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 1

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

Corresponding author: Dr. Chuanjian Wu (e-mail: [email protected]).

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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 2

magnetization Ms and remanence Mr) at room temperature equilibrium diagram at 700ºC. In addition, the transformation
were carried out using vibrating sample magnetometer (VSM) is discovered on crystallographic spinel structures by Li et al.
(Lake Shore 7410) with an applied field 15kOe. [18]: low-temperature (800-900ºC) tetragonal phase (t-
CuFe2O4) and high-temperature (~1000ºC) cubic phase (c-
III. EXPERIMENTAL RESULTS AND DISCUSSIONS CuFe2O4). Therefore, it is concluded that the bismuth copper
oxides and copper ferrites could form on the grain boundary
A. Microstructure Observation regions and in the grains, respectively.
Fig.1 presents the typical fracture surface morphologies C. Sintering Mechanism
observed by FESEM for barium hexaferrites samples. It is
The melting point of bismuth oxides is 820ºC [19], while
clearly demonstrated in Fig.1 (a) that grain growth is not
bismuth copper oxides, located at the triple junction, could wet
complete and the densification degree is comparatively
more effectively grain boundaries and form a liquid-channel
inadequate. From Fig.1 (b), the grain sizes increase to 2~3μm,
structure. The eutectic melting point of ceramic composites
hexagonal-flake grains gradually emerge, and yet some pores
(bismuth copper oxide and bismuth oxide) plunges to 770ºC
are still detected. While doped with 3.0wt% Bi2O3+3.0wt%
[20]. D. Lisjak et al. [11], [12] had suggested that the low-
CuO additives at 920 ºC, barium hexaferrites show a further
temperature formation (copper ferrites) in the grains is also
densification and grain sizes are more uniform. As listed in
propitious to promote the ion and vacancy transformation
Table I, the density (d) of barium hexaferrites with 3.0wt%
among and in the grains, and then beneficial to promoting the
Bi2O3+3.0wt% CuO additives is approximately
sintering of barium and strontium hexaferrites. By introducing
5.21~5.25g/cm3, which is far beyond the sintered samples
collectively driving force in the grains and on the grain
with no (4.21~4.35g/cm3) and Bi2O3 (5.01~5.08g/cm3)
boundaries, the sintering temperature of barium hexaferrites
additives. It is concluded that the combination of 3.0wt%
with Bi2O3+CuO additives is therefore reduced to 920ºC, and
Bi2O3+3.0wt% CuO additives efficiently promotes sintering
the sintered samples become also dense.
densification of barium hexaferrites at the low temperature.
FIG.3: HERE
FIG.1: HERE
The backscattered electron (BE) image of barium D. Magnetic Properties
hexaferrites with 3.0wt% Bi2O3+3.0wt% CuO additives at The magnetic properties (saturation magnetization and
920ºC is plotted in Fig.2. Grains and grain boundaries are remanence) of barium hexaferrites with no, 3.0wt% Bi2O3 and
marked in the box and point, respectively. Obviously, Bismuth 3.0wt% Bi2O3+3.0wt% CuO additives are demonstrated in
element is not detected in the grains but on the grain Table I. With the increase of sintering temperature, saturation
boundaries, and whilst copper element is simultaneously magnetization of barium hexaferrites with no, 3.0wt% Bi2O3
observed in the grains and on the grain boundaries. By and 3.0wt% Bi2O3+3.0wt% CuO additives shows a constant
calculating the photoelectron counting areas, the molar ratio of increase, and the corresponding remanences achieve the
copper element in the grains and on the grain boundaries is maximum at 1350ºC, 1020ºC, and 920ºC, respectively. As
approximately 2.4:1, which indicates that copper oxide is known, the Ms and Mr could be calculated by the following
more prone to reside in the grains. relation: [21]
FIG.2: HERE Mr  s  d (1)

B. Crystallographic Characteristics Ms  k  M r (2)

To investigate the composition of grains and grain where d and σs are the density and specific saturation
boundaries, the X-ray diffraction patterns for barium magnetization, respectively. The influence of the uniform
hexaferrites samples are illustrated in Fig.3. As shown, a weak microstructure is reflected by “k”. Obviously, barium
hematite peak could be seen in the XRD pattern of pre- hexaferrites with Bi2O3+CuO additives are more uniform and
sintering powders, and all the detected diffraction peaks are denser. It is thus found that magnetic properties (saturation
well indexed to hexagonal P63/mmc symmetry (barium magnetization and remanence) of barium hexaferrites with
hexaferrite) in the sintered samples with no and Bi2O3 Bi2O3+CuO additives are consumedly superior to sintered
additives. But for sintered barium hexaferrites with samples with no and Bi2O3 additives.
Bi2O3+CuO additives, the XRD pattern shows three TABLE I: HERE
distinguishable peaks: main phase is barium hexaferrite, two
For the same sintering temperature, magnetic properties of
tiny phases are copper ferrite and bismuth copper oxide.
barium hexaferrites with different additives are given in Fig.4.
Meanwhile, the sharper peak at 32.1o indicates crystal
As it is doped with Bi2O3 additives at 1020ºC, an initial
structure of barium hexaferrites with Bi2O3+CuO additives
increase in saturation magnetization and remanence followed
grows more completely. As indicated by Mallika et al. [17],
by a subsequent decrease is observed, and the corresponding
the bismuth copper oxides (Bi4CuO7/Bi2CuO4 and
maximum reaches 346kA/m at 3.0wt%, and 229kA/m at
Bi2CuO4/Bi2Cu2O5) have been already confirmed by the phase

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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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4.0wt%, respectively (see Fig.4(a)). From Fig.4(b), saturation [11] D. Lisjak, “The low-temperature sintering of M-type hexaferrites,” J.
Eur. Ceram. Soc., vol 32, pp. 3351-3360, 2012.
magnetization of barium hexaferrites with same Bi2O3 and
[12] D. Lisjak and R. Lebourgeios, “The low-temperature sintering
different CuO additives shows an analogous trend with Fig.4 mechanism of Sr hexaferrite using the addition of CuO,” J. Am. Ceram.
(a). When it is doped with same CuO additives, saturation Soc., vol 95, pp. 3025-3030, 2012.
magnetization of sintered samples with additional Bi2O3 [13] V. A. Rane, G. J. Phatak, and S. K. Date, “Ultra-high-frequency
behavior of BaFe12O19 hexaferrite for LTCC substrates,” IEEE Trans.
additives at 3.0wt% surpass one at 2.0wt% and 4.0wt%. For
Magn., vol 49, pp. 5048-5054, 2013.
remanence (see Fig.4 (c)), it could be seen that sintered [14] Y. L. Liu, Y. X. Li, H. W. Zhang, D. M. Chen, and Q. Y. Wen, “Study
samples demonstrate comparatively outstanding performance on magnetic properties of low temperature sintering M-barium
while it is doped with 3.0wt% Bi2O3+3.0wt% CuO additives. hexaferrites,” J. Appl. Phys., vol. 107, pp. 09A507-1-09A507-5, 2010.
[15] D. M. Chen, Y. L. Liu, Y. X. Li, W. G. Zhong, and H. W. Zhang,
FIG.4: HERE “Microstructure and magnetic properties of low-temperature sintered
CoTi-substituted barium ferrite for LTCC application,” J. Magn. Magn.
Mater., vol. 323, pp. 2837-2840, 2011.
IV. CONCLUSION
[16] L. C. Li et al., “Attractive microwave-absorbing properties of M-
Barium hexaferrites were successfully synthesized by the BaFe12O19 ferrite,” J. Alloy Compd., vol. 557, pp. 11-17, 2013.
conventional oxide ceramic process at low temperature with [17] C. Mallika and O. M. Sreedharan, “Thermodynamic stabilities of ternary
oxides in Bi-Cu-O system by solid electrolyte EMF method,” J. Alloy
Bi2O3/CuO additives. Bi2O3 additives gather around grain Compd., vol. 216, pp. 47-53, 1994.
boundary regions, and whilst CuO additives both in the grains [18] N. H. Li, S. L. Lo, C. Y. Hu, C. H. Hsieh, and C. L. Chen, “Stabilization
and on the grain boundary regions. The combination of Bi2O3 and phase transformation of CuFe2O4 sintered from simulated copper-
and CuO on the grain boundaries, and Fe2O3 and CuO in the laden sludge,” J. Hazard. Mater., vol. 190, pp. 597-603, 2011.
[19] Z. Yu, K. Sun, L. Z. Li, Y. F. Liu, Z. W. Lan, and H. W. Zhang,
grains results in the formation of low-melting phase (bismuth “Influences of Bi2O3 on microstructure and magneti properties of MnZn
copper oxide and copper ferrite), respectively. Saturation ferrite,” J. Magn. Magn. Mater., vol. 320, pp. 919-923, 2008.
magnetization of barium hexaferrites with no, 3.0wt% Bi2O3 [20] N. V. Lyskov, Y. G. Meltlin, V. V. Belousov, and Y. D. Tretyakov,
and 3.0wt% Bi2O3+3.0wt% CuO additives increase “Microstructure and conduction of composites Bi2CuO4-Bi2O3 near the
eutectic melting point,” Russ. J. Electroochem., vol. 41, pp. 596-601,
continuously with increasing sintering temperature, and the 2005.
corresponding remanences achieve the maximum at 1350ºC, [21] F. Kools, A. Morel, R. Grössinger, J. M. Le Breton, and P. Tenaud,
1020ºC, and 920ºC, respectively. As the amount of Bi2O3 is “LaCo-substituted ferrite magners, a new class of high-grade ceramic
magnets; intrinsic and microstructural aspects,” J. Magn. Magn. Mater.,
3.0wt% at 1020ºC, saturation magnetization and remanence vol. 242-245, pp. 1270-1276, 2002.
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.

REFERENCES
[1] V. G. Harris, “Modern microwave ferrites,” IEEE Trans. Magn., vol 48, Fig.1. SEM micrographs for barium hexaferrites samples, and the typical
pp. 1075-1104, 2012. pores on grain boundary regions are marked in the rectangular frame: (a)
[2] C. Sun and K. Sun, “Sol-gel synthesis of Ce-substituted BaFe12O19,” J. without additives, 1325ºC; (b) 3.0wt% Bi2O3, 1020ºC; (c) 3.0wt%
Mater. Sci., vol 42, pp. 5676-5679, 2007. Bi2O3+3.0wt% CuO, 920ºC.
[3] Z. Guo, W. Zhang, H. Ji, B. Peng, and W. Zhang, “Influence of substrate
temperature on the texture of barium ferrite film by magnetron
sputtering,” Appl. Surf. Sci., vol. 255, pp. 4443-4445, 2009.
[4] Y. J. Chen, A. L. Geiler, T. Y. Chen, T. Sakai, C. Vittoria, and V. G.
Harris, “Low-loss barium ferrite quasi-single-crystals for microwave
application,” J. Appl. Phys., vol. 101, pp. 09M501-1-09M501-3, 2007.
[5] R. C. Pullar, “Hexagonal ferrites: a review of the synthesis, properties
and applications of hexaferrite ceramics,” Prog. Mater. Sci., vol 57, pp.
1191-1334, 2012.
[6] G. H. An et al., “Novel method for low temperature sintering of barium
hexaferrite with magnetic easy-axis alignment,” J. Eur. Ceram. Soc., vol
34, pp. 1227-1233, 2014.
[7] V. G. Harris et al., “Ba-hexaferrite films for next generation microwave
devices (invited),” J. Appl. Phys., vol. 99, pp. 08M911-1-08M911-5,
2006.
[8] P. Jenus, D. Lisjak, D. Kuscer, D. Makovec, and M. Drofenik, “The
low-temperature cosintering of cobalt ferrite and lead zirconate titanate
ceramic composites,” J. Am. Ceram. Soc., vol 97, pp. 74-80, 2014.
[9] Z. L. Zheng and H. W. Zhang, “Complex permittivity and permeability
of low-temperature sintered M-type barium hexaferrite in Ka-band Fig.2. Backscattered electron image of barium hexaferrites with 3.0wt%
frequency rang,” IEEE Trans. Magn., vol 49, pp. 4230-4233, 2013. Bi2O3+3.0wt% CuO additives at 920ºC: (a) grains; (b) grain boundaries.
[10] Y. Song, C. L. Ordóñez-Romero, and M. Wu, “Millimeter wave notch
filter based on ferromagnetic resonance in hexagonal barium ferrites,”
Appl. Phys. Lett., vol. 95, pp. 142506-1-142506-3, 2009.

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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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