J O U R N A L O F T H E M E C H A N I C A L B E H AV I O R O F B I O M E D I C A L M AT E R I A L S

3 (2010) 565573

available at www.sciencedirect.com

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

Research paper

Mechanical properties of low modulus titanium alloys

designed from the electronic approach
P. Laheurte a, , F. Prima b , A. Eberhardt c , T. Gloriant d , M. Wary e , E. Patoor c
a Universit de Metz, FRE CNRS 3143 Laboratoire dEtude des Textures et Application aux Matriaux, Ile du Saulcy, F57012 Metz cedex,

France
b CHIMIE ParisTech, UMR CNRS 7045 Laboratoire de Physico-Chimie des Surface, 11 rue Pierre et Marie Curie, F-75231 Paris cedex 5, France
c Universit de Metz, FRE CNRS 3236 Laboratoire de Physique et Mcanique des Matriaux, Ile du Saulcy, F57012 Metz cedex, France
d INSA Rennes, UMR CNRS 6226 Sciences Chimiques de Rennes/Equipe Chimie-Mtallurgie, 20 avenue des Buttes de Cosmes CS 70839,
35708 Rennes cedex, France
e Arts et Mtiers ParisTech 4, Rue Augustin Fresnel 57078 Metz cedex, France

A R T I C L E

I N F O

A B S T R A C T

Article history:

Titanium alloys dedicated to biomedical applications may display both clinical and me-

Received 18 March 2010

chanical biocompatibility. Based on nontoxic elements such as Ti, Zr, Nb, Ta, they should

Received in revised form

combine high mechanical resistance with a low elastic modulus close to the bone elas-

30 June 2010

ticity (E = 20 GPa) to significantly improve bone remodelling and osseointegration pro-

Accepted 1 July 2010

cesses. These elastic properties can be reached using both lowering of the intrinsic modulus

Published online 24 July 2010

by specific chemical alloying and superelasticity effects associated with a stress-induced

phase transformation from the BCC metastable beta phase to the orthorhombic 00 marten-

Keywords:

site. It is shown that the stability of the beta phase can be triggered using a chemical

Beta titanium alloys

formulation strategy based on the electronic design method initially developed by Mori-

Low modulus

naga. This method is based on the calculation of two electronic parameters respectively

Superelasticity

called the bond order (Bo ) and the d orbital level (Md ) for each alloy. By this method, two

Stress-induced martensite

titanium alloys with various tantalum contents, Ti29Nb11Ta5Zr and Ti29Nb6Ta5Zr

(wt%) were prepared. In this paper, the effect of the tantalum content on the elastic modulus/yield strength balance has been investigated and discussed regarding the deformation
modes. The martensitic transformation 00 has been observed on Ti29Nb6Ta5Zr in
contrast to Ti29Nb11Ta5Zr highlighting the chemical influence of the Ta element on the
initial beta phase stability. A formulation strategy is discussed regarding the as-mentioned
electronic parameters. Respective influence of cold rolling and flash thermal treatments
(in the isothermal omega phase precipitation domain) on the tensile properties has been
investigated.
c 2010 Elsevier Ltd. All rights reserved.

Corresponding author. Tel.: +33 03 87 31 53 70.

E-mail address: pascal.laheurte@univ-metz.fr (P. Laheurte).

c 2010 Elsevier Ltd. All rights reserved.

1751-6161/$ - see front matter
doi:10.1016/j.jmbbm.2010.07.001

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1.

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Introduction

Metallic implants and osseointegrated prostheses are currently made from CrCo alloys, stainless steels or conventional ( + ) titanium alloys such as TA6V ELI alloy. The
titanium alloys are mainly used in the biomedical field thanks
to their unique combination of mechanical properties and
their superior biocompatibility. However, the potential toxic
effect of some chemical elements such as vanadium or aluminium has been pointed out for a long time. Therefore, this
is a strong driving force for the development of a next generation of alloys with improved compositions with respect to
the general biocompatibility criterion. One of the major keys
for successful applications is connected to the use of materials with reduced modulus since long-term clinical investigations indicate that insufficient load transfer from artificial
implants to adjacent remodelling bone may result in bone
resorption and potential loosening of the prosthetic device.
This effect called stress shielding effect is a direct result
of the stiffness mismatch between implant material and surrounding natural bone (Meunier et al., 1990; Niinomi, 2008).
With respect to this concept called isoelasticity, the beta
titanium alloys display superior properties compared to stainless steels and CoCr alloys with elastic modulus approaching the 6080 GPa range. However, these values are still 3
or 4 times higher than the cortical elastic modulus (20 GPa).
Additional decrease of the apparent elastic modulus can be
achieved from the ability of these metastable titanium alloys to undergo a stress-induced martensitic transformation
during deformation. This transformation, from the parent
phase retained in a metastable state after water quench and
the orthorhombic 00 martensite, results in an extrinsic low
pseudo-modulus that can be modulated through microstructural control.
The ideal material should possess good strength, high fatigue resistance, and a low elastic modulus matching the
bone elasticity. Considerable efforts have been devoted by
materials engineers to enhance the yield strength and to
reduce the modulus. However, for a long time, all these
compositions have been formulated principally by trial and
error methods, with no physical background representing the
optimum choices. Therefore, to reduce the intrinsic modulus of Ti alloys, Morinaga et al. (1988) developed an innovative approach based on electronic design of alloys (called
the d-electron alloy design method). They showed a relationship between some elastic properties of titanium alloys and the value of two electronic parameters respectively
called the average bond order Bo which is a measure of
the covalent bond strength between titanium and alloying
elements and Md , the average d orbital energy level of formulated titanium alloys, correlating with the average electronegativity and the radius of elements. The Bo and Md
values calculated on conventional titanium alloys give a
Bo Md map (Fig. 1), where , + and -type titanium regions are clearly defined (Abdel-Hady et al., 2006; Kurada
et al., 1998). Calculations were made for alloying chemical element, using a cluster based method called DVX (Morinaga
et al., 1988). Based on this formulation strategy and considering only bio-inert alloying elements such as Nb, Ta or Zr, they
finally developed an optimized quaternary beta titanium alloy

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called TNTZ (TitaniumNiobiumTantalumZirconium) with

the nominal composition (wt%) of Ti29Nb13Ta4.6Zr (Niinomi et al., 2007). Improvements were obvious both from the
biocompatibility and from the mechanical point of view since
elastic moduli of around 60 GPa were found. The electronic
design approach allows the comparison of titanium alloys
with very different chemical compositions. The interest of
this electronic approach is undeniable, showing reliable and
consistent experimental results for binary titanium systems
such as TiNb or TiTa (Abdel-Hady et al., 2006; Kurada et al.,
1998). However, we presently think that extension to multielementary alloys actually rises open questions since electronic interactions between alloying elements are not taken
into account into the DVX- model (using a composite approach). As a result, the respective influence of each alloying
element on the mechanical behaviour remains unclear with
regard to multielementary (ternary or quaternary) systems.
On this basis, starting from the well-known TNTZ system
(Ti29Nb13Ta4.6Zr) (referred as TN13TZ in this paper), we
formulated modified TNTZ compositions Ti29Nb11Ta5Zr
(TN11TZ) and Ti29Nb6Ta5Zr (TN6TZ) with various tantalum contents to investigate and compare mechanical
properties such as elastic modulus, yield strength and stressinduced martensitic transformation ability. The results are
discussed in relation to their respective position in the Bo Md
electronic diagram and remaining questions are highlighted.

2.

Experimental methods

Chemical formulation of the titanium alloys were performed

following the Morinaga model based on the cluster DVX
method. Electronic parameters Bo and Md for each alloy were
P
calculated from the following expressions: Md =
Xi (Md )i
P
et Bo =
Xi (Bo )i where Xi is the molar fraction of the i
element and (Md )i , (Bo )i the numerical values of Md and Bo
for each alloying element. The Ti29Nb11Ta5Zr (TN11TZ)
and Ti29Nb6Ta5Zr (TN6TZ) (wt%) alloys were prepared
using cold crucible levitation melting technique (CCLM). The
ingots were subsequently homogenized at 1223 K for 12 h
under inert argon atmosphere and then cold rolled with
controlled reduction in thickness of 1.90 (true deformation).
For thermal treatments, the specimens were encapsulated in
quartz tubes under a partial pressure of high-purity argon.
The specimens were quenched into water by breaking the
quartz tubes. After the solution treatment (1173 K, 2 h), XRD
measurements were conducted at room temperature with Cu
Ka radiation. Tensile tests were carried out at a strain rate of
2.7 103 s1 . The gage length of specimens was 30 mm and
an extensometer was used for all the mechanical testing. For
each tensile cycle, the recovered deformation, the apparent
elastic modulus, the incipient modulus and the critical phase
transformation stresses are measured (Fig. 2). Specimens for
TEM observation were prepared by a conventional twin-jet
polishing technique. TEM observations were conducted using
a JEOL 2000F instrument operated at 200 kV.

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Fig. 1 Evolution of electronic parameters for TN13TZ, TN11TZ and TN6TZ as a function of the tantalum content.

Fig. 2 Stress-induced transformation, recovered

deformation, and different definitions of Young modulus
(Ea : apparent modulus; Ei : incipient modulus).

3.

Results and discussion

3.1.

Chemical formulation from d energy electron method

Ti29Nb11Ta5Zr (TN11TZ) Ti29Nb6Ta5Zr (TN6TZ) have

been designed as modified TNTZ alloys from the initial Niinomi composition Ti29Nb13Ta4.6Zr. Electronic parameters such as Bo (Bond order), Md (d orbitals level of energy)
and e/a (electron to atom ratio) are reported in Table 1 and it
can be seen from the Bo /Md map Fig. 1 that they belong to the
same group of alloys with neighbouring electronic parameters. The Bo /Md map connects directly with the relative chemical stability of the high temperature BCC phase and gives
a sight on the theoretical as-quenched microstructure. From

these data, it is possible to reach information on the subsequent deformation mode and the macroscopic mechanical
properties since stress-induced phase transformation, mechanical twinning or dislocations slip can occur as a function
of the chemical stability of beta phase (Morinaga et al., 1988).
The figurative spots are spread along the tantalum alloying
vector with increasing Bo and e/a values when the tantalum
content is increased (keeping the Md value quite constant).
From a direct reading of the Bo /Md map, different sets of conclusions can be deducted from the relative position of the
TNTZ alloys on the map: (i) with respect to the Ms = RT (room
temperature) dotted line, we are theoretically dealing with
a series of metallic systems with quenched microstructure
displaying coexistence of both and 00 martensite. (ii) the
higher the tantalum content, the lower the Ms temperature,
which is fully consistent with other investigations conducted
by different authors (Buenconsejo et al., 2009; Kim et al., 2006;
Miyazaki et al., 2006; Sakaguchi et al., 2005) (iii) increasing of
the Ta content should result in decreasing the Young modulus of the alloy. Hypothesis supported by the work of Song
et al. (1999) on binary systems but not by the work of Tane
et al. (2008) who showed theoretically that the Young modulus
was decreasing with e/a value for various binary titanium systems. Moreover, some discrepancies arises from microstructural investigations on TN13TZ (Niinomi et al., 2007) in which
no 00 precipitation is observed after water quench. The hypothesis of an existing shift between the theoretical position
of the transformation lines on the Bo Md map (extrapolated from transformation lines of various binary systems)
and the experimental ones on multielementary systems can
be reasonably made. These shifts can result in unexpected
as-quenched microstructures and unpredictable subsequent
mechanical behaviour. However, experimental evidence has
to be produced regarding the behaviour of the two neighbouring compositions we studied here.

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Table 1 Electronic parameters calculated from the

DVX method for TN13ZT, TN11ZT and TN6ZT alloys.
Alloy ref.
TN13TZ
TN11TZ
TN6TZ

Ta Content
(wt%)
13
11
6

Bo

Md

2.878
2.875
2.865

2.464
2.463
2.460

e/a
4.248
4.236
4.209

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with our results since the three different alloys possess e/a
values comprised between about 4.21 and 4.25. From these
values, prediction can be made that the TN6TZ system will
present a Martensite Start temperature very close to room
temperature (just below, actually) with a low mechanical stability of phase upon deformation.

3.3.
Mechanical properties of as-quenched TN6TZ and
TN11TZ alloys

Table 2 EDX compositional analysis.

Alloys
Ti29Nb6Ta5Zr (TN6TZ)
Ti29Nb11Ta5Zr (TN11TZ)

3.2.

Elements wt% (normalised)

Ti
Nb
Ta
Zr
55.70.7
54.90.5

29.50.7
28.40.6

6.10.7
11.30.5

5.10.6
4.90.3

Composition and microstructure

Since the capacity of beta titanium alloys to undergo martensitic transformation is closely connected to chemical composition through Ms variations, EDX compositional analysis has
been performed on the TN11TZ and TN6TZ alloys to check
the chemical homogeneity after a 12 h homogenization treatment of at 1123 K. Average chemical compositions are reported on Table 2.
After solution treatment (1173 K, 2 h), the samples are
water quenched and the microstructures are analysed using
optical microscopy and X-ray diffraction traces. Optical microscopy images are presented on Fig. 3. Optical microscopy
revealed that these microstructures display equiaxed grains
with an average diameter of approximately 50 m. Only
grains were visible on these micrographs with no evidence
of 00 precipitation in the beta matrix. A possible precipitation of nanosized athermal omega phase cannot be detected
with optical microscopy due to the small size of these particles. The absence of 00 precipitation after the water quenching is confirmed by the X-ray diffraction profiles of TN6TZ
and TN11TZ alloys (Fig. 4) in which only diffractions peaks
can be indexed. It can be noticed that the as-quenched structures are single phased with no 00 phase meaning that the Ms
temperature is below room temperature (however, XRD cannot detect a trace amount of phases). Surprisingly, these microstructural results are consistent with the extensive work
of Niinomi et al. (2007) on the TN13TZ system. Therefore, it
suggests that there is probably a discrepancy between the position of the Ms + RT theoretical line and the experimental
transformation lines of multielementary alloys on the Bo Md
electronic map, since this series of quaternary alloys obviously possesses martensite transformations below room temperature. It can be reasonably concluded that the effects of
various beta stabilizers on as-quenched microstructures obtained in binary systems have to be extrapolated to more
complex alloys with a lot of precaution. However, supplementary information can be taken from the electron to atom (e/a)
scale that has been built for titanium alloys. On Fig. 5, the
as-quenched microstructures are reported as a function of
e/a values. We can see that the stability of the beta phase
increases when the e/a ratio rises towards high values. The
stability limit of a fully phased titanium alloy has been calculated to be around 4.20. This can be reasonably connected

Mechanical characterization of the as-quenched alloys has

been performed using tensile tests at room temperature. For
linear elastic materials the tensile Youngs modulus (Ei ) is defined as the slope of linear elastic range before yielding. However, for materials exhibiting nonlinear elastic behaviour, the
above definition no longer applies. Both incipient and apparent Youngs moduli can be adopted to characterize the elastic
behaviour of such materials, as illustrated in Fig. 2. The apparent Young modulus is a good measure of stiffness at large
strains and the incipient Young modulus is a more appropriate quantity to characterize the elastic compatibility with human bone. The superelastic characterization of specimens is
described as two kinds of recovered strains respectively described as SE . (defined as recovered superelastic strain) and
E (pure elastic recovered strain upon unloading).
The tensile stressstrain curves on as-quenched TN6TZ
and T11TZ are presented on Fig. 6 and can be compared with
TN13TZ. The tensile stressstrain curves TN6TZ et TN11TZ
exhibit superelasticity behaviour (noted SE ). Therefore,
both TN6TZ and TN11TZ undergo a stress-induced phase
transformation 00 during the mechanical tests in
contrast to TN13TZ, where no 00 could be detected and which
exhibits a classical elasto-plastic behaviour. The occurrence
of stress-induced 00 precipitation has been confirmed on
X-ray diffraction traces (Fig. 4) made on deformed TN6TZ
samples where small 00 peaks can be detected after
mechanical testing. One can notice that the critical stress
to trigger the martensitic transformation is decreased when
tantalum content is lower: 250 MPa for the TN11TZ alloy
and 170 MPa for TN6TZ with a larger martensitic plateau for
the TN6TZ. These results are fully consistent with the fact
that Ta element induces a decrease of the Martensite Start
temperature (about 30 K/at.%) from Miyazaki et al. (2006) work
independently from the number of alloying elements in the
material. For the TN13TZ, the Ms temperature is apparently
too low below the room temperature. As a consequence,
plastic deformation occurs before the critical stress for
martensitic transformation can be reached. One interesting
feature is the evolution of the incipient modulus a function
of the Ta content. During the first loading cycle, TN11TZ and
TN6TZ both display a linear elastic behaviour corresponding
to the elastic deformation of single phase and the elastic
modulus have been measured to be respectively 50 GPa and
43 Gpa. Comparison with Niinomis work is interesting since
the modulus on TN13TZ has been measured at 60 GPa in
the as-quenched state (Niinomi et al., 2007). This comparison
suggests that, in this series of titanium alloys, Ta element
could contribute to increase the intrinsic modulus. This is not
in accordance with some results on binary TiTa alloys where
Ta is shown to result in Young modulus decrease. Sakaguchi

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Fig. 3 Optical images of as-quenched microstructures after solution treatment (1173 K, 2 h): (a) TN6TZ, (b) TN11TZ.

Fig. 4 X-ray diffraction profiles of TN6TZ and TN11TZ alloy solutions treated at 1173 K for 1.8 ks followed by water
quenching and TN6TZ alloy solution treated at 1173 K for 1.8 ks followed by water quenching and deformed by tensile test
(10%).

Fig. 5 Expected structures of Ti alloys after water quench with respect to electron to atom ratio scale.

et al. (2005) shows the elastic modulus of Ti30NbXTa5Zr

alloys as a function of their Ta content. The lowest elastic
modulus of 67 GPa is observed in 10Ta. The elastic modulus
decreases when the Ta content increases up to 10 mass%, and
it increases when the Ta content increases over 10 mass%.
This suggests as well that additional decrease of the modulus
can be reached on the TNTZ series by minor modifications
of chemical compositions. However, TN13TZ has been
developed to optimize the strength/modulus balance and we
can clearly see that the composition modification has been
detrimental to the ultimate tensile strength (UTS) level of

the as-quenched samples. The UTS value is progressively

decreased from 600 (TN13TZ) to 570 and 400 MPa when Ta
content is lowered. This clearly highlights a possible solution
strengthening effect of the Ta element.
Cyclic loadingunloading during tensile test causes gradual decrease of the incipient modulus and apparent modulus
with increasing tensile strain For example, for the TN11TZ
the incipient modulus at the sixth loading is 30 GPa (Fig. 7);
this is half the incipient modulus obtained during the first
loading. Cyclic loadingunloading causes gradual increase of
the recovery strain and gradual decrease of stress transforma-

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and it is caused by interfacial friction and creation or rearrangement of defects during the martensitic transformation.
The effect of defect generation and rearrangement is high in
the first cycle, and less significant with each additional cycle.

3.4.

Fig. 6 Stressstrain curves of TN6TZ, TN11TZ and

TN13TZ, during tensile tests on the as-quenched specimen.

tion due to the presence of martensite. The solution-treated

(ST + WQ) of TN6TZ revealed recovered elastic deformation
(recov. ) of 1.5% (max) at room temperature owing to a small
transformation stress and a low slip stress. As to TN11TZ,
the recovery strain (2.2% max) and the critical stress for slip
are higher (Fig. 8). The critical transformation stress SIM decrease with increasing the number of dformation cycle. An
internal stress field assisting the martensitic transformation
is formed by the accumulation of dislocations introduced during cyclic loading. TN11TZ SIM for is smaller than that of
TN6TZ. The difference can be explained by lower Ms, below
room temperature. SIM is a measure of energy dissipation

Strategies to improve the strength/modulus balance

We have seen that both the modulus and the tensile strength
were reduced on the modified TNTZ alloys. One of the ideas
arising from this first set of results could be to optimize this
balance: keeping the advantageous low modulus properties
but with increased tensile strength. Several possibilities are
offered by thermomechanical treatments. Improved strength
could be obtained by a prior heavy deformation sequence
(cold rolling treatment) or by prior flash (brief) thermal
treatment at low aging temperature (typically 573 K) to favor
the nucleation of nanostructured isothermal phase that can
potentially act as powerful barriers for dislocations slip.

3.4.1.

Heavy cold rolling

Both types of samples (solution-treated samples) have been

cold rolled with a very high rolling rate of 160%. Microstructural investigations have been carried out using TEM analysis.
The cold rolled microstructure (Fig. 9) has been shown to be
very perturbed with a very high density of dislocations and a
high volume fraction of stress-induced 00 .
Tensile curves of heavily cold rolled TN6 TZ and TN11 TZ
samples are reported on Fig. 10. Pseudoelastic behaviour involving nonlinear elasticity can be clearly seen from these
40.0

55
TN11TZ/ST 900C+WQ

45
40

Apparent modulus (GPa)

incipient modulus (GPa)

50

TN6TZ/ST 900+WQ

35
30
25
20

35.0
TN11TZ-ST 900C+WQ

30.0
TN6TZ-ST 900+WQ

25.0
20.0
15.0

15
0

4
6
Plastic strain (%)

4
6
8
10
Tensile deformation (%)

12

Fig. 7 Evolution of incipient modulus and apparent modulus as a function of cyclic loadingunloading tensile test on the
as-quenched specimen.

220
Critical transformation stress
(MPa)

Recovery strain (%)

2.5
2
1.5
1
TN6TZ/ST 900C+WQ

0.5
TN11TZ/ST 900C+WQ

270
TN6TZ/ST 900C+WQ

170

TN11TZ/ST 900C+WQ

120
70
20

0
0

10

Tensile strain (%)

12

14

Plastic strain (%)

Fig. 8 Dependence of recovery strain and critical transformation stress obtained by cyclic loadingunloading tensile test
on the as-quenched specimen.

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Fig. 9 TN6 TZ after cold rolling treatment (160%)a dark field TEM image and the corresponding selected area diffraction
pattern.

1000
900
800

Stress (MPa)

700
600
500
400
300
200
100
0
0

0.5

1.5

2.5

3.5

4.5

Strain (%)

Fig. 10 Stressstrain curves of TN6 TZ and TN11 TZ alloys as cold rolled.

curves but no additional martensitic transformation apparently occurs. This pseudoelastic behaviour probably originates from the deformation of an initial dual microstructure
+ 00 resulting in 00 variant reorientations and/or interfaces sliding between laths of martensite. In addition, the
deformation defects caused during cold rolling increase the
yield strength of phase, which also enhances the resistance of a martensite transformation. As a result, much more
transforming driving force is needed to induce the martensite phase during tensile processing at room temperature.
The decrease of the apparent modulus with the increase
deformation is in agreement with the evolution observed
by Matsumoto et al. (2007), allotted to the formation of a
(200)00 [010]00 texture of the 00 phase and to the crystallographic anisotropy of the 00 phase. The incipient modulus of
the cold rolled alloy measured from the stressstrain curve is
of 50 GPa (true = 1.60) and 42 GPa (true = 2.60) for TN6TZ
and 65 GPa (true = 1.60) for TN11TZ; the maximum recovered
strain is of 2%.

3.4.2. Flash treatment in the isothermal omega temperature

domain
Metastable Ti alloys are typically known to precipitate additional phases ( and phases) during thermomechanical
treatments. The morphology, size and distribution of these
precipitates determine in large part the mechanical properties of the alloy. It is known that precipitates can be formed

during quenching by a diffusionless martensitic mechanism

(ath ) and during aging by a diffusion controlled process
(iso ). Previous work on the iso precipitation has shown that
nucleation density of phase was depending mainly on the
temperature and growth mechanisms were driven by exodiffusion of beta stabilizer elements and an enrichment of beta
matrix in beta stabilizers. The isothermal omega phase range
of existence is usually situated between 473 and 673 K depending on the chemical stability of the parent phase. The
usual drawback associated with omega precipitation is connected to the coherency strains at the / interface. This can
result in severe embrittlement if the iso volume fraction is
high (Laheurte et al., 2005). The other drawback, in the frame
of this study, is the potential chemical stabilization of the beta
phase during omega growth, that can result in the severe decrease of the Ms temperature and a subsequent suppression
of the superelastic effect. Is has been previously shown that
a flash treatment (short duration treatment) could result in a
dense precipitation of iso particles with a limitation of final
volume fraction of the omega phase (by limitation of growth)
and no subsequent embrittlement (Prima et al., 2000a,b). A
thermal aging of 15 min at 573 K has been carried out on
as-quenched TN6TZ samples. Comparative tensile tests are
reported on Fig. 11. The tensile curves show that the nanoprecipitation of isothermal omega phase results in a large
increase of the tensile strength but with a similar level of superelastic effect and an improved elastic recovery of almost

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600

Stress (MPa)

500
400
300
200

STA573K/15min

100

ST(1173K-1h)+WQ
0

Strain (%)

Fig. 11 Cyclic stressstrain curves of TN6TZ water quenched and subsequently heat treated at 300 C 15 min.

3% of strain. The other interesting feature is the conservation of a very low incipient modulus of about 40 GPa. These
evolutions are due to a combination of effects. The plastic deformation is retarded because of interactions between dislocations and the nanoscaled omega particles dispersed in the
beta matrix. The precipitation of phase affects the distribution of the solute content in phase. The stability of phase
is strengthened because of the slight enrichment of stabilizing elements Nb, Ta, and Zr during the flash heat treatment.
As a result, much more transforming driving force is needed
to induce the martensite phase during tensile processing at
room temperature. A compromise has to be found concerning flash treatment because if the treatment is over timed,
the chemical stabilization of beta phase becomes too high and
the martensitic transformation is suppressed. Additional research is ongoing on the ideal flash treatment (temperature
and time) resulting in the good compromise of low modulus,
improved tensile strength and superelastic effect.

corresponds to the covalent bonding strength between Ti

and an alloying element, since Youngs modulus decreases
with decreasing bonding strength between atoms. Incipient
modulus of Ti at room temperature can be decreased to
about 30 GPa. This value is close to Youngs modulus of
bone. The observed low young modulus is associated with
the feature in the premartensite transformation. The alloys
we studied are deformed at a low stress by stress-induced
martensitic transformation. High strength as well as low
Youngs modulus are needed for the applications.

Acknowledgement
This work was supported by the National Research Agency
(No. ANR-08MAPR-0017)

REFERENCES

4.

Summary and perspectives

Two Ni-free Ti alloys with modified TNTZ compositions

were designed using the d-electron alloy design method
developed by Morinaga et al. and compared with the original
TN13TZ alloys. The following conclusions can be drawn from
this study. From the obtained results it was highlighted
that lowering the Ta content was resulting in an additional
decrease of the intrinsic modulus from 60 GPa for TN13TZ
to 43 for TN6TZ accompanied by a decrease of the ultimate
tensile strength. From the microstructural investigations,
some discrepancy raised between the theoretical position
of the Martensitic Start (Ms) line and the experimental
one, resulting in a relative lack of prediction concerning
as-quenched microstructures. It suggested that extension
of the electronic design approach from binary systems to
multielementary alloys has to be considered with some
precaution. Finally some simple strategies such as heavy
cold rolling or flash thermal treatment have been proposed
to optimize the strength/modulus balance of the developed
alloys. Bo and Md parameters cannot be regarded as sole
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