Materials Characterization 172 (2021) 110855

Contents lists available at ScienceDirect

Materials Characterization
journal homepage: www.elsevier.com/locate/matchar

Microstructure globularization of high oxygen concentration dual-phase

extruded Ti alloys via powder metallurgy route
Abdollah Bahador a, *, Junko Umeda a, Hamidreza Ghandvar b, Tuty Asma Abu Bakar b,
Ridvan Yamanoglu c, Ammarueda Issariyapat a, Katsuyoshi Kondoh a
a
JWRI, Osaka University, 11-1 Mihogaoka, Osaka, Ibaraki 567-0047, Japan
b
Faculty of Mechanical Engineering, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia
c
Kocaeli University, Engineering Faculty, Metallurgical and Materials Engineering Department, Kocaeli, Turkey

A R T I C L E I N F O A B S T R A C T

Keywords: Research related to the substitution of ubiquitous elements for high-cost rare elements during the fabrication of
Microstructure characterization high-performance Ti alloys has attracted significant attention. The microstructure evolution is, however, chal­
α+β titanium lenging when several elements with different properties are used. This research aims to study the effect of Si
Dynamic globularization
addition on the microstructure formation of the dual-phase Ti alloys in the presence of solid solution-forming
Hot extrusion
elements such as Fe and Cu, and a high oxygen concentration. Ti–4Fe–0.5O–3Cu (TFOC) alloys with different
Powder metallurgy
Si contents (0.2, 0.4, and 0.6 wt%) were fabricated from the elemental powders using spark plasma sintering,
followed by hot extrusion. The TFOC sintered alloys with 0.2 and 0.4% Si showed very similar microstructures in
the lamellae α+β dual-phase. The coarsening of α colonies and primary β grains was remarkable when Si content
increased to 0.6%. The obtained primary β grains were, however, significantly smaller than those in previous
studies. In contrast, the refined globular α grains (respective grain sizes = 2.6 and 2.2 μm) embedded in the β
matrix were observed in the hot extruded TFOC–0.2Si and TFOC–0.4Si alloys due to dynamic globularization.
Additionally, EBSD analysis clarified that the hot extruded alloys had the strong fiber textures of (1010) and
(101) for α and β phases respectively, which were consistent with the XRD results. High-resolution TEM ex­
amination demonstrated that Ti2Cu and Ti3Cu intermetallics of a length of 100–400 nm could form preferentially
at α/β interfaces. The experimental results showed that 0.4 wt% Si added to TFOC alloys formed fine globular
microstructures in the presence of hot plastic deformation.

1. Introduction
The α+β titanium alloys form a wide range of high-performance al­
loys that are used for different applications, i.e., biomedical and aero­
space industries, due to their high specific strength and excellent
corrosion resistance [1,2]. Utilization of β-stabilizing isomorphous re­
fractory elements (Nb, Ta, and Mo) is well established in the processing
of Ti alloys [3–5]. However, due to the comparatively high cost and high
melting point of this group of alloying elements, ubiquitous elements
(Fe, O, Cu and Si) have gained preference for the fabrication of cost-
effective dual phase titanium alloys [6,7]. Fe is known as an effective
and inexpensive β stabilizer. It was reported that the stabilizing effect of
1 mass% Fe is equivalent to that of 2.9 mass% Mo [5]. Oxygen with high
solubility (34 at.%) in α-Ti is a well-known element which is used for
strengthening of Ti alloys via interestitial solid solution strengthening
[8]. Zhang et al. [9] showed that Cu improves the antibacterial prop­
erties of Ti alloys, and enhances the strength significantly when Ti2Cu
precipitate is formed. Si is added to Ti alloys to increase their creep
resistance [10]. However, it is necessary to optimize the content of Si
and Cu additions, particularly when they are added along with other
alloying elements, to avoid the impairment of ductility due to their
higher contents. Using first-principle calculations, Li et al. [11] claimed
that the number of d electrons of transition metals has a significant effect
on attraction or repulsion of Si atoms. Beside, Fe, Cu, and Si are eutec­
toid elements and have limited solubility in the α-Ti, thus, triggering the
formation of intermetallic compounds [12]. The solubilities of these
elements in α-Ti are as follows; Fe: maximum 0.5 wt% [13], Cu: less than
1 wt% [14], and Si: Very low solubility of the order of about 1 wt% and
5 wt% in α and β, respectively.
Generally, thermomechanical treatment strongly influences the

* Corresponding author.
E-mail address: abdollah@jwri.osaka-u.ac.jp (A. Bahador).

https://doi.org/10.1016/j.matchar.2020.110855
Received 23 June 2020; Received in revised form 19 October 2020; Accepted 24 December 2020
Available online 26 December 2020
1044-5803/© 2020 Elsevier Inc. All rights reserved.
A. Bahador et al.
microstructure of α+β titanium alloys, whereby different grain mor­
phologies, size, and phase fractions can be obtained. Fine lamellar
morphology is seen when the Ti alloy is deformed in the β phase
following by slow cooling. On the contrary, when a Ti alloy is deformed
in the α+β phase, the microstructure consists of equiaxed morphology
[15]. The lamellar microstructure is characterized by relatively low
tensile ductility, moderate fatigue properties, and good creep and crack
growth resistance. The equiaxed (globular) microstructure has a better
balance of high strength and ductility at room temperature, as well as
fatigue properties, which noticeably depend on the crystallographic
texture of the hcp α phase [16]. For instance, the yield strength of the
well-known alloy Ti–6Al–4V is improved to 1030 MPa when the
microstructure is comprised of fine globular α + β [17].
Therefore, understanding the effect of hot deformation on the
microstructure control and phase fractions is very crucial as it de­
termines the mechanical properties. In this study, as a state-of-art
approach, spark plasma sintering (SPS) was employed to produce
Ti–Fe–O–Cu–xSi (x = 0.2, 0.4, and 0.6 wt%). SPS facilitates the fabri­
cation of highly dense powder metallurgy components with grain
growth control in a short time [18,19]. The sintered alloys were then
subjected to hot deformation in the α+β phase to obtain the equiaxed
α+β microstructure. The resultant microstructures are discussed in the
context of sintering and hot deformation to understand the effect of Si
addition in the presence of other α and β stabilizer elements.
2. Materials and method
Three Ti–4Fe–0.5O–3Cu–xSi (x = 0.2, 0.4, and 0.6 wt%) blends were
prepared using conventional mechanical milling with ZrO2 balls and a
ball to powder ratio of 1:5. The average particle sizes of starting powders
were as follows; Ti: 45 μm, Fe: 5 μm, Cu: 45 μm, Si: 5 μm, and TiO2: 0.5
μm (TiO2 was used to add oxygen in the specimens). SPS was employed
to consolidate the mixed powders using the following parameters:
heating rate of 20 ◦ C/min, sintering temperature of 1000 ◦ C held for 60
min under 30 MPa uniaxial pressure. The sintered specimens were
subjected to hot extrusion by pre-heating at 850 ◦ C for 5 min using an
extrusion speed and as extrusion ratio of 6 mm/min and ~18, respec­
tively. All the sintered specimens except TFOC–0.6Si were successfully
extruded, the reasons for which have been explained in the later sec­
tions. The oxygen, nitrogen, and hydrogen contents were measured in all
steps of fabrication for the starting and mixed powders, as well as sin­
tered and hot extruded specimens using an Oxygen–Nitrogen–Hydrogen
analyzer (EMGA-830, HORIBA).
The produced specimens were examined using X-ray diffraction
(XRD, SHIMADZU, XRD-1600) to identify their constituent phases with
Cu-Kα radiation and a scanning speed of 2 deg./min. The electron
backscatter diffraction (EBSD) technique was employed to study the
crystallographic orientation, phase fraction, and average grain size. For
EBSD observations, the sintered and hot extruded specimens were
conventionally ground with 400 and 1000 grit sandpaper and polished
using an 0.05-μm alumina particle solution, followed by vibratory pol­
ishing (VibroMet® 2, Buehler) for approximately 8 h in a colloidal silica
polishing suspension. The EBSD system included a camera (TSL Digi­
View IV, EDAX) attached to a field emission scanning microscope
(FESEM, JSM-6500F, JEOL). A transmission electron microscope (HR-
TEM, JEM-2100F, JEOL) operating at 200 kV was employed for high-
resolution microstructural observations and scanning transmission
electron microscope (STEM) imaging. The TEM samples were prepared
using a focused ion beam (MultiBeam FIB system, JIB-4500) incorpo­
rated in a scanning electron microscope (SEM) operated at 30 kV.
Microhardness was measured using a Shimadzu (HMV-G) tester by
applying a 980.7 mN force for a 10 s dwell time. To verify the accuracy
of the results, 25 points in a rectangular pattern were measured for each
specimen and the average value was considered.
2
Materials Characterization 172 (2021) 110855
3. Results and discussion
3.1. Oxygen–Nitrogen–Hydrogen measurement
The mixed powders successfully consolidated to an almost fully
dense state and the SPS alloys showed a density of about 4.7 g/cm3
measured by the Archimedes’ principle. Fig. 1 shows the oxygen­
–nitrogen–hydrogen content during the fabrication steps. It was found
that pure Ti as a metal matrix consisted of ~0.29 wt% oxygen, while Fe
and Si contained higher amounts of ~0.34 wt% and ~0.6 wt%,
respectively. Cu showed the least oxygen content of about 0.05 wt%.
Nitrogen and hydrogen contents were lower than 0.03 wt% in all the
initial powders, except in Fe which contained 1.1 wt% (Fig. 1a).
Nevertheless, the volume fractions of these additive elements are
limited, and as illustrated in Fig. 1(b–d), nitrogen and hydrogen
amounts were almost constant after mixing, sintering, and hot extrusion
(nitrogen: ~0.55 wt%). The oxygen content increased to 0.49 wt% in
0.2Si SPS and 0.4Si SPS, and further to 0.51 wt% in 0.6Si SPS specimen.
The oxygen content did not change after the hot extrusion of 0.2Si SPS
and 0.4Si SPS, while 0.6Si SPS specimen presented a considerably high
oxygen content (0.61 wt%). This high amount of oxygen and Si solutes
may have affected the hot extrusion in HExt.TFOC-0.6Si alloy.
3.2. Microstructure characterization
The XRD pattern shown in Fig. 2 reveals the microstructure and
existing phases in the sintered and hot extruded specimens. In the full
spectra, it is easy to distinguish the high-intensity peaks emitted from
(100)α and (110)β in HExt.TFOC-0.2Si and HExt.TFOC-0.4Si specimens.
This is evidence of a strong texture evolution in a direction parallel to
hot extrusion at lower Si contents. High magnified peaks clearly show
the decline in the intensity of α and β phases after hot extrusion at (200)
and (211), and (110), (103), and (112), respectively. Additionally, the
presence of Ti2Cu and Ti3Cu are evidenced by a diffraction peak indi­
cating (110) and (411) in both sintered and hot extruded specimens
containing 0.2Si and 0.4Si, whereas it is not clear when the Si increased
to 0.6 wt%.
Fig. 3 displays the EBSD imaging of sintered specimens including α
and β phases separately. The sintered samples included colonies of α
lathes developed inside as well as along the grain boundaries of primary
β grains. This is a typical microstructure for dual-phase titanium alloys
[20]. It is well established that the colony size of α and the primary β
grain size are two main factors in determining mechanical properties of
lamellar α+β phase [21]. Primary β grain boundaries act as nucleation
sites for α phase and directly contribute to both α colony and lath size
[22]. Lütjering [23] has shown that the larger the colony size of α, the
weaker the slip barrier along the primary β grain boundaries, resulting in
low strength and ductility. Therefore, the EBSD mapping of α and β
phase was investigated in terms of phase fractions, lath thickness, and
colony of α phase, and the grain size of primary β phase. The α and β
phase fractions were almost similar in TFOC–0.2Si and TFOC–0.4Si with
a slightly higher amount of α phase (54 and 55 vol%, respectively).
However, the α phase fraction in TFOC–0.6Si remarkably increased up
to about 73 vol% (Fig. 3). Interestingly, this increment was almost
consistent with the α lath thickness and the colony size of α. The α lath
thickness marginally diminished from 2.7 μm in TFOC–0.2Si to 2.5 μm in
TFOC–0.4Si, and then increased to 3.8 μm in TFOC–0.6Si (Fig. 4a).
However, the colony size of α increased significantly to 46 μm in the
high Si content specimen, compared to only 25 μm in TFOC–0.2Si and
28 μm in TFOC–0.4Si (Fig. 4b). The average grain size of primary β in the
sintered specimens was measured using the intercept method (according
to ASTM E112) and 63 μm, 60 μm, and 65 μm was revealed with respect
to increasing Si content. Notably, the grain size of the primary β phase
was considerably lower than that in the previous studies [24–26] as
shown in Fig. 5. This is associated with the efficient solute drag effect of
multiple alloying elements which lowers primary β grain boundary
A. Bahador et al. Materials Characterization 172 (2021) 110855

Fig. 1. Oxygen–nitrogen–hydrogen contents measured during the various steps of the process such as (a) initial powders, (b) after milling (MP: mixed powders), (c)
sintered specimens, and (d) hot extruded rods.

Fig. 2. XRD spectra of sintered (SPS) and hot (HExt) extruded alloys.

mobility and impedes of the grain growth [27].

fg = 1 − exp[ − k.(ε − εc )n ] (1)
Fig. 6 presents the significant influence of hot extrusion at (α+β)
phase region on the microstructure of HExt.TFOC–0.2Si and HExt.
where fg is the volume fraction of dynamic globularization α, εc is the
TFOC–0.4Si composites. It is clearly shown that α lathes have been
critical strain for initiation of dynamic globularization, n is the Avrami-
changed to a globular morphology, and dispersed in the β-phase matrix
exponent, and k is the kinetic constant ad temperature-dependent factor.
due to dynamic globularization. The kinetics of dynamic globularization
However, in the current work, we consider the complete globulari­
has been explained by Song et al. [28] for TC11 dual phase titanium. It
zation of α phase based on the microstructure observations (only limited
has been explained that the deformation temperature and the strain rate
amount of α lathes can be seen in the HExt.TFOC–0.2Si). An average
are critical parameters whereby globularization fraction and globulari­
grain size of 2.6 μm and 2.2 μm was calculated for HExt.TFOC–0.2Si and
zation size can be controlled. The globularization fraction increases with
HExt.TFOC–0.4Si, respectively, using OIM analysis. On the contrary,
strain in a sigmoid way, and it follows the Avrami type equation [29]:

3
A. Bahador et al. Materials Characterization 172 (2021) 110855

attributed to the incomplete hot extrusion.

The separated α and β phase images show almost identical amounts
of α (0.58 vol%) and β (0.42 vol%) phases in all the produced alloys. It is
also evident that grains are oriented dominantly toward <1010> and
〈101〉 in α and β phases, respectively. It implies the formation of a strong
texture and suggests that these directions are parallel to the hot extru­
sion direction. This strong texture formation in lower Si content speci­
mens was in good agreement with the XRD results. In order to further
study the developed textures, pole figures. (PF) and pole plots of HExt.
TFOC–0.4Si was extracted from OIM analysis (Fig. 7). The (1010) PF of α
phase shows a strong intensity in the center of the map along with a
strong ring around. This ring is normally formed due to the crystal
symmetry (Fig. 7a). The PF can be compared to the pole plot, as shown
in Fig. 7b. The large peak at 0 angular distance is due to a strong
alignment of the <1010> crystal directions with the sample normal. The
smaller peak at 60 angular distance is due to ax-symmetrical variants of
<1010> directions. At a first glance, an asymmetric texture at the (101)
PF of β phase is understandable (Fig. 7c). However, this is probably an
indication of an annular texture and it can occur when two sides of the
sample are not parallel. With this consideration, when we smooth and
shift the pole plot, two smaller peaks move to 60 and 90 angular dis­
tances which comply with the standard peaks of (101) fiber texture
(Fig. 7d).
Fig. 8 shows the schematic illustration of microstructure change
supported by FESEM micrograph to understand the mechanism of
globularization. In the initial steps (I, II) acicular α is enlarged by pre-
heating of sintered specimen to α+β region. When the extrusion is
applied α colonies and β grains are slowly oriented with respect to the
applied stress. This process occurs with shearing and kinking of the α
colonies which is governed by the magnitude of the local deformation.
In the next step (III), dislocations of both signs are preferentially
generated along the shear line at the kinking zones. It is followed by
annihilation of opposite sign dislocations due to dislocation cross and
slip which results in the existence of the same sign dislocations [30].
This consequently triggers high energy interface formation at the shear

Fig. 3. IPF mapping, and separated α and β phases demonstrating phase frac­
tions in the SPS alloys; (a) TFOC–0.2Si, (b) TFOC–0.4Si, and (c) TFOC–0.6Si.

HExt.TFOC–0.6Si showed significantly different microstructure as

compared with those with a lower Si content, demonstrating a bimodal
structure comprised of partially globularized and refined α lathes that
are recrystallized in the β grains. This microstructure evolution is Fig. 5. Effect of Fe, B, and Si on the primary β grain size of dual-phase Ti alloys.

Fig. 4. Variation of (a) α lath thickness and (b) α colony size with respect to Si content in SPS specimens.

4
A. Bahador et al.
Fig. 6. IPF mapping, and separated α and β phases demonstrating phase fractions in the hot extruded rods; (a) HExt.TFOC–0.2Si, (b) HExt.TFOC–0.4Si, (c) HExt.
TFOC–0.6Si, (d) IPF triangle of HExt.TFOC–0.4Si and (e) schematic illustration of crystallographic orientations in α and β phases.
line (IV). The crystallographic orientation of α and β phases emerged
with a strong texture that arises from (1010) and (101) planes which are
known to promote soft deformation in HCP and BCC metals respectively
[31,32]. Finally, continuous applied stress and high energy interfaces
facilitate the migration of interfaces and lowering the energy by forming
the globules (V) [33].
TEM observations of HExt.TFOC–0.2Si including HR and STEM im­
ages are illustrated in Figs. 9 and 10. The STEM images revealed the
existence of some precipitations along grain boundaries (Fig. 9a). To
identify their composition, quantitative elemental point scanning using
TEM-attached EDS and HR imaging were performed. Table 1 presents
the EDS obtained from the illustrated points. The point scanning results
at locations 1 and 4 were compared to PDF cards (00–055-0296 Cu25.00
Ti75 at.% and 01–078-9518, Cu33.33 Ti66.67 at.%) and the pre­
cipitations were matched with Ti3Cu and Ti2Cu intermetallics, respec­
tively. These precipitations were dominantly located at the α/β grain
interfaces (~100–400 nm length and ~50 nm width). However, their
5
Materials Characterization 172 (2021) 110855
limited amount was also found at the β/β interface (~100 nm length and
~20 nm width), as shown in Fig. 9b. The grain boundary precipitation of
the Ti2Cu intermetallic has already been reported in a previous study by
Yao et al. [34] on the annealed Ti–Cu alloys. The grain boundaries are
the main locations where a high density of defects, dislocations, and
solute concentrations is present. As a result, the grain boundary can be
inferred to be the favored region for the intermetallics to nucleate. On
the contrary, Cu can easily diffuse into the β matrix, but has low solu­
bility in α-Ti, due to which, these intermetallic grew preferentially in the
supersaturated α phase.
The EDS elemental scanning performed at locations 2 and 3 presents
the quantitative analysis of the alloying elements in the α and β grains.
Similar to the EDS mapping, these results also show that Fe and Cu
dominantly dissolve in the β phase (β stabilizers), while oxygen and Si
diffuse almost identically in both phases.
Fig. 10a shows the HR images of Ti3Cu intermetallics in which L and
R represent the right (α grain) and left sides (β grain) of the precipitate,
respectively, and M represents the precipitate. Inverse Fast Fourier (FFT)
A. Bahador et al. Materials Characterization 172 (2021) 110855

Fig. 7. PF and pole plots of HExt.TFOC–0.4Si, where (a) PF mapping of α, (b) pole plot of α, (c) PF mapping of β, and (d) pole plot of β.

Fig. 8. Schematic illustration of α phase globularization during hot extrusion and FESEM micrograph.

images also are presented for each neighbor grains, where high dislo­
cation densities were revealed in the α phase near the precipitates. The
lattice fringe measurements in α and β indicate a crystallographic
orientation similar to that found in XRD. In contrast, the lattice fringe of
the incoherent precipitate matched with Ti3Cu showed different orien­
tations. The existence of Ti3Cu can be explained as follows. First, Ti2Cu
precipitates from β-Ti in the sintering step during cooling by the
following eutectoid reaction.
β − Ti→α − Ti + Ti2 Cu
In the pre-heating of hot extrusion step, Ti3Cu is formed by the
reaction of pre-existing Ti2Cu and β-Ti, according to Canale and Servant
[35]:
Ti2 Cu + (β − Ti) ↔ Ti3 Cu (3)
Based on the TEM observations, it is assumed that Ti2Cu has partially
transformed to Ti3Cu due to the short holding time of pre-heating. The
existence of Ti2Cu was evidenced by the HR image and lattice fringes in
the inverse FFT image (Fig. 10b).
In addition, Fig. 10c shows the selected area diffraction patterns
(2)
(SADPs) corresponding to the locations marked in Fig. 9b. The SADPs of
α grain are displayed in Fig. 10c (1) as a reference pattern. Fig. 10c (2,3)

6
A. Bahador et al.
Fig. 9. STEM imaging and EDS examinations at different locations and interfaces (α/β and β/β) of HExt.TFOC–0.2Si.
shows the SADPs by tilting from α and β grains, respectively. The tilt on
the α grain was easier to detect from the clear diffraction spots of Ti2Cu
intermetallic and capture the related dark field image. The TEM obser­
vations also show that the formation of this intermetallic precipitate is
limited on the β/β interfaces, and is primarily found at the α/β interfaces.
However, its fraction of the intermetallic is small. It is generally known
that a high density of Ti2Cu can be formed from supersaturated α-Ti via
annealing and aging heat treatments of binary Ti–Cu [34,36].
The SADPs obtained from β grain parallel to [113]β zone axis is
shown in Fig. 10c (4). Distinct spots are seen in 1/3 and 2/3 of {112}β,
confirming the presence of ω phase formation in β grains. This generally
agrees with the previous studies on extruded Ti alloy [37,38]. Addi­
tionally, Kilmametov et al. [39] claimed that Ti containing 4 wt% Fe has
the highest possibility of ω phase development. The presence of this
phase is also evident in the corresponding dark field image. It is neces­
sary to mention that ω phase formation was seen to be limited. Ac­
cording to literature, oxygen has a suppression effect, particularly when
its content is about 0.5 wt% (reported for cold-worked β-Ti alloy) [40].
However, new research reports contradict this hindering effect of oxy­
gen. For instance, Chou et al. [41] recently claimed that a high oxygen
7
Materials Characterization 172 (2021) 110855
content not only stabilizes the ω phase, but also changes its morphology
from an ellipsoid to an elongated rod during isothermal aging.
3.3. Microhardness analysis
Microhardness evaluation of sintered and hot extruded specimens is
illustrated in Fig. 11. The SPS specimens showed a monotonically
increasing microhardness with respect to increasing Si solute. However,
the increment ratio at 0.6 Si was higher than those specimens with a
lower Si content, arising from a difference in microstructure. The α lath
thickness may play the main role in the microhardness of dual phase
titanium alloys by hindering the dislocation slip and triggering dislo­
cation pile-ups. As a general rule, the Hall-Petch equation also can be
written as following to show this microstructure relation to the micro­
hardness [42];
H = H0 + kH δ− 0.5
(4)
where, H is microhardness, H0 and kH are constants, and δ is the α lath
thickness. However, there is a contradiction in SPS.TFOC-0.6Si which
A. Bahador et al. Materials Characterization 172 (2021) 110855

Fig. 10. HR-TEM and inverse FFT images showing (a) Ti3Cu and (b) Ti2Cu intermetallics; (c) diffraction patterns and dark field images obtained from marked areas
in Fig. 9.

might be due to the higher volume fraction of α phase, considering that α

Table 1
phase is harder than β phase.
Elemental EDS point analysis results from Fig. 9a.
Microhardness results did not show a significant difference after hot
Spectrum Ti (at.%) Fe (at. O (at Cu (at Si (at Composition extrusion of low Si content specimens (0.2 and 0.4 wt% Si). On the
%) %) %) %)
contrary, the hardness increased significantly in the alloy with 0.6 wt%
59.80± 3.76 ± 3.45 ± 32.65 ± 0.34 ± Ti3Cu Si which has a bi-modal microstructure and different crystallographic
2.99 0.18 0.17 1.63 0.01
orientations. Although the Hall-Petch effect is considered in the hard­
② 90.46± 0.13 ± 3.55 ± 5.54 ± 0.32 ± Ti-α
4.52 0.0 0.17 0.27 0.01
ness of alloys, the crystallographic orientation of the grains also con­
③ 80.63± 6.73 ± 3.22 ± 9.03 ± 0.39 ± Ti-β tributes effectively. Since a high texture development indicates a low
4.03 0.33 0.16 0.45 0.02 misorientation angle and a nearly-identical slip direction between
④ 68.08± 4.06 ± 4.31 ± 23.0 3± 0.51 ± Ti2Cu adjacent grains, this leads to an easy occurrence of dislocation glide and
3.4 0.2 0.21 1.15 0.02
its movement into the adjacent grain using less force, while a higher

8
A. Bahador et al.
Fig. 11. Variation of microhardness of SPS and HExt. TFOC alloys with respect
to Si content.
force is needed for a dislocation to cross the grain boundary in differ­
ently textured adjacent grains [43]. Therefore, HExt.TFOC-0.2Si and
HExt.TFOC-0.4Si with highly textured equiaxed microstructures have
lower microhardness than the HExt.TFOC-0.6Si with randomly textured
and bi-modal microstructure. In addition, high oxygen content of HExt.
TFOC-0.6Si may also increase the microhardness.
4. Conclusions
Three different blends of pre-mixed Ti–4Fe–5O–3Cu–xSi (x = 0.2,
0.4, and 0.6 wt%) powder were densified using SPS process and pro­
cessed further by hot extrusion. The aim was to fabricate cost-effective
dual-phase titanium alloys and study the effect of Si addition on
microstructure, phase fraction, and morphology of grains. The sintered
specimens showed dual-phase (α+β) titanium, where α lathes were
located inside and along the primary β grain boundaries. The Si addition
resulted in slightly coarsening of primary β grains, especially when it
increased to 0.6 wt%. The hot extrusion at the temperature of dual-phase
stability successfully altered the lamellar grain morphology of sintered
alloys to refined globular shaped with a grain size of 2.6 and 2.2 μm in
HExt.TFOC–0.2Si and HExt.TFOC–0.4Si, respectively. The α and β phase
fractions were almost similar after hot extrusion in all the alloys with the
ratio of α/β: ~6/4. Additionally, EBSD analysis clarified the strong
crystallography alignment in both α and β phases of hot extruded
specimen resulted in the development of (1010) α and (101) β fiber
textures, which agreed with the XRD characterization. TEM in­
vestigations revealed the existence of Ti2Cu and Ti3Cu intermetallics
which preferentially formed along α/β interfaces. Si and O were found to
diffuse homogenously in both α and β phase while Fe and Cu mainly
diffused into the β phase. These results showed a successful control of
the microstructure in achieving fine equiaxed grains of α+β dual-phase
when the Si content did not exceed 0.4 wt% in the presence of a high
concentration of oxygen. The ability to control the microstructure has
implications on the strengthening of dual-phase titanium alloys using
ubiquitous elements. In future work, mechanical properties, including
strengthening and deformation mechanisms based on grain size and
solid solution effects, will be discussed. Additionally, considering the
potential for high-temperature applications, the stabiliy of the alloys at
high temperatures will be studied using in-situ SEM observations.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
9
Materials Characterization 172 (2021) 110855
Acknowledgments
This work was supported by Project to Create Research and Educa­
tional Hubs for Innovative Manufacturing in Asia, Osaka University, of
the Special Budget Project of the Ministry of Education, Culture, Sports,
Science, and Technology. A part of this study was also financially sup­
ported by Cross-ministerial Strategic Innovation Promotion Program
(SIP), “Materials Integration for revolutionary design system of struc­
tural materials” (Funding agency: JST). The authors would like to
specially thank Mr. Takeshi Murakami for his technical support during
TEM observations.
References
[1] I. Yadroitsev, P. Krakhmalev, I. Yadroitsava, Selective laser melting of Ti6Al4V
alloy for biomedical applications: temperature monitoring and microstructural
evolution, J. Alloys Compd. 583 (2014) 404–409, https://doi.org/10.1016/j.
jallcom.2013.08.183.
[2] K. Kapoor, P. Ravi, D. Naragani, J. Park, J.D. Almer, M.D. Sangid, Materials
Characterization Strain rate sensitivity, microstructure variations, and stress-
assisted β → α phase transformation investigation on the mechanical behavior of
dual-phase titanium alloys, Mater. Charact. 166 (2020), 110410, https://doi.org/
10.1016/j.matchar.2020.110410.
[3] V. Brailovski, S. Prokoshkin, M. Gauthier, K. Inaekyan, S. Dubinskiy, M. Petrzhik,
M. Filonov, Bulk and porous metastable beta Ti-Nb-Zr(Ta) alloys for biomedical
applications, Mater. Sci. Eng. C 31 (2011) 643–657, https://doi.org/10.1016/j.
msec.2010.12.008.
[4] A. Bahador, S. Kariya, J. Umeda, E. Hamzah, K. Kondoh, Tailoring microstructure
and properties of a superelastic Ti–Ta alloy by incorporating spark plasma sintering
with thermomechanical processing, J. Mater. Eng. Perform. 28 (2019) 3012–3020,
https://doi.org/10.1007/s11665-019-04061-8.
[5] X.H. Min, K. Tsuzaki, S. Emura, K. Tsuchiya, Enhancement of uniform elongation in
high strength Ti-Mo based alloys by combination of deformation modes, Mater. Sci.
Eng. A 528 (2011) 4569–4578, https://doi.org/10.1016/j.msea.2011.02.071.
[6] D.V. Louzguine, H. Kato, A. Inoue, High strength and ductile binary Ti-Fe
composite alloy, J. Alloys Compd. 384 (2004) 10–12, https://doi.org/10.1016/j.
jallcom.2004.03.114.
[7] M. Kikuchi, Y. Takada, S. Kiyosue, M. Yoda, M. Woldu, Z. Cai, O. Okuno, T. Okabe,
Mechanical properties and microstructures of cast Ti-Cu alloys, Dent. Mater. 19
(2003) 375–381, https://doi.org/10.1016/S0109-5641(02)00080-5.
[8] B. Sun, S. Li, H. Imai, T. Mimoto, J. Umeda, K. Kondoh, Fabrication of high-
strength Ti materials by in-process solid solution strengthening of oxygen via P/M
methods, Mater. Sci. Eng. A 563 (2013) 95–100, https://doi.org/10.1016/j.
msea.2012.11.058.
[9] E. Zhang, X. Wang, M. Chen, B. Hou, Effect of the existing form of cu element on
the mechanical properties, bio-corrosion and antibacterial properties of Ti-Cu
alloys for biomedical application, Mater. Sci. Eng. C 69 (2016) 1210–1221, https://
doi.org/10.1016/j.msec.2016.08.033.
[10] W. Jia, W. Zeng, Y. Zhou, J. Liu, Q. Wang, High-temperature deformation behavior
of Ti60 titanium alloy, Mater. Sci. Eng. A 528 (2011) 4068–4074, https://doi.org/
10.1016/j.msea.2011.01.113.
[11] Y. Li, Y. Chen, J.R. Liu, Q.M. Hu, R. Yang, Cooperative effect of silicon and other
alloying elements on creep resistance of titanium alloys: insight from first-
principles calculations, Sci. Rep. 6 (2016) 1–8, https://doi.org/10.1038/
srep30611.
[12] R.P. Kolli, W.J. Joost, S. Ankem, Phase stability and stress-induced transformations
in beta titanium alloys, JOM 67 (2015) 1273–1280, https://doi.org/10.1007/
s11837-015-1411-y.
[13] A.S. Gornakova, B.B. Straumal, A.N. Nekrasov, A. Kilmametov, N.S. Afonikova,
Grain boundary wetting by a second solid phase in Ti-Fe alloys, J. Mater. Eng.
Perform. 27 (2018) 4989–4992, https://doi.org/10.1007/s11665-018-3300-3.
[14] S.Y. Chang, L.C. Tsao, Y.H. Lei, S.M. Mao, C.H. Huang, Brazing of 6061 aluminum
alloy/Ti-6Al-4V using Al-Si-Cu-Ge filler metals, J. Mater. Process. Technol. 212
(2012) 8–14, https://doi.org/10.1016/j.jmatprotec.2011.07.014.
[15] F.W. Syed, V. Anil Kumar, R.K. Gupta, A.K. Kanjarla, Role of microstructure on the
tension/compression asymmetry in a two-phase Ti-5Al-3Mo-1.5V titanium alloy,
J. Alloys Compd. 795 (2019) 151–162, https://doi.org/10.1016/j.
jallcom.2019.04.272.
[16] J. Sieniawski, W. Ziaja, K. Kubiak, M. Motyk, Microstructure and mechanical
properties of high strength two-phase titanium alloys, Titan. Alloy. - Adv. Prop.
Control. (2013), https://doi.org/10.5772/56197.
[17] M. Motyka, K. Kubiak, J. Sieniawski, W. Ziaja, Phase transformations and
characterization of α + β titanium alloys, Compr. Mater. Process. 2 (2014) 7–36,
https://doi.org/10.1016/B978-0-08-096532-1.00202-8.
[18] A. Bahador, E. Hamzah, K. Kondoh, T.A. Abu Bakar, F. Yusof, H. Imai, S.N. Saud,
M.K. Ibrahim, Effect of deformation on the microstructure, transformation
temperature and superelasticity of Ti-23 at% Nb shape-memory alloys, Mater. Des.
118 (2017) 152–162, https://doi.org/10.1016/j.matdes.2016.12.048.
[19] A. Bahador, E. Hamzah, K. Kondoh, T. Asma Abubakar, F. Yusof, J. Umeda, S.
N. Saud, M.K. Ibrahim, Microstructure and superelastic properties of free forged
Ti–Ni shape-memory alloy, Trans. Nonferrous Metals Soc. China 28 (2018)
502–514, https://doi.org/10.1016/S1003-6326(18)64683-7.
A. Bahador et al.
[20] R. Yamanoglu, E. Efendi, F. Kolayli, H. Uzuner, I. Daoud, Production and
mechanical properties of Ti-5Al-2.5Fe-xCu alloys for biomedical applications,
Biomed. Mater. 13 (2018), https://doi.org/10.1088/1748-605X/aa957d.
[21] D. Jeong, Y. Kwon, M. Goto, S. Kim, High cycle fatigue and fatigue crack
propagation behaviors of β-annealed Ti-6Al-4V alloy, Int. J. Mech. Mater. Eng. 12
(2017) 1–10, https://doi.org/10.1186/s40712-016-0069-8.
[22] J. Tiley, T. Searles, E. Lee, S. Kar, R. Banerjee, J.C. Russ, H.L. Fraser, Quantification
of microstructural features in α/β titanium alloys, Mater. Sci. Eng. A 372 (2004)
191–198, https://doi.org/10.1016/j.msea.2003.12.008.
[23] G. Lütjering, Influence of processing on microstructure and mechanical properties
of (α + β) titanium alloys, Mater. Sci. Eng. A 243 (1998) 32–45, https://doi.org/
10.1016/s0921-5093(97)00778-8.
[24] M.J. Bermingham, S.D. McDonald, M.S. Dargusch, D.H. StJohn, The mechanism of
grain refinement of titanium by silicon, Scr. Mater. 58 (2008) 1050–1053, https://
doi.org/10.1016/j.scriptamat.2008.01.041.
[25] S. Tamirisakandala, R.B. Bhat, J.S. Tiley, D.B. Miracle, Grain refinement of cast
titanium alloys via trace boron addition, Scr. Mater. 53 (2005) 1421–1426, https://
doi.org/10.1016/j.scriptamat.2005.08.020.
[26] Y. Liu, L.F. Chen, H.P. Tang, C.T. Liu, B. Liu, B.Y. Huang, Design of powder
metallurgy titanium alloys and composites, Mater. Sci. Eng. A 418 (2006) 25–35,
https://doi.org/10.1016/j.msea.2005.10.057.
[27] J. Shen, B. Chen, J. Umeda, J. Zhang, Y. Li, K. Kondoh, Rate sensitivity and work-
hardening behavior of an advanced Ti-Al-N alloy under uniaxial tensile loading,
Mater. Sci. Eng. A 744 (2019) 630–637, https://doi.org/10.1016/j.
msea.2018.12.066.
[28] H.W. Song, S.H. Zhang, M. Cheng, Dynamic globularization kinetics during hot
working of a two phase titanium alloy with a colony alpha microstructure, J. Alloys
Compd. 480 (2009) 922–927, https://doi.org/10.1016/j.jallcom.2009.02.059.
[29] X. Ma, W. Zeng, F. Tian, Y. Zhou, The kinetics of dynamic globularization during
hot working of a two phase titanium alloy with starting lamellar microstructure,
Mater. Sci. Eng. A 548 (2012) 6–11, https://doi.org/10.1016/j.msea.2012.03.022.
[30] T. Seshacharyulu, S.C. Medeiros, J.T. Morgan, J.C. Malas, W.G. Frazier, Y.V.R.
K. Prasad, Hot deformation and microstructural damage mechanisms in extra-low
interstitial (ELI) grade Ti-6Al-4V, Mater. Sci. Eng. A 279 (2000) 289–299, https://
doi.org/10.1016/S0921-5093(99)00173-2.
[31] W.B. Hutchinson, M.R. Barnett, Effective values of critical resolved shear stress for
slip in polycrystalline magnesium and other hcp metals, Scr. Mater. 63 (2010)
737–740, https://doi.org/10.1016/j.scriptamat.2010.05.047.
10
Materials Characterization 172 (2021) 110855
[32] M. Zhang, J. Zhang, D.L. McDowell, Microstructure-based crystal plasticity
modeling of cyclic deformation of Ti-6Al-4V, Int. J. Plast. 23 (2007) 1328–1348,
https://doi.org/10.1016/j.ijplas.2006.11.009.
[33] C.H. Park, K.T. Park, D.H. Shin, C.S. Lee, Microstructural mechanisms during
dynamic globularization of Ti-6A1-4V alloy, Mater. Trans. 49 (2008) 2196–2200,
https://doi.org/10.2320/matertrans.L-MRA2008832.
[34] X. Yao, Q.Y. Sun, L. Xiao, J. Sun, Effect of Ti2Cu precipitates on mechanical
behavior of Ti-2.5Cu alloy subjected to different heat treatments, J. Alloys Compd.
484 (2009) 196–202, https://doi.org/10.1016/j.jallcom.2009.04.095.
[35] P. Canale, C. Servant, Thermodynamic assessment of the Cu-Ti system taking into
account the new stable phase CuTi3, Zeitschrift Fuer Met. Res. Adv. Tech. 93
(2002) 273–276, https://doi.org/10.3139/146.020273.
[36] Z. Lincai, D. Xiaoming, Y. Wei, Z. Man, S. Zhenya, Effect of prestrain on
precipitation behaviors of Ti-2.5Cu alloy, High Temp. Mater. Process. 37 (2018)
487–493, https://doi.org/10.1515/htmp-2017-0006.
[37] R.J. Talling, R.J. Dashwood, M. Jackson, D. Dye, On the mechanism of
superelasticity in gum metal, Acta Mater. 57 (2009) 1188–1198, https://doi.org/
10.1016/j.actamat.2008.11.013.
[38] J. Coakley, V.A. Vorontsov, K.C. Littrell, R.K. Heenan, M. Ohnuma, N.G. Jones,
D. Dye, Nanoprecipitation in a beta-titanium alloy, J. Alloys Compd. 623 (2015)
146–156, https://doi.org/10.1016/j.jallcom.2014.10.038.
[39] A.R. Kilmametov, Y. Ivanisenko, A.A. Mazilkin, B.B. Straumal, A.S. Gornakova, O.
B. Fabrichnaya, M.J. Kriegel, D. Rafaja, H. Hahn, The α→ω and β→ω phase
transformations in Ti–Fe alloys under high-pressure torsion, Acta Mater. 144
(2018) 337–351, https://doi.org/10.1016/j.actamat.2017.10.051.
[40] M. Tane, T. Nakano, S. Kuramoto, M. Niinomi, N. Takesue, H. Nakajima, ω
Transformation in cold-worked Ti-Nb-Ta-Zr-O alloys with low body-centered cubic
phase stability and its correlation with their elastic properties, Acta Mater. 61
(2013) 139–150, https://doi.org/10.1016/j.actamat.2012.09.041.
[41] K. Chou, E.A. Marquis, Oxygen effects on ω and α phase transformations in a
metastable β Ti–Nb alloy, Acta Mater. 181 (2019) 367–376, https://doi.org/
10.1016/j.actamat.2019.09.049.
[42] H. Galarraga, R.J. Warren, D.A. Lados, R.R. Dehoff, M.M. Kirka, P. Nandwana,
Effects of heat treatments on microstructure and properties of Ti-6Al-4V ELI alloy
fabricated by electron beam melting (EBM), Mater. Sci. Eng. A 685 (2017)
417–428, https://doi.org/10.1016/j.msea.2017.01.019.
[43] A. Bahador, J. Umeda, S. Tsutsumi, E. Hamzah, F. Yusof, H. Fujii, K. Kondoh,
Asymmetric local strain, microstructure and superelasticity of friction stir welded
Nitinol alloy, Mater. Sci. Eng. A 767 (2019) 138344, https://doi.org/10.1016/j.
msea.2019.138344.