Materials Research Express

PAPER

Bi2O3 adjusting equivalent permeability and permittivity of M-type barium

ferrite for antenna substrate application
To cite this article: Jie Li et al 2019 Mater. Res. Express 6 056113

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 Mater. Res. Express 6 (2019) 056113 https://doi.org/10.1088/2053-1591/ab069c

PAPER

Bi2O3 adjusting equivalent permeability and permittivity of M-type

RECEIVED
16 January 2019
barium ferrite for antenna substrate application
REVISED
29 January 2019
ACCEPTED FOR PUBLICATION
Jie Li1 , Li Guo1, Yan Yang1,2, Yiheng Rao1 , Gongwen Gan1 and Huaiwu Zhang1
12 February 2019 1
State Key Laboratory of Electronic Thin Films and Integrated Devices, University of Electronic Science and Technology of China,
PUBLISHED Chengdu, 610054, People’s Republic of China
2
27 February 2019 The Collaborative Innovation Center of Integrated Computation and Chip Security, Chengdu University of Information Technology,
Chengdu, 610225, People’s Republic of China

Keywords: BiFeO3 formation, M-type barium ferrite, magnetic properties, dielectric properties, antennas substrate

Abstract
In this paper, Co-Ti doped M-type barium ferrite [Ba(CoTi)1.22Fe9.56O19] was prepared at low
temperature (925 °C) in O2 atmosphere with different amounts of Bi2O3 sintering additive
(x=5–14 wt%). XRD showed superfluous Bi2O3 additive led to BiFeO3 phase formation, which is the
important factor to adjust properties of material. SEM revealed that the grain size diminished
gradually. For magnetic and dielectric properties, with different amounts of Bi2O3, saturation
magnetization (Ms) decreased and coercivity (Hc) gradually increased. Complex magnetic perme-
ability and dielectric permittivity presented excellent regularity, and the equivalent permeability and
permittivity were obtained when x=5 wt%. At x=5 wt%, the real part of permeability (μ′) and
permittivity (ε′) were about 18.3 at a range of 10 MHz–1.0 GHz, the magnetic loss (tan δμ) was about
3.4×10−2, and the dielectric loss (tan δε) was about 2.8×10−3. It showed that Bi2O3 not only
lowered the sintering temperature of ferrite, but also adjusted the magnetic and dielectric properties,
and the material has potential to apply for miniaturizing efficient antennas at high frequency.

Introduction

As mobile devices are made smaller through advances in communication technologies and critical advances in
materials science, the ministration of antennas has become increasingly important [1–4]. The rapid
development of technology required antennas to become small, light-weight, and portable communication
devices. The fundamental question is the physical size of antennas. Conventional antennas have large physical
dimensions (about 40 cm). Hence, many solutions have been proposed to tailor the size of antennas [5–8].
Substrate material is a crucial factor on the property of antennas. Traditionally, dielectric material was the main
material to make the antenna substrate [9]. Recently, to meet new requirement of antennas, modified ferrite has
been frequently studied in antenna applications, such as Li4Ti5O12-Co2Z ferrite, NiZn-NiZnCo ferrite, In-NiZnCo
ferrite, Ir-Co2Z ferrite, and NiZn-W type ferrite [10–15]. These materials had excellent magnetic permeability and
dielectric permittivity and low loss. Among these researches, Harris et al used BiFeO3 to tailor M-type barium
ferrite having equivalent permeability and permittivity (μ′≈ε′≈12), which was an effective way to improve
magnetic and dielectric properties [16–19]. Based on our previous research [6, 20], in this study, in O2 atmosphere,
superfluous Bi2O3 sintering aids were added in Co-Ti doped barium ferrite to lower temperature and adjust
permeability and permittivity. Due to O2 sintering atmosphere, excellent permeability and permittivity were
obtained when Bi2O3 content was 5 wt% and the sintering temperature was 925 °C. The magnetic structure and
properties of low temperature co-fired CoTi doped M-type barium ferrites are discussed.

Experimental

CoTi co-substitution M-type barium ferrites, Ba(CoTi)1.22Fe9.56O19, with various Bi2O3 contents
(x=5–14 wt%), were synthesized using analytical grade BaCO3, Fe2O3, Co2O3, and TiO2 via solid state

© 2019 IOP Publishing Ltd

Mater. Res. Express 6 (2019) 056113 J Li et al

Figure 1. x-ray diffraction patterns of ferrite samples with various contents of Bi2O3.

reactions. The powders were mixed using a ball mill for 16 h in a Teflon vial with zirconia balls and deionized
water as the milling media. The mixed powder was dried and then pre-sintered at 1100 °C for 4 h in oxygen gas.
The pre-sintered powder was milled again for 12 h in deionized water with various Bi2O3 constants. After drying,
the powder was granulated by adding 8 wt% of polyvinyl alcohol (PVA) as a binder and pressed into 2–3 mm
thick plates. The compacted samples were sintered at 925 °C for 6 h in oxygen gas.
The phase compositions of the samples were determined using an x-ray diffractometer (XRD, DX-2700,
Haoyuan Co., China) with Cu Kα radiation. The microstructures of the samples were characterized using a
scanning electron microscope (SEM, JEOL, JSM-6490, Japan). Magnetization hysteresis loops were measured
using a vibrating sample magnetometer (VSM, MODEL, BHL-525, Japan), and the saturation magnetization and
coercivity were calculated from magnetization hysteresis loops. The complex magnetic permeability and dielectric
permittivity were measured using an Agilent 4991 impedance analyzer (Agilent Technologies, Palo Alto, USA).

Results and discussions

Figure 1 shows the XRD patterns of ferrite samples with various Bi2O3 contents. Firstly, it shows that all samples had
the typical peaks of the M-type barium ferrite phase, which indicates that ferrites were synthesized at low temperature
under oxygen gas with Bi2O3 sintering aid. Meanwhile, the second phase (BiFeO3) was found in samples. In low
temperature co-fired ferrite technology, the contents of sintering aids usually were below 3 wt% [21]. In the present
experiment, the Bi2O3 contents were from 5 wt% to 14 wt%. Hence, superfluous Bi2O3 would form the second phase
BiFeO3. With increased x, the peak intensities of BiFeO3 also increased. Multiferroic BiFeO3 material presented
ferroelectric and weak ferromagnetism, and reduced the magnetic loss of samples. The formation of BiFeO3 would
use Fe3+ ions of ferrite, which led to the lack of iron for CoTi doped M-type barium ferrite.
The SEM images of samples are shown in figure 2. Under the same temperature, the grain size became
smaller with increased x, and some small particles adhered to the ferrite. Appropriate amounts of Bi2O3 brought
the ferrite along effectively, and superfluous Bi2O3 impeded the growth of ferrite. Meanwhile, superfluous Bi2O3
synthesized BiFeO3, which existed among the grains of ferrite. In addition, high sintering temperature advanced
the growth of sample grains. More homogeneous grain size would play an active role in the magnetic and
dielectric properties of samples.
M-type barium ferrite is an excellent permanent magnet material. Recently, based on applied on high
frequency, Co-Ti substitution could decrease magnetocrystalline anisotropy, which would decrease coercivity
and increase magnetic permeability. The appropriate amount of Co-Ti substitution could give M-type barium
show good soft magnetic properties. Figure 3 shows the magnetic hysteresis loops of samples with different
Bi2O3 contents. Saturation magnetization (Ms) and coercivity (Hc) extracted from the loops are given in figure 4
as functions of Bi2O3 contents. Figure 3 shows that under low sintering temperatures, the samples exhibited
good soft magnetic properties. With increasing x, saturation magnetization decreased and coercivity gradually
increased. At 925 °C, Ms decreased from 39.99 emu g−1 to 27.92 emu g−1, and Hc increased from 59.05 Oe to
65.20 Oe. At the low sintering temperature, the addition of Bi2O3 aids diluted the magnetic property of ferrite.
The formation of BiFeO3 was distributed among the ferrite grains, which reduced the force between grains,
resulting in an increase in Hc.

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Mater. Res. Express 6 (2019) 056113 J Li et al

Figure 2. SEM images of samples under different concentrations of Bi2O3.

Figure 3. Magnetic hysteresis loops of Co-Ti substitution barium ferrite with different x values.

In the present experiment, complex magnetic permeability and complex dielectric permittivity of samples
were the research focus, especially under oxygen gas. Figure 5 shows the real part of magnetic permeability and
the real part of dielectric permittivity of samples with different Bi2O3 contents sintered at 925 °C. For the real
part of permeability (μ′) of samples, the value deceased gradually with increasing Bi2O3. At 925 °C, μ′ decreased
from 18.3 (x=5 wt%) to 10.7 (x=14 wt%). The decrease of μ′ was mainly from non-magnetic Bi2O3 aids.
More non-magnetic materials diluted the magnetic property of ferrite. Meanwhile, the melting point of Bi2O3
was 825 °C, and high temperature can result in the volatilization of superfluous Bi2O3 aids, which results in
increased magnetic permeability.
For the real part of dielectric permittivity (ε′), the value increased gradually with increased Bi2O3. At 925 °C, ε′
increased from 18.1 (x=5 wt%) to 23.5 (x=14 wt%). Bi2O3 lowered the sintering temperature due to its low

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Mater. Res. Express 6 (2019) 056113 J Li et al

Figure 4. Effects of Bi2O3 contents on saturation magnetization and coercivity of samples.

Figure 5. The real part of permeability and permittivity of samples with various Bi2O3 contents sintered at 925 °C.

melting point and liquid phase sintering theory. In the sintering process, BiFeO3 material is synthesized by Bi3+ ion
and Fe3+ ion. BiFeO3 is a non-magnetic compound, which dilutes the magnetic property of ferrite. BiFeO3 has
excellent dielectric properties, which can increase the dielectric permittivity of materials. Based on our previous
research, the amount of Bi2O3 was below 3 wt% on lower co-fried ferrite [6]. When Bi2O3 was 5 wt%, only a small
quantity of Bi2O3 produced BiFeO3, so the ε had a lower value. With increasing Bi2O3, the BiFeO3 ratio increased,
which led to a high ε′ value. For ferrite sample, appropriate temperature promoted grain growth and led to higher
ε′ values. This was because high temperature samples had higher densification and bigger grain sizes.
Comparing the samples with different temperatures and different additives, the samples (x=5 wt%) at
925 °C had nearly equivalent permeability and permittivity at a range frequency of 1–300 MHz. As shown in
figure 6, when the Bi2O3 content was 5 wt%, the 925 °C sample had a μ′ of about 18.3, a ε′ of about 18.1, a tan δμ
of 3.4×10−2 and a tan δε of 2.8×10−3.
The materials contained two-phase materials, Co-Ti doped M-type barium ferrite and BiFeO3 material. For
the two-phase materials, an effective medium approximation can be used to predict permeability and
permittivity with different phase concentrations. In the most commonly used Maxwell-Garnet (MG) model, the
effective permeability (μeff) and permittivity (εeff) are given as
ee - em
eeff = em + 3pem
ee + 2em - pe (ee - em)
me - mm
meff = me + 3(1 - pe ) me
mm + 2me - (1 - pe )(mm - me )
Where εe, εm, μe and μm represent the permittivity and permeability of BiFeO3 dielectric material and
Ba(CoTi)1.20Fe9.6O19 ferrite material, respectively, and p is the volume percent of BiFeO3 phase. From our
previous study and other researchers’ reports, we assigned parameters as follows: BiFeO3 material in O2

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Mater. Res. Express 6 (2019) 056113 J Li et al

Figure 6. Magnetic-dielectric properties of samples with 5 wt% Bi2O3 contents.

atmosphere, εe≈60, μe≈2, CoTi doped barium ferrite in O2 atmosphere, εm≈15, μm≈30. Based on these
dates, it obtained p=0.018. In present experiment, the content of Bi2O3 additive is 5 wt%, which contained two
parts, about 3 wt% Bi2O3 is lower temperature of material and about 2 wt% Bi2O3 is format BiFeO3 dielectric
formation. Hence, the results were in accordance with the experiment.
For ferrites, the whole magnetic loss tangent tan δμ is composed of three parts, the eddy current loss tangent
tan δe, hysteresis loss tangent tan δa, and the remaining loss tangent tan δc, abiding by the following equation:
tan dm = tan de + tan da + tan dc
Tan δe results from the electro-magnetic induction, causing core fever and generating power dissipation, Tan δa
is caused by hysteresis, the method to lower the area of the hysteresis loop and Hc. When ferrite material had
regular shape, uniform thick border grains and less pores, and had small anisotropy, a low tan δa was obtained. In
addition, low Fe2+ content can also decrease tan δc. The results showed that the Bi2O3 enhanced Co-Ti doped
M-type barium ferrite was an excellent substrate material for high frequency antenna applications.

Conclusion

In this study, Co-Ti doped barium ferrite were synthesized at low temperatures (925 °C) in O2 atmosphere with
different amounts of Bi2O3 sintering additive (x=5–14 wt%). The materials contained two phases and
presented magnetic and dielectric properties. In oxygen atmosphere, the materials had a high value of equivalent
permeability and permittivity. At x=5 wt%, the real part of permeability (μ′) and permittivity (ε′) were about
18.3 (925 °C) at a range of 10 MHz–1.0 GHz, and the magnetic loss (tan δμ) and the dielectric loss (tan δε) were
about 3.4×10−2 and 2.8×10−3, respectively. The results showed that the Bi2O3 enhanced Co-Ti doped
M-type barium ferrite was an excellent substrate material for high frequency antenna applications.

Acknowledgments

This work was supported by the National Nature Science Foundation of China (No. 51602036), and by Chengdu
Research Project (2016-HM01-0025-SF), and Guizhou Province Key R&D Program (2016-3011).

ORCID iDs

Jie Li https://orcid.org/0000-0001-5382-5901
Yiheng Rao https://orcid.org/0000-0003-4809-8484

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