14:120.
[27] Okamoto H. Journal of Phase Equilibria 2000;21:311.
[28] Chen G, Zhang W, Liu Z, Li S, Kim YW. In: Kim YW, editor. Gamma titanium
aluminides. Warrendale, PA: TMS; 1999. p. 371e80.
[29] Appel F, Oehring M, Paul JDH, Klinkenberg Ch, Carneiro T. Intermetallics 2004;
12:791e802.
[30] Chladil HF, Clemens H, Leitner H, Bartels A, Gerling R, Marketz WT. Advanced
Engineering Materials 2005;7e12:1131e4.
[31] Malinov S, Novoselova T, Sha W. Materials Science and Engineering A 2004;
386:344e53.
[32] McQuay PA. Materials Science and Engineering A 1994;185:55e63.
[33] Saunders N. In: Kim YW, editor. Gamma titanium aluminides. Warrendale, PA:
TMS; 1999. p. 183e8.
[34] Shao G, Tsakiropoulos P. In: Kim YW, editor. Gamma titanium aluminides.
Warrendale, PA: TMS; 1999. p. 189e94.
[35] Beschliesser M, Clemens H, Kestler H, Jeglitsch F. Scripta Materialia 2003;49:
279e84.
[36] Yeoh LA, Liss KD, Bartels A, Chladil H, Avdeev M, Clemens H, et al. Scripta
Materialia 2007;57:1145e8.
[37] Backfolk K, Holmes R, Ihalainen P, Sirvio P, Triantafillopoulos N, Peltonen J.
Polymer Testing 2007;26:1031e40.
[38] Terner M, Biamino S, Epicoco P, Penna A, Hedin O, Sabbadini S, et al. Steel
Research International 2012;83(10):943e9.
[39] Beretta S, Filippini M, Patriarca L, Pasquero G, Sabbadini S. Key Engineering
Materials 2011;465:531e4.
[40] Filippini M, Beretta S, Patriarca L, Pasquero G, Sabbadini S. Journal of ASTM
International May 2012;9(5).