Journal of Alloys and Compounds 471 (2009) 90–92

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Journal of Alloys and Compounds

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Interfacial reaction and the dominant diffusing species in Mg–Ni system

M.Y. Tsai, M.H. Chou, C.R. Kao ∗
Department of Materials Science & Engineering, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei City, Taiwan

a r t i c l e i n f o a b s t r a c t

Article history: The solid–solid interfacial reaction in the Mg–Ni binary diffusion couples was studied for the first time
Received 5 November 2007 in bulk form. The reaction temperature was at 400, 430, 450, and 480 ◦ C, with reaction time ranging
Received in revised form 26 March 2008 from 10 to 75 h. The Mg–Ni phase diagram shows two stable compounds, Mg2 Ni and MgNi2 , at these
Accepted 26 March 2008
temperatures, but only Mg2 Ni was observed at the interface after the reaction. The growth of Mg2 Ni
Available online 12 May 2008
followed the parabolic kinetics, and the apparent activation energy was determined to be 120 kJ/mol. The
dominant diffusing species was identified by using thin W lines as markers. After the reaction, these W
Keywords:
markers located near the Mg/Mg2 Ni interface, suggesting that Mg was the dominant diffusing species in
Hydrogen storage materials
Mg2 Ni
Mg2 Ni. This is consistent with the general trend that in many metal/metal systems the dominant diffusing
Intermetallic compounds species are usually the majority elements in the compounds that formed first.
Thermodynamic properties © 2008 Elsevier B.V. All rights reserved.
Interdiffusion

1. Introduction It was found that only Mg2 Ni formed. Nevertheless, no detailed

Mg-based alloys are of great potential for use as hydrogen stor-
age materials. The theoretical hydrogen storage capacities of Mg
and Mg2 Ni are 7.6 and 3.6 wt.%, respectively, among the highest of
known metal-hydrides [1–3]. Mg-based alloys have the additional
benefits of being abundant in nature, light in weight, inexpensive,
and non-toxic [3–5]. Pure Mg oxidizes easily, and its ability for
the sorption of hydrogen molecules degrades substantially when
oxidized [5]. The compound Mg2 Ni does not suffer from this prob-
lem, and is considered a promising and practical hydrogen storage
material [5].
Mechanical alloying is the major approach for preparing Mg–Ni
alloys for hydrogen storage applications [6–9]. It was reported
that a shorter alloying time would produce an amorphous Mg–Ni
alloy [6,7], and a longer alloying time could produce the crys-
talline Mg2 Ni phase [8,9]. The formation of crystalline Mg2 Ni phase
implies that atomic diffusion plays a role in the intermixing of Mg
and Ni atoms. Despite its importance in hydrogen storage applica-
tions, very little is known about the diffusion in the Mg–Ni binary
system. According to the Mg–Ni binary phase diagram [10,11], there
are two stable compounds, Mg2 Ni and MgNi2 , at temperature below
760 ◦ C. A literature search revealed only two studies related to the
interdiffusion between Mg and Ni. In 1992, the thin film reaction
between Ni (80 nm) and Mg (300 nm) at 225 ◦ C was reported [12].
∗ Corresponding author. Tel.: +886 2 3366 3745; fax: +886 2 3366 3745.
E-mail addresses: s8966051@yahoo.com.tw, crkao@ntu.edu.tw (C.R. Kao).
growth kinetics data for the formation of this phase was reported.
In 1995, the reaction between bulk molten Mg and solid Ni plate
was studied at 660 and 680 ◦ C [13]. It was again found that only
Mg2 Ni formed. The kinetic data reported in this study were lim-
ited because the reaction was carried out for only three different
lengths of time (5, 10, and 15 min) at two different temperatures.
In view of the fact data the Mg–Ni binary reaction data is still
lacking, the objective of the present study is to investigate the
binary reaction between Mg and Ni and to establish the growth
kinetics of the reaction product. Additionally, the dominant diffus-
ing species is also to be identified by using the marker technique.
2. Experimental
The end members of the diffusion couple were Mg sheets (99.95 wt.%) and Ni
sheets (99.5 wt.%) with the same cross-section area (10 mm × 6 mm). The thick-
nesses of Mg sheets and that of Ni sheets were 1 and 0.4 mm, respectively. The
surfaces of the Mg and Ni sheets were metallurgically polished before assembly,
and were then etched in 5% and 15% Nital solution, respectively. A diffusion couple
was assembled by sandwiching one Mg sheet between two Ni sheets in a S304 stain-
less steel sample holder, shown schematically in Fig. 1. Before the sample holder was
loaded, it was sprayed with boron nitride powder to prevent the interaction between
the sample holder and the sheets. The sample holder with the diffusion couple was
then placed in a diameter quartz tube, evacuated to a vacuum of 5 mTorr, sealed,
and put into furnace to react. The reaction temperatures were at 400, 430, 450, and
480 ◦ C, and the reaction time ranged from 10 to 75 h. At these temperatures, both
Mg and Ni remained in their solid states.
After the reaction, each diffusion couple was quenched in water, taken out of the
sample holder, encapsulated in epoxy, and metallographically polished for analysis.
The reaction zone of each diffusion couple was examined by an optical microscope.
The thickness of the reaction product was measured at regular intervals on its optical
micrograph. For each sample, about 30 data points were measured, and the average

0925-8388/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
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 M.Y. Tsai et al. / Journal of Alloys and Compounds 471 (2009) 90–92
Fig. 1. Schematic drawing of the sample holder used in the diffusion couple exper-
iment. The screws of the sample holder were tightened to keep the two disks in
contact. The whole sample holder was enclosed in an evacuated quartz capsule
during reaction to prevent oxidation.
thickness was reported. An electron microprobe (EPMA), operated at 15 keV, was
used to measure the composition of each phase and the concentration profiles of
the diffusion couples. In EPMA analysis, the standards used were pure Ni and pure
Mg, and the weight percentages of Ni and Mg were measured independently, and
the total percentage was within 100 ± 1 wt.% in each case. It was estimated that the
accuracy of the compositions determined in this study was within 1 wt.%.
The marker experiment was carried out by depositing parallel W lines on the
surface of the Ni plates before the assembly of the diffusion couples. The W stripes
were 3-␮m wide and 0.5-␮m thick. No evidence of interaction with Ni or Mg was
observed during the reaction of the diffusion couples.
3. Results and discussion
For all the temperatures (400–480 ◦ C) and the reaction time
(10–75 h) used in this study, the only intermetallic compound
observed was Mg2 Ni. According to the Mg–Ni phase diagram
[10,11], there is another intermetallic phase MgNi2 which is also sta-
ble at these temperatures. Nevertheless, MgNi2 was not detected,
even after careful examination along the Mg–Ni interface by using a
SEM at high magnification. The observation that only Mg2 Ni formed
is the same as in the thin film reaction at 225 ◦ C [12], and in the
reaction between Ni and molten Mg carried out at 660–680 ◦ C [13].
As shown in Fig. 2, Mg2 Ni formed after the reaction at 480 ◦ C for
45 h exhibited a layered morphology. This layered morphology is
quite characteristic for solid-state reactions, and is different from
the scallop morphology often observed in the reaction between
solid and liquid, such as the reaction between Ni and molten Mg
[13]. Reactions at all other temperatures and reaction time used in
this study always produced only Mg2 Ni with this layered morphol-
ogy. The composition of this Mg2 Ni was determined to be 31 at.%
Ni by using EPMA. Line-scan across the reaction zone showed that
Fig. 2. Backscattered electron micrograph showing the reaction product after reac-
tion at 480 ◦ C for 45 h. The only reaction product formed was Mg2 Ni.
91
Fig. 3. X-ray diffraction pattern of the reaction product after annealing at 480 ◦ C
for 75 h, showing the formation of the Mg2 Ni phase. The Ni peaks were from the Ni
sheet beneath Mg2 Ni. This pattern was taken from a fracture diffusion couple, with
a thin fractured layer of Mg2 Ni remained over the Ni substrate.
there was only a very slight concentration gradient across this layer,
and Mg2 Ni could indeed be classified as a line compound. X-ray
diffraction pattern, shown in Fig. 3, revealed that the compound
formed was indeed the hexagonal Mg2 Ni phase. This diffraction
pattern was taken from a fractured half of a diffusion couple, with
a thin layer of Mg2 Ni remained over the Ni substrate. The Ni side
of the fractured diffusion couple was used for the diffraction mea-
surement because, if MgNi2 had formed, MgNi2 would have formed
between Mg2 Ni and Ni. As shown in Fig. 3, no diffraction peak
from MgNi2 was detected. Some Ni peaks were present from the
Ni substrate beneath the Mg2 Ni layer.
As mentioned earlier, the second Mg–Ni stable phase, MgNi2 ,
was not observed in this or earlier studies [12,13]. In the literature,
three probable reasons had been proposed for the missing of one
or more phases in a binary diffusion couple [14]. The first reason
was that the missing phase(s) were actually there, but were too
thin to be resolved by the characterization techniques used. The
second and the third reasons assumed that the missing phase(s)
indeed does not form due to the nucleation barrier or slow growth
kinetics, respectively. The second reason, the nucleation barrier, is
self-explanatory and is not discussed further here. The third rea-
son, the slow growth kinetics, had been shown to be the case
for the Ni–Bi system [14] and for the Ti–Al system [15]. In these
two systems, it was shown that if the interdiffusion coefficient for
the missing phase was substantially lower than the other phases,
then this phase would disappear even though this phase had been
Fig. 4. Thickness of Mg2 Ni plotted against the reaction time. This illustrates that the
growth of Mg2 Ni was diffusion controlled.
92 M.Y. Tsai et al. / Journal of Alloys and Compounds 471 (2009) 90–92
Fig. 5. Plot of ln K versus the inverse temperature (1/T). From the slope of this plot,
the activation energy for k was determined to be 120 kJ/mol.
Fig. 6. Backscattered electron micrograph showing the reaction product for reaction
at 480 ◦ C for 30 h. The W markers located near the Mg side, suggesting that Mg was
the dominant diffusing species.
present initially. Under such a condition, the phase with a higher
interdiffusion coefficient will grow at the expense of the neighbor-
ing phase with a lower interdiffusion coefficient until the latter
disappear completely. In this study, our evidence is not strong
enough to conclude which one of the three reasons is the root cause
for the missing MgNi2 .
The growth kinetics for Mg2 Ni is presented in Fig. 4. The growth
of Mg2 Ni clearly followed the parabolic kinetics, suggesting that
the growth was diffusion controlled. The thickness versus time data
were fitted to the equation, d = (Kt)1/2 , where d is the thickness of
Mg2 Ni in m and t is the reaction time in s, to obtain the growth
constant K in m2 /s. The growth constant K was defined in such a
way so that it had the same dimension as the diffusion coefficient.
The activation energy for K was then obtained by plotting ln K versus
the inverse temperature, as shown in Fig. 5. From the slope of the
line in Fig. 5, the activation energy was determined to be 120 kJ/mol.
The location of the W markers after reaction at 480 ◦ C for 30 h
is shown in Fig. 6. These W markers located near the Mg/Mg2 Ni
interface, suggesting that Mg was the dominant diffusing species
in Mg2 Ni. This observation is consistent with the general trend that
in many metal/metal systems the dominant diffusing species are
usually the majority elements in the initially formed compounds
[16].
The growth constant for the formation of Mg2 Ni is quite appre-
ciable. For example, according to Fig. 4, the Mg2 Ni layer grew
to about 10-␮m thick in 10 h at 400 ◦ C. At a typical hydrogen
absorption–desorption temperature of 200 ◦ C, the data in Fig. 4 can
be extrapolated to show that 0.033 ␮m of Mg2 Ni will form in 1 h. In
view of the fact that many Mg–Ni alloys for hydrogen storage appli-
cations have nano-crystalline microstructure, it can be concluded
that nano Mg or Ni powder will be converted into Mg2 Ni rather
quickly even at 200 ◦ C.
4. Summary
The interfacial reaction between solid Mg and solid Ni was stud-
ied for the first time in bulk form. Only one compound, Mg2 Ni,
was observed in the Mg–Ni binary diffusion couples aged at 400,
430, 450 and 480 ◦ C. The other stable compound MgNi2 was not
detected in the diffusion couple. The growth of Mg2 Ni followed the
parabolic kinetics, suggesting the reaction was diffusion controlled.
The apparent activation energy for the growth constant was deter-
mined to be 120 kJ/mol. This value is near the lower boundary of the
range where the vacancy diffusion mechanism dominates. Marker
experiment showed that Mg was the dominant diffusing species in
Mg2 Ni.
Acknowledgement
This research was supported by National Science Council of ROC
through grant NSC-94-2218-E-008-012.
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