Journal of Alloys and Compounds 619 (2015) 411416

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

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

The formation of intermetallic compounds during interdiffusion

of MgAl/MgCe diffusion couples
Jiahong Dai a, Bin Jiang a,b,, Xin Li a, Qingshan Yang a,b, Hanwu Dong b, Xiangsheng Xia c, Fusheng Pan a,b
a

College of Materials Science and Engineering, National Engineering Research Center for Magnesium Alloys, Chongqing University, Chongqing 400044, China
Chongqing Academy of Science and Technology, Chongqing 401123, China
c
No. 59 Institute of China Ordnance Industry, Chongqing 400039, China
b

a r t i c l e

i n f o

Article history:
Received 24 July 2014
Received in revised form 2 September 2014
Accepted 7 September 2014
Available online 16 September 2014
Keywords:
Magnesium
Intermetallic compounds
Diffusion
Substitution
Kinetics

a b s t r a c t
The formation of AlCe intermetallic compounds (IMCs) during interdiffusion of MgAl/MgCe diffusion
couples prepared by solidliquid contact method was investigated at 623 K, 648 K and 673 K for 24 h,
48 h and 72 h, respectively. During the whole diffusion process, Al was the dominant diffusing species,
and it substituted for Mg of the MgCe substrate. Five AlCe IMCs of Al4Ce, Al11Ce3, Al3Ce, Al2Ce and AlCe
were formed via the reaction of Al and Ce. The formation of Al4Ce as the rst kind of IMC was rationalized
on the basis of an effective Gibbs free energy model. The activation energy for the growth of the total diffusion reaction layer was 36.6 kJ/mol.
2014 Published by Elsevier B.V.

1. Introduction
As the lightest metal structural materials, magnesium alloys
have high specic strength, excellent castability, and easy recyclability [1,2]. The current commercial use of magnesium alloys is
mainly focused on the MgAl-based alloys [3], as Al improves the
castability and mechanical properties at room temperature [4].
However, the application of commercially available MgAl based
alloys is limited to room or near room-temperature applications
because of their inferior creep resistance and lower strength at elevated temperatures [5]. The addition of cerium (Ce) is one of the
effective methods to optimize the microstructure and improve elevated temperature mechanical properties of MgAl alloys, due to
the formation of relatively thermally stable AlCe intermetallic
compounds (IMCs) [6].
The AlCe IMCs have attracted special attentions in recent
years. Many investigations of IMCs have been done when Ce is
added to MgAl alloys. For example, the morphologies of AlCe
IMCs in MgAlRE alloys are reported [7,8]. Al11Ce3 and Al3Ce
are acicular-like shaped and Al2Ce is quadrate-like shaped. The
thermal stability of Al11Ce3 and Al2Ce is investigated in

Corresponding author at: College of Materials Science and Engineering, National

Engineering Research Center for Magnesium Alloys, Chongqing University, Chongqing 400044, China. Tel.: +86 135 94190166; fax: +86 65111140.
E-mail address: jiangbinrong@cqu.edu.cn (B. Jiang).
http://dx.doi.org/10.1016/j.jallcom.2014.09.071
0925-8388/ 2014 Published by Elsevier B.V.

Mg3.4Al2.4Ce0.3Y0.3Mn alloy [9]. The alloy is annealed at

473 K for 800 h, while A111Ce3 and Al2Ce phases exhibit good thermal stability with no signicant changes in size and shape. However, there is still some scientic confusion about the phase
formation process in MgAlCe ternary system need to be claried.
Knowledge of thermodynamics and diffusion kinetics is important
to understand the complex phase transformations and precipitations behavior in materials. Although there have been active diffusion kinetics and thermodynamics studies on the MgAl [10,11]
and AlCe [12,13] binary systems, no systematic thermodynamics
and diffusion kinetics studies have been performed for the
MgAlCe ternary system so far.
The diffusion couple technique is valuably experimental for the
studies of IMCs forming process. Previously, there are a great number of studies of the diffusion coefcients and IMCs in Mg alloy
through the diffusion couple technique. The diffusion coefcients
of Al in Mg alloy and intermetallic phases at 573 K, 623 K and
673 K are reported in literatures [10,14]. The intermetallic phases
are investigated in the MgCe system through a diffusion couple
[15]. In the diffusion couple, four intermetallics are formed as:
Mg11Ce, Mg39Ce5, Mg3Ce and MgCe. Recently, diffusion couples of
Mg0.667Ce0.333 and Al0.667Ce0.333 are employed to determine the
thermodynamic evaluation and optimize the AlMgCe ternary
system [16]. However, the interdiffusion of MgAlCe ternary system is not fully reported.
The present study employs the diffusion couple technique and
focuses on the IMCs formation at MgAl/MgCe interface. The

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IMCs formation is predicted by the thermodynamic model. The

growth kinetics of the diffusion reaction layers are determined
simultaneously.
2. Experimental
A solidliquid contact method was employed to produce the MgAl/MgCe diffusion couples. Pure Mg (99.98 wt.%), pure Al (99.99 wt.%) and MgCe (Mg20 wt.%
Ce, melting point: 868 K) master alloy were used. Al was added into Mg to form of
MgAl (Mg40 wt.% Al, melting point: 733 K) master alloys. The alloys were melted
several times to ensure the composition homogeneity. A rectangular piece of MgCe
master alloy was polished with 200-grit SiC paper, and then cleaned with acetone to
make sure an oxide free surface. MgAl master alloy was melted under a protective
atmosphere of CO2 + 0.5 vol.% SF6. The melt was then taken from the furnace under
the cover gas of CO2 + 0.5 vol.% SF6 and MgCe master alloy was immediately submerged into the MgAl melt. Due to the higher thermal expansion coefcient of
MgAl alloy compared with that of MgCe alloy, an intimate contact between
MgAl and MgCe alloys was formed during solidication. The samples were
encapsulated in quartz tubes. Quartz tubes were placed in a furnace, and heat treated at 623 K, 648 K and 673 K for 24 h, 48 h and 72 h, respectively, and then the
samples were quenched in cold water to be rapidly cooled.
The diffusion couples were polished by conventional metallographic technique
using diamond paste with an oil-based extender and studied via optical microscopy
(OM), scanning electron microscopy (SEM). The intermetallic phases formed at the
diffusion reaction layers were identied by energy dispersive spectroscopy (EDS)
and X-ray diffractometer (XRD). To determine the growth kinetics of the diffusion
reaction layers, the thicknesses of the diffusion reaction layers were examined from
optical micrographs of the cross-sections. An average thickness was obtained from
20 individual measurements.

3. Results and discussion

3.1. Identication of reaction products
Optical micrographs of the cross-sections of the diffusion couples annealed at 623 K, 648 K and 673 K for 72 h are shown in
Fig. 1. As is seen in these micrographs, several reaction sub-layers
are observed to form at the MgAl/MgCe interfaces, and located
in the MgCe substrate. The thickness of the total diffusion
reaction layer increased evidently when increasing the annealing
temperature, which is about 155 lm, 173 lm and 200 lm in
Fig. 1(a)(c), respectively. It can be seen that signicant microstructure variations are found for the different temperatures.
In order to identify the phase constitution of the diffusion reaction layers, X-ray diffraction examination is carried out. The X-ray
diffraction on the diffusion reaction layers shown in Fig. 1(c) is carried out on two sub-layer after grinding down to the corresponding
depth. Indexing the spectra shown in Fig. 2, Al4Ce, Al11Ce3, Al3Ce
and Mg are identied on the lower sub-layer. Different to the lower
sub-layer, there are Al2Ce and AlCe in the top sub-layer. This is
attributed to the complexity of these phases mixture of such
regions. Further investigations are required to elucidate the formation of the IMCs microstructures.

Fig. 1. Optical micrographs of the diffusion reaction layers for the diffusion couples
annealed at (a) 623 K, (b) 648 K, and (c) 673 K for 72 h.

3.2. Microstructural of the diffusion reaction layers

Fig. 3(a)(c) shows SEM back-scattered electron (BSE) images of
the different layers formed in the diffusion couples annealed at
673 K for 24 h, 48 h and 72 h, respectively. It is observed that several reaction layers exist between the two substrates. The microstructure varies for different holding times and the total
thickness of these layers increases signicantly. At the holding
time of 24 h, the acicular-like intermetallics in the reaction layer
are not obvious. When the holding time reaches 48 h, the
acicular-like intermetallics can be obviously seen in the reaction
layer. With further increasing of holding time, the thickness of
the acicular-like intermetallics layer increases to about 110 lm.
In order to study the diffusion behavior thoroughly, Fig. 3(c),
which is for the sample annealed at 673 K for 72 h, is taken into
consideration. Four layers are visible from the MgAl substrate to

Fig. 2. X-ray diffraction patterns of the reaction products after annealed at 673 K
for 72 h.

MgCe substrate, as named as IIV, respectively. It can be found

that there are kinds of IMCs with different shapes in the diffusion
reaction layers. The existence of diffusion reaction layer I may be a
result of Als intrinsically faster diffusion. In this layer,

J. Dai et al. / Journal of Alloys and Compounds 619 (2015) 411416

413

Fig. 3. SEM images of the diffusion reaction layers for the diffusion couples annealed at 673 K for (a) 24 h, (b) 48 h, (c) 72 h, and high magnication images of (d) the region 1,
(e) the region 2, (f) the region 3.

concentration of Al lower than the substrate of MgAl, and it presents a distribution of gradient decrease distribution showed Fig. 4.
Fig. 3(d)(f) is high magnication images of the regions 13,
respectively. For layers II and III, they are mainly composed of particle-like intermetallics, but the macro morphology is different. In
the layer IV, there are a lot of acicular-like intermetallics, which are
grown along the diffusion direction. Besides, a few quadrate-like
intermetallics particles can be found by careful BSE observations
nearby the MgCe substrate. While the EDS results taken from
the testing positions denoted in Fig. 3(d)(f) are summarized in
Table 1. Nevertheless, AlCe is not detected in BSE micrograph, even
after careful examination along the interface by using BSE at high
magnication. The probable reason is that the AlCe phase is too
small to be resolved by the used characterization techniques.
Fig. 4 shows the analysis of the EDS line scan across the diffusion couple in the sample is annealed at 673 K for 72 h, shown in

Fig. 4. Composition prole along the line scan shown in Fig. 3(c).

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J. Dai et al. / Journal of Alloys and Compounds 619 (2015) 411416

Table 1
EDS results taken from different positions of the diffusion layers as denoted in Fig. 3.
Zone

Mg (at.%)

Al (at.%)

Ce (at.%)

Al/Ce ratio

Phase

A
B
C
D
E
F

68.61
73.82
67.18
63.97
75.99
94.93

25.57
21.10
25.98
27.82
15.90
5.07

5.82
5.08
6.84
8.21
8.11
0

4.39
4.15
3.79
3.38
1.96

Al4Ce
Al4Ce
Al11Ce3
Al3Ce
Al2Ce
Solid solution

Fig. 3(c). The line scan contains data for 20 points. The concentration prole of Mg is a slight uctuation in layers II and III, but it is
increased in layers I and IV. The distribution of Al is decreased
gradually in layers I and IV, while the Al content remains to be a
constant from layer II to layer III. The concentration prole of Ce
is almost at in all zones. Because of the higher Al content in the
MgAl substrate and the higher Mg content in the MgCe substrate, Al atoms incline to diffuse to MgCe substrate and Mg
atoms to MgAl substrate. The concentration proles show that
the substitution of Mg is taken place by Al, and AlCe IMCs are
formed by AlCe reaction, along with their diffusion direction. It
can be concluded that the total diffusion reaction layers located
in the MgCe substrate, which is in good agreement with optical
micrographs in Fig. 1. This suggests that Al is the dominant diffusing species during the diffusion process, which may be related that
the diffusion of Al is faster than that of Ce in Mg. Al has a lower
melting point (933 K) than Ce (1072 K), and it may require less
activation energy for Al to migrate. In addition, the atomic radius
of Al (143 pm) is smaller than Ce (185 pm) which can allow Al to
move easily than Ce in Mg.
Fig. 5 shows the MgAlCe calculated isothermal section at
673 K [17], where the points are the line scan of the diffusion
couple annealed at 673 K for 72 h, and mainly located in
Al11Ce3 + (Mg), Al11Ce3 + Al3Ce + (Mg), Al3Ce + Al2Ce + (Mg) and
Al2Ce + (Mg) phase elds. The diffusion path of the diffusion couple
is along the line with points. Nevertheless, no related data for Al4Ce
in ternary phase diagram of the MgAlCe system was reported, so
it cannot nd the corresponding region in the phase diagram. AlCe
cannot be determined in the phase elds of the diffusion path
through. From the analysis of the MgAlCe calculated isothermal

Fig. 5. MgAlCe calculated isothermal section at 673 K.

section at 673 K, it can be concluded that Al11Ce3, Al3Ce and Al2Ce

are identied in the diffusion reaction layers.
3.3. Formation of intermetallic compounds
Annealing in the temperature range of 623673 K in the present
study resulted in the formation of Al4Ce, Al11Ce3, Al3Ce, Al2Ce and
AlCe between MgAl/MgCe in the diffusion process. The thermodynamic behavior is an important factor for the sequence of AlCe
IMCs layer. Since MgAl, MgCe and AlCe compounds can form in
the MgAlCe ternary system. The Miedemas model [18] for the
enthalpy of formation is used to determine the standard molar
enthalpies of the formation of MgAl, MgCe and AlCe binary systems. As shown in Fig. 6(a), the standard molar enthalpy of the formation of the AlCe binary system is far lower than those of MgCe
and MgAl binary systems, which indicates that AlCe IMCs prefer
to be formed in the MgAlCe ternary system in the same
condition.
In previous studies [12,19,20] showed that the thermochemical
properties of AlCe phases have been studied, but the values of the
standard enthalpy of the formation of these phases are widely discrepant. So the effective heat of formation (EHF) model cannot be
used to predict the formation of the rst phase in AlCe binary system. It is well known that the Gibbs free energy of a chemical reaction is an effective criterion to judge whether or not this reaction
will occur. If Gibbs free energy is less than zero, the chemical reaction occurs. Moreover, among all possible reactions, the reaction
with the lowest Gibbs free energy tends to occur.
The Gibbs free energy for a solid solution phase in a binary
system AB can be represented mathematically as follows [21]:

Fig. 6. (a) Formation enthalpies of the MgAl, MgCe and AlCe binary systems and
(b) Gibbs free energies of the formation of different AlCe IMCs as the function of
temperature.

J. Dai et al. / Journal of Alloys and Compounds 619 (2015) 411416

GS C A GA C B GB DHSmix T DSSmix

415

where CA and CB are the mole fractions of A and B elements, respectively. GA and GB are the Gibbs free energy of the pure element A and
B, respectively. DHSmix is the enthalpy change during intermixing,
DSSmix RC A ln C A C B lnC B is the ideal entropy of intermixing,
and T is the temperature. The enthalpy change of a solid solution
phase can be determined by the semi-experimental Miedemas
model:

DHSmix DHC DHE DHS

where the three terms are the chemical, elastic, and structural contributions, respectively. The chemical term DHC can be expressed
by:



S
Sol
DHC C A C B C SB DHSol
A in B C A DH B in A

S
where DHSol
A in B is the solution enthalpy of A in B, C B is the degree to
which A atoms are in contact with B atoms. The elastic term for a
solid solution phase is often calculated by:

DHE C A C B C B DHeA

in B

C A DHeB

in A

DHeB in A

where
is the elastic contribution to the heat of solution of B
in A in the solid solution phase. DHS is different from zero only for
transition metaltransition metal alloys [22]. For the AlCe solutions, Al a main group metal and Ce is a transition metal, so the
structure contribution DHS 0.
Based on the equations described above, the values of Gibbs free
energies are calculated in the temperature range 623673 K and
the results obtained are shown in Fig. 6(b). The parameter values
for calculations are taken from the literature [23]. It can be found
in this gure that in this temperature range, the Gibbs free energy
of Al4Ce is more negative than the other phases, resulting in the
preferential formation of Al4Ce at the interface, and Al11Ce3 is the
second, and the sequence of following IMCs is Al3Ce, Al2Ce and
AlCe, which are in good agreement with the experimental
observations.

Fig. 7. (a) Relationship between the thickness of the diffusion reaction layers and
the square root of treatment times for all the diffusion couples and (b) an Arrhenius
plot of the diffusion reaction layers growth.

K K 0 exp



Q 0
RT

Q0
RT

3.4. Growth behavior of the diffusion reaction layers

or

Growth kinetics for the diffusion reaction layers are evaluated

by examining all the diffusion couple samples. The experimental
growth rates of the diffusion reaction layers follow typical parabolic
trends with time, suggesting that the growth is controlled by diffusion process, and can be described by the empirical equation:

ln K ln K 0 

d Kt1=2

where d is the thickness of the diffusion reaction layer in meter and

t is the reaction time in second, and K the growth constant in m2/s.
The growth constant K was dened in such a way so that it had the
same dimension as the diffusion coefcient.
The growth kinetics for the diffusion reaction layers are presented in Fig. 7(a). It can be seen that linear regression analysis
gives best-t straight lines, and most of the linear correlation coefcient values (R2) for these plots are higher than 0.98. The result
indicated that the growth kinetics is well conformed to the parabolic law, so the growth of the diffusion reaction layers is volume
diffusion-controlled in the studied temperature range [21]. With
Eq. (5) the reaction rates of the diffusion reaction layers formation
are calculated. At 623 K, 648 K and 673 K, the growth constants of
the total diffusion reaction layers are 8.90  1014 m2/s,
1.15  1013 m2/s and 1.50  1013 m2/s, respectively. These K values are similar to the experimental ones of Brennan et al. [10],
especially at 623 K.
The following Arrhenius-type relationship is used to determine
the apparent activation energy for diffusion controlled growth:

where K0 is the pre-exponential factor, Q0 is the activation energy, R

is the gas constant, and T is the absolute temperature. The activation energy can be obtained from the plots of ln K versus the reciprocal of temperature T, as shown in Fig. 7(b). The calculated
apparent activation energy for the growth of the total diffusion
reaction layer is 36.6 kJ/mol. The activation energy is slightly lower
than those of Brennan et al. [10] and DAS et al. [11], which may be
related to the melting temperature of the MgAl alloy is lower than
Al [24].
4. Conclusions
The formation of intermetallic compounds (IMCs) during interdiffusion of MgAl/MgCe diffusion couples has been investigated
at 623 K, 648 K and 673 K for 24 h, 48 h and 72 h, respectively. The
conclusions are summarized as follows:
(1) During the whole diffusion process, Al was the dominant diffusing species. Al atoms substituted for Mg ones and formed
AlCe IMCs.
(2) Five AlCe IMCs of Al4Ce, Al11Ce3, Al3Ce, Al2Ce and AlCe were
formed via the reaction of Al and Ce. The deduction of thermodynamics explains the formation of Al4Ce as the rst
phase in the diffusion reaction interface.

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J. Dai et al. / Journal of Alloys and Compounds 619 (2015) 411416

(3) The growth of the IMCs was volume diffusion-controlled. At

623 K, 648 K and 673 K, the growth constants of the total
diffusion
reaction
layers
were
8.90  1014 m2/s,
13
2
13
2
1.15  10
m /s and 1.50  10
m /s, respectively. The
activation energy for the growth of the total diffusion reaction layer was calculated to be 36.6 kJ/mol.

Acknowledgments
The authors are grateful for the nancial supports from Chongqing
Science and Technology Commission (CSTC2013jcyjC60001,
CSTC2012JJJQ50001, cstc2012ggB50003), National Natural Science
Foundation of China (51171212), and The National Science and
Technology Program of China (2013DFA71070, 2013CB632200),
and the Fundamental Research Funds for the Central Universities
(CDJZR13138801, CDJXS12131106).
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