Composites: Part A 36 (2005) 551–557

www.elsevier.com/locate/compositesa

Formation of MgO and Mg–Zn intermetallics in an Mg-based

composite by in situ reactions
Cheng-Ji Deng, M.L. Wong, M.W. Ho, Peng Yu, Dickon H.L. Ng*
Department of Physics, The Chinese University of Hong Kong, Shatin, Hong Kong, China
Received 8 April 2003; revised 20 August 2004; accepted 7 September 2004

Abstract
The fabrication and microstructural characterization of an Mg-based metal matrix composite, which is reinforced by MgO ceramic and
Mg–Zn intermetallics is described. The fabrication process involved the mixing and pressing of Mg and ZnO powders, and was followed by
sintering of the green compact at a temperature below the melting point of Mg. The order of appearance of the in situ formed reinforcements,
namely MgO and Zn–Mg eutectic, in the Mg matrix during sintering was investigated. Based on the Gibbs’s free energy associated with each
reaction, a model for the formation of this composite is postulated.
q 2004 Elsevier Ltd. All rights reserved.

Keywords: A. Metal-matrix-composites (MMC); B. Microstructure; E. Sintering; Reaction model

1. Introduction during sintering. Recently, more in situ methods that can be

Magnesium with a specific gravity of 1.74 is one of the
lightest structural metals available. Thus, Mg-based alloys
and composites are being produced to replace parts that are
traditionally made from steel, aluminum or plastics [1,2].
Different types of Mg-based MMCs can be fabricated by
various techniques [3,4]. For example, the fiber-reinforced
Mg-MMCs are made by using high-pressure infiltration of
molten Mg into ceramic assemblies [5], and the graphite
fiber-reinforced Mg-MMCs are produced by casting tech-
niques [6]. There are attempts to synthesize Mg-MMCs by
in situ reactions. Matin et al. [7] have synthesized Mg-
MMCs that are reinforced by the in situ formed particulate
via the reactions between Mg and KBF4 at 750 8C, and via
the reactions between Mg and K2TiF6 at 800 8C. The
majority of these methods used to fabricate Mg-MMCs are
operated at temperatures above the melting point of Mg at
649 8C [8–10], and there is a great concern in the
evaporation of Mg during fabrication. In order to reduce
the loss of Mg, it is necessary to maintain the Mg-MMC
formation temperature below the melting point of Mg
operated at relatively lower temperatures have been
developed. They involve the reactions between metal
oxide, such TiO2 [11], and CuO [12], and Mg to produce
MgO particles or rods reinforcements. After the reaction,
the reduced metal usually further reacts with Mg to form
intermetallic phases in the Mg base. In this work, Mg
powder is allowed to react with ZnO powder at a
temperature below the melting point of Mg. During
fabrication, an Mg matrix is produced, and also Zn from
the reduced ZnO reacts with Mg to form the Mg–Zn
intermetallic phases, while the remaining O reacts with Mg
to form the MgO. These in situ products, Mg–Zn and MgO,
serve as reinforcements to toughen the Mg-based matrix.
The overall objective of the work is to produce an MgO and
Mg–Zn intermetallics reinforced Mg-based matrix compo-
site material by using the in situ techniques, and associate
with this to investigate the reaction mechanism in the
formation of this product at a temperature below 550 8C.
2. Experiments

* Corresponding author. Tel.: C85 2609 6392; fax: C85 2603 5204. An Mg powder mixture, containing 50 wt% ZnO,
E-mail address: dng@phy.cuhk.edu.hk (D.H.L. Ng). is ground and cold-pressed under 550 MPa to form
1359-835X/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2004.09.001
552 C.-J. Deng et al. / Composites: Part A 36 (2005) 551–557

10-mm-diameter discs. Differential thermal analysis (DTA)

is conducted to determine the temperatures at which the
reactions between Mg and ZnO take place during sintering.
During the analysis, the sample is heated in argon
atmosphere in the furnace of the DTA analyzer where the
temperature is increased from ambient to 600 8C. The green
samples are then sintered separately in different tube
furnaces in argon atmosphere for half an hour. The sintering
temperatures are set slightly above those temperatures at
which the DTA peaks appear. After sintering, the sample is
allowed to cool down to room temperature inside the off-
powered furnace. In a separate study on the effect of the rate
of cooling on the microstructure of sintered sample, a
sample was sintered at about 550 8C for half an hour before
it is cooled to room temperature using a step-wise cooling
procedure. Microstructural and elemental analyses are
conducted by using a LEO scanning electron microscope
(SEM) and energy dispersive X-ray spectroscopy (EDX),
respectively. X-ray diffractometry (XRD) with Cu Ka
source is used to obtain diffraction patterns of the sintered
samples.

3. Results and discussion

3.1. DTA, SEM, and EDX analyses

The DTA curve of the Mg–50 wt% ZnO sample is shown
in Fig. 1. Two exothermic peaks are found at about 410 and
530 8C in the curve. This suggests that one or more reactions
have occurred in the vicinity of these two temperatures.
Based on this result, the green samples are separately sintered
for half an hour at 450 and at 550 8C, temperatures slightly
higher than the temperatures where the two exothermic peaks
are located. The microstructure of the Mg–50 wt% ZnO
green sample is shown in the SEM micrograph in Fig. 2(a).
It can be seen that large Mg grains (w10 mm) are embedded
in the much finer ZnO powder (Ow0.1 mm). Such
morphology is also found in some samples that have
been sintered at temperatures below 400 8C. However, for
Fig. 2. (a) A SEM micrograph of an Mg–50 wt% ZnO green sample. (b) A
SEM micrograph of the sample sintered at 450 8C. The dark and gray
patches are the Mg and the ZnO, respectively. The bright regions are the
newly formed MgO that surrounds the Zn-rich region.
the sample that is sintered at 450 8C, some newly formed
phases are found in positions of the original ZnO, which are
located between Mg grains as shown in Fig. 2(b). The EDX
analysis shows that these in situ formed phases are MgO and
Zn. The MgO phase is not conductive to electrons; thus, it
appeared bright in the SEM image. The analysis also reveals
that some of the ZnO has been reduced to Zn, and this newly
formed zinc is isolated from Mg by the newly formed MgO.
When the sample is sintered at a 550 8C, the boundary regions
between the Mg grains contain mostly MgO and Mg–Zn
intermetallics. An SEM micrograph of the boundary region
in the sample sintered at 550 8C is shown in Fig. 3. EDX
analysis is performed in the locations labeled A and B in the
micrograph. It is found that these two regions contain
intermetallic phases having the Mg:Zn atomic ratios of 1:10
and 1:1, respectively. These results suggest that in the central
region of the boundary zone (e.g. at A), the intermetallic is
Zn-rich, whereas region closer to Mg grain (e.g. at B), MgZn
intermetallic is found.

3.2. XRD analysis

Fig. 1. DTA curve of the Mg–50 wt% ZnO sample scanned at a rate of The diffraction patterns of the green sample and the
20 8C/min in argon atmosphere. sintered Mg–50 wt% ZnO samples are shown in Fig. 4. Only
 C.-J. Deng et al. / Composites: Part A 36 (2005) 551–557 553

Table 1
A summary of the XRD results: phases in the samples sintered at 450 and
550 8C

Sinter- Compo- Phases detected

ing tem- sition Mg Zn MgO ZnO MgZn Mg2- Mg7
perature (wt% Zn3 Zn3
(8C) ZnO)
450 5, 10, 20 # # # #
50 # # # #
550 5, 10, 20 # # #
50 # # # # #

XRD. After these samples are sintered at 450 8C, their

Fig. 3. A SEM micrograph of the sample sintered at 550 8C. The locations A
and B correspond to the regions having the Mg to Zn atomic ratios of 1:10
and 1:1, respectively.
peaks that correspond to Mg and ZnO are found in the
pattern of the green sample. In the pattern of the sample
sintered at 450 8C, peaks that correspond to Mg, Zn, MgO
and ZnO are identified. The appearance of Zn and MgO in
the sample indicates that chemical reactions between Mg
and ZnO have already taken place below 450 8C. Such a
result is consistent with those found in the EDX analysis on
the same sample where the newly formed Zn and MgO are
found in the boundary regions. In the case of the sample
sintered at 550 8C, the pattern contains Mg, MgO, and Mg–
Zn intermetallic peaks, and the peaks that correspond to Zn
or ZnO are not found. Furthermore, the intermetallic peaks
are those corresponding to the MgZn, Mg2Zn3 and Mg7Zn3
phases. Again, these XRD results are consistent with the
EDX analyses, which suggest that multi-intermetallic
phases are formed after the Mg–50 wt% ZnO sample has
been sintered at 550 8C. Some other sintered samples having
lower ZnO contents (5–20 wt% ZnO) are also studied by
diffraction patterns are basically the same as that of the
Mg–50 wt% ZnO sample, and the only difference is that the
Zn and the ZnO peaks in the XRD patterns of these samples
are less intensive. When these low ZnO content samples are
sintered to 550 8C, their diffraction patterns, in addition to
the Mg and the MgO peaks, exhibit only one set of
intermetallic peaks that corresponds to the MgZn phase. A
summary of the XRD results showing the detected phases in
the Mg–50 wt% ZnO and those samples having lower ZnO
contents are listed in Table 1.
3.3. Mg–Zn intermetallic phases
The Mg–Zn binary alloy phase diagram [13] is shown in
Fig. 5. It is evident that Mg7Zn3 is a metastable phase and
Mg2Zn3 is an intermediate phase. Their presence in the
Mg–50 wt% ZnO sintered sample suggests that the phase
transformation of the sintered products have not been
completed. In an attempt to remove these Mg2Zn3 and
Mg7Zn3 residual phases and to secure a single stable MgZn
phase in this Mg–ZnO product, a step-wise cooling
procedure is introduced to the sample right after it has
been sintered at 550 8C. In this cooling procedure, the
sample is treated according to the following consecutive
thermal conditions: (i) kept at 400 8C for 1 h to prevent the
formation of MgZn2, (ii) lowered to 345 8C and kept for 2 h
to remove Mg2Zn3, and (iii) lowered to 325 8C and kept for

Fig. 4. The XRD patterns of the Mg–50 wt% ZnO samples: the green
sample, the samples sintered at 450 8C, and the sample sintered at 550 8C. Fig. 5. A phase diagram of the Mg–Zn binary alloy system [13].
554 C.-J. Deng et al. / Composites: Part A 36 (2005) 551–557
Fig. 6. Microstructure of Mg–MgZn eutectic produced by the step-wise
cooling procedure.
4 h to remove Mg7Zn3. The sample now contains the two-
phase Mg–MgZn eutectic and the MgO intergranular
regions, and these components are embedded in the Mg
matrix. The microstructure of the Mg–MgZn eutectic of
such a sample is shown in Fig. 6. This result implies that the
microstructure of low temperature sintered ZnO–Mg MMC
can be modified from one that contains multi Mg–Zn phases
engulfed by in situ formed MgO to the one that contains
only a single phase MgZn eutectic alloy with MgO, by
applying a relatively slow but simple step-wise cooling
procedure.
4. Formation of ZnO–Mg MMC
4.1. Chemical reactions
When a cold-pressed Mg–50 wt% ZnO sample is
sintered in an argon atmosphere at temperature between
400 and 550 8C, the possible chemical reactions and their
corresponding Gibbs’s free energy functions are given by
[14]:
ZnOðsÞ Z ZnðlÞ C 0:5O2ðgÞ (1)
DG0T Z 348360 K 103:28TðJÞ
MgðsÞ C 0:5O2ðgÞ Z MgOðsÞ (2)
DG0T Z K601230 C 107:59TðJÞ
The combination of these two reactions will give:
MgðsÞ C ZnOðsÞ Z MgOðsÞ C ZnðlÞ (3)
DG0T Z K252870 C 4:31TðJÞ
The subscripts s and l indicate whether the reactants and
the products are in the form of solid or liquid, respectively.
With reference to the DTA results in Section 3.1, it is
expected that Reaction (3) will occur at about 410 8C. As the
sintering temperature increases to about 530 8C, liquid-Zn
in the product reacts with the remaining Mg to form the
molten Mg–Zn alloy. During heating, and during solidifica-
tion that follows, the reactions can be described as follows:
O530 8C
heating : MgðsÞ C ZnðlÞ 
/ Mg–ZnðlÞ (4)
furnace-cooling : Mg–ZnðlÞ / MgðsÞ C Mgx ZnyðsÞ (5)
step-wise cooling : Mg–ZnðlÞ / MgðsÞ C MgZnðsÞ (6)
4.2. Order of priority of the reactions
The sequence of the reactions between Mg and ZnO
during sintering may be postulated. The Gibbs’s free energy
ðDG0T Þ in the formation of ZnO is determined to be K278 kJ
at 410 8C (while the reduction of ZnO to Zn is 278 kJ,
according to Eq. (1)), and it is K528 kJ in the formation of
MgO (by Eq. (2)). Thus, the formation of MgO is more
probable than that of ZnO. It is more energetically
favourable for the oxidation of Mg to occur when it reacts
with ZnO to produce MgO and the reduced Zn (according to
Eq. (3)). Based on the result of the DTA analysis, the
temperature at which this reaction will occur is 410 8C. At
this temperature, MgO is readily formed with an associated
DG0T of K250 kJ. Such a claim is further supported by the
XRD result obtained from the sample sintered at 450 8C.
The diffraction pattern of the sample contains peaks
corresponding to Mg, Zn, MgO and ZnO phases. After
this reaction, as temperature further increases, Zn remains in
liquid form as pure Zn has a melting point of 420 8C. A
simple calculation shows that when Reaction (3) is
completed, the ratio of the remaining solid-Mg to the
newly formed liquid-Zn is 47:53. According to the Mg–Zn
phase diagram in Fig. 5, the melting point of Mg–Zn with
such a composition will be about 347 8C. Therefore, it is
expected that the in situ formation of Zn via Reaction (3)
will be followed immediately by the reaction between
liquid-Zn and solid-Mg forming the Mg–Zn alloy. However,
our DTA result indicates that such a reaction does not occur
until a higher temperature (at about 530 8C) is reached, and
this is the temperature where the second peak in the DTA
curve is located. The delay of the reaction is due to the
presence of in situ formed MgO that surrounds the newly
formed liquid-Zn, and isolates them from the Mg grains.
Thus, a higher temperature (thermal energy) is required for
the Mg atoms from the Mg grains to diffuse across the MgO
zone into the newly formed Zn before the reaction of molten
Zn and Mg can take place. At a temperature above 530 8C,
the molten Zn then reacts with the rest of the Mg metal to
form the molten Mg–Zn alloy according to Reaction (4).
The Mg–Zn intermetallic phases are detected when XRD is
conducted on the sample sintered at 550 8C, and also
the second peak in the DTA curve corresponds to such
 C.-J. Deng et al. / Composites: Part A 36 (2005) 551–557 555

a formation of the Mg–Zn intermetallic phases. In a re-run

DTA curve of the same sample (not shown), two
endothermic peaks are found between 350 and 403 8C.
This further confirms that the sintered sample contains the
MgZn, Mg2Zn3, and Mg7Zn3 phases, and they melt within
this temperature range. The described sequence of reactions
is also consistent with the SEM and EDX analyses. As
shown in Fig. 2(b), the micrograph of the Mg–50 wt% ZnO
sintered at 450 8C indicates the presence of MgO and Zn-
rich grains, but no Mg–Zn intermetallic is detected. In the
micrograph of the sample sintered at 550 8C (in Fig. 3), Mg–
Zn intermetallics are observed, but pure Zn and ZnO have
not been found.

Fig. 8. The average atomic percentages of Mg, O and Zn in the locations

4.3. Diffusion during sintering labeled I–VI in the micrograph of Fig. 7.

The initial formation of MgO is the most probable
product in the reaction between Mg and ZnO since MgO has
a relatively low Gibbs’s free energy of formation among all
the possible reactions. It is commonly known that the
diffusion coefficients of the elements in the chemical
components also play a decisive role in the occurrence of
a reaction. To illustrate the distribution of the various
products in the early stage of sintering, an Mg–50 wt% ZnO
sample is examined after sintering at 550 8C for about
30 min. The interfacial regions between the Zn-rich grain
and the Mg grain at locations labeled I–VI in Fig. 7 are
characterized by EDX. The uncertainty in the EDX analysis
for Mg and Zn is less than 5%, while that of oxygen is less
than 10%. The atomic percentages of Mg, Zn, and O at these
sites are shown in the plots in Fig. 8. The concentration of
Zn is maximum (Ow85 at.%) in site I. It decreases to
w10 at.% in site II, and is undetectable in site VI. This
indicates that Zn is rather immobile, and it tends to stay in
its original position throughout sintering. In an earlier work
by Hoffman and Lauder [15], it was reported that the
coefficient of diffusion of oxygen in ZnO had the same
magnitude as that of zinc in ZnO, but that the coefficient of
diffusion of oxygen would be increased as the partial
pressure of O2 decreased. In our case, the sample is sintered
in argon protective atmosphere and the partial pressure
of O2 is reduced accordingly; hence, the diffusivity
of oxygen in ZnO of the sample during sintering has been
enhanced. As a result, most of the oxygen atoms (in site I)
escape from ZnO to the nearby Mg neighbors in the first half
hour of sintering. Thus, the oxygen atoms are mostly found
between site I and site IV where they have reacted with
magnesium to form MgO. Some Mg is also found in site I
due to diffusion, but most of the Mg remains in the Mg grain
between site III and site VI in the initial stage of sintering.
Therefore, in the formation of MgO, the oxygen atoms have
to be transported from ZnO to the Mg grains for such
reaction to occur.
To investigate further the distribution of the various
products in the final stage of sintering, another Mg–50 wt%
ZnO sample is sintered at 550 8C for 4 h. Fig. 9 shows the
microstructure of this sample. The atomic percentages of
Mg, Zn and O at locations Q, R, S, and T in the micrograph
(Fig. 9) are shown in Fig. 10. The result indicates that the
Mg atoms have migrated into site Q, and have reacted
with Zn to form Mg–Zn. Thus, the atomic percentage of Mg

Fig. 7. A SEM micrograph shows the microstructure of the Mg–50 wt% Fig. 9. A SEM micrograph shows the microstructure of the Mg–50 wt%
ZnO sample sintered at 550 8C for 0.5 h. ZnO sample sintered at 550 8C for 4 h.
556 C.-J. Deng et al. / Composites: Part A 36 (2005) 551–557
Fig. 10. The average atomic percentages of Mg, O and Zn in the locations
labeled Q, R, S and T in the micrograph of Fig. 9.
and that of Zn are almost the same in region between sites Q
and R. According to the work of Kofstad [16], the
coefficient of diffusion of Mg in MgO is given by
DMg Z 24:9 !10K6 expðK330; 000=RTÞ m2 =s, and is a lot
larger than that of O in MgO where
DOxy Z 4:3 !10K9 expðK344; 000=RTÞ m2 =s. As a result,
most of the O atoms tend to remain in their original
position in MgO (in site R) and are unlikely to break away
from the ionic bonding with Mg even after prolonged
sintering; therefore, we also observe that the amount of O is
maximum in site R. We notice that the atomic ratio of Mg
to O is almost 1:1 in site R; thus, we expect that the
migrated Mg atoms to form the Mg–Zn near site Q are not
originated from the nearby MgO, but are coming from the
Mg grain (in site T). Such an Mg transport is possible and
has been enhanced by the high mobility of Mg atoms in
MgO when the sintering temperature is higher than 530 8C
(where the second DTA peak appears).
To summarize, the sequence of formation of the ZnO–
Mg MMC is as follows. When the sample is heated to about
410 8C, oxygen atoms diffuse from ZnO toward the nearby
Mg matrix, and MgO is formed in situ in the interfacial
regions between the Zn-rich and the Mg grains. As the
temperature is further increased, the diffusion rate and the
transport of the O atom increases until all O atoms of ZnO
have been diffused across the grain boundary toward the Mg
region forming solid MgO and liquid Zn. At higher
temperature (about 530 8C), Mg atoms in the Mg grains
then diffuse across the MgO layer into the liquid Zn, and
react with liquid Zn to form the Mg–Zn intermetallics,
namely MgZn, Mg2Zn3 or Mg7Zn3.
5. Conclusions
The process of fabricating Mg-based MMC reinforced
with the ceramic MgO and Mg–Zn intermetallics can be
operated at a temperature below the melting point of Mg.
The process involves the mixing, cold pressing, and
sintering of the powder mixture of Mg and ZnO at 550 8C.
The in situ formation of the MgO and the Mg–Zn occurs at
w410 and w530 8C, respectively. In low ZnO content
mixture (%20 wt% ZnO) the single phase stable MgZn
intermetallic can be obtained, whereas high ZnO content
mixture produces multi-phases Mg–Zn intermetallics, but
they will transform into the stable MgZn phase when
subjected to a prolonged step-wise cooling procedure. A
reaction model has been proposed. In the model, the Gibbs’s
free energy of formation of the products and the diffusion
constants of O, Zn and Mg atoms are the decisive factors for
the formation of MgO and Mg–Zn intermetallic. On the
other hand, the technological conditions such as fired
temperature, cooling rate and duration of treatment are the
crucial factors to determine the formation of Mg–Zn
intermetallic phases and the microstructure on the Mg-
based metal matrix composite. The process makes use of
ZnO powder instead of pure Zn, at an operational
temperature well below the melting point of Mg metal,
and provides an economical route to make structural and
functional Mg-based composite components for engineering
applications.
Acknowledgements
This work was supported by The Chinese University of
Hong Kong—United College Lee Hysan Foundation and
Endowment Fund Research Grant Scheme (Project code:
CA11048), and by the RGC 2001 Competitive Earmarked
Research Grant (Project code: 2150303).
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