Acta Materialia 115 (2016) 242e249

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Experimental and theoretical evidence of displacive martensite in an

intermetallic Mo-containing g-TiAl based alloy
Svea Mayer a, *, Manuel Petersmann b, Franz Dieter Fischer b, Helmut Clemens a,
Thomas Waitz c, Thomas Antretter b
a
Department of Physical Metallurgy and Materials Testing, Montanuniversitaet Leoben, Roseggerstr. 12, 8700 Leoben, Austria
b
Institute of Mechanics, Montanuniversitaet Leoben, Franz-Josef-Str. 18, 8700 Leoben, Austria
c
Physics of Nanostructured Materials, Faculty of Physics, University of Vienna, Boltzmanngasse 5, 1090 Vienna, Austria

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

Article history: In this study the martensitic transformation behavior of a Mo-bearing g-TiAl based alloy was investi-
Received 10 April 2016 gated. Therefore, a homogenization treatment within the single b-phase field region followed by water
Received in revised form quenching has been carried out, whereby the majority of the disordered b-phase transforms into hex-
2 June 2016
agonal a20 -martensite during cooling. Since the b to a transformation in the intermetallic b-solidifying
Accepted 2 June 2016
Available online 10 June 2016
Tie44Ale3Moe0.1B alloy (at%) occurs at very high temperatures causing enhanced diffusional processes,
a very locally diffusion-controlled transformation together with a displacive, hence purely martensitic
transformation take place. This work investigates the displacive martensite formation in the high-
Keywords:
Titanium aluminides
temperature regime using state-of-the-art experimental methods as well as modelling concepts from
Martensitic phase transformation the phenomenological theory of martensite crystallography. The high temperature at which the trans-
Electron microscopy formation takes place suggests the preference of plastic slip over twinning. This fact has also been
High-energy X-ray diffraction verified by transmission electron microscopy, as no twinning has been observed after generation of
Phenomenological crystallographic theory single martensite variants forming an invariant interface plane with the initial b-lattice. Such invariant
interfaces are formally possible according to the phenomenological theory of martensite crystallography,
if the Bain strains of the martensite variants are superimposed by additional simple shear.
© 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

1. Introduction
Urgent topics concerning energy efficiency and environmental
policies require novel approaches to materials design. One recent
example is the implementation of lightweight intermetallic g-TiAl
based alloys as structural materials in aerospace and automotive
applications. For their use, balanced mechanical properties at a
high level as well as an excellent hot-workability have to be ach-
ieved by adding alloying elements, such as Mo, which acts as a
strong b-stabilizer. The disordered body-centered cubic (bcc) b-
phase (A2, Im3m) is of great technological importance due to its
beneficial effect on the solidification and hot-deformation behavior
of TiAl alloys [1e4]. As an example for b-solidifying alloys, the
* Corresponding author.
E-mail addresses: svea.mayer@unileoben.ac.at (S. Mayer), manuel.petersmann@
unileoben.ac.at (M. Petersmann), franz-dieter.fischer@unileoben.ac.at (F.D. Fischer),
helmut.clemens@unileoben.ac.at (H. Clemens), thomas.waitz@univie.ac.at
(T. Waitz), thomas.antretter@unileoben.ac.at (T. Antretter).
solidification pathway from the liquid to the stable solid for alloy
Tie44Ale3Moe0.1B (in at%) is L / Lþb / b / aþb /
aþbþg / aþb/boþg / aþboþg / a/a2þboþg / a2þboþg. In
thermodynamic equilibrium at room temperature the phases a2-
Ti3Al (D019, P63/mmc), bo-TiAl (B2, Pm3m) and g-TiAl (L10, P4/mmm)
co-exist. The phase constituents close to thermodynamic equilib-
rium at different temperatures are well studied by means of in-situ
diffraction techniques employing synchrotron radiation and neu-
trons as reported in Refs. [5,6]. Technological processes such as hot-
working and heat treatments, however, are more or less far from
thermodynamic equilibrium, which first influence the solid-state
phase transformation b to a and hence the resulting microstruc-
ture and thus the mechanical properties of the specific alloy.
Therefore, the material’s behavior under non-equilibrium condi-
tions has to be investigated.
In general, on slow cooling from the single b-phase field, the
equiaxed a-phase initially nucleates and grows at the b-grain
boundaries, leading to a significant grain refining effect [3,7]. Bur-
gers [8] was one of the first who investigated the lattice

http://dx.doi.org/10.1016/j.actamat.2016.06.006
1359-6454/© 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
 S. Mayer et al. / Acta Materialia 115 (2016) 242e249
correspondences between the parent b- and the product a-phase in
Ti- and Zr-based alloys. He noticed that the basal plane (0001) of a
is derived from a (011)b plane. The close-packed ½111b and ½111b
directions are lying onD that Especific basal plane, which corresponds
to the close-packed
D E 1120 directions. This accountsD for four
E of
a
the six 1120 directions, while the remaining two 1120 di-
a a
rections are derived from the [100]b as well as ½100b directions.
Due to symmetry reasons, six crystallographically equivalent lattice
correspondences are possible [9,10]. The Bain strain and the rigid
body rotation exactly maintain the (011)b and (0001)a planes par-
allel, while the rotation makes the close-packed directions coincide
within a tolerance of 1.5 [10]. It should also be noted that the
Burgers orientation relation renders the (112)b plane nearly parallel
to the ð1100Þa plane [10]. This last correspondence will additionally
confirm our calculation results presented in section 3.
The morphology of the hexagonal a-phase is strongly depen-
dent on the cooling rate, as is known from a þ b titanium alloys, i.e.
moderate cooling rates lead to colony and/or basket-weave mi-
crostructures. Thereby, based on a diffusional ledge mechanism, a
colony of Widmanst€ atten a-plates precipitates at b-grain bound-
aries, at grain boundary allotriomorphs or intragranularly during
cooling from the b-phase field region [11,12]. The retained b-matrix
in between is highly enriched with Ti and alloying elements that
partition to the b-phase, as reported in Ref. [7]. In case of localized
short-range diffusion due to a higher cooling rate the a-formation
occurs through a massive transformation without any change in
chemical composition. The rapid growth is therein propagated by
migration of the interface, which is typically serrated or faceted.
And last of all, very fast cooling or quenching from the single b-
phase field region in the course of a homogenization treatment
leads to a displacive martensitic transformation [13].
According to reference [7], a martensitic transformation in bi-
nary b-solidifying g-TiAl based alloys can only occur in rapidly
solidified Tie48Al (in at%) powders during the atomization process,
but not via a solid-state b/a transformation, even under ice-brine
quenching. The reason for this is explained by the high T0 tem-
perature of about 1330  C for an Al-content of 40 at%, for which the
massive transformation is preferred [14]. In a2-Ti3Al-based alloys,
however, the bcc b-phase transforms martensitically upon fast
cooling below the martensite start temperature Ms, similar to many
Ti-based alloys [11], to the disordered hexagonal close-packed
(hcp) a0 -phase, which rearranged into the ordered a20 , as reported
in Ref. [15]. Associated with an increasing Al-content, Ms increases
from about 900  C for pure Ti to 1150  C for stoichiometric a2-Ti3Al
[15]. The influence of b-stabilizing elements, such as Nb, V or Mo,
on the martensitic transformation of ternary titanium aluminides is
considered in the following.
Strychor et al. [16] analyzed the effect of Nb on the stabilization
of the b-phase, during the solution annealing in the single b-phase
field region followed by rapid cooling, by measuring Ms. For a2-
Ti3Al-xNb alloys (5 at% < x < 17 at%), the obtained results show that
below 5 at% Nb the formation of hcp a20 -martensite occurs,
whereas an increasing Nb-content reduces Ms (as well as the
martensite finish temperature, Mf) even below room temperature
at 10 at% Nb, allowing the retention of b [15]. An increasing amount
of Mo (3e4 at%) in a2-Ti3Al-based alloys causes a substantial
decrease in the b-transus temperature and furthermore a stabili-
zation of bo at room temperature [17]. Hence, for high cooling rates
the microstructure of Ti-(20e24)Al-(3e4)Mo alloys (in at%) con-
sists of a20 -plates within the bo-matrix [18,19]. In case of g-TiAl
based alloys the b-decomposition mechanism changes from
massive (Tie42Ale5V, in at%) to martensite (Tie42Ale10V and
Tie38Ale5V, in at%), after homogenization annealing in the single
b-phase field region followed by water quenching, with a rising
content on b-stabilizing elements and a reduced Al-content,
243
respectively, as shown for TieAleV alloys in Ref. [20]. Recently,
Hu et al. [21] determined in an ice-brine quenched
Tie44Ale4Nbe4Hfe0.1Si (at%) alloy an incomplete martensitic
transformation followed by a diffusional b/a or massive trans-
formation, in dependence on the local microstructure.
The analysis and determination of the influence of continuous
cooling, most popularly water quenching, on the solid state high
temperature b/a transformation mechanism and microstructure
development in a multi-phase TieAleMo alloy is an important part
of the present work. Even though the occurrence of martensite in
Ti-based alloys is well established, the range of existence and
morphology of the corresponding phases in ternary Mo-containing
g-TiAl based alloys needs to be determined, since the mechanical
properties are extremely sensitive to the microstructure. Therefore,
the disordered b to ordered hexagonal a20 -martensite trans-
formation has been investigated experimentally by means of
scanning electron microscopy (SEM), electron backscatter diffrac-
tion (EBSD) analysis, transmission electron microscopy (TEM) and
in-situ high-energy X-ray diffraction (HEXRD) experiments. Along
with the combined use of the phenomenological theory of
martensite crystallography (PTMC), a unique approach to verify the
occurring displacive martensite formation in the
Tie44Ale3Moe0.1B alloy (at%) is elaborated. Last but not least
because, up until now, the transformation has been characterized
as diffusional, i.e. crystallographic theories based on a coherent
interface matching, above all the edge to edge model (E2EM),
where the main principle is the parallelism of close-packed di-
rections [22], have been used. In the present study it will be shown
that the predictions of the PTMC match the experimental obser-
vations thus confirming the presence of martensite in Mo-
containing g-TiAl based alloys.
2. Material and experimental details
The Mo-containing g-TiAl based alloy chosen for the current
work was produced on an industrial scale facility via centrifugal
casting by GfE Metalle und Materialien GmbH, Germany, in form of
cylindrical ingots with a length of 200 mm and a diameter of
53 mm, for details see Ref. [3]. Subsequently, these ingots were hot-
isostatically pressed (HIP) at 1200  C for 240 min at a maximum
pressure of 200 MPa followed by furnace cooling. This processing
step was performed in order to eliminate casting defects, e.g. re-
sidual porosity, and to provide near-equilibrium conditions. By
means of X-ray fluorescence spectroscopy, the chemical composi-
tion was measured as average value at different locations of the
HIPed ingot to be Ti-44.58Al-3.23Mo-0.12B (at%). The small amount
of B is added to refine the microstructure during solidification by
the formation of borides. The subsequent b-homogenization
treatment was conducted in a laboratory high-temperature furnace
RHF 16/15 from Carbolite, where the specimen was annealed in the
single b-phase field region at 1450  C for 30 min and then water
quenched. The microstructure of the two sample states with regard
to the morphology of the appearing phases was initially investi-
gated by SEM. These measurements were conducted on a Zeiss EVO
50 operating in back-scattered electron (BSE) mode at an acceler-
ation voltage of 15 kV. The microscope is additionally equipped
with an Inca Dry Cool energy-dispersive X-ray spectrometer (EDS)
from Oxford Instruments for analytical characterization. In order to
determine the crystalline structure and orientation relationship of
both phases, EBSD analysis was performed at the Materials Center
Leoben Forschung GmbH (MCL), Leoben, Austria, using an EDAX
DigiView IV EBSD system on a dual beam Zeiss Auriga workstation
operating at 20 kV with a step size of 10 nm. The specimens were
therefore prepared metallographically followed by electrolytic
polishing, according to [23]. For the TEM investigations at the
244 S. Mayer et al. / Acta Materialia 115 (2016) 242e249
University of Vienna the specimens were electrolytically thinned to
electron transparency using a TenuPol-5 with an A3-electrolyte
from Struers at an applied voltage of 22 V and a flow rate of 10
and studied with a Philips CM200 microscope operated at 200 kV
equipped with an EDAX energy-dispersive X-ray microanalysis
(EDXMA). HEXRD experiments have been carried out for the in-situ
determination of the lattice parameters of the individual phases as
a function of temperature. The measurements were performed at
the high-energy materials science (HEMS) beamline at Petra III at
DESY (Deutsches Elektronen Synchrotron) in Hamburg, Germany,
which is operated by the Helmholtz-Zentrum Geesthacht, where
the beam had a mean energy of 100 keV (l ¼ 0.124 Å). To this end
samples with a diameter of 4 mm and a length of 10 mm in the
HIPed condition were induction-heated to 1450  C, held for 2 min
to avoid excessive grain growth and subsequently quenched at the
highest rate possible in a quenching and deformation dilatometer
DIL 805A/D from Baehr-Thermoanalyse GmbH. The temperature
was controlled using a type B thermocouple, which was spot-
welded on a Ta-platelet working as diffusion barrier to the sam-
ple surface. For recording the diffraction pattern a PerkinElmer flat
panel detector of the type XRD 1622 was used. The Debye-Scherrer
rings were azimuthally integrated by applying the software fit2D
[24]. Finally, the experimental evidence for the bcc to hcp
martensitic transformation was established for the investigated
Tie44Ale3Moe0.1B alloy. This type of displacive transformation
was also reported for polymers [25], pure Ti [9,26], Zr [10] and/or
metallic alloys as ZreNb, see Ref. [27], and most recently, by Hu and
Jiang [21] for a Nb bearing g-TiAl based alloy. Both, our experi-
mental work and the experiments reported in the literature have
motivated us to study the martensite formation by a consistent
theory which is described in the next section.
3. Theoretical concept for the martensitic transformation
The three most frequently used theoretical concepts to describe
the martensitic transformation process are:
(i) Introduction of order parameters hi as function of atomic
displacements xj, formulation of a Helmholtz free energy F(hi
(xj)) as a function of the order parameters and minimization
of this free energy, see the pioneering work by Falk [28]. This
concept was then followed in the phase field approach for
martensitic transformation, see Zhang and Purdy [29,30], Y.
Wang and co-workers [31,32] and recently Schmitt et al. [33].
It should be further mentioned that the formation of Wid-
mansta €tten structures has most recently been dealt in
Ref. [34] by a phase field method, which in principle belongs
to this general concept, see also [35].
(ii) Molecular dynamics (MD) simulations, e.g. see Refs. [36,37].
For the particular case of a bcc to hcp transformation as it
occurs in Zr the concept has been demonstrated in Ref. [36].
As another example we refer to [37] where martensite for-
mation induced by the stresses ahead of a crack tip has been
investigated in a 2D MD study.
(iii) The PTMC as followed here, starting with the ideas of Bain
who considered linear mappings of the lattice vectors lead-
ing to the Bain strain. The specific approach used here goes
back to Wechsler, Liebermann and Read [38] as well as
Bowles and Mackenzie [39,40] in the 1950’s. Their theory is
formulated on the premise that the martensite-parent habit-
plane is essentially undistorted and unrotated. Phenome-
nology suggests the existence of such an invariant plane.
While the theory is purely geometric, it is also supported
from elastic energy consideration following Eshelby’s inclu-
sion theory. Intuitively it is clear that minimum strain energy
is obtained for an isolated transforming domain when the
minimum misfit due to the transformation strain is parallel
to a long dimension of the domain and the maximum misfit
is parallel to a short dimension. As a result, the martensite
forms as a plate. Thus the assumptions of the PTMC are
consistent with the minimization of the strain energy of an
enclosed plate.
It should be pointed out that habit-planes are the most
frequently observed objects in studies of displacive martensitic
transformations. For further theoretical treatment all calculated
habit-planes are expressed relative to the common basis of the
cubic parent phase given by the lattice vectors {[100], [010], [001]}
and the following notation convention is adopted: tensorial quan-
tities that are not represented in this cubic coordinate system are
marked with a prime, e.g. U′ for the Bain strain in a representation
relative to its principal axes, i.e. appearing as diagonal matrix. As a
first step we correlate the parent b-Ti(Al) (Fig. 1a) to the product a-
Ti(Al)/a2-Ti3Al-phase (Fig. 1b) by verifying the Burger’s orientation
relationship which is outlined in section 4. To this end a pole figure
is calculated under the assumption of the applicability of the Bur-
ger’s relation along with the absolute position of the crystal in the
EBSD image and compared to the measured pole figure.
The PTMC is applied to provide a theoretical proof for the ex-
istence of a displacive martensitic transformation. It is essentially
based on the fact that the total deformation gradient F after
transformation leaves at least one plane (here habit-plane between
the parent and martensite phase) undistorted and unrotated. F can
be decomposed according to the polar decomposition theorem into
F ¼ RU, where R is the skew-symmetric rotation matrix and U the
symmetric Bain strain tensor, for which Wechsler et al. [38] intro-
duced the term “pure part of the deformation”. It has been shown,
e.g. see Wechsler et al. [38], equations (17) till (21) therein, Simha
[41], Bhattacharya [42,43], and James and co-workers [44], that a
necessary and sufficient condition for such a plane to exist is that
the middle eigenvalue of U l2 ¼ 1, while the maximum eigenvalue
l1  1 and the minimum eigenvalue l3  1. In this case U becomes
diagonal in a Cartesian coordinate system following the convention
according to Pitsch and Schrader [45]:
.pffiffiffi
2 3 2c 2ab 0 0 3
a
h1 0 0 pffiffiffi .pffiffiffi
6 7
U ¼4 0
0
h2 0 5¼ 4 0 3aa 2ab 0 5
.
0 0 h3
0 0 aa ab
(1)
where ab, aa and ca are the lattice parameters of the b- and the a-
phase, respectively.
The reader is also referred to the work of S.C. Wang [9] who
applied the same concept for pure Ti. After the transformation it is
found that the Burgers relation can be transferred to the Pitsch-
Schrader relation by applying a rotation of the hexagonal lattice
around the c-axis (Fig. 1c) by an angle of ±5.26 , see Ref. [10]. Note
that due to two possible rotations for each Ui (i ¼ 1 … 6) 12 possible
deformation gradients Fj (j ¼ 1 … 12) are obtained in one and the
same cubic basis.
4. Results and discussion
4.1. Experiment
The microstructural features of the investigated
Tie44Ale3Moe0.1B alloy in the as-HIPed and b-homogenized
condition were characterized by SEM in the BSE mode. Fig. 2a
 S. Mayer et al. / Acta Materialia 115 (2016) 242e249 245

Fig. 1. Crystallographic relation between the bcc parent and hcp product phase. a) Pitsch-Schrader [45] coordinate system with a centered atom position as origin in the parent
phase. b) The grey (101)b plane from a) becomes the basal plane of the hexagonal product phase. Note that for the Bain strain the atoms in the middle plane of the hexagonal phase
do not play any role and are therefore not shown. c) Illustration of the rotation related to the closely packed lines in the parent and product phase.

displays the SEM image after casting and HIP, where lamellar
(a2þg)-colonies as well as globular g-grains are present. Within the
individual a2-lamellae small bo-precipitates are embedded. How-
ever, the majority of the bo-phase is located along the colony
boundaries. From the established phase diagram in Ref. [46] and
the prevailing microstructure, the phase transformation sequence
as mentioned in the introduction can be confirmed. Since this
sample state is not in full thermodynamic equilibrium, a homoge-
nization annealing in the single b-phase field region, followed by
water quenching was applied. As the b-transus temperature Tb
depends on the alloy composition, the determination was con-
ducted by differential scanning calorimetry yielding a Tb of
~1410  C, referring to [47]. Fig. 2b shows the SEM image of the
microstructure after the b-homogenization and subsequent water
quenching. At the first glance the microstructure consists of coarse
precipitated a2-plates (dark contrast) along prior b-grain bound-
aries, at grain boundary allotriomorphs and situated within the bo-
matrix. This diffusion-controlled b/a transformation occurred
through air cooling in the course of transferring the sample from
the high-temperature furnace to the water bath. The relatively slow
cooling of the sample caused the transition from the single b-to the
(aþb)-phase field region, due to the high Tb, before the quenching
process sets in, providing the conditions for a diffusionless trans-
formation process. However, the a-precipitates formed by
diffusion-assisted processes are far from thermodynamic
equilibrium.
A closer examination of the retained bo-matrix (light contrast)
shows a fine acicular substructure (Fig. 2c) whose formation has
not been completely elucidated in the literature in case of Mo-
containing g-TiAl based alloys. However, in Tie44Ale7Nb [48],
Tie44Ale5Nbe2Mn [48], Tie44Ale4Nbe4Hfe0.1Si [21] and
Tie44Al-8X-(0e0.2)Si-(0e1)B (X ¼ Nb, Zr, Ta, Hf) [1] alloys, acicular
a2-laths arise at high cooling rates due to the decomposition of the
b-phase by secondary lath formation and/or a Widmansta€tten
transformation, i.e. by diffusional processes, where changes in
chemical composition between the parent and the product phase
appear. In our case, however, EDS analyses reveal that both phases,
present at room temperature in Fig. 2c, have the same chemical
composition. This is also backed up by TEM-EDS and is an indica-
tion of a purely displacive transformation in this area of the
microstructure, where diffusion-controlled nucleation and growth
processes of the g- and a2-phase are suppressed and the b-phase,
which is ordered at room temperature, cannot be fully retained by
water quenching.
Based on the corresponding literature on diffusionless phase
transformations in g-TiAl based alloys, an increasing amount of b-
stabilizing elements and/or a decreasing Al-content promotes the
martensitic transformation towards the massive transformation
because of shifting and simultaneously narrowing the a-phase field
region to lower temperatures, so that the involving short-range
diffusion across the parent/product interface is hampered [20]. In
spite of the high Al-content of the selected Tie44Ale3Moe0.1B
alloy, but due to the strong b-stabilizing effect of Mo [49], no single
a-phase field region is present and moreover, according to Fig. 3, no
irregular interfaces with the parent b-phase appear [13,20,21,50],
providing a first experimental evidence of the martensitic b / a20
transformation during rapid continuous cooling. In addition, the
TEM image in Fig. 3 illustrates that no twinning occurs after

Fig. 2. SEM images taken in BSE mode of the investigated TiAleMo alloy in the a) as-HIPed and b), c) b-homogenized and water quenched condition; c) is taken from the area
marked with a square in b).
246 S. Mayer et al. / Acta Materialia 115 (2016) 242e249
Fig. 3. Bright field TEM image of the b-homogenized and water quenched condition
showing different variants of a20 -martensite embedded in the bo-matrix (see Fig. 2c).
Note that no signs of mechanical twinning within the a20 -variants can be detected.
generation of single martensite a20 -variants, offering decisive in-
formation for the theoretical approach to elucidate the trans-
formation mechanism (as described in section 3).
For characterizing the prevailing phases by determining their
crystalline structure and phase fractions as well as their lattice
parameters near the transformation temperature, in-situ HEXRD
experiments were carried out. First, in the b-homogenized and
water quenched condition, besides the bcc bo-phase, strong
diffraction peaks of the hcp a2-phase were detected at room tem-
perature, which imply, along with the microstructural morphology
shown in Fig. 2, the occurrence of acicular a20 -martensite next to
the precipitated coarse a2-plates. Due to the same ordered hcp
crystalline structure of the two hexagonal phases at room tem-
perature, it is not possible to determine their individual fractions by
means of Rietveld analysis, resulting in 87 vol% a2/a20 and 13 vol%
bo. In a second step, the lattice parameters aa20 and ca20 of the
martensite as well as ab of the high-temperature b-phase were
established in-situ in the course of the martensitic transformation
during quenching from the single b-phase field region at 1450  C,
which leads to aa20 ¼ 0.290 nm, ca20 ¼ 0.466 nm and ab ¼ 0.323 nm.
Such an accurate determination of the high-temperature lattice
parameters is essential for the crystallographic calculations.
Finally, from the experimental point of view, EBSD analyses
were performed on the fine needle-like microstructure of the
martensite (Fig. 2c) to determine the orientation relationship be-
tween the parent b- and the product a20 -phase. Fig. 4a and b shows
the pole figure of (0001)a20 and {110}bo planes respectively,
Fig. 4. Pole figures from EBSD analyses of a) the a20 - and b) bo-orientation; c) calculated pole figure of (110) plane vectors verifying the applicability of the underlying Burgers
orientation relationship, where six orientation variants of the hexagonal a20 -lattice can be developed within one parent b-crystal as verified experimentally by EBSD conducted on
the Tie44Ale3Moe0.1B alloy after b-homogenization and water quenching (see microstructure in Fig. 2c).
recorded in the area of one initial parent grain, showing all six
possible a20 -variants, formed within the analyzed b-grain at high
temperature. The underlying Burgers orientation relationship has
also been verified by analytically reproducing the recorded pole
figures. To this end the calculated Bain strain tensors Ui (see section
3) were rotated into the specimen coordinate system and displayed
in the usual stereographic projection of a pole figure, as shown in
Fig. 4c. As can be seen in Fig. 4 the a20 - and bo-orientation coincides
exactly with the theoretical assumption of the crystal lattices,
proving that the (0001)a20 pole of each a20 -variant corresponds to a
{110}bo pole of the matrix.
4.2. Theory
The lattice parameters measured by means of HEXRD near the
transformation
pffiffiffi temperature yield intermediate middle eigenvalue
l2 of ca20 = 2ab ¼ 1:020 for Ui and hence do not quite fulfill the
condition for a habit-plane (see section 3). As a remedy the Ui must
be corrected by an additional distortion, which does not affect the
lattice structure (lattice invariance) [38]. Twinning would be such a
mechanism, however it has not been observed experimentally (see
section 4.1). Also note that the small volumetric change observed
during transformation in the dilatometer experiments is already
contained in the Ui. Alternatively, a small amount of plastic defor-
mation due to an additional simple shear represented by a tensor Sk
can be superimposed, where the index k indicates the slip system
enabling the simple shear. Consequently the total deformation
gradient becomes Fik ¼ SkUiR. The assumption of an additional
plastic deformation is reasonable considering that the structural
transformation takes place at high temperatures. Note that this
additional shear will not exhibit in the pole-figure since it leaves
the lattice invariant. It should be mentioned that also Khachaturyan
[51] and co-workers supported most recently the argument that a
shear strain, superimposed to the Bain strain, allows an energeti-
cally favorable arrangement of martensite variants. If the volume is
sheared by the vector l on a plane whose normal is given by the
(reciprocal lattice) vector m and if it is assumed that the slip activity
is equivalently spaced, i.e. slip occurs on every dth plane, then the
slip deformation is:
1
S0 ¼ I þ l5m (2)
d
In a coordinate system defined by l, m and l  m, the defor-
mation gradient representing the shear S′ takes the simple form:
 S. Mayer et al. / Acta Materialia 115 (2016) 242e249 247

2 3 there exist two solutions for a habit-plane [44,53,54] leading to a

1 g 0 total number of 24 habit-planes with minimum shear g. The
S ¼ 40
0
1 05
0 0 1 listed in Appendix I.
where g ¼ 1/d is the shear-magnitude, i.e. the length of the vector l.
In a next step the following slip systems (given by their glide plane
normal vector and corresponding in-plane slip direction vector) are
investigated:
Slip plane families: {{100}, {110}, {112}, {102}, {311}}
Shear direction families: {<100>, <110, <111>, <113>}
Both family types have been selected corresponding to Otte [52]
and Srivastava [27] and it has been calculated that the slip planes
and their corresponding slip directions can form 126 physically
distinct slip systems. Otte [52] pointed out that an accurate deter-
mination of lattice parameters present at elevated temperatures is
imperative for the crystallographic calculations, because they are
quite sensitive to small deviations of the input data. The amount of
g is determined from the characteristic equation:
detðSk Ui  lIÞ ¼ 0
by requiring l2 ¼ 1. Equation (4) has been evaluated for all Sk (k ¼ 1
… 126) representing the physically distinct slip systems and each
out of all martensite variants Ui (i ¼ 1 … 6) yielding 126 solutions
for g. It is reasonable to assume that in accordance with energetic
arguments nature will select the smallest possible value out of
those 126 admissible solutions. Following this notion two equal
minima for jgj are found in two specific <111> {112} slip systems for
each martensite variant. E.g., for the martensite variant U1, repre-
sented in the cubic basis by
2 3
b 0 g
U1 ¼ 4 0 a 0 5
g 0 b
(3) calculated habit-plane normal c m and shape strain vectors b are
As mentioned above the smallest possible shear has been found
for the two specific <111> {112}b shear systems for each martensite
variant. Its magnitude is jgj ¼ 0:0354, see Table 1. Evidently, only a
tiny shear correction is necessary to achieve l2 ¼ 1 which agrees
with the observation that the Burgers orientation relation renders
the bcc (112)b plane nearly parallel to the hcp ð1100Þa plane [10].
The second lowest value of the required shear magnitude of
jgj ¼ 0:0409 is about 15% higher than the found absolute minimum
and has been calculated for a <111> {110}b slip system; see also Otte
[52]. Even though other shear systems might actually appear at
high temperatures, it is reasonable to assume that the shear system
yielding the lowest shear amplitude is the most favorable one and
will thus be realized in nature.
Note that only a comparison of experimental and calculated
orientation relationships is not enough to reflect the displacive
nature of the martensitic transformation product leading to its
(4) characteristic plate morphology, since the pole figures depend only
on the crystallography, not on the morphology. This means, if the
martensite formed e.g. as spheres, the pole figures would look
exactly the same. Therefore, in this study we compare the calcu-
lated habit-planes with the experimentally recorded EBSD image.
In order to enable a direct comparison, the traces of the habit-
planes have been calculated by intersecting them with the
“micrograph plane” of the specimen and are illustrated in Fig. 5.
The calculated habit-planes and the orientation of the
martensite variants in the EBSD image are compared assuming that
the invariant plane is parallel to the longitudinal direction of the
martensite plate. This comparison shows a very good agreement.
(5)

where b ¼ 1.0598, a ¼ 0.8978 and g ¼ 0.0398, calculated with the

lattice parameters determined by HEXRD on the investigated
Tie44Ale3Moe0.1B alloy (see section 4.1), the minimum magni-
tude for the required shear g occurs h in i the systems
m11 ¼ 121 ; l11 ¼ ½111 and m21 ¼ ð121Þ; l21 ¼ 111 . Note again,
that without the additional shear an invariant plane is strictly not
possible. In Table 1 all determined shear systems where the
required shear magnitude is a minimum are listed for all Ui. Since
two shear systems have been found for each Ui causing the calcu-
lated minimum shear there are 12 modified Bain strains ½Sj Ui j with
j ¼ 1,2. Now the modified Bain strains are used for the calculation of
the invariant habit-planes. The compatibility condition between
the parent phase and a single variant of product phase reads:

Ri ½Sj Ui j  I ¼ b5 c
m (6)

with the unknowns Ri, b and c m . Equation (6) is also known as
habit-plane equation because c m is the normal to the habit-plane; b
is the so called shape strain vector, giving the magnitude and the
direction of the transformation [53]. b and cm are obtained using a
result reported by Ball and James [54] as well as Hane and Shield
[53], equations (22) and (23) therein. Note that for every ½Sj Ui j
Fig. 5. Illustration of all calculated habit-plane traces plotted in the plane of the EBSD
image. The martensite a20 -variants in the EBSD as well as the habit-planes are colored
according to their related pole figure spots in Fig. 4a. For each of the three major
martensite variants in the EBSD, i.e. U2 (red), U1 (bright blue) and U5 (yellow), for
details see Table 1, the orientation of the martensite plate agrees very well with one of
the four calculated habit-planes for the according variant (drawn as bold line). The
resolution of the other martensite variants is insufficient for a clear definition of a
longitudinal direction of the martensite plate. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this article.)

Table 1
Shear systems requiring the minimum shear in order to fulfill the condition for an invariant plane for each martensite variant Ui.

U1 U2 U3 U4 U5 U6

l [111] ½111 ½11 1 ½111 ½111 ½111 [111] ½111 ½111 [111] ½111 ½111
m ð121Þ (121) ð112Þ ð112Þ ð121Þ ð1 21Þ ð112Þ (112) (211) ð211Þ ð211Þ ð211Þ
248 S. Mayer et al. / Acta Materialia 115 (2016) 242e249

Note that only four habit-plane traces appear for each martensite and Bernhard Sartory for professional EBSD operation. Financial
variant. Considering the calculated magnitude of necessary shear support by the Austrian Federal Government (in particular from
for the invariant interface and keeping in mind that the slip must Bundesministerium für Verkehr, Innovation und Technologie and
have a rational burgers vector to be lattice invariant the interface Bundesministerium für Wissenschaft, Forschung und Wirtschaft)
will be indented at every d ¼ 0; 03541 y28th plane, see Equation €
represented by Osterreichische Forschungsfo€rderungsgesellschaft
(2) (the presentation of experimental evidence and proof will be mbH and the Styrian and the Tyrolean Provincial Government,
given in a forthcoming publication). € rderungsgesellschaft mbH
represented by Steirische Wirtschaftsfo
and Standortagentur Tirol, within the framework of the COMET
5. Summary Funding Programme, Project A1.14, is gratefully acknowledged. The
research activities have also received funding from the German
While the b / a0 martensitic transformation is explored in BMBF project O3X3530A and the European Community’s 7th
many Ti alloys, their principles have been intensively studied and Framework Programme (FP7/2007-2013) under Grant Agreement
implications are reasonably well described, there are only scarce No. 226716.
activities in the field of light-weight g-TiAl based alloys. In order to
understand the evolution of the micro- and nanostructure and
further their impact on mechanical properties detailed experi- Appendix A
mental investigations, such as heat treatments, scanning electron
Habit-plane normal c
m and shear direction b, where
microscopy, electron backscatter diffraction analysis, transmission
electron microscopy and in-situ high-energy X-ray diffraction ex- z ¼ 0.607630740008901, h ¼ 0.365292192793851 and
periments combined with the crystallographic phenomenological x ¼ 0.705227975678855 as well as ο ¼ 0.0768840122456506,
theory of martensitic transformation were carried out. It follows c ¼ 0.117114210512645 and j ¼ 0.117128144090466.
that for extremely fast cooling in the course of the b-homogeni-
zation treatment diffusion is inhibited. Consequently, precipitation    
c
m e U1: ð z h x Þ, h z x , ðh z x Þ, z h x
and growth of the g- and a2-phase is suppressed, and instead an      
c
m e U2: z x h , h x z , ðz x h Þ, h x z
acicular martensitic hexagonal a20 -phase appears within the bo-    
c
m e U3: h x z , ðz x h Þ, ð h x z Þ, z x h
matrix. Being a a20 -martensitic variant, however, implies that both      
c
m e U4: h z x , z h x , ðz h x Þ, h z x
phases a20 and bo have the same chemical composition and are        
c
m e U5: x h z , x z h , x z h , x h z
related by the Burgers orientation relationship. This has been      
c
m e U6: x h z , x z h , ðx z h Þ, x h z
experimentally proved in the Tie44Ale3Moe0.1B alloy during
water quenching from the single b-phase field region. Using
transmission electron microscopy, it has been verified that single
martensite variants directly form an invariant interface plane with    
the initial b-lattice, which is only rarely reported in the literature b e U1: ½ ο c j , j c ο , ½ ο c j , j c ο
       
contrary to a twinned martensite. Also the phenomenological be U2: ο j c , j ο c , j ο c , ο j c
       
be U3: j c ο , ο c j , j c ο , ο c j
theory of martensite crystallography clearly suggests the event of a    
be U4: j ο c , ½ ο j c , ½ ο j c , j ο c
martensitic formation, with a simple shear superimposed to the    
be U5: c j ο , ½ c ο j , ½ c ο j , c j ο
Bain strain. Several shear systems were investigated and the lowest
be U6: ½ c j ο , ½ c ο j , ½ c ο j , ½ c j ο 
shear magnitude was calculated on two specific <111> {112} shear
systems for each martensite variant. From the modified deforma-
tion gradients all possible habit-planes for all 6 martensite variants
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