Journal of Magnetism and Magnetic Materials 426 (2017) 375379

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Journal of Magnetism and Magnetic Materials

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

Ferromagnetic glass ceramics and glass bers based on the composition

of SiO2-CaO-Al2O3-B2O3-Fe2O3 glass system
crossmark

Jianan Liu , Chaofeng Zhu, Meimei Zhang, Yanfei Zhang, Xuena Yang
Key Laboratory of Processing and Testing Technology of Glass & Functional Ceramics of Shandong Province, Qilu University of Technology, Jinan 250353,
China

A R T I C L E I N F O A BS T RAC T

Keywords: Ferromagnetic glass-ceramics and glass bers were obtained by the melt-method from the glass system SiO2-
Ferromagnetic glass CaO-Al2O3-B2O3-Fe2O3 without performing any nucleation and crystallization heat treatments. Glass-ceramics
Magnetite and glass bers were characterized by x-ray diraction, scanning and transmission electron microscopy,
Spontaneous crystallization magnetic measurements, and thermal expansion instrument. The inuence of alumina content on the
spontaneous crystallization of magnetite, magnetism properties and thermal expansion performances in glass
were investigated. We examined the crystallization behavior of the glasses and found that the spontaneous
crystallization capacity of magnetite and magnetism properties in base glass increases with increasing the
content of alumina. The ferromagnetic glass bers containing magnetite nano-crystals are also obtained.

1. Introduction nanoparticles allows a wide range of industrial, biological and medical

The materials with electromagnetic wave absorption performance
have attracted great attention in recent years [15]. The application of
radar-absorbing materials can reduce the radar cross-section of the
target eectively, thus contributing to the stealthy defense system [6].
Many research groups have been studying the preparation and the
electromagnetic properties of absorbers [7].
Ferrite powders and subsequent bulk ceramics sintered from the
ferrite powders are the most common materials used for microwave
absorbers and electromagnetic devices. However, their applications are
limited due to a high-density. In order to reduce the density, nano-
crystals magnetic glass materials have recently attracted a great
attention [8]. As an important magnetic material, Fe3O4 has been
reported extensively in view of its excellent microwave absorption
property [912]. At present, the study of absorbing materials mainly
focuses on iron series [13,14], carbon system [15], ceramic system
[1620], and conductive polymer class [21], etc. The addition of large
amounts of Fe2O3 to glass system is interesting in the light of the
numerous investigations from the past two decades, especially with
respect to the utilization of natural minerals or wastes for the
production of glassy or glassceramic materials [22].
Magnetite is a magnetic mineral which naturally occurs in numer-
ous geological formations. Although magnetite has been a subject of
scientic research for decades, some of its advanced properties are still
not fully understood. The use of magnetite as a constituent of magnetic
applications [23]. The present work is about the SiO2-CaO-Al2O3-B2O3-
Fe2O3 system. The magnetic properties of the glass-ceramics are highly
sensitive to the variations of their structures and chemical composi-
tions [24]. We nd the magnetite crystals are spontaneously formed
during the cooling from the melting temperature to forming tempera-
ture. The novelty of the present work is that ferromagnetic glass bers
containing magnetite nano-crystals were one-step drawing by the
traditional production method without any heat treatment process.
The ferromagnetic glass bers can be used to synthesize composite
materials, such as glass ber with resin, which can be employed in
aviation, military and other elds. These composite materials not only
reduce the weight of the equipment, but also have the function of
absorbing electromagnetic wave. The ferromagnetic glass bers possess
wide application prospect.
2. Experimental
2.1. Fabrication of glass ceramics and glass bers
Our target was to obtain a glass-ceramic, so a melting step was
necessary to achieve the nucleation of magnetite cooling from melting
temperature in liquid-derived amorphous phase. The base glasses with
the compositions listed in Table 1 were prepared by the melt quenching
method using analytical grade reagents SiO2, Al(OH)3, CaCO3, Fe2O3
and H3BO3 as starting materials. The starting materials were appro-

Corresponding author.
E-mail address: lja@qlu.edu.cn (J. Liu).

http://dx.doi.org/10.1016/j.jmmm.2016.11.055
Received 10 October 2016; Received in revised form 13 November 2016; Accepted 14 November 2016
Available online 17 November 2016
0304-8853/ 2016 Elsevier B.V. All rights reserved.
J. Liu et al. Journal of Magnetism and Magnetic Materials 426 (2017) 375379

Table 1
Nominal Compositions of Samples (in wt%).

Composition No. CaO Al2O3 Fe2O3 B2O3 SiO2

1# 22 0 40 8 30
2# 19 3 40 8 30
3# 16 6 40 8 30
4# 13 9 40 8 30

priately weighed and thoroughly mixed, then melted in corundum

crucibles at 1460 C for 40 min to obtain homogeneous glass melts.
Then three types of forming processes were performed. First, the fast-
quenched sample was obtained by pouring the glass melt into cold
water to preserve the high-temperature structure of the glass. Second,
the molten glass was poured onto a stainless-steel plate to obtain two
bulk samples, one is cooled naturally in air, the other was annealed at
560 C for 30 min in a mue furnace. Third, the glass bers with
dierence diameters were drawing from the glass melt at a proper
temperature. The eect of calcium aluminum ratio on magnetite
spontaneous crystallization in glasses was discussed under the invari-
able contents of SiO2, Fe2O3 and B2O3.

2.2. Characterizations

The XRD measurements were made by X-ray diraction (XRD)

using Cu K radiation. The room-temperature magnetic properties of
the bulk glass and glass bers were investigated using a vibrating
magnetometer (VSM) at 450 KA/m magnetic eld. The morphologies
of bers were examined by Scanning Electron Microscopy (SEM, JEOL
JSM-7600F). These as-prepared glass-ceramics were ground into
powders with alcohol in agate mortar and etched in boiling 2N acetic
acid for 1 h. The precipitate was collected on a lter, washed with
water, and dried at 100 C [8]. The obtained samples were investigated
using Transmission Electron Microscopy (TEM, JEOL-2100F) in order
to obtain information concerning the structural and morphology of
these glass-ceramics. The glass transition temperature (Tg), softening
point (Ts) and coecient of thermal expansion (CTE) were obtained
from Orton Standard Dilatometers which were carried out on annealed
glass samples with a length of about 26 mm.

3. Results and discussion

3.1. X-ray diraction patterns

The XRD patterns of the glass samples are shown in Fig. 1. The
characteristic halo of amorphous phase can be observed in the range of
2030 for all of samples [25]. From Fig. 1(a), the diraction lines of
quenched glass in cold water are characteristic of amorphous material.
For samples 3# and 4#, the weak diraction peaks are observed. The
results show that the quenched sample preserves the high temperature
glassy state. Otherwise, it can be seen from Fig. 1(b) and (c) that some
diraction peaks are clearly observed. The intensity of diraction peak
increases with increasing the content of alumina. All detectable peaks
Fig. 1. XRD patterns of samples. (a) melt-quenched samples; (b) naturally cooled
can be indexed to the magnetite crystalline phase Fe3O4 (PDF#85- samples; (c) annealed samples.
1436). The results show that the magnetite crystals were spontaneously
formed in the glass cooling from melt to room temperature.
The compositions are non-alkali, in this system iron oxide sub-
Table 2
stitutes for alkali metal oxide to provide free oxygen in glass forming.
Magnetite crystal size (nm).
SiO2, Al2O3 and B2O3 are glass forming oxide. In addition, Fe2O3 and
CaO are network modiers. The spontaneous crystallization behavior of Composition No. Quenched Naturally cooled Annealed glasses
magnetite in glass depends on the alumina content. Therefore, the glasses glasses
ferromagnetic glass-ceramics were obtained and no other subsequent
3# 12 24 34
nucleation and crystallization treatments are necessary. From the full 4# 15 26 40
width at half maximum for the peak of (311), the crystallite sizes of the
crystalline phases were calculated by using the DebbieScherrer

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J. Liu et al. Journal of Magnetism and Magnetic Materials 426 (2017) 375379

Fig. 2. The schematic diagram showing the mechanism of the spontaneous crystallization of magnetite.

formula given by [26]: D=(K)/(cos), where D is the crystallite size,

is the X-rays wavelength (1.54060 ), K=0.89 (the Scherrer constant),
is the width of line at the half-maximum intensity in radians and is
the diraction angle. The results are show in Table 2.
The mechanism of the spontaneous crystallization of magnetite in
molten glass during the cooling process is shown in Fig. 2. For pure
silica and boron oxide, it is dicult to form a uniform melt because of
their dierent structure. Silica is a frame structure and boron oxide
belongs to layer structure. When the glass melt is cooled from melting
temperature, they gathered together to form a system, respectively, and
form mutual miscibility of two glass phases.
Iron is a polyvalent element, and a magnetic element. It has two
valences +2 and +3. The oxide includes FeO, Fe2O3 and Fe3O4. The
Fe3O4 is natural paramagnetic materials. When the content of Fe2O3
increases, the structure of boron is changed. The boron structure is
changed from triangular unit to tetrahedron by capturing oxygen irons
form iron oxides. Thus, the structure of boron is changed from layer to
frame shape. So, silica and boron oxide formed uniform glass during
cooling from high temperature. At the same time, the oxygen ion of
ferric oxide was snatched to prompt the spontaneous crystallization of
magnetite. Al3+ ion has two kind of coordination states in glass, i.e.,
located in the tetrahedron or octahedron. Because the eld strength of
Fe3+ is smaller than that of Al3+, Al3+ seizes the non-bridge oxygen to
form [AlO4] tetrahedron. It connects the broken network to form a
unied network with [SiO4] tetrahedron. This change tends to close the
structure of glass, also is favorable for the formation of magnetite
(Fe3O4). In wide concentration range, the addition of Fe2O3 to the
borosilicate glasses results in phase separation and subsequent crystal-
lization of dierent iron-bearing phases, including magnetite. With the
gradual substitution of CaO with Al2O3, more and more oxygen ions in
the iron oxide were snatched and the more magnetite crystals are
formed spontaneously. So, the intensity of diraction peaks increased
gradually with increasing the Al2O3 content.

3.2. Magnetic measurements

The hysteresis graphs of quenched glasses in cold water, naturally

cooled glasses and annealed glasses at 450 KA/m VSM magnetic elds
are shown in Fig. 3. All the samples with composition 1# do not display
magnetism. For quenched glasses in cold water, only samples 3# and 4#
exhibit magnetism. For the naturally cooled glasses and annealed
glasses with compositions 2#, 3# and 4#, all the observed magnetic
behaviors are similar to soft magnetic materials with narrow hysteresis
loop and low coercivity [27,28]. The saturation magnetization and the
coercive force of all glasses increase with decreasing cooling ratio.
Under a magnetic eld of 450 KA/m, the saturation magnetization and
the coercive force of the annealed glass 4# are 16.8 A m2/kg and
6.2 KA/m, respectively. For all samples, the annealed glass has a larger
saturation magnetization and coercive force value compared with the
quenched glasses. The reason is that magnetite crystallized more
perfectly at lower cooling rate. According to the literature, the coercive Fig. 3. Hysteresis graphs of glasses. (a) melt-quenched samples; (b) naturally cooled
force depends drastically on the crystal dimensions [29]. samples; (c) annealed samples.
The inuence of the substitution of CaO with Al2O3 on magnetic
parameters of annealed glasses, such as the saturation magnetization
(Ms) and coercivity (Hjc), are shown in Fig. 4. It can be seen that the

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J. Liu et al.
Fig. 4. Inuence of the content of alumina on the magnetism properties of glasses.
values of Ms and Hjc increase with increasing the content of Al2O3,
indicating that the spontaneous crystallization ability of magnetite is
enhanced with increasing the content of Al2O3.
3.3. Scanning electron microscopy
Fig. 5(a) and (b) shows the SEM images of glass bers with the
composition 4#. The shape of glass bers is round rod with even
thickness, and the diameter of the glass bers is about 25 m. The
surface of glass bers is smooth and at without any defects. The
results show that the composition 4# is suitable for drawing glass
bers.
3.4. Transmission electron microscopy
The TEM micrographs of glass bers with the composition 4# are
shown in Fig. 5c and d. The low-magnied TEM image (Fig. 5c) shows
that the bers composed of irregular nanoparticles with the average
size of 20 nm. The high-magnied TEM image (Fig. 5d) illustrates the
periodic fringe spacing of 0.25 nm which corresponds to the (311)
plane of cubic Fe3O4 [5].
The selected glass bers with diameter of 50, 100 and 200 m for
the composition 4# were ground into powders. Room temperature
Fig. 5. SEM (a, b) and TEM (c, d) images of glass bers with the composition 4#.
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Journal of Magnetism and Magnetic Materials 426 (2017) 375379
Fig. 6. Hysteresis graphs of glass bers for composition 4# with dierent diameters.
hysteresis graphs of glass ber powders are shown in Fig. 6. The
saturation magnetization (Ms) of glass bers increases with increasing
diameter. For glass bers with diameter of 100 and 200 m, the
saturation magnetization is 4.2 and 4.8 A m2/kg, respectively. The
observed magnetic behavior of glass ber with the diameter of 50 m is
dierent to others. At the eld of about 140 KA/m, the magnetic
moment is saturated. However, the saturation magnetization decreases
with increasing magnetic eld. This phenomenon may be due to the
diamagnetism is produced when the saturation magnetization is
smaller. The results show that the drawing rate aects the magnetic
performance of glass bers.
3.5. Thermal expansion properties
The expansion curve of annealed glasses with alumina as reference
at ratio of 5 C/min using Orton thermal expansion instrument are
shown in Fig. 7. From the linear part of the dilatometric curves, the
values of CTE between 30 and 300 C for glasses 1#, 2#, 3# and 4# were
obtained as 6.76, 3.89, 6.27 and 7.05106 K1, respectively. For
samples 1#, 3# and 4#, the curves behavior is characteristic glass
expansion curve with only one peak. Their glass transition temperature
(Tg) and softening point (Ts) are 594 C, 605 C, 625 C and 644 C,
J. Liu et al.
Fig. 7. Thermal expansion curves of annealed samples.
Fig. 8. Thermal expansion performances of annealed glasses versus content of Al2O3.
668 C, 678 C, respectively. In addition, there are tow peaks in the
curve of sample 2#. The temperature is 556 C and 712 C, respectively.
The result reveals that the precipitation of a nano-size droplet phase in
glassy matrices implies the occurrence of liquidliquid phase separa-
tion in glass 2# during cooling.
The inuence of Al2O3 content on softening point (Ts) and
coecient of thermal expansion (CTE) of annealed glasses is shown
in Fig. 8. With 3 wt% Al2O3 substituting for CaO, we nd that the value
of Ts is biggest and the CTE is minimum. When the content of Al2O3 is
lower 3 wt%, Al3+ can seize non-bridge oxygen and form [AlO4]
tetrahedron considering that Al3+ acts as a network former. [AlO4]
tetrahedron can connect with the [SiO4] unit. So the broken network is
connected, which can close the structure and reduce the CTE of glass.
When the content of Al2O3 is over 3 wt%, the CET increases and Ts
decreases. On the one hand, there are more Al3+ seizing the bridge
oxygen into the glass network. Because [AlO4] tetrahedron has larger
volume than [SiO4] tetrahedron, the glass structure becomes loose with
increasing alumina content. As a result, the CET of glasses increases
gradually. On the other hand, Al2O3 as intermediate oxides lls up the
glass structure interstices, thus preventing bond bending which con-
sequently increases CTE [30].
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Journal of Magnetism and Magnetic Materials 426 (2017) 375379
4. Conclusions
The ferromagnetic glass-ceramics containing unique magnetite
nano-crystals have been successfully prepared using the melt method
by magnetite spontaneous crystallization without any nucleation and
crystallization heat treatments during cooling from melt temperature.
The alumina content aects the performance of magnetite spontaneous
crystallization. For composition 3#, it is easy to draw ferromagnetic
glass bers with uniform diameters about 25 m, smooth surfaces, no
defects and containing magnetite nano-crystals. The saturation mag-
netization and coercivity of annealed glasses increases with increasing
alumina concentration. When the content of Al2O3 is 3 wt%, the CTE
and Ts of annealed glass are 3.89106/C and 712 C, respectively.
This composition of glass can be drawn to ferromagnetic nano-crystals
glass bers without any nucleation and crystallization treatments. The
saturation magnetization (Ms) of glass bers with 50 m diameter
obtained from composition 4# is 1.7 A m2/kg at eld of about 140 KA/
m.
Acknowledgments
The present work is nancially supported by the Natural Science
Foundation of Shandong Province (Grant No. ZR2015EM030), the
National Natural Science Foundation of China (51402156), Shandong
Provincial Natural Science Foundation, China (ZR2014EMQ003), and
State Key Laboratory of Silicate Materials for Architectures, Wuhan
University of Technology (SYSJJ2014-13).
References
[1] S.M. Salman, S.N. Salama, H.A. Abo-Mosallam, Ceram. Int. 42 (2016) 8650.
[2] K. Osouli-Bostanabad, E. Hosseinzade, A. Kianvash, Appl. Surf. Sci. 356 (2015)
1086.
[3] J.W. Yi, S.B. Lee, J.B. Kim, S.K. Lee, J. Magn. Magn. Mater. 361 (2014) 182.
[4] B.N. Huang, C.J. Li, J.N. Wang, J. Magn. Magn. Mater. 335 (2013) 28.
[5] N. Dong, F.Z. He, J.L. Xin, Q.Z. Wang, Z.Q. Lei, B.T. Su, Mater. Lett. 141 (2015)
238.
[6] M.Z. Wu, H.H. He, Z.S. Zhao, X. Yao, J. Phys. D 33 (2000) 2398.
[7] X.G. Meng, Y.Z. Wan, Q.Y. Li, J. Wang, Appl. Surf. Sci. 257 (2011) 10808.
[8] D.D. Zaitsev, E.A. Gravchikova, P.E. Kazin, A.V. Garshev, Yu.D. Tretyakov, Inorg.
Mater. 42 (3) (2006) 326.
[9] K. Jia, R. Zhao, J.C. Zhong, X.B. Liu, J. Magn. Magn. Mater. 322 (2010) 2167.
[10] S.B. Ni, X.L. Sun, X.H. Wang, Mater. Chem. Phys. 124 (2010) 353.
[11] J. Wei, J.H. Liu, S.M. Li, J. Magn. Magn. Mater. 312 (2007) 414.
[12] Y.J. Chen, P. Gao, C.L. Zhu, J. Appl. Phys. 106 (2009) 054303.
[13] M.X. Yu, X.C. Li, R.Z. Gong, J. Alloy. Compd. 456 (2008) 452.
[14] N.M. Ferreira, A.V. Kovalevsky, M.A. Valente, Ceram. Int. 42 (2016) 2693.
[15] R. Wang, F. He, Y.Z. Wan, Y. Qi, J. Alloy. Compd. 514 (2012) 35.
[16] F.Z. Song, X.Q. Shen, J. Xiang, J. Alloy. Compd. 507 (2010) 297.
[17] M. Arias, V.M. Pantojas, O. Perales, J. Magn. Magn. Mater. 323 (2011) 2109.
[18] W.L. ku, P. Intawin, T. Tunkasiri, J. Ruangsuriya, Ceram. Int. 41 (2015) S464.
[19] H.A. Martnez-Rodrguez, J.F. Jurado, J. Restrepo, Ceram. Int. 42 (2016) 12606.
[20] J.J. Liu, C.R. Gong, G. Liang, J. Sol-Gel Sci. Technol. 61 (1) (2012) 185.
[21] J.H. Zhu, S.Y. Wei, D. Rutman, Polymer 52 (2011) 2947.
[22] R. Harizanova, G. Volksch, C. Russel, J. Mater. Sci. 45 (2010) 1350.
[23] C. Worsch, M. Buttner, P. Schaaf, R. Harizanova, J. Mater. Sci. 48 (2013) 2299.
[24] L.P. Guo, X.Q. Shen, X.F. Meng, Y.H. Feng, J. Alloy. Compd. 490 (2010) 301.
[25] P. Pascuta, A. Vladescu, G. Borodi, J. Mater. Sci.: Mater. Electron. 23 (2012) 582.
[26] J.I. Langford, A.J.C. Wilson, J. Appl. Cryst. 11 (1978) 102.
[27] M. Baikousi, S. Agathopoulos, I. Panagiotopoulos, J. Sol-Gel Sci. Technol. 47
(2008) 95.
[28] G.D. Li, S.Y. Feng, D.L. Zhou, J. Mater. Sci.: Mater. Med. 22 (2011) 2197.
[29] S. Chikazumi, S. Taketomi, M. Ukita, et al., J. Magn. Magn. Mater. 65 (1987)
24551.
[30] H.R. Fernandes, D.U. Tulyaganov, A. Goel, J. Therm. Anal. Calorim. 103 (2011)
827.