Journal of Alloys and Compounds 592 (2014) 196–201

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Journal of Alloys and Compounds

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

Effect of co-modification by Ba and Sb on the microstructure

of Mg2Si/Mg–Zn–Si composite and mechanism
Ke Chen a,⇑, Ziquan Li b
a
College of Engineering, Nanjing Agricultural University, Nanjing 210031, China
b
College of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics, No. 29 Yudao Street, Nanjing 210016, China

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

Article history: Mg2Si/Mg–Zn–Si composite was in situ synthesized and modified by the addition of Ba and Sb; the
Received 16 March 2013 microstructure and tensile properties of the resulting composites were investigated. Results show that
Received in revised form 2 December 2013 the co-modification with Ba and Sb effectively refined the morphology of Mg2Si as follows: The primary
Accepted 4 December 2013
Mg2Si particles were modified to fine polygonal particles <15 lm; when the Ba content was 1.0 wt.%, the
Available online 11 December 2013
average size of primary Mg2Si particles decreased with increasing Sb mass fraction. The ultimate tensile
strength and elongation values of the composites increased with increasing Sb content. This was
Keywords:
attributed to the formation of fine Ba2Sb particles that acted as the heterogeneous nucleation sites for
Mg2Si
Modification
the primary Mg2Si particles, resulting in a refined distribution of these precipitates. The dispersion of
Microstructure the refined Mg2Si particles strengthened the composite and improved the ductility.
Heterogeneous nucleation Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction further application. However, the advantages and prospects of low-

The development of structural materials, particularly for the
automotive industry, is always aimed at lower weights and higher
performances as well as material saving and energy reduction.
Compared to the traditional metals and alloys, metal matrix com-
posites (MMCs) are considered as an important development ori-
entation because of their high specific strength, high hardness,
high stiffness, and other excellent properties [1–4]. Among the re-
cent studies on the light alloys, such as Al and Mg alloys, magne-
sium silicide (Mg2Si) was found as an excellent intermetallic
reinforcement because of its low density, high rigidity, wear resis-
tance, and heat resistance [5–7]. Moreover, Mg2Si is environment-
friendly and economical because of the abundance of Mg and Si in
the Earth’s crust [7,8]. Another advantage of Mg2Si is that it can be
in situ synthesized by the precipitation of Mg and Si in alloys. If
Mg2Si precipitates as fine particles, the alloy can be considered
as an in situ synthesized Mg2Si particle-reinforced MMC.
Compared to external addition methods, the in situ formation of
Mg2Si during the smelting process is convenient, economical, and
results in a higher interface strength [9,10]. However, when large
amounts of Si (>2%) are added to Mg alloy, primary Mg2Si dendrites
and eutectic Chinese-script Mg2Si particles appear [11–13]. Pri-
mary and eutectic Mg2Si particles are coarse (with sizes
>100 lm); they have sharp straight boundaries. This inevitably
damages the mechanical properties of Mg alloys and prevents their
⇑ Corresponding author. Tel.: +86 18751909360.
E-mail addresses: ckyfckyf@gmail.com, ckyf@njau.edu.cn (K. Chen).
cost and eco-friendly Mg–Si alloy inspire researchers to change the
morphology of the Mg2Si in the alloy from dendrites/Chinese-
script type to particles in order to produce Mg2Si-reinforced mag-
nesium matrix composites [14,15,6].
The modification of Mg2Si by microalloying is a popular method
because it is convenient and no complicated equipment is required.
Recently, La, Sr, B, Bi, and Sb have been used to modify Mg2Si during
the smelting process, thus obtaining interesting refining effects on
the final microstructures [11–13,16–21]. For example, B and Bi
have been used to modify Mg–Si alloy; the modification mechanism
involves poisoning, i.e., the inhibition of Mg2Si growth by changing
the solidification conditions [13,18]. Better modifiers are still
needed because finer reinforcements usually afford better proper-
ties. Sb transformed Chinese-script eutectic Mg2Si into equiaxed
particles by increasing the number of heterogeneous nucleation
sites [19,20]; in addition, Ba was shown as an effective modifier
for Mg2Si [21]. Therefore, a combined effect of Ba and Sb is highly
expected and desired. In this study, Ba and Sb were added to
Mg–Zn–Si alloy to prepare the Mg2Si/Mg–Zn–Si composite, and
their effects and co-modification mechanism were investigated.
2. Experimental procedures
The commercially available Mg ingot (>99.9 wt.%), Zn ingot (>99.8 wt.%), and Si
(>99.8 wt.%) were used to prepare the master alloy Mg–6Zn–4Si. The Mg and Zn in-
gots were melted to 700 °C in a steel crucible, and then the Si particles were added.
The melt was heated above 750 °C for 20 min. After the homogenization by
mechanical stirring for 5 min and deslagging, the melt was cast into a steel mould,

0925-8388/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jallcom.2013.12.041
 K. Chen, Z. Li / Journal of Alloys and Compounds 592 (2014) 196–201
which was preheated at 250 °C while its temperature was below 700 °C. The master
alloy ingots were sliced for the subsequent experiments.
Appropriate amounts of pure Ba (>98 wt.%) and Sb (>99 wt.%) were added to the
remelted master alloys. Then the melts were heated at 750 °C for 15 min. After stir-
ring and deslagging, the melts were cast into a preheated steel mould (with a size of
100  80  20 mm3). The entire smelting process was carried out in an electric
resistance furnace protected by a gas mixture of 1 vol.% SF6 + 99 vol.% CO2. The
Ba and Sb contents of the ingots are listed in Table 1. In the previous study, 1.0%
Ba was found to be optimum [21]. Therefore, only the Sb content was varied in this
study.
The samples were cut from the middle of the ingots, grinded, polished, and
etched by a 0.4 vol.% nitric alcohol solution. The microstructures of the samples
were observed using a XJP-300 optical microscope (OM). The average areas of the
primary Mg2Si grains in each optical image were measured using the Image-pro
Plus 5.0 software. The crystal structures and chemical compositions of the phases
were analyzed using a Bruker D8-advance X-ray diffraction (XRD), energy disper-
sive spectrometer (EDS) mounted on a LEO 1550 scanning electron microscope
(SEM), FEI QUANTA200 SEM, and JEM2000EX transmission electron microscope
(TEM).
The tensile specimens with a gauge dimension of 15  6  2 mm3 were ma-
chined from the billets along the longitudinal axes. The tensile tests were carried
out using a computer-controlled SANS-CMT5105 universal testing machine at a
constant crosshead speed of 0.2 mm/min. Each ingot was tested 5 times both at
room temperature and 150 °C to calculate its average ultimate tensile strength
(UTS) and elongation values.
3. Results and discussion
3.1. Effect of co-modification on composite microstructure
The OM micrographs of the alloys are shown in Fig. 1. The
microstructure of Mg–6Zn–4Si master alloy consists of primary
Mg2Si, eutectic Mg2Si, MgZn, and a-Mg (Fig. 1(a)). The primary
Mg2Si precipitates exist as coarse dendrites or are polygonal in
shape, whereas the eutectic Mg2Si precipitates have Chinese-script
morphology. The semi-continuous chains of MgZn intermetallics
distributed among the a-Mg and eutectic Mg2Si precipitates.
As shown in the previous study [21], 1.0 wt.% Ba significantly
changed the morphology of the primary Mg2Si from dendrites
to polygonal particles (Fig. 1(b)) with the concomitant reduction
in the Chinese-script eutectic Mg2Si. In this case, the addition of
Sb reinforced the modification as follows: The primary Mg2Si par-
ticles became much smaller as the Sb content increased (Fig. 1(b–
f)). The primary Mg2Si particle size was estimated by measuring
the average particle area in the OM micrograph. Fig. 2 shows
the relationship between the Sb content and the average area of
primary Mg2Si particles. When the Sb content reaches its peak va-
lue (1.0 wt.%), the primary Mg2Si particles exhibit the finest size
with an average area of 121.56 lm2 in the OM micrograph
(Fig. 1f). However, the size of the primary Mg2Si particles slightly
changed in alloys 3, 4, and 5. The average sizes of the primary
Mg2Si particles were all below 15 lm. Thus, there was no need
to add more Sb.
In the high magnified OM image (Fig. 1g), the fine particles,
indicated by arrows, are observed inside the primary Mg2Si precip-
itates. In order to verify their composition and elucidate the mod-
ification mechanism, further analyses were carried out. Fig. 3a
shows the SEM image of alloy 4, in which tiny particles are also ob-
served inside the primary Mg2Si precipitates and at the Mg2Si/ma-
trix interfaces. The EDS analysis of this microgranule showed that
it contains Ba and Sb (Fig. 3b). Fig. 4a shows the TEM dark-field im-
age of alloy 4. The very fine particle A in Fig. 4a is an intermetallic
Table 1
Alloy number and nominal Ba/Sb contents.
Alloy no. 0 1 2 3 4 5
Ba content (wt.%) 0 1.0 1.0 1.0 1.0 1.0
Sb content (wt.%) 0 0 0.25 0.5 0.75 1.0
197
phase containing Ba and Sb. Fig. 4b shows the selected-area diffrac-
tion pattern of area A. The SADP indexing analysis identified the
tiny particle as Ba2Sb.
3.2. Modification mechanisms of Ba+Sb addition
The modification mechanisms and refinement of the Mg2Si pre-
cipitate by adding various elements have been discussed in the
previous studies. For example, Sb or Ba mainly increased the
amount of nucleation sites, thus decreasing the Mg2Si particle size.
Sb formed Mg3Sb2 particles [19], which acted as the nucleation
sites for Mg2Si. Although BaMg2Si2 can play a similar role when
Ba was added to the alloy [21], in the case of the simultaneous
addition of Sb and Ba, as performed in this study, no Mg3Sb2 or
BaMg2Si2 particles were observed. Instead, several fine Ba2Sb
particles were detected inside the Mg2Si precipitate. This could
be explained by the electronegativity of the different atoms. Elec-
tronegativity is a chemical property that describes the tendency
of an atom to attract the shared pair of electrons (or electron den-
sity) toward itself. In general, the larger the difference between
electronegativities of the two atoms, the higher is the tendency
of their combination leading to compound formation. The electro-
negativities of Ba, Sb, Mg, and Si are 0.89, 2.05, 1.31, and 1.98,
respectively. Apparently, the electronegativity difference between
Ba and Sb is much larger than that between Ba and Mg, or that be-
tween Sb and Mg. Therefore, Ba and Sb combined to form Ba2Sb
rather than Mg3Sb2 or BaMg2Si2 as reported in the other studies
[19,21].
Further analysis is needed to find out whether Ba2Sb could act
as the nucleation site for the formation of Mg2Si. The lattice misfit
among Ba2Sb and Mg2Si was calculated according to the Bramfitt’s
theory of heterogeneous nucleation. The lattice misfitting mathe-
matical mode [22] by Bramfitt is shown as follows:
 
 i
3 d
i 
ðhklÞ
X ½uv ws cos h  d½uv wn 
dðhklÞs ¼  100%
n i
i¼1 3d½uv wn
where the (h k l)s is the low-index crystal plane of the heteronucleus,
the [u v w]s is the low-index crystal orientation in the (h k l)s plane;
the (h k l)n is the low-index crystal plane of the new crystal nucleus,
the [u v w]n is the low-index crystal orientation in the (k h l)n plane;
d[uvw]s and d[uvw]n are atomic spatial distances along the [u v w]s and
[u v w]n orientations; and h is the angle between [u v w]s and [u v w]n
orientations (h < 90°).
The face-centered tetragonal Ba2Sb (lattice parameters:
a = 5.22 Å, c = 18.46 Å) belongs to I4/mmm (139) space group with
the Pearson symbol tI12 [23]. Mg2Si has a face-centered cubic
structure with a lattice constant of a = 6.39 and belongs to Fm-
3 m (225) space group with the Pearson symbol cF12 [24]. The
crystal structures of Ba2Sb and Mg2Si are shown in Fig. 5, and the
atomic arrangements of (0 1 0)Ba2Sb and (0 0 1)Mg2Si planes are
shown in Fig. 6. The atoms distributed on the (0 1 0)Ba2Sb and
(0 0 1)Mg2Si planes in a similar manner. The misfit between these
two planes was calculated according to the above formula, and
the results are shown in Table 2. The misfit between the (0 1 0)Ba2Sb
and (0 0 1)Mg2Si planes is 11.8%. The coherent interface theory and
Bramfitt’s theory [22] indicate that if the mismatch between two
planes is below 15%, one phase can act as the heterogeneous nucle-
ation site for another. Therefore, Ba2Sb is an effective heteroge-
neous nucleation substrate for the primary Mg2Si particles. The
formation of large amounts of tiny Ba2Sb particles increased the
nucleation rate of the primary Mg2Si particles. Therefore, the
growth of primary Mg2Si nuclei to dendrite structure was hindered
before the completion of solidification, i.e., the primary Mg2Si
phase could be refined.
198 K. Chen, Z. Li / Journal of Alloys and Compounds 592 (2014) 196–201
(a)
eutectic
Mg 2 Si
primary Mg 2 Si
(c)
(e)
(g)
Fig. 1. OM of alloys: (a) alloy 0, (b) alloy 1, (c) alloy 2, (d) alloy 3, (e) alloy 4, (f) alloy 5, (g) OM of alloy 4 at a higher magnification.
At the beginning of the solidification, many primary Mg2Si nu-
clei grow fast and consume most Si atoms. This process is known as
the nonequilibrium solidification at a high cooling rate. The Si con-
tent in the residual melt was much less than the eutectic content;
therefore, a small amount of eutectic Mg2Si formed. The reduction
in Chinese-script eutectic Mg2Si particles will be beneficial to the
mechanical properties of the materials; the alloy can be regarded
as a Mg2Si particles-reinforced Mg–Zn–Si matrix composite with
great application potential.
The combined alloying with Ba and Sb results in a better mod-
ification effect compared to the alloying with Ba or Sb separately
(b)
MgZn
(d)
(f)
because the average particle size of the primary Mg2Si particles
in this study was much less than that observed after adding only
one of these elements [21,25,26]. This is because a low fraction
of Ba2Sb formed when a small amount of Ba and Sb were added
(<1 wt.%), and Ba2Sb did not aggregate or grow significantly. After
the Ba2Sb precipitated, the excess Ba or Sb atoms could also form
different compounds, e.g., BaMg2Si2 or Mg3Sb2, as the nuclei of
the primary Mg2Si particles. Therefore, the primary Mg2Si particles
did not grow to larger dimensions with increasing Ba or Sb content
after a certain amount, i.e., no over-modification phenomenon was
observed in this study.
 K. Chen, Z. Li / Journal of Alloys and Compounds 592 (2014) 196–201 199

300
average area of primary Mg2 Si / (µm)2
(a)
Mg
250

200

150

A
100

50 Mg2 Si

0
0.00 0.25 0.50 0.75 1.00 1.25
Sb content / wt%

Fig. 2. The relationship between Sb content and average area of primary Mg2Si
grains in OM image.
(b) ( 3 0 5) Ba 2 Sb

3.3. Tensile properties of the composites

In order to elucidate the effect of the alloying on mechanical (0 2 0) Ba 2 Sb

properties, the tensile tests were performed at ambient and high
temperatures. Fig. 7 shows the average UTS and elongation to frac-
ture of alloys 0–5. Obviously, the UTS and elongation of ZS64 alloy
are quite low. After 1% Ba was added, the UTS and elongation values (0 2 0) Ba 2 Sb
of alloy 1 significantly increased. Further, the addition of Sb (0.25–
1%) increased the UTS at ambient temperature (from 174.2 to (0 0 4) Ba 2 Sb
194.8 MPa) and 150 °C (from 155.9 to 173.3 MPa), while it slightly
increased the elongation to fracture of the alloy. In general, the
Ba+Sb addition significantly improved the tensile properties of the
composites with a better performance even at higher temperature.
The typical SEM images of the fracture surfaces of composites Fig. 4. TEM dark-field image of alloy 4 (a) and SADP indexing of area A (b).
are shown in Fig. 8. The cross-section of ZS64 alloy (Fig. 8a) contains
some brittle fracture parts. The flat tear surfaces are the Mg2Si fine Mg2Si particles on the surface, indicating that the cracks hardly
crystal planes, where the cracks extended rapidly. The alloy has propagated though these precipitates.
high fragility; therefore, its UTS and elongation values are very The morphology of the second-phase particles has a critical
low. However, the fracture surface of alloy 5 (Fig. 8b) shows dim- effect on the mechanical properties of the composite. Although
ples; therefore, the rupture has a ductile nature. There are unbroken Mg2Si could provide interesting properties such as high rigidity

(a)

50

2000
(b) 1800 Mg Si
1600

1400

1200

1000

800

600

400

200 Sb Ba
10
0
0 2 4 6 8 10

Energy / keV

Fig. 3. SEM micrograph of alloy 4 (a) and EDS test result of tiny particle inside primary Mg2Si grains (b).
200 K. Chen, Z. Li / Journal of Alloys and Compounds 592 (2014) 196–201

Ba atom and thermal stability, the flat particle/matrix interfaces and the
sharp edges of coarse Mg2Si caused the stress concentration in
Sb atom
ZS64 alloy. Under the tensile load, cracks nucleated and propa-
Mg atom gated along the edges of the Mg2Si dendrite and Chinese script eu-
Si atom tectic Mg2Si. In contrast, the fine polygonal Mg2Si particles prevent
the crack nucleation and propagation, thus they significantly im-
proved the UTS and elongation to fracture of the alloy. When Sb
content increased, the Mg2Si particles become finer, and the
mechanical properties of the alloy improved. Thus, the variation
in the morphology of Mg2Si particles resulted in brittle–ductile
transition of the alloy.
(0 1 0)
4. Conclusions

(1) The alloying of Ba and Sb could effectively modify and refine

(0 0 1) the Mg2Si particles in Mg2Si/Mg–Zn–Si composite as fol-
lows: The primary Mg2Si particles were modified from
dendritic to fine polygonal particles; when the Ba content
Ba2 Sb Mg2 Si was 1.0 wt.%, the average particle size of primary Mg2Si
decreased with increasing Sb content. The primary Mg2Si
Fig. 5. Crystal structures of Ba2Sb and Mg2Si.
precipitates were <15 lm when 1.0 wt.% Ba and >0.5 wt.%

[0 0 1]Ba2Sb [ 1 0 0]Mg2Si [0 0 1]Ba2Sb

[ 1 0 0] Mg2Si
[ 1 0 1]Ba2Sb [ 1 1 0]Mg2Si [ 1 0 1]Ba2Sb
[ 1 1 0] Mg2Si

[0 1 0]Mg2Si

[ 1 0 0]Ba2Sb [ 1 0 0]Ba2Sb [0 1 0]Mg2Si

(0 1 0) Ba2Sb (0 0 1) Mg2Si

Fig. 6. Comparison of atomic arrangements in (0 0 1)Mg2Si and (0 1 0)Ba2Sb.

Table 2
Calculated values of planar disregistry between Mg2Si and Ba2Sb.

ð1 1 0ÞBa2 Sb //ð0 0 1ÞMg2 Si ð0 0 1ÞBa2 Sb //ð0 0 1ÞMg2 Si ð0 1 0ÞBa2 Sb //ð0 0 1ÞMg2 Si

½h k lBa2 Sb  1 0]
[1  1 1]
[1 [0 0 1] [0 1 0]  1 0]
[1  0 0]
[1  0 0]
[1  0 1]
[1 [0 0 1]
½h k lMg2 Si [0 1 0]  1 0]
[1  0 0]
[1 [1 1 0] [0 1 0]  1 0]
[1 [0 1 0]  1 0]
[1  1 0]
[1
d½hklBa2 Sb 7.38 9.54 6.05 5.22 7.38 5.22 5.22 4.00 6.05
d½hklMg2 Si 6.39 4.52 6.39 4.52 6.39 4.52 6.39 4.52 6.39
h deg 0 5.7 0 0 0 0 0 4.5 0
d 43.6% 15.04% 11.8%

220 14
200
150 ºC (a) 150 ºC (b)
room temperture 12 room temperture
180
160 10
Elongation / %

140
UTS / MPa

120 8

100
6
80
60 4
40
2
20
0 0
0 1 2 3 4 5 0 1 2 3 4 5
Alloy number Alloy number

Fig. 7. Tensile properties of alloys: (a) UTS, (b) elongation.

 K. Chen, Z. Li / Journal of Alloys and Compounds 592 (2014) 196–201
(a)
Mg 2 Si
100 m
Fig. 8. Secondary electron images of tensile fracture surfaces: (a) alloy 0, (b) alloy 5.
Sb were added; no over modification was observed. There-
fore, the addition of Ba and Sb can provide a better effect
than only the addition of Sb or Ba separately.
(2) Tiny Ba2Sb particles appeared inside the primary Mg2Si
grains in the composite containing Ba and Sb; the crystal lat-
tice misfit between Ba2Sb and Mg2Si was small enough.
Therefore, the Ba2Sb could act as the heterogeneous nucle-
ation substrate for the primary Mg2Si precipitates. The
numerous nucleation sites of primary Mg2Si precipitates
resulted in its refinement.
(3) The tensile properties of composite improved with the addi-
tion of Ba and Sb; in particular, the UTS value increased with
the addition of Sb. The refined Mg2Si particle dispersion
strengthened the composite and improved the ductility.
Acknowledgements
This research is supported by Science–Technology Innovation
Foundation for Young Scientist of Nanjing Agricultural University
(No. KJ2010030).
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