Journal of the European Ceramic Society 25 (2005) 1681–1688

Influence of SiO2 and CaO additions on the microstructure

and magnetic properties of sintered Sr-hexaferrite
J. Töpfera,b,∗ , S. Schwarzerb,1 , S. Senzc , D. Hessec
a Fachhochschule Jena, FB Werkstofftechnik, Carl Zeiss Promenade 2, 07745 Jena, Germany
b Hermsdorfer Institut für Technische Keramik e.V., M.-Faraday-Str. 1, 07629 Hermsdorf, Germany
c Max-Planck-Institut für Mikrostrukturphysik, Weinberg 2, 06120 Halle, Germany

Received 16 April 2004; accepted 20 June 2004

Available online 17 August 2004

Abstract

The effect of simultaneous addition of CaO and SiO2 on the microstructure and magnetic properties of sintered SrO-excess Sr-hexaferrites
was studied. Both additives markedly affect the grain growth behavior and the magnetic properties. CaO-additions promote densification,
which results in increased remanence, but due to simultaneuous grain growth the coercivity drops to <100 kA/m. SiO2 additions are known
to suppress grain growth. Simultaneous addition of CaO and SiO2 is shown to be very beneficial in tailoring a dense microstructure with
relatively small grains. The ratio of CaO/SiO2 was found to be optimum at about 1, and magnets with a remanence of 430 mT and a coercivity
of 300 kA/m were obtained. Transmission electron microscopy (TEM) studies and investigations by energy-dispersive analysis of X-rays
(EDX) in the scanning TEM (STEM) mode show that both CaO and SiO2 are concentrated at grain boundaries and grain junctions forming
an amorphous secondary phase.
© 2004 Elsevier Ltd. All rights reserved.

Keywords: Ferrites; Hard magnets; Grain size; Grain boundaries; S5 Fe12 O19

1. Introduction are manufactured as anisotropic ferrites, i.e. the ferrite par-

ticles are oriented in a magnetic field during molding. A
Hard ferrites of the Ba- or Sr-hexaferrite system are the large remanence BR = JS αρ requires a high density ρ and
major permanent magnetic material. These magnets are man- anisotropy factor α of the sintered microstructure. If both
ufactured on large scale worldwide (300.000 and 50.000 t per quantities approach 100% the remanence becomes equal to
year in Europe in 19941 ). Hard ferrites have been introduced the saturation polarization JS . With a saturation magnetiza-
as new technically important magnetic materials in the 1950.2 tion of 74.3 emu/g at room temperature for SrFe12 O19 4 BR
Recently, Kools et al.3 have reviewed the status of this mature of a sintered magnet is 0.476 T at maximum. In practice,
family of ceramic materials. Nevertheless, the improvement the remanence of a typical high-remanence ferrite is BR =
of ferrite materials with respect to specific material parame- 400–420 mT. This is due to (i) the composition being not
ters or application fields is still a vital field of research. that of a stochiometric ferrite SrO·6Fe2 O3 (magnets are pre-
One crucial issue is the development of ferrite grades with pared with an excess of SrO) and (ii) the particle orientation
large remanence and energy product. Standard hard ferrites being non-ideal and some residual porosity remaining. For
high-remanence materials it is essential to create a dense,
∗
anisotropic microstructure by firing at high temperature. On
Corresponding author. Tel.: +49 3641 20 5450; fax: +49 3641 20 5451.
the other hand, grain growth is detrimental with respect to
E-mail address: joerg.toepfer@fh-jena.de (J. Töpfer).
1 Present address: Magnetfabrik Schramberg, M.-Planck-Str. 15, 78713 the coercivity because of the formation of multi-domain par-
Schramberg-Sulgen, Germany. ticles. A large coercivity requires small grains with a size

0955-2219/$ – see front matter © 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jeurceramsoc.2004.06.003
1682 J. Töpfer et al. / Journal of the European Ceramic Society 25 (2005) 1681–1688

smaller than the critical size for single domain particles of 2. Experimental
about 1 ␮m.5 To produce magnets with large remanence and
coercivity, it is essential to precisely tailor the ceramic pro- 2.1. Sample preparation
cess which in turn controls the complex interplay between a
dense microstructure and grain growth. Ferrite powder parti- All ferrite samples were prepared using the standard ce-
cles should have dimensions below 1 ␮m to allow some un- ramic process. The raw materials SrCO3 (grade B, Solvay
avoidable grain growth during sintering and to limit the grain Barium Strontium GmbH, Hannover, Germany) and Fe2 O3
size in the sintered magnets to a few microns. Taguchi6 and (EKO Recycling GmbH, Eisenhüttenstadt, Germany) were
Schwarzer et al.7 reported on sub-micron powders prepared mixed in a molar ratio SrO:Fe2 O3 = 1:5.6–5.8 and granulated.
by improved calcination and milling procedures which allow The granules (3–10 mm diameter) were calcined at 1300 ◦ C
the preparation of high-performance magnets with large re- for 0.5 h. The calcined granules were coarse milled in a rotary
manence (BR = 0.44 T). Substitution of La and Co for Sr and vibration mill to a specific surface area of s = 1–2 m2 /g.
Fe has emerged as a different approach to increase the ferrite SiO2 and CaCO3 were added in various concentrations and
performance, high-remanence magnets with BR = 0.45 T and then the ferrite powders were fine milled in an attrition mill for
HCI > 300 kA/m have been introduced.3,8 24 h (batch size: 2 kg ferrite powder, 20 kg steel balls (3 mm
The formation of the desired dense microstructure with diameter) and 3 l water). This procedure gives a powder with
small oriented grains is controlled by the addition of sin- a mean particle size of about 1 ␮m and a specific surface of
tering additives. Several systems have been proposed by 11–12 m2 /g. To study the effect of the additive concentration
Arendt.9 SiO2 was introduced as grain growth inhibitor in on the ferrite microstructure samples SF0–SF2 were prepared
hexaferrites.10 The mechanism of the action of SiO2 in fer- without any, or with either 0.5 wt.% SiO2 or CaO addition. In
rites was studied by Haberey and Kools.11,12 The sintering all other samples SiO2 and CaO were added simultaneously,
behavior and mechanism of grain boundary motion hindrance whereas the total additive concentration (SiO2 + CaO) of sam-
was studied in detail by Kools13,14 and a new mechanism of ples SF3–SF7 is 1 wt.% (Table 1). The additives were charac-
reaction induced grain growth impediment (RIGGI) has been terized by their specific surface: SiO2 (360 m2 /g) and CaCO3
proposed. Simultaneous addition of 0.45% CaO and 0–0.6% (8 m2 /g). The ferrite slurry was pressed in a magnetic field
SiO2 as another option to suppress grain growth has been in- of 560 kA/m (field parallel to the direction of pressure) into
vestigated; a large remanence and a coercivity of 250 kA/m discs of 52 mm in diameter and 4–6 mm in height. The sam-
were obtained.15 Moreover, there are some indications that ples were sintered at a peak temperature of 1200–1300 ◦ C.
the size of the additives might also play a crucial role in deter-
mining their effectiveness for microstructure control. Positive 2.2. Measurements
effects of fine-grained silica16 and the uniform incorporation
of Ca and Si utilizing a sol–gel route17 were demonstrated. The particle size of the powders was measured with a
In this paper we report on microstructural control of the Sympatec laser scattering system with a dry dispersion unit
magnetic properties by simultaneously adding CaO and SiO2 (system Rodos). The specific surface of the powders was de-
in a concentration range from 0 to 1 wt.%. We address the termined by adsorption of nitrogen in a BET apparatus (Mi-
following issues: (i) determination of the optimum additive cromeritics). The magnetic properties of the sintered mag-
concentrations and (ii) role of additives in microstructure for- nets were measured at room temperature with a permagraph
mation. Using both additives we prepared anisotropic dense (Magnet-Meßtechnik Ballanyi) on polished discs. The ce-
Sr-ferrite magnets with a remanence of BR = 430–440 mT ramic microstructures were analyzed on polished and ther-
and a coercivity HCI = 250–300 kA/m. mally etched faces of the magnets (parallel to the applied

Table 1
Concentration of additives, S/C ratio (SiO2 /CaO), magnetic properties and density of samples sintered at 1280 ◦ C
Sample SF SiO2 (wt.%) CaO (wt.%) S/C ratio Density (g/cm3 ) BR (mT) HIC (kA/m) BHmax (kJ/m3 )
0 – – – 5.03 430 156 –
1 0.50 – – 4.79 387 296 –
2 – 0.50 – 5.02 433 116 –
3 0.75 0.25 3 4.96 421 284 32.8
4 0.60 0.40 1.5 4.93 415 300 31.6
5 0.50 0.50 1 4.98 424 282 32.6
6 0.40 0.60 0.67 5.05 436 178 26.8
7 0.25 0.75 0.33 4.79 413 118 15.2
8 0.60 0.60 1 4.97 406 289 29.2
9 0.80 0.60 1.33 4.93 398 320 28.7
10 1.00 0.60 1.67 4.94 406 301 28.8
 J. Töpfer et al. / Journal of the European Ceramic Society 25 (2005) 1681–1688 1683

Fig. 1. Particle size distribution of Sr-ferrite powder during attrition milling; inset: SEM micrograph of powder milled for 24 h with d50 = 1 ␮m.

pressure and field) by SEM (Zeiss). TEM and EDX analy- To optimize the microstructure formation, i.e. to obtain
ses were performed with a Philips CM20FEG transmission sintered samples with high density and only little grain
electron microscope. growth several sintering regimes were tested. One set of sinter
The Fe2+ concentration was determined by chemical titra- experiments was performed at 1250 ◦ C for 45 min. For sam-
tion after dissolution of the powdered sample in hydrochloric ples SF3–SF7 a gradual increase in density and grain size
acid in argon. The Fe2+ was titrated with a 0.05N Ce4+ so- with decreasing ratio SiO2 /CaO (S/C) was observed. A seri-
lution under a flow of argon, with potentiometric detection ous problem was the appearance of abnormal grain growth.
of the equivalent point. The detection limit of that titration The tendency to form huge grains with size of about 100 ␮m
is given by the first drop of Ce4+ solution (V ≈ 0.03 ml), in a matrix of grains of size of about 2–5 ␮m also increases
which corresponds to 0.08 wt.% Fe2+ for 100 mg of a ferrite with decreasing S/C ratio. The best results were observed with
sample. sintering at a peak temperature of 1280 ◦ C for a short period
of time after heating (and cooling) the samples with 3 K/min
to 1150 ◦ C. Similar results were reported by Besenicar and
3. Results Drofenik18 after sintering at 1260 ◦ C for only 3 min they ob-
served an almost dense microstructure (97%) with acceptable
The change of the particle size distribution of the Sr- magnetic properties.
ferrite powder during attrition milling and the morphology The microstructure of magnets SF0–SF2 sintered at
of the fine-milled powder with a mean particle size of 1 ␮m 1280 ◦ C is shown in Fig. 2. The SEM micrographs were
is shown in Fig. 1. The composition of sintered magnets pre- taken perpendicular to the direction of pressure and mag-
pared from this powder was controlled by chemical analysis; netic field during wet molding; the view is along the basal
a ratio SrO:Fe2 O3 = 1:5.94 has been observed. planes of the platelet shaped ferrite particles. If one takes into

Fig. 2. SEM micrographs of sample SF0–SF2 sintered at 1280 ◦ C.

1684 J. Töpfer et al. / Journal of the European Ceramic Society 25 (2005) 1681–1688

Fig. 3. SEM micrographs of magnets SF3–SF7 sintered at 1280 ◦ C.

account the size of the fine-milled powder of about 1 ␮m, it is The addition of 0.6% CaO (sample SF6) seems very ef-
obvious that grain growth predominately occurs perpendicu- fective for densification, but 0.4% SiO2 is not sufficient to
lar to the hexagonal c-axis. Without additives (SF0) a dense avoid substantial grain growth and the subsequent decrease of
and anisotropic microstructure with platelet-shaped grains of coercivity. A series of magnets (SF8–SF10) with 0.6% CaO
1–2 ␮m in height and about 3–5 ␮m in length is observed. and different SiO2 concentrations was prepared (Table 1). In-
Similar results are obtained for sample SF2 with only CaO deed, the grain size of samples sintered at 1280 ◦ C is reduced
addition. Addition of 0.5 wt.% SiO2 significantly reduced the compared to sample SF6. Consequently, the coercivity is in-
grain size (SF1, Fig. 2b) as well as the density. The shape of creased up to around 300 kA/m. On the contrary, with SiO2
the particles also changes; the particles are less platelet-like concentrations increasing from 0.6 to 1% (S/C ratio from
with a smaller aspect ratio. This is reflected in the magnetic 0.67 to 1.67) the density of the magnets is reduced to below
properties (Table 1). The dense microstructure of magnets 5 g/cm3 and thus the remanent induction is also reduced. The
SF0 and SF2 is transformed into high remanence, but due increased absolute concentration of non-magnetic additive
to the relatively large platelet-shaped grains the coercivity is phase contributes to the reduced BR .
low. For magnet SF1 the coercivity is increased to almost
300 kA/m, but BR is reduced.
The microstructure of samples SF3–SF7 (Fig. 3), i.e. with
simultaneous SiO2 and CaO addition, but various S/C ratios,
shows significant changes in the size of the grains. Whereas
in samples with large C/S ratio small grains with 2–3 ␮m
in length are observed, samples with smaller C/S ratio show
longer grains of up to 5 ␮m. Grain growth along the hexagonal
c-axis hardly occurs, whereas perpendicular to this axis the
grains grow, i.e. the aspect ratio tends to increase if the S/C
ratio becomes smaller. The density of the sintered magnets
SF3–SF7 (Table 1) slightly increases up to a S/C = 0.67, only
SF7 with S/C = 0.33 has a reduced density of 4.79 g/cm3 . The
demagnetization curves are shown in Fig. 4, the magnetic
parameters are collected in Table 1. The variation of BR and
Hc with the concentration of additives (expressed as C/S ratio)
is shown in Fig. 5. Fig. 4. Demagnetization curves of magnets SF3–SF7 sintered at 1280 ◦ C.
 J. Töpfer et al. / Journal of the European Ceramic Society 25 (2005) 1681–1688 1685

Fig. 5. Remanence BR and coercivity HIC as a function of the S/C ratio

(SiO2 /CaO) for magnets SF3–SF7 sintered at 1280 ◦ C.
Fig. 7. EDX line scan through a three-grain junction of sample SF5.

To check whether the addition of SiO2 and CaO promotes The corresponding incoherent dark field transmission image
the formation of Fe2+ selected samples were analyzed by (not shown here) shows that the nature of the solidified grain
chemical titration. SF0 without any additives and SF2 with boundary phase is amorphous. An EDX line scan through one
the addition of 0.5 wt.% CaO have no detectable concentra- of the triple grain junctions (Fig. 7) shows that the Fe signal is
tion of Fe2+ . Addition of 0.5 wt.% SiO2 (SF1) gives 0.12 ± strongly reduced at the center of the junction, whereas Ca is
0.03% Fe2+ . For sample SF5 (0.5 wt.% SiO2 and CaO) no enriched. The detection of Si is more difficult, because of the
Fe2+ was found. overlap of the Si-K␣ and Sr-L␣ signals at about 1.6–2.0 keV.
The appearance of the additives in the ceramic microstruc- The signal in Fig. 7 contains contributions of both elements
ture has been studied by STEM and EDX. Fig. 6 shows a and shows increased intensities at the junction; the Sr-K␣
three-grain junction between neighboring grains with a di- signal also shows a slight increase. From that analysis it can-
hedral angle of about 60◦ . The liquid phase continuously not be concluded whether Si or Sr is enriched at the grain
wets the grains and a thin grain boundary layer is detected. junction. In Fig. 8a scan is made across another position of
the sample. The upper part of Fig. 8 shows the line of the
scan crossing a grain junction in the left center of the fig-
ure as well as two grain boundaries in the right-hand part
of the figure (marked with arrows). The three intergranular
areas are also recognized in the scan of the brightness. The
iron signal again is strongly reduced at the grain junction and
boundaries. To better detect the Si signal, regions of inter-
est (ROI) have been selected (e.g. 1.56–1.8 keV for Si and
1.8–2.0 keV for Sr). Although a complete discrimination be-
tween Si and Sr signals is not achieved in this way due to
the limited energy resolution of the detector, the sensitivity
for the Si signal is considerably higher in the first ROI, and
that for the Sr signal in the second. The lower panel of Fig. 8
shows the recorded intensities. Unambiguously Si is enriched
at the grain junction and grain boundary phase. The variation
of the Ca intensity also clearly signals an increase at the grain
junction. For the Sr signal a slight enhancement relative to
the grain has been observed which does not allow to interpret
whether Sr is a significant part of the grain boundary phase
or not.

4. Discussion

The role of SiO2 as an additive for micro-structural con-

Fig. 6. TEM image of a three-grain junction of sample SF5 with 0.5% SiO2 trol of hard ferrite magnets has been explained as liquid
and 0.5% CaO sintered at 1280 ◦ C. phase forming agent.9–11 From very detailed studies, the
1686 J. Töpfer et al. / Journal of the European Ceramic Society 25 (2005) 1681–1688

Fig. 8. (a) EDX line scan through sample SF5 crossing one three-grain junction and two grain boundaries (upper panel, marked by arrows) and variation of
brightness (lower panel) and (b) and (c) element concentrations as recorded at selected energies.

action of silica has been categorized as being dependent on liquid phase is expected to react with the calcium silicates
the ratio SiO2 additive over SrO-excess concentration.13,14 formed from CaO and SiO2 additives. The composition of the
Technical hard ferrite compositions have a Fe2 O3 /SrO ra- liquid phase determines the rate of grain growth of the fer-
tio <6 making the excess SrO a ready candidate for reac- rite particles. During cooling CS-rich phases seem to become
tions with silica at elevated temperatures. According to the solidified as amorphous grain boundary phases as shown by
proposed phase diagram SrO–SiO2 –Fe2 O3 at 1250 ◦ C the electron microscopy. Another indication for such mechanism
addition of SiO2 causes the appearance of liquid or solid is the fact, that only for SF1 a detectable Fe2+ concentration
minority phases depending on the SiO2 and SrO-excess has been observed. In agreement with the observations of
concentrations.14 Kools14 this is a result of partial incorporation of Si into the
If SiO2 and CaO (or CaCO3 ) are added simultaneously, ferrite lattice. For SF5 no Fe2+ has been found signaling
both components are expected to react and to form Ca-silicate that the reaction of SiO2 with CaO and not with ferrite is
(CS)-phases at low temperature. The formation of CS-phases favored.
has been observed at temperatures as low as 600–800 ◦ C.19 The magnetic properties of a hexaferrite are determined by
In the CaO–SiO2 system the first eutectic temperatures ap- its chemistry and microstructure. To obtain high-remanence
pear at 1436 ◦ C,20 i.e. above the sintering temperature of the magnets a dense microstructure with well aligned particles
ferrite. On the other hand, if Sr-ferrite with excess SrO is and possibly little non-magnetic secondary phase is neces-
sintered above the eutectic temperature of 1210 ◦ C,21,22 the sary. If a large coercivity is desired the particle size should
 J. Töpfer et al. / Journal of the European Ceramic Society 25 (2005) 1681–1688 1687

be in the order of the critical diameter dc for single domain ity. The additives form a Ca-silicate rich amorphous phase at
behavior given by: multiple-grain junctions and grain boundaries.
√
18 (AK1 )
dc =
µ0 Ms2 Acknowledgements

where K1 is the magnetocrystalline anisotropy constant, The authors would like to thank Mr. D. Kätzel (Tridelta
A is the exchange energy constant and Ms is saturation GmbH) for wet molding of the samples and Mrs. M. Friedrich
magnetization.23 For Sr-ferrite dc ≈ 1 ␮m.5 The coerciv- and Mr. E. Hartmann for the preparation of SEM micro-
ity according to the Stoner–Wohlfahrt situation of non- graphs of polished samples. This work was supported by
interacting single-domain particles with the anisotropy pro- a grant (B409-99005) from the Thüringer Ministerium für
vided by magneto-crystalline anisotropy is: Wissenschaft, Forschung und Kultur (TMWFK), Germany.


2K1
HIC = 0.48 − NMs
µ0 Ms References
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