Recent Progress in the Development

REVIEWS
of Gamma Titanium Aluminide
Alloys**
By Fritz Appel,* Ulrich Brossmann, Ulrich Christoph,
Stefan Eggert, Peter Janschek, Uwe Lorenz, Johann Müllauer,
Michael Oehring, and Jonathan D. H. Paul

Intermetallic titanium aluminides offer an attractive combination of low

density and good oxidation and ignition resistance with unique mechani-
cal properties. These involve high strength and elastic stiffness with excellent high temperature reten-
tion. Thus, they are one of the few classes of emerging materials that have the potential to be used in
demanding high-temperature structural applications whenever specific strength and stiffness are of
major concern. However, in order to effectively replace the heavier nickel-base superalloys currently in
use, titanium aluminides must combine a wide range of mechanical property capabilities. Advanced al-
loy designs are tailored for strength, toughness, creep resistance, and environmental stability. These
concerns are addressed in the present paper through global commentary on the physical metallurgy
and associated processing technologies of c-TiAl-base alloys. Particular emphasis is paid on recent de-
velopments of TiAl alloys with enhanced high-temperature capability.

1. Introduction the titanium aluminides. As the desired properties often lead

to conflicting alloy design concepts the balance of these prop-
In recent years considerable efforts have been made in the erties has to be carefully chosen. This needs a detailed under-
development of c-TiAl-base alloys for use in high tempera-
ture structural application, where low density and good high ±
temperature strength and Youngs modulus retention are of [*] Dr. F. Appel, Dr. U. Brossmann, Dr. U. Christoph,
major concern.[1±3] Owing chiefly to these properties titanium S. Eggert, U. Lorenz, Dr. J. Müllauer, Dr. M. Oehring,
aluminides provide a significant potential for innovative Dr. J. D. H. Paul
applications in advanced energy conversion systems, in that Institute for Materials Research
they may be used to replace the heavier nickel-base superal- GKSS Research Centre Geesthacht GmbH
loys at moderately high temperatures of about 700 C. The Max-Planck-Str., D-21502 Geesthacht (Germany)
most important pay-off areas in the automotive and aero Email: [email protected]
industry have been assessed in a recent conference proceed- P. Janschek
ings.[2] Fundamental to such applications, almost by defini- Thyssen Umformtechnik Turbinenkomponenten GmbH
tion, is a good balance of mechanical properties over a wide P.O. Box 100 963, D-42809 Remscheid (Germany)
temperature range. This includes damage tolerance, ductility, [**] The authors gratefully acknowledge continuous support of Ms.
fracture toughness, fatigue strength, and creep resistance. In E. Tretau. They are especially indebted to Prof. Dr. R. Wagner
most of these properties the titanium aluminides are inferior for many stimulating discussions and permanent support of
to the nickel-base superalloys, even if the comparison is made the work. The financial support of this research by the Helm-
on a strength to weight basis. This impedes their practical use holtz-Gemeinschaft (HGF-Strategiefonds) and the German
and is the driving force for the current research and develop- Federal Ministry for Education and Research (grant
ment aimed towards improving the mechanical properties of No. 03N3030Co) is gratefully acknowledged.

ADVANCED ENGINEERING MATERIALS 2000, 2, No. 11 1438-1656/00/1111-0699 $ 17.50+.50/0 699

 Appel et al./Recent Progress in the Development of Gamma Titanium Aluminide Alloys

standing of the relevant failure processes. Thus, apart from inadequate to provide the necessary information. Thus, con-
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brief descriptions of the deformation phenomena, we shall be ventional transmission electron microscopy (TEM) imaging
primarily concerned with the micromechanisms of deforma- techniques have been coupled with high resolution electron
tion and fracture which apparently limit the respective microscopy (HREM) to characterize the relevant processes.[8]
mechanical properties. On the basis of this understanding
recent advances in the development of novel high-strength 3. Alloy Compositions and Microstructures
alloys will be discussed. These novel alloys seem capable of
expanding the service range of c-TiAl-base alloys. In the final Currently most efforts on titanium aluminides have been
section of the article some attention will be given to the pro- focused on c-TiAl-base alloys which are slightly lean in Al
cessing of TiAl alloys and the manufacturing of components. and microalloyed with several third elements.[1-3] These have
led to very complex alloys with the general composition (in
at.-%) Ti±(45±49) Al + (0.3±10) X, with X designating alloying
2. Experimental Methods elements, such as Cr, Nb, V, Ta, Si, B, and C. The major
In recent years much emphasis has been placed on the me- phases in these alloys are c-TiAl with the tetragonal L1o
chanical characterization of titanium aluminide alloys. The structure and a2-Ti3Al with the hexagonal DO19 structure.
experiments described in this paper were designed in order When these alloys are produced by conventional ingot metal-
to identify the microprocesses of strength, plasticity and frac- lurgy under relatively slow cooling, a lamellar morphology is
ture. The alloys investigated were characterized in terms of formed which consists of thin parallel a2(Ti3Al) and c-TiAl
tensile strength, ductility, creep strength, and fracture tough- platelets with the orientation relationship[9,10]
ness as has been described elsewhere.[4±7] The factors control-
{111}ck(0001)a2 and á11Å0]cká112Å0ña2 (1)
ling the dislocation mobility were investigated over a wide
temperature range by determining temperature and strain There is a random occurrence of six c variants, which can
rate sensitivities.[5] Since many aspects of deformation and formally be described by rotations of one lamella relative to
fracture are intimately linked to defect configurations at the its neighbor by multiples of 60 around [111]c.[11±14] Thus, in
atomic level, standard techniques of metallography are often addition to a2/c interfaces different types of c/c interfaces

Fritz Appel studied physics at the Martin-Luther University in Halle. In 1973 he received a doctoral degree for a thesis on thermodynamical glide
parameters of plastic deformation. In 1987 he completed work on his habilitation thesis in the area of dislocation cutting processes and dipole
mechanisms. In 1990 he moved to the GKSS research centre and became group leader for the develpment of titanium aluminides in 1993. Since
then he has worked in particular on the transmission electron microscopic analysis of deformation processes, the thermodynamic analysis of plastic
deformation and mechanical properties. In 1999 he was awarded with the Tammann-Prize from the Deutsche Gesellschaft für Materialkunde e.V.
Ulrich Brossmann received his diploma (M.S.) and Phd. degrees from the University of Stuttgart in 1992 and 1998 respectively. In april
1998 he joined the group of Prof. Kronmüller at the Max-Planck Institut für Metallforschung, Stuttgart. His research activities in Stuttgart
focused on defects and diffusion in intermetallic aluminides and oxide ceramics. He joined the GKSS research centre in april 1999.
Ulrich Christoph trained as a precision engineer before entering the University of Hamburg, where he studied physics. In 1991 he started
his MSc. degree in the Institute for Materials Research at the GKSS research centre. In 1997 he was awarded with a Phd. for research on so-
lution and precipitation hardening of c-TiAl alloys.
Stefan Eggert joined the reactor safety research team when he arrived at GKSS in 1982. Between 1988 and 1994 he was part of the under-
water technology group where he worked on remote welding of deep water structures and on multiphase pumping systems for the oil indus-
try. In 1994 he started working on gamma titanium aluminide alloys in the research group.
Uwe Lorenz worked as a precision engineer in the Institute for Metal Physics at the University of Göttingen where he was involved in the de-
sign and construction of an analytical field ion microscope. In 1979 he joined the group of Prof. R. Wagner at the GKSS research centre and
worked on the defect characterisation of materials. Since 1987 he has worked on intermetallic alloys with particular emphasis on c-TiAl alloys.
Johann Müllauer studied physics at the University (TU) of Berlin. He started working on nuclear fuel materials within the GKSS research
centre. In 1986 he achieved his Phd. from the University of Hamburg. Since 1990 his research activities have concentrated on the develop-
ment of c-TiAl based alloys.
Michael Oehring studied physics at the Universities of Stuttgart and Göttingen. In 1988 he received a doctoral degree from the University
of Göttingen for a thesis in metal physics. After postdoctoral research in Göttingen he joined the GKSS research centre in 1989 where he
worked on mechanical alloying. Since 1993 he has worked in the group of Fritz Appel on the development of c-TiAl alloys.
Jonathan Paul studied at Manchester University and graduated in 1991 with a Phd. in metallurgy. Between 1991 and 1992 he performed
postdoctoral research in Manchester. In 1993 he started working on gamma titanium aluminides within the French Commissariat à l'Øner-
gie atomique. In 1995 he joined GKSS, continuing to work on TiAl alloys. He was employed in DERA, Farnborough between 1997 and
1999 and worked on titanium MMC's. In 1999 he returned to GKSS to continue his work on TiAl alloys.
Peter Janschek graduated in metallurgy from the Technical University of Aachen (Germany) in 1984. After graduation he joined Thyssen
Uniformtechnik as a project engineer in the isothermal forging group. Since 1995 he has been head of engineering and technology, responsi-
ble for the design and development of blades and discs for use in power generating and aeroengine applications.

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occur. Accommodation of misfit which arises because of dif- are listed in Table 1. Further details will be provided at the

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ferences in lattice parameters and crystal structure leads to respective examples and the respective processing routes are
dense structures of interfacial dislocations and coherency described in Section 6.
stresses.[3,8,14] These structural features of the lamellar mor-
phology are demonstrated in Figure 1. Upon loading lamellar
materials, stress induced structural changes of misfitting in- 4. Deformation Behaviour
terfaces can occur, which have various implications on the Titanium aluminides are relatively brittle materials, exhib-
deformation and fracture phenomena of lamellar titanium iting little plasticity at ambient temperatures. Typical for such
aluminides. deformation behavior is that the gliding dislocations are
By thermomechanical treatments a broad variety of micro- either too low in density or too immobile to allow the speci-
structures can be generated, which are often characterized in
men to match the superimposed strain rate. At elevated tem-
terms of the volume fraction of lamellar colonies and peratures titanium aluminides suffer from insufficient creep
equiaxed c grains; these are fully-lamellar, nearly-lamellar, resistance and structural changes. Such behavior is often as-
duplex, and near gamma structures.[1] Figure 2 demonstrates sociated with dislocation climb and the operation of diffusion
the appearance of these microstructures when observed by assisted dislocation sources.[3] Thus, the factors governing the
light microscopy or scanning electron microscopy (SEM) in multiplication and mobility of the dislocations might be im-
the backscattered electron (BSE) mode. portant in several different ways and will now be considered.
The alloys investigated in the present study have a wide
range of compositions and microstructures, which for brevity
4.1. Generation of Perfect Dislocations
Deformation of c-TiAl is closely related to its L1o structure
and occurs exclusively on {111} planes along close-packed
directions by ordinary dislocations 1/2á110] and superdislo-
cations 1/2á112Å] and á011]. The c-phase may also deform by
order twinning along 1/6á112Å]{111}.[3,15] Clearly, the contribu-
tion these different mechanisms make to the total deforma-
tion depends on the alloy composition and test temperature.
In two-phase alloys deformation is mainly confined to the
c-TiAl phase and provided by ordinary dislocations with the
Burgers vector b = 1/2á110], followed by order twinning and
glide of superdislocations with the Burgers vectors b = 1/
2á112] and b = á011], respectively.[3,15] Ordinary dislocations
have compact core structures,[16] which suggests that cross slip
and climb are relatively easy. Multiplication of these disloca-
tions can therefore take place through the operation of disloca-
tion sources incorporating stress driven cross slip or climb as
has been observed in disordered metals.[17] At room tempera-
ture multiplication has been found to be closely related to jogs
in screw dislocations, which were probably generated by cross
slip.[3,18] Possible mechanisms are schematically sketched in
Figure 3a. Since the jogs are immobile in the direction of the
motion of the screw dislocations, dislocation dipoles are
trailed at the jogs. The anchored segments bow out under the
applied stress in a fashion similar to a Frank±Read source. The
adjacent dipole arms can overcome their elastic interaction
and pass each other, if the applied shear stress is larger than[19]

(2)

Fig. 1. Mismatch structures and coherency stresses at lamellar interfaces in (a2 + c)-ti- l is the shear modulus, m is Poisson's ratio and h the height
tanium aluminides. a) Lamellar microstructure of a Ti±48 Al±2 Cr alloy. Foil orienta- of the jog. If the bowing process continues, the dipole arms
tion á101]c. b) High resolution image of an a2/c interface in sheet material of an alloy
Ti±47 Al±3.7 (Nb,Cr,Mn,Si)±0.5 B. Note the significant tilt misfit and the high density can effectively behave independently of each other and act as
of interfacial dislocations (arrowed) which are manifested by an additional (111)c single ended dislocation sources, Figure 3a, stage (iii). Fig-
plane. Foil orientation á101]cká112Å0ña2. c) Dislocation loops with Burgers vector b = 1/
2á110] emitted from a semicoherent interface under the action of coherency stresses.
ure 3b shows a dislocation dipole trailed at a high jog, which
Ti±48 Al±2 Cr, foil orientation close to á101]. is probably in the initial stage of this multiplication mecha-

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titanium aluminides relatively nar-

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row dipoles can probably act as dislo-

cation sources as suggested by Equa-
tion 2. Dipoles of smaller height,
which cannot multiply at the given
stress, will be pinched off from the
dislocation, Figure 3a, stage (iv).
These defects can also operate as dis-
location sources when in later stages
of deformation the flow stress in-
creases as it has been recognized.[3]
At elevated temperatures multipli-
cation of ordinary dislocations occurs
through the operation of Bardeen±
Herring climb sources.[3] Figure 4
demonstrates the growth of climb
sources during a period of about
350 min through a sequence of micro-
graphs, which were taken as part of
an in situ study performed at 820 K.
Accordingly, dislocations were gen-
erated by the nucleation and growth
of prismatic loops (arrow 1). Since ex-
pansion of each loop is achieved by
Fig. 2. Microstructures of a c-TiAl-base alloy of the composition Ti±47 Al±3.7 (Nb,Cr,Mn,Si)±0.5 B (at.-%): a) Coarse
nearly lamellar microstructure of the ingot material (optical microscopy), b)±d) backscattered electron SEM micrographs the removal of one atomic plane, the
of microstructures established by extrusion and subsequent forging followed by heat treatments at different temperatures mechanism seems to be exhausted
T, b) equiaxed microstructure, T = 1300 C, c) duplex microstructure, T = 1340 C, d) nearly-lamellar microstructure,
T = 1360 C.
after only one cycle of the source. The
expanding loop designated with
Table 1. Composition, microstructure and HIP treatment of the alloys investigated. arrow 2 contains a jog; thus climb occurs on different atomic
planes. After one cycle of the source a new dipole is gener-
ated so that the mechanism is regenerative. The character of
the point defects involved in the formation of the climb
source was not identified in the present study. However,
there is an increasing awareness that vacancies predominate
in thermal equilibrium over interstitials in many intermetal-
lics including c-TiAl.[20,21] Apparently, the critical vacancy
supersaturation required to operate a Bardeen±Herring
source is relatively low. The observed kinetics of loop growth
was evaluated in terms of a relevant model existing in the lit-
erature.[17,22] A critical supersaturation of vacancies Cv/Cv0 = 3
to 1.7 was obtained,[3] which is very small in comparison to
those produced by high temperature annealing and rapid
cooling. Thus, Bardeen±Herring sources can probably operate
throughout the entire period where annealing out of excess
vacancies takes place.
A mechanism common to both low and elevated tempera-
tures is the emission of dislocations from the lamellar inter-
faces. The process was found to be closely related to mis-
match structures and coherency stresses present at the
semicoherent interfaces.[3,8,18,23,24] The coherency stresses are
comparable with the yield stress of the material and give rise
nism. Since the anchorings of the segments are formed by to the formation of loop structures adjacent to the interfaces
cross glide, the dislocations may expand and multiply in such (Fig. 1c). Dislocation segments of such a configuration are
a way that slip spreads from one slip plane to the next, thus expected to be released from the interfaces when an addi-
producing wide slip bands. Due to the high flow stress of the tional shear stress is superimposed. Extended dislocation

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Fig. 4. Operation of Bardeen-Herring dislocation climb sources during an in situ heat-
ing experiment inside the TEM at T = 820 K. Details: 1) nucleation and growth of
Fig. 3. Cross glide and multiplication of ordinary dislocations in c-TiAl. a) Schematic prismatic dislocation loops, 2) expansion of a dislocation loop containing two jogs
drawing of the behavior of a jogged screw dislocation, i) and ii) anchoring of the dislo- (small arrow). After one cycle of the source a new dipole is generated so that the mecha-
cation at jogs of height h, iii) operation of dipole arms as single or double ended disloca- nism is regenerative. Ti±48 Al±2 Cr, predeformation at T = 300 K to strain e = 3 %.
tion sources, iv) and v) trailing and termination of dipoles at small jogs. At higher
stresses, the dipole arms may overcome their elastic interaction and operate as single or
double ended dislocation sources (dashed lines). b) Initial stage of multiplication of an The mechanisms described here support dislocation gen-
ordinary 1/2á110] dislocation by cross glide corresponding to stage (iii) in Figure 3a.
The dipole arms trailed at the jog (arrow 1) in the screw dislocation are widely separat- eration and are therefore beneficial for the ductility and dam-
ed so that they could pass each other and may act as single ended source. Note the emis- age tolerance of the material at ambient temperatures. The
sion of the dislocation loops from the interface (arrow 2). Ti±48 Al±2 Cr, compression
at T = 300 K to strain e = 3 %.
mechanisms are, on the other hand, a serious limitation for
the creep resistance and structural stability of the material un-
glide processes starting from the interfaces are therefore a sig- der long-term exposure, which will be considered in Sec-
nificant feature of the deformation structure of lamellar tion 5.4.
alloys. As an example Figure 5a demonstrates the dislocation
structure adjacent to semicoherent a2/c interfaces observed
4.2. Twin Nucleation
after deformation at room temperature. In most cases the dis-
locations have a Burgers vector b = 1/2á110] inclined to the la- Likewise, lamellar interfaces were found to be the preva-
mellar interfaces and, thus, contribute to shear deformation lent sites for twin nucleation. Misfit dislocations with a favor-
across the lamellae. able core configuration can be rearranged into twin embryos.
Dislocation emission from the interfaces may effectively Figure 6a shows the formation of a stacking fault at a misfit
contribute to the accommodation of stress concentrations. In dislocation of an a2/c interface, which may be considered as
lamellae which are unfavorably oriented for 1/2á110] glide or the initial stage of twin nucleation. A later stage of the process
twinning significant constraint stresses can be developed due is demonstrated in Figure 6b. Again, the mechanism seems to
to the shape change of deformed adjacent lamellae. The con- be supported by the coherency stresses present at the inter-
straint stresses are believed to assist overcoming of the high faces. Details of the dislocation reactions involved in twin
Peierls stresses expected for the superdislocations, thus glide nucleation have been discussed.[3,25] The present observation
processes of these dislocations are locally initiated. This provides phenomenological evidence that mechanisms asso-
behavior is demonstrated in Figure 5b. ciated with heterogeneous nucleation sites are most impor-

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Fig. 5. Generation of dislocations at lamellar interfaces. Ti±48 Al±2 Cr, compression at

T = 300 K to strain e = 3 %. a) Initiation of glide processes of ordinary dislocations
with Burgers vector b = 1/2á110] at a2/c interfaces. Foil orientation close to á101].
b) Generation of superdislocations in front of immobilized twins. Due to its á110] ori-
entation parallel to the compression axis, lamella c2 is unfavorably oriented for glide of
1/2á110] dislocations and twinning. The generation of superdislocations (mostly of type
1/2á112Å] in lamella c2 is probably supported by high constraint stresses exerted by the
deformation twins immobilized in the adjacent lamellae c1 and c3.

tant for twinning in c-TiAl. This view is also supported by

the fact that twinning in Al-rich single-phase alloys at low
temperatures is apparently very difficult.[26] This might be in
part a consequence of the fact that lamellar interfaces are al-
most absent in these materials. The observed interface related
twin nucleation and generation of perfect dislocations are cer-
tainly beneficial for the material ductility. The mechanisms
are, on the other hand, a serious limitation to the structural
stability and strength properties at elevated temperatures.

4.3. Dislocation Mobilities Fig. 6. Heterogeneous nucleation of deformation twins in two-phase titanium alumi-
nide alloys. a) Formation of a stacking fault at a misfit dislocation of an a2/c interface.
The stress experienced by an individual dislocation results Sheet material of an alloy Ti±47 Al±3.7 (Nb,Cr,Mn,Si)±0.5 B. Tensile deformation at
from the superposition of the applied stress r with stresses T = 300 K to failure at ef = 2.8 %. b) Generation of deformation twins at an interface
c/cT between c variants with true twin orientation. The tilt misfit of the interface is ac-
from internal sources. An effective stress r* is therefore commodated by an array of misfit dislocations (arrowed). The narrow twins (1) and (2)
defined as were nucleated from the misfit dislocations. The defect designated with (3) probably rep-
resents an embryonic twin. Ti±48 Al±0.37 C, compression at 300 K to strain e = 3 %.
r* = r ± rl (3)
minides represent a typical example of internal stresses.
where rl is the internal stress arising from long-range elas- Deformation may be considered as thermally activated dislo-
tic stress fields present in the material. The coherency stresses cation motion, which is driven by the effective stress r*. In
existing at the lamellar interfaces of two-phase titanium alu- the framework of this model the strain rate é is given by[27,28]

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é = é0exp±DG/kT (4)

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and the total stress r may be described as[5]

r = rl + r* = rl + (f/V)(DF* + kTlné/é0) (5)

The parameters involved in Equations 4 and 5 are: DG:

Gibbs free energy of activation, DF*: free energy of activation,
k: Boltzmann constant. é0 is proportional to the mobile dislo-
cation density and considered to be constant. The Taylor fac-
tor f = 3.06 was used to convert r and é to average shear
quantities. V = lbDR is the activation volume, which contains
the obstacle distance l, the Burgers vector b and the activation
distance DR. V can be described as the number of atoms that
have to be coherently thermally activated for overcoming the
glide obstacles by the dislocations. It is therefore expected
that V will undergo a significant change when there is a
change of the mechanism that controls the glide resistance of
the dislocations. The activation parameters defined by Equa-
tions 3±5 were related to temperature and strain rate sensitiv-
ities of the flow stress r by[5,27,28]

V = fkT/(Dr/Dlné)T (6)

(7)
Fig. 7. Dependence of the flow stress r and the reciprocal activation volume 1/V of bin-
ary and niobium containing alloys on the deformation temperature. The drawn lines re-
Qe º DH = ±TV(Dr/DT)é /f (8) fer to the values of a Ti±47 Al±2 Cr±0.2 Si alloy with a near gamma microstructure.
Values estimated at strain e = 1.25 % and strain rate é = 4.16 ´ 10±4 s±1.
Qe is the experimental activation energy, which is identical
to the activation enthalpy DH when the stress is independent
of obstacle distance.[27,28] For an assessment of thermally acti-
vated processes contributing to deformation, flow stresses
and reciprocal activation volumes were compared according
to Equation 5. The temperature dependence of the values es-
timated at the beginning of deformation is demonstrated in
Figure 7.[5,29] The behavior is almost typical of all two-phase
alloys. The flow stress is nearly independent of temperature
up to about 950 K and then decreases. In contrast 1/V passed
through a broad minimum at temperatures between 500 and
800 K, which indicates that significant changes in the micro-
mechanisms controlling the dislocation velocity occur. Thus,
separate consideration will be given to the domains I, II, and
III designated in Figure 7. The activation parameters esti-
mated in domain I (T = 295 K) are typically[3,5,29] V = (70±
130)b3, DG = 0.7±0.85 eV, DF* = 1.3 eV. V was referred to the
Burgers vector of ordinary dislocations. The small value of V
and the relatively high activation energies suggest that the
glide resistance of the dislocations arises from a dense ar-
rangement of strong obstacles. These features of dislocation
dynamics become evident in the dislocation structure ob-
served after room temperature deformation, as demonstrated
Fig. 8. Dislocation dynamics in domain I of the r(T)-curve shown in Figure 7. Pinning of
in Figure 8. A detailed analysis indicates that the dislocation screw dislocations with Burgers vector b = 1/2á110] by localized obstacles and jogs (ar-
velocity under these conditions is controlled by a combined row 1). Additional glide resistance arises probably from a lattice friction mechanism. This
is indicated by the observation that the dislocations in the unloaded sample are still bowed
operation of localized pinning, jog dragging and lattice fric- out in a smooth arc. Note the dislocation dipoles and debris defects which are trailed and
tion.[3,5] terminated at jogs (arrow 2). Ti±48 Al±2 Cr, compression at T = 300 K to strain e = 3 %.

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This type of glide resistance probably disappears at about the species causing the static and dynamic strain ageing ef-
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600 K, which is suggested by the small value of 1/V. Never- fects in c-TiAl have not yet been clearly identified.
theless, the flow stress r is practically constant in this temper- Deformation at elevated temperatures (domain III) is char-
ature domain. It is therefore speculated that the dislocation acterized by a strong increase of 1/V with T. At the same time
mobility in domain II of the r(T)-curve is impeded by another 1/V strongly increases with e (Fig. 10a). This indicates the on-
mechanism. c-Base alloys exhibit in the intermediate temper- set of a new thermally activated process as deformation pro-
ature interval (450±650 K) discontinuous yielding and a nega- ceeds. The activation parameters estimated for two-phase al-
tive strain rate sensitivity.[30,31] These phenomena are usually loys at T = 1100 K are typically[3,5,29] V = (50±90)b3, DH = 2.9±
associated with the Portevin±LeChatelier effect,[17,19] which 3.2 eV. For comparison, the Ti self-diffusion energy of c-TiAl
arises from the dynamic interaction of diffusing defects with was estimated as Qsd = 3.01 eV,[32] while recent measure-
the dislocations. The resulting glide resistance and strain age- ments have led to Qsd = 2.6 eV.[33] This is indicative of a diffu-
ing effects were investigated using the classical yield-point sion assisted dislocation mechanism. Climb of ordinary
return technique,[31] demonstrated in Figure 9a. The observed 1/2á110] dislocations has been recognized on different c-base
fast kinetics (Fig. 9b) and low activation energy of the ageing
process of Qa = 0.6±0.8 eV[31] are not consistent with data
from the literature on the mobility of defects in c-TiAl. Thus,

Fig. 9. Deformation behavior in domain II of the r(T)-curve shown in Figure 7. Porte-

vin±LeChaletier effect in a Ti±47 Al±2 Cr±0.2 Si alloy with near gamma microstruc-
ture. a) Sequence of static strain ageing experiments performed at T = 523 K under a Fig. 10. Deformation behavior in domain III of the r(T)-curve (Fig. 7). a) Dependence
relaxing stress. The stress increments Dr were measured as the difference in stress be- of the reciprocal activation volume 1/V on strain e for the deformation temperatures
fore ageing and the peak level on reloading. Different time intervals t between unload- ÑT = 293 K, DT = 973 K, l T = 1100 K. Values estimated at é = 4.16 ´ 10±4 s±1.
ing and subsequent reloading are indicated. b) Kinetics of strain ageing under relaxing b) Climb of ordinary dislocations observed during in situ heating inside the TEM.
loads and the deformation parameters indicated. Ti±48 Al±2 Cr, predeformation at T = 300 K to strain e = 3 %.

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Table 2. Parameters characterizing the interaction of á011] superdislocations with per- In two-phase alloys, boron additions are often used for refin-

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ovskite precipitates according to Figure 14c. r(e = 3 %) is the flow stress measured in
macroscopic compression at room temperature to strain e = 3 % (Ti±48 Al±0.37 C).
ing and stabilizing the microstructure.[38,39]
Undoubtedly, the nature and scale of the microstructure
plays an important role in the strengthening of two-phase al-
loys. As with many other materials the flow stress decreases
with increasing grain size and, thus, has been described in
terms of a Hall±Petch relation. Apparently, the effectiveness
titanium alloys by post mortem[34] and in situ TEM studies.[3,5] of grain boundary strengthening in two-phase TiAl alloys is
Figure 10b demonstrates a TEM in situ observation of dislo- much enhanced, which is reflected by relatively large Hall±
cation climb in a Ti±48 Al±2 Cr alloy. The samples used were Petch constants of Ky = 1.0 to 4 MPa Hm[3,36] and may in part
predeformed at 300 K to strain e = 3 %, which introduced suf- be attributed to the difficulty of propagating slip across the
ficient dislocations for observation and certainly a small various types of internal boundaries under conditions of re-
supersaturation of intrinsic point defects due to jog dragging stricted slip and cross slip.[3] Significant progress has been
processes.[35] The dislocation configuration changes into a he- achieved in describing the strength of fully-lamellar micro-
lical configuration which suggests that vacancies become ab- structures in terms of dislocation pile-up models, which indi-
sorbed in the core and thereby convert the dislocation line cate that these materials are mainly strengthened by the la-
into a helix. These structural changes probably occur under mellar interfaces.[40] However, there appears to be no single
the combined action of thermomechanical stresses and osmo- theoretical model which satisfactorily accounts for the large
tic climb forces. body of experimental observations on more complex micro-
The observed diffusion assisted dislocation processes are structures. Particular problems arise for duplex structures
believed to be generally important for the high temperature which are often rich in detail encompassing different length
deformation of c-base alloys. Processing routes of titanium parameters being relevant for the dislocation mean free path.
aluminides often involve thermal treatments followed by rap- More details on this subject is provided in the literature.[3,40±42]
id cooling, which certainly leads to large vacancy supersa- Alloys with a fully-lamellar microstructure are beneficial
turations. Highly non-equilibrium conditions may also occur for fracture toughness and high temperature strength but suf-
due to hot- or cold-working of the material. Dislocation mo- fer from poor ductility at low and ambient temperatures. Du-
tion in large vacancy supersaturations seems therefore to be a plex structures are conducive to tensile ductility but exhibit
common situation for the deformation of technical alloys. poor high temperature strength and creep resistance. Because
Climb induced defect structures are mostly formed with slow of these potential trade-offs between the mechanical proper-
rates, thus they are of minor interest if fast strain rates have to ties, microstructural conditions that are advantageous for
be realized as this is the case in conventional constant strain toughness and ductility might not be beneficial for other
rate tests. However, the mechanisms are expected to play an mechanical properties. In view of the recent conference pro-
important role for creep deformation, when only small strain ceedings[2] it might be anticipated that a fine-grained fully-
rates are superimposed. transformed lamellar structure has the best balance of
strength, ductility, toughness and creep resistance that meets
many demands for engineering applications. There are excel-
5. Mechanical Properties lent reviews[1,2,36] on the correlation between microstructure
For engineering applications titanium aluminides must and mechanical properties and the reader is referred to these
possess a good balance of various mechanical properties. In articles for further details and references.
order to limit the scope of this review, consideration will only Titanium aluminides are being considered to replace the
be given to strength, ductility, creep resistance and toughness. more dense nickel-base or iron-base superalloys over certain
ranges of temperature and stress. Thus, their mechanical
properties have to be assessed against the high standard set
5.1. Microstructures, Yield Strength, and Ductility
by the superalloys. At an intended service temperature of
The deformation and fracture characteristics of titanium 700 C strength and creep resistance of the titanium alumi-
aluminide alloys are sensitively dependent on the composi- nides are inferior to those shown by the superalloys, even if
tion, the partitioning of ternary and quaternary elements and density compensated data are compared. This is probably a
the microstructure.[1,2,15,36] While much work has been done direct consequence of thermally activated dislocation climb
in this field during the past decade our knowledge has not processes described in the previous section, which make the
been progressed far beyond the following rules. In general, a mechanical behavior of the titanium aluminides strongly rate
reduction of the Al content increases the strength level, but dependent. Thus, the strength properties degrade at low
tends to reduce ductility and oxidation resistance. The addi- strain rates such as those which occur under creep conditions.
tion of ternary elements such as Cr, Mn, or V up to amounts Thus, now that the basic problems of the titanium aluminides
of about 2 at.-% for each is known to increase the ductility of have been solved, perhaps the greatest interest is now fo-
two-phase alloys,[37] for reasons that are not altogether clear. cused on how to improve their high temperature capability.

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5.2. Solid Solution Effects due to Niobium Additions ary and superdislocations, Figure 11b. In Nb containing alloys
REVIEWS

the superdislocations were found to be widely dissociated,

In an attempt to enhance the strength of titanium alumi- which has seldom been observed in conventional alloys.
nides significant efforts have been made in order to establish Furthermore, as demonstrated in Figure 12, dissociated super-
solid solution hardening. However, the effects of ternary and
quaternary elements are not always clear as microalloying
may lead to changes of phase equilibria and microstructures.
In this respect, the most reliable information was obtained
from investigations of polysynthetically twinned crystals
(PST) as these materials always have a fully-lamellar micro-
structure. Solution strengthening due to V, Cr, Mn, Mo, Ta,
Nb, and Zr has been recognized when adding 0.6±1 at.-% of
these elements to binary PST crystals.[43] However, the ques-
tion remains whether or not the lamellar spacings are changed
by these additions, which has a significant effect on the yield
strength[41] and may thus easily mask solution hardening. Re-
cently, it has been shown that a significant strengthening effect
can be achieved on polycrystalline alloys when Nb is added
with an amount of 5±10 at.-% to polycrystalline two-phase al-
loys.[29,37,44] The strengthening effect was investigated by ana-
lyzing flow stresses and activation parameters[29] as described
in Section 4.2. These experiments involve Nb containing alloys
and binary alloys with the equivalent Al contents and are
thought to ascertain the effects of off-stoichiometric deviations
on the microstructure and yield strength. The results esti-
mated at the beginning of deformation are shown in Figure 7.
For comparison, the data for a conventional Ti±47 Al±2 Cr±
0.2 Si alloy is given. There is a significant strengthening effect
for binary and ternary alloys containing 45 at.-% Al, when
compared with the conventional material. The strengthening
effect is almost independent of the Nb content. This becomes
clearly evident because no strengthening is noticeable for Ti±
48 Al±10 Nb. The values of the reciprocal activation volume es-
timated for the binary alloys are very similar to those of the Nb
Fig. 11. Effect of large Nb additions on the microstructure and deformation behavior of
containing alloys. Furthermore, up to at least 973 K, 1/V is al- (a2 + c) titanium aluminides. a) High resolution image showing the lamellar micro-
most independent of the aluminium content. The similarity in structure observed in Ti±45 Al±10 Nb. Note the small lamellar spacings and the high
density of a2 lamellae. b) Deformation twins generated in Ti±45 Al±5 Nb by compres-
the yield stresses and the activation volumes of the binary and
sion at 973 K to strain e = 3 %. Twinning partial dislocations (arrowed) are piled up
Nb containing alloys leads us to believe that Nb substitutes against a lamellar boundary.
into the Ti lattice sites and that the related strength increase is
simply a consequence of the reduced aluminium content. This
view is supported by ALCHEMI (atom location channelling
enhanced microanalysis) studies, which revealed that Nb sole-
ly occupies the Ti sublattice.[45,46] This leads to an increase of
the a2 volume fraction in transformed regions and to a refine-
ment of the microstructure. Thus, the high flow stress of TiAl
alloys containing a large addition of Nb can be rationalized in
terms of a Hall±Petch mechanism. Figure 11 demonstrates the
fine microstructure of TiAl-alloys containing large Nb addi-
tions and pile-up structures of twinning partial dislocations.
However, the Nb containing alloys exhibit at room tempera-
ture an appreciable ductility, whereas the binary alloys of the
same Al content do not. This finding also indicates that signifi-
cant changes of the deformation mechanism occurred due to
the large Nb additions. TEM observations have revealed that Fig. 12. Deformation structure observed in a Ti±45 Al±10 Nb alloy after tensile defor-
mation at T = 300 K to a plastic strain e = 1 % and flow stress r = 1050 MPa. Note
1/6á112Å]{111} order twinning is the prominent deformation the widely dissociated superdislocations, stacking faults, and deformation twins coex-
mechanism when compared with the contributions from ordin- isting in a deformed c grain.

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dislocations, planar faults, and twins often coexist in the same that a carbon solid solution is a much less effective strength-

REVIEWS
grain or lamella; thus, it is speculated that the stacking fault en- ening agent than a dispersion of perovskite precipitates. The
ergies of c-TiAl are lowered by the Nb additions and that twin different deformation behavior is also manifested in the acti-
nucleation can occur by the superposition of extended stacking vation volume. At room temperature the homogenized and
faults on alternate {111} planes.[25,47] Thus, mechanical twinning quenched materials exhibit relatively large values of 1/V,
is expected to be relatively easy in TiAl alloys containing a large which slightly increase with c. It is therefore concluded that
addition of Nb and apparently compensates for the lack of inde- soluted carbon atoms act as weak glide obstacles, which ap-
pendent slip systems which can simultaneously operate at giv- parently can easily be overcome with the aid of thermal acti-
en stress. This might be the reason that with this class of alloys vation. In contrast, the reciprocal activation volume de-
appreciable plastic tensile elongations of 1±2 % at room temper- creased with c, when the material was aged and the carbon
ature can be achieved at yield stresses in excess of 1000 MPa.[47] was present as Ti3AlC precipitates. Figure 13a also includes
the values of carbon doped materials which were tested after
hot isostatic pressing (HIP) followed by slow cooling. After
5.3. Precipitation Hardening due to Carbon Additions
this treatment carbon is present as a coarse dispersion of the
Appreciable improvements in high temperature strength H-phase Ti2AlC.[48] These particles form athermal glide
and creep resistance have also been achieved by carbon addi- obstacles, which is clearly indicated by the strong decrease of
tions.[48,49] A systematic series of carbon doped materials with 1/V with c. However, the coarse dispersion of this phase
the base line composition Ti±48.5 Al±(0.02±0.4) C were sub- seems to be less effective in strengthening the material.
jected to different thermal treatments. Annealing at 1523 K
and quenching resulted in a carbon solid solution, whereas
Ti3AlC precipitates of perovskite type were formed by subse-
quent ageing at 1050 K. The precipitates are elongated along
the c-axis of the c matrix and exhibit significant coherency
stresses due to their mismatch with the c matrix.[48] These
structural features lead to a strong glide resistance for all
types and characters of dislocations. Figure 13 shows the de-
pendence of the flow stress on the carbon concentration c for
these two series of materials. For the materials containing per-
ovskite precipitates the flow stress strongly increases with c.
On contrary, the flow stress is practically independent of the
carbon concentration when carbon is in solution. This shows

Fig. 14. Precipitation hardening of c-TiAl alloys; analysis of dislocation structures in a

Ti±48 Al±0.37 C alloy observed after room temperature compression to strain e = 3 %.
Fig. 13. Hardening of c-TiAl alloys by carbon additions. Dependence of the flow stress a) Pinning of [011] superdislocations by Ti3AlC perovskite precipitates which are mani-
r and the reciprocal activation volume 1/V on the carbon concentration. a) Homoge- fested as white contrast dots. The insert shows line tension configurations calculated for
nized and quenched materials with carbon atoms in solid solution or in form of tiny ag- different stresses and projected into the image plane. b) Pinning of twinning partial
glomerates. b) Homogenized and aged materials which contain a fine dispersion of dislocations (arrowed) by precipitates. c) Assessment of the precipitation hardening in
Ti3AlC perovskite precipitates. The lines drawn in (a) refer to the alloy condition after terms of dislocation/point obstacle interactions; lc: obstacle distance, q: major semi-axis
hot isostatic pressing, where carbon is present as a coarse dispersion of the H-phase of line tension configurations of dislocations describing the curvature of bowed out
Ti2AlC, which is apparently less effective for hardening the material. segments, w: angle of attack, fm: interaction force.

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The high glide resistance of the perovskite precipitates also of the Dorn equation. A brief review of the recent advances
REVIEWS

becomes evident in TEM observations. As demonstrated in has been given by Parthasarathy et al.[61] Most creep studies
Figures 14a and b perfect and twinning partial dislocations on TiAl alloys were carried out at high stresses, resulting in
were effectively pinned by the precipitates. The obstacle spac- high strain rates and almost short-term tests. Thus, not
ing along the dislocations was typically lc = 50±100 nm. The surprisingly, the observed mechanisms are not so different
high glide resistance provided by the precipitates is mani- from those recognized after conventional deformation at con-
fested by the strong bowing-out of the dislocation segments. stant strain rates of approximately é = 10±4 s±1. It is only
The dislocation±obstacle interactions were analyzed in terms recently[62±65] that long-term creep tests at low stresses have
of the parameters defined in Figure 14c. The effective shear been performed, which are perhaps more relevant to the
stress acting on the dislocation segments were determined by intended service conditions. The intention of this section is to
comparing their curvature with line tension configurations.[49] address this imbalance of information by presenting long-
This led to an average value sc = 300 MPa which is in good term creep studies. The test parameters involve low stresses
agreement with the flow stress r = 1000 MPa, which had been of ra = 80±140 MPa in order to achieve low creep rates.[62±65]
applied during macroscopic compression to strain e = 3 %. Figure 15 demonstrates the creep curves of different two-
r can be converted into an average shear stress s = r/M = phase alloys determined under these conditions. As with
330 MPa using the Taylor factor M = 3.06. Thus, the harden- other mechanical properties the creep characteristics of c-base
ing effect achieved by the perovskite precipitates can solely alloys are sensitive to the nature and scale of the microstruc-
be attributed to their strong interaction with all types and ture. Fully-lamellar microstructures exhibit the best creep
characters of dislocations. A detailed assessment of the acti- resistance (Fig. 15b), and, thus, will be mainly considered
vation parameters and the TEM observations led to the con- here. However, depending on the temperature and stress con-
clusion that overcoming of the precipitates results in an ather- ditions, the primary creep strain of fully-lamellar materials
mal stress contribution,[3] which is maintained up to can exceed that of duplex material. This might be a critical
relatively high temperatures. However, as with the TiAl±Nb problem for the application of the otherwise creep resistant
alloys, twin nucleation seems to be relatively easy. Twin nu-
clei were often found together with widely separated super-
dislocations.[25] Thus, it is tempting to speculate that the twins
originate from overlapping stacking faults trailed by the
superdislocations. The process is certainly supported by the
high coherency stresses occurring at the precipitates. In this
way a fine dispersion of deformation twins can be generated,
which is certainly beneficial for the ductility of the material.
Hardening of two-phase titanium aluminides by fine disper-
sions of Ti3AlC precipitates seems therefore to be a suitable
metallurgical technique for improving the high temperature
strength and creep resistance.

5.4. Creep Properties

Design concepts for advanced energy conversion systems
and aeroengines require low creep deformation of the compo-
nents in order to ensure that the clearance between the rotat-
ing parts and their casings can be kept small. Thus, the mate-
rials used should have a good creep resistance, which must
be present in the earlier stages of deformation. Creep strength
and rupture life are therefore critical issues regarding the
high temperature applications of c-base titanium aluminides.
This problem became evident during the past five years and
has attracted many research activities. The creep properties
were found to depend on both alloy composition and micro-
structure[50±59] and considerable improvements have been
achieved by optimizing these two factors, for a review see
Beddoes et al.[60] As with many other materials the creep
properties are strongly dependent on test parameters, which Fig. 15. Creep characteristics of two-phase titanium aluminides. a) Ti±48 Al±2 Cr, du-
is manifested by the large variation of the steady-state creep plex microstructure, b) Ti±47 Al±3.7 (Nb,Mn,Cr,Si)±0.5 B, 1) investment casting,
nearly-lamellar microstructure, lamellar spacings 0.1±1.5 lm, 2) investment casting +
stress exponent with stress and temperature. Much emphasis HIP, duplex microstructure, 3) investment casting + HIP + heat treatment at Ta + DT
has been placed on describing the experimental data in terms = 1380 C, nearly-lamellar microstructure, lamellar spacings 10 nm±0.5 lm.

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fully-lamellar materials. In crept samples dense dislocation

REVIEWS
structures adjacent to lamellar interfaces have been observed,
lending support to the hypothesis that the high primary creep
rate of lamellar materials is associated with the emission of
dislocations from the interfaces.[62±64] This view has also been
confirmed by TEM in situ observations.[3]
Later stages of creep deformation are characterized either
by dynamic recrystallization (at high stresses and tempera-
tures) or by the competition between order twinning, disloca-
tion glide, and climb (at intermediate stresses and tempera-
tures). The operation of a certain mechanism also depends on
alloy composition and microstructure. However, in most
cases a stress/temperature domain exists in which creep is
mainly controlled by climb of ordinary dislocations. For la-
mellar alloys this domain lies between stresses of 100 to
200 MPa and temperatures of 650 to 750 C.
During long-term creep of lamellar materials significant
structural changes occur.[63,64] These processes are enhanced
by high creep stresses and temperatures, but seem to be a
general problem during long-term creep exposure. Figure 16
demonstrates the structural changes which are associated
with c/c interfaces. A prominent feature is the formation of
multiple-height ledges perpendicular to the interfacial
plane.[63,64] The high resolution micrograph demonstrates an
initial stage of the process. It is speculated that these large
ledges arise from one-plane steps, which moved under diffu-
sional control along the interfaces and were piled-up at misfit
dislocations (arrowed in Fig. 16). The ledges had often grown
into zones which extended over about 10 nm. The atomic ar-
rangement in these zones is reminiscent of the 9R structure
and, thus, can formally be rationalized by two shear pro-
cesses on adjacent (111)c planes along the true twinning
1/6[112Å], and one anti-twinning operation 1/3[1Å1Å2] on every
third (111)c plane.[65] When the slabs grow further it might be Fig. 17. Recrystallization processes at c/c interfaces observed after long-term creep of a
Ti±48 Al±2 Cr alloy. Creep conditions: T = 700 C, ra = 140 MPa, t = 5988 h, strain
energetically favorable to nucleate a new c grain and this sit- e = 0.69 %. a) Recrystallized c grain (designated as cr) formed at a ledge of an inter-
uation is apparently demonstrated in Figure 17. The driving face joining twin related c variants. b) Higher magnification of the region arrowed in
Figure 17a. Note the orientation relationship (001)k(11Å1Å) between the recrystallized
grain and the parent c lamella.

forces for the interface processes seem in part to arise from

changes of the phase equilibria.[64] Because the phase bound-
aries of the (a + c) two-phase field in the binary Ti±Al phase
diagram are strongly dependent on the temperature, the vol-
ume fractions of the a2 and c phases in c based alloys might
be particularly sensitive to the thermal history of the material.
For instance, after heat treatments above the eutectoid tem-
perature, a2 volume fractions can be obtained, which are
higher than the equilibrium value at the service temperature
of 700 C. Thus, during long-term creep, dissolution of the a2
phase is expected. This view is supported by TEM observa-
tions made on a2/c interfaces (Fig. 18a), which exhibit a high
density of ledges when compared with c/c interfaces.[64] As a
consequence of these processes a serious degradation of the
Fig. 16. Structural changes at cc interfaces observed after long-term creep of a duplex microstructure occurs. It consists of fragmentation of the la-
Ti±48 Al±2 Cr alloy. Creep conditions T = 700 C, ra = 140 MPa, t = 5988 h, strain
e = 0.69 %. Formation of a high ledge, note the misfit dislocation (arrowed) which is
mellae and the formation of new c grains leading to a com-
manifested by an additional (111)c plane parallel to the interface. plex conversion of the lamellar morphology to a fine spheroi-

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dized microstructure (Fig. 18b). More on this subject is pro- However, it has been established by field-ion microscopy that
REVIEWS

vided in separate studies.[42,63,64] A characteristic feature of a2-Ti3Al preferentially scavenges oxygen, carbon, and nitro-
the microstructure of crept samples is the presence of precipi- gen from c-TiAl in the two-phase alloys.[66] Accordingly, in
tates, as demonstrated in Figure 19.[64] Most, if not all precipi- a2-Ti3Al the solubility limit for these elements is at least one
tates are situated at isolated dislocations and the mismatch order of magnitude higher than in c-TiAl. It may thus be en-
structures of sub-grain boundaries and lamellar interfaces. visaged that the precipitation effects result from the a2 ® c
Denuded zones were observed next to decorated defects, in- phase transformation described in the previous section. In the
dicating that the precipitates were heterogeneously nu- newly formed c phase the concentration of these elements
cleated. The nature of the precipitates could not be identified. can easily exceed the solubility limit so that precipitation of
oxides, nitrides, or carbides occurs. The heterogeneous nucle-
ation of the precipitation certainly leads to a strong pinning
of the dislocations and embrittlement of the material, which
is certainly harmful for its damage tolerance after long-term
service.

5.5. Fracture Toughness

Like other intermetallics titanium aluminides suffer from

brittleness at low and ambient temperatures, which makes
processing difficult and hinders practical use. The fracture
behavior is known to be very sensitive to microstruc-
ture.[1,67,68] Intergranular fracture and cleavage are the domi-
nant fracture mechanisms in the duplex microstructures,
while interfacial delamination, translamellar fracture and de-
cohesion of lamellar colonies are the most important pro-
cesses in lamellar alloys. This intrinsic brittleness persists up
to temperatures of about 700 C and has been attributed to a
combined effect of low cohesion strength, insufficient defor-
mation modes which can simultaneously operate at a given
stress, and low dislocation mobility. For toughening the mate-
rial a lamellar microstructure is beneficial, because shear liga-
ment bridging, crack deflection, and microcrack shielding oc-
cur.[67] Fully-lamellar microstructures with randomized
Fig. 18. Structural changes at a2/c interfaces observed after long-term creep of a Ti±
48 Al±2 Cr alloy at T = 700 C, ra = 110 MPa, t = 13 400 h, e = 0.46 %. a) Formation
colony orientations exhibit relatively large toughnesses of KQ
of ledges in a2c and c/c interfaces, note the significantly higher density of ledges in the = 25±30 MPa Hm. For a more comprehensive discussion of
a2/c interface. b) Spheroidization of a2 lamellae due to the formation of c grains (desig- the correlation between fracture toughness and microstruc-
nated as cr).
ture the reader is referred to a recent review.[67]
The variation of the fracture toughness with temperature
is shown in Figure 20 for two different microstructures.[67]

Fig. 19. Heterogeneous nucleation of precipitates at dislocations observed after long-

term creep of a Ti±48 Al±2 Cr alloy; T = 700 C, ra = 110 MPa, t = 13 400 h, e = Fig. 20. Dependence of the fracture toughness KQ on the test temperature for nearly-la-
0.46 %. mellar and near gamma microstructures of a Ti±47 Al±2 Cr±0.2 Si (at.-%) alloy.

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The observed behavior again indicates that resistance against multiplication rate of the dislocations are low. The mecha-

REVIEWS
unstable crack propagation can most effectively be derived nisms governing the dislocation mobility in the plastic zone
from toughening mechanisms related to the lamellar mor- at room temperature were found to be quite similar to those
phology. However, the temperature dependence of the frac- in bulk material, namely lattice friction, localized pinning,
ture toughness of the near gamma materials suggests that and jog dragging. Due to this high glide resistance the dislo-
crack tip plasticity can also lead to appreciable toughening, a cations may easily be outrun by the crack. In this respect de-
topic, which has received far less attention. In this context formation twinning might be very effective as twins can rap-
TEM observations of crack tips have been performed on two- idly propagate. Crack tip shielding by twinning has been
phase titanium aluminides with different microstructures.[18] recognized[25] by HREM of crack tips.
Figure 21 demonstrates a high-resolution image of a crack, From the discussion in Section 5.2 it can be suspected that
which propagated in a thin foil of a lamellar alloy. The crack the high glide resistance of the dislocations will be drastically
followed {111}c planes which indicates that c-TiAl is prone to reduced at elevated temperatures due to thermal activation
cleavage fracture on these planes. This finding is consistent and the operation of diffusion assisted climb processes. Un-
with the earlier predictions of Yoo and Fu,[69] who calculated like the situation at room temperature, the glide processes
the ideal cleavage energies for different crystallographic can easily spread within the plastic zone so that the con-
planes of c-TiAl. Crack propagation across the lamellae is straints due to the local crystallography and slip geometry
characterized by various interactions of the crack tip with la- are less restrictive. It is therefore expected that the problems
mellar boundaries, involving crack deflection, and crack tip associated with the lack of independent slip systems (which
immobilization so that a much more tortuous crack path is can simultaneously operate at a given stress) can in part be
traversed.[18] Ahead of the crack tip a plastic zone is formed, compensated so that the crack tips are effectively shielded.
which is often extended over several lamellae and consists of Thus, the fracture mechanism changes from cleavage at low
deformation twins and dislocations. Thus, the shape of the temperatures to energy absorbing ductile forms at elevated
plastic zone is strongly determined by the crystallography of temperatures.[67]
these slip elements. In the high resolution image shown in In view of the observed cleavage fracture it is suspected
Figure 21 the crack tip plasticity apparently becomes evident that unfavorably oriented c grains or lamellae may provide
by the two dislocations which are arranged in a dipole config- easy crack paths. Once nucleated on {111}c planes, the cracks
uration. Stable crack growth requires the plastic zone to keep are subjected to high tensile stresses and can rapidly grow to
with the cleavage crack, which is difficult if the mobility and a critical length. It is speculated that large colonies with la-
mellar interfaces perpendicular to the loading axis may have
particularly detrimental effects on the tensile strength of
polycrystalline material. For technical application of a brittle
material its reliability is most important. The variation of
strength within a given volume of such material can be ana-
lyzed in terms of Weibull statistics. Figure 22 shows the data
obtained on different two-phase alloys and ranked in Weibull
plots.[6] Fine-grained materials typically exhibit a Weibull

Fig. 22. Weibull plot of the fracture toughness determined on different two-phase tita-
Fig. 21. A crack in an (a2 + c) TiAl alloy with a lamellar microstructure. Note the nium aluminides, (1 ± F) failure probability. T = 25 C, loading rate vm =
cleavageÐlike fracture on {111}c planes, the deflection of the crack at the interface c1/ 0.01 mm min±1. & Ti±48 Al±2 Cr, crack propagation parallel to the interfaces; l Ti±
c2, the generation of a dislocation dipole (insert), and the immobilisation of the crack at 47 Al±3.7 (Nb,Cr,Mn,Si)±0.5 B, duplex microstructure, 20 % c grains; n Ti±47 Al±
the a2 lamella. 3.7 (Nb,Cr,Mn,Si)±0.5 B, duplex microstructure, 80 % c grains.

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modulus of m = 18±24, whereas the values for coarse-grained Zdziobek et al.[72] for this composition. By quantitative EDX
REVIEWS

lamellar materials are m = 7±10. For comparison, values of m analysis taken from this material (one line scan is presented
= 5±15 are common for glasses and ceramics. Thus, the relia- in Fig. 23) concentrations of about 44 at.-% Al and 10 at.-%
bility of coarse-grained lamellar materials seems to be of criti- Nb were determined in the dendrites whereas in interdendri-
cal importance for the design of structural components, tic regions the Al and Nb concentrations amounted to 49 at.-
which requires adequate safety factors. % Al and 7.5 at.-% Nb, respectively. The concentration varies
on a scale of about 1 mm and thus extended coarse-grained
single-phase c regions occur,[73] which are certainly detrimen-
6. Processing tal for the mechanical properties.
As already discussed in the previous section, microstruc- For ingot breakdown isothermal forging,[74±77] canned non-
isothermal forging,[78,79] and canned hot extrusion[80,81] have
tural optimization and control of c-TiAl alloys is of particular
concern with respect to balanced mechanical properties. been applied and investigated in quite a number of studies.
Thus, wrought processing is beneficial because it allows a In general, c alloys exhibit limited hot ductility and a strong
broad range of tailored microstructures to be developed and, dependence of the flow stress on strain rate and temperature.
in particular, offers the possibility of obtaining lamellar mi- As has been discussed in a recent review by Semiatin et al.[82]
crostructures with both refined colony sizes and lamellar a critical tensile stress in the workpiece should not be ex-
spacings. As mentioned above this microstructural form has ceeded for successful crack-free forging. For cast materials
the best potential to achieve an attractive and balanced prop- this critical stress varies between 200 and 500 MPa depending
on alloy composition and microstructure. Thus, forging
erty profile.[1,2,36,70,71] For the refinement of colony sizes there
exist different possibilities. Lamellar colonies are formed should be performed at moderate strain rates <10±1 s±1 and
from a grains when the material is cooled from the a field under isothermal or near-isothermal conditions which can be
which for engineering alloys lies above ~1300 C. The rapid realized by canning the billets. Higher strain rates are possi-
grain growth in this temperature range thus leads to coarse ble for canned hot extrusion which usually is carried out at
colonies. Control of the a grain size can be achieved by hot temperatures above 1250 C.
working directly in the a field. However, for this type of pro-
cessing route further hot working steps, e.g., near-net shaping
of parts by closed-die forging are not possible because the re-
fined lamellar microstructure would be again destroyed by
dynamical recrystallization. If hot working is carried out in
the (a + c) or (a2 + c) field multiple hot working steps can be
utilized. In this case, the lamellar microstructure is formed by
a final heat treatment. The a grain size can then be controlled
by the presence of second phases, e.g., borides.
For the work presented here ingots were used, which had
been produced by double or triple VAR (vacuum arc remelt-
ing) or by induction skull melting. The ingot production was
found to be a critical processing step, especially if ingots of
large diameters are needed. One problem are macroscopic
pores which could not be completely closed by hot working
and can even lead to cracking of the material on forging. With
respect to hot working, further the strong texture of ingot ma-
terial has to be regarded, which varies over the cross-section
of the ingot and can give rise to anisotropic flow of the mate-
rial on hot working. The most severe problem, however, con-
nected with ingot production are macro- and microsegrega-
tions of Al because the mechanical properties sensitively
depend on the Al content. Owing to the Ti±Al phase diagram
engineering alloys might pass through two peritectic reac-
tions on solidification and therefore the segregation of Al can
hardly be avoided in the ingot material. In Figure 23 the den-
dritic morphology of a 150 kg ingot of composition Ti±45 Al±
10 Nb ingot is demonstrated.[72] Elemental energy dispersive
X-ray (EDX) mapping shows that the interdendritic regions Fig. 23. EDX microanalyses performed on Ti±45 Al±10 Nb ingot material: the left side
shows EDX maps of the Ti, Al, and Nb distribution, on the right side is a BSE image
are rich in Al and depleted in Nb as it is expected from the in- together with quantitative line scans from the same specimen region.The line along
vestigations of the ternary Ti±Al±Nb phase diagram by which the scans were taken is indicated on the BSE image.

714 ADVANCED ENGINEERING MATERIALS 2000, 2, No. 11

Appel et al./Recent Progress in the Development of Gamma Titanium Aluminide Alloys

In the framework of this study, canned hot extrusion and Figure 25 shows different microstructures obtained after

REVIEWS
isothermal forging of billets with and without cans have been extrusion with a ratio of 7:1. Extrusion above Ta led to a
applied for ingot breakdown. For successful hot extrusion an nearly-lamellar microstructure with refined colony size
adequate can design is an important factor. As suggested in whereas extrusion below Ta resulted in duplex microstruc-
the literature[83] a conventional Ti alloy and an austenitic steel tures in which the lamellar and equiaxed microstructural con-
were used as can materials. However, at the temperatures stituents were present in a banded morphology. Both constit-
and strain rates (u » 1 s±1) usually applied for the hot extru- uents of the microstructure were particularly refined; in
sion of c alloys the flow stress of the can materials used is be- lamellar regions the colony size was typically 20 lm, in the
tween 250 to 300 MPa lower than that of the billet material. equiaxed bands the grain size was around 1 lm. Banded mi-
This leads to non-uniform extrusion resulting in strong varia- crostructures were often observed in hot-worked c alloys and
tions of the core diameter in extruded rods and to cracking were attributed to inhomogeneities in the Al content due to
during extrusion. The flow stress mismatch between can and segregation during peritectic solidification.[74,76] As has been
billet material can be significantly reduced by an appropriate described earlier the Ti±45 Al±10 Nb cast material exhibited
can design. It was found that the thickness of the can and a significant variations in the Al and Nb content on a scale of
heat insulation between can and billet are particularly impor- around 1 mm. Similar variations in concentration were also
tant. As suggested by Semiatin and Seetharaman[83] a heat in- found after extrusion (Fig. 26) and explain the formation of
sulation allows the can to be air cooled for a controlled dwell- the banded microstructure. In single phase c regions in which
period prior to extrusion while heat losses of the billet are re- grain growth on dynamic recrystallization is not impeded by
duced. By the temperature difference between can and billet a grains coarse-grained bands are formed, whereas in regions
the flow stress mismatch is decreased. Heat losses at tempera- of low Al content lamellar colonies or, depending on extru-
tures above 1200 C are primarily determined by radiation. sion temperature, fine-grained (a2 + c bands are developed.
Thus, a novel can design was developed, which effectively Thus, chemical homogeneity is concluded to be a prerequisite
prevented heat transfer by both radiation and conduction.[84] to obtain microstructural homogeneity on hot working. Be-
Using this design uniform crack-free extrusion was achieved cause the segregation of Al could not be entirely removed by
resulting in rods with a constant core diameter. As the core practically feasible heat treatments (up to some hours at
diameter amounted to the value expected for equal flow 1400 C) multistep hot working followed by selected heat
stresses of the can and billet materials, the flow stress mis- treatments after each working step seems to be beneficial.
match apparently had been minimized.
Usually hot extrusion was carried out on billets with a
diameter of 81 mm which were extruded by an extrusion
ratio of 7:1 to rods with a round cross-section. However,
the novel can design described above could also be used
for successful extrusion of billets with much larger dimen-
sions (diameter 204 mm, length up to 700 mm) which were
extruded into rectangular shapes with a ratio of 10:1
(Fig. 24). As this technique leads to large amounts of
wrought material of favorable geometry being processed in
one step, hot extrusion appears to be an effective method
for ingot breakdown.

Fig. 25. Microstructure of a Ti±45 Al±10 Nb alloy after extrusion at different tempera-
tures: a) duplex microstructure after extrusion at a temperature of 1300 C, b) nearly
Fig. 24. Extruded rod obtained from a large ingot of a c-based alloy with high Nb con- lamellar microstructure after extrusion at a temperature of 1360 C. The extrusion
tent (extrusion ratio 10:1). direction is horizontal in the images.

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 Appel et al./Recent Progress in the Development of Gamma Titanium Aluminide Alloys
REVIEWS

Fig. 26. BSE image of the microstructure of extruded Ti±45 Al±10 Nb material and
quantitative EDX linescans which were taken along the line shown in the BSE image
(extrusion temperature 1250 C, extrusion ratio 7:1).
Fig. 27. Ingot material of a c-based alloy during isothermal forging and the obtained
In addition to hot extrusion isothermal forging was also pancake of diameter 581 mm.

applied for the primary processing of ingot material. In order

to find suitable forging conditions the results of a systematic described previously for hot extrusion. This type of canning
study on the forging of a c alloy based on Ti±47 Al in the allowed a significant decrease in the forging temperature as
range 900 to 1250 C and 10±3 to 10 s±1 were taken as guidance. well as an increase in the height reduction attainable in a sin-
In this study, which included microstructural examinations, gle-step forging. In general, fine equiaxed microstructures
relatively small workpieces 20 mm in diameter were used. were obtained after forging but significant fractions of
Crack-free isothermal forging was possible in a relatively retained lamellar colonies were also present and the micro-
wide processing window, however, almost fully-recrystal- structure showed some banding as already described for
lized microstructures with optimum microstructural homoge- extruded material.
neity were only found for strain rates £ 10±2 s±1. In this re- The microstructural refinement obtained in the primary
stricted processing range, isothermal forging was wrought material reduced the susceptibility to cracking in
successfully performed on various alloys with up to 80 % re- any secondary hot working step and thus allowes the materi-
duction in height using billets with diameters between 80 and al to be worked by closed-die forging and rolling techniques
270 mm. As shown in Figure 27 large crack-free pancakes to produce mill products. Within the frame work of a joint
with diameters up to 581 mm were obtained. However, it project together with the companies Thyssen Umformtechnik
was observed that careful control of the temperature was es- Turbinenkomponenten GmbH (Remscheid, Germany) and
sential. Heat losses which can occur due to insufficient con- Rolls-Royce Deutschland GmbH (Dahlewitz, Germany, for-
trol of die temperatures for instance resulted in cracking of merly BMW Rolls-Royce) the complete processing technology
the bulge surfaces. Therefore, in a further series of forgings for the production of a high-pressure aeroengine compressor
the billets were canned using a can design which aimed at an blade from a c alloy has been explored. The processing route
effective thermal isolation between can and billet as already included hot extrusion, closed-die forging and electro-chemi-

716 ADVANCED ENGINEERING MATERIALS 2000, 2, No. 11

Appel et al./Recent Progress in the Development of Gamma Titanium Aluminide Alloys

cal milling for the final shaping. The material used in the

REVIEWS
study had a composition Ti±47 Al±3.7 (Nb,Cr,Mn,Si)±0.5 B
(at.-%). Compression test flow curves of the extruded materi-
al were used to determine a suitable processing window for
secondary hot working and to model isothermal closed-die
forging behavior (Fig. 28). Using optimal secondary forging
conditions more than 200 blades were successfully produced
(Fig. 29). After forging a substantial improvement of the mi-
crostructural homogeneity was observed both in the blade
foil and the root when compared to the as-extruded material.
Prior to electro-chemical milling the material was subjected to
a final heat-treatment at the a transus temperature which re-
sulted in a very homogeneous lamellar microstructure with a
mean colony size of 130 lm. The same processing technology
was also successfully applied to alloys which had been signif-
icantly strengthened by applying the methods described in
the previous chapter, i.e., by adding high amounts of Nb and Fig. 29. High-pressure compressor blades for an aeroengine made from a c alloy. The
reducing the Al content as well as by microalloying with car- blades were produced by hot extrusion followed by closed-die forging and electro-chemi-
cal milling.
bon. In conclusion, the production of c-based alloy turbine
components by wrought processing still poses some prob-
lems but appears promising from a technical point of view, in 7. Mechanical Properties of Advanced Alloys
particular with respect to the mechanical properties of ad-
vanced alloys which will be presented in the following. Tensile and fracture mechanical tests were performed on
differently hot extruded and heat treated alloys. Compiled
data for some alloy compositions are listed in Table 3. The
Ti±45 Al±10 Nb alloy shows remarkably high tensile strength
both at room temperature and 700 C. In particular, the tensile
properties of this alloy are impressive if the specific strength
is considered which up to 750 C exceeds that of high-
strength superalloys as well as high-temperature Ti alloys
(Fig. 30). In this respect some c-based alloys including this
Nb containing alloy are now outstanding for applications up
to 700 C. As discussed in Section 5.2 the strength of Nb con-
taining alloys investigated in this article should in particular
be attributed to microstructural refinement as a consequence
of the reduced Al content. Relatively high tensile strength can
also be obtained for an alloy microalloyed with C.

Table 3. Tensile properties (de/dt = 2.1 ´ 10±5 s±1) and fracture toughnesses (loading
rate 0.01 mm/min) of different hot extruded c alloys. For fracture mechanical tests
chevron-notched specimens were used. r0.2: yield strength, rF: fracture strength, eF:
plastic tensile elongation, KQ: fracture toughness, (p) crack propagation parallel and
(o) perpendicular to the extrusion direction, HT: heat treatment.

Fig. 28. Finite volume simulation of isothermal forging of a high-pressure compressor

blade±effective plastic strain: a) 50 % stroke, b) finish forged.

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 Appel et al./Recent Progress in the Development of Gamma Titanium Aluminide Alloys

For the Ti±45 Al±10 Nb alloy with duplex microstructure challenge is to establish these mechanisms without compro-
REVIEWS

an appreciable room temperature ductility has been observed mising other desirable properties. This needs a detailed un-
(Table 3). An even higher room temperature ductility of 2.5 % derstanding of the micromechanisms of deformation and
was determined for a Nb containing alloy with optimized fracture which limit the desired mechanical properties.
composition (see Table 3). The attractive tensile properties of
Nb containing c-based alloys may in part be attributed to the
high twin activity in Nb containing alloys as described ear-
lier. Further, the fracture toughnesses of the Ti±45 Al±10 Nb ±
were found to be similar to those of conventional c-basedal- [1] Y.-W. Kim, D. M Dimiduk, in Structural Intermetallics
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