The Effect of Thermal Pre-Treatment of Titanium Hydride

(TiH2) Powder for Magnesium Alloy Processing in Argon

Condition
Franciska P.L 1,a), Aprilia Erryani 1, Dhyah Annur2, and Ika Kartika1
1
Research center for Metallurgy and Material, Indonesian Institute of Science
2
Development and Application Unit for Biocompatible Implant Materials in Orthopedics, Indonesian Institute of
Science
a)
Corresponding author: fran011@lipi.go.id

Abstract. Titanium hydride powders are used to enhance the foaming process in the formation of highly porous metallic
material with a cellular structure. In order to improve foaming characteristics the TiH2 powder as foaming agent was subjected to
various heat treatments prior at 450 and 500°C during 2 hours in argon condition to processing to shift hydrogen release up into
the melting range of the Mg-Ca-Zn alloy. To study the formation mechanism, the thermal behavior of titanium hydride and
hydrogen release in Mg-Ca-Zn alloy foam during the sinter process in argon condition are investigated by scanning electron
microscopy (SEM), Energy Dispersive Spectroscopy (EDS), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and
differential thermal analysis (DTA). Qualitatively, EDS analysis shows that the pre-treatment of TiH2 in argon at 500°C for 2
hours produces a higher oxygen content on the surface of the powder particle TiH 2. DTA/TGA results showed that thermal pre-
treatment in TiH2 at 450°C, which released the hydrogen gas at 560°C in heat treatment or sinter when used as foaming agent in
Mg alloy. Meanwhile, thermal pre-treatment in TiH2 at 500°C, which released the hydrogen gas at 670°C in heat treatment or
melting condition. Thermal pre-treatment TiH2 results in a shift in the decomposition temperature to higher temperatures, but
with a reduction in amount of gas released which increase with increasing thermal treatment temperature. From SEM
investigation of TiH2 as foaming agent in Mg alloy that sintered at 600°C, it was found that distribution ranges of pore diameters
are larger with TiH2 which pre-treated at 450°C. It might the thickness of oxide layer different from different pretreatment
temperatures, leading to the differences of the decomposition temperature. The oxide layer of TiH2 particles is responsible for the
observed shift in decomposition temperature and can prepare the stabile foam that stabilize forming of cell walls and avoid to
their collapse in higher temperatures.

Keyword: TiH2, foaming agent, Mg alloy, metal foam, oxide layer, thermal decomposition

INTRODUCTION

Over the years many different approaches have been explored to improve the properties of implants, for
Over the years many different approaches have been explored to improve the alloys, for example by reducing the
stiffness, by make porosities in Mg alloys which permits bone ingrowth into the implant. In comparison with dense
materials, porous materials have a number of advantages, because their interconnected porous structure allows in-
growth of new tissues and the passage of nutrients. Furthermore, the porous structure typically yields a reduced
Young’s modulus closer to that of human bone while the scaffold can still maintain enough strength to satisfy load-
bearing demands[1, 2].
The manufacture and application of porous metals have recently been reviewed by Banhart[3]. The
foaming agent creates the space within the structure and so choice of the right foaming agent is crucial to the
process. Titanium hydride is often used in the foaming of low melting point metals such as aluminum, magnesium
and aluminum alloys because a large amount of hydrogen is released during heating [4-8]. The thermodynamic and
kinetics of the Ti-H system have been extensively studied [9, 10]. TiH2 has been found to start to release free
hydrogen gas at around 400°C, but large scale gas does not occur until above 500°C [6]. To delay the gas release
during foaming process closer or above the melting point of alloys, pre-heat treating of the TiH2 in air has been
used, as the result oxide film on the surface o the hydride are formed [11].
In this paper, different pretreatment temperatures in argon condition were applied on titanium hydride
powders to investigate the effect of oxidation on the decomposition behavior of TiH 2 and morphology pore size of
TiH2 as foaming agent in Mg alloy after sintered. Based on the knowledge and a better understanding of the
mechanism we are able to produce Mg alloy metal foam using titanium hydride as the foaming agent.

EXPERIMENTAL

Pre-treatment TiH2 as foaming agent were prepared by Titanium hydride fine powders 0.06-0.3 µm in size
and had a purity of 98.5% supplied by Merck. To study the thermal evolution in an argon atmosphere, titanium
hydride powders were treated in argon condition in tube furnaces (at 3.0 g) were placed in a ceramic crucible and
heated at 450 and 500°C. The heating rate was typically 5°C/min and the samples were treated for 2 hours at the
selected temperature and cooled to room temperature in the furnace.
To study the foam structure, the powders for metal foam production were mixed by 93 wt.% magnesium
powder, 1 wt.% calcium powder, zinc 3 wt.% powder and 3 wt.% TiH 2 pre-treatment was added as the foaming
agent in shaker mill for 30 minutes to produce a homogeneous distribution of all components. The powder mixture
prepared for uniaxial pressing is shaped in cylindrical dies on a hydraulic press. After milling the powders alloy then
sintering at temperature 600°C in argon condition and TiH2 foaming agent releases gas and large volumes of
hydrogen gas are rapidly produced.
The PM process consists of mixing metal powder and a powdered blowing agent, compacting the mix to a
dense semi- finished product by cold pressing. In a final step the foamable precursor material is expanded by
heating it under melting point of its matrix metal. This transfers the metal into a semi- liquid viscous state and
simultaneously makes the blowing agent decompose, thus releasing gas and creating a highly porous structure [12].
Those alloys led to biocompatible metal foam magnesium alloys for orthopedics.
The morphology of TiH2 powders and Mg alloy after sintering was obtained by a JEOL JSM-6390A
scanning electron microscope (SEM) equipped with energy dispersive spectrometer (EDS). Differential thermal
analysis (DTA) was used to analyze the thermal decomposition temperatures of the original or heat treated TiH2
powders. The differential thermal analysis (DTA) was monitored from room temperature to 1000°C with the heating
rate of 5°C /min.

RESULT AND DISCUSSION

SEM and EDS TiH2 Powder

The morphology of the titanium hydride powders which pre-treated by thermal in argon condition in 450,
480 and 500°C for 2 hours is depicted in FIGURE.1. Seen the morphology of TiH2 which the powders particle size
is variable about 2.4-40 µm, also has an angular shaped, and irregular the powder surface. There is no obvious
difference and significantly influence morphology change between TiH2 powders pre-treatment in argon in various
temperature treatment.

(a) (b)
 FIGURE. 1. SEM images of thermal pre-treatment TiH2 powder particles; a) 450°C, b) 500°C

From FIGURE.2. shows the distribution of O (greenery) and Ti particle (redness) almost overlapping or
same location. It can be implied that formed the oxide on Ti particle. On TiH 2 thermal pre-treatment at 500°C can be
seen ( FIGURE 2c.1.) that the distribution of O particle are denser and may indicated that oxide on Ti particle which
is formed also higher. From EDS mapping unsure on FIGURE.2. suggesting that titanium in the titanium hydride
powders is easily oxidized at elevated temperature despite the continuous argon flow.

(a) (a1) (a2)

(b) (b1) (b2)

FIGURE.2. Mapping EDS images of thermal pre-treatment TiH2 powder particles; a) 450°C, b) 500°C

FIGURE. 3 shows the spot elemental composition of the thermal pre-treatment TiH2 powders by EDS and
its morphology. Titanium element has a great affinity to oxygen element and heat treatment can make surface layer
TiH2 decomposed to Ti and H2, Ti will attach to the un-decomposed TiH2 [13]. Fig. 3a and b, can be detected in the
large particles of Ti that TiH2 thermal pre-treated at 500°C resulting O higher than pre-treated at 450°C. It is
suggesting that titanium in the titanium hydride powders was easily oxidized at elevated temperature during thermal
pre-treatment despite the continuous argon flow.
 002 002
8000 8000
7200 7200

TiKa

TiKa
6400 6400
5600 5600
002
002
4800 4800
Counts

Counts
4000 4000

OKa TiLl TiLa

OKa TiLl TiLa

30
30 µm
µm
30 µm

3200 3200
Element Mass% Atom% Element Mass% Atom%

TiKb
TiKb

2400 2400
O 15.85 36.05 O 23.09 47.33
1600 1600
Ti 84.15 63.95 Ti 76.91 52.67
800 800
Total 100 100 Total 100 100
0 0
0.00 3.00 6.00 9.00 12.00 15.00 18.00 21.00 0.00 3.00 6.00 9.00 12.00 15.00 18.00 21.00

keV keV

FIGURE. 3. EDS result in TiH2 thermal pre-treatment; a) 450°C, b) 500°C

DTA/TGA

The TGA results acquired for the thermal pre-treatment titanium hydride powders in Fig. 5, performed
applying a heating rate of 5°C/min from room temperature up to 1000°C. Curve showed the release of hydrogen and
the decomposition behavior of thermal TiH2 powder as a function of heat flow, temperature and weight loss (∆m). It
can be observed in Fig 5a. that from TGA curve the weight loss increases from 520°C to 1000°C, and this is
relatively significant between 550°C and 680°C. Until 1000C, curve increase slowly. It possibly involves a slow and
stable phase transition process in this early stage. Heat flow during the heating process was monitored by DTA.
From DTA curve, there are two predominant endothermic peaks, the subsequent reactions occur quickly at about
550°C and 640°C and it can be deduced that decomposition of titanium hydride is fastest at these two points. Since
decomposition of titanium hydride requires external energy, there are obvious decomposition reactions involving
two different phase transitions in these two temperature ranges. The positive maximum of the DTA curve indicates
an endothermal reaction. As the temperature is increased to 510°C the reaction proceeds slowly, but accelerates in
the next temperature range 520–620°C, indicating that the first stage of titanium hydride decomposition is almost
complete at 560°C. The second decomposition stage occurring in the temperature range 620-650°C requires the
supply of a large amount of external energy. From the Fig.5a, it was showed that the hydrogen decomposition of
TiH2 powder which is pre-treated at 450°C, started at temperature 520°C.
In Fig 5b. from TGA curve, weight loss increases from 600°C to 1000°C, and this is relatively significant
between 650°C and 720°C, and immediately increases. It migt associated with a loss of weight and strong evolution
of hydrogen. From DTA, as the temperature is increased to 600°C the reaction proceeds slowly, but accelerates in
the next temperature range 610–690°C, indicating that the first stage of titanium hydride decomposition is almost
complete at 670°C. The second decomposition stage occurring in the temperature range 690-820°C. From the
Fig.5a, it was showed that the hydrogen decomposition of TiH 2 powder which is pre-treated at 500°C, started at
temperature 610°C.
Several authors reported, prominent H2 release accompanied by mass loss from as-received TiH2 starts at
about 400 °C and peaks in various temperature regimes. After performing an oxidation pre-treatment, the onset
temperature of TiH2 can be shifted up to between 500 and 550 °C, and the H 2 release curve is modified to exhibit a
single-peak[11, 14-16]. These pre-treatment with argon was a useful property since it improves metal foam
generation. The effect was attributed to oxide layers around the cores of TiH 2 particles which build up during heat
treatment and act as diffusion barriers to hydrogen[14].
Oxide layers on titanium hydride particles modify their hydrogen desorption behaviour because they form an
efficient diffusion barrier[17, 18]. Hydrogen not only has to diffuse through the bulk titanium matrix from the inner
region of each particle towards the surface but also has to overcome the oxide barrier which is an additional kinetic
hindrance. This effect is already known and has been exploited to control hydrogen evolution from TiH 2 in metal
foam manufacture[15]. In addition to this effect one could speculate that differences in thermal expansion
coefficients between the hydride core and the oxide shell could create cracks in the oxide layer which would
facilitate gas desorption. It is reported that helium and nitrogen are unable to remove the oxygen attached to the
surface of the powders due to their light masses and argon is a better gas to protect titanium hydride from
oxidation[19]. If the hydride is exposed to argon during heating, the oxygen present will renew the thinning oxide
layers on the surface, immediately close eventual gaps in the oxide shell created by thermal stresses and finally
create an increasingly thick oxide layer which forms an effective barrier for hydrogen diffusion and further retards
desorption[20].

(a)

(b)
FIGURE. 4. DTA-TGA result in TiH2 thermal pre-treatment; a) 450°C, b) 500°C
XRD

With an higher thermal pre-treatment TiH2 in temperature, more oxide higher peak are formed. Increase in
temperature, diverse titanium oxides with higher hydride stoichiometry start to form on powder particulate surfaces,
because both hydrogen emission and oxygen entrance flow increases interactively. In thermal Ti3O layers start
forming on the particle’s surface, as alongside hydrogen emission, a small amount of oxygen atoms entered within
titanium lattice This means that the process of hydrogen emission changes from physical process to chemical
process too [21].

a
.

b
.

FIGURE. 5. XRD result in TiH2 thermal pre-treatment; a) 450°C, b) 500°C

SEM Image After Sinter with Mg Alloy

Metal alloys can be foamed by mixing into them as a foaming agent that releases gas when heated. The
widely used foaming agent titanium hydride (TiH2) begins to decompose into Ti and gaseous H2. By adding titanium
hydride particles to powder Mg-Ca-Zn at sintering temperature 600°C, large volumes of hydrogen gas are rapidly
produced, creating bubbles that can lead to a closed-cell foam and provided foam. In FIGURE 6. can be seen the
foam of Mg-Ca-Zn-TiH2 that pre-treated TiH2 in 450°C (a) and foam of Mg-Ca-Zn-TiH2 that pre-treated TiH2 in
500°C (b). It showed that the pores are isolated and closed-cell. From Fig. 6, a, the distribution ranges of pore
diameters of magnesium foams are about 3-10 µm using pretreated titanium hydrides with temperatures 450°C.
From Fig. 6.b, the distribution ranges of pore diameters of magnesium foams are about 0.5-5 µm using pretreated
titanium hydrides with temperatures 500°C, smaller than TiH 2 pre-treated 450°C. The content of pre-treated TiH2 at
450°C, leading to the more concentrated pore size as described below.
From the DTA result in FIGURE 4 (a), decomposition is almost complete in 560°C in TiH2 pre-treated
450°C, while 670°C in TiH2 pre-treated 500°C. So, when the TiH2 as foaming agent are sintered in Mg alloy at
temperature 600°C, the hydrogen in TiH2 pre-treated 450°C in Mg alloy completely released ahead and can break
through the oxide layer as barrier and make foams. As a result, the hydrogen gas TiH 2 pre-treated 500°C in Mg alloy
subsequently generated needs higher sintering temperature to pass through the compact oxide layer. Meanwhile, the
thermal pre-treatment of TiH2 as foaming agent in the Mg alloy present experiment and the thickness of oxide layer
different from different pretreatment temperatures, leading to the differences of the decomposition temperature as
shown in FIGURE. 4.
 (a) (b)

FIGURE 6. SEM result Mg-Ca-Zn alloy sintering temperature at 600°C using TiH2 thermal pre-treatment; a)
450°C, b) 500°C as foaming agent

CONCLUSION

We have investigated hydrogen release from titanium hydride under argon in two different temperature 450°C
and 500°C during 2 hours. From DTA curve, hydrogen release occurs in two stages for TiH2 pre-treatment 450°C is
between 520-620°C and 620-650°C and for TiH2 pre-treatment 500°C is between 610-690°C and 690-820°C.
Higher thermal pre-treatment temperature of TiH2, contains higher O composition, meanwhile more oxide film that
formed as a result increasing delay of gas release. The difference of decomposition temperature of TiH2 after pre-
heat treatment has been reported due to the presence of an oxide layer which act as a barrier to gas release.
Magnesium alloy foam prepared using TiH2 pretreated at 450°C as foaming agent possess larger pore size and more
homogeneous distribution when sintering process at 600°C.

ACKNOWLEDGMENTS

The authors would like to acknowledge Indonesian Institute of Sciences (LIPI)-Research Center for Metallurgy
and Material for providing financial support and research facilities
.

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