Microstructural characterisation of Ti–Nb–
(Fe–Cr) alloys obtained by powder metallurgy
A. Amigó*1, J. Zambrano1,2, S. Martinez1 and V. Amigó1
b alloys based on the Ti–Nb alloy
system are of growing interest to the
biomaterial community. The addition of
small amounts of Fe and Cr further
increases b-phase stability, improving
the properties of Ti–Nb alloy. However,
PM materials sintered from elemental
powders are inhomogeneous due to
restricted solid state diffusion and
mechanical alloying provides a route to
enhance mixing and elemental
diffusion. The microstructural
characteristics and bend strength of Ti–
Nb–(Fe–Cr) alloys obtained from
elemental powder mixture and
mechanical alloyed powders are
compared. Mechanical alloying gives
more homogeneous compositions and
particle morphology, characterised by
rounded, significantly enlarged
particles. In the sintered samples a and
b phase are observed. The a phase
appears at the grain boundaries and in
lamellae growing inward from the edge,
and is depleted in Nb. The b phase is
enriched with Nb, Fe and Cr. The
addition of Fe and Cr significantly
increases the mechanical properties of
Ti–Nb alloys, providing increased
ductility.
Titanium alloys are attractive for
biomedical applications due to their
lower modulus, superior
biocompatibility and excellent corrosion
resistance compared with stainless
steels and Co–Cr alloys. Ti6Al4V has
been become the most used implant
materials, but it is known that V and Al
are toxic for the human body.1,2 b
titanium alloys with lower modulus of
elasticity and greater strength have
recently been developed and it has
been reported that Ti–Nb alloys exhibit
complete biocompatibility. The
presence of bcc titanium (b phase) at
1
Institute of Materials Technology (ITM–UPV)
University Polytechnic of Valencia, Spain
2
Center for Materials Research, University of
Carabobo, Venezuela
*Corresponding author, email
anamma@posgrado.upv.es
ß 2014 Institute of Materials, Minerals and Mining
Published by Maney on behalf of the Institute
316 DOI 10.1179/0032589914Z.000000000210
room temperature decreases the
elastic modulus, improving the stress
shielding problem and making these
alloys attractive for implant
applications.3–5
Multicomponent titanium alloys can
be classified as a, azb or b, type
alloys, often via the use of aluminium
and molybdenum equivalent values
(Aleq and Moeq). It has been shown that
tensile strength tends to increase with
increasing Aleq and Moeq, whereas
fracture toughness decreases
gradually.6,7 The addition of small
amounts of Fe and Cr increases b
phase stability, therefore improving the
properties of Ti–Nb alloys. The
molybdenum equivalent for Ti–Nb–Fe–
Cr alloys can be calculated as
½Moeq ~½Nb=3:6z1:25½Crz2:5½Fe
Powder metallurgy has been used as a
low cost manufacturing route for
titanium alloy parts since the 1970s,
owing to its near-net shape capability
and high materials utilisation rate.
However, to date there have been
relatively few reports on the PM
fabrication of Ti–Nb based alloys.8–12
However, PM routes based on
elemental powders have the
disadvantage of producing
inhomogeneous microstructures,
owing to the limited time available for
diffusion during sintering. Mechanical
alloying (MA) has the potential to
produce homogeneous materials from
blended elemental powder. The energy
imparted to the particles in a high-
energy ball mill produces repeated
welding, fracturing, and rewelding.13
Table 1 Molybdenum equivalents and particle size distributions of elementally
blended (EB) and mechanically alloyed (MA) powder samples
Particle size distribution/mm
Alloy Moeq/% d10
Ti15Nb3Cr EB 7.92 9.76
Ti15Nb3Cr MA 7.92 36.53
Ti15Nb1.5Fe1.5Cr EB 9.79 10.99
Ti15Nb1.5Fe1.5Cr MA 9.79 34.50
Ti15Nb3Fe EB 11.67 10.24
Ti15Nb3Fe MA 11.67 30.05
Powder Metallurgy
Powder mixtures can be mechanically
activated to induce chemical reactions
at low temperatures, extending solid
solubility limits, developing amorphous
phases and enabling intimate mixing of
elements. The heavy plastic
deformation introduced into the
particles is manifested as crystal
defects such as dislocations, vacancies
and stacking faults, which greatly
enhances the diffusivity of solute
elements in the matrix. The
temperature rise during milling further
aids diffusion. All these effects
increase the chemical homogeneity
obtained in PM samples during
sintering, as well as increasing
sinterability.
The potential of MA as an initial step
for manufacturing homogeneous Ti–
Nb–Fe–Cr alloys has been investigated
in the present work. Ti–Nb based alloys
obtained by the PM process using
elemental blended powders are
compared with those from
mechanically alloyed Ti, Nb, Fe and Cr
powder mixtures. The molybdenum
equivalent was varied in an attempt to
improve the mechanical properties of
Ti–Nb alloy with a view to its use as a
biomedical material.
Experimental procedure
The nominal compositions of the
powders used were Ti15Nb3Cr,
Ti15Nb1.5Fe1.5Cr and Ti15Nb3Fe (wt-
%). Commercial Ti (99.7%, –325
mesh), Nb (99.8%, –325 mesh) and Cr
(99%, –325 mesh) powders were
supplied by Alfa Aesar and Fe (–230
mesh) powder by Högänas. Elemental
d50 d90
23.21 45.89
79.48 198.44
28.97 172.72
83.53 237.90
24.73 50.83
67.16 175.24
2014 VOL 57 NO 5

1 SEM image of Ti15Nb1.5Fe1.5Cr powder: a elemental blend; b after MA for 45 min; c transverse section of MA agglom-
erate. Particles identified by EDS and SEM
powders were blended (Bioengineering
Inversin) in a closed vial for 20 min. The
compositions were chosen on the basis
of the molybdenum equivalents, as
presented in Table 1. The reported d10,
d50 and d90 values represent particle
diameters for which 10, 50 and
90 mass-% of the powder particles
have a smaller equivalent diameter; a
significant increase of particle size
distribution was observed following MA.
2 SEM images of as-sintered microstructures produced from elemental blends
and mechanical alloyed powders: a Ti15Nb3Cr EB; b Ti15Nb3Cr MA; c Ti15Nb1.
5Fe1.5Cr EB; d Ti15Nb1.5Fe1.5Cr MA; e Ti15Nb3Fe EB; f Ti15Nb3Fe MA
Mechanical alloying was performed
in a model PM 400/2 Retsch planetary
ball mill with chromium steel vial and
balls at a rotation speed of 300 rpm.
The ball to powder weight ratio was
10:1. Each milling batch had a mass of
20 g. To prevent an excessive
temperature rise of the powder, milling
was stopped at 45 min, and the
grinding bowl was allowed to cool for
20 min. To minimise powder oxidation,
Powder Metallurgy
NEWS AND VIEWS
milling was carried out under an argon
atmosphere.
Both EB and MA powders were
compacted in a universal testing
machine (Instron 432, load cell 500 kN)
at a compaction pressure of 600 MPa.
The die was rectangular with
dimensions of 30612 mm; the powder
mass required to obtain a sample height
of 5 mm was about 7 g. All specimens
were sintered under high vacuum (10–4–
10–5 mbar) in a tubular furnace
(Carbolite HVT 15/75/450) at 1280uC.
After a dwell time of 2 h, the samples
were furnace cooled at 10 K min21.
Particle size distribution was
determined on particles suspended in
distilled water using a Mastersizer 2000
laser diffractometer. Transverse
sections of the sintered samples were
prepared for metallographic
examination using an optical
microscope (Nikon LV100). To quantify
phases and internal porosity, NIS-
Elements image analysis software was
used. Backscattered electron images
(BSE) of the microstructure were
obtained in a SEM (Jeol JSM6300).
Energy dispersive spectroscopy (EDS)
was performed using an Oxford
Instruments X-ray detector.
Hardness measurement were
performed on an automatic hardness
tester (Centaur HD-9-45) using a load of
10 kgf. The elastic modulus was
measured ultrasonically using a digital
Echograph (Karl Deutsch). Bend tests
were carried out on a universal testing
machine (Instron 4204, 50 kN load cell)
according to standard EN ISO3325.14
Results and discussion
It can be seen from Fig. 1a and b that
an increase of particle size and
agglomeration of particles to large
aggregates occurred during milling. It
would appear that in the early stages of
milling the force of the impacts
plastically deforms the particles,
2014 VOL 57 NO 5 317
NEWS AND VIEWS
3 Variation of bend strength of Ti15Nb–(Cr,Fe) alloys with molybdenum equivalent
producing work hardening and fracture.
The new surfaces created enable the
particles to weld together leading to an
increase of particle size. As can be
seen in Fig. 1c, the ductile alloying
element particles are flattened to
platelets by a micro-forging process.13
The SEM images in Fig. 2 reveal that
the microstructures of both EB and MA
samples are mainly composed of azb
colonies. The EB material contains very
fine, almost continuous grain boundary
a (GBa) and lamellar a plates, which
grew from the GBa into the adjacent b
matrix (Fig. 2a,c,e). In the MA samples,
a duplex azb microstructure with
lamellae a plates is observed, the
number of plates decreasing with
increasing Moeq (Fig. 2b,d,f).15,16
The EB samples showed less
porosity than MA samples (Table 2),
which can be attributed to the increase
of the particle size distribution
(between 3 or 4 times) of the MA
powders and the increased particle
hardness (lower compressibility) due to
plastic deformation during the MA
process. As a result, neck formation
decreases, and the complete
elimination of pores becomes
difficult.17
Table 2 Internal porosity and phase distribution of elemental blend (EB) and
mechanical alloyed (MA) samples
Alloy Internal porosity/%
EB
Ti15Nb3Cr EB 4.3¡0.2
Ti15Nb1.5Fe1.5Cr EB 3.3¡0.5
Ti15Nb3Fe EB 4.1¡0.4
MA
Ti15Nb3Cr MA 8.0¡0.3
Ti15Nb1.5Fe1.5Cr MA 8.4¡0.4
Ti15Nb3Fe MA 10.8¡1.7
318 Powder Metallurgy 2014 VOL 57
The bend tests showed relatively
high ultimate strengths for the EB
materials, values that are almost
competitive with cast Ti–Nb alloys: Lee
et al.18 reported a bend strength of
1550 MPa for cast Ti15Nb. The
hardening of powder particles during
MA, due to the severe plastic
deformation characteristic of the
process, results in insufficient
densification when using conventional
pressing and sintering. Obviously, the
remanent porosity is the most important
factor influencing the difference of bend
strength observed in Fig. 3. It would be
expected that alternative compaction
processes such as hot isostatic pressing
or spark plasma sintering (SPS),
characterised by superposed
temperature and pressure, will give
better properties. The use of fast
densification processes such as SPS
can improve the mechanical properties
of sintered MA material, but the
reduced element diffusion for EB
materials leads to inferior properties
compared with conventionally pressed
and sintered material.19 A decrease in
the bend strength was observed with
increasing Moeq, reflecting the larger
proportion of b phase.
Phase distribution/%
a b
24.1¡2.5 75.9¡2.5
36.7¡1.5 63.3¡1.5
29.4¡0.5 70.6¡0.5
32.6¡3.9 67.4¡3.9
33.4¡4.8 66.6¡4.8
42.2¡4.5 57.8¡4.5
NO 5
The elastic modulus of cp-Ti is
typically 120 GPa.20 The appearance of
b phase causes a decrease in elastic
modulus, with values of 75–83 GPa
being obtained for the EB materials and
50–59 GPa for the MA materials, as
measured by ultrasonic methods. The
lower values for the MA samples
reflect their higher levels of porosity
(Table 2). Other work has reported
values of 68–50 GPa for cast Ti–Nb–Si
alloys.21
Hardness tests exhibit higher values
for EB (around 370 HV10) than for MA
(around 220 HV10) samples, with the
exception of the Ti15Nb3Fe MA alloy
(322 HV10). The high hardness of this
alloy reflects the distribution of the a
and b phases in the duplex
microstructure obtained following MA
of alloys containing Fe. Hardness
values of 320 HV have been reported
for Ti30Nb(0–7.5)Ta cast alloys.22
Conclusions
In the present study, Ti–Nb–Fe–Cr
alloys produced from mechanically
alloyed powders possessed a higher
level of porosity than elementally
blended powder compacted and
sintered with the same parameter set.
This porosity may be a result of plastic
deformation during MA, which reduced
the compressibility of the
agglomerated powders obtained.
Stabilisation of the a phase as a result
of oxygen uptake during MA may also
affect the properties obtained; this
possibility is worthy of further study.
The sintered EB materials presented
a lamellar microstructure, whereas the
MA materials exhibited a duplex
microstructure. These microstructural
changes and the residual porosity
values are reflected in the bend
strengths and hardness values
obtained.
As expected, the elastic modulus
decreases with increasing porosity. The
molybdenum equivalent of the alloy
influences bend strength but does not
appear to have a significant influence
on the elastic modulus. Nevertheless,
clarification of these observations in a
more systematic study would be
beneficial.
Acknowledgements
This paper is based on a presentation at
Euro PM 2014, organised by EPMA in
Salzburg, Austria on 21–24 September
2014. This work was funded by UPV by
the Staff Training Program for Predoc-
toral Researchers dated 28 February

2014. The Ministry of Science and
Innovation of Spain by project research
MAT2011–28492–C03 and Generalitat
Valenciana by ACOMP / 2014/151.
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