i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 0 4 7 e1 0 5 8

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Influence of the ECAP and HEBM processes and

the addition of Ni catalyst on the hydrogen storage
properties of AZ31-x Ni (x¼0,2,4) alloy

Song-Jeng Huang, Veeramanikandan Rajagopal*, Addisu Negash Ali

Department of Mechanical Engineering, National Taiwan University of Science and Technology, No. 43, Keelung Rd.,
Sec. 4, Da'an Dist., Taipei, Taiwan, ROC

article info abstract

Article history: In this work, the hydrogen sorption properties of AZ31 magnesium alloys with various
Received 6 September 2018 additions of nickel (Ni) (i.e., Ni (X ¼ 0, 2, 4) wt.%) were investigated. Cast ingots with
Received in revised form different AZ31/NiP compositions were fabricated using a gravitating mechanical stir cast-
22 October 2018 ing (GMSC) method. Two different processes, namely, equal channel angular pressing
Accepted 4 November 2018 (ECAP) and high energy ball milling (HEBM) were performed to improve its hydrogen
Available online 5 December 2018 storage properties. The particle size of the sample powders were measured by laser
diffraction analysis. The microstructures, powder morphologies, and phase transformation
Keywords: were characterized by optical microscopy (OM), scanning electron microscopy (SEM) and x-
Hydrogen storage ray diffraction (XRD) analysis. The hydrogen sorption kinetics were measured by a Sievert's
AZ31-Mg alloy type apparatus. The results showing the impact of the ECAP and HEBM processes on the
Ni catalyst hydrogen storage properties were compared. The AZ31-4 Ni ECAP processed sample
Equal channel angular pressing, showed a maximum hydrogen storage capacity of 7.0 wt.% at 2322 s with complete
(ECAP) desorption of all the hydrogen in less than 5 min at a temperature of 375  C. On the other
High energy ball milling (HEBM) hand, the pure AZ31 alloy which was treated with the HEBM process showed the maximum
hydrogen capacity of 6.5 wt.% at 2393 s with desorption of all the hydrogen within 6 min. In
addition, the activation energy, as illustrated by the Kissinger plot, revealed that the
activation energy of the ECAP processed AZ31-4 Ni was 104.73 (KJ/mol), obviously lower
than the material processed by HEBM and pure MgH2.
© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

the automobile industry as a source of green energy.

Introduction
Increasing demand for energy to meet the requirements of
modern society drives efforts to discover and develop new
sources of sustainable energy. Hydrogen is a feasible ecolog-
ically friendly substitute for fossil fuels that could be used in
Furthermore, hydrogen is also considered as a potential
source of energy for future energy systems. However, the
general use of hydrogen is presently obstructed by its storage
technology, especially for applications such as automobiles
powered by hydrogen, fueled internal ignition engines. One
solution would be the deposition of hydrogen in metal

* Corresponding author.
E-mail address: grveera01@gmail.com (V. Rajagopal).
https://doi.org/10.1016/j.ijhydene.2018.11.005
0360-3199/© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
1048 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 0 4 7 e1 0 5 8
hydrides, a method which exhibits excellent characteristics
such as a large volumetric storage capacity and safety pro-
tection [1,2].
MgH2 is one of the most attractive metal hydrides for
hydrogen storage owing to its higher theoretical gravimetric
capacity of 7.6 wt.%, and the abundance and reuseability of Mg
make it an economical [3,4]. Nevertheless, the practical
implementation of MgH2 for hydrogen storage has not been
attained because of its lower hydrogen absorption/desorption
kinetics, and larger thermodynamic stability. To achieve bet-
ter hydrogenation/dehydrogenation kinetics, the metal hy-
drides have to be heated up to a temperature of 673K with a
hydrogen pressure of 3 MPa [3]. Furthermore, the addition of
various catalysts to Mg metal can have a significant effect on
stimulating the hydrogen sorption kinetics. In particular, the
transition metals (Ni, Fe, Cu, Ti, V) can be used as a catalyst to
increase the sorption kinetics of hydrogen molecules on the
surface of Mg and its alloy materials. The hydrogen molecules
diffuse quickly into the Mg crystal lattice leading to an
improved rate of hydrogenation and dehydrogenation.
Notably, the addition of the catalyst enhances the hydrogen
storage performance even at a moderate temperature [5e7].
Among the transition metals, Ni has been utilized to decrease
the thermodynamic stability of metal hydride [8e10].
Currently, some researchers have focused on the adaption
of deformation methods, in particular the equal channel
angular pressing (ECAP) technique to treat and deform bulk
alloy materials for hydrogen storage [11,12]. In 2015, Asselli
et al. reported the hydrogen storage kinetics of a ZK60 alloy
produced through the ECAP process and subsequent accu-
mulative roll-bonding (ARB) process [13]. In another study of a
commercial ZK60 alloy, the grain size was decreased to
250 nm by the ECAP process which is the lowest size value
ever reached by this deformation method. More importantly,
this material showed a maximum hydrogen storage capacity
of 6.6 wt.%. An investigation of the durability of the materials
showed no decline in storage capability or kinetics for up to
1000 hydrogen-sorption cycles [14]. After subjecting Mg2Ni
monocrystalline powders to plastic strain by the ECAP and
cold rolling process it was concluded that the microstructure
and the nanostructure are directly correlated to the hydrogen
storage behaviors [15]. In order to attain sub-micron sized
micro grains in Mg2Ni alloys and Mg from the Mg-Ni, the alloy
materials are first treated using the ECAP process, following by
the cold rolling technique. The obtained material shows a
maximum hydrogen storage capacity of about 6 wt.% [16].
Others have focused on the effects of mechanical milling.
Composite alloys of various compositions were prepared with
particle sizes lower than 400 nm by hydriding combustion
synthesis followed by the mechanical milling process. In the
Mg-Ni composites, the Mg2Ni compound dispersed uniformly
results enhanced the hydrogen-sorption rate and capacity
even at low temperature. The quantity of Ni catalyst materials
also has a direct influence on the capacity and kinetics [17]. In
another study, alloys of different composition were synthe-
sized by mechanical alloying with varying milling times. The
Ni distribution over Mg after various ball milling times (15 and
30 h) was evaluated. The results were based on the dispersion
of the Ni content and the milling time [18]. The combined ef-
fect of ECAP and ball milling on a ZK60 magnesium alloy has
been examined by monitoring the absorption and desorption
properties. The desorption occurred at a faster rate at a tem-
perature of 300  C with a pressure of 2 atm. A 5.2 wt.%
hydrogen release was observed at 20 min in the materials
subjected to both ECAP and ball milling and 26 min in the
materials subjected to ECAP alone [19]. Thus, past studies
show that ECAP and high energy ball milling (HEBM) can
enhance the hydrogen storage properties of Mg and Mg alloys.
In this work, cast ingots composed of AZ31/NiP alloys were
produced by the gravitating stir casting method. Both ECAP
plastic deformation and HEBM milling processes were per-
formed to produce defects along the grain boundaries. The
colliding of the particles in the powders is expected to
enhance the kinetics of sorption. The hydrogenation proper-
ties depend on the microstructures and the weight percent-
ages of the Ni contents. Hence, the hydrogenation results
were comparatively studied among the two processing effects
with similar particle size distribution for different alloys by
constant volume method.
Experimental procedure
Materials and methods
Material preparation
The Mg-based AZ31 alloy was obtained from Kuangyue Co.,
Ltd. and the 99.90% pure Ni-Particles (Nip) were purchased
from First Chemical Works Co., Ltd. Nip with particles with
~25 mm in size was used as a catalyst with the AZ31 alloy
(AZ31/Nip). Samples with three different compositions, 0 wt.%
of Nip (AZ31-0 Ni), 2 wt.% of Nip (AZ31-2 Ni) and 4 wt.% of Nip
(AZ31-4 Ni), were fabricated through the gravitating me-
chanical stir casting (GMSC) method. During the casting pro-
cess, CO2þSF6 gases were supplied at 400  C to avoid burning
AZ31 magnesium alloy and argon gas was also supplied at
700  C to prevent oxidation. A stabilization time of 15 min for
every 100  C incremental increase in temperature up to 700  C
was maintained during the casting process. After 760  C the
AZ31/Nip melt was stirred with two stirrers for 5 min at
300 rpm to attain a uniform distribution of Nip throughout the
Mg alloy. Finally the melt alloy was poured into a mold located
inside the furnace chamber to produce the AZ31/Nip cast in-
gots [20,21].
Sample billets with dimensions of 11.5  11.5  75 mm
were sliced from the cast ingots and then kept in a furnace at
a temperature of 410  C for 24 h for homogenization treat-
ment. The microhardness was measured using a Vickers
microhardness tester (Akashi MVK-H1). After homogeniza-
tion, the sample billets were plastically deformed through the
equal channel angular pressing (ECAP) technique with a
channel angle of 120 with 8 passes and route type Bc (rotation
of 90 in the same direction for each pass) after 30 min of
preheating time. After each squeeze, samples were subse-
quently immersed in water. The temperature of the ECAP
mold was sustained at 300  C for all passes. The temperature
oscillation of the die was ±5  C. To remove the oxide layer
after ECAP process the surfaces of the sample billets were
polished by silicon carbide polishing sheets. Then the solid
billets were comminuted into powder by a filing process 1 h
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 0 4 7 e1 0 5 8
prior to hydrogenation to reduce the possibility of oxide layer
formation.
In the HEBM process, homogenized samples were rasped
manually then milled in a planetary type machine (Retsch
PM100) with a ball to power ratio of 30:1 in an inert atmo-
sphere to prevent oxidation. The rotation speed milling was
maintained at 300 rpm for a milling time of 4 h for the AZ31-
0 Ni sample, and 3 h for the AZ31-2 Ni and AZ31-4 Ni (AZ31-
Ni) samples. The powder transmission process was carried
out inside a glove box in an inert atmosphere.
Characterization
Particle size distributions were measured by a Malvern mas-
tersizer model 2000. The microstructure of the solid samples
was observed by optical digital microscopy and the powder
morphologies were obtained through scanning electron mi-
croscopy (SEM) (model JSM-6390LV) equipped with an EDS
(Energy dispersive spectroscope) before and after hydrogena-
tion. The phases of the prepared alloys were observed through
XRD analysis (model Bruker D2 phaser with Cu Ka radiation).
Hydrogen storage kinetics
The hydrogenation kinetic properties were investigated using
a Sivert's type volumetric apparatus with a fixed volume. The
volume of the system 0.0000217 m3 was calculated while the
0.1 g of powder samples inside the chamber. During the acti-
vation, temperature was elevated to 375  C from room tem-
perature while the powder samples were placed inside the
chamber. The heating process was conducted at the rate of
5  C/min for 80 min with a hydrogen atmosphere. The ab-
sorption rate during hydrogenation was calculated at 375  C
under 3.5 MPa hydrogen pressure while the desorption con-
ducted at the pressure of 0.8 MPa. The average of five stabi-
lized cycle values was taken in the calculation to get precise
results. The properties of thermal decomposition were char-
acterized by DSC (Differential scanning calorimetry) with N2
atmosphere. The activation energy of AZ31-4 Ni was calcu-
lated by the Kissinger equation method. Furthermore, the
Scheme 1 e Diagram outlining preparation and hydrogenation mechanisms of the alloy materials.
1049
experimental and the hydrogenation mechanisms are sum-
marized in Scheme 1.
Results and discussion
Microhardness
The effects of adding the catalyst on the microhardness re-
sponses of AZ31/Nip alloys were investigated. The micro
hardness values (HV) of the pure AZ31 Mg alloy, 2 and 4 wt.%
Ni magnesium alloys in as-cast conditions were 46.08 ± 3.70,
57.50 ± 4.41 and 60.82 ± 4.04 HV and for homogenized samples
the micro hardness values were 43.14 ± 3.62, 47.04 ± 2.39 and
50.62 ± 3.32, respectively. In general, the microhardness of the
samples showed higher values for AZ31-Ni as compared to
pure AZ31. Increasing the weight percentage of Nip had a
significant influence on the microhardness showing an
increasing trend. After homogenization the hardness of the
materials was apparently lower than the as-cast condition
which could reduce the phenomenon of fracturing during
plastic deformation.
Microstructural analysis
To inspect the microstructures, optical digital microscopic
(OM) analysis was carried out for the samples of AZ31-0 Ni,
AZ31-2 Ni, and AZ31-4 Ni under three conditions, namely cast,
homogenized, and ECAP processed samples, as displayed in
Fig. 1. The As-cast AZ-Mg alloys generally exhibited Al12Mg17
as a secondary phase which is known as the brittle phase
which caused a higher micro hardness. Here, the homogeni-
zation process was performed at 410  C for 24 h to increase the
ductility during ECAP deformation. Fig. 1(a) and (b) show the
microstructure of the as-cast-AZ31 alloy before and after ho-
mogenization. The alloy contains cluster-like Al12Mg17 as
shown in Fig. 1(a) while Fig. 1(b) shows that the secondary
phase has dissolved. During the homogenization process, the
1050 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 0 4 7 e1 0 5 8

Fig. 1 e OM microstructure of: (a) as-cast AZ31, (b) homogenized AZ31, (c) ECAPed AZ31 (8pass), (d) as-cast AZ31-2 Ni (e)
homogenized AZ31-2 Ni, (f) ECAPed AZ31-2 Ni (8 pass), (g) as-cast AZ31-4 Ni and (h) homogenized AZ31-4 Ni, (i) ECAPed AZ31-
4 Ni.

elevated temperature increased the Al solubility which caused
the Al12Mg17 to dissolve into the matrix Mg phase [22].
Fig. 1(d) and (g) clearly show that the addition of Nip during
the casting process produced the AlNi phase which agglom-
erated on the surface of the a-Mg phase. The addition of nickel
contents to the liquefied Mg-Al in the temperature range from
650 C to 900  C with different wt.% of (110) Al can produce
phase precipitation of the AlNi. This confirms the dissolution
reaction between the Al and Ni elements that were present in
the casting crucible [23]. In addition, the presence of the
Al12Mg17 phase also confirms the reaction between the Mg-Al
elements. As it can be seen from Fig. 1(e) and (h), Al12Mg17
became immersed into the Mg phase, with some precipitation
of AlNi on the surface of the magnesium. As shown in Fig. 1(c),
(f) and (i), the grain sizes were refined through the plastic
deformation process and this created more grain boundaries.
After 8 passes of ECAP, the uniformity of grain refinement was
higher for the alloy with the Nip addition compared to the pure
one. Furthermore, observations showed a large number of
coarse grains surrounded by refined grains with more defects
induced through deformation. Similar defects were detected
in the microstructure of the AZ31 that was processed by the
ECAP process [24]. The existence of large numbers of grain
boundaries and higher defect density assists in the improve-
ment of the rate of hydrogenation.
The energy dispersive spectrometry (EDS) elemental anal-
ysis of surface compositions for the different cast materials
are shown in Fig. 2. Fig. 2(a and b) shows highly concentrated
secondary phases containing the Mg,Al,Zn, Ni elements which
confirms the compositions of pure AZ31. The detection of Mg
and Al with larger amount exhibit the presence of Al12Mg17
phase. The spectrum for the AZ31-Ni alloys are presented in
Fig. 2(cef) from observations for the alloy AZ31-Ni (2,4 wt.%.),
detection of Al, Ni elements as a major peak for a particular
phase indicates that the possibilities of AlNi phase on the
surface. Hence the addition of Ni element produces the AlNi
phase, evident that the reaction between Al and Ni in the cast
crucible.
Scanning electron microscopy was performed to analyze
the features of the surface morphology of the prepared AZ31/
Nip alloy powders; see the images presented in Fig. 3. Fig. 3(a)
shows the AZ31/Nip alloy after being treated through the ECAP
process combined with manual filing, Observe the defined
elongated nature of the structures in the powder, which are
less than a hundred micrometers. In general, the hydrogen
storage performance of the alloys showed higher efficiency
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 0 4 7 e1 0 5 8 1051

Fig. 2 e EDS analysis results: (a,b) as-cast AZ31-0 Ni, (c,d) as-cast AZ31-2 Ni, (e,f) as-cast AZ31-2 Ni.

with the ECAP and filing process than without the filing pro-
cess due to its higher surface to volume ratio produced by
filing [14,25]. Such a process produces a synergistic effect for
proficient diffusion of the hydrogen molecules which leads to
favorable hydrogenation properties. It is suspected that ball
milling also helps to produce an effective surface to volume
ratio, as indicated by the morphology of the ball milled AZ31/
Nip alloys displayed in Fig. 3(b). This material contains parti-
cles quite similar in size with smoother surfaces than the filed
powders.
The SEM results of the filed alloy powders revealed saw-
toothed surfaces and the ball milled powders had smooth
surfaces decorated with tiny particles. The evolution of the
morphology of the alloy powders upon hydrogenation treat-
ment is presented in Fig. 3(c) and (d), for the ECAP-processed
and ball milled samples, respectively. The hydrogenated
filed sample appears to be fragmented with a significant
reduction in particle size. The ball milled and hydrogenated
samples had rough surfaces due to the occurrence of nucle-
ation throughout the surface of the alloys. The rough surface
is clearly visible in Fig. 3(e). There are two reasons for this: (1)
the metal matrix changes into a tetragonal MgH2 lattice
structure from a hexagonal Mg structure, that produces
changes in the lattice dimensions; (2) the unequal pressure
concentration engendered by the pressurized hydrogen gas
nucleation, leads to ruptures on the surface.
1052 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 0 4 7 e1 0 5 8

Fig. 3 e SEM morphology of the AZ-Alloy (a) ECAP: before hydrogenation, (b) HEBM: before hydrogenation, (c) ECAP: after
hydrogenation, (d) HEBM: after hydrogenation, (e) magnified image after hydrogenation.

Particle size distribution analysis influence of the surface area. Fig. 4 presents the particle size
distribution curves in the same region. The observations show
The average particle size values and particle size distributions the average particle values to be in the range of 45e60 mm.
were evaluated using a laser diffraction method before hy- From the analysis, it can be seen that the increment in the Ni
drogenation. Table 1 shows the average particle sizes for the particle volume influences the hardness and the particle size
obtained AZ31/Nip alloys that were filed after the ECAP pro- values in terms of the milling time.
cess and HEBM, after a milling time of 4 h for pure AZ31 and
3 h for the AZ31-Ni alloys. Different milling times were XRD pattern analysis
required in order to obtain similar particle sizes to reduce the
X-Ray diffraction analysis was carried out for different con-
ditions such as-cast, homogenized, before and after hydro-
Table 1 e Average particle size of the AZ-alloy powder. genation on samples with three different compositions to
S. no Sample Process Average particle determine the different phases. The XRD patterns of the AZ31-
name size (mm) 0 Ni (wt. %) alloys are presented in Fig. 5. From the observa-
1 AZ31-0 Ni ECAP 51.709
tions, it can be seen that the AZ31 alloys exhibited sharp Mg
2 AZ31-0 Ni HEBM 53.927 peaks as a major phase, ascribed to the good crystallization
3 AZ31-2 Ni ECAP 50.861 phenomenon attained during the casting process. The exis-
4 AZ31-2 Ni HEBM 47.898 tence of the Mg peaks after hydrogenation confirmed the
5 AZ31-4 Ni ECAP 51.512 incompleteness of the reaction between Mg and hydrogen to
6 AZ31-4 Ni HEBM 58.923
produce MgH2.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 0 4 7 e1 0 5 8
Fig. 4 e Particle size distribution of AZ-alloy powders.
The XRD results for the AZ31-2 Ni, AZ31-4 Ni alloys before
and after hydrogenation are exhibited in Fig. 6. AZ31 alloyed
with Ni, can be seen to have compounds of pure Mg, Al12Mg17,
AlNi, Mg2Ni as major phases in the as-cast condition which
confirms the presence of Mg-Al-Ni elements while the
Al12Mg17 phase has vanished during homogenization. From
past studies, it is known that the addition of Ni to a Mg-Al alloy
with 3.3% Al content will have a solubility of 0.65% Ni in the
Mg matrix. The residual Ni element reacts with Al to produces
the AlNi phase in the liquid state [23]. Here, in the AZ31 with
Ni alloys, it is noted that the AlNi phase identified by XRD
verifies the reaction between the Al and the Ni and affects the
solubility of Ni in the Mg matrix. It is also found that the Mg2Ni
phase has a tiny intensity which is evidence of the reaction of
excess Ni with the major Mg. After the homogenization pro-
cess, the AlNi phase is still present in the AZ31-Ni alloys, with
small changes in the intensity. The Al12Mg17 phase is found
after plastic deformation (ECAP) and mechanical ball milling
in pure AZ31 and in the alloy with the addition of Ni. The
addition of Ni into the Mg-Al alloy allowed this to form, and
enhanced the quantity of the Al12Mg17 phase in the matrix
[26]. Detection of the AlNi phase with its negligible intensity
Fig. 5 e XRD patterns of pure AZ31: (a) ECAP and (b) HEBM.
1053
shows that the AlNi phase dissolved into the matrix during
the ECAP process; see Fig. 6(a, c). The phenomenon of dynamic
recrystallization (DRX) and the thermal energy produced
during ECAP could have caused the dissolution of AlNi into the
Mg matrix. After squeezing, the samples were subsequently
dipped into water which could stop the phase evolution. In
contrast, the XRD results show the presence of the AlNi phase
for ball milling. It is evident that the energy produced during
high energy ball milling does not affect the AlNi thus it is
present in the matrix before hydrogenation. The AlNi phase
can be identified even after hydrogenation; see Fig. 6(b, d). The
presence of the AlNi phase after hydrogenation indicates that
AlNi does not react with the hydrogen molecules. The ob-
tained XRD patterns reveal that the a-Mg phase was trans-
formed into the b-MgH2 phase during the hydrogenation
process, and the Mg2NiH4 phase was also found to have a very
small intensity in the AZ31-4 Ni alloy. The alloy powders
processed by ball milling contained a higher intensity of a-Mg
after hydrogenation as compared to the alloys that were
processed by the ECAP technique.
Hydrogenation properties
The hydrogen storage and kinetic properties of pure AZ31 and
AZ31-Ni alloys which were treated through different methods
such as ECAP and ball milling were measured. The effects of
the different processing procedures and the addition of Ni
particles were compared. The kinetic properties were calcu-
lated at the same temperature of 375  C and a similar particle
size distribution. Fig. 7 shows the absorption and desorption
characteristics of the AZ31/Nip alloy samples. From the ob-
servations, it can be noted that the samples treated thorough
ECAP show more stable absorption than the powdered sam-
ples milled by the HEBM process; see Fig. 7(a, c, e). The milled
alloy materials show a tendency for hydrogenation to prog-
ress, indicating that the reaction is still not finished. Hence,
the ECAP process significantly influences the rate of the re-
action. Materials treated with the ECAP process (with the Bc
route) were deformed in three planes which produces the
more grain boundaries causing the grain structure to be
refined uniformly [27]. The hydrogenation consists of three
main steps: nucleation, diffusion of hydrogen atoms into the
1054 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 0 4 7 e1 0 5 8
Fig. 6 e XRD patterns of AZ31 with Ni: (a) AZ31-2 Ni: ECAP, (b) AZ31-2 Ni: HEBM, (c) AZ31-4 Ni: ECAP, (d) AZ31-4 Ni: HEBM.
Mg matrix and reaction between the magnesium and
hydrogen. During deformation, the dislocation density in-
creases with an increasing number of passes to produce a
larger quantity of dislocations [28,29]. The produced disloca-
tions act as trapping sites [30], while the grain boundaries act
as the nucleation paths for the hydrogen diffusion which
further enhances nucleation [13]. Thus, processing with the
ECAP method encourages the kinetics of hydrogenation and
increases the volume of hydrogen reaction to magnesium for
the same reaction time.
The hydrogen storage capacity and reaction time for
different compositions of AZ31/Nip alloys are shown in
Table 2. From the XRD patterns, it can be seen that the AlNi
phase dissolves into the matrix during the ECAP process
which is considerably produces the Mg-solid solution. It is
presumed that the dissolved solid solution phase influences
the quantity of magnesium involved in the reaction. It can be
observed from the absorption capacity of the different mate-
rials that an increase in the Ni content in the alloy increases
the magnesium solid solution during the deformation process
which could enhance the quantity of Mg available to react
with the hydrogen thereby increasing the kinetics. Hence, the
volume of reactive magnesium (R-Mg) is comparatively larger
for the AZ31-4Ni alloy than other materials for a specific re-
action time. It reaches the maximum capacity of 7.0 wt.% in
2322 s which is faster than in a previous study [31] and the
entire amount of hydrogen is desorbed in less than 5 min. The
reaction between the Mg- Ni elements produces a tiny amount
of Mg2NiH4 which enhances the hydrogenation kinetics.
However, the attainment of saturated hydrogenation for
Mg2NiH4 is extremely difficult even after 450 min at high
temperature, as observed through in-situ XRD [32]. In the case
of the ball milled sample, the AlNi phase does not dissolve
during this milling time. A non-reacting AlNi phase influences
the hydrogenation capacity. It can be seen that the addition of
Ni could increase the AlNi phase in the matrix causing a
reduction in capacity. Therefore, the maximum absorption
capacity of 6.5 wt.% was observed for the pure AZ31 alloy in
which the compound AlNi does not exist in the matrix. For
AZ31-2 Ni, the maximum capacity reached was 6.4 wt.%.
Similarly, AZ31-4 Ni which had a higher Ni content, had the
lowest hydrogen storage capacity of 6.2 wt.% after 2359 s. It
can be seen that the material subjected to the ECAP process
demonstrated comparatively better results than that the
material processed by high energy ball milling.
Activation energy
Additionally, the thermal decomposition properties were
calculated for the AZ31-4 Ni alloy after deformation by ECAP
and high energy ball milling. In order to determine the influ-
ence of different processing and catalytic effects on the acti-
vation energy, the alloys (AZ31-4 Ni -ECAP and HEBM) were
hydrogenated for preparation of hydrides. Then the powdered
materials were subjected to differential scanning calorimetric
analysis in the temperature range of 30e500  C. Three types of
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 0 4 7 e1 0 5 8 1055

Fig. 7 e Kinetic curve of AZ31-alloys: ECAP VS HEBM: (a) AZ31-0 Ni absorption, (b) AZ31-0 Ni desorption, (c) AZ31-2 Ni
absorption, (d) AZ31-2 Ni desorption, (e) AZ31-4 Ni absorption, (f) AZ31-4 Ni desorption.

Table 2 e Hydrogen storage absorption capacity and reaction time for AZ31/Ni alloys with different compositions.
Sample Temperature  C Absorption Desorption Absorption Desorption
capacity (wt.%) capacity (wt.%) time (s) time (s)
AZ31-0 Ni ECAP 375 6.5 ± 0.04 6.5 ± 0.05 2256 ± 350.65 355 ± 47.97
AZ31-2 Ni ECAP 375 6.7 ± 0.04 6.7 ± 0.04 2152 ± 371.9 260 ± 15.84
AZ31-4 Ni ECAP 375 7.0 ± 0.04 7.0 ± 0.04 2322 ± 196.01 294 ± 34.51
AZ31-0 Ni HEBM 375 6.5 ± 0.05 6.5 ± 0.04 2393 ± 174.34 332 ± 17.27
AZ31-2 Ni HEBM 375 6.4 ± 0.07 6.4 ± 0.00 2390 ± 113.96 287 ± 19.32
AZ31-4 Ni HEBM 375 6.2 ± 0.04 6.2 ± 0.04 2359 ± 187.05 253 ± 31.10
1056 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 0 4 7 e1 0 5 8
Fig. 8 e DSC curves: (a) AZ31-4 Ni-ECAP, (b) AZ31-4 Ni-HEBM.
Fig. 9 e Kissinger plots: (a) AZ31-4 Ni- ECAP, (b) AZ31-4 Ni-HEBM.
changes in temperature rate were followed in (DSC), namely,
15  C, 20  C, 25  C/min, as shown in Fig. 8. The activation en-
ergies of the prepared alloys were calculated by Kissinger
plots. The Kissinger plots of the AZ31-4 Ni alloy are shown in
Fig. 9. The dehydrogenation behavior of the material is rele-
vant to the activation energy barrier for the release of H2 gas
from the MgH2. It can be seen that the alloy AZ31-4 Ni
deformed by ECAP has activation energy of 104.73 (KJ/mol),
and for the same alloy (AZ31-4 Ni) which was milled by HEBM
process shows the activation energy of 111.45 (KJ/mol). The
materials processed by ECAP exhibited the lower activation
energy means that the applying processing route could in-
fluence the activation energy. Furthermore, the addition of
different Ni composites to MgH2 affect the activation energy
by decreases the onset temperature level for hydrogen
desorption. Hence, the Alloy AZ31-4 Ni treated through two
process shows the activation apparently lower than the pure
MgH2 which has a value of 161.9 (KJ/mol) [33].
Conclusions
In this study, AZ31-0 Ni, AZ31-2 Ni, and AZ31-4 Ni alloys were
fabricated through the gravitating mechanical stir casting
(GMSC) process. Significant grain size refinements and
increased defect density were observed after deformation
through the ECAP process. The ECAP-processed AZ31-4 Ni
alloy showed a maximum hydrogen storage capacity of
7.0 wt.% within 2322 s and all the hydrogen was desorbed in
less than 5 min at a temperature of 375  C. The reason for the
high hydrogen storage and rapid release of AZ31-4 Ni was
presumed that the dissolving of AlNi phase into the matrix
during the ECAP process. It is presumed that this influenced
and enhanced the quantity of reactive magnesium (R-Mg)
which was involved in the reaction, causing the increasing
tendency upon increase of the Ni contents. Furthermore,
some of the Ni content may also react with Mg to form a tiny
amount Mg2NiH4 which also the reason for the hydrogenation
rate enhancement.
The AlNi phase was not seen to dissolve during the ball
milling process and it was also found that AlNi formed after
the hydrogenation process which confirms that AlNi does not
participate in the reaction with the hydrogen molecules. Thus,
the increment of the Ni contents in the Mg matrix caused a
reduction in the hydrogen storage capacity. As a result, in the
HEBM process, the pure AZ31 alloy absorbed the maximum
capacity of 6.5 wt.%; for AZ31-2 Ni and AZ31-4 Ni the absorbed
capacity was 6.4 and 6.2 wt. % respectively. The activation
energy for the AZ31-4 Ni alloy was estimated through a Kis-
singer plot. It was revealed that the addition of Ni and the
deformation processes reduced the activation energy by
104.73 (KJ/mol) for the samples deformed by ECAP which is
obviously lower than the material processed by HEBM and
pure MgH2. Overall, the observations that the AZ31-4 Ni
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 0 4 7 e1 0 5 8
material which was processed by ECAP showed better kinetics
with higher sorption capacity.
Acknowledgment
The authors would like to acknowledge the financial support
received from the Ministry of Science and Technology of
Taiwan for this research under the grant number MOST 106-
2221-E-011 -008 -MY2. We also wish to express our gratitude to
Prof. Chun Chiu (NTUST-Taiwan) for the assistance with the
Sievert's apparatus and also sincerely thank Prof. Eugen Rab-
kin (Technion-Israel) for his support and guidance.
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