Acta Materialia 55 (2007) 3727–3733

www.elsevier.com/locate/actamat

Synthesis, growth mechanism and magnetic properties

of SiO2-coated Co nanocapsules
X.F. Zhang a, X.L. Dong a,*, H. Huang a, B. Lv a, X.G. Zhu a, J.P. Lei a,
S. Ma b, W. Liu b, Z.D. Zhang b
a
State Key Laboratory for Materials Modification by Laser, Ion and Electron Beams, and School of Materials Science and Engineering,
Dalian University of Technology, Dalian, Liaoning 116024, China
b
Shenyang National Laboratory for Materials Science, Institute of Metal Research, and International Center for Materials Physics,
Chinese Academy of Sciences, Shenyang 110016, China

Received 30 October 2006; received in revised form 12 February 2007; accepted 12 February 2007
Available online 5 April 2007

Abstract

The growth mechanism and magnetic properties of SiO2-coated Co nanocapsules synthesized by the arc-discharge method were inves-
tigated. Most of the as-prepared products were nanocapsules with a core/shell structure consisting of a Co core and a SiO2 shell, while
some of them displayed a rod-like configuration. The formation of the SiO2 nanorods was governed by an extended vapor–liquid–solid
(VLS) mechanism and Co nanoparticles acted as a catalyst for the growth of the nanorods. The Co/SiO2 nanocapsules were annealed at
300, 400 and 500 C, respectively, for 30 min in air, in order to observe their oxidation behavior. The crystalline grains of the Co/SiO2
nanocapsules clearly grew during annealing. After annealing at 500 C, the ferrimagnetic Co3O4 phase appeared. The grain size effect,
oxidation behavior and magnetic properties are discussed in detail for the nanocapsules.
 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Co nanocapsules; Arc-discharge; VLS growth mechanism; Magnetic properties

1. Introduction ticles also provides a chance to synthesize advanced func-

tional materials with new microstructures and novel
Much attention has been paid to magnetic metallic physical properties. In our latest work, we found that a
nanoparticles by virtue of their potential for applications special type of nanocapsule with a dielectric outer shell
in fields such as magnetic recording media, catalysis, drug and magnetic metallic core possessed excellent microwave
delivery and microwave absorbents [1–4]. However, appli- absorption properties, and is a promising candidate for a
cations have been limited because these particles suffer microwave absorbent material [4].
from rapid environmental degradation and oxidation. An Nanocapsules have been synthesized by a variety of
advance in this regard is the encapsulation of nanoparticles methods, including sol–gel [5], annealing [6] and arc-dis-
inside protective outer shells, namely ‘‘nanocapsules’’. In charge [7]. Various materials, such as carbon [8], polymers
general, the outer shells of the nanocapsules protect the [9], boride [10] and metal oxides [11], have been utilized to
metal nanoparticles from degradation and provide an encapsulate the metal nanoparticles. Recently, SiO2-coated
opportunity to investigate the intrinsic properties of the metal nanocapsules have been intensively studied. How-
encapsulated nanoparticles. The encapsulation of nanopar- ever, little work have devoted to SiO2-coated nanocapsules
with magnetic-metal cores [12–14]. Wu et al. [12,13] used a
wet chemical approach to prepare SiO2-coated ferromag-
*
Corresponding author. netic nanocapsules, and their procedure consisted of mak-
E-mail address: dongxl@dlut.edu.cn (X.L. Dong). ing colloidal solutions, annealing the solutions and

1359-6454/$30.00  2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2007.02.019
3728 X.F. Zhang et al. / Acta Materialia 55 (2007) 3727–3733

calcination. Vadalaa et al. [14] succeeded in producing

SiO2-coated Co nanocapsules by using heat treatment to
pyrolyze the polysiloxane block copolymers. In practice,
the metal/SiO2 nanocapsules, involving both a magnetic
core and a dielectric shell, are a special kind of nanocom-
posite that exhibit multi-loss mechanisms, which would
be significant for absorbing electromagnetic waves.
In this article, the SiO2-coated Co nanocapsules are syn-
thesized by a modified arc-discharge method, using Co and
SiO2 micro-powders as raw materials. It is found that the
Co nanoparticles are uniformly encapsulated with amor-
phous SiO2 shells. A new growth mechanism is proposed
for synthesizing nanocapsules with a metal core and an
oxide shell, which extends the conventional vapor–liquid–
solid (VLS) mechanism. An annealing process is carried
out to observe the grain size effect and the oxidation behav-
ior in the Co/SiO2 nanocapsules. The structure, growth
mechanism and magnetic properties of the SiO2-coated Fig. 1. X-ray diffraction patterns of Co/SiO2 nanocapsules: (a) as-
prepared, (b)–(d) annealed at 300, 400 and 500 C, respectively, in air
Co nanocapsules are discussed in detail. for 30 min.

2. Experimental
plane of face-centered cubic (fcc)-Co phase. In addition
The modified arc-discharge method was described else- to the fcc-Co peaks, there are (1 0 0), (0 0 2) and (1 0 1) peaks
where [15]. The Co and SiO2 powders (several tens of of hexagonal close packed (hcp)-Co phase. It is well known
micrometers in size) were homogeneously mixed in a 5:1 that bulk Co crystallizes in a hcp structure at room temper-
weight ratio of Co to SiO2. The mixture was pressed into ature, while it forms an fcc-Co phase at higher tempera-
bulk and then used as the anode, while the tungsten rod tures. The existence of the fcc-Co phase in the present
served as the cathode. The chamber was evacuated and a nanocapsules is mainly ascribed to the small size: i.e. the
mixture of H2 and Ar was introduced to give the desired surface energy of fcc-Co nanoparticles is lower than that
pressure. Evaporating the compacted bulk of Co and of hcp-Co nanoparticles [16]. The non-equilibrium solidifi-
SiO2 powders resulted in as-prepared products, which were cation process affected by the fast-cooling condition is also
labeled as sample (a). The as-prepared products were an important factor. This is similar to the reasons for the
annealed at 300, 400 and 500 C, respectively, for 30 min existence of fcc-Co in Co nanoparticles in our previous
in air, which were then labeled as samples (b), (c) and (d). report [8]. The Co3O4 phase appears in sample (d)
The phase structures and the oxidation behavior of the (annealed at 500 C). There is no evidence for the existence
nanoparticles were investigated by means of X-ray diffrac- of other oxides such as CoO and Co2O3. It is known that
tion (XRD) using Cu Ka (k = 0.154056 nm) radiation with below 925 C in air, the Co3O4 phase is more stable than
a voltage of 40 kV and a current of 30 mA. The morphol- the CoO or the Co2O3 phase [17]. These results imply that
ogy and microstructures were observed by high-resolution the SiO2 shells have the ability to protect Co nanoparticles
transmission electron microscopy (HRTEM) plus electron against oxidation below 500 C.
energy dispersive spectroscopy (EDS) with emission volt- The grain sizes of pure Co cores in the nanocapsules are
ages of 200 kV. Fourier transform infrared spectroscopy calculated by using the Scherer formula Dhkl = Kk/(B cos h)
(FTIR) was recorded in order to confirm the existence of from the half-height width of the (1 1 1) peak. As shown in
the outer shells of SiO2 in the nanocapsules. The magnetic Fig. 2, the grain sizes promptly increase after annealing
properties were measured by a superconducting quantum above 300 C, implying the coarsening of the crystal Co
interference device (SQUID, Quantum Design) magnetom- core. It is evident that the SiO2 shells have the ability to
eter at temperatures from 5 to 300 K. hinder the coarsening of the Co nanoparticles at 300 C.
However, it is difficult to impede the diffusion of Co atoms
3. Results and discussion at temperatures higher than 300 C. It should be noted here
that no peak corresponding to SiO2 phase was detected by
3.1. Composition and phase structure XRD for samples (a)–(d). However, the existence of SiO2
in the nanocapsules has been proved by the infrared spectra
Fig. 1a–d shows XRD patterns of SiO2-coated Co nano- of sample (a), which ranges from 4000 to 700 cm 1. As
capsules from the as-prepared sample and the the samples shown in Fig. 3, the strong IR absorption peaks at 1088
annealed at different temperatures. It can be seen from and 791 cm 1 agree well with the characteristics of SiO2
Fig. 1 that all the XRD patterns present a broad diffraction [18]. The peak at 1088 cm 1 can be assigned to the asym-
peak at 2h = 44.2, which corresponds to the (1 1 1) lattice metric stretching vibration of the bond ”Si–O–Si” in the
 X.F. Zhang et al. / Acta Materialia 55 (2007) 3727–3733 3729

Si–O tetrahedron. The peak at 791 cm 1 is relatively

weaker, corresponding to the vibration of the Si–O–Si sym-
metric stretch. Combined with the XRD results, it is con-
cluded that the SiO2 phase of the Co/SiO2 nanocapsules
is in an amorphous state, which is confirmed by HRTEM
images and EDS analysis in the following subsection.

3.2. Morphology and growth mechanism

TEM was performed to study the structure, morphology

and growth mechanism of the Co/SiO2 nanocapsules. As
shown in Fig. 4a, the Co/SiO2 nanocapsules are spherical
in shape with diameters from 80 to 100 nm and the SiO2
shell is about 8 nm thick. The HRTEM image in Fig. 4b
reveals that the nanocapsule has a ‘‘core/shell’’ structure
with a clearly distinguishable interface. The inner Co core
is crystalline and the outer SiO2 shell is amorphous. The
results are similar to those of Co(SiO2) composites pre-
Fig. 2. Mean crystalline grain size of the fcc-Co phase for the nano pared by other methods [12–14]. One obvious dissimilarity
capsules (a)–(d), calculated from XRD peaks of the (1 1 1) lattice plane. to the previous results [12–14] is that there are SiO2 nano-
rods with a diameter of 10–20 nm and a length of up to
100–150 nm (see Fig. 5a and b). It is confirmed from the
HRTEM image of Fig. 5c that the SiO2 nanorods are in
an amorphous state, which originates from the abducing
growth of the SiO2 shell in the nanocapsules. Moreover,
according to the chemical composition determined by
EDS analysis in Fig. 5d, the nanorods are mainly com-
posed of Si and O, whereas the cores mainly consist of
Co. This result confirms the ‘‘core/shell’’ structure of nano-
capsules, in good agreement with the analysis of XRD and
FTIR. One nanorod has one Co nanoparticle at its end,
and its outer diameter is nearly equal to the size of the
Co nanoparticle. These phenomena provide significant evi-
dence for the growth mechanism of SiO2 nanorods.
To date, a variety of silica nanostructures, including car-
rot-shaped rods [19], pea-podded nanowires [20] and
brush-like arrays [21], have been synthesized by several
methods. The VLS model [22] has been used to explain
the growth mechanism for these various nanostructures
Fig. 3. Infrared reflection spectrum of the Co/SiO2 nanocapsules. in special shapes. Typically, solid catalyst nanoparticles

Fig. 4. (a) TEM and (b) HRTEM images of the Co/SiO2 nanocapsules.
3730 X.F. Zhang et al. / Acta Materialia 55 (2007) 3727–3733

Fig. 5. (a, b) TEM, (c) HRTEM images and (d) EDS analysis of rod-like Co/SiO2 nanocapsules.

exist at the end of the one-dimensional (1-D) nanostruc- catalysts, such as metallic compounds and oxides [24,26].
tured materials obtained from the VLS process. Usually, Lieber et al. reported an approach to synthesize semicon-
the sizes of the catalyst nanoparticles are comparable to ductor nanowires by a laser ablation method in which bin-
the diameters of connected nanowires or nanorods. ary bulk alloys, e.g. Si–Fe, Si–Ni and Ge–Fe, were used as
As for the present SiO2 nanorods, the morphologies are the vaporized targets [24]. It was proved that all of the Si
different from any observed ones governed by conventional (or Ge) nanowires can be catalyzed by FeSi2, NiSi2 and
VLS growth mechanism. The main features in our SiO2 FeGe2 alloy nanoparticles, instead of the metallic Fe or
nanorods are somewhat similar to previously reported Ni nanoparticles. According to this rule, the intermetallic
results [23,24], in which gallium and iron were, respectively, compound Co–Si can act as a catalyst to form Si nanowires
used as a catalyst for the large-scale growth of highly aligned or nanorods in the absence of oxygen. However, this func-
silica and silicon nanowires. The reasons for our amorphous tion of catalysis will change when oxygen participates.
SiO2 nanorods may include: (i) Co nanoparticles could be Pan et al. discussed the important role of oxygen origi-
used as catalysts to simultaneously catalyze the growth of nating from system leakage in the formation of SiO2
numerous SiO2 nanorods; and (ii) the SiO2 nanorods pre- nanowires, which was responsible for preventing the com-
pared by the present method are more disordered due to a bination of Ga and Si [23]. The synthesis of SiO2 nanorods
lack of substrate, in comparison with other methods such and SiO2-coated Co nanocapsules in this work was done
as laser ablation, thermal evaporation and chemical vapor with the participation of stoichiometric oxygen supplied
deposition [19–24]. Due to the non-equilibrium thermody- from the micro-sized raw SiO2 powders. The growth pro-
namic process during arc-discharge synthesis, rapid evapo- cess of the present SiO2 nanorods can be divided into
ration and cooling restrain the consecutive growth of two stages: the nucleation of liquid droplets and the forma-
rod-like SiO2, and a great number of nanocapsules persist tion of the nanorods from the droplets by the VLS mecha-
in the present products. Therefore, we conclude that the nism. In the first stage, by evaporating the metallic catalyst
growth mechanism of our SiO2 nanorods is an expanded and SiO2, the mixed vapor with supersaturated Co, Si and
VLS mechanism [25]. O atoms are dispersed in the reaction chamber. Since the
The 1-D nano-materials synthesized by the VLS growth bond dissociation energy of the Si–O bond (798 kJ mol 1)
mechanism have been recently extended by using various is about twice that of the Co–O bond (368 kJ mol 1) at
 X.F. Zhang et al. / Acta Materialia 55 (2007) 3727–3733 3731

298 K, the O atoms would preferentially combine with Si to

form stable SiO2. Furthermore, the Gibbs free energies of
Co3O4, CoO and SiO2, at room temperature, are 774,
214 and 856 kJ mol 1, respectively [27]. It is reasonable
to conclude that SiO2 is more stable than other kinds of
oxides and forms individual cells that participate in further
processes. As the process continues, the mixed vapor pro-
duces a nano-scaled nucleation of Co clusters and SiO2
cells. The final size of the nanocapsules is dominated by
the size of liquid droplets. In the second stage, the metal
liquid droplets absorb the Si and O atoms from vapor to
become supersaturated, and they continuously grow in
one direction with the catalysis of metal until solidification.
Analogous to Pan et al.’s results [23], oxygen plays an
important role in formation of the SiO2 nanorods and
the outer shells of the Co/SiO2 nanocapsules, and effec-
tively prevents the combination of Co and Si. In particular,
the stoichiometric oxygen is controlled and supplied by the
raw materials of micron-sized SiO2 powders in this work.
This process could be developed to fabricate a wide range
of nanostructures in various shapes. In fact, the growth
mechanism of SiO2 nanorods and Co/SiO2 nanocapsules
leads to an extended concept of the conventional VLS
mechanism, known as the ‘‘stoichiometric oxygen-assisted
VLS mechanism’’.

3.3. Magnetic properties

In order to measure the zero-field-cooling (ZFC) and

field-cooling (FC) magnetization curves, several steps were
followed: (i) sample (a) was cooled in zero field from room
temperature to 5 K; (ii) a magnetic field was applied to
Fig. 6. ZFC–FC magnetization curves of SiO2-coated Co nanocapsules
measure the ZFC magnetization in a warming process from
under an applied magnetic field of (a) 0.02 T and (b) 1 T.
5 to 300 K; (iii) the FC curve was measured in the same
applied field in a cooling process from 300 to 5 K. The
ZFC and FC magnetization curves were measured in mag- Néel temperature TN is about 33 K [28]. The Co3O4 is
netic fields of 0.02 and 1 T from 5 to 300 K. Fig. 6a shows paramagnetic from 33 to 300 K. This indicates that there
the temperature dependence of ZFC and FC magnetization exists another material with a TN close to 220 K. There-
measured in a magnetic field of 0.02 T. No superparamag- fore, it can be speculated that there is an antiferromagnetic
netic relaxation behavior was found in this field. In other CoO phase, which corresponds to a Néel temperature vary-
words, the SiO2-coated Co nanocapsules (sample (a)) ing from 50 to 270 K. Its TN decreases monotonously with
exhibited a ferromagnetic (FM) state at room temperature. decreasing size, based on the finite-size effect theory [29–
The ZFC curve recorded in a magnetic field of 1 T is shown 31]. Above TN, the magnetic moment for the CoO phase
in Fig. 6b. FC and ZFC data at 1 T coincide, indicating flips freely within the measurement time, and the material
that the magnetic field can effectively help the frozen spins exhibits paramagnetic features. It was reported that the
overcome their energy barriers. It is noteworthy that a Néel temperature for a CoO phase in Co/CoO bilayers
weak magnetic transition peak is present at about 220 K. was around 220 K, in good agreement with our result. It
As is well known, antiferromagnetic (AFM) material was further evaluated that the average thickness of the
(CoO) or ferrimagnetic material (Co3O4) usually has a CoO layer was about 3.9 nm [30]. In fact, it is believed that
magnetic transition at low temperatures. However, the Néel temperatures in ‘‘core/shell’’ type nanocapsules or
XRD pattern in Fig. 1 for sample (a) does not show any nanoparticles are variable, in comparison to the Co/CoO
other diffraction peaks corresponding to the Co3O4 or bilayers. However, determining the exact size is beyond
CoO phase. Considering our previous results on the the scope of the present investigation. Meanwhile, it was
‘‘core/shell’’ type nanocapsules [8], there may be only a lit- shown that the magnetization changes very little at
tle oxide sandwiched in the ‘‘core/shell’’ interface, which is 220 K. This also implies that only a little CoO phase exists
undetectable by XRD. Here, it is unlikely that the magnetic in the present nanocapsules, in accordance with the judg-
transition at 220 K arises from Co3O4 material because its ment above.
3732 X.F. Zhang et al. / Acta Materialia 55 (2007) 3727–3733

is concluded that the growth is likely to be governed by

an extended VLS mechanism and the Co nanoparticles
may play an important role in catalysis. This method can
open a new way to the synthesis of a series of new ‘‘core/
shell’’ type nanocapsules with the assistance of oxygen,
e.g. metallic nanocapsules coated with TiO2, ZnO, Al2O3
and MnO2. When the annealing temperature was 300 C
or less, the grain sizes of the nanocapsules are relatively sta-
ble as a consequence of the isolation of the SiO2 protective
shell. But after annealing at temperatures above 400 C, the
grains show obvious growth. The ferrimagnetic Co3O4
phase appears after annealing at 500 C. The effects of crys-
tal size, oxidation behavior and magnetic properties in the
nanocapsules have been discussed in detail.

Acknowledgments

Fig. 7. Hysteresis loops at 5 and 295 K for SiO2-coated Co nanocapsules The authors acknowledge the support from the National
after field cooling. The insert is a magnification of the graph near the Natural Science Foundation of China (50371012,
origin. 50332020) and Natural Science Foundation of Liaoning,
China (20032125). Special thanks are due to Mr. Nigel
Fig. 7 shows the hysteresis loops of the SiO2-coated Co Pemberton-Pigott for help in manuscript preparation.
nanocapsules (sample (a)) measured at 295 K and 5 K,
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