Materials Science & Engineering A 739 (2019) 491–498

Contents lists available at ScienceDirect

Materials Science & Engineering A

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

Microstructural and mechanical properties of α-titanium sintered material T

via thermal decomposition of additive chromium oxide particles
Kondoh Katsuyoshia, , Ikemasu Ryuhoa, Umeda Junkoa, Kariya Shotaa, Anak Khantachawanab
⁎

a
Osaka University, Japan
b
King Mongkut's University of Technology Thonburi, Thailand

ARTICLE INFO ABSTRACT

Keywords: The pre-mixed pure Ti and Cr2O3 powder was consolidated by spark plasma sintering (SPS) and hot extrusion to
Powder metallurgy fabricate α-titanium (Ti) materials with oxygen (O) and chromium (Cr) elements by powder metallurgy (PM)
Titanium process. The Cr2O3 particles were completely decomposed during SPS, and then O and Cr atoms were dissolved
Chromium oxide in α-Ti matrix. Oxygen atoms were remarkably improved the mechanical strength of PM Ti-O-Cr alloys by their
Solid solution
solid solution hardening effect. The Cr solution and Ti4Cr precipitates had important roles to obstruct the grains
Grain refinement
Zener pinning
coarsening behavior by the solute drag and Zener pinning effects, respectively. The solid solution strengthening
Solute drag effect by Cr atoms, however, was very limited due to a small Cr solubility of about 0.35 at% in α-Ti phase of Ti-O-
Cr alloys. Since Ti4Cr precipitates with 10–20 µm diameters were not so fine, they hardly contributed to the
precipitation hardening of Ti-O-Cr alloys.

1. Introduction
Titanium (Ti) and its alloys are widely used as aircraft components,
chemical products plant and medical devices due to their high specific
strength, excellent corrosion resistance and biocompatibility [1–3]. For
the further improvement of their mechanical properties, the alloying
design by using the expensive rare metals was mainly discussed in the
previous studies. From a viewpoint of the sustainable use of rare metals,
however, a long-term strategy in the novel materials design and pro-
cessing must be established [4]. For example, carbon (C), oxygen (O),
nitrogen (N), hydrogen (H) and silicon (Si), which are ubiquitous re-
sources, are employed as the alloying elements to improve the me-
chanical properties of Ti materials by PM process [5–12]. In particular,
O and N atoms are representative α-Ti phase stabilizer, and effectively
improve the mechanical strength of Ti materials by their solid solution
hardening behaviors because of a large solubility of both elements inα-
Ti phase shown in Ti-O and Ti-N binary phase diagrams [13]. At the
same time, it is well known that the ductility significantly decreases
with increase in their contents. In the recent studies, however, PM Ti-O
and Ti-N materials revealed a good balance between high strength and
excellent ductility. In preparation of these Ti materials, the pre-mixed
pure Ti and TiO2 or TiN powder was used as the starting materials. The
additive TiO2 or TiN particles were decomposed during sintering, and O
or N atoms originated from them were dissolved intoα-Ti matrix. In this
study, the elemental mixture of pure Ti powder and chromium oxide
(Cr2O3) particles was employed to fabricate PM Ti-O-Cr alloys. In SPS
process [14], the additive Cr2O3 particle was decomposed, and O and Cr
elements were dissolved in α-Ti phase. The lattice constant changes by
these solution atoms were quantitatively evaluated by using XRD (X-ray
Diffraction) profiles of PM Ti-O-Cr and Ti-O alloys. Increasing in the
Cr2O3 content, not only Cr solution, but also Ti-Cr precipitates at α-Ti
grain boundaries were effective to obstruct the grain coarsening. Mi-
crostructures changes were investigated through SEM (Scanning Elec-
tron Microscope) with EBSD (Electron Back Scattering Diffraction),
EPMA (Electron Probe Microanalysis) and TEM (Transmission Electron
Microscope) with EDS (Energy Dispersive X-ray Spectrometry) analysis.
Tensile properties of PM Ti-O-Cr alloys were evaluated, and the
strengthening mechanism was discussed by using their microstructures
analysis results.
2. Experimental procedure
A mean particle size of pure Ti powders (TC-450, Toho Technical
Service Co.) and Cr2O3 particles (KOJUNDO Chemical Laboratory CO.)
are 27.8 µm and 2.5 µm, respectively. Both raw powder materials have
a purity of 99.9%. The elemental mixture powder of them was prepared
by ball milling process for 3.6 ks, where the mixing ratio of Cr2O3
particles to the pre-mixed powder was 0–5 mass%. They were

⁎
Corresponding author.
E-mail address: kondoh@jwri.osaka-u.ac.jp (K. Katsuyoshi).

https://doi.org/10.1016/j.msea.2018.10.081
Received 28 February 2018; Received in revised form 16 October 2018; Accepted 16 October 2018
Available online 18 October 2018
0921-5093/ © 2018 Elsevier B.V. All rights reserved.
K. Katsuyoshi et al.
consolidated by SPS at 873 K～1273 K in vacuum (6 Pa) to fabricate the
sintered billets with 42 mm diameter. The applied pressure of 30 MPa
and sintering time of 3.6 ks were used in SPS process. The homo-
genization heat treatment at 1273 K for 3.6ks in vacuum (20 Pa) was
additionally applied to these Ti sintered materials. Finally, hot extru-
sion was carried out to prepare the dense Ti materials, where the pre-
heating temperature of the samples was 1273 K and an extrusion ratio
of 12.8 (Φ43 mm→Φ12 mm) were employed. Oxygen, nitrogen, hy-
drogen and carbon contents of the extruded rods were analyzed, and
microstructures observation was conducted by using optical micro-
scope, SEM and TEM-EDS. EBSD with Orientation Imaging Microscopy
(OIM) analysis was useful to evaluate their textures and grain size
distribution. XRD analysis was also applied to quantitatively measure
the lattice constant changes ofα-Ti crystals in a-axis and c-axis direc-
tions because O and Cr solution atoms significantly influenced the lat-
tice expansion. Two tensile test specimens were machined from each
extruded rod, and used to evaluate the tensile properties at room
temperature under a strain ratio of 5.0 × 10−4 /s.
3. Results and discussion
3.1. Oxygen and chromium distribution in Ti sintered materials
Ellingham diagram [15] shows the TiO2 formation free energy,
ΔG[TiO2] is much small compared to ΔG[Cr2O3] in a wide temperature
range from 300 K to 1500 K. It means Cr2O3 particles of the pre-mixed
raw powder are completely reduced during SPS at 873 K～1273 K.
When using the pre-mixed Ti-5mass% Cr2O3 powder, Fig. 1 shows XRD
profiles of Cr2O3 raw particle, the mixture powder, the sintered mate-
rials at 873 K~1273 K and pure Ti material sintered at 1273 K. The
analysis results of Cr2O3 peak at 2θ = 33.2–34.0 degree and that of Ti
(0 0 0 2) peak at 37.0–39.0° are (a) and (b), respectively. A very small
diffraction peak of Cr2O3 was detected in the profiles of Ti materials
sintered at 873 K and 973 K as shown in Fig. 1(a), while the same peak
was never detected in Ti materials sintered at 1073 K or more. Re-
garding Ti (0 0 0 2) diffraction peak in Fig. 1(b), increasing in the
sintering temperature up to 1073 K, the peak gradually shifted to the
lower diffraction angle. It means a distance between the basal planes of
α-Ti crystal, having a hexagonal close-packed (hcp) structure, in-
creased, and the lattice expansion of α-Ti crystal in c-axis direction
occurred. Fig. 2 reveals the dependence of the lattice values in c-axis
direction of Ti-5mass% Cr2O3 and pure Ti sintered materials on the
sintering temperature. They were calculated from the XRD profiles
shown in Fig. 1(b) by using Bragg law [16]. Pure Ti sintered materials
have a constant lattice value (~ 4.685Å) when the sintering tempera-
ture changed from 873 K to 1273 K. On the other hand, in the case of Ti-
5.0 mass% Cr2O3 sintered materials, the lattice constant remarkably
Fig. 1. XRD profiles of Cr2O3 particle, Ti-5.0 mass% Cr2O3 raw mixture powder, their sintered materials at 873 K~1273 K and pure Ti sintered material at 1273 K:
2θ = 33.2°~34.0° (a) and 37.0°~39.0° (b).
492
Materials Science & Engineering A 739 (2019) 491–498
Fig. 2. Dependence of lattice constants in c-axis direction of Ti-5.0 mass%
Cr2O3 and pure Ti sintered materials on sintering temperature.
increased and reached 4.716Å with increasing the temperature up to
1073 K. Furthermore, a very small lattice constant difference in sin-
tering at between 1073 K and 1273 K was detected. The previous stu-
dies suggest that O solution causes the lattice constant increase in c-axis
of hcp-Ti crystal because O atom is one of the interstitial solution ele-
ments of α-Ti [7,17]. In addition, a relative intensity of Cr2O3 diffrac-
tion peak decreased with increasing the sintering temperature as shown
in Fig. 1(a). These results indicate that O atoms solution into α-Ti
crystal occurred after decomposition of Cr2O3 particles in SPS and re-
sulted in the increment of the lattice constant in c-axis when the sin-
tering temperature increased from 873 K to 1273 K. Therefore, the SPS
temperature of 1273 K was employed to consolidate the pre-mixed Ti-
Cr2O3 powder in this study.
XRD analysis was applied to Ti-X mass% Cr2O3 (X = 0–3) sintered
materials after the homogenization heat treatment at 1273 K for 3.6 ks
in vacuum. Fig. 3 shows a dependence of the lattice constants of α-Ti in
c-axis (a) and a-axis (b) direction on the oxygen content of Ti-X% Cr2O3
sintered materials. At the same time, those of Ti-Ymass%TiO2
(Y=0–1.5) materials prepared in the previous study [7] were also used
as comparison data. These lattice constants were calculated from the
diffraction peaks of (1 0−1 3) and (1 1−2 2) planes in α-Ti crystals of
each material. As shown in (a), in the case of Ti-Cr2O3 sintered mate-
rials, the lattice constant in c-axis direction proportionally increased
with increase in the oxygen content. An increasing ratio (a gradient of
the approximation straight line) is 5.6 × 10−3 Å/O atom), and has a
good agreement with that of Ti-TiO2 materials (5.7 × 10−3Å/O atom).
This is because Ti-Cr binary phase diagram [13] reveals a Cr solubility
limit inα-Ti phase is about 0.6 at%, and then Cr solution effect on the
lattice expansion of α-Ti crystal is very small. That is, the lattice
K. Katsuyoshi et al.
Fig. 3. Dependence of lattice constants in c-axis (a) and a-axis (b) directions on oxygen content of Ti-Cr2O3 and Ti-TiO2 sintered materials.
constant increment is mainly due to O solid solution in the case of Ti-
Cr2O3 sintered materials as well as Ti-TiO2 materials. As for the lattice
constant change in a-axis direction shown in (b), it shows a constant
value and independent of the oxygen content. This tendency is similar
to the results in the previous studies on Ti materials with O solid so-
lution [7,18,19].
3.2. Grains refining behavior of Ti extruded materials
Fig. 4 shows inverse pole figure (IPF) maps in the cross-section of
extruded Ti-Cr2O3 materials, where the Cr2O3 content is 0 mass% (a),
0.25 mass% (b), 0.5 mass% (c), 1.0 mass%(d) and 3.0 mass% (e). The α-
Ti mean grain size calculated from EBSD results significantly decreased
with increase in the Cr2O3 content. All specimens mainly consist of
equiaxed grains and a texture with (0 0 0 1) basal planes parallel to the
extrusion direction. When the grains are refined, the crystal rotation
Fig. 4. Inverse pole figure (IPF) maps of extruded Ti-Cr2O3 materials and mean grain size, where Cr2O3 contents is 0 mass% (a), 0.25 mass% (b), 0.5 mass% (c), 1.0
mass%(d) and 3.0 mass% (e).
493
Materials Science & Engineering A 739 (2019) 491–498
easily occurs by plastic deformation during extrusion. Therefore, the
extruded Ti-Cr2O3 materials with fine grains revealed the randomized
orientation as shown in Fig. 4(c)~(e).
Fig. 5 reveals a dependence of mean grain size of Ti-Cr2O3 and Ti-
TiO2 extruded materials on the oxygen content. The mean grain size of
each specimen was calculated by using IPF maps in EBSD analysis. In
both, the grain size becomes constant when O content reaches about
1.5 at%. Ti-Cr2O3 materials, however, indicate a remarkable grain re-
finement compared to Ti-TiO2 materials. It is obvious that Cr dis-
tribution in the Ti matrix is significantly effective for the grain refining
behavior, and the role of Cr elements on α-Ti grains refinement will be
discussed in later.
Fig. 6 shows EMPA and TEM-EDS analysis results of Ti-5.0 mass
%Cr2O3 extruded material. The point analysis by TEM-EDS reveals that
about 3.0 at% O atoms uniformly exist inside ofα-Ti grains and their
boundaries. On the other hand, Cr elements are locally detected at the
K. Katsuyoshi et al.
Fig. 5. Dependence of mean grain size of extruded Ti-Cr2O3 and Ti-TiO2 ma-
terials on oxygen content.
grain boundaries, and their average content of 16.1 at% is much large
compared to the inside of α-Ti grains with 0.35 at% Cr. By considering
the Ti-Cr binary phase diagram showing that Cr solid solubility limit in
α-Ti phase is about 0.6 at%, Cr solution content of 0.35 at% inα-Ti
grains is smaller than this solubility in the phase diagram. The previous
study reported that an experimental solubility of Cr elements in α-Ti
phase significantly decreases compared to that in the Ti-Cr phase dia-
gram when both Cr and N atoms dissolve in α-Ti at the same time [20].
Therefore, this material also shows a smaller Cr solubility of about
0.35 at% due to the solid solution of both Cr and O atoms in α-Ti. On
the other hand, as mentioned above, Cr content of 16.1 at% at grain
boundaries extremely exceeds Cr solubility limit, and then Cr elements
locally precipitate as Ti-Cr compounds at the boundaries after sintering.
An electron diffraction analysis by TEM was conducted for phase
identification of these Cr elements shown in Fig. 6(e). The diffraction
pattern successfully detected the above precipitates as Ti4Cr inter-
metallic compounds as shown in Fig. 7(b), and α-Ti structures were
observed inside the grains in (c). In addition, as shown in Fig. 6(e),
TEM-EDS analysis on Cr elements segregated at the grain boundary
(No.6-13) indicates Ti: Cr = 80:16（at%）, and this atomic ratio is
Fig. 6. EPMA results of extruded Ti-5.0 mass%Cr2O3 material; Ti (a), Cr (b), O (c), backscattered (BS) electron image (d) and TEM-EDS analysis results (e) of O, Ti
and Cr elements content (at%) inside α-Ti grains and compounds near grain boundary. No.1–5 and 14–18 (+): Inside of α-Ti grains, No.6–13 (•): Inside of compounds
at grain boundary.
494
Materials Science & Engineering A 739 (2019) 491–498
almost equivalent to the composition ratio of Ti4Cr compounds. It is
concluded that a small amount of Cr atoms uniformly dissolved in α-Ti
phase and most of them precipitated as Ti4Cr compounds at the grain
boundaries of Ti-5.0 mass%Cr2O3 material.
In order to investigate the effect of Cr elements on the grain refining
behavior of Ti-Cr2O3 extruded materials shown in Fig. 5, the micro-
structural analysis by EBSD was conducted on Ti-X mass% Cr2O3
(X = 0, 0.25, 1.0) materials before and after heat treatment (H.T) in
vacuum. The H.T condition at 823 K for 86.4 ks was employed in
consideration of α-Ti recrystallization temperature of 723 K. Fig. 8
shows the changes in IPF maps and a mean grain size of Ti-Cr2O3 ma-
terials before and after H.T, where the Cr2O3 content is 0 mass% (a),
0.25 mass% (b) and 1.0 mass% (c). In the case of as-extruded Ti-
0.25%Cr2O3 material before H.T shown in (b), it has fine equiaxed α-Ti
grains (2.91 µm) compared to pure Ti material (5.82 µm) shown in (a).
The addition of 0.25mass%Cr2O3 particle means 0.15 at% Cr elements
contained in the material, which is smaller than Cr solubility in α-Ti
(0.35 at%) as mentioned above. That is, most of Cr elements are dis-
solved as the solution atoms in the grains, and their solute drag was
active to obstruct the grains coarsening. This is because the extruded
rods were rapidly cooled in the atmosphere after hot extrusion, and
there was not enough time for their coarsening behavior in cooling. On
the other hand, pure Ti material with no Cr2O3 addition shows a re-
markable grain growth after H.T (9.63 µm) as shown in (a). When 0.25
mass%Cr2O3 particle was contained, its specimen also revealed a large
increment of the mean grain size from 2.91 µm to 7.20 µm via H.T in
(b). Furthermore, in the case of Ti-1.0 mass%Cr2O3 material in (c), the
grain coarsening behavior was completely stopped, and no change in α-
Ti grain size was observed in the specimen after H.T at 823 K. Fig. 9
indicates Cr mapping results and backscattered electron (BSE) images
by EDS of Ti-Xmass%Cr2O3 extruded materials, where X is 0.25% in (a)
and 1.0% in (b), respectively. As mentioned above, most of Cr elements
are dissolved in the matrix, and a very few Cr precipitates locally exist
at the grain boundaries of (a) Ti-0.25 mass%Cr2O3 material. It means
that both Cr solute drag [21,22] and Zener pinning [23–25] by the
precipitates are limited to obstruct the grains growth during a long-time
H.T at 823 K for 3.6 ks. On the other hand, a lot of Ti4Cr precipitates
uniformly dispersed along the grain boundaries of (b) Ti-1.0 mass
%Cr2O3 material, and resulted in the complete control of grains coar-
sening behavior by Zener pinning in the specimen after H.T at 823 K
shown in Fig. 8(c). When Zener pinning effect is active to obstruct the
grain growth, its growing force (σ) balances the dragging force by the
K. Katsuyoshi et al. Materials Science & Engineering A 739 (2019) 491–498

Fig. 7. Electron diffraction patterns of extruded Ti-5.0 mass% Cr2O3 material, TEM image (a), diffraction patterns of Ti4Cr near grain boundary (b) and α-Ti (c) in
grain.

Fig. 8. Changes in IPF maps and mean grain size of extruded Ti-Cr2O3 materials before and after heat treatment at 823 K for 86.4 ks in vacuum, where Cr2O3 content
is 0 mass% (a), 0.25 mass% (b) and 1.0 mass% (c).

495
K. Katsuyoshi et al. Materials Science & Engineering A 739 (2019) 491–498

Fig. 9. Chromium mapping and backscattered electron images of extruded Ti-Cr2O3 materials with Cr2O3 content of 0.25 mass% (a) and 1.0 mass% (b).

precipitates at the boundaries ( Gpta ), which is express as Eq. (1) by
Zener-Smith model [23].
d
Gpta nV
2 (1)
where, d, n and V is a diameter, a number density per unit area, and
molar volume of precipitates, respectively. As mentioned above in
Fig. 9, a number density of Ti4Cr precipitates of Ti-1.0 mass%Cr2O3
material is much larger than that of Ti-0.25 mass%Cr2O3 one.
Therefore, according the above Eq. (1), it is concluded that Zener drag
effect by Ti4Cr compounds at the grain boundaries is dominant to ob-
struct α-Ti grains coarsening behavior of Ti-1.0 mass%Cr2O3 material.
3.3. Tensile properties of Ti-Cr2O3 materials and their strengthening
mechanism
Fig. 10 shows a dependence of yield stress (a) and elongation to
failure (b) of Ti-Cr2O3 and Ti-TiO2 extruded materials on the O content

Fig. 10. Dependence of yield stress (a) and elongation to failure (b) of extruded Ti-Cr2O3 and Ti-TiO2 materials on oxygen content.
496
K. Katsuyoshi et al. Materials Science & Engineering A 739 (2019) 491–498

at the ambient temperature. The yield stress (YS) of the former re-
markably increases with increase in O content as well as Ti-TiO2 ma-
terials, which are strengthened by O solid solution mechanism [26]. As
shown in (b), a high enough elongation more than 20% is obtained until
the addition of 1.0 mass% Cr2O3 particles (oxygen content; 1.90 at%).
In the case of Ti-3.0 mass% Cr2O3 material (O content; 3.53 at%),
however, it is remarkably reduced to about 2%, and the specimen is
very brittle due to a lot of Ti4Cr compounds dispersed in the matrix. On
the other hand, focusing on the gradient of YS line of each specimen
shown in Fig. 10(a), Ti-Cr2O3 material has two different slopes in the
relationship between YS and oxygen content even though the gradient
of Ti-TiO2 material is constant (276.2 MPa/at% O). In particular, the
slope of Ti-Cr2O3 materials with 1.90 at% O or less (512.9 MPa/at% O)
is significantly large. It means these materials are strengthened by both
O and Cr elements originated from Cr2O3 particles. On the other hand,
when O content is over 1.90 at%, the slope of Ti-Cr2O3 materials
(272.5 MPa/at% O) is almost equal to that of Ti-TiO2 materials. It in- Fig. 11. YS increment of theoretical using Labusch model and revised experi-
dicates the main strengthening factor is O solid solution hardening mental* as function of oxygen content of extruded Ti-Cr2O3 materials. * Effect
when Ti-Cr2O3 materials contain more than 1.90 at% O elements. of grain refinement on YS increment was removed from original experimental
In consideration of both α-Ti grains refinement and solid solution values.
behaviors of the extruded Ti-Cr2O3 materials with O content less than
1.90 at% shown in Fig. 5, the strengthening factors by the grain re- specimen employed in the previous works [9] are used in this study.
finement, O and Cr solid solution are effective. The quantitative eva- Fig. 11 shows Δσy[sss] by O solution using the above Eq. (3) shown as
luation of each factor of Ti-Cr2O3 materials is carried out as follows; “Theoretical” and the revised experimental as function of O content of
First of all, the grain refining effect (σy[gr], gr; grain refining) can be Ti-Cr2O3 extruded materials, where “revised experimental” means the
estimated by using Hall-Petch equation express as shown below YS increment after removing the grain refining effect (Δσy[gr]) from the
[27,28]; original experimental values. The theoretical and revised experimental
1 results increase with increasing the O content, and the theoretical re-
y [gr ] = y0 + Kd 2 (2)
sults are also generally consistent with the experimental values. The
where, K is Hall-Petch constant (18.6 MPa/mm −1/2
[17]) and d is a strict analysis, however, indicates that the revised experimental is
mean grain size of the specimen. Table 1 shows the oxygen content, a 40 MPa larger than the theoretical. Fig. 12 reveals a difference between
meanα-Ti grain size, and YS increment (Δσy[gr]) calculated by Eq. (2) the above theoretical and experimental results (Δσy[d], d; difference) as
of Ti-Cr2O3 and Ti-TiO2 extruded materials. The YS increment function of the Cr content of Ti-Cr2O3 extruded materials. Δσy[d] is
(94–232 MPa) by grains refining of Ti-Cr2O3 materials is much larger constant in the Cr content more than about 0.35 at%, which means an
than that (20–32 MPa) of Ti-TiO2 materials due to the remarkable grain experimental solid solubility of Cr atoms in α-Ti shown in Fig. 6(e). As
refinement by Zener pinning effect of the former as shown in Fig. 5. mentioned above, the grains refining behavior, O and Cr elements solid
With regard to the solid solution strengthening effect (Δσy[sss], sss; solution are the main strengthening factors of Ti-Cr2O3 extruded ma-
solid solution strengthening), O and Cr elements are active as the dis- terials. In addition, when Ti4Cr precipitation hardening is active to
solved atoms to increase the lattice constant in c-axis of hcp α-Ti improve their mechanical property, the estimated diameter of such
crystals of Ti-Cr2O3 materials. At first,Δσy[sss] by oxygen solution is effective precipitates is less than about 25 nm [31]. The size of Ti-Cr
calculated by using Labusch limit shown as follows [29]; precipitates is, however, about 2–10 µm as shown in Fig. 9, and then
1
their precipitation hardening effect is very limited. On the other hand,
0 1 Fm4 c 2w 3
y [sss ] = =
SF SF 4Gb9 (3)

where, Schmid factor (SF) of 0.44–0.45 is measured by SEM-EBSD

analysis on each specimen. A maximum attractive force (Fm) of
6.22 × 10−10 [30], which was experimentally and theoretically de-
termined in the previous study regarding Ti extruded materials with O
solution, is employed. The O solution concentration (c), four parabolic
arcs of width (w), shear modulus (G), and Burger's vector (b) of each

Table 1
Oxygen content, mean grain size and YS increment estimated by Hall-Petch
equation of extruded Ti-Cr2O3 and Ti-TiO2 materials.
Oxygen content Mean grain YS increment by grain
(at%) size, d/μm refinement, Δσy[GR]/MPa

Cr2O3 0.98 5.8 －

1.16 2.9 94.0
1.35 2.3 136.2
1.90 1.5 230.2
3.53 1.4 232.1
TiO2 0.65 11.6 － Fig. 12. Relationship between experimental YS increment* and chromium
1.35 9.3 19.5 contents of extruded Ti-Cr2O3 materials. * Effects of grain refinement and
1.76 8.2 31.7
oxygen solid solution on YS increment were removed from original experi-
2.34 8.7 25.9
mental values.

497
K. Katsuyoshi et al.
in consideration of the Cr solubility in α-Ti matrix of 0.35 at% and the
saturated Δσy[d] of about 40 MPa in Cr content of 0.35 at% or more, it
[8]
is concluded that the difference ofΔσy[sss] between the theoretical and
experimental values shown in Fig. 11 is due to Cr solution strength-
ening effect, not by Ti4Cr precipitation hardening behavior. [9]
4. Conclusions [10]
Microstructural and mechanical properties of PM Ti-Cr2O3 mate- [11]
rials, containing the dissolved O and Cr atoms and Ti4Cr precipitates
after a thermal decomposition of Cr2O3 particles in sintering, were in-
[12]
vestigated. The Cr dissolved atoms and Ti4Cr compounds were effective
to obstruct the grain growth by the solute drag and Zener pinning, re-
spectively, and resulted in the mechanical strength improvement by α- [13]
Ti grains refinement. Both O and Cr elements had important roles to
[14]
improve yield stress by each solution hardening behavior. The former, [15]
however, was much effective to the strength improvement compared to
Cr solution atoms. Ti4Cr precipitates with 10–20 µm diameters were not [16]
so fine, and then hardly contributed to their precipitation hardening for [17]
the mechanical improvement of PM Ti-O-Cr materials.
[18]
Acknowledgement [19]
A part of this study was financially supported by Japan Science and
[20]
Technology Agency under Industry-Academia Collaborative R&D
Program “Heterogeneous Structure Control: Towards Innovative [21]
Development of Metallic Structural Materials” and JSPS KAKENHI
[22]
Grant Number JP16H02408. The authors also show thanks to Mr.
Yoshinori Muraki, Mitsuo Horie, Ryoji Minamitani and Hisashi Imai for [23]
their technical supports and operation in the experiments.
[24]
References [25]
[1] A.K.M. Nurul Amin (Ed.), Titanium Alloys-Towards Achieving Enhanced Properties
for Diversified Applications, InTech, London, 1928. [26]
[2] J.C. Williams (Ed.), Titanium and Titanium Alloys, Springer-Verlag, New York,
1982.
[3] G. Lütjering, J.C. Williams (Eds.), Titanium, Springer-Verlag, New York, 2003. [27]
[4] E. Nakamura, K. Sato, Managing the scarcity of chemical elements, Nat. Mater. 10
(2011) 158–161. [28]
[5] K. Kondoh, T. Threrujirapapong, H. Imai, J. Umeda, B. Fugetsu, Characteristics of [29]
powder metallurgy pure titanium matrix composite reinforced with multi-wall
carbon nanotubes, Compos. Sci. Technol. 69 (2009) 1077–1081. [30]
[6] S. Li, B. Sun, H. Imai, T. Mimoto, K. Kondoh, Powder metallurgy titanium metal
matrix composites reinforced with carbon nanotubes and graphite, Composites A 48
(2013) 57–66. [31]
[7] B. Sun, S. Li, H. Imai, T. Mimoto, J. Umeda, K. Kondoh, Fabrication of high-strength
498
Materials Science & Engineering A 739 (2019) 491–498
Ti materials by in-process solid solution strengthening of oxygen via P/M methods,
Mater. Sci. Eng. A 563 (2013) 95–100.
J. Shen, B. Chen, J. Umeda, K. Kondoh, Microstructure and mechanical properties of
CP-Ti fabricated via powder metallurgy with non-uniformly dispersed impurity
solutes, Mater. Sci. Eng. A 716 (2018) 1–10.
K. Kondoh, B. Sun, S. Li, H. Imai, J. Umeda, Experimental and theoretical analysis of
nitrogen solid-solution strengthening of PM titanium, Int. J. Powder Metall. 50
(2014) 35–40.
T. Mimoto, J. Umeda, K. Kondoh, Strengthening behaviour and mechanisms of
extruded powder metallurgy pure Ti materials reinforced with ubiquitous light
elements, Powder Metall. 59 (2016) 223–228.
X.X. Ye, H. Imai, J.H. Shen, B. Chen, G.Q. Han, J. Umeda, M. Takahashi, K. Kondoh,
Strengthening-toughening mechanism study of powder metallurgy Ti-Si alloy by
interrupted in-situ tensile tests, J. Alloy. Compd. 694 (2017) 82–92.
X.X. Ye, H. Imai, J.H. Shen, B. Chen, G.Q. Han, J. Umeda, K. Kondoh, Study of
twinning behavior of powder metallurgy Ti-Si alloy by interrupted in-situ tensile
tests, Mater. Sci. Eng. A 679 (2017) 543–553.
J.L. Murray (Ed.), Phase Diagrams of Binary Titanium Alloys, ASM International,
Metals Park, Ohio, 1987.
B. Ertuğ (Ed.), Sintering Applications, InTech, London, 2013.
B. Ihsan, O. Knacke (Eds.), Thermochemical Properties of Inorganic Substances,
Springer-Verlag, New York, 1973.
W.L. Bragg, The Diffraction of Short Electromagnetic Waves by a Crystal,
Proceedings of the Cambridge Philosophical Society, 17, 1912, pp. 43–57.
H. Conrad, Effect of interstitial solutes on the strength and ductility of titanium,
Prog. Mater. Sci. 26 (1981) 123–403.
S. Yamaguchi, Interstitial order-disorder transformation in the Ti-O solid solution. I.
Ordered arrangement of oxygen, J. Phys. Soc. Jpn. 27 (1969) 155–163.
O. Yamamoto, K. Alvarez, T. Kikuchi, M. Fukuda, Fabrication and characterization
of oxygen-diffused titanium for biomedical applications, Acta Biomater. 5 (2009)
3605–3615.
T. Ando, K. Nakashima, T. Tsuchiyama, S. Takai, Microstructure and mechanical
properties of a high nitrogen titanium alloy, Mater. Sci. Eng. A 486 (2008) 228–234.
J.W. Cahn, The impurity-drag effect in grain boundary motion, Acta Metall. 10
(1962) 768–798.
K. Lücke, H.P. Stüwe, On the theory of impurity controlled grain boundary motion,
Acta Metall. 19 (1971) 1087–1099.
C. Zener, quoted by C. S. Smith, Grains, Phases, and interfaces: an interpretation of
microstructure, Trans. AIME 175, 1948, pp. 15–51.
M. Hillert, On the theory of normal and abnormal grain growth, Acta Mater. 13
(1965) 227–238.
N. Maazi, N. Rouag, Consideration of Zener drag effect by introducing a limiting
radius for neighbourhood in grain growth simulation, J. Cryst. Growth 243 (2002)
361–369.
B. Chen, J. Shen, X. Ye, J. Umeda, K. Kondoh, Advanced mechanical properties of
powder metallurgy commercially pure titanium with a high oxygen concentration,
J. Mater. Res. 32 (2017) 3769–3776.
E.O. Hall, Variation of hardness of metals with grain size, Nature 173 (1954)
948–949.
N.J. Petch, J. Iron Steel Inst. 173 (1953) 8–25.
R. Labusch, A statistical theory of solid solution hardening, Phys. Status Solidi 41
(1970) 659–669.
S. Kariya, M. Fukuo, J. Umeda, K. Kondoh, Quantitative analysis on solid solution
strengthening by light elements in pure titanium sintered materials by using
Labusch model, J. Jpn. Soc. Powder Powder Metall. 65 (2018) 407–413.
P. Haasen (Ed.), Physical Metallurgy, 2nd edition, Cambridge University Press, New
York, 1987.