Journal of Magnetism and Magnetic Materials 404 (2016) 170–174

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Journal of Magnetism and Magnetic Materials

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

Synthesis and characteristics of La3 þ –Co2 þ substituted Sr-hexaferrites

for microwave LTCC circulators
Long Peng n, Lezhong Li, Rui Wang, Yun Hu, Xiaoqiang Tu, Xiaoxi Zhong
Sichuan Province Key Laboratory of Information Materials and Devices Application, College of Optoelectronic Technology, Chengdu University of Information
Technology, Chengdu 610225, Sichuan, PR China

art ic l e i nf o a b s t r a c t

Article history: The La3 þ –Co2 þ substituted Sr0.7La0.3Fe11.7Co0.3O19 ferrites with 2–5 wt% Bi2O3  B2O3  SiO2  ZnO (BBSZ)
Received 17 June 2015 glass were synthesized by conventional sintering (CS) method, microwave sintering (MS) method, and
Received in revised form hot press sintering (HPS) method at a low sintering temperature of 850 °C compatible with the low
7 November 2015
temperature co-fired ceramics (LTCC) systems, respectively. These ferrites were chiefly characterized by
Accepted 11 November 2015
X-ray diffraction, precision density balance, and vibrating sample magnetometer. It is observed that the
Available online 12 November 2015
addition of BBSZ can promote the low temperature sintering of the ferrites, as well as the formation of
Keywords: M-type phase. But the excessive addition of non-magnetic BBSZ is inclined to reduce the magnetic
M-type hexaferrites properties for the ferrites. Detailed effects of the BBSZ amount on their low temperature sintering
Microwave sintering
characteristics are revealed and explained. The proper addition of BBSZ is suggested to be 4, 4, and 5 wt%
Hot press sintering
for the CS ferrites, MS ferrites, and HPS ferrites, respectively. Notably, the obtained MS ferrites can
LTCC technology
Circulators provide relatively high saturation magnetization of 65.3 emu/g, magnetic anisotropy field of 1528.8 kA/
m, and intrinsic coercivity of 336.1 kA/m as low temperature sintered M-type hexaferrites for use in
microwave LTCC circulators.
& 2015 Published by Elsevier B.V.

1. Introduction
With rapid development of microwave passive integration
technology, some very compact devices have been demonstrated
by low temperature co-fired ceramics (LTCC) technology, such as
inductors, capacitors, transformers, filters, and T/R modules [1–4].
However, the non-reciprocal components like circulators, isolators,
and phase-shifters are difficult to be integrated by LTCC technol-
ogy due to the absence of low temperature sintered microwave
ferrites with high performance [5]. It is worthwhile to note that
the M-type hexaferrites (MFe12O19, M ¼Ba/Sr) with good perma-
nent magnetic properties and gyromagnetic properties simulta-
neously have been considered as the most promising low tem-
perature sintered ceramics for use in microwave LTCC circulators
[6–13]. In order to decrease the sintering temperature of the
M-type hexaferrites to a suitable value compatible with LTCC
systems, some glass and metallic oxide were used as sintering aids
[14–18]. Typically, Liu et al. prepared the Zn2 þ –Ti4 þ substituted
Ba(ZnTi)xFe12  2xO19 ferrites with 3–5 wt% Bi2O3  B2O3  SiO2 at low
sintering temperatures, and the optimal saturation magnetization
reached 63.5 emu/g, but a poor coercivity of 18 kA/m was obtained
n
Corresponding author.
E-mail address: penglong@cuit.edu.cn (L. Peng).
[17]. The M-type hexaferrites can not be self-biased for use in LTCC
circulators unless they have a large coercivity to counteract the
effect of shape-dependent demagnetization field on the hysteresis
loops. How to synthesize the low temperature sintered M-type
hexaferrites with enhanced magnetic properties is significant for
the realization of microwave LTCC circulators.
Our previous work has revealed that the La3 þ –Co2 þ ions can
partially substitute the Sr2 þ –Fe3 þ ions for the low temperature
sintered Sr1  xLaxFe12  xCoxO19 (x¼ 0–0.5) ferrites, and the im-
proved saturation magnetization, magnetic anisotropy field, and
intrinsic coercivity were obtained [19]. Moreover, the microwave
sintering and hot press sintering processes are well known as the
candidate method to prepare high performance ferrites with low
sintering temperature and short sintering time. Therefore, the
La3 þ –Co2 þ substituted Sr-hexaferrites with Bi2O3  B2O3  SiO2
 ZnO (BBSZ) glass as sintering aids were prepared by conventional
sintering (CS) method, microwave sintering (MS) method, and hot
press sintering (HPS) method at a low sintering temperature in
this work, respectively. Detailed effects of the BBSZ amount on
their crystal structure, sintering density, and magnetic properties
were chiefly investigated. Besides, the potential application of the
low temperature sintered Sr-hexaferrites in microwave LTCC cir-
culators was also discussed based on the tensor permeability of
magnetized gyromagnetic ferrites [12].

http://dx.doi.org/10.1016/j.jmmm.2015.11.041
0304-8853/& 2015 Published by Elsevier B.V.
 L. Peng et al. / Journal of Magnetism and Magnetic Materials 404 (2016) 170–174 171

2. Experimental

Starting materials of SrCO3 (98.0 wt%), Fe2O3 (99.0 wt%), La2O3

(99.99 wt%), and Co2O3 (99.0 wt%) powders were weighed in the
composition of Sr0.7La0.3Fe11.7Co0.3O19 for preparing the
La3 þ –Co2 þ substituted ferrites. The mixed powders were calci-
nated at 1250 °C for 2 h and then ball-milled with 2–5 wt% BBSZ
glass at 400 r/min for 4 h to get powders with average particle size
about 1.1–1.2 μm. Powders with 6 wt% polyvinyl alcohol (PVA)
binder were pressed into disks with a diameter of 12 mm at
45 MPa, and then sintered at 850 °C by CS method for 2 h, MS
method for 30 min, and HPS method for 30 min, respectively.
Work frequency and output power of the microwave sintering
furnace (GER-M2) is 2.45 GHz and 2000 W. Maximal sintering
temperature and pressure of the customized hot press sintering
system can arrive at 1000 °C and 60 MPa. 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 Kα radiation. Magnetization curves and magnetic hysteresis
loops were tested by vibrating sample magnetometer (VSM, Ver-
salab) with applied magnetic field from  1600 to 1600 kA/m.
Effective magnetic anisotropy constant and magnetic anisotropy
field were calculated by the law of approach to saturation (LATS)
within an applied magnetic field region from 1200 to 1600 kA/m
[18–20].

3. Results and discussion

Effect of the BBSZ amount on the crystal structure of the

Sr0.7La0.3Fe11.7Co0.3O19 ferrites prepared by different sintering
method is shown in Fig. 1. For the CS ferrites with different BBSZ
amount, the M-type phase coexists with the non-magnetic
α-Fe2O3 phase and SrO2 phase, as shown in Fig. 1(a). When the
BBSZ amount reaches 4 wt%, more Fe2O3 participates in the reac-
tion to produce M-type phase, thus the observed diffraction in-
tensity of α-Fe2O3 phase decreases obviously. This indicates that
the addition of BBSZ promotes the formation of M-type phase at
low sintering temperatures. However, the ferrites with pure
M-type phase can not be obtained even when the BBSZ amount
increases to 5 wt%. Unlike the CS ferrites, the MS ferrites and HPS
ferrites with single M-type phase are successfully synthesized
when the BBSZ amount reaches 4 and 5 wt%, respectively, as
shown in Fig. 1(b) and (c). Microwave sintering and hot press
sintering promote the formation of M-type phase at low sintering
temperatures from the XRD measurement, which is associated
with their distinctive sintering mechanisms [21,22]. Moreover, the
obtained pure M-type phase suggests that the La3 þ –Co2 þ ions
partially substitute the Sr2 þ –Fe3 þ ions, and there has a great op-
portunity to synthesize the low temperature sintered M-type
hexaferrites with enhanced magnetic properties [8].
Effect of the BBSZ amount on the sintering density of the
Sr0.7La0.3Fe11.7Co0.3O19 ferrites prepared by different sintering
method is presented in Fig. 2. When the BBSZ amount increases
from 2 to 4 wt%, the sintering density of the CS ferrites, MS ferrites,
and HPS ferrites rapidly increases from 4.13, 4.36, and 4.42 g/cm3
to 4.41, 4.68, and 4.74 g/cm3, respectively. With further increased Fig. 1. Effect of the BBSZ amount on the crystal structure of Sr0.7La0.3Fe11.7Co0.3O19
BBSZ amount, the sintering density of the CS ferrites, MS ferrites, ferrites prepared by (a) CS method, (b) MS method, and (c) HPS method.
and HPS ferrites changes slightly, which reaches to the saturated
value as high as 4.46, 4.70, and 4.74 g/cm3, respectively. It is gen-
erally believed that the melting of BBSZ at the grain boundary microwave sintering and hot press sintering can provide a higher
leads to the transient liquid sintering for the ferrites and the mass efficiency to increase the macro densification of the low tem-
transportation and diffusion among the ferrites are promoted, thus perature sintered ferrites.
the elevated sintering density is observed [16]. Obviously, the Effect of the BBSZ amount on the saturation magnetization (ss)
172 L. Peng et al. / Journal of Magnetism and Magnetic Materials 404 (2016) 170–174

Fig. 2. Effect of the BBSZ amount on the sintering density of Sr0.7La0.3Fe11.7Co0.3O19

ferrites prepared by CS method, MS method, and HPS method.

of the Sr0.7La0.3Fe11.7Co0.3O19 ferrites prepared by different sinter-

ing method is shown in Fig. 3. For the CS ferrites, the saturation
magnetization gradually increases from 47.5 to 59.7 emu/g when
the BBSZ amount increases from 2 to 4 wt%, and then it decreases
to 56.2 emu/g with further increased BBSZ amount, as shown in
Fig. 3(a). According to the analysis of crystal structure and sinter-
ing density, we know that the addition of BBSZ promotes the low
temperature sintering of the ferrites, as well as the formation of
M-type phase. This can clearly explain the increased saturation
magnetization with increasing BBSZ amount. On the contrary, the
addition of non-magnetic BBSZ glass is inclined to reduce the
magnetic properties for the ferrites. Excessive addition of BBSZ as
high as 5 wt% is responsible for the decreased saturation magne-
tization. It is reasonable to deduce that the suitable addition of
BBSZ is 4 wt% for the CS ferrites. Seen from Fig. 3(b), the compli-
cated relationship between the saturation magnetization and the
BBSZ amount is observed for the MS ferrites. When the BBSZ
amount increases from 2 to 3 wt%, the saturation magnetization
exhibits a slow increase from 57.0 to 58.8 emu/g, but it rapidly
increases to 65.3 emu/g with BBSZ amount of 4 wt%. This sig-
nificant increment of saturation magnetization is strongly corre-
lated with the phase transformation observed by the XRD results,
where the multiphase structure transforms to single M-type phase
structure. However, the saturation magnetization slightly de-
creases to 64.1 emu/g when the BBSZ amount further increases to
5 wt%. It can be also attributed to the excessive addition of non-
magnetic BBSZ glass in accordance with the CS ferrites. Depen-
dence of the saturation magnetization on the BBSZ amount for the
HPS ferrites as listed in Fig. 3(c) is also suggested to be dominated
by the improved formation of M-type phase against to the ex-
cessive addition of non-magnetic BBSZ glass. The saturation
magnetization has a large increment from 49.8 to 60.5 emu/g
when the BBSZ amount increases from 2 to 4 wt%. With further
increased BBSZ amount, the saturation magnetization still has a
slight increase, and the maximal value arrives at 60.9 emu/g.
For the polycrystalline permanent magnetic materials, the ef-
fective magnetic anisotropy constant Keff can be obtained accord- Fig. 3. Effect of the BBSZ amount on the saturation magnetization of
Sr0.7La0.3Fe11.7Co0.3O19 ferrites prepared by (a) CS method, (b) MS method, and
ing to the law of approach to saturation (LATS) [18–20]. By the
(c) HPS method.
LATS, the differential susceptibility χd (dM/dH) is given as:
⎛ 3c ⎞ 1
χd = Ms ⎜ aH + 2b + …⎟ + χp susceptibility, and a, b, and c denote the different magnetic re-
⎝ H ⎠ H3 (1)
sistance in the magnetization process. It is clear that the coeffi-
where M is the magnetization, H is the external magnetic field, Ms cient b can be gained from the slope of dM/dH  1/H3 straight
is the saturation magnetization, χp is the paramagnetic linear relation under moderate external magnetic field.
 L. Peng et al. / Journal of Magnetism and Magnetic Materials 404 (2016) 170–174 173

Besides, the coefficient b can be also calculated by solving the

equilibrium state of magnetization process as follow:

1 ⎛ ∂Fk ⎞2
b= ⎜ ⎟
2μ 02 Ms2 ⎝ ∂θ ⎠ (2)

where θ is the angle between Ms and H in a grain, μ0 is the per-

meability of vacuum, and Fk is the magnetic anisotropy energy.
Obviously, the coefficient b originates in the magnetic resistance of
magnetic anisotropy to the magnetization vector.
The M-type hexaferrites exhibit polycrystalline structure con-
stituted by lots of grains with different easy magnetization axis
directions. Thus, the coefficient b can be calculated by seeking the
average value of ∂Fk/∂θ. Due to the uniaxial anisotropy of the
M-type hexaferrites, the coefficient b can be easily calculated in
spherical coordinates system as follow:
4 Keff 2
b=
15 μ 02 Ms2 (3)

Consequently, the effective magnetic anisotropy constant Keff is

obtained, as well as the magnetic anisotropy field Ha (2Keff/Ms).
Fig. 4 gives the magnetic hysteresis loop of the
Sr0.7La0.3Fe11.7Co0.3O19 ferrites prepared by different sintering
method with appropriate amount of BBSZ. It is found that the MS
ferrites can provide a higher intrinsic coercivity Hci as 336.1 kA/m
compared with the CS ferrites and HPS ferrites, which possess a
value of 205.7 and 214.8 kA/m, respectively. Difference of intrinsic
coercivity for these ferrites can be attributed to the different
magnetic anisotropy according to the calculation results. The ef-
fective magnetic anisotropy constant Keff and magnetic anisotropy
field Ha arrive at 1.95  105 J/m3 and 1472.4 kA/m for the CS fer-
rites, 2.35  105 J/m3 and 1528.8 kA/m for the MS ferrites, and
2.14  105 J/m3 and 1484.8 kA/m for the HPS ferrites, respectively.
As we know, the calculated Keff and Ha strongly depend on the
shape of magnetization curve, which is mainly determined by the
magnetic domain structure. So, the CS, MS, and HPS methods are
suggested to affect the magnetic domain structure remarkably,
and the direct experimental proof remains to be investigated later.
Large magnetic anisotropy field is important for the realization
of self-biased LTCC circulators utilizing the M-type hexaferrites
[11–13]. Notably, the obtained MS ferrites with 4 wt% BBSZ can
provide relatively high saturation magnetization, intrinsic coer-
civity, and magnetic anisotropy field as low temperature sintered
M-type hexaferrites for use in microwave LTCC ferrite devices [15–
18].
It is well known that the tensor permeability of the magnetized
gyromagnetic ferrite materials is the primary foundation for the
microwave ferrite circulators. The coefficients of tensor perme-
ability μ and k are defined as:
ω0 ωm
μ=1+
ω 02 − ω2 (4)

and
ωω m
k=
ω 02 − ω2 (5)

where ω is the radian frequency, ω0 is the ferromagnetic re-

sonance radian frequency, and ωm is the magnetization radian
frequency, and
ω 0 = γH0 (6)

Fig. 4. Magnetic hysteresis loop of the Sr0.7La0.3Fe11.7Co0.3O19 ferrites prepared by

(a) CS method with 4 wt% BBSZ, (b) MS method with 4 wt% BBSZ, and (c) HPS ω m = γMs (7)
method with 5 wt% BBSZ.
where H0 is the internal field and γ is the gyromagnetic ratio. The
magnetic anisotropy field Ha contributes to the internal field H0 as:
174 L. Peng et al. / Journal of Magnetism and Magnetic Materials 404 (2016) 170–174
Fig. 5. Calculated frequency dependence of k/μ without external bias field for the
MS ferrites with 4 wt% BBSZ.
H0 = Hext + Ha − NMs (8)
where Hext is the external bias field and N is the demagnetization
factor.
Traditional junction circulators need strong external bias field
commonly provided by permanent magnets. Evidently, the large
magnetic anisotropy field plays an outstanding role to remove the
external bias field for the LTCC circulators. Fig. 5 presents the
calculated frequency dependence of k/μ without external bias field
(Hext ¼0) for the MS ferrites with 4 wt% BBSZ. The observed re-
sonance of k/μ begins after 40 GHz, and the ferromagnetic re-
sonance frequency f0 (0.5ω0/π) arrives at 44.8 GHz. Before ferro-
magnetic resonance, the value of k/μ increases with increasing
frequency. In order to keep effective gyromagnetic properties, the
MS ferrites are suggested to work at a frequency region from 34 to
40 GHz for the LTCC circulators, where the k/μ varies from 0.25 to
0.48 accordingly.
4. Conclusions
By the help of BBSZ addition, the La3 þ –Co2 þ substituted
M-type Sr0.7La0.3Fe11.7Co0.3O19 hexaferrites are successfully pre-
pared by CS method, MS method and HPS method at a low sin-
tering temperature of 850 °C. Increased BBSZ amount from 2 to
5 wt% can improve the low temperature sintering of the ferrites
evidently, which is found to be strongly correlated with the crystal
composition and sintering characteristics. Large addition of BBSZ
as high as 5 wt% leads to high sintering density of 4.46 g/cm3 for
the CS ferrites, 4.70 g/cm3 for the MS ferrites, and 4.74 g/cm3 for
the HPS ferrites. Appropriate addition of BBSZ enhances the sa-
turation magnetization, which can be attributed to the improved
formation of M-type phase against to the excessive addition of
non-magnetic BBSZ glass. Compared with the CS ferrites and HPS
ferrites, the MS ferrites with optimal BBSZ amount of 4 wt% exhibit
relatively high saturation magnetization of 65.3 emu/g, magnetic
anisotropy field of 1528.8 kA/m, and intrinsic coercivity of
336.1 kA/m. Furthermore, the calculation results based on the
tensor permeability suggest that the obtained MS ferrites possess
an important potentiality for use in LTCC circulators with a sui-
table work frequency from 34 to 40 GHz.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China under Grant no. 51502025, Scientific Research
Foundation of Education Office of Sichuan Province of China under
Grant no. 13Z198, and the Open Fund of Sichuan Province Key
Laboratory of Information Materials and Devices Application.
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