Processing and Characterizing Titanium Alloys
Mechanical Property Optimization
via Microstructural Control of New
Metastable Beta Titanium Alloys
N. Clment, A. Lenain, and P.J. Jacques
B-titanium alloys are increasingly
used thanks to their high mechanical
properties resulting from a clever choice
of processing parameters. The effects of
heat-treatment conditions on the micro-
structure of two recent B-metastable
titanium alloys are investigated in this
study, along with the resulting mechani-
cal properties.
INTRODUCTION
Titanium, although a trendy indica-
tion of high-tech in consumer products,
remains much less used than other struc-
tural materials due to difculties in the
extractive and forming processes. Only
requirements for outstanding mechani-
cal properties can justify a growing use
of titanium alloys in applications like
the aerospace industry for which the
low density of titanium is denitively
a major advantage. Recent develop-
ment programs such as Boeing 787 or
B alloys. Two fami- It is thus possible to retain the more
Airbus A380 planes conrm this steadily
increasing use of titanium. Besides aero-
space applications, a wider use in the
automotive industry was attempted with
the low-cost Timetal-LCB (Ti-LCB)
alloy, while the medical, chemical, and
B transformation is com- cation advantages is responsible for the
sporting goods sectors account for the
diversication of titanium uses.
50
The required high-level properties
depend on several strengthening mecha-
nisms such as grain size, solid solution
atoms, and precipitation hardening,
which all can be tuned during the various
processing steps, leading to particular
microstructures. A deep understand-
ing of the phase transformations and
microstructural modications occurring
during processing are thus required to
allow the improvement of the mechanical
performances.
BASIC CONCEPTS AND
ALLOY CLASSIFICATION
Pure titanium presents an allotropic
phase transformation at 882C between
the body-centered cubic (bcc) and hex-
agonal-close-packed structures stable at
high and low temperatures, respectively.
The presence of alloying elements alters
the transformation temperature, bringing
about multiphase A
lies of alloying elements called B-stabi-
lizing and A-stabilizing are usually
considered, depending on their ability
to lower or increase the transformation
temperature. The effect of these elements
regarding the A
monly expressed with respect to refer-
ence elements, namely aluminum for the
Figure 1. The classication of some
titanium alloys based on their
Mo eq and Al eq contents. 2 Mo eq =
Mo+2V/3+Nb/3+3(Fe+Cr), Al eq =
Al+Sn/3+Zr/6+10(02+N2+H2).
Overview
B-stabilizing elements and molybdenum
for the A-stabilizing elements.1 In Figure
1, some titanium alloys are classied fol-
lowing their aluminum-equivalent (Aleq)
and molybdenum-equivalent (Moeq) con-
tents, bringing about the families near
A (presenting a dominant A phase and a
lack of heat-treatment response), AB
(with the commonly used Ti-6Al-4V),
and B-metastable, the main topic of
this study.
PHASE TRANSFORMATIONS
IN BETA-METASTABLE
ALLOYS
As can be seen on the schematic phase
diagram of Figure 2, the B-metastable
alloys contain enough B-stabilizing
elements to prevent the B-phase decom-
position into Aa or Aaa martensite upon
quenching (i.e., the metastable tempera-
ture is lowered below room temperature).
ductile bcc phase in a metastable state
for easy processing before developing a
high-strength, closer-to-equilibrium AB
microstructure by subsequent aging. This
combination of performance and fabri-
growing use of B-metastable alloys in a
market still dominated by the common
Ti-6Al-4V.
The B m AB Phase
Transformation
Depending on the level of Moeq, aging
at a given temperature after quenching
from the B phase eld will lead to various
amounts of A precipitation. At relatively
high temperatures, A precipitates nucle-
ate heterogeneously at grain boundaries
and other defects such as recovered
subgrain boundaries or dislocation cells,3
while a more homogeneous distribution
of nuclei results from a lower-tem-
perature aging. In this latter case, the
JOM January 2007

Figure 2. A schematic pseudo-binary cut
of multielement titanium alloys.
precipitates are usually plate-shaped,
with marked growth orientation prefer-
ences, bringing about basket-weave-type
microstructures. Crystallographic orien-
tation relationships of different kinds4 are
observed between the A precipitates and
the B matrix, and a transformation path-
way by lattice shearing and short-range
atomic movement has been reported for
the description of the transformation.5
The B-to-A transformation could thus
be considered as a displacive transfor-
mation, bearing in mind that a chemical
composition change occurs with the
long-range migration of intersititial and
substitutional atoms, as in classical dif-
fusive transformations.
The W phase
Decomposition of the metastable B
phase usually leads to a lower-energy
AB mixture. However, at low tempera-
tures this decomposition becomes slug-
gish, and other, metastable by-products
can form. Depending on the degree
of stabilization of the parent B phase,
these phases are either a non-compact
hexagonal or a trigonal phase called
W, or a solute-lean bcc phase called
Ba.1,6 The W phase can form unavoid-
ably by a displacive mechanism on
quenching (athermal W). Furthermore,
the W precipitation can also be thermally
activated with a certain amount of diffu-
sion of atoms toward the B matrix taking
place after an initial shearing step.6 This
isothermal W is thought to be responsible
for a severe embrittlement.7
TWO REPRESENTATIVE
ALLOYS
This study deals with two B-meta-
stable alloys, Ti-LCB and Ti-5553. Their
chemical compositions are given in
2007 January JOM
Table I. Nominal Compositions and B-Transus Temperatures of the Ti-5553 and Ti-LCB
Alloys (in weight percent)
Ti Al Mo V Cr Fe TB(C)
Ti-5553 Bal. 5 5 5 3 0.3 870
Ti-LCB Bal. 1.5 6.8 4.5 810
Table I. Ti-LCB, developed by Timet in ing plates about 20 m long and 0.5 m
the 1990s, responded to high titanium to 1 m thick. At 500C, the B matrix is
alloy costs by using as the major alloying completely transformed into an entangle-
element the inexpensive Fe-Mo com- ment of residual B and ne A precipitates
pound widely used in the steel industry. homogeneously nucleated within the
The more recent Ti-5553 alloy was whole grains.
designed based on the older Russian alloy The transmission-electron microscope
VT22 to primarily fulll high-strength (TEM) micrograph of Figure 4 shows that
forging applications. A lower-strength extreme renement of the A precipitation
state with improved toughness and occurs for aging below 400C. These
damage tolerance is under consideration A precipitates present an elongated
for other parts of aircraft structure.2
As represented in Figure 1, the amount
of B-stabilizer elements in the two alloys
is different, even though their respec-
tive metastable temperatures are below
room temperature. They are both more
B-stabilized than several aerospace alloys
in use, such as Ti-17 or B-CEZ. Further-
more, both are age-hardenable since the
fully B structure that can be retained on
quenching will decompose into an AB
mixture during aging. The volume frac-
tion, location, and morphology of the a 50 Mm
decomposition products strongly inu-
ence the alloys mechanical properties.
Morphologies of the A
Precipitates
The scanning-electron micrographs in
Figure 3 present typical microstructures
obtained when aging the Ti-5553 alloy
for 3.6 ks at 800C, 700C, or 500C,
respectively, after homogenization
above the B transus. By changing the
aging temperature, both the amount and b 50 Mm
morphology of the A phase are modied.
At 800C (i.e., 70C below the transus
temperature), the nucleation is scarce and
the precipitates remain quite equiaxed.
Several pairs of precipitates growing
side-by-side suggest some degree of
cooperative nucleation of these A precipi-
tates. At 700C, prior B grain boundaries
are almost completely covered by an A
film (Figure 3mowensbyko b)
with many parallel plates growing toward c 5 Mm
the grain interior. Their size is limited
Figure 3. Scanning-electron micrographs
and they do not form the large colonies of solution-treated and aged Ti-5553 alloy
encountered in common AB titanium for 3.6 ks at different aging temperatures:
alloys. Intragranular precipitates are (a) 800C, (b) 700C, and (c) 500C.
also present within the B matrix, form-
51

Figure 4. A dark-eld (DF) TEM micrograph
of the Ti-5553 alloy solution treated
and aged at 300C (zone axis [113]B ,
showing the nanoscale A phase. Insert:
the corresponding SAD pattern with the
A spot selected for DF.
needle-like morphology oriented in two
directions almost perpendicular to each
other.
By combining two aging temperatures,
a bimodal A grain size can be generated,
bringing about a synergetic effect on the
mechanical properties. Figure 5 presents
such a bimodal A precipitation with large
primary A precipitates in a transformed
B matrix hardened by ne secondary
A platelets. The slight differences of
B
primary A grain size, distribution, and
secondary A platelet lengths are related
to small changes in the processing param-
eters (e.g., forging or aging temperatures)
relative to the B-transus temperature.
In addition to the needle-like mor-
phology, the A precipitates present a
strong tendency to form continuous
lms along grain or subgrain boundaries,
with a detrimental effect on mechanical
properties. The dotted line on Figure 5a
corresponds to a primary B grain bound-
ary; A precipitates are connected to each
other along this boundary. Preventing
the occurrence of such lms is a major
concern for the titanium metallurgist.
This can be achieved by forging in the
AB eld, by avoiding too-slow cooling
rates, or by cold working before aging.
Once a precipitation without A-lm
is obtained, solutionizing treatment
above the B-transus temperature has
to be avoided to keep the disconnected
primary A globules.
W Precipitation
The Ti-5553 and Ti-LCB alloys both
form an athermal W phase on quench-
ing, but to very different extents. The
52
selected-area diffraction (SAD) patterns
shown on Figure 6b present clearly
identied W reections for the Ti-LCB
sample, where only faint streaks are
visible for the Ti-5553 alloy (Figure 6a).
This suggests that the formation of the W
phase is more extended for the Ti-LCB
alloy. The stability of the B phase with
respect to the W precipitation cannot be
explained through the concept of Moeq.
Indeed, the effect of alloying elements
on the BmW transformation is different
from the BmA transformation. Many
binary alloys like Ti-Mo,8 Ti-Mn,9
or Ti-V10 with similar heat-treatment
conditions present much stronger W
reections. The same is observed for
other multicomponent alloys without
aluminum.11 Indeed, it has been shown
previously12 that aluminum can delay
or even suppress the W precipitation in
titanium alloys. Aluminum thus seems
to play an opposite role in the BmA and
BmW transformations.
MICROSTRUCTURE
MECHANICAL PROPERTY
RELATIONSHIPS
As already stated in the introduction,
the state of the microstructure of the A
alloys strongly inuences the mechanical
properties. Figure 7 presents the micro-
a 10 Mm
b 10 Mm
Figure 5. Scanning-electron micrographs
of bimodal microstructures resulting from
two-step heat treatments on the (a) Ti-5553
and (b) Ti-LCB alloys.
hardness of the Ti-5553 alloy after aging
at different temperatures. Starting from
the as-quenched B state, the hardness
rst increases, presents a maximum for
the aging treatment conducted at 400C,
and then decreases. This evolution can
be directly related to the state of the A
precipitates illustrated in Figure 3. The
coarser and scarcer A plates, resulting
from heat treatments above 700C, have
a relatively poor hardening efciency.
Renement of the precipitates coincides
with the hardness increase. The drop
below 400C results from the lack of
thermal activation to allow a complete
precipitation of the A phase in the consid-
ered time scale. This result is in contrast
with previous studies13 on W-forming
alloys where a strong hardening occurs
in this low aging temperature range.
Figure 8 summarizes the uniaxial
tensile properties of the Ti-5553 alloy
aged at different temperatures between
300C and 800C. The high strength of
the Ti-5553 is conrmed by these tensile
tests. However, ductility becomes an
issue for the lowest aging temperatures
for which the hardest samples exhibit a
totally brittle behavior. A maximum ten-
Figure 6. The SAD patterns of (a) Ti-5553
and (b) Ti-LCB alloys in the solution-
treated and quenched condition and in
the [110]B zone axis. The W reections are
much more marked for the Ti-LCB.
JOM January 2007
 6.5
6

5.5


H (GPa)
5 Bimodal
4.5
that the lack of ductility due to the ne


4 secondary A could be minimized thanks
3.5 As Quenched




3
0 200 400 600
Aging Temperature (C)
Figure 7.The microhardness of the Ti-5553
alloy aged at different aging temperatures.
The as-quenched and bimodal A grain
states are also represented.
1,600

a strength of 1,320 MPa, identical to

1,400
 10


Strength (MPa)
Bimodal  

1,200
 ACKNOWLEDGEMENTS
1,000

 Bimodal 4
 800  2




0 tive impact on ductility. Nevertheless,
600
400 200
600 800 1,000
Aging Temperature (C)
Figure 8. The tensile properties of the Ti-
5553 alloy as a function of the aging
temperature (circles are for strength, hollow
triangles for elongation to fracture). The
dotted curve corresponds to the evolution
when brittle fracture occurs.
sile strength of ~1,500 MPa is reached for
the sample aged at 500C. The strength
then continuously decreases for higher
aging temperatures. For the samples
aged below 500C, fracture occurred in
the elastic range. The highest strength
expected from microhardness cannot be
reached, due to the embrittlement of the
alloy aged at lower temperatures.
It is generally agreed that the aged W
phase (isothermal W) is responsible for
a severe embrittlement. The proposed
mechanism is an intense slip which leads
to a local failure along the slip band. It
has been shown14 that the W density is
reduced within the slip bands, suggest-
ing that shearing of the precipitates
accounts for the strain localization. This
mechanism would lead to rapid fracture
in tensile loading, but it would give an
easier plastic deformation in compres-
sion since slip planes without precipitates
are created. Comparing Figures 7 and 8
shows that a similar reasoning could be
considered in the case of a nanometric
A phase appearing for low-temperature
aging treatments (i.e., aged at 300C,
see Figure 4) that presents a brittle
tensile fracture and a lower hardness.
However, since cracking occurs before
macroscopic yielding, the exact fracture
2007 January JOM
mechanism remains unclear.
Bimodal microstructures are reported
as a means to recover some ductility in
aged B alloys. Indeed, it was shown1,15

to larger A grains while maintaining a
800 relatively high strength. However, the
results presented in Figure 8 do not show
that the bimodal microstructure pres-
ents signicantly better properties than
single-aging-step specimens. Indeed, the
bimodal microstructure sample presents
12
Elongation at Fracture (%)
the specimen aged at 600C. However,
8
the fracture strain is much smaller for
6 this bimodal microstructure sample.
Other studies16 showed that increasing
the amount of primary A has a nega-
bimodal microstructures are often pre-
ferred since they present smaller B grain
sizes that result from a processing route
below the B transus temperature.1
CONCLUSIONS
B-titanium alloys show great promise
in structurally demanding applications
where their benecial properties out-
weigh their high cost. Microstructural
control allows the tailoring of these
mechanical properties. Indeed, these
alloys present a range of microstructures
resulting from variations of the process-
ing parameters, leading to different levels
of strength and ductility.
Among them, the Ti-5553 and Ti-LCB
alloys present a great variety of micro-
structures bringing about highly desir-
able properties. Though relatively heav-
ily alloyed, they maintain a rather low
density offering a unique combination of
specic properties. The stability of the
bcc B phase at room temperature allows
cold working and further aging to form
precipitates whose size and morpholo-
gies span several orders of magnitude.
The numerous phase transformations
that can take place in B alloys are both
a strength and a weakness. They offer
extra freedom to the scientist or engineer,
but a lack of knowledge or control can
bring about microstructural instabilities
that are deleterious to the improvement
of the mechanical properties.
Strengthening mechanisms in B-meta-
stable alloys rely mainly on the A phase
precipitation. While the A precipitation
can provide high strength, the price to
pay in terms of ductility is often too
high. More complex processing routes
combining mechanical and thermal acti-
vations are thus needed to enhance the
strength-ductility balance. More work is
needed to describe accurately the phys-
ics of the onset of plastic deformation
within these samples. Critical informa-
tion about the fracture mechanisms will
be learned by the characterization of the
damaged zones in deformed specimens.
In particular, the TEM characterization
of strained specimens will show the
effect of dislocation glide on the very
ne precipitates population.
P.J. Jacques acknowledges the
National Fund for Scientic Research
in Belgium. The work of N. Clement was
supported by the Walloon Region through
the Winnomat Programme. The authors
would like to thank TIMET-Savoie for
providing the material and Techspace
Aero.
References
1. Gerd Ltjering and James C. Williams, Titanium
(Berlin, Germany: Springer-Verlag Berlin Heidelberg,
2003).
2. S.L. Nyakana, J.C. Fanning, and R.R. Boyer,
JMEPEG, 14 (2005), pp. 799811.
3. N. Clement et al., Proc. Int. Conf. Solid-Solid Phase
Transformations in Inorganic Materials 2005, ed.
J.M. Howe et al. (Warrendale, PA: TMS, 2005), pp.
603608.
4. P.M. Kelly and M.-X. Zhang, Metall. Mater. Trans. A,
37A (2006), pp. 833839.
5. W.G. Burgers, Physica, 1 (1934), pp. 561586.
6. S. Sikka, Y. Vohra, and R. Chidambaram, Prog.
Mater. Sci., 27 (1982), pp. 245310.
7. J. Williams, B. Hickman, and D. Leslie, Metall. Trans.,
2 (1971), pp. 477484.
8. S. Banerjee and U. Naik, Acta Mater., 44 (1996), pp.
36673677.
9. D. Doraiswamy and S. Ankem, Acta Mater., 51
(2003), pp. 16071619.
10. A. Jaworski and S. Ankem, Rev. Adv. Mater. Sci., 10
(2005), pp. 1120.
11. S. Nag, R. Banerjee, and H. Fraser, Mate. Sci.
Engr., 25 (2005), pp. 357362.
12. E. Harmon and A. Troiano, Trans. ASM, 53 (1961)
pp. 4353.
13. A. Gysler, G. Ltgering, and V. Gerold, Acta Metall.,
22 (1974), pp. 901909.
14. E. Levine, S. Hayden, and H. Margolin, Acta Metall.,
22 (1974), pp. 14431448
15. G. Terlinde, H.-J Rathjen, and K.-H. Schwalbe,
Metall.Trans. A, 19A (1988), pp. 10371049
16. J.C. Fanning, JMEPEG, 14 (2005), pp. 788791.
N. Clment, A. Lenain, and P.J. Jacques are with
Universit Catholique de Louvain, Dpartement
des sciences des matriaux et des procds, IMAP,
Place Sainte Barbe 2, B-1348 Louvain-la-Neuve,
Belgium. A. Lenain is also with Techspace Aero,
Herstal, Belgium. For more information contact
P.J. Jacques (32) 10-47-24-32; fax (32) 10-47-40-28;
e-mail Jacques@imap.ucl.ac.be.
53