Journal of Alloys and Compounds 385 (2004) 156–159

Characteristics of titanium–hydrogen solid solution

Daigo Setoyama∗ , Junji Matsunaga1 , Hiroaki Muta,
Masayoshi Uno, Shinsuke Yamanaka
Department of Nuclear Engineering, Graduate School of Engineering, Osaka University,
2-1 Yamada-oka, Suita, Osaka 565-0871, Japan

Received 28 January 2004; received in revised form 28 April 2004; accepted 28 April 2004

Abstract

The mechanical properties of titanium–hydrogen solid solution (0–7.84 at.% H) were studied to reveal the influence of hydrogen on the
characteristics of titanium. The elastic moduli such as Young’s and shear moduli of titanium–hydrogen solid solution decreased with increasing
of hydrogen content. The influence of hydrogen content for decreasing of elastic moduli was independent of temperature. The microhardness
for the solid solution was also decreased with increasing of hydrogen content. The electronic structure of the titanium–hydrogen solid solution
was evaluated by a first principle molecular orbital calculation. The mechanical properties of titanium–hydrogen solid solution were discussed
in terms of the calculation results.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Titanium–hydrogen solid solution; Molecular orbital method; Elastic modulus; Hardness

1. Introduction theoretically, using by the first principle molecular orbital

calculation [7].
Titanium and its alloys have been extensively utilized in
various fields such as chemical plants, nuclear materials [1]
and aerospace components, because the titanium alloys have
2. Experimental procedure
high chemical durability as well as high strength. The infor-
mation on the mechanical properties of titanium is therefore
The pure titanium (99.9%) polycrystalline cantilever
necessary and has therefore been studied [2–4] to develop
(45 mm × 10 mm × 1 mm) was used in the present study.
titanium-based alloys. On the other hand, titanium is paid
The modified Sievert’s UHV apparatus executed the hy-
attention as hydrogen storage material since titanium has
drogenation of the titanium. The hydrogen content of the
high affinity on hydrogen. However, it is generally said that
specimens was measured by hydrogen analyzer (HORIBA,
hydrogen pickup weakens the material strength, and the in-
EMGA-621). The details of these conditions were described
formation on the hydrogen embrittlement of titanium is still
in our previous paper [8]. The elastic moduli were obtained
inadequate. Yamanaka et al. [5,6] reported that the mechan-
by high temperature multiple elastometer (NTP, EG-HT),
ical properties of zirconium in the IV group are deteriorated
based on the cantilever characteristic vibration technique.
by hydrogen addition. Therefore, it is possible that titanium
The characteristic vibration frequencies were between 12
is also affected by hydrogen. From such points of view, the
and 16 Hz. The Vickers hardness was measured by high
mechanical properties of titanium–hydrogen solid solution
temperature Vickers hardness tester (NIKON, QM-1). The
were studied by means of not only experimentally but also
test was repeated five times on each temperature. The hy-
drogen content of the samples and the range of temperature
∗ Corresponding author. Tel.: +81-6-6979-7905;
for these tests are illustrated in the Ti–H diagram (Fig. 1).
fax: +81-6-6879-7889. The electronic structures of the hydrogen solid solu-
E-mail addresses: dsetoya@stu.nucl.eng.osaka-u.ac.jp (D. Setoyama),
j-matsunaga@stu.nucl.eng.osaka-u.ac.jp (J. Matsunaga).
tion have been evaluated by a first-principles molecular
1 Co-corresponding author. Tel.: +81-6-6879-7905; orbital (MO) calculation. The MO calculations were per-
fax: +81-6-6875-7889. formed by the DV-X␣ cluster method based on the local

0925-8388/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2004.04.132
 D. Setoyama et al. / Journal of Alloys and Compounds 385 (2004) 156–159
Fig. 1. The hydrogen content and measured temperature range of the
samples in the Ti–H phase diagram.
density function approximation. The DV-X␣ method is a
non-relativistic first principles method using Slater’s X␣
potential as the exchange-correlation term. The details of
the DV-X␣ method have been discussed at length in the
literature [9–11].
3. Results and discussion
Fig. 2 shows the changes of Young’s moduli on hydrogen
content and temperature. The solid marks indicate the re-
sults of solid solution (␣ phase), the open marks indicate the
results of two phase area which consist of both precipitated
hydride and matrix (␣ + ␦ phase). In Fig. 2a, the Young’s
modulus of ␣-Ti decreased with increasing of hydrogen
content. The decreasing of the modulus was independent
of temperature. The slope dE/dCH was −1.73 GPa/at.% H.
Fig. 2b shows that the change of Young’s modulus on tem-
perature change. In the ␣ phase area, the Young’s modulus
also decreased with increasing of temperature, which is in
good agreement with the reported tendency [3] (solid line
and dotted line). The decreasing of the modulus was also
independent of hydrogen content. The slope dE/dT was
−0.059. Therefore, the decreasing of Young’s modulus was
fitted by the following equation:
E = 127.9 − 0.059T − 1.73CH (GPa)
where E, T, CH are Young’s modulus (GPa), temperature
(◦ C) and hydrogen content (at.%), respectively. The dashed
lines in the Fig. 2a and b is drawn by the above equation.
In the ␣ + ␦ phase area, the elastic moduli did not de-
crease with increasing of hydrogen content, because of the
higher Young’s modulus of the hydride. And these results
are consistent with the reference data [3]. Fig. 3 shows the
change of shear moduli on hydrogen content and tempera-
ture. The open and solid marks indicate the same meaning
in Fig. 2. It was also found that the decreasing of shear
modulus had same tendency as that of Young’s modulus.
157
Fig. 2. (a) Change in the Young’s modulus E for hydrogenated Ti with
hydrogen content; (b) change in the Young’s modulus E for hydrogenated
Ti with temperature.
Therefore, the decreasing of shear modulus was fitted by
the following equation:
G = 42.5 − 0.033T − 0.946CH (GPa) (2)
where G, T, CH are shear modulus (GPa), temperature (◦ C)
and hydrogen content (at.%), respectively. The dashed lines
in the Figs. 3a and 2b are drawn by the above equation.
The solid and dotted lines are from the literature [3]. The
Vickers hardness of solid solution is shown in Fig. 4. The
Vickers hardness also decreased with hydrogen addition
and temperature. From this result, the Vickers hardness was
(1)
fitted by the following equation:
Hv = 188 + 9.55 × 10−4 T 2 − 0.71T − 1.50CH (3)
where Hv , T and CH are Vickers hardness, temperature
(◦ C) and hydrogen content (at.%), respectively. The dashed
lines in the Fig. 4a and b is drawn by the above equation.
The hydrogen solution softens the mechanical properties of
titanium elastically and plastically.
The electronic structure of titanium–hydrogen solid so-
lution was evaluated by the first principle molecular orbital
calculation. The lattice parameters and hydrogen content
of the ␣ phase-titanium clusters are shown in Table 1 [12].
158 D. Setoyama et al. / Journal of Alloys and Compounds 385 (2004) 156–159

Fig. 3. (a) Change in the shear modulus G for hydrogenated Ti with

hydrogen content; (b) change in the shear modulus G for hydrogenated
Ti with temperature.

The same lattice parameters were adopted for every cluster

(Fig. 5). The hydrogen contents are 0, 2.70, 5.26, 7.69 at.%, Fig. 4. (a) Change in the Vickers hardness Hv for hydrogenated Ti with
hydrogen content; (b) change in the Vickers hardness Hv for hydrogenated
respectively. A smearing technique [13,14] was applied for Ti with temperature.
the problem in our systems containing many heavy metal
atoms. In smearing technique, the Fermi energy was cal-
culated using the Gaussian broadening technique with a
smearing parameter of 0.05 eV. Fig. 6 shows change of total
bond order between all of Ti pairs. Bond order is a crite-
rion of covalent binding [15]. The bond order between Ti
atoms decreased with the increasing of hydrogen content.
Fig. 7 shows the density of states of solid solution. The
peak of hydrogen 1s orbital can be seen around −5 eV by
the solution of hydrogen. Moreover, 3d orbital of titanium
decreased with increasing of hydrogen content. It was con-
sidered that the bonding between titanium atoms decreases

Table 1
The parameters of cluster models
Cluster model Lattice parameter (Å) Hydrogen content
(at.% H)
a-axis c-axis

Ti36 2.9506 4.6835 0.00

Ti36H1 2.70
Ti36H2 5.26
Fig. 5. The cluster models of (a) Ti36; (b) Ti36H1 (2.70 at.% H); (c)
Ti36H3 7.69
Ti36H2 (5.26 at.% H); and (d) Ti36H3 (7.69 at.% H).
 D. Setoyama et al. / Journal of Alloys and Compounds 385 (2004) 156–159
Fig. 6. Change in the total bond order of the clusters for hydrogen solid
solution with the hydrogen content.
Fig. 7. Density of states from (a) Ti36; (b) Ti36H1; and (c) Ti36H2 cluster.
Fig. 8. The distribution of charge density for (2 0 2 3) plane of Ti36H3
cluster.
because the electrons of 3d orbital used between titanium
atom and hydrogen atom. This analysis can explain the
experimental results of the softening qualitatively.
159
Fig. 8 shows the distribution of charge density around a
hydrogen atom on titanium–hydrogen solid solution cluster.
The bond between the center of hydrogen atom and the first
nearest titanium atoms (Ti(a) ) is visible, but those between
titanium atoms are not easy to see. In contrast, the bond
between the first nearest titanium (Ti(a) ) and the second
nearest titanium atoms (Ti(b) ) are formed strongly. This
distribution of the charge density is proof of decreasing of
bonding power between titanium atoms by hydrogenation.
4. Conclusion
The mechanical properties were studied for titanium–
hydrogen solid solutions. The elastic moduli such as
Young’s and shear moduli of titanium–hydrogen solid solu-
tion decreased with increasing of hydrogen content. Solute
hydrogen was found to lead the reduction of the microhard-
ness of Ti.
The electronic structure of the titanium–hydrogen solid
solution was estimated by molecular orbital calculation. It
was found from the calculation that the solute hydrogen
atom in an interstitial site drew off the 3d electrons from the
metallic bond onto the Ti–H bond. This appears to weaken
the surrounding metallic bonds. These results provide an
explanation for the change in the mechanical properties of
Ti with hydrogen addition.
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