processes
Article
Investigation on the La Replacement and Little Additive
Modification of High-Performance Permanent Magnetic
Strontium-Ferrite
Ching-Chien Huang 1, * , Chin-Chieh Mo 1,2 , Guan-Ming Chen 3 , Hsiao-Hsuan Hsu 4 and Guo-Jiun Shu 4, *






Citation: Huang, C.-C.; Mo, C.-C.;
Chen, G.-M.; Hsu, H.-H.; Shu, G.-J.
Investigation on the La Replacement
and Little Additive Modification of
High-Performance Permanent
Magnetic Strontium-Ferrite. Processes
2021, 9, 1034. https://doi.org/
10.3390/pr9061034
Academic Editor: Sung-Churl Choi
Received: 14 May 2021
Accepted: 10 June 2021
Published: 12 June 2021
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
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iations.
Copyright: © 2021 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
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Attribution (CC BY) license (https://
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4.0/).
Processes 2021, 9, 1034. https://doi.org/10.3390/pr9061034
1 Department of Mechanical Engineering, National Kaohsiung University of Science and Technology,
Kaohsiung 807618, Taiwan; commi.ee93g@nctu.edu.tw
2 MagPower Corporation Corporation, Pingtung 90093, Taiwan
3 Research & Development Department, Green Energy & System Integration, China Steel Corporation,
Kaohsiung 81233, Taiwan; 189837@mail.csc.com.tw
4 Department of Materials & Mineral Resources Engineering, National Taipei University of Technology,
Taipei 10608, Taiwan; hhhsu@ntut.edu.tw
* Correspondence: huangcc@nkust.edu.tw (C.-C.H.); gjshu@mail.ntut.edu.tw (G.-J.S.)
Abstract: In this work, an experiment was carried out to investigate the preparation condition of
anisotropic, Fe-deficient, M-type Sr ferrite with optimum magnetic and physical properties by chang-
ing experimental parameters, such as the La substitution amount and little additive modification
during fine milling process. The compositions of the calcined ferrites were chosen according to the
stoichiometry Lax Sr1-x Fe12-2x O19 , where M-type single-phase calcined powder was synthesized with
a composition of x = 0.30. The effect of CaCO3 , SiO2 , and Co3 O4 inter-additives on the Sr ferrite
was also discussed in order to obtain low-temperature sintered magnets. The magnetic properties
of Br = 4608 Gauss, b Hc = 3650 Oe, i Hc = 3765 Oe, and (BH)max = 5.23 MGOe were obtained for Sr
ferrite hard magnets with low cobalt content at 1.7 wt%, which will eventually be used as high-end
permanent magnets for the high-efficiency motor application in automobiles with Br > 4600 ± 50 G
and i Hc > 3600 ± 50 Oe.
Keywords: magnet; strontium-ferrite; replacement; cobalt; additives; fine mill; motor; automobile
1. Introduction
Hexagonal magneto-plumbite-type strontium ferrite (SrFe12 O19 ) has material charac-
teristics, such as a stable crystal structure, high coercivity and magnetic energy product,
and magnetic anisotropy (K1 ) [1], so it is widely used in permanent magnet motors and
various electronic devices, which is an important basic functional material in the electronics
industry. In recent years, with the development of the green economy and environmental
protection industry, the miniaturization and high-performance requirements of electronic
components have gradually increased, accompanied by strong demand for the miniaturiza-
tion and high performance of magnets. High-performance permanent magnet ferrites with
high remanence (Br ), high coercivity (i Hc ), and high magnetic energy product ((BH)max )
are new market needs for the rapid development of the world’s electronic information
and automobile industries [2,3]. In order to improve the various physical and magnetic
properties of strontium ferrite, research is mainly carried out on two aspects: formula
and process conditions. After years of exploration and research, it has been discovered
that simply by optimizing the process parameters of ferrite, such as the particle size and
distribution after ball milling, the calcination temperature curve, the sintering temperature
curve, and the compression molding process, some performance indexes of strontium
ferrite can be optimized to a certain level. However, compared with its various theoretical
values, there is still a big gap [4–9]. In a material, by doping a small amount of other
elements or compounds, the material will produce specific optical, electrical and magnetic
https://www.mdpi.com/journal/processes
Processes 2021, 9, 1034 2 of 11

properties. For strontium ferrite, the proper amount of doping can also improve its mag-
netic and physical properties, but it is of great significance for the determination of the
doping amount and doping method. How the magnetic properties of permanent ferrites
through ion substitution can be improved has become an important way to accelerate
the performance of permanent ferrites. This starts from the crystal structure and micro-
scopic morphology, uses the basic theory of micro-magnetoelectronic spin to optimize
ion substitution, and fundamentally promotes the research and developmental process
of high-performance permanent magnet ferrites [10–15]. In recent studies, a significant
improvement has been made in SrFe12 O19 ferrite by a combined replacement of La3+ in Sr2+
site and Co2+ in Fe3+ , and the simultaneous substitution of lanthanum and cobalt could
obviously enhance the intrinsic coercivity i Hc when keeping the remanence Br invariant.
However, past research has often designed a calcined La-Co base formula composition
to acquire large Br and large i Hc at the same time [13–19]. It ought to be noticed that the
design of the formula requires the participation of valuable metal component cobalt to be
used in the calcination formula in the form of oxide, such as Co3 O4 , which has a big hazard
of mass production and greater cost. Previously, several literatures have been conducted
with the goal of making Sr ferrite either with lower cobalt content or without cobalt [5,20];
however, such permanent materials possess lower magnetic characteristics. Furthermore,
finer magnetic powder mill (<0.65 µm) and wet magnetic molding processes give magnets
better performance due to a single magnetic domain grain size and higher alignment.
Yet, for wet magnetic molding, it would be hard to press slurry in the mold; thus, the
conventional processing technique nearly reached its limit [21–23]. As far as the current
situation is concerned, the use of cobalt in combination with an extensive range of critical
businesses and technical applications is of essential vital importance, and therefore its
value has been continuously increased. Regarding the issue above, it is critical to develop a
Fe-deficient M-type Sr ferrite calcination formula without any addition of cobalt during the
calcination process and as little cobalt used in the secondary additive as possible to modify
the magnetic properties of M-type ferrite hard magnets. In this study, a non-stoichiometric
formula composed of Lax Sr1-x Fe12-2x O19 was chosen to form Fe-deficient M-type Sr fer-
rites with x = 0.30. For this formula, n = 11.4, where n is the mole ratio of (La+Sr): (Fe).
Among the calcined formula, no cobalt element is used in the calcined powder, which
can reduce the cost of M-type ferrite permanently. When the mole ratio n is smaller than
12, the ferrites take an Fe-deficient formula. Differently from past studies, the results in
this work have the following merits. First, the valuable metal component, cobalt, was not
used in the main calcined formula; thus, the price of calcining powder was cheap, which
was beneficial to mass production. Next, the secondary additive, such as Co3 O4 , CaCO3 ,
and SiO2 doped after calcining are profoundly adjustable. While Co3 O4 was added with
CaCO3 and SiO2 , the amount of Co3 O4 doped as the secondary additive after calcining
is little, allowing it to be more economical to modify the magnetic properties of Sr ferrite
and enhance mass production. In this work, a calcined formula without precious cobalt
is brought to execution. The magnetic properties could be modified by a little amount of
Co3 O4 with two other important additives, CaCO3 and SiO2 , added after calcining instead
of during the calcination step to satisfy customers’ need for permanent ferrite magnet with
high performance, low material prices, small batch production, easy manufacturing, large
process-adjusting windows, and excellent economy. Our experimental results found that
with a Fe-deficient calcined formula with a “Cobalt-free” recipe design and optimized
process parameters, magnetic performance was obtained as follows:

Br = 4608 Gauss, b Hc = 3710 Oe,

i Hc = 3765 Oe, and (BH)max = 5.23 MGOe

Processes 2021, 9, 1034 3 of 11

2. Experimental Procedure
2.1. Sample Preparation
In this study, Fe-deficient M-type Sr ferrite magnets have been synthesized by the
conventional ceramic method. Nonstoichiometric compositions were selected on the basis
of the chemical composition Lax Sr1-x Fe12-2x O19 , where La content (x) varied from 0.28 to
0.32, and Sr content (1-x) from 0.70 to 0.74. The raw material Fe2 O3 is manufactured by
the acid recycle Ruthner process of the China Steel Corporation (CSC) in Taiwan [7,24]
with high purity (>99.5%) and Specific Surface Area (SSA) = 3.5 ± 0.2 m2 /g. The SrCO3
with >98% purity and different particle sizes of 1.0~2.5 µm was used as another starting
material to clarify the influence of its particle size on the magnetic properties of Sr ferrite.
First, the raw material Fe2 O3 , SrCO3 , and La2 O3 powders and the additive CaCO3 were
wet-mixed by an attritor, and then granulated for calcination. A single phase of submicron-
sized Sr ferrite powder was prepared by calcining in an electric furnace at 1270 ± 5 ◦ C
for 1 h in air at increments of 10 ◦ C. The calcination granules were vacillated vigorously
in a vibration mill to achieve a powder size of approximately 2.2 ± 0.1 µm on average.
Next, the additives CaCO3 , SiO2 , and Co3 O4 were doped in different concentrations by
fine-milling the mixture for about 9 h in a stainless steel ball-miller before sintering. This
step guarantees a narrower particle-size distribution with a mean size about 0.70 ± 0.05 µm
measured by a Fisher subsieve sizer (Fisher, Waltham, MA, USA), which is important for
achieving good performance. Here, we further explain why the two-stage grinding process
was performed in the experiment. For the traditional manufacturing process of permanent
ferrite materials, the two-stage milling process will be carried out in sequence. These two
different milling processes have different purposes for the preparation of permanent ferrite.
For the first stage of milling, we can call it pulverization, or “coarse milling”. This coarse
milling is usually carried out by a vibrating mill, which is a more vigorous process and
able to grind the calcined granules from a centimeter-level size to µm-level size in a shorter
time. We usually grind the calcined granules to a powder size of about 2.2 ± 0.1 µm on
average through this “coarse milling” process. Because the first stage of the milling process
already ground the calcined granules to a relatively smaller size, the second stage of the
milling process, that is, the fine milling process, is usually used to grind the magnetic
powder to a smaller size of less than 1 µm (0.70 ± 0.5 µm in this study) by a ball mill
to fit the permanent magnet process requirements. Because the ball milling process is a
relatively mild grinding process, it can achieve a narrow and single-peak magnetic particle
size distribution, which is necessary for achieving better magnetic performance, but will
take a longer time. However, if we do not grind the calcined granules through the coarse
milling process first, but directly use the ball mill to grind, this will cause the required
grinding time to become quite long, and it will not be easy to achieve the aforementioned
particle size distribution results. The milled slurry was pressed into tablets of Φ26.5 mm
in diameter and 13 mm in height under a magnetic field of about 1.5 Tesla and 100 MPa
pressure (according to the Japanese Industrial Standard, JIS C2501). The pressed tablets
were sintered at a peak temperature of 1230 ± 5 ◦ C for 1 h.

2.2. Measurements
X-ray diffraction (XRD, Cu-Kα radiation) was used for the phase identification of the
calcined magnetic powder. The powder size distribution of SrCO3 was measured by the
Sympatec laser-scattering system under the sample analysis volume of 0.5 g using a dry
dispersion unit (system Rodos). The magnetic properties (Br , i Hc , and (BH)max ) of the
sintering magnets were measured at room temperature by the NIM-2000 HF Hysteresis
graph meter (China National Measuring Science Research Institute) on the polished discs.
The b Hc describes the magnetic field which makes the B distribution in the magnet change
direction. The b Hc is smaller than i Hc , which is the field necessary to demagnetize the
polarization or magnetization to zero. Usually, we use i Hc to represent the intrinsic
magnetic properties of permanent magnet materials. Scanning electron microscopy (SEM;
Processes 2021, 9, x FOR PEER REVIEW 4 of 12

Processes 2021, 9, 1034 4 of 11

intrinsic magnetic properties of permanent magnet materials. Scanning electron micros-

copy (SEM; Zeiss) was used to analyze the ceramic microstructures on the polished and
Zeiss) wasetched
thermally used to analyze
faces of thethe ceramic
magnets microstructures
(perpendicular onapplied
to the the polished andand
pressure thermally
field).
etched faces of the magnets (perpendicular to the applied pressure and field).
3. Result and Discussion
3. Result and Discussion
3.1. Effect
Effect of Calcined
of Calcined Ferrite
Ferrite Stoichiometry
Stoichiometry
The general formula
The general formula of of M-type
M-type ferrite
ferrite isis AFe
AFe12O 19, where A = Ba or Sr, and a part of
12 O19 , where A = Ba or Sr, and a part of
these elements can be replaced by rare-earth elements.Among
these elements can be replaced by rare-earth elements. Among them,
them, a part
a partof of
Fe Fe could be
could
substituted by cobalt (Co) to obtain better magnetic performance
be substituted by cobalt (Co) to obtain better magnetic performance that would result that would result in high
intrinsic
in magnetization
high intrinsic Ms and anisotropic
magnetization magneticmagnetic
Ms and anisotropic field strength HA [13–19].
field strength HA Besides,
[13–19].
the element
Besides, at the A at
the element position can be substituted
the A position by other
can be substituted byrare-earth elements,
other rare-earth such assuch
elements, La,
since La 3+ (1.17 3+Å), Ba 2+ (1.22 Å),2+ and Sr 2+ (1.32 Å)2+ share almost
as La, since La (1.17 Å), Ba (1.22 Å), and Sr (1.32 Å) share almost the same radius. the same radius. La has the
highest
La solid
has the solution
highest solidlimit for M-type
solution limitferrites,
for M-typeand the substitution
ferrites, and theofsubstitution
La at the A position
of La at
the A position can enhance the solid content of Co that substitutes Fe, and
can enhance the solid content of Co that substitutes Fe, which is critical which beneficial
is criticalto
the improvement of the magnetic characteristics of Sr ferrite [11,13,16,25].
and beneficial to the improvement of the magnetic characteristics of Sr ferrite [11,13,16,25]. To investigate
theinvestigate
To influence ofthe theinfluence
amount of of La
thesubstituted
amount of for La Sr in the calcined
substituted for Srferrite
in theon the magnetic
calcined ferrite
properties,
on the magnetic a non-stoichiometric formula composed
properties, a non-stoichiometric formula of La xSr1-xFe12-2x
composed ofOLa
19 was selected
x 1-x 12-2x O19
Sr Fe to
formselected
was Fe-deficient
to formSr base M-type ferrite
Fe-deficient Sr basewith M-typex = 0.28~0.32.
ferrite with It can be seen from
x = 0.28~0.32. thebe
It can experi-
seen
mental
from results
the in Figure results
experimental 1 that thein substitution
Figure 1 thatamount of La2O3 inamount
the substitution the calcined
of Laferrite
2 O3 in must
the
be sufficient to react with cobalt added during the fine-milled
calcined ferrite must be sufficient to react with cobalt added during the fine-milled processprocess to promote the dif-
fusion
to of Cothe
promote ionsdiffusion
in the sintering
of Co ions reaction
in thetosintering
achieve better
reactionmagnetic properties.
to achieve When x =
better magnetic
0.32, the level
properties. of Brx= =4536G
When 0.32, and iHc = 4362Oe
the level can be and
of Br = 4536G obtained.
i Hc = It can be can
4362Oe clearly determined
be obtained. It
that be
can theclearly
higherdetermined
the amountthat of Lathe2O3higher
in the thecalcined
amount ferrite,
of Lathe O
2 3 higher
in the the Br
calcinedand H .
ferrite,
i c How-
the
ever, ifthe
higher theBr amount
and i Hof La2O3 in the
c . However, calcined
if the amount ferrite
of Lais2 Otoo
3 in high, it will cause
the calcined ferriteaismismatch
too high,
it willthe
with cause a mismatch
Co added with the Coresulting
after calcination, added after in acalcination,
decrease in resulting
magneticin a decrease
properties in
[24].
magnetic properties [24]. The X-ray diffraction patterns of
The X-ray diffraction patterns of the Sr ferrite M-type ferrite LaxSr1-xFe12-2xO19 calcinedthe Sr ferrite M-type ferrite
La x Sr1-x Fe
powders 12-2x O
with x 19 calcined are
= 0.28~0.34 powders
given with x = 0.28~0.34
in Figure 2. It can be areseen
given thatinthe
Figure
XRD2.patterns
It can beof
seen that the XRD
the magnetic patterns
powders withofLa thecontent
magnetic (x) powders
= 0.28~0.34 withandLaSrcontent
content(x)(1-x)
= 0.28~0.34
= 0.66~0.72 andare
Sr
content
all in good(1-x) = 0.66~0.72
agreement with arethe
allSrinbase
good agreement
M-type ferritewith
JCPDS the card no. M-type
Sr base 84-1531ferrite JCPDS
and illustrate
card no. 84-1531
a single-phase and illustrate
hexagonal a single-phase hexagonal structure.
structure.

4600 4600

4536
4520

4500
Br (Gauss)

4472
4362 4400
i

4303
Hc (Oe)

4420 4289
Br
4400
4203
H
i c
Before Calcination: 4200
CaCO3=0wt%
After Calcination:
Co3O4=1.8wt%, CaCO3=0.8wt%, SiO2=0.45wt%
4300 o
Calcination Temp.=1270 C
o
Sintering Temp.=1230 C
4000
0.28 0.30 0.32 0.34

x in LaxSr1-xFe12-2xO19
Figure 1.
Figure 1. Dependence
Dependence of of B
Brr and
and iiH
Hcc of
of the
the fabricated
fabricated sintered
sintered magnet
magnet on
on the
the xx value
value of
of the
the formula
formula
LaxSr1-xFe12-2xO19 calcined ferrite.
Lax Sr1-x Fe12-2x O19 calcined ferrite.
Processes 2021, 9, 1034 5 of 11
Processes 2021, 9, x FOR PEER REVIEW 5 of 12

200

190

180 JCPDS card no. 84-1531 SrFe12O19

170

160

150
u.)

140

130
(a.

120
)

xBao-C
= 0.28
Intensity

110

100
(

90

80
xBao-S
= 0.30
70

60
MP-C
x = 0.32
50

40

30

20
xMP-S
= 0.34
10

5 10 20 30 40 50 60 70 80 90

2θ/ two theta

Figure
Figure 2.
2. XRD patterns of the
the ferrite
ferrite La
LaxxSr
Sr1-x
1-xFe
Fe12-2xOO
12-2x 19 calcine powders
19 calcine powderswith
withLa
Lacontent
content(x)
(x)from
from0.28
0.28to
to0.34,
0.34,and
and Sr
Sr content
content
(1-x)
(1-x) from 0.66~0.72.
from 0.66~0.72.

In
In order
order to investigate
investigate the influence of the main raw material SrCO33 with different
particle
particle sizes
sizesononthe
themagnetic
magneticproperties,
properties,two twodifferent
different particle
particlesizes of SrCO
sizes of SrCO3 are used
3 are for
used
experiments
for experiments in this work.
in this work. Table
Table1 shows
1 shows the
theparticle
particlesize
sizeanalysis
analysisresults,
results,and
and Figure
Figure 3
shows
shows thethe particle
particle size
size distribution,
distribution, where where both
both werewere measured
measured by the Sympatec laser
scattering system
scattering system under
under thethe sample
sample analysis
analysis volume
volume of 0.5 g. The The SEM micrograph of
SrCO33 powders is shown in Figure 4. From the above results, itit can
SrCO powders is shown in Figure 4. From the above results, can bebe found
found that the
morphology and
morphology andsizes
sizesofofthethetwo
twodifferent types
different of SrCO
types 3 are3very
of SrCO are different. FigureFigure
very different. 5 shows 5
an SEManofSEM
shows the La Sr1-xLa
ofx the Fex12-2x
Sr1-xFeO19 calcine
12-2x powders
O19 calcine with two
powders withdifferent types of
two different SrCO
types as the3
of3 SrCO
raw
as thematerial. From From
raw material. the results of Figure
the results 6, it can
of Figure 6, itbecan
observed that ifthat
be observed the if
SrCO 3 with3 with
the SrCO finer
particle
finer size (expressed
particle by theby
size (expressed D50
thevalue in Table
D50 value 1) is used
in Table 1) is as theas
used main
the raw
mainmaterial, the Br
raw material,
of SrBrferrite
the will decrease
of Sr ferrite significantly,
will decrease while the
significantly, i Hc will
while the iincrease slightly. slightly.
Hc will increase Corresponding
Corre-
to the SEM results of the calcined magnetic powder in Figure
sponding to the SEM results of the calcined magnetic powder in Figure 5, it could 5, it could be foundbethat the
found
calcined magnetic powder with a finer particle size of SrCO
that the calcined magnetic powder with a finer particle size 3of SrCO3 as the main raw as the main raw material
has smaller
material hasgrains
smallerofgrains
approximately 1~1.5 µm,
of approximately which
1~1.5 μm,also causes
which alsothe remanence
causes Br to be
the remanence
Brelatively low. In contrast,
r to be relatively the calcined
low. In contrast, magneticmagnetic
the calcined powder with powdera coarser
with aparticle
coarsersize with
particle
SrCO as the main raw material has a larger size of approximately
size with SrCO3 as the main raw material has a larger size of approximately 1.5~3 μm and
3 1.5~3 µm and tends to
have a relative hexagonal plate, and its corresponding magnetic
tends to have a relative hexagonal plate, and its corresponding magnetic properties are properties are also better.
also better.
Table 1. The particle size analysis results of the two different types of raw material SrCO3 .
Table 1. The particle size analysis results of the two different types of raw material SrCO3.
D10 (µm) D50 (µm) D90 (µm)
SrSO3 (Coarse Particle) D10 (μm)
0.70 ± 0.02 2.50 ±D0.02
50 (μm) D90±(μm)
6.10 0.02
SrSO
SrSO 3 (Coarse Particle)
3 (Coarse Particle)
0.70 ± 0.02 1.00 ±
0.50 ± 0.02 2.50
0.02± 0.02 6.10±±0.02
2.30 0.02
SrSO3 (Coarse Particle) 0.50 ± 0.02 1.00 ± 0.02 2.30 ± 0.02
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1.6
1.6
1.6 SrCO33 (Coarse
SrCO
SrCO (Coarse Particle)
(Coarse Particle)
Particle)
3
SrCO
SrCO (Fine
SrCO33 (Fine Particle)
(Fine Particle)

Distribution
Particle)

Density Distribution
1.4
1.4
1.4 3

1.2
1.2
1.2

1.0
1.0
1.0

0.8
0.8
0.8
Density

0.6
0.6
0.6

0.4
0.4
0.4

0.2
0.2
0.2

0.0
0.0
0.0
0.1
0.1
0.1 111 10
10
10
Particle (μm)
Figure 3.
Figure
Figure 3. Particle
3. Particle size
Particle size distribution
size distribution of
distribution of two
of two different
two different raw
different raw material
raw material SrCO3333 measured
material SrCO
SrCO measured by
measured by the
by the Sympatec
the Sympatec
Sympatec
laser
laser
laser scattering
scattering
scattering system.
system.
system.
laser scattering system.

(a)
(a)
(a) (b)
(b)
(b)
Figure
Figure
Figure4. 4. The
4.The SEM
TheSEM micrograph
SEMmicrograph
micrographof ofoftwo
two
twodifferent
different raw
raw
different material
material
raw SrCO
SrCO
material powders:
33 powders:
SrCO (a) coarse-particle
(a) coarse-particle
Figure 4. The SEM micrograph of two different raw material SrCO 3 powders:
3 powders: (a) (a) coarse-particle
coarse-particle
SrCO
SrCO
SrCO 33,, (b)
, (b)
(b) fine-particle
fine-particle
fine-particle SrCO
SrCO
SrCO
SrCO3 , (b) fine-particle SrCO3 .
3
33..
3 .

(a)
(a)
(a) (b)
(b)
(b)
Figure 5.
Figure
Figure 5. The
The SEM
SEM of
of the
the La
LaxxxSr
Sr1-x Fe12-2x
1-xFe O1919 calcined
12-2xO calcined powders
powders with with two
two different
different particle
particle sizes
sizes of
of
Figure 5.5. The SEM
The SEM of
of the
the La
La Sr 1-xFe12-2xO19 calcined powders with two different particle sizes of
x Sr1-x Fe12-2x O19 calcined powders with two different particle sizes of
SrCO
SrCO
SrCO as
33 as the
the raw
raw material:
material: (a)
(a) coarse-particle
coarse-particle SrCO
SrCO Scheme
33Scheme 3,
3, (b)
(b) fine-particle
fine-particle SrCO
SrCO 33..
SrCO33as asthe
theraw
rawmaterial:
material:(a)(a)coarse-particle
coarse-particleSrCO SrCO33Scheme 3, (b) fine-particle
, (b) fine-particle SrCO3 . SrCO3.
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4450
4450
4413
4600
4600 H 4413
iH c 4400
i c 4400

(Gauss)
4362

BBr (Gauss)
4362

i i cc
HH (Oe)
4550 4350
4550 4350

(Oe)
4536
4536
r

4300
4500 4300
4500 4478 Before Calcination:
4478
Br
B
Before
La0.32SrCalcination:
0.68
La0.32Sr0.68
Fe11.36O19, CaCO3=0wt%
Fe11.36O19, CaCO3=0wt% 4250
r After Calcination: 4250
After Calcination:
Co O =1.8wt%, CaCO =0.8wt%, SiO2=0.45wt%
4450 Co33O44=1.8wt%, CaCO33=0.8wt%, SiO2=0.45wt%
4450 o o
Calcination Temp.=1270o C; Sintering Temp.=1230o C
Calcination Temp.=1270 C; Sintering Temp.=1230 C 4200
1.0 1.5 2.0 2.5 4200
1.0 1.5 2.0 2.5
Particle Size
Particle Size (D
(D50)) of
of SrCO
SrCO3 ((μμm)
m)
50 3
Figure 6. Magnetic properties of Sr ferrite with different particle sizes of raw material SrCO3.
Figure 6.
Figure 6. Magnetic
Magnetic properties
properties of
of Sr
Sr ferrite
ferrite with
with different
different particle
particle sizes
sizes of
of raw
raw material
material SrCO
SrCO3..
3
The additive CaCO3 could promote densification and uniform grain growth of hard
The additive CaCO 3 could promote densification and uniform grain growth of hard hard
ferrite, resulting in high3 remanence, but at the same time, iHc must be sacrificed [24, 25,
ferrite, resulting in highhigh remanence,
remanence, butbut atat the
thesame
sametime,
time,i HiHcc must
must be be sacrificed
sacrificed [24–26].
[24, 25,
26] . Enhancement of Br could also be obtained by using Co3O4 in calcined material, and
26] . Enhancement
Enhancement of Br could
of B could also bealso be obtained
obtained by usingby Co
usingO4 Co 3O4 in calcined
in calcined material,material,
and Co3andO4
Co3O4 reduces iHrc much better than CaCO3, but the3cost of Co3O4 is much higher than
Co3O4 reduces
reduces i Hc much iHc better
much thanbetterCaCO
than3 ,CaCO 3, but
but the costthe cost
of Co 3 Oof4 isCo 3O4 ishigher
much muchthan higher than
adding
adding CaCO3. Therefore, this study discusses the effect of adding CaCO3 before calcina-
CaCO
adding 3 . CaCO
Therefore, this study
3. Therefore, discusses
this the effectthe
study discusses of adding
effect ofCaCO
adding 3 before
CaCO calcination on the
3 before calcina-
tion on the improvement of magnetic properties. It can be seen from the comparison of
improvement of magnetic of
tion on the improvement properties.
magneticItproperties.
can be seenItfrom
can betheseen
comparison
from theofcomparison
the magnetic of
the magnetic properties in Figure 7 that the addition of CaCO3 before calcination can fur-
properties
the magnetic in Figure 7 thatinthe
properties addition
Figure 7 that ofthe
CaCO before
addition
3 of calcination
CaCO 3 can
before further
calcinationincrease
can B
fur-r,
ther increase Br, but excessive CaCO3 will cause a decrease in both Br and iHc, especially in
but excessive CaCO will cause a decrease in both
ther increase Br, but 3excessive CaCO3 will cause a decrease B r and H , especially in H .
i inc both Br and iHic, especially
c The main in
iHc. The main reason for the decrease of Br due to excessive CaCO3 is caused by too much
reason
iHc. The for the reason
main decrease Br decrease
forofthe due to excessive
of Br due CaCO 3 is caused
to excessive CaCO by too
3 is much
causednon-magnetic
by too much
non-magnetic phases in the calcined ferrite. Here, it is more appropriate to control the
phases in the calcined
non-magnetic phases ferrite. Here, it isferrite.
in the calcined more appropriate to control
Here, it is more the addition
appropriate of CaCO
to control the3
addition
at of CaCO
0.15% before 3 at 0.15% before calcination.
calcination.
addition of CaCO 3 at 0.15% before calcination.

4600
4600
4362 4355 4400
4362 4350 4400
4355 4350
4298
4580
4580
H
iH c
4298
4231
4300
4300
i c 4231 4190
(Gauss)

4563 4190 4200

BBr (Gauss)

4558 4563 4200

4560 4558
4560
i i cc
HH (Oe)

4546 4100
4542 4546 4100
4542
4540 4536
(Oe)
r

4000
4540 4536 4530 4000

Br
B
Before Calcination:
Before
La0.32SrCalcination:
0.68
Fe11.36O19
4530
3900
La0.32 Sr0.68 Fe11.36 O19 3900
4520 r After Calcination:
4520 After
Co O Calcination:
=1.8wt%, CaCO =0.8wt%, SiO2=0.45wt%
Co33O44=1.8wt%, CaCO33=0.8wt%, SiO2=0.45wt% 3800
o o 3800
Calcination Temp.=1270o C; Sintering Temp.=1230o C
Calcination Temp.=1270 C; Sintering Temp.=1230 C
4500 3700
4500
0.00 0.05 0.10 0.15 0.20 0.25 0.30 3700
0.00 0.05 0.10 0.15 0.20 0.25 0.30
CaCO3added
CaCO added Before
Before Calcination
Calcination (wt%)
(wt%)
3
Figure7.7.Dependence
Figure Dependenceof ofBBr rand
andi H
iHcc of
of the
the sintered
sintered magnet
magnet on
onthe
theamount
amountof
ofCaCO
CaCO33added
addedin
inthe
the
Figure 7. Dependence of Br and iHc of the sintered magnet on the amount of CaCO3 added in the
La 0.32Sr0.68Fe
La0.32 Fe11.36O19
0.68 11.36 19O calcined
calcined ferrite.
ferrite.
La0.32Sr0.68 Fe11.36O19 calcined ferrite.
Processes 2021,9,9,1034
Processes2021, x FOR PEER REVIEW 88ofof11
12

Forpermanent
For permanentferrite,ferrite,the
thecost
costofofLaLa2 O
2O3 used
3
usedforforproduction
productionof ofthe
themagnet
magnetaccounts
accounts
for more than 10% of the total raw material cost. This study wishes
for more than 10% of the total raw material cost. This study wishes to reduce the amount to reduce the amount
ofLa
of La22OO33 in
in the
the calcined
calcined ferrite
ferrite to
to further
further reduce
reducethe thetotal
totalcost,
cost,but
butthe
themagnetic
magneticproperties
properties
mustalso
must alsobe beconsidered.
considered.The Theeffect
effectof ofCaCO
CaCO33addedaddedbefore
beforecalcination
calcinationon onthethemagnetic
magnetic
propertiesisisdiscussed
properties discussedabove.above.In Inthis
thissection,
section,in inorder
orderto tomodify
modifythe themagnetic
magneticproperties
properties
afterreduced
after reducedLa Laininthe
thecalcined
calcinedformula,
formula, thethe influence
influence of of
CaCOCaCO 3 added
3 added after
after calcination
calcination is
is investigated. The abnormal grain growth with a severe duplex
investigated. The abnormal grain growth with a severe duplex structure is usually observed structure is usually ob-
served
in M-type in ferrites
M-typewithout
ferrites additives,
without additives,
and is more andobvious
is moreatobvious at atemperature
a sintering sintering tempera-
higher
ture 1200
than higher◦ C.than
SiO21200
can °C. SiO2 as
be used cana little
be used as a little
additive to formadditive to form
a liquid phasea forliquid phase for
suppressing
suppressing
grain growthgrain growth and
and enhancing theenhancing
coercivitythe ofcoercivity
hard ferrite of hard ferrite
[27,28]; [27,28];
however, a however,
decreaseda
decreased
sintered sintered
density density
results results inBrdecreased
in decreased . Thus, theBsimultaneous
r. Thus, the simultaneous
addition of CaCO addition
3 and of
SiO
CaCO2 after
3 and calcination
SiO 2 after is needed
calcination forismoderating
needed for grain growth
moderating inhibition
grain growth and promoting
inhibition and
the sinteredthe
promoting density [20,27,28].
sintered density It can
[20, 27,be seen
28]. from
It can be the
seenexperimental results in Figure
from the experimental results 8in
that
Figurewhile x (La
8 that content)
while x (Ladecreases from 0.32from
content) decreases to 0.30,
0.32thetooverall
0.30, the magnetic propertiesprop-
overall magnetic are
significantly improvedimproved
erties are significantly by the combined addition addition
by the combined of CaCOof 3 and
CaCO SiO 2 after
3 and SiOcalcination.
2 after calci-
When
nation. CaCO
When 3 =CaCO
0.7 wt% 3 = and SiO2 and
0.7 wt% = 0.25SiOwt% added
2 = 0.25 wt% after calcination,
added the overallthe
after calcination, magnetic
overall
properties can reach acan
magnetic properties better
reachstate, whichstate,
a better met the requirements
which of high-efficiency
met the requirements motor
of high-effi-
applications
ciency motorinapplications
automobilesinwith Br > 4600with
automobiles ± 50BGr >and4600i H±c 50
> 3600
G and ±iH50c >Oe [29].
3600 ± 50 Oe [29].

4326 4365
4640
4625 SiO2=0.45wt% 4250
4620 SiO2=0.25wt% 4613
i
Hc 3984
4000
4600 Br
Br (Gauss)

4585 3750
3852

i
Hc (Oe)
4578
4580 4586 3665
4566 3500
4560
3485
Br 3515

4540 i
Hc 4542 4537
3250

3000
Before Calcin.: La0.3Sr0.7Fe12.4O19, CaCO3=0.15wt%
4520
After Calcin.: Co3O4=1.8wt%
2862 2750
o o
Calcination Temp.=1270 C; Sintering Temp.=1230 C
4500
0.5 0.6 0.7 0.8 0.9 1.0 1.1
CaCO3 added After Calcination (wt%)
Figure8.8.Dependence
Figure DependenceofofBBr rand
andi H
iHcc of
of the
the sintered
sintered magnet
magneton
onthe
theamount
amountofofCaCO
CaCO3 3added
addedafter
afterthe
the
calcinationprocess.
calcination process.

Inorder
In order toto improve the magnetic
magnetic performance
performanceofofthe thesintered
sinteredferrite
ferritemagnet,
magnet, both
both La
and
La andCoComustmustbe be
used
usedat the same
at the sametimetimeto to
increase
increasethethereactivity
reactivityof Co 2+ with
2+ with
of Co La3+La. If3+only
. If
La isLa
only contained in theinpermanent
is contained the permanentmagnet ferrite,
magnet the effect
ferrite, of improving
the effect Br andBiH
of improving willi H
r cand not
c
will not be obvious.
be obvious. This is because
This is because when Lawhen and Co La and Co undergo
undergo a substitution
a substitution reactionreaction
in the per- in
the permanent
manent ferrite,ferrite,
the ratiotheofratio
La toofCo Laneeds
to Co to needs
reachtoareach
certain a certain value, iswhich
value, which is not
not suitable
suitable
for valuesfor which
values are
which
too are tooorlarge
large or too [3,
too small small [3,11–18].
11–18]. Past studies
Past studies usuallyusually designed
designed a cal-
acining
calcining
La-Co La-Co system
system material
material formula
formula to simultaneously
to simultaneously achieve
achieve high high
Br andBrhigh
and ihigh
Hc [3,
iH c [3,11–18].
11–18]. It should
It should be noticed
be noticed that that
this this design
design of the
of the formula
formula requires
requires thethe participationof
participation
of
thetheprecious
preciousmetal
metalelement
elementofofcobalt
cobaltto to be
be doped
doped in the calcining
calcining formula,
formula, which
whichmay may
result
result in lower production flexibility, big mass-production hazards, and greater costs.In
in lower production flexibility, big mass-production hazards, and greater costs. In
this
thisstudy,
study,cobalt
cobaltwas
wasadded
added asas
a little additive
a little additive after thethe
after calcination
calcinationprocess,
process,andand
replaced
replaced Fe
during
Fe duringthe sintering process.
the sintering FromFrom
process. the result shown
the result in Figure
shown 9, the9,
in Figure magnetic properties
the magnetic proper- of
Sr ferrite
ties of Sr are moderately
ferrite modified
are moderately by Co3 O
modified simultaneously
by4 Co 3O4 simultaneouslyaddedadded
with CaCO and SiO
with 3CaCO 3 and2
 Processes
Processes 2021,
2021, 9,
9, xx FOR
FOR PEER
PEER REVIEW
REVIEW 99 of
of 12
12
Processes 2021, 9, 1034 9 of 11

SiO
SiO22 after
after calcination.
calcination. At At aa lower
lower amount
amount of of Co
Co33O
O44 added
added after
after calcination
calcination (Co
(Co33O
O44 == 1.7
1.7
after
wt%),
wt%), calcination.
the
the goal ofAt
goal of Brra>>lower
B 4600 ±±amount
4600 50
50 G of Co
G and
and Hcc3>>O3600
iiH added
43600 50after
±± 50 Oe calcination
Oe could
could be (Co3 O4 at
be achieved
achieved =
at1.7
thewt%),
the same
same
the goal of Br > 4600 ± 50 G and i Hc > 3600 ± 50 Oe could be achieved at the same time.
time.
time.

4613
4613 4615
4615
4608
4608 4608
4608 4200
4200

4600 4593
4593
4600
4100
4100
4572
4572
3985
3985
4000
4000
4560
Br
4560 3930
3930
Br (Gauss)
3898
3898

i
Hc (Oe)
3852
3852 3900
3900
4520
4520
3765
3765 3800
3800

4480
4480
Hc
i
Before
Before Calcination:
Calcination:
3700
3700

La
La0.3 Sr
Sr0.7Fe
Fe11.6 O
O19,, CaCO
CaCO33=0.15
=0.15 wt%
wt%
0.3 0.7 11.6 19 3600
3600
3516
3516 After Calcination:
After Calcination:
4440
4440
CaCO33=0.7wt%,
CaCO =0.7wt%, SiO SiO22=0.25wt%
=0.25wt% 3500
3500
o o o o
Calcination Temp.=1270 C;
Calcination Temp.=1270 C; Sintering
Sintering Temp.=1230
Temp.=1230 CC
4400
4400 3400
3400
1.6
1.6 1.8
1.8 2.0
2.0
Co33O44 added After Calcination (wt%)
Figure 9.
Figure9.
Figure Dependence
9.Dependence of
ofBBBrrrand
Dependenceof and iH
andiiHHccc of
of the sintered
the sintered magnet
sinteredmagnet on
magneton the
onthe amount
theamount of
amountof Co
ofCo 3O
Co33O added
O444added after
addedafter the
afterthe
the
calcination
calcination process.
process.
calcination process.

Figure
Figure
Figure 10 10 presents
presents thethemicromorphology
the micromorphologyof
micromorphology ofofthe
thetheferrite
ferrite La
ferrite 0.3Sr
LaLa
0.3 Sr Sr
0.30.7
0.7 Fe
Fe Fe
11.4
0.711.4O 19 sintered
O11.4
19 mag-
O19 sintered
sintered mag-
net at
magnet 1230
at °C
1230 ◦ C with
with additive CaCO
additive CaCO = 0.7 wt%,
= 0.7 SiO
wt%, = 0.25
SiO =wt%
0.25 and
wt% Coand O Co= 1.7O wt%
= added
1.7 wt%
net at 1230 °C with additive CaCO3 = 0.7 3 3 wt%, SiO2 = 0.25
2 2 wt% and Co3O4 = 1.7 3 4 3 4wt% added
after
after calcination.
added The
The grains
after calcination.
calcination. grainsThe in the
the magnet
ingrains in theare
magnet plate-shaped,
magnet
are and
and the
are plate-shaped,
plate-shaped, the normal
normaland the direction
normal
direction of
of
direction
plate-likeof
plate-like plate-like
grains
grains grains with
harmonizes
harmonizes harmonizes
with the easywith
the easy the easy magnetization
magnetization
magnetization axis
axis (i.e.,
(i.e., C-axis).
C-axis). axisThe (i.e.,
The C-axis).
alignment
alignment
The
of alignment
of the
the pressed of
pressed the pressed
powder
powder was
was not powder
not was not
annihilated
annihilated annihilated
during
during the duringprocess
the sintering
sintering the sintering
process and
and has process
has good
good
and has good
uniformity
uniformity of uniformity
of grain
grain size of grain size approximately
size approximately
approximately smaller than 22smaller
smaller than μm; than
μm; thus,
thus, the
the 2 µm;
grains
grains thus, the grains
would
would be
be ori-
ori-
would
ented be
and oriented
grown, and
bringinggrown,
about bringing
the high about the
performance high ofperformance
the
ented and grown, bringing about the high performance of the sintering ferrite magnets, sintering of the
ferrite sintering
magnets,
ferrite
which magnets,
which can
can also
also be which
be can from
observed
observed also
frombe theobserved
the B-H from the
B-H hysteresis
hysteresis B-Hshown
curves
curves hysteresis
shown in curves
in Figure
Figure 11.shown
11. The
The mag- in
mag-
Figure
netic 11.
netic results The magnetic
results obtained
obtained in results
in this obtained
this study
study are in
are betterthis
better thanstudy are
than traditional better than
traditional Sr-La-Co traditional
Sr-La-Co ferrites ferrites [3, Sr-La-Co
[3, 16–18],
16–18],
ferrites
and
and help
help[3,16–18],
to
to achieve andthe
achieve help
the to achieve
purpose
purpose of the purpose
of high-end
high-end permanentof high-end
permanent magnets
magnets permanent
and
and large-scalemagnets
large-scale and
indus-
indus-
large-scale
trial industrial production.
trial production.
production.

Figure 10.
10. The
Figure 10. The SEM
The SEMof
SEM ofthe
of theLa
the La 0.3Sr
0.3
La 0.7Fe
Sr0.7 11.4O
Fe11.4 O1919 sintered
sintered magnet
magnet with
with additive
additive CaCO
CaCO33 == 0.7
0.7 wt%,
wt%, SiO
SiO22 ==
Figure 0.3 Sr0.7 Fe11.4 O19 sintered magnet with additive CaCO3 = 0.7 wt%,
0.25
0.25 wt%
SiO = 0.25and
wt% and
wt%Co 33O
CoandO44 ==Co
1.7
1.7Owt%
wt% addedwt%after
added
= 1.7 after
added calcination.
calcination.
after calcination.
2 3 4
Processes 2021, 9, 1034
Processes 2021, 9, x FOR PEER REVIEW 10 of 12
10 of 11

5000

4000

3000

2000
J (Gauss) 1000

-1000

-2000

-3000

-4000

-5000

-6000 -4000 -2000 0 2000 4000 6000

H (Oe)
Figure 11.
Figure 11.TheThe
B-HB-Hhysteresis curve of
hysteresis the La
curve of0.3Sr0.7Fe
the La11.4O19
0.3 Srsintered
0.7 Fe11.4magnet with additive
O19 sintered magnet CaCO 3 = additive
with
0.7 wt%, SiO2 = 0.25 wt% and Co3O4 = 1.7 wt% added after calcination.
CaCO3 = 0.7 wt%, SiO2 = 0.25 wt% and Co3 O4 = 1.7 wt% added after calcination.

4. Conclusions
Conclusions
In
In this
this study,
study,the
theferrite
ferriteformula
formulaand andprocess
process technique
technique of of
high-performance
high-performance aniso-
anisotropic
tropic Fe-deficient Sr base M-type ferrite magnets were successfully
Fe-deficient Sr base M-type ferrite magnets were successfully developed, and the developed, and themagnetic
magnetic characteristics, such as Br and iHc, were obviously ameliorated. We especially
characteristics, such as Br and i Hc , were obviously ameliorated. We especially emphasize
emphasize that the calcining material formula of LaxSr1-xFe12-2xO19 developed by this re-
that the calcining material formula of Lax Sr1-x Fe12-2x O19 developed by this research does
search does not include the precious metal cobalt, the amount of La2O3 in the calcined
not include the precious metal cobalt, the amount of La O3 in the
ferrite is small, and a little amount of the additive Co3O4 is 2added
calcined ferrite is small,
after the calcination
and a little amount of the additive
process, which overcomes high-cost technical Co 3 4 bottlenecks, such as excessive La2process,
O is added after the calcination O3 and which
overcomes
Co3O4 contained high-cost technical
in the magnet bottlenecks,
in order such
to achieve highascharacteristics
excessive La2inOthe 3 and Coand
past, 3 O4wecontained
in the magnet inimprove
comprehensively order tomagnetic
achieve characteristics
high characteristics in the past,
and production and we
efficiency. comprehensively
Besides, the
improve
incorporation magnetic
of CaCO characteristics
3, SiO2, and Coand 3O4 inproduction efficiency.
the fine-milling Besides, the
step is well-suited for incorporation
promot- of
CaCO
ing the3 ,intrinsic
SiO2 , and Co3 Oproperties,
magnetic 4 in the fine-milling
densification,stepandis possible
well-suited
grainfor promoting
uniformity of M-the intrin-
typemagnetic
sic Sr ferrite without allowing
properties, for too much
densification, grain
and growthgrain
possible and making the magnetic
uniformity of M-typepow-Sr ferrite
der moreallowing
without easily aligned
for toobymuch
the applied
grain field.
growth Theandextreme
makingutilization of thesepowder
the magnetic three addi-
more easily
tives added
aligned afterapplied
by the calcination presents
field. the opportunity
The extreme utilizationto achieve
of thesehigh
threemagnetic
additivesproperties
added after cal-
(i.e., Br = presents
cination 4608 Gauss,thebH c = 3650 Oe, iHc = 3765 Oe, and (BH)max = 5.23 MGOe) under the
opportunity to achieve high magnetic properties (i.e., Br = 4608 Gauss,
little Co3O4 addition of 1.7 wt%, which are desirable for higher-grade brushless DC motor
b Hc = 3650 Oe, i Hc = 3765 Oe, and (BH)max = 5.23 MGOe) under the little Co3 O4 addition of
applications, especially in modern electric vehicles.
1.7 wt%, which are desirable for higher-grade brushless DC motor applications, especially
Author Contributions: Conceptualization, Ching-Chien Huang and Chin-Chieh Mo; methodology,
in modern electric
Hsiao-Hsuan vehicles.
Hsu; software, Guan-Ming Chen; validation, Ching-Chien Huang and Chin-Chieh
Mo; formal analysis, Hsiao-Hsuan Hsu; investigation, Ching-Chien Huang; resources, Chin-Chieh
Mo; dataContributions:
Author curation, Chin-Chieh Mo; writing—original
Conceptualization, draftC.-C.M.;
C.-C.H. and preparation, Ching-Chien
methodology, Huang
H.-H.H.; and ; G.-M.C.;
software,
writing—review
validation, and
C.-C.H. andediting, Guo-Jiun
C.-C.M.; formal Shu; visualization,
analysis, Chin-Chieh Mo;
H.-H.H.; investigation, supervision,
C.-C.H.; Ching-
resources, C.-C.M.; data
Chien Huang
curation, and Guo-Jiun
C.-C.M.; Shu; project
writing—original administration,
draft Ching-Chien
preparation, C.-C.H.; Huang; funding
writing—review andacquisition,
editing, G.-J.S.; visu-
Chin-Chieh Mo. All authors have read and agreed to the published version of the manuscript
alization, C.-C.M.; supervision, C.-C.H. and G.-J.S.; project administration, C.-C.H.; funding acquisition,
Funding: All
C.-C.M.. Thisauthors
research received
have read no
andexternal
agreedfunding
to the published version of the manuscript.
Institutional
Funding: Review
This Boardreceived
research Statement:
noNot applicable.
external funding.
Informed Consent Statement: Not applicable.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.
Processes 2021, 9, 1034 11 of 11

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