Journal of Magnetism and Magnetic Materials 393 (2015) 399403

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Journal of Magnetism and Magnetic Materials

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

Effect of LaCO substitution on the crystal structure and magnetic

properties of low temperature sintered Sr1
xLaxFe12
xCoxO19 (x 0
0.5) ferrites
Long Peng n, Lezhong Li, Rui Wang, Yun Hu, Xiaoqiang Tu, Xiaoxi Zhong
Sichuan Province Key Laboratory of Information Materials and Devices Application, Chengdu University of Information Technology, Chengdu 610225, China

art ic l e i nf o

a b s t r a c t

Article history:
Received 5 February 2015
Received in revised form
31 May 2015
Accepted 3 June 2015
Available online 6 June 2015

The LaCo substituted Sr1
xLaxFe12
xCoxO19 (x 00.5) ferrites with appropriate Bi2O3 additive were
prepared at a low sintering temperature of 890 C compatible with LTCC (low temperature co-red
ceramics) systems, and the effect of LaCo substitution on their crystal structure and magnetic properties
was investigated. The results show that the pure M-type phase is successfully obtained when the LaCo
substitution amount x does not exceed 0.3. However, the single M-type phase structure transforms to
multiphase structure with further increased x, where the -Fe2O3 phase and La2O3 phase coexist with
the M-type phase. Moreover, the saturation magnetization Ms, magnetic anisotropy eld Ha, intrinsic
coercivity Hci, and Curie temperature TC of the ferrites depend on the LaCo substitution amount
strongly, which are suggested to be determined by the partially substitution of La3 Co2 ions for
Sr2 Fe3 ions with x not higher than 0.3. It is found that the obtained Sr1
xLaxFe12
xCoxO19 (x 0.2 and
0.3) ferrites can provide improved magnetic properties (Ms 4 62 emu/g, Ha 41400 kA/m, and
Hci 4320 kA/m) as low temperature sintered M-type hexaferrites for microwave LTCC applications.
& 2015 Elsevier B.V. All rights reserved.

Keywords:
SrFe12O19 ferrites
LaCo substitution
Low temperature sintering
LTCC technology

1. Introduction
Due to the rapid development of LTCC (low temperature cored ceramics) passive integration technology, the M-type hexaferrites (BaFe12O19 and SrFe12O19 ferrites) with good permanent
magnetic properties and gyromagnetic properties have been
considered as the most promising low temperature sintered materials for use in microwave and millimeter wave LTCC ferrite
devices, typically including the nonreciprocal circulators and isolators [15]. Because of high sintering temperature above 1200 C,
the conventional M-type hexaferrites cannot co-re with the inner
electrode metal Ag with melting point of 961 C in LTCC systems.
Interestingly, the sintering temperature of these ferrites can be
reduced to 900 C by using some glass phase or metallic oxide as
sintering aids, but their magnetic properties decrease accordingly
[69]. How to improve their low temperature sintering characteristics is signicant for the miniaturization and integration of
new microwave LTCC modules. For the M-type hexaferrites prepared at traditional high sintering temperatures, the ion substitution has been revealed as an effective method to improve
their saturation magnetization Ms, magnetic anisotropy eld Ha,
n

Corresponding author.
E-mail address: penglong@cuit.edu.cn (L. Peng).

http://dx.doi.org/10.1016/j.jmmm.2015.06.005
0304-8853/& 2015 Elsevier B.V. All rights reserved.

and intrinsic coercivity Hci, such as the Al substitution, Gd substitution, La substitution, LaCo substitution, ZnTi substitution
etc. [912]. Nevertheless, the further investigations about the effect of ion substitution on the crystal structure and magnetic
properties for the M-type hexaferrites prepared at low sintering
temperatures compatible with LTCC systems are very necessary.
Our previous work indicated that the sintering temperature of
the SrFe12O19 ferrites prepared by the conventional solid phase
method can be reduced to 900 C even much lower by using Bi2O3
as sintering aids [13]. In order to improve their low temperature
sintering magnetic properties, the LaCo substituted Sr1
xLax
Fe12
xCoxO19 (x 00.5) ferrites with appropriate Bi2O3 additive
were further prepared at low sintering temperatures in this work,
and the detailed effect of LaCo substitution amount on their
crystal structure and magnetic properties was investigated.

2. Experimental
The starting materials of SrCO3 (98 wt%), Fe2O3 (99 wt%), La2O3
(99.99 wt%), and Co2O3 (99 wt%) powders were weighed in the
composition of Sr1
xLaxFe12
xCoxO19 (x 00.5) for preparing the
nominal LaCo substituted ferrites. The mixed powders were calcinated at 1250 C for 2 h and crushed by planetary ball mill at
400 r/min for 4 h with 3 wt% Bi2O3 (99 wt%) additive to get

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L. Peng et al. / Journal of Magnetism and Magnetic Materials 393 (2015) 399403

powders with average grain size of 1.11.2 m. These powders

were further pressed into disks with diameter of 12 mm at
45 MPa, and then sintered at 890 C for 2 h. Particle size of the
powders was tested by laser particle analyzer (JL-1178). Sintering
density was measured by precision density balance (FA2004J) with
resolution of 0.1 mg based on the Archimedes method. Crystal
structure was detected by X-ray diffraction (XRD, DX-2700) with
Cu K radiation. Magnetic hysteresis loop, magnetization curve,
and Curie temperature (TC) were tested by vibrating sample
magnetometer (VSM, Versalab). Effective magnetic anisotropy
constant (Keff) and magnetic anisotropy eld (Ha) were calculated
by the law of approach to saturation (LATS) within an external
eld region from 1200 to 1600 kA/m.

3. Results and discussion

XRD
patterns
of
the
low
temperature
sintered
Sr1
xLaxFe12
xCoxO19 (x 00.5) ferrites are presented in Fig. 1.
For the ferrites without LaCo substitution (x 0), the pure M-type
phase is observed. It indicates that the complete reaction of SrCO3
and Fe2O3 to produce SrFe12O19 ferrites occurs by the help of Bi2O3
additive. It is well known that the sintering temperature of M-type
hexaferrites usually reaches above 1200 C, and Fe2O3 cannot fully
participate in the reaction to produce M-type phase at low sintering temperatures. But the appropriate addition of Bi2O3 promotes the formation of M-type phase at low sintering temperatures, which is strongly correlated with the formation of Bi2O3 liquid phase [13]. Notably, the pure M-type Sr1
xLaxFe12
xCoxO19
hexaferrites are successfully obtained when the LaCo substitution
amount x does not exceed 0.3, suggesting that the La3 Co2 ions
partially substitute the Sr2 Fe3 ions. However, the single
M-type phase structure transforms to multiphase structure with
further increased x, where the -Fe2O3 phase and La2O3 phase
coexist with the M-type phase.
Lattice constants a and c of the low temperature sintered
Sr1
xLaxFe12
xCoxO19 (x 00.5) ferrites are calculated from the
interplanar spacing dhkl corresponding to (107) peak and (114)
peak of M-type phase by

dhkl = (

4 h2 + hk + k 2
l2 1/2
+
)
3
a2
c2

(1)

where h, k, and l are the Miller indices.

Fig. 2. Lattice constants of the low temperature sintered Sr1
xLaxFe12
xCoxO19
(x 00.5) ferrites.

Moreover, the porosity P of the low temperature sintered

Sr1
xLaxFe12
xCoxO19 (x 00.5) ferrites is calculated by

P=1

ds
dx

(2)

2M
NV

(3)

V = 0.8666a2c

(4)

dx =

where ds is the sintering density, dx is the X-ray density, M is the

molar mass, V is the lattice volume, and N is the Avogadros
number.
Lattice constants of the low temperature sintered
Sr1
xLaxFe12
xCoxO19 (x 00.5) ferrites is shown in Fig. 2. It is
clear that the LaCo substitution amount x provides a weak effect
on the lattice constant a but a strong effect on the lattice constant
c. When x increases from 0 to 0.3, the lattice constant c decreases
from 23.011 to 22.964 nm gradually, which is associated with the
partially substitution of La3 Co2 ions for Sr2 Fe3 ions and
different ionic radius between La3 (0.122 nm) and Sr2
(0.127 nm), and Co2 (0.072 nm) and Fe3 (0.064 nm). With further increased x, the single M-type phase structure transforms to
multiphase structure. The appearance of -Fe2O3 phase and La2O3
phase is suggested to impede the grain growth along c axis direction, and a very low value of c (22.872 nm) is obtained when x
reaches 0.5. Detailed lattice constants of the Sr1
xLaxFe12
xCoxO19
(x 00.5) ferrites are listed in table 1 correspondingly, as well as
the sintering density and calculated porosity.
Magnetic hysteresis loops of the low temperature sintered
Sr1
xLaxFe12
xCoxO19 (x0 and 0.2) ferrites with external eld
from
1600 to 1600 kA/m are shown in Fig. 3. It is found that
the appropriate LaCo substitution improves their magnetic
Table 1
Lattice constants, sintering density, and calculated porosity of the low temperature
sintered Sr1
xLaxFe12
xCoxO19 (x 00.5) ferrites.

Fig. 1. XRD patterns of the low temperature sintered Sr1
xLaxFe12
xCoxO19 (x 0
0.5) ferrites.

Substitution
amount x

a (nm) c (nm)

V (nm3) dx (g/cm3) ds (g/cm3) P (%)

0
0.1
0.2
0.3
0.4
0.5

5.863
5.875
5.875
5.877
5.877
5.860

685.5
688.3
687.8
687.3
687.3
680.6

23.011
23.010
22.996
22.964
22.961
22.872

5.115
5.123
5.130
5.133
5.134
5.184

4.680
4.615
4.563
4.465
4.421
4.432

8.5
9.9
11.1
13.0
13.9
14.5

L. Peng et al. / Journal of Magnetism and Magnetic Materials 393 (2015) 399403

401

Fig. 3. Magnetic hysteresis loops of the low temperature sintered Sr1
xLaxFe12
xCoxO19 (x 0 and 0.2) ferrites.

properties obviously. The saturation magnetization Ms and intrinsic

coercivity
Hci
of
the
LaCo
substituted
Sr0.8La0.2Fe11.8Co0.2O19 ferrites reaches 65.4 emu/g and 331.7 kA/m
respectively, while the SrFe12O19 ferrites just provide low Ms of
61.1 emu/g and Hci of 294.5 kA/m. In M-type structure, the nineteen Fe3 ions are distributed at ve different crystallographic
sites with different superexchange interaction in the cell structure,
including the 4f1 (two Fe3 ions) and 4f2 (two Fe3 ions) sites
with down-spin conguration, and 12 k (six Fe3 ions), 2a (one
Fe3 ion), and 2b (one Fe3 ion) sites with up-spin conguration.
Previous Mssbauer investigations have revealed that the substitution of Sr2 by La3 is associated with a valence change of
Fe3 Fe2 at 2a or 4f2 sites, and Co2 is substituted for Fe3 at
2a or 4f2 sites too [14,15]. If more Co2 ions occupy the 4f2 site
rather than the 2a site, the total magnetic moment of the M-type
phase will be certainly strengthened, contributing to the increased
saturation magnetization Ms. Besides, the substitution of Sr2 by
La3 with lower crystallographic symmetry increases the magnetic anisotropy eld Ha, and there has a great opportunity to
observe the enhanced intrinsic coercivity Hci.
For the polycrystalline permanent magnetic materials, the effective magnetic anisotropy constant Keff can be obtained by the
law of approach to saturation (LATS) [13,16]. According to the
LATS, the differential susceptibility d (dM/dH) is given as

3c 1
d = Ms aH + 2b +

+ p

H H3

(5)

where M is the magnetization, H is the external eld, p is the

paramagnetic susceptibility, the coefcients a, b, and c denote
different magnetic resistance in the magnetization process. It is
clear that the coefcient b can be obtained from the slope (2bMs)
of a straight linear relation of dM/dH
1/H3 under moderate external eld.
Besides, the coefcient b can also be calculated by solving the
equilibrium state of magnetization process as follow:

b=

Fk 2
1

2 02 Ms2

(6)

where is an angle between the Ms direction and H direction in a

grain, 0 is the permeability of vacuum, and Fk is the magnetic
anisotropy energy. Obviously, the coefcient b originates in the
magnetic resistance of magnetic anisotropy to the magnetization
vector.
The M-type Sr1
xLaxFe12
xCoxO19 hexaferrites exhibit polycrystalline structure constituted by lots of grains with different

easy magnetization axis directions. So, the coefcient b is calculated by seeking the average value of Fk/. Due to the uniaxial
anisotropy of the hexagonal structure, the coefcient b of the
ferrites is easily calculated in spherical coordinates system as follow:

b=

4 Keff 2
15 02 Ms2

(7)

Therefore, the effective magnetic anisotropy constant Keff of the

ferrites can be calculated, as well as the magnetic anisotropy eld
Ha (2Keff/Ms).
Magnetic properties of the low temperature sintered
Sr1
xLaxFe12
xCoxO19 (x 00.5) ferrites are shown in Fig. 4. It is
clear that the saturation magnetization Ms and intrinsic coercivity
Hci of the ferrites increase rst and then decrease when the LaCo
substitution amount x increases from 0 to 0.5. Enhanced Ms higher
than 62 emu/g and Hci higher than 320 kA/m are obtained for the
ferrites with x from 0.1 to 0.3. Maximal value of the Ms and Hci is
found to be 65.4 emu/g and 348.2 kA/m when x reaches 0.2 and
0.3, respectively. Detrimental effect of the non-magnetic -Fe2O3
phase and La2O3 phase on the magnetic properties is observed for
the ferrites with excessive LaCo substitution amount. When the
substitution amount increases to 0.5, the Ms decreases to
56.8 emu/g and the Hci decreases to 299.7 kA/m. Moreover, the
non-monotonic dependence of the effective magnetic anisotropy
constant Keff and magnetic anisotropy eld Ha on the LaCo substitution amount is observed. Interestingly, the Keff and Ha gradually increase with increasing substitution amount in the single
phase region with x r0.3, denoting that the La3 and Co2 ions
have gone into the M-type structure for substituting the Sr2 and
Fe3 ions respectively. It is worthwhile to note that the obtained
Sr1
xLaxFe12
xCoxO19 (x 0.2 and 0.3) ferrites provide relatively
high magnetic properties as low temperature sintered M-type
hexaferrites for use in microwave LTCC ferrite devices [79,13],
typically including Ms above 62 emu/g, Ha above 1400 kA/m, and
Hci above 320 kA/m.
When the LaCo substitution amount increases from 0.3 to 0.5,
the magnetic anisotropy eld Ha decreases slightly but the intrinsic coercivity Hci decreases swiftly for the low temperature
sintered Sr1
xLaxFe12
xCoxO19 ferrites. From the StonerWohlfarth
theory, the intrinsic coercivity of permanent magnetic materials
with strong magnetic anisotropy can be expressed as [17]

Hci = k j ex

2Keff
Ms
Neff
0
Ms

(8)

402

L. Peng et al. / Journal of Magnetism and Magnetic Materials 393 (2015) 399403

Fig. 4. Magnetic properties of the low temperature sintered Sr1
xLaxFe12
xCoxO19 (x 00.5) ferrites.

where Neff is the effective demagnetization factor, k, j, and ex is

a factor correlated with the grain orientation, the shapes and sizes
of nucleation or pinning defect area, and the effect of intergranular
exchange coupling interactions on the intrinsic coercivity, respectively. It is suggested that the appearance of -Fe2O3 phase
and La2O3 phase provides complicated effect on the grain growth
and microstructure for the Sr1
xLaxFe12
xCoxO19 ferrites (x40.3).
From the measured results, the excessive LaCo substitution
(x 0.4 and 0.5) produces more structure defect and leads to decreased coercivity factor of k  j  ex and increased Neff, which
are responsible for the rapid decreased coercivity.
Fig. 5 shows the Curie temperature of the low temperature
sintered Sr1
xLaxFe12
xCoxO19 (x 00.5) ferrites, and the measured results of the Sr1
xLaxFe12
xCoxO19 (x00.25) ferrites
sintered at traditional high sintering temperatures from Ref. [10]
are also given for comparison. Our experimental results denote
that the Curie temperature TC of the ferrites gradually decreases
from 449 to 421 C in the single phase region with LaCo substitution amount x from 0 to 0.3. The LaCo substitution reduces
the Fe3 OFe3 superexchange interaction in M-type phase, and
the decreased TC is associated with the appearance of so-called
canting spin structure for the M-type hexaferrites [10]. It suggests
that the La3 and Co2 ions can get into the magnetoplumbite
structure of the ferrites prepared by conventional solid phase
method at low sintering temperatures. However, the TC rapidly
decreases to a value lower than 405 C when x further increases to
0.4 and 0.5, where the single M-type phase structure transforms to
multiphase structure. The possible reason is that the appearance of
-Fe2O3 phase results in the composition deviation and lattice
deformation for the stoichiometric Sr1
xLaxFe12
xCoxO19 ferrites,
which can also reduce the Fe3 OFe3 superexchange

Fig. 5. Curie temperature of the low temperature sintered Sr1
xLaxFe12
xCoxO19
(x 00.5) ferrites and traditional high temperature sintered Sr1
xLaxFe12
xCoxO19
(x 00.25) ferrites [10].

interaction in M-type phase.

4. Conclusions
In summary, the M-type Sr1
xLaxFe12
xCoxO19 (x 00.5)
hexaferrites are successfully prepared by conventional solid phase

L. Peng et al. / Journal of Magnetism and Magnetic Materials 393 (2015) 399403

method at a low sintering temperature compatible with LTCC

systems. Analysis of their crystal structure, magnetic properties
and Curie temperature strongly suggests that the La3 Co2 ions
can partially substitute the Sr2 Fe3 ions, and the saturation
magnetization Ms, magnetic anisotropy eld Ha, and intrinsic
coercivity Hci are improved as results. It is found that the efcient
maximal La-Co substitution amount for the ferrites is determined
as 0.3. When the substitution amount exceeds 0.3, the pure
M-type phase transforms to multiphase structure, where the
M-type phase coexists with the non-magnetic -Fe2O3 phase and
La2O3 phase, and the depressed magnetic properties are inevitably
observed.
Typically,
the
obtained
La-Co
substituted
Sr0.8La0.2Fe11.8Co0.2O19 ferrites and Sr0.7La0.3Fe11.7Co0.3O19 ferrites
can provide enhanced magnetic properties as low temperature
sintered M-type hexaferrites for use in microwave LTCC ferrite
devices, including Ms of 65.4 and 62.6 emu/g, Ha of 1420.7 and
1580.9 kA/m, and Hci of 331.7 and 348.2 kA/m, respectively.

Acknowledgments
This work is supported by the National Public Welfare Fund
Industry Research under Grant no. 201410026, the Scientic Research Foundation of Education Ofce of Sichuan Province under

403

Grant no. 13Z198, and the Young and Middle-Aged Academic

Leaders of Scientic Research Funds of Chengdu University of Information Technology under Grant no. J201222.

References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]

A. Bahadoor, Y. Wang, M.N. Afsar, J. Appl. Phys. 97 (2005) 10F105.

K.A. Korolev, L. Subramanian, M.N. Afsar, J. Appl. Phys. 99 (2006) 08F504.
Y.J. Yang, X.S. Liu, D.L. Jin, et al., J. Magn. Magn. Mater. 355 (2014) 254.
T. Jensen, V. Krozer, C. Kjaergaard, Electron. Lett. 47 (2011) 111.
B.K. ONeil, J.L. Young, IEEE Trans. Microw. Theory. Tech. 57 (2009) 1669.
R. Karmazin, O. Dernovsek, N. Ilkov, et al., J. Eur. Ceram. Soc. 25 (2005) 2029.
Y.X. Li, Y.L. Liu, H.W. Zhang, et al., J. Appl. Phys. 105 (2009) 07A745.
D.M. Chen, Y.L. Liu, Y.X. Li, et al., J. Magn. Magn. Mater. 324 (2012) 449.
Y.L. Liu, Y.X. Li, H.W. Zhang, et al., J. Appl. Phys. 107 (2010) 09A507.
X.S. Liu, P. Hernandez-Gomez, K. Huang, et al., J. Magn. Magn. Mater. 305
(2006) 524.
X.S. Liu, W. Zhong, S. Yang, et al., J. Magn. Magn. Mater. 238 (2002) 207.
G. Litsardakis, I. Manolakis, C. Serletis, et al., J. Magn. Magn. Mater. 316 (2007)
170.
L. Peng, Y.B. Hu, C. Guo, et al., Chin. Phys. Lett. 32 (2015) 017502.
L. Lechevallier, J.M. Le Breton, J. Magn. Magn. Mater. 290291 (2015) 1237.
P. Tenaud, A. Morel, F. Kools, et al., J. Alloys Compd. 370 (2004) 331.
L. Peng, X.Q. Tu, L.Z. Li, et al., J. Nanoelectron. Optoelectron. 8 (2013) 458.
C.B. Rong, H.W. Zhang, J. Zhang, et al., J. Appl. Phys. 95 (2004) 1351.