Progress in Aerospace Sciences 55 (2012) 1–16

Contents lists available at SciVerse ScienceDirect

Progress in Aerospace Sciences

journal homepage: www.elsevier.com/locate/paerosci

Advances in gamma titanium aluminides and their

manufacturing techniques
Kunal Kothari 1, Ramachandran Radhakrishnan 2, Norman M. Wereley n
Composites Research Laboratory, Department of Aerospace Engineering, University of Maryland, College Park, MD 20742, USA

a r t i c l e i n f o abstract

Available online 20 July 2012 Gamma titanium aluminides display attractive properties for high temperature applications. For over a
Keywords: decade in the 1990s, the attractive properties of titanium aluminides were outweighed by difficulties
Titanium aluminide encountered in processing and machining at room temperature. But advances in manufacturing
Intermetallics technologies, deeper understanding of titanium aluminides microstructure, deformation mechanisms,
Manufacturing techniques and advances in micro-alloying, has led to the production of gamma titanium aluminide sheets. An
Deformation mechanisms in-depth review of key advances in gamma titanium aluminides is presented, including microstructure,
Microstructure evolution deformation mechanisms, and alloy development. Traditional manufacturing techniques such as
Alloy development ingot metallurgy and investment casting are reviewed and advances via powder metallurgy based
manufacturing techniques are discussed. Finally, manufacturing challenges facing gamma titanium
aluminides, as well as avenues to overcome them, are discussed.
& 2012 Elsevier Ltd. All rights reserved.

Contents

1. Titanium aluminides: An overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

1.1. What are intermetallics? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2. Importance of titanium aluminides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.3. Challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.4. Titanium aluminides v. superalloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.5. Phases of titanium aluminides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.6. Alloy composition and microstructure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2. Factors affecting mechanical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.1. Ductility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.2. Creep resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.3. Fatigue life . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.4. Fracture toughness. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.5. Tensile strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.6. General remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3. Microstructural evolution and phase transformations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.1. Near gamma microstructure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.2. Duplex microstructure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.3. Nearly-lamellar microstructure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.4. Fully lamellar microstructure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4. Crystal structure and deformation mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.1. Crystal structure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.2. Deformation mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.3. Polysynthetically twinned (PST) crystals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.4. Effect of lamellar structure on deformation modes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

n
Corresponding author. Tel.: þ1 301 910 2272; fax: þ1 301 314 9001.
E-mail address: Wereley@umd.edu (N.M. Wereley).
1
Graduate Research Assistant.
2
Visiting Assistant Scientist.

0376-0421/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.paerosci.2012.04.001
2 K. Kothari et al. / Progress in Aerospace Sciences 55 (2012) 1–16

4.5. Effect of a2-Ti3Al on deformation modes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

4.6. Anomalous yield strength behavior. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.7. General remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5. Alloy development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5.1. Effect of Nb. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5.2. State of the art TiAl alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
6. Manufacturing techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
6.1. Ingot metallurgy and casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
6.2. Powder metallurgy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
6.3. State-of-the-art in TiAl sheet manufacturing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
6.4. Manufacturing challenges and opportunities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
7. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

1. Titanium aluminides: An overview Gamma titanium aluminides have also been slated for use in
General Electric’s GEnex gas turbine engine designed for the
Titanium aluminides have attracted significant attention in the Boeing’s 787 Dreamliner [17]. Titanium aluminides are being
last 20 years for their attractive properties that have the potential used in low pressure turbine (LPT) blades. In addition, titanium
to enable high temperature automobile and aerospace applica- aluminides were also investigated for use in High Speed Civil
tions [1–7]. A foremost application under consideration for Transport (HSCT) aircraft [8]. High speed civil transport aircraft
titanium aluminides is high performance gas turbine engines [8]. were designed to fly at Mach 2.4, while they take-off and land at
Due to its low density and high strength, titanium aluminides conventional airports and meet environmental protection agen-
have become front-runners in replacing nickel-based superalloys cy’s environmental goals of reduced exhaust and noise pollutions
in gas turbine engines. Replacement of Ni-based superalloy parts [18]. To meet these stringent requirements, a titanium aluminide
with titanium aluminides is expected to reduce the structural based divergent flap was proposed for noise attenuation and
weight of high performance gas turbine engines by 20–30% [9]. exhaust reduction Figs. 2–4.
Hence, a significant increase in engine performance and fuel
efficiency may be realized by utilizing titanium aluminides in
gas turbine engines. Titanium aluminides fall in the class of 1.3. Challenges
materials known as intermetallics.
Titanium aluminides have found limited, but very challenging
commercial applications in the automobile and aerospace indus-
1.1. What are intermetallics? try. A broader requirement for titanium aluminides is to match
Ni-based superalloys in performance as well as cost. The density
Intermetallics are compounds formed from two metals. Their of titanium aluminides is half that of superalloys, and, hence,
crystal structure and properties are completely different from replacement of Ni-based superalloys with titanium aluminides is
their parent metals [10]. Usually after the formation of an expected to produce leaner and efficient structural systems. To
intermetallic alloy, a long range ordering is developed in the date, titanium aluminides lag behind Ni-based superalloys in
material. This long range ordering places restriction on the mechanical performance and significantly in production costs.
deformation modes. These restrictions usually are manifested as This is mainly due to its low room temperature ductility and so
increased strength (at least at elevated temperatures), reduced that its development has been further held back by a lack of
ductility and fracture toughness [11]. Apart from titanium alu- engineering design practices for low ductility materials. Even so,
minides, examples of other intermetallics include NiAl, and FeAl. there have been significant advances made by the NASA Glenn
Research Center, Plansee (Austria), and GKSS Research Center
(Germany) in developing manufacturing techniques to produce
1.2. Importance of titanium aluminides
titanium aluminide sheets. As a result, the cost of titanium
Titanium aluminides display attractive properties such as low
density, high strength, high stiffness and good corrosion, creep,
and oxidation resistance. As discussed earlier, due to the long
range order of intermetallics, titanium aluminides lack room
temperature ductility and fracture toughness. Fatigue crack
growth rates are also an area of concern [12,13]. In the past, the
attractive properties of titanium aluminides were outweighed by
their difficulties in processing and machining at room tempera-
ture. However, advances in manufacturing technologies, deeper
understanding of titanium aluminide’s microstructure, deforma-
tion mechanisms, and advances in micro-alloying, has led to the
first commercial use of titanium aluminides in high performance
turbochargers for Formula One and sports cars [14]. Exhaust
valves made of titanium aluminides have been used to replace
the existing Ti-6242, Ti-1100, and IMI 834 alloys. Turbocharger
wheels made out of titanium aluminides have been prototyped
and tested to replace Ni-based superalloys. Till date, there are
about thousand titanium aluminide turbocharger wheels and
exhaust valves in service [15,16] Fig. 1. Fig. 1. TiAl turbocharger wheels made by Howmet Corporation [15].
 K. Kothari et al. / Progress in Aerospace Sciences 55 (2012) 1–16
Fig. 2. Photos of LPT hardware scheduled for production, Ti–48%Al–2%Cr–2%Nb
(at%): (a) LPT blade casting (b) portion of disk and some blades ready for assembly
[10].
Fig. 3. Structural materials developed with temperature and speed for aircraft as a
function of the expected performances [3].
aluminide sheets is expected to fall to as low as $150/lb,
contingent on its wide acceptance in several commercial applica-
tions [19]. Table 1 provides a list of potential applications for
titanium aluminides in the aerospace industry.
1.4. Titanium aluminides v. superalloys
As mentioned earlier, the density of titanium aluminides is
half that of Ni-based superalloys. Titanium aluminides also dis-
play good high temperature oxidation and creep resistance, as
well as excellent high temperature strength and modulus reten-
tion. But, titanium aluminides lack room temperature ductility
and fracture toughness. Table 2 compares the mechanical proper-
ties of titanium aluminides with Ni-based superalloys at room
temperature and high temperatures.
As shown in Table 2 [20,21], titanium aluminides are con-
siderably (65 times) more costly to fabricate than Ni-based
superalloys. Along with this, mechanical properties such as room
temperature ductility, and yield strength are less favorable than
Ni-based superalloys. Over the past 15 years, considerable
research has been done to refine the microstructure of titanium
aluminides, so that improvements in the ductility, as well as
3
Fig. 4. Proposed divergent flap prototype fabricated from cast TiAl (Ti–48Al–2Cr–
2Nb) [7].
strength, in titanium aluminides has been realized. Below is a
general overview of the phases of titanium aluminides.
1.5. Phases of titanium aluminides
Titanium aluminides have been found to exist in three differ-
ent phases, namely Ti3Al (a2), TiAl (g), and TiAl3. Of these phases,
only the Ti3Al (a2), and TiAl (g) phases have been found to be of
any engineering significance. The phase diagrams in Figs. 5 and 6
show the aforementioned phases. As shown, the Ti3Al (a2) phase
has aluminum content between 22% and 39% (at%),3 while the
TiAl (g) phase contains 48.5% to 66% (at%) aluminum. A dual
phase of titanium aluminides with a mixture of a2 and g phase
exists between 37% and 49% aluminum content [22].
The a2 phase has been found to exhibit good high temperature
strength, but has very low ductility. Along with this, it also has a
high rate of Oxygen and Hydrogen absorption, which in turn leads
to further embrittlement at high temperatures [23,24]. On the
other hand, the g phase exhibits excellent oxidation resistance
and has very low hydrogen absorption, but its room temperature
ductility is close to none. Research has been conducted in refining
the microstructure of these phases as well as their micro-alloying
[25]. But none of the problems associated with these phases have
been completely solved. Hence, these two phases by themselves
do not have much of engineering significance. But a mixture of
these two phases which exists between 40 wt% and 48 wt% of
aluminum has been found to be very viable for several structural
applications [26,27].
3
All the elemental concentrations mentioned henceforth will be in at%, unless
specified otherwise.
4 K. Kothari et al. / Progress in Aerospace Sciences 55 (2012) 1–16

Table 1
Potential applications for titanium aluminides [18].

Vehicle Component Number of vehicles Projected usage

Global first strike/tomahawk missiles Hot structures, compressor, nozzle 2000 þ 30,000 lbs þ
Comanche helicopter Nozzles, IR suppression system 500þ 10,000 lbs þ
F-22, JSF Nozzles, exhaust structures, engine components 700þ 100,000 lbs þ
Military space plane Thermal Protection System (TPS), wingbox and vertical tail hot structures 2þ 5,000 lbsþ
Re-usable launch vehicles (RLVs) TPS, wingbox and vertical tail hot structures 2–8 20,000–80,000 lbs

Table 2
Comparison of titanium aluminides to superalloys [20,21].

Property TiAl-base alloys Superalloys

3
Density (gm/cm ) 3.7–3.9 8.3
Room temperature modulus (GPa) 160–176 206
Yield strength (MPa) 400–630 1000
Tensile strength (MPa) 450–700 1200
Ductility at room temperature (%) 1–3 15
Creep limit (1C) 1000 1090
Oxidation (1C) 900–1000 1090
Cost ($/lb) 1300a 20

a
Cost is for Gamma Met PX Titanium Aluminide Alloy fabricated by Plansee,
Austria.

Fig. 6. Central portion of the Ti–Al phase diagram [27].

fully lamellar microstructure have exhibited mechanical properties

Fig. 5. Ti–Al phase diagram [9].
This dual a2 þ g phase has been found to be very sensitive to its
microstructure, grain size, and small volumes of micro-alloying
constituents [28]. There have been several techniques, which
have been established to refine the microstructure along with
small micro-alloying additions by which the dual phase has
exhibited ductility as high as 6% [29]. Additionally, the dual phase
alloys have also exhibited room temperature and high tempera-
ture strengths equivalent to that of superalloys [30]. The creep
and oxidation resistance have also been shown to be acceptable
for temperatures up to 850 1C [3,31].
1.6. Alloy composition and microstructure
The dual phase of titanium aluminides has exhibited a wide
range of microstructures depending on the heat-treatment [32].
These microstructures have been broadly classified into four cate-
gories, namely (1) near-gamma, (2) duplex, (3) nearly-lamellar, and
(4) fully lamellar [28,33]. Of these microstructures, the duplex and
conducive for a range of commercial applications [34].
As shown in Fig. 6, the fully-lamellar microstructure is
obtained by heat-treatment at temperature (T1 in Fig. 6) in the
pure a phase field. Upon cooling to room temperature, the a-Ti
phase precipitates into alternate plates of a2 and g plates forming
a fully lamellar morphology. This microstructure is usually
characterized with coarse grains in the range of 200 mm to
1000 mm.
The duplex microstructure is obtained by heat-treatment in
the a þ g phase field at a temperature (T3 in Fig. 6) where the a/g
phase volume ratio is equal to 1. The duplex microstructure
consists of fine fully lamellar colonies along with equiaxed
gamma grains. The mixture of these two grain morphologies
forms a very fine microstructure with an average grain size in the
range of 10 mm.
The nearly-lamellar microstructure forms at an intermediate
temperature (T2 in Fig. 6) between that of fully lamellar and
duplex in the a þ g phase field, where the a/g phase volume ratio
is greater than 1. It is characterized by a majority of lamellar
colonies with some equiaxed gamma grains forming an average
grain size in the range of 150 mm to 200 mm.
Finally, the near-gamma microstructure is formed by heat-
treatment at much lower temperatures (T4 in Fig. 6) in the a2 þ g
phase field. This microstructure is characterized by equiaxed
gamma grains with a2 precipitates forming at the grain bound-
aries. The average grain size for this microstructure usually ranges
between 30 mm and 50 mm.
Due to its very fine grain size, the duplex microstructure
exhibits the best ductility and strength at room temperature,
but at higher temperatures creep and fatigue resistance is very
 K. Kothari et al. / Progress in Aerospace Sciences 55 (2012) 1–16 5

low. The fully lamellar microstructure on the other hand is
crippled with low ductility and strength due to its coarse grain
size, but has excellent creep and fatigue resistance properties.
Hence, over the past decades, the development of gamma tita-
nium aluminides have been geared towards development of
microstructures having the best features of duplex and fully
lamellar microstructure properties [35–37].
As shown in the phase diagram, at 450% Al, titanium
aluminides exist in the pure gamma phase. The microstructure
for this alloy composition is characterized by equiaxed gamma
grains exhibiting no ductility. Even after microstructural refine-
ment and small alloy additions this alloy composition shows very
little improvement in ductility. Therefore, this alloy composition
has been considered to be of no engineering significance [38].
The alloy composition with aluminum concentration o40%
results in the formation of a2 (Ti3Al) phase. This phase exhibits
better room temperature ductility than alloy composition with Al
concentration 450% (pure g phase). Yet the ductility is unaccep-
table from an engineering standpoint. The a2 (Ti3Al) phase, when
alloyed with high Nb content (410 wt%), is known to respond to
thermo-mechanical treatment to produce a range of microstructures
similar to the dual phase (a2 þ g) alloys. These microstructures as
shown in Fig. 8, are fully lamellar, bi-modal and equiaxed.
Similar to dual phase (a2 þ g) alloys, the range of microstructures
in a2 alloy exhibit a host of desirable properties. The bi-modal
microstructure exhibits good ductility, but the creep resistance over
600 1C is an issue. Fully lamellar microstructure exhibits excellent
creep properties, but its room temperature ductility is very low.

Fig. 7. Microstructure types in dual phase titanium aluminides (a) fully lamellar, (b) nearly lamellar, (c) duplex, and (d) near-gamma [37].

Fig. 8. Microstructures of a2 created by different thermo-mechanical treatments, (a) Bi-modal (b) equiaxed, and (c) lamellar [10].
6 K. Kothari et al. / Progress in Aerospace Sciences 55 (2012) 1–16
Fig. 9. Elongation and Vickers Hardness of Ti–Al binary alloys measured over a
range of Al concentrations (at%). The Vickers hardness is shown for as-cast,
thermo-mechanically processed, and annealed material at room temperature as
well as at 1000 1C [19].
By varying the Nb concentration in the a2 phase, the room
temperature ductility for a2 phase was increased to as high as
4–5%. The ternary a2 alloys, that have been researched widely
include Ti–24%Al–11%Nb and Ti–25%Al–10%Nb–3%V–1%Mo (at%).
Due to large additions of Nb, the density corrected strength for these
alloys and similar ternary alloys was equivalent to that of conven-
tional titanium alloys and Ni-based superalloys [21]. Hence, further
development of these alloys has not received much attention.
The alloy composition with Al concentration between 40% and
48.5% yield dual (a2 þ g) phase alloys. As discussed earlier, these
alloys exhibit a range of microstructural morphologies depending
on the thermo-mechanical processing. Several researchers have
shown that ductility of these dual phase alloys increases with the
increase in Al concentration up to 48% and then decreases with
increase in Al concentration beyond 50% [20,38,39]. As shown in
Fig. 9, Ti–48Al exhibits the maximum ductility in a Ti–Al inter-
metallic binary alloy. The specific ductility of the alloy further
depends on the microstructure type and grain size, which in turn
is governed by thermo-mechanical processing. Hence, the actual
ductility of the alloys is not listed in Fig. 9.
2. Factors affecting mechanical properties
2.1. Ductility
The duplex microstructure formed with fine lamellar colonies
and equiaxed gamma grains exhibit the best ductility in dual
phase alloys. The presence of the lamellar structure aids the
deformation mechanisms of the gamma phase [40]. The presence
of lamellar structure is usually characterized by a ratio of lamellar
grains to that of the gamma grains (L/g). In general, the ductility
in the dual phase alloys is dictated by four main factors, (1) grain
size, (2) L/g ratio, (3) changes in lattice dimensions, and (4) impur-
ity level [29,38]. As discussed earlier, decrease in grain size leads
to increase in ductility. This is due to the fact that as the grain
size decreases, the volume of defects such as grain boundaries
increase, which in turn aids in the deformation mechanisms. The
L/g ratio of 0.3 to 0.4 produces the maximum ductility in the dual
phase alloy. The L/g ratio is further dependent on the a2/g ratio.
The a2/g phase ratio of 3% to 15% exhibits maximum ductility.
Above this range the grain growth becomes pronounced, when
heat-treated in the a þ g phase field and below it the brittle a2
eliminates the beneficial effect of refined microstructure. All these
values are mainly governed by the Al concentration and are in the
optimum range, when the Al concentration is 48%. Therefore, Ti–
48Al alloy exhibits the best ductility.
The lattice dimension as controlled by the tetragonality ratio
(c/a) and unit cell volume has a significant impact on ductility.
The g phase crystallizes into the L10 type face centered cubic
structure and has a small tetragonality ratio. This ratio decreases
as the Al concentration is decreased. A decrease in the c/a ratio or
an increase in the symmetry of the crystal structure increases
ductility in the g phase. Also, decreasing the unit cell volume of
the lattice increases ductility. This can be achieved by adding
small ternary or quaternary alloying constituents. An in-depth
discussion of ternary and quaternary alloying additions is pre-
sented in a later section. Finally, by reducing of impurities such as
oxygen and nitrogen, the ductility has been observed to increase
significantly. For example, reduction of oxygen from 800 ppm to
370 ppm increased the ductility from 2% to 2.7%.
2.2. Creep resistance
The creep resistance in dual phase titanium aluminides is mainly
controlled by the microstructural morphology and aluminum con-
tent. An increase in Al content usually increases creep resistance.
Fully lamellar structures with coarse grain size show better creep
resistance over fine-grained duplex microstructures. The increased
creep resistance for a lamellar structure is attributed to the a2 laths
acting as reinforcements [38]. The creep-rupture strength is higher
for duplex microstructures at temperatures up to 650 1C, above
which the lamellar structure shows higher rupture strength. In
general, the fully lamellar microstructure has been found to be more
conducive to creep resistance. But the problem associated with fully
lamellar structure is its low room temperature ductility due to its
large coarse grains. Therefore, much research effort is directed
towards decreasing grain size of the fully-lamellar microstructure
[38,40].
2.3. Fatigue life
The factors affecting fatigue are similar to that for creep. The
duplex microstructure shows high fatigue crack growth rates,
while the crack growth in fully-lamellar microstructure is a slow
process [41,42]. Upto 800 1C, the fine-grained duplex microstruc-
ture increases fatigue life, but at higher temperatures, the fully-
lamellar microstructure exhibits longer fatigue life [11].
2.4. Fracture toughness
The fracture toughness for the fine-grained duplex microstruc-
ture is found to be in the range of 10 MPa m½ to 16 MPa m½.
These values are much higher for fully-lamellar microstructures
and are found to be as high as 30 MPa m½. It has been observed
that the duplex microstructure exhibits little plastic strain near
the onset of crack extension and no resistance to crack propaga-
tion, whereas the lamellar structure yields large plastic strains
near the crack tip and increased resistance to crack propagation
with crack length [39].
 K. Kothari et al. / Progress in Aerospace Sciences 55 (2012) 1–16
2.5. Tensile strength
The tensile strength of dual phase titanium aluminides is
inversely proportional to the grain size as expected from the
Hall–Petch relationship [43]. Due to the coarse grain size in fully
lamellar microstructures, the tensile strength is low compared to
that of fine grained duplex microstructure. The tensile strength
shows an anomalous behavior at high temperatures, where it
shows an increase in strength with increase in temperature up to
a certain point and then shows a decrease in strength with
increasing temperature. This behavior has been found to be
characteristic of intermetallics due to their long range ordering.
The increase in yield strength with temperature in TiAl can be
explained by the anomalous hardening caused due to cross-slip
of dislocations on to octahedral planes. This will be discussed
in detail in the section describing the deformation mechanisms
in TiAl.
2.6. General remarks
As discussed above, the mechanical properties of dual phase
titanium aluminides are very sensitive to microstructural mor-
phology. The duplex microstructure exhibits good room tempera-
ture ductility and strength, but for high temperature properties
such as creep and fatigue resistance, a fully lamellar microstruc-
ture is desirable. The low room temperature ductility and
strength of fully lamellar microstructure is due to its coarse
grains. By decreasing the grain size in fully lamellar structure,
the room temperature ductility and strength are expected to
increase. There have been several thermo-mechanical processing
routes suggested to obtain a fine grained fully lamellar structure.
To further understand the evolution of microstructures after
thermo-mechanical processing, the knowledge of phase transfor-
mations in the dual phase titanium aluminides is important. The
next section discusses various phase transformation mechanisms
in dual phase titanium aluminides.
3. Microstructural evolution and phase transformations
As discussed earlier, the microstructure of the dual phase
titanium aluminides can be broadly classified into four types,
(1) near-gamma, (2) duplex, (3) nearly lamellar, and (4) fully-
lamellar. In the following paragraphs, the evolution of these
microstructures is discussed.
3.1. Near gamma microstructure
The near-gamma microstructure is formed when the material
is heat-treated in the a2 þ g phase field. Heat-treatment in this
phase field results in the coarsening of the existing g grains. The
microstructure as shown in Fig. 7d, is characterized by coarse
gamma grain regions with fine gamma grain stringer regions with
dispersed alpha-2 particles.
3.2. Duplex microstructure
The duplex microstructure is produced by heat treatment in
the a þ g phase field. The temperature in the a þ g phase field is
such that the a/g volume ratio is close to 1. In this case, the heat-
treatment results in the dissociation of the existing a2 particles.
Additional a precipitates are nucleated to grow into a plates in
the {1 1 1} habit planes at the expense of gamma phase. The
initially predominant gamma phase is gradually reduced in
volume until the equilibrium volume fraction is reached and
grain growth occurs. The growth of gamma grains is limited by
7
the dispersed alpha phase, which also experiences growth. These
competitive processes result in the formation of a fine-grained
structure as shown in Fig. 7c.
3.3. Nearly-lamellar microstructure
At temperatures greater or lower than where the duplex
microstructure forms (i.e., where the a/g volume ratio is close
to 1), coarsening of the predominant phase occurs. Hence, heat-
treatment at temperatures below the duplex microstructure
temperature leads to coarsening of gamma grains and formation
of near-gamma microstructure, while heat-treatment above the
duplex microstructure temperature results in the coarsening of
alpha grains and formation of nearly-lamellar microstructure. The
nearly-lamellar microstructure is characterized by coarse lamellar
structure with fine gamma grains.
3.4. Fully lamellar microstructure
Finally, heat-treatment in the alpha phase field above the
alpha-transus line (Ta) results in the formation of large grained
fully lamellar microstructure. The lamellar structure forms in
three different ways and hence is classified into three different
types: type I, II, and II [28,29].
Type I lamellar structure is formed by heat-treatment above
the Ta line followed by air-cooling. It is formed via the following
reaction.
a-a þ gp -Lða=gÞ-Lða2 =gÞ
In this reaction, plate like gamma precipitates (gp) begin to
precipitate out of alpha matrix at the a/a þ g line and grow
radially to result in the high temperature lamellar structure,
L(a/g). This structure transforms at low temperatures to L(a2/g)
structure simply by a-a2 ordering reaction. This occurs below
the a/a þ a2 line.
Type II lamellar structure is observed in the duplex micro-
structure. In this structure, the alpha-2 plates contain anti-phase
boundaries (APB) which are continuous across the thin gamma
plates. For this type of lamellar structure, the nucleation of
gamma precipitates (gpt) and their growth into plates (gp) is
preceded by the a-a2 ordering reaction. The whole process can
be expressed as
a-a2 -a2 þ gpt -a2 þ gp -Lða2 =gÞ
Type III lamellar structure is formed when the heat-treatment
is done well below the duplex microstructure temperature. Here
the predominant phase is g with minor a2 particles (ap2 ). Upon
heating, the ap2 in the gamma matrix (gm) disorders to ap and
grow into alpha plates (ap) to yield a lamellar structure L(g/a),
which upon cooling transforms to lamellar structure L(g/a2) by
simple a-a2 reaction. The entire reaction can be expressed as
follows:
heating cooling
gm þ ap2 ! gm þ ap -Lðg=aÞ!Lðg=a2 Þ
4. Crystal structure and deformation mechanisms
A review of crystal structure and deformation mechanisms of
titanium aluminides gives a deeper insight into the effect of
microstructural morphology on its mechanical properties Fig. 10.
4.1. Crystal structure
The g-TiAl phase has (ordered face centered tetragonal) L10
type structure as shown in Fig. 11a. The tetragonality is due to
8 K. Kothari et al. / Progress in Aerospace Sciences 55 (2012) 1–16
different atomic radii of Ti and Al. For the stoichiometric com-
pound, the tetragonality ratio is 1.02. This tetragonality ratio
increases to 1.03, with increasing aluminum concentration and
decreases to 1.01 with decreasing aluminum concentration [20].
The a2-Ti3Al phase has a DO19 (hexagonal closed packed) type
structure as shown in Fig. 11b.
4.2. Deformation mechanisms
It has been established that the main deformation modes in
g-TiAl are slip and twinning, both operating on the close-packed
{1 1 1} planes [44]. Due to the face-centered cubic type structure of
the g-TiAl phase, slip occurs on the close-packed {1 1 1} planes. The
layered arrangement of atoms on the successive (0 0 2) planes and
the tetragonality ratio of 1.02 results in two types of dislocations
with ½/1 1 0S type Burgers vectors on {1 1 1} planes [45].
More specifically these are ordinary dislocations with Burgers
vector ½ o1 1 0], and superdislocations with Burgers vectors
Fig. 10. Dependence of mechanical properties such as fracture toughness,
strength, elongation, impact resistance (IR), creep resistance (CR), and grain size
on the microstructure type, where NG is near-gamma, NL is nearly lamellar and FL
is fully-lamellar [37].
Fig. 11. Crystal structure for, (a) g-TiAl, and (b) a2-Ti3Al.
o1 0 1] [46,47]. (For g-TiAl, the miller indices convention was
introduced by Hug et al., , where, in the notation oh k l] or {h k l]
only h and k are mutually permutable, while l is fixed and can be
positive or negative) [48]. In the single phase g-TiAl o1 0 1]
superdislocations dominate at low temperatures while at high
temperatures (above about 800 1C) slip by ½ o1 1 0] ordinary
dislocations, and also twinning, become controlling deformation
modes. In contrast, in the dual phase TiAl with lamellar structure,
twinning and glide of ½ o1 1 0] ordinary dislocations prevail at
low temperatures and glide of superdislocations becomes signifi-
cant only at high temperatures. The ½o1 1 2] type superdisloca-
tions have also been reported in TiAl [20]. Fig. 12 shows the
ordinary ½o0 1 1] dislocations as well as the o0 1 1] and
½o1 1 2] type superdislocations.
The L10 structure can be twinned by the {1 1 1}o1 1 2]
variants of the normal fcc twinning mode. As shown in Fig. 12,
the Burgers vector b3 ¼ 1=6½112 preserves the order of g-TiAl and
this twinning mode is therefore called true twinning. Partial
dislocations by Burgers vectors b1 ¼ 1=6½211 and b2 ¼ 1=6½121
change the order of g-TiAl and are called pseudo-twinning.
At room temperature, the o0 1 1] type superdislocations have
very limited mobility due to the covalent nature of Ti–Ti, and
Ti–Al bonds. Their mobility is further inhibited due to the
formation of extrinsically faulted dipoles. Segments of the trailing
superpartials, 1/6[112] type, form faulted dipoles, which must be
extended as deformation proceeds [49]. This explains the low
room temperature ductility in single phase g-TiAl, where o0 1 1]
superdislocations are the dominant deformation modes at room
temperature. o0 1 1] type superdislocations can be dissociated
into two ½ o0 1 1] dislocations separated by an antiphase
boundary (APB). The o0 1 1] type superdislocation can be further
dissociated by
h i 1h i 1h i 1h i
101 ¼ 112 þ 101 þ 211
6 2 6
Fig. 12. Potential slip and twinning systems in the g-TiAl {1 1 1} planes (Circles of
varying sizes indicate atoms on different parallel {1 1 1} planes) [44].
 K. Kothari et al. / Progress in Aerospace Sciences 55 (2012) 1–16
with superlattice intrinsic stacking fault (SISF) between 1=6½112
and 1=2½101 partials, and the complex stacking fault (CSF)
between 1=2½101 and 1=6½211 partials [50].
In dual phase TiAl, the presence of a2-Ti3Al as secondary phase
results in ½o1 1 0] ordinary dislocations and twinning to
become the dominant deformation modes. Twinning is mainly
caused by the presence of lamellar structure in dual phase TiAl
[51,52]. As discussed earlier, the lamellar structure is formed by
heat-treatment in the a or a þ g phase field. The formation of g
plates from a is described above. The nucleation from the a phase
proceeds from the stacking fault by the movement of 1/3
/1 0 1 0S Shockley partials [21,29]. The resulting lamellar struc-
ture has the crystallographic orientation relationships ½0 1 1g ==
½1 1 2 0a2 9ð1 1 1Þg ==ð0 0 0 1Þa2 between the alpha-2 plates
and gamma plates, with gamma plates being twin related. The
[101], and [110] directions are not equivalent to [0 1 1] direction
on {1 1 1} plane due to the tetragonality in the L10 structure of g
phase. Directions of /1 1 2 0Son the basal plane in the a phase
(hexagonal closed packed) and a2 phase (hexagonal D019) are all
equivalent as shown in Fig. 12. Hence, six interfaces arise from the
combination of the three possible directions of the c-axis of the g
phase and the ordered nature of the two phases [40].
The mechanical properties of the lamellar microstructures in
TiAl depend on the lamellar orientation with respect to the
loading axis and lamellar microstructure variables such as grain
size, thickness, and spacing of g and a2 lamellae and g domain
size. However, the lamellar orientation has far more influence
than lamellar microstructural variables. In order to fully under-
stand the effect of lamellar orientation on its properties, TiAl
crystals where the entire crystal consists of only a single lamellar
grain were produced and characterized. Since numerous thin twin
related lamellae are contained in the major constituent g phase,
these crystals are named polysynthetically twinned (PST) crystals
from analogy with the phenomenon ‘‘polysynthetic twinning’’,
observed in mineral crystals.
4.3. Polysynthetically twinned (PST) crystals
As mentioned above, the PST crystals have a single lamellar
grain. The mechanical properties of the PST crystals depend strongly
on the lamellar orientation relative to the loading axis. PST crystals
also display anisotropic macroscopic flow behavior. When the
orientation of the lamellae is perpendicular to that of the loading
axis, the PST crystal exhibits excellent strength and poor ductility. In
the parallel orientation of the lamellae with respect to the loading
axis, some ductility and strength was observed. The strength in this
case is not as high as the perpendicular orientation case. These
deformation modes in parallel and perpendicular directions are
referred to as hard modes.
At the intermediate orientations, such that the lamellae form
an angle of 301–601 with respect to the loading axis (soft mode),
the yield stress is much lower but the elongation is significantly
higher than the hard modes. The orientation dependence of the
yield stress and ductility of PST crystals is due to the fact that
shear occurs parallel to the lamellar boundaries when the
lamellar orientation is such that it forms an angle of 301–601
with the loading axis (deformation in soft mode) but it occurs
mostly on {1 1 1} planes intersecting the lamellar boundaries
when the lamellae is either parallel or perpendicular (hard mode)
to the loading axis.
4.4. Effect of lamellar structure on deformation modes
In dual phase TiAl with duplex and fully lamellar microstruc-
ture morphologies, the presence of a2-Ti3Al phase is usually in the
form of lamellar structure. In a lamellar structure, the orientation
9
of the lamellae with respect to loading axis plays a significant
role in the control of deformation mechanisms. As discussed
above, with more lamellae oriented in the soft mode, the ductility
increases. Hence, it is desirable to have maximum lamellae
oriented in the soft mode. In different grains lamellae will be
oriented at different angles relative to stress-axis, and when grain
size is large, it is likely that fewer grains are oriented favorably for
slip. Hence, fully lamellar structures with coarse grains suffer
from low ductility.
On the other hand, duplex microstructure with fine grains
exhibit good ductility. Due to the presence of more grains per unit
volume, the probability of grains with lamellae oriented in the
soft mode will increase. As a result, the ductility in duplex
microstructure is higher than that in fully lamellar microstruc-
ture. A decrease in grain size has been correlated to increase in
ductility by several researchers [39]. The duplex microstructure
does not perform well in terms of creep and fatigue resistance at
high temperatures compared to that of fully lamellar microstruc-
ture. Hence, it has been suggested by several researchers that
refining the grain size in fully lamellar microstructures could
potentially solve the problem of low ductility.
As discussed earlier, fully lamellar microstructures are formed
by heat-treatment in the a phase field. The diffusion process in
the a phase field is very rapid due to thermal activation and the
absence of second phase barriers. Therefore the grain growth is
also rapid. In order to circumvent this, several thermo-mechanical
treatments along with small alloy additions have been proposed.
These will be discussed in the next sections.
4.5. Effect of a2-Ti3Al on deformation modes
As mentioned earlier, in single phase g-TiAl the deformation
modes are dominated by o1 0 1] type dislocations. Ordinary
dislocations of ½o1 1 0], and twinning are hardly observed. But
in two phase (a2 þ g) TiAl, where the dominant phase is g-TiAl,
the deformation modes are dominated by ordinary dislocations
½o1 1 0] and twinning. This phenomenon has been explained in
terms of a2-Ti3Al acting as a gettering agent to improve the purity
of g-TiAl phase [49].
In other independent studies it has been concluded that by
reducing interstitials and impurities in nominally pure g-TiAl
phase, the directionality of the bonds between the Ti atoms
reduces. This in turn leads to increased mobility of dislocations
with ½o1 1 0], and 1/6o 1 1 2] Burgers vectors. The 1/6o1 1 2]
Burgers vectors are order twinning defects. It has been proposed
that in dual phase (a2 þ g) TiAl, where the dominant phase is
g-TiAl, the a2-Ti3Al laths getter the interstitial impurities from
their adjacent g-TiAl laths. Hence, an increase in the mobility of
dislocations with ½o1 1 0], and 1/6o1 1 2] Burgers vectors is
observed in dual phase (a2 þ g) TiAl. The solubility of interstitial
impurities in a2-Ti3Al is greater than that in g-TiAl.
4.6. Anomalous yield strength behavior
In single phase g-TiAl, anomalous increase in flow stress is
observed with increase in temperature up to a certain point. This
increase in strength usually begins to occur around 200 1C
and peaks between 600 1C and 700 1C depending on the alloy
composition. As discussed earlier, in single phase g-TiAl room
temperature deformation is controlled by o0 1 1] superdisloca-
tions, which have limited mobility. As the temperature increases,
ordinary dislocations ½ o1 1 0] and twinning become active and
are relatively mobile, but the o0 1 1] dislocations become
increasingly blocked as they adopt a thermally activated non-
planar configuration and thereby give rise to the flow anomaly
[53]. These o0 1 1] superdislocations dissociate into a primary
10 K. Kothari et al. / Progress in Aerospace Sciences 55 (2012) 1–16
plane with stacking faults and APBs as discussed earlier. With the
increase in temperature, segments of the o0 1 1] cross-slip onto
the adjoining octahedral planes [54]. Since these cross-slipped
superdislocations are highly immobile, an increase in flow stress
with increase in temperature occurs. But as temperature
increases further, the o0 1 1] superdislocations dissociate into
unit ½o1 1 0] and ½o1 1 2] superdislocations, which are suffi-
ciently mobile such that the strength decreases following the flow
stress peak.
In the dual phase TiAl, similar behavior is observed except that
the temperature range of anomalous yield strength behavior is a
bit contracted and flow stress peaks appear at a bit lower
temperatures. The deformation mechanism in dual phase TiAl
responsible for such behavior is the interaction of ½ o1 1 0]
screw dislocations on adjoining {1 1 1} planes. These interactions
become frequent at higher temperatures and as a result an
increase in strain is followed by formation of jogs, dislocation
dipoles and debris defects [55]. The ½o1 1 0] dislocations are
pinned by these defects and the number of pinned dislocations
increases with the temperature. At higher temperatures due to
thermal activation, the jog-dislocation climbing occurs, which
results in decreased strength with temperature [56].
4.7. General remarks
The deformation mechanisms in TiAl have been investigated
over years and have been helpful in explaining the effect of
microstructural morphology especially that of lamellar structure
on the mechanical properties of TiAl. From the above discussions,
several conclusions can be made regarding approaches to enhance
mechanical properties in TiAl.
i. The brittle nature of single phase g-TiAl is due to dominant
nature of the o1 0 1] type dislocations, which are primarily
sessile due to extrinsically faulted dipoles.
ii. The glissile slip systems of twinning and ordinary dislocations,
1/6 o1 1 2] and ½ o1 1 0], respectively become active due to
the presence of a2-Ti3Al. The secondary a2-Ti3Al phase acts as
a gettering agent to improve the purity of g-TiAl phase and
hence enables slip via ordinary dislocations and twinning
dominant.
iii. The deformation modes in lamellar structures are dependent
on its orientation (soft mode or hard mode) with respect to
the loading axis. Fully lamellar microstructures with good
room temperature ductility and high strength can be devel-
oped by refining its grain size.
The discussion so far has been limited to the binary TiAl alloys.
Significant accomplishment has been made in enhancing the
mechanical properties of TiAl by small alloy additions. The next
section will look into various alloy additions explored in TiAl so
far and its effect on mechanical properties. Along with this, three
state-of-the art alloys developed by several commercial vendors
are discussed.
5. Alloy development
The dual phase (a2 þ g) TiAl have shown good response to
small alloying additions. In general, the alloying additions for TiAl
can be broadly divided into three different categories [44] with
the following compositions (in at%):
Ti45-52 Al45-48 X1-3 Y2-5 Z o 1
where X, Y and Z represent the three categories of alloying
additions. These alloying elements more or less affect the position
of the phase boundaries in the Ti–Al binary phase diagram
[20,28,57,58].
The X additions are usually elements which increase the
ductility of TiAl. They lower the stacking fault energy and thereby
increase the propensity of twinning. Usually elements such as Cr,
Mn, and V fall in this category.
The Y additions such as Nb, Ta, W, and Mo increase the
oxidation and creep resistance at high temperatures in TiAl. The
effect of Nb in varying levels is discussed in more depth in the
next section.
Finally, the Z alloying elements are usually B or C. Boron is
primarily used as a grain refiner to produce fully lamellar
microstructures with fine microstructures. Since, B is not soluble
in TiAl, it acts as an impediment to grain growth in the a phase
field to form fully lamellar structures. Carbon additions further
increase the strength of TiAl due to Ti3AlC perovskite precipitates.
C also increases the creep resistance of TiAl. The Ti3AlC perovs-
kites act as glide obstacles with long-range stress fields, which
cannot be overcome with the aid of thermal activation [31].
Table 3 lists the mechanical properties enhanced by the various
alloy additions.
5.1. Effect of Nb
Nb is especially used to increase oxidation and creep resistance.
Over the years, alloys with Nb additions have been developed and
can be classified into four different types [31,58,59].
i. Ti–48Al–2Nb
ii. Ti–(46–47)Al–(2–3)Nb
iii. Ti–45Al–(5–10)Nb
iv. Ti–45Al–(5–7)Nb–RM (refractory metals)
Alloys with high Nb content with type III and IV are also
known to increase the high temperature strength by solid solu-
tion strengthening. Recently large amounts of Nb in the order of
5% to 10% have been used in TiAl alloys to form a new class of TiAl
alloys known as TNB alloys [9,60,61,62,63,64] and TNM
alloys [65]. In these types of alloys, Nb plays a critical role in
increasing high temperature strength along with creep and
oxidation resistance.
The Nb atoms occupy Ti atomic sites and reduce the Al content
in the gamma phase. This shifts the a phase boundary to the left
and thereby lowers the processing temperatures to produce fully
lamellar structures. With low processing temperatures, grain
growth can be controlled, which leads to the refinement of the
microstructure and increase in strength.
Nb has also been reported to increase the tetragonality ratio of
TiAl, which enhances its structural anisotropy and hence its
strength [63]. Recently, Nb has also been reported to increase
Table 3
Effect of selected alloying elements on mechanical properties of TiAl.
Element Effect
Nb Increases oxidation and creep resistance in small amounts, also
increases high temperature strength if added between 5% and 10%
Ta Increases oxidation and creep resistance and tendency for hot
cracking
V Increases ductility
W Oxidation and creep resistance
B Grain refiner
C Increases creep and oxidation resistance
Cr Increases ductility if added in small amounts; increases oxidation
resistance if added in the range of 8%
Mn Increases ductility
Mo Increases strength, and creep and oxidation resistance.
 K. Kothari et al. / Progress in Aerospace Sciences 55 (2012) 1–16 11

the intrinsic strength of the gamma phase in Ti–45Al alloys [66]. 6.1. Ingot metallurgy and casting
Twinning in TiAl has been found to be enhanced by Nb, which in
turn suppresses pre-mature failure due to the inherent brittleness Ingot metallurgy and casting routes involve producing TiAl
of TiAl [67]. Along with strengthening effects, Nb is also known to ingots and castings by skull melting [64]. The resulting micro-
increase the diffusion activation energy in TiAl. This leads to structure of the ingots is characterized by large columnar grains
control of high creep rates in TiAl at temperatures above 700 1C. consisting of chemical inhomogeneities, and segregation as
Initially, Nb was used primarily to increase the oxidation shown in Fig. 14 [20]. The differences in the melting points and
resistance of TiAl alloys [68]. This was achieved in type I and II the densities of the constituent elements and peritectic solidifica-
alloys listed above by small Nb additions. The a2 phase has a tion process leads to segregation and chemical inhomogeneities
greater solubility for oxygen than the g phase. At high tempera- [83]. The chemical inhomogeneities are seen even on a micro-
tures, absorption of oxygen by a2 results in further embrittlement scopic level from one lamellar to the next within a single lamellar
of TiAl. More recently it has been reported that Nb decreases the grain [84]. Further, the solidification process occurs at the pure
a2 phase in TiAl alloy and hence decreases its oxygen solubility alpha phase field as shown in Fig. 6. Hence, the grain growth is
[66]. Also, Nb promotes the formation of Al2O3 which in turn very rapid and leads to formation of large columnar grains [85].
increases the oxidation resistance of TiAl. Significant improvements in chemical homogeneity and micro-
structure refinement can be achieved by thermo-mechanical
processing and the associated dynamic recrystallization [86]. As
5.2. State of the art TiAl alloys discussed earlier, the thermo-mechanical processing conditions,
alloy chemistry and microstructure evolution have an intimate
The alloy development in TiAl over the last 20 years has resulted correlation [87]. Hence, a tight optimization of the alloy composition
in four state-of-the-art alloys with exceptional high temperature and thermo-mechanical processing parameters is required to
mechanical properties. These four alloys are listed in Table 4 with achieve a more homogeneous crystallization and refined micro-
their compositions and strengths [11,26,27,30,69,70,71,72]. structure [88].
Several thermo-mechanical routes such as hot-rolling, forging,
and extrusion have been successfully utilized on titanium alumi-
6. Manufacturing techniques nide ingots to produce parts with refined microstructure and
improved chemical homogeneity [30,32,89,90]. These thermo-
Investment casting, ingot metallurgy (IM), and powder metal- mechanical treatments are performed in the (a þ b) phase field
lurgy (PM) are popular techniques that have been used to produce (shown in Fig. 6) [91]. This is usually in the temperature range of
TiAl parts. More recently, advanced techniques such as direct
rolling [19,73,74], laser forming, and mechanical alloying have
been investigated with good success. Several rapid sintering/
consolidation techniques such as plasma pressure compaction,
spark plasma sintering, pulse discharge sintering, high density
infrared processing and explosive consolidation have also been
successful in forming TiAl with desired mechanical properties
[75–82].
One of the biggest drawbacks of TiAl compared to that of
Ni-based superalloys is its production cost. This is largely due to
the fact that processing techniques for materials with fairly low
ductility do not exist. Further, due to the long-range ordering of
TiAl up to its melting point, their processing temperatures are
fairly high. This requires capital investment in processing equip-
ment with good high temperature characteristics.
Investment casting, ingot metallurgy and powder metallurgy
techniques have been successful at producing TiAl parts with
desirable mechanical properties only after a series of post proces-
sing steps, like hot-isostatic pressing, ageing, annealing, and hot
working. This further adds to the production costs of TiAl.
Advanced techniques such as direct rolling, laser forming, and
spark plasma sintering have been aimed at reducing the post-
processing steps for TiAl. These processes usually require less
time compared to the traditional techniques and can form
complicated shapes without much post-processing. But the pro-
blems associated with these techniques involve porosity and Fig. 13. TiAl ingots with coarse columnar grains ready for homogenization
scalability Fig. 13. process.

Table 4
TiAl state-of-the-art alloys.

Alloy name Composition (at%) Alloy strengths

General Electric, USA: 48-2-2 [11,27] Ti–48Al–2Cr–2Nb Ductility, fracture toughness, and oxidation resistance
Plansee, Austria: g–MET [30,69] Ti–45Al–(5–10)Nb High temperature strength, creep, fatigue, and oxidation resistance
GKSS Research Center, Germany: TNB Alloy [26,70] Ti–(45–47)Al–10Nb High temperature strength, creep, and oxidation resistance
Martin Marietta Laboratories, USA: XDTM TiAl [71,72] Ti–45Al–2Mn–2Nb–0.8B Ductility, high temperature strength, stiffness, creep, and oxidation resistance
12 K. Kothari et al. / Progress in Aerospace Sciences 55 (2012) 1–16
Fig. 14. Processing routes required for the production of high-pressure aero-engine compressor blades from a TiAl ingot [30].
1200 1C to 1350 1C. The thermo-mechanical treatments con-
ducted between 1200 1C and 1250 1C result in a fine-grained
duplex microstructure with the grain size as low as 5 mm [30].
At temperatures close to 1350 1C a fully lamellar microstructure
with average colony size of 100 mm is obtained. The colony size is
usually controlled by introducing small amounts of Boron as
discussed earlier.
In order to achieve chemical homogeneity, the primary TiAl
ingots and castings produced by melting have to be free of
impurities. Hence, as an alternative to skull melting, several other
cleaner processes such as vacuum arc remelting, and cold-hearth
plasma arc melting have been employed. In vacuum arc remelting
[92], large rods consisting of given amount of Ti, Al and master
alloys are cold welded to each other in an inert atmosphere. The
cold welded electrode is then melted in a vacuum arc furnace. The
electrode is melted to a primary ingot, which is then remelted
twice to improve chemical homogeneity and reduce segregation.
Finally, in the cold-hearth plasma arc melting process, the metal
alloy is melted and poured into a water-cooled copper hearth
forming a solid skull. This acts like a secondary hearth of the same
composition as the parent alloy. Without the solid skull, harmful
refractories could be picked up and cause melt-related inclusions.
This also allows enough time for inclusions to sink into the skull or
dissolve into the melt before the alloy is poured into a water-cooled
copper crucible for solidification. For this reason, this process is
referred to as a ‘‘clean melting’’ process. Cold-hearth melting is an
alternative method to other melting techniques, such as vacuum arc
remelting, where alloy cleanness is of great significance. Electron
beams and plasma-arc heating are both effective heat sources that
are suitable for this type of clean melting.
As mentioned above, most of the ingot metallurgy and casting
techniques result in the formation of coarse columnar grains
consisting of chemical inhomogeneity and segregation. This is
solved by further thermo-mechanical treatments. The ingots are
either extruded or forged to desired shapes with further heat
treatments to relieve any residual stresses. Fig. 14 illustrates the
post-processing steps required for forming a TiAl compressor
blade. Apart from thermo-mechanical treatments, the ingots and
castings are also subjected to hot-isostatic pressing (HIP) to
improve homogeneity and refine microstructure. The microstruc-
ture is further refined by ageing treatments [28].
6.2. Powder metallurgy
Powder metallurgy (PM) offers the potential for minimizing
many of the problems associated with large ingot production and
reducing the overall cost of the final TiAl component. Many of the
problems associated with ingot metallurgy (IM), such as center-
line porosity, chemical inhomogeneity, regions of varying density
and microstructure can be solved by powder metallurgy. Further,
powder metallurgy enables the development of new alloys that
cannot be made by conventional ingot metallurgy [93].
Gas atomization of pre-alloyed powder [94] followed by hot
isostatic pressing or consolidation by extrusion to full density has
been the general route taken in powder metallurgy. Mechanical
alloying (MA) of the elemental powders to form the alloy powders
of TiAl has also been investigated [95–97] with success in
obtaining metastable to stable TiAl phases. One of the biggest
problems associated with mechanical alloying is contamination of
the powders from the milling media and the container.
Hot isostatic pressing (HIP) of powder compact is a very
popular powder metallurgy based method to produce TiAl billets
[59,98–104]. In this process, gas atomized powder of high purity
is canned. The can is usually made of commercially pure Ti.
The can is then degassed at  500 1C under high vacuum after
which the can is sealed gas tight. The canned powder compact is
subjected to isostatic pressure in the range of 100MPa to 150 MPa
at a temperature range of 1200 1C to 1400 1C depending on the
desired microstructure. This is done for about 2 h to 6 h. The
consolidated powder compact is de-canned to produce billets.
Some of the post processing steps after hot isostatic pressing
involve hot extrusion, isothermal forging and hot rolling to sheets.
In hot isostatic pressing, the porosity in the final part is limited
and the microstructure is homogeneous with little segregation.
The drawback of hot isostatic pressing is that it requires exposure
to high temperatures for several hours. This leads to grain growth.
Hence, there is limited flexibility in hot isostatic pressing to
control the grain size of the final part.
In powder metallurgy, the presence of impurities in the
powders in the form of interstitial elements leads to porosity
[103,105]. Gas atomization process has been successful in produ-
cing high purity TiAl powders. In this process, the molten metal is
produced by either consumable or nonconsumable arc melting.
The metal is subsequently atomized using an annular gas flow
nozzle. For gas atomization of TiAl alloys only inert gases such as
Argon or Helium can be used because of the highly reactive melt.
However, during atomization the liquid metal interacts with the
inert gas environment, leading to the entrapment of gas within
the particles in spherical pores [106–110].
For comparison purposes, sheets of TiAl alloys of similar
chemical composition have been produced by powder metallurgy
and ingot metallurgy routes [8]. In powder metallurgy, gas
 K. Kothari et al. / Progress in Aerospace Sciences 55 (2012) 1–16
atomized TiAl powder was consolidated into a prematerial rec-
tangle. The prematerial was then canned, and hot-rolled into TiAl
sheets. In the ingot metallurgy process, an ingot of TiAl was
forged into a pancake prematerial. This pancake was then
machined into rectangle shape, canned, and hot rolled into sheets.
The yield from the ingot metallurgy process was found to be
much lower than that of powder metallurgy process. Also, the
powder metallurgy route has been found to be more cost-
effective than IM. But, areas of microporosity have been found
in powder metallurgy processed TiAl sheets, and consequently
this has been found to limit the strength of the material [8].
Hence, it is very important that the process of powder synthesis is
very clean and inhibits the presence of impurities.
Most of the current powder metallurgy processes have been
successful in producing TiAl parts, which will require further hot-
working or machining to produce the final component. Metal
injection molding (MIM) and spray forming are two powder
metallurgy methods, which strive to produce near-net shape
parts with minimal post processing [111]. The basic steps in
metal injection molding are the kneading of a feedstock by
mixing the powders with a binder, usually consisting of wax
and polymers; the molding of the part; the extraction of most of
the binder components and final sintering in order to obtain
highly dense parts. Porosity and contamination are some of
the challenges in using metal injection molding for producing
TiAl parts.
In spray forming, a melt stream is atomized using low pressure
argon gas. The droplets and partly solidified droplets are gathered
on a substrate which is positioned at a certain distance below
the gas nozzle. In this way, high density deposits with high
chemical and microstructural homogeneity as well as low purity
levels can be obtained. There has been very limited work done
on spray forming of titanium aluminides and hence the data on
the spray formed components is very limited to determine its
success [112].
6.3. State-of-the-art in TiAl sheet manufacturing
Plansee, Austria has been a pioneer in producing TiAl sheet
material using both ingot metallurgy and powder metallurgy
techniques. For powder metallurgy based technique, gas atomized
powders are consolidated by hot isostatic pressing and subse-
quently rolled on a conventional hot-rolling mill using Plansee’s
patented Advanced Sheet Rolling Process [113,114]. For ingot
metallurgy based technique, TiAl ingots produced by vacuum arc
remelting are treated by hot isostatic pressing and rolled by
Advanced Sheet Rolling Process. The microstructural homogene-
ity and mechanical properties of these sheets have been found to
be consistent and superior to most TiAl based alloys. The cost for
these sheets is currently at $1300/lb, but is expected to go as low
as $150/lb over the years.
An alternate approach has been used to produce thin g-TiAl
sheets at a lower cost [3]. In this approach, cast g-TiAl is directly
rolled into thin sheets, thereby eliminating costly and wasteful
intermediate steps. Direct rolling of cast plates into thin sheets
has been demonstrated for a number of g-TiAl alloys. This process
has been developed by NASA Glenn research center in Cleveland,
Ohio [19]. For direct-rolling, the as-cast TiAl alloy does not
undergo additional process steps such as atomizing, hot isostati-
cally pressing, extruding or conditioning, prior to being encapsu-
lated. Once the TiAl alloy is cast as a preform, the as-cast TiAl
alloy preform is encapsulated and directly rolled to form TiAl
sheets [115]. Limited microstructural and mechanical property
evaluations on these sheets have produced encouraging results. It
has been estimated that the direct rolling may lead to a cost
13
reduction of  35% over the conventional powder metallurgy and
ingot metallurgy routes.
6.4. Manufacturing challenges and opportunities
The manufacturing techniques for TiAl via both ingot metal-
lurgy and powder metallurgy routes have been advanced enough
to produce TiAl parts with desirable mechanical properties. As a
result, these processes have found use in producing TiAl parts for
several high temperature applications in the aerospace and
automobile industry. But the cost associated with TiAl, especially
due to its post processing steps after ingot production or powder
consolidation, has outweighed its benefits of weight savings.
Hence, advanced near-net shaping manufacturing methods with
minimal post-processing methods are being investigated for TiAl.
Also, methods to refine fully-lamellar microstructures are being
actively investigated. As discussed earlier, fully-lamellar micro-
structures with fine grain sizes and lamellar spacing may possess
mechanical properties with acceptable room temperature ductility
and toughness and excellent high temperature characteristics such
as creep and fatigue resistance. Several thermo-mechanical
treatments have been employed to achieve this. These thermo-
mechanical treatments are quite involved due to the complex
thermodynamic Ti–Al system. Achieving thermo-dynamic equili-
brium in fine spaced lamellae with small grain sizes requires
carefully designed heat-treatments. Fine grained microstructures
in TiAl have a tendency to deteriorate into Widmanstätten struc-
tures [70] even before reaching service temperature of the TiAl
part. Therefore, a lot research has concentrated on reducing the
grain size of the material by powder metallurgy techniques. Here
the starting powder particle size is reduced to a considerable
extent so that the grain size in the consolidated sample is also
small. With this technique the grain size can be lowered into the
nanometer range [116]. A decrease in the grain size up to the
nanometer range has the potential of increasing the strength and
ductility of the material significantly [21].
High energy ball milling and attrition milling have been used
to reduce powder particle size of the TiAl powders [116–118].
Pre-alloyed TiAl powders have been ball-milled for up to 50 h to
form amorphous TiAl powders with particle size in the sub-
micrometer to nanometer range. One of the advantages of milling
is that it disorders the lattice to improve the dislocation motion.
This is especially important in TiAl, where due to its long range
ordering its ductility is limited by immobility of the superdisloca-
tions as discussed earlier [119].
Mechanical alloying (MA) route has also been used to reduce
powder particle size [74,120–122]. For mechanical alloying, pure
Ti and Al powders are ball-milled for several hours to form a Ti–Al
solution, which is partly disordered and its particle size is reduced
considerably from the starting elemental powder particle size.
Several studies have been conducted to consolidate the milled
powders to produce TiAl with ultra-fine grains in the sub-micron
to nanometer range [123–125]. The consolidation processes used
for this were typical sintering or hot isostatic pressing processes.
Due to the small particle size, diffusion in the milled powders is
very rapid and hence grain growth is very rapid too. The grain
growth can be controlled by rapid consolidation of the powders.
Finally, metal matrix composites (MMCs) based on TiAl have
also been considered as potential solution to enhance its high
temperature service range. TiAl based metal matrix composites
reinforced with TiC, TiB2, TiB, Al2O3 and TiN [121,126–131] have
been considered. TiAl metal matrix composites reinforced with
titanium borides have been very popular due to the grain refining
characteristics of Boron. XDTM TiAl alloy with needle-shaped TiB2
particulates have been produced via casting process and have
displayed excellent room temperature ductility and high
14 K. Kothari et al. / Progress in Aerospace Sciences 55 (2012) 1–16
temperature characteristics. But several studies have focused on
using more economical approaches such as mechanical alloying.
In mechanical alloying, the reinforcement and matrix powders are
mechanically alloyed and consolidated to produce the desired
TiAl metal matrix composite.
7. Conclusion
Titanium aluminides have made strong gains in terms of
acceptance in the aerospace and automobile industries. Although,
a wide acceptance of titanium aluminides in various industries is
still lacking, several improvements in manufacturing and proces-
sing techniques have made titanium aluminide materials
potential candidates for several high temperature applications.
Research over the past two decades has led to a deeper under-
standing of the inter-relationships between microstructural mor-
phology, phase evolution, and deformation mechanisms. This in
turn has led to the development of advanced powder metallurgy
based (PM) manufacturing techniques, which negotiate the low
workability of titanium aluminides. Advanced powder metallurgy
based novel manufacturing opportunities exist to produce near-
net shape parts of TiAl with enhanced mechanical properties.
Along with this, several new challenges emerge in terms of
characterization of a whole new set of TiAl based alloys produced
by these novel powder metallurgy based techniques. Also, chal-
lenges lay ahead in the implementation of these techniques for
the industrial production of near-net shape TiAl parts.
Besides solving manufacturing issues, it is also important that
new processing techniques address the issues of developing
titanium aluminides with a balance of desirable mechanical
properties. The new processing techniques can probably achieve
this balance by incorporating some of the mechanical property
enhancement mechanisms such as, (1) Control of microstructural
morphology, (2) Small alloying additions, such as Nb, Cr, and B,
(3) Reduction of grain size to sub-micrometer to nanometer
range, and (4) Reinforcement with discontinuous particulates or
fibers.
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