Materials Letters 157 (2015) 277280

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Microstructure and magnetic properties of W-type hexagonal ferrites

Ba1
xSrxFe22 Fe316 O27
Farui Lv, Xiansong Liu n, Shuangjiu Feng, Kai Huang, Xiaofei Niu, Xin Huang, Feng Huang,
Yuqi Ma, Shuai Jiang, Yingchun Wu
Engineering Technology Research Center of Magnetic Materials, School of Physics & Materials Science, Anhui University, Hefei 230601, PR China

art ic l e i nf o

a b s t r a c t

Article history:
Received 17 March 2015
Received in revised form
29 April 2015
Accepted 30 April 2015
Available online 28 May 2015

3+
A series of W-type hexagonal ferrites with the composition Ba1 x Srx Fe22+Fe16
O27 (0 r x r1) were prepared
by the ceramic process in a reducing atmosphere during the whole process of pre-sintering and sintering.
The phase composition, micro-morphology, and magnetic properties of the particles were investigated
by XRD, SEM, and VSM. The results of XRD show that the single phase was observed in the W-type
ferrites with different Sr content. The micro-morphology of the particles exhibits the uniform plane
hexagonal structures of W-type ferrites with different Sr content. The coercivity (Hc) of the particles
increases with the increase of Sr content (x), while the saturation magnetization (Ms) of the particles rst
decreases with x from 0 to 0.2, and then begins to increase when x continues to increase.
& 2015 Elsevier B.V. All rights reserved.

Keywords:
W-type ferrites
The ceramic process
Microstructure
Magnetic properties

1. Introduction
The hexagonal ferrite was rst discovered in 1950s [1] and since
then, people began to become more and more interested in it. It
was widely used as permanent magnets, microwave devices, magneto-optics and magnetic recording media due to their excellent
oxidation resistance, high coercivity, remanence, magnetic energy
product and uniaxial magnetocrystalline anisotropy [2,3]. The
M-type ferrites have become the mainstream of hexagonal ferrites,
however, the performance of them is close to its limitation, and it is
so difcult to improve their magnetic properties rapidly [4]. The
formula of W-type ferrites is BaMe2Fe16O27 where Me2 is usually a
rst row transition metal or some other divalent cation (e.g. Mg2 ,
Zn2 , Mn2 , Fe2 , Co2 and Ni2 ), meanwhile, the Ba2 can be
replaced by one or two metal ions of other groups (e.g. Sr2 , Pb2
and Ca2 ) [5]. In the structure of W-type ferrites, the [0001] axis of
R blocks and [111] axis of S blocks appeared at the same time. In
addition, the R blocks and S blocks can overlap together along the caxis in a way of SSRS*S*R*, where the structures of them are
BaFe6O11 and Me2Fe4O8 respectively, and the * means a rotation of
the blocks through 180 around the c-axis [68].
2+
3+
W-type ferrites were rst reported as the Fe2+
2 W (BaFe2 Fe16 O27 )
and initially treated only as a combination of the mixed phase of M
and X ferrites [9]. Besides, as a result of the existence of Fe2 , the
conductive performance is far superior to BaM ferrites [10,11].
n

Corresponding author. Fax: 86 551 65107674.

E-mail address: xiansongliu@ahu.edu.cn (X. Liu).

http://dx.doi.org/10.1016/j.matlet.2015.04.151
0167-577X/& 2015 Elsevier B.V. All rights reserved.

Nevertheless, the reports of Fe2+

2 W ferrites prepared by the ceramic
process are relatively less for the reasons that the Fe2 is easily
oxidized to Fe3 and makes the experiment so difcult. In this
work, we prepared Fe2+
2 W ferrites by the ceramic process with the
method of controlling the oxygen partial pressure strictly under the
protection of nitrogen [12].

2. Material and methods

3+
O27 (x 0, 0.2,
All samples of W-type ferrites Ba1 x Srx Fe22+Fe16
0.5, 0.8 and 1.0) were synthesized by the ceramic process. Raw
materials used in this work were BaCO3 (99% purity), SrCO3 (99%
purity), and Fe2O3 (98% purity). The raw materials were weighted
3+
according to a stoichiometric composition of Ba1 x Srx Fe22+Fe16
O27,
where x 0, 0.2, 0.5, 0.8 and 1.0. Then the raw materials were
charged in a ball mill together with a diameter of 8 mm. The
mixtures of the raw materials were milled for 4 h with an angular
velocity of 80 rpm and a ball-to-powder weight ratio of 15:1. The
mixed powder was dried at 100 C for 10 h in an oven, and presintered at 1290 C in nitrogen for 3 h in a mufe furnace. The presintered samples were crushed to particles by a vibration mill.
The phases of the samples were investigated by X-ray diffraction (XRD) using Cu K radiation. And the morphology of the
samples was observed by using a HITACHI S-4800 scanning electron microscopy (SEM). At the same time, the saturation magnetization (Ms) and coercivity (Hc) were measured by a Riken Denshi
BH-55 vibrating sample magnetometer (VSM).

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F. Lv et al. / Materials Letters 157 (2015) 277280

3. Results and discussion

Table 1
Effects of Sr-substitution on lattice constants (a and c), c/a, Ms and Hc for the

3.1. Microstructure

3+
W-type ferrites Ba1 x Srx Fe22+Fe16
O27 samples.

Fig. 1
shows
the
X-ray
diffraction
patterns
of
3+
Ba1 x Srx Fe22+Fe16
O27 (x 0, 0.2, 0.5, 0.8 and 1.0) magnetic powders
pre-sintered in nitrogen at 1290 C for 3 h. The XRD patterns of all
the samples are totally compatible with the JCPDS data for
BaFe18O27 (PDF#75-0406) and do not show any extra peaks compared to those observed for the standard W-type ferrites. Therefore, it is convinced that single W-type ferrites are synthesized.
The lattice constants a and c for all the samples are calculated from
the values of the dhkl corresponding to (1010) peaks and (116)
peaks by the following relation and the values are listed in Table 1.
1/2
4 h2 + hk + k 2
l2

+
dhkl =
3
a2
c2

Sample (x)

c ()7 0.001

a ()7 0.001

c/a Ratio

Ms (emu/g)

Hc (Oe)

0
0.2
0.5
0.8
1.0

32.810
32.836
32.701
32.667
32.572

5.879
5.90
5.88
5.879
5.872

5.581
5.566
5.562
5.557
5.547

69.95
69.31
69.75
71.01
72.69

255.36
257.78
260.98
262.56
263.45

(1)

Here, dhkl is the interplanar spacing, and h k and l are the Miller
indices.
From the table we can see that, the values of a and c for all the
samples rst increase and then decrease regularly with the increasing of x, which were very different with that of unsubstituted
ferrites. Both a and c reach the maximum values (5.8997 and
32.8364 ) when x 0.2, respectively. When x 40.2, the lattice
constant a decrease slightly, while the lattice constant c decrease
signicantly. The results are in agreement with that reported by
Ahmad et al. [5,13]. The variation of the lattice constants a and c
with the increase of Sr content (x) is mainly due to the fact that the
ionic radius of Sr2 (1.12 ) is smaller than that of Ba2 (1.35 ).
The crystal axis ratios c/a for all samples are also listed in Table 1
and shown in Fig. 2. There is considerable variation in constant c
than a because of c-axis is the easy axis in W-type hexaferrites and
it is easier to orient the spin directions along c-axis which is vertical to the hexagonal based plane [12].
3+
The SEM micrographs for W-type ferrites Ba1 x Srx Fe22+Fe16
O27
(x 0, 0.2, 0.5, 0.8 and 1.0) are shown in Fig. 3. These micrographs
indicated that platelets-shape grains have well dened hexagonal
shape with micron scale grain size and the tropism of grains is
random. The shape of the materials plays an important role in
various applications in different eld and it has been reported

3+
Fig. 1. X-ray diffraction patterns for the W-type ferrites Ba1 x Srx Fe22+Fe16
O27 . (a)
x 0 (b) x 0.2 (c) x 0.5 (d) x 0.8 (e) x 1.0 and (f) JCPDS diffraction data.

Fig. 2. Crystal axis ratio of c/a with different Sr content (x).

earlier that the platelet shaped hexaferrites can be used in microwave absorbing coatings [14]. Moreover, the decrease of the
grain size can be attributed to the fact that the ionic radius of Sr2
is smaller than Ba2 with the increase of Sr content.
3.2. Magnetic properties
The magnetic hysteresis loops for W-type ferrites
3+
Ba1 x Srx Fe22+Fe16
O27 (x 0, 0.2, 0.5, 0.8 and 1.0) were measured and
3+
the loop for W-type ferrite Ba0.5Sr0.5Fe22+Fe16
O27 was shown in
Fig. 4(a). The saturation magnetization (Ms) and coercivity (Hc) are
also listed in Table 1, and the inuence of Sr content on the saturation magnetization (Ms) and coercivity (Hc) of the W-type
ferrites is shown in Fig. 4(b). As can be seen from Fig. 4(b), the
saturation magnetization (Ms) is very high, while coercivity (Hc)
was low, from which the soft character of magnets was observed
and the result is in agreement with that reported by Albanese et al.
[15] and Ram et al. [16]. As can be seen from the variation of Ms
and Hc with different x contents, Hc increases slightly with the
increase of x, while Ms decreases rst with x from 0 to 0.2, and
then increases from 0.2 to 1.0. Both Hc and Ms reach the maximum
values (72.79 emu/g and 263.45 Oe) when x 1, respectively.
The high saturation magnetization (Ms) of W-type ferrites is
caused by superexchange interaction across one oxygen atom
(Fe3 OFe3 ) and two oxygen atoms (Fe3 OOFe3 ) [17].
Due to the substitution of the Ba2 ions by the smaller Sr2 ions,
the lattice constants rst increase and then decrease as Table 1
indicates. Correspondingly, the similar changed trend with lattice
constants also appeared over the distance of FeO being parallel to
the c-axis, which lead to the superexchange interaction rst reduce and then strengthen, which caused the change of Ms.
The value of coercivity Hc increases with the increases of the Sr

F. Lv et al. / Materials Letters 157 (2015) 277280

279

3+
Fig. 3. SEM micrographs for all W-type ferrites Ba1 x Srx Fe22+Fe16
O27 samples.

content. According to ferromagnetic theory, the coercivity in

W-type hexaferrite can be explained by the equation as follows:

Hc = 0.64

K1
Ms

(2)

where K1 is the magnetocrystalline anisotropy constant and Ms is

the saturation magnetization. Since Ms changes slightly, it can be
concluded that reasons for the variation of Hc may be contributed
to the difference in the magnetocrystalline anisotropy of the Sr2
and Ba2 ions by substituting Sr2 (1.12 ) for Ba2 (1.35 ). The
increased magnetocrystalline anisotropy causes an enhancement

in coercivity. In other words, the magnetocrystalline eld increases

when Ba2 is replaced by the smaller Sr2 .

4. Conclusions
3+
W-type hexagonal ferrites Ba1 x Srx Fe22+Fe16
O27 (x 0, 0.2, 0.5,
0.8 and 1.0) have been successfully synthesized by the ceramic
process in nitrogen. The Sr2 ions substituted Ba2 ions in order
to investigate the microstructure and magnetic properties of
hexaferrites. The results of XRD conrmed the appearance of a
pure phase hexagonal crystal structure. The study of SEM showed

3+
3+
Fig. 4. Magnetic properties of W-type ferrites Ba1 x Srx Fe22+Fe16
O27 samples: (a) magnetic hysteresis loop for W-type ferrite Ba0.5Sr0.5Fe22+Fe16
O27 ; and (b) variation of
saturation magnetization (Ms) and coercivity (Hc) with x increase.

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F. Lv et al. / Materials Letters 157 (2015) 277280

that the ferrites have formed the hexagonal structure and the
particles distributed evenly. The saturation magnetization (Ms) is
very high while the coercivity (Hc) only has a few oersteds, which
show the soft character of the investigated ferrites.

Acknowledgments
The authors acknowledge the nancial support from the National Natural Science Foundation of China under Grant nos.
51272003, 51472004, 11375011 and 21271007, the Natural Science
Foundation of Anhui Province under Grant no. 1408085MA12, the
Key Program of the Education Department of Anhui Province
(Grant nos. KJ2013B057 and KJ2012A027), Anhui University 211
Project Academic Innovation Team Projects under Grant no.
02303402, and from the Research Fund for the Doctoral Program
of Higher Education of China under Project 20123401110008.

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