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fully edited. Content may change prior to final publication. Citation information: DOI
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Low-temperature Sintering of Barium Hexaferrites with Bi2O3/CuO

Additives

Chuanjian Wu1, Zhong Yu1, Guohua Wu1, Ke Sun1, Yan Yang2, Xiaona Jiang1, Rongdi Guo1 and Zhongwen Lan1
1
State Key Laboratory of Electronic Thin Films and Integrated Devices, University of Electronic Science and Technology of
China, Chengdu 610054, China
2
Department of Communication and Engineering, Chengdu Technological University, Chengdu 611730, China

Barium hexaferrites BaFe12O19 with Bi2O3/CuO additives were synthesized by the conventional oxide ceramic process. The results
manifest that, Bi2O3 additives mainly concentrate on the grain boundary regions, and whilst CuO additives could both enter into the
grain and segregate at the grain boundary regions. The appropriate sintering temperature of barium hexaferrites with Bi2O3 and
Bi2O3+CuO additives reach 1020ºC and 920ºC, respectively. As the amount of Bi 2O3 is 3.0wt%, the specimens of BaFe12O19 show
saturation magnetization (Ms) of 346kA/m, remanence (Mr) of 227kA/m and density (d) of 5.06g/cm3. Meanwhile, the combination of
3.0wt% Bi2O3 and 3.0wt% CuO additives significantly promotes grain growth and sintering densification, with a high saturation
magnetization of 371kA/m and density of 5.23g/cm3 for BaFe12O19, which are pretty close to theoretical values (380kA/m, 5.28g/cm3).
Moreover, the corresponding remanence could also rise by 10% comparing to the sintered samples with 3.0wt% Bi2O3.

Index Terms—Barium hexaferrites, Bi2O3/CuO additives, Low-temperature sintering, Magnetic properties, Density.

at low temperature (900~950ºC), and then failed miserably at

I. INTRODUCTION
years, barium hexaferrites [M-type BaFe12O19
I N RECENT
(BaM)] have been extensively applied in microwave devices,
permanent magnets and magnetic recording materials for their
fairly large magnetocrystalline anisotropy (17.5kOe), high
Curie temperature (450ºC), relatively large density (5.28g/cm3)
and magnetization (380kA/m) [1]-[3]. As a conventional
permanent magnetic material, the sintering temperature of
barium hexaferrites without additives could reach up to
1300ºC [4], [5]. However, high temperature could increase the
necking and grain growth of particles, and then degrade the
magnetic properties [6]. And with the high-frequency,
integrated and miniaturized development of microwave
devices, more attentions to the next generation magnetic
materials have been devoted to the low-temperature sintering,
which is determined by the melting temperature of device’s
electrodes and various interdiffusion phenomena [7], [8]. The
low-temperature sintered ferrites are usually characterized by
uniform microstructure, densification and high saturation
magnetization, which are beneficial to the properties of high-
frequency devices [9], [10]. Therefore, it is essential to reduce
sintering temperature to 1000ºC or lower, for co-sintering with
Au and Ag (900~950ºC) [11].
The driving force for solid-state sintering is the capillary
pressure and the chemical potential difference. This driving
force is relatively small as compared with the chemical driving
force from the chemical reaction [12]. Many studies related to
decreasing the sintering temperature of barium hexaferrites
have been concentrated on introducing the liquid-phase
sintering and low-temperature formation [13]-[16]. All those
sintered samples presented a relatively low density (less than
5.10g/cm3) and saturation magnetization (less than 350kA/m)
meeting demand for the excellent high-frequency microwave
devices. However, one managed to solve this problem at the
low temperature by the combinational sintering aids of Bi2O3
and CuO additives. Meanwhile, a detailed investigation on the
low-temperature sintering mechanism of barium hexaferrites
with Bi2O3+CuO additives was also presented.
II. EXPERIMENTAL PROCEDURE
Barium hexaferrites with a composition of stoichiometric
BaFe12O19 were prepared by the conventional oxide ceramic
process. The analytical-grade raw materials, BaCO3, and
Fe2O3 were weighed in stoichiometric proportion and mixed
homogeneously in zirconia ball mills for 12h. The mixed
powders were dried, and calcined at 800ºC for 2h in air.
Various contents of xBi2O3+yCuO (x=0.0-5.0wt%, y=0.0wt%;
x=2.0-4.0wt%, y=0.0-5.0wt%) additives were added into the
presintered powder and wet-milled for 12h. The resulting
powders were dried, granulated with 12wt% polyvinyl alcohol
(PVA) and pressed to disk-shaped pellets
(Ф21mm×Ф11mm×h5mm) at 60MPa. Then the green flans
were sintered at various temperatures from 900 to 1350 ºC for
2h in atmosphere and left to cool to room temperature inside a
furnace.
The cross-section morphology was observed by field
emission scanning electron microscope (FESEM) (JEOL JSM-
7800F). The elemental analysis of grain boundary and grain
was characterized by energy dispersive X-ray spectroscopy
(EDS) analyzer connected with the FESEM (JEOL JSM-
7800F). The phase structures of the sintering samples were
identified by X-ray diffractometer (XRD) (DX-2700) with Cu-
Kα radiation. The bulk densities d were measured by
Archimedes method. Magnetic properties (saturation

Corresponding author: Dr. Chuanjian Wu (e-mail: wcjuestc2005@gmail.com).

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This article has been accepted for publication in a future issue of this journal, but has not been fully edited. Content may change prior to final publication. Citation information: DOI
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EU-13
magnetization Ms and remanence Mr) at room temperature
were carried out using vibrating sample magnetometer (VSM)
(Lake Shore 7410) with an applied field 15kOe.
III. EXPERIMENTAL RESULTS AND DISCUSSIONS
A. Microstructure Observation
Fig.1 presents the typical fracture surface morphologies
observed by FESEM for barium hexaferrites samples. It is
clearly demonstrated in Fig.1 (a) that grain growth is not
complete and the densification degree is comparatively
inadequate. From Fig.1 (b), the grain sizes increase to 2~3μm,
hexagonal-flake grains gradually emerge, and yet some pores
are still detected. While doped with 3.0wt% Bi2O3+3.0wt%
CuO additives at 920 ºC, barium hexaferrites show a further
densification and grain sizes are more uniform. As listed in
Table I, the density (d) of barium hexaferrites with 3.0wt%
Bi2O3+3.0wt% CuO additives is approximately
5.21~5.25g/cm3, which is far beyond the sintered samples
with no (4.21~4.35g/cm3) and Bi2O3 (5.01~5.08g/cm3)
additives. It is concluded that the combination of 3.0wt%
Bi2O3+3.0wt% CuO additives efficiently promotes sintering
densification of barium hexaferrites at the low temperature.
FIG.1: HERE
The backscattered electron (BE) image of barium
hexaferrites with 3.0wt% Bi2O3+3.0wt% CuO additives at
920ºC is plotted in Fig.2. Grains and grain boundaries are
marked in the box and point, respectively. Obviously, Bismuth
element is not detected in the grains but on the grain
boundaries, and whilst copper element is simultaneously
observed in the grains and on the grain boundaries. By
calculating the photoelectron counting areas, the molar ratio of
copper element in the grains and on the grain boundaries is
approximately 2.4:1, which indicates that copper oxide is
more prone to reside in the grains.
FIG.2: HERE
B. Crystallographic Characteristics
To investigate the composition of grains and grain
boundaries, the X-ray diffraction patterns for barium
hexaferrites samples are illustrated in Fig.3. As shown, a weak
hematite peak could be seen in the XRD pattern of pre-
sintering powders, and all the detected diffraction peaks are
well indexed to hexagonal P63/mmc symmetry (barium
hexaferrite) in the sintered samples with no and Bi2O3
additives. But for sintered barium hexaferrites with
Bi2O3+CuO additives, the XRD pattern shows three
distinguishable peaks: main phase is barium hexaferrite, two
tiny phases are copper ferrite and bismuth copper oxide.
Meanwhile, the sharper peak at 32.1o indicates crystal
structure of barium hexaferrites with Bi2O3+CuO additives
grows more completely. As indicated by Mallika et al. [17],
the bismuth copper oxides (Bi4CuO7/Bi2CuO4 and
Bi2CuO4/Bi2Cu2O5) have been already confirmed by the phase
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2
equilibrium diagram at 700ºC. In addition, the transformation
is discovered on crystallographic spinel structures by Li et al.
[18]: low-temperature (800-900ºC) tetragonal phase (t-
CuFe2O4) and high-temperature (~1000ºC) cubic phase (c-
CuFe2O4). Therefore, it is concluded that the bismuth copper
oxides and copper ferrites could form on the grain boundary
regions and in the grains, respectively.
C. Sintering Mechanism
The melting point of bismuth oxides is 820ºC [19], while
bismuth copper oxides, located at the triple junction, could wet
more effectively grain boundaries and form a liquid-channel
structure. The eutectic melting point of ceramic composites
(bismuth copper oxide and bismuth oxide) plunges to 770ºC
[20]. D. Lisjak et al. [11], [12] had suggested that the low-
temperature formation (copper ferrites) in the grains is also
propitious to promote the ion and vacancy transformation
among and in the grains, and then beneficial to promoting the
sintering of barium and strontium hexaferrites. By introducing
collectively driving force in the grains and on the grain
boundaries, the sintering temperature of barium hexaferrites
with Bi2O3+CuO additives is therefore reduced to 920ºC, and
the sintered samples become also dense.
FIG.3: HERE
D. Magnetic Properties
The magnetic properties (saturation magnetization and
remanence) of barium hexaferrites with no, 3.0wt% Bi2O3 and
3.0wt% Bi2O3+3.0wt% CuO additives are demonstrated in
Table I. With the increase of sintering temperature, saturation
magnetization of barium hexaferrites with no, 3.0wt% Bi2O3
and 3.0wt% Bi2O3+3.0wt% CuO additives shows a constant
increase, and the corresponding remanences achieve the
maximum at 1350ºC, 1020ºC, and 920ºC, respectively. As
known, the Ms and Mr could be calculated by the following
relation: [21]
Mr  s  d (1)
Ms  k  M r (2)
where d and σs are the density and specific saturation
magnetization, respectively. The influence of the uniform
microstructure is reflected by “k”. Obviously, barium
hexaferrites with Bi2O3+CuO additives are more uniform and
denser. It is thus found that magnetic properties (saturation
magnetization and remanence) of barium hexaferrites with
Bi2O3+CuO additives are consumedly superior to sintered
samples with no and Bi2O3 additives.
TABLE I: HERE
For the same sintering temperature, magnetic properties of
barium hexaferrites with different additives are given in Fig.4.
As it is doped with Bi2O3 additives at 1020ºC, an initial
increase in saturation magnetization and remanence followed
by a subsequent decrease is observed, and the corresponding
maximum reaches 346kA/m at 3.0wt%, and 229kA/m at
This article has been accepted for publication in a future issue of this journal, but has not been fully edited. Content may change prior to final publication. Citation information: DOI
10.1109/TMAG.2015.2434834, IEEE Transactions on Magnetics
EU-13 3

4.0wt%, respectively (see Fig.4(a)). From Fig.4(b), saturation
magnetization of barium hexaferrites with same Bi2O3 and
different CuO additives shows an analogous trend with Fig.4
(a). When it is doped with same CuO additives, saturation
magnetization of sintered samples with additional Bi2O3
additives at 3.0wt% surpass one at 2.0wt% and 4.0wt%. For
remanence (see Fig.4 (c)), it could be seen that sintered
samples demonstrate comparatively outstanding performance
while it is doped with 3.0wt% Bi2O3+3.0wt% CuO additives.
FIG.4: HERE
IV. CONCLUSION
Barium hexaferrites were successfully synthesized by the
conventional oxide ceramic process at low temperature with
Bi2O3/CuO additives. Bi2O3 additives gather around grain
boundary regions, and whilst CuO additives both in the grains
and on the grain boundary regions. The combination of Bi2O3
and CuO on the grain boundaries, and Fe2O3 and CuO in the
grains results in the formation of low-melting phase (bismuth
copper oxide and copper ferrite), respectively. Saturation
magnetization of barium hexaferrites with no, 3.0wt% Bi2O3
and 3.0wt% Bi2O3+3.0wt% CuO additives increase
continuously with increasing sintering temperature, and the
corresponding remanences achieve the maximum at 1350ºC,
1020ºC, and 920ºC, respectively. As the amount of Bi2O3 is
3.0wt% at 1020ºC, saturation magnetization and remanence
show a trend of increasing initially and then decreasing. The
sintered samples of 3.0wt% Bi2O3+3.0wt% CuO additives at
920ºC show uniform microstructure, a high saturation
magnetization of 371kA/m and density of 5.23g/cm3.
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This article has been accepted for publication in a future issue of this journal, but has not been fully edited. Content may change prior to final publication. Citation information: DOI
10.1109/TMAG.2015.2434834, IEEE Transactions on Magnetics
EU-13 4

■Copper ferrite ●Barium hexaferrite ●

▼Hematite ◆Bismuth copper oxide (d)
●
● ● ●
◆ ● ■ ● ■

(c)
Intensity (a.u.)

(b)

(a)
▼ ▼

26 28 30 32 34 36 38
2 Theta (degree)
Fig.3. X-ray diffraction patterns for barium hexaferrites: (a) pre-sintering
powders; (b) without additives, 1325ºC; (c) 3.0wt% Bi2O3, 1020ºC; (d)
3.0wt% Bi2O3+3.0wt% CuO, 920ºC.

360 240
(a)
Ms
320 200
Mr (kA/m)
Ms (kA/m)

Mr 400
3.0wt% Bi2O3, 1020℃

200
M (kA/m)

0
280 160
-200

-400
-15000 -7500 0 7500 15000
H (Oe)
240 120
0 1 3 2 4 5
Bi2O3 contents (%)
380
(b)
360
Ms (kA/m)

340
2.0 wt% Bi2O3
320 3.0 wt% Bi2O3
4.0 wt% Bi2O3
300
0 1 2 3 4 5
CuO contents (%)
260
(c)
240
Mr (kA/m)

220 2.0 wt% Bi2O3

3.0 wt% Bi2O3
4.0 wt% Bi2O3
200
0 1 2 3 4 5
CuO contents (%)
Fig.4. Magnetic properties of barium hexaferrites with different additives: (a)
Ms and Mr, Bi2O3, 1020ºC; (b) Ms, Bi2O3+CuO, 920ºC; (c) Mr, Bi2O3+CuO,
920. The inset in Fig.4 (a) presents the typical hysteresis loop of barium
hexaferrites with Bi2O3+CuO at 920ºC.
TABLE I
DENSITY AND MAGNETIC PROPERTIES OF BARIUM HEXAFERRITES WITH NO,
3.0wt% Bi2O3 AND 3.0wt% Bi2O3+3.0wt% CuO ADDITIVES
Samples without additives 3.0wt%Bi2O3 3.0wt%Bi2O3+3.0wt%CuO
T (ºC) 1300 1325 1350 1000 1020 1040 900 920 940
d(g/cm3) 4.21 4.28 4.35 5.01 5.06 5.08 5.21 5.23 5.25
Ms(kA/m) 298 307 314 319 346 347 364 371 375
Mr(kA/m) 160 175 176 201 227 213 229 251 245

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