Effect of heat treatment on magnetic properties of iron-based soft

magnetic composites with Al

2
O
3
insulation coating produced by solgel
method
Maryam Yaghtin

, Amir Hossein Taghvaei, Babak Hashemi, Kamal Janghorban

Department of Materials Science and Engineering, School of Engineering, Shiraz University, Shiraz, Iran
a r t i c l e i n f o
Article history:
Received 23 May 2013
Received in revised form 28 June 2013
Accepted 1 July 2013
Available online 18 July 2013
Keywords:
Composite materials
Solgel process
Magnetic measurements
X-ray diffraction
a b s t r a c t
In this study, inuences of the annealing process on the magnetic properties of new soft magnetic com-
posite (SMC) materials with alumina insulator coating were investigated. Iron powders were coated with
alumina by the solgel process at room temperature. The results of energy dispersive X-ray spectroscopy
(EDS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and density measurements
showed that the iron powders were uniformly coated by a thin layer of alumina coating with high ther-
mal stability. Magnetic measurements indicated that the annealing treatment increased the permeability
of the composites at low and medium frequency ranges. It was shown that the annealed composites
exhibited noticeably higher frequency stability of the magnetic permeability compared to the heat trea-
ted pure iron compacts at the same annealing temperature. The results of the loss separation implied that
the heat treatment suppressed the hysteresis loss coefcient while it increased the eddy current loss
coefcient of the SMCs. The annealed SMCs showed a lower eddy current loss and higher hysteresis loss
coefcients compared to the relaxed pure iron compacts due to the preservation of the alumina coating
after heat treatment.
2013 Elsevier B.V. All rights reserved.
1. Introduction
Recent developments in the powder metallurgy techniques
have made soft magnetic composites (SMCs) interesting for the
electromagnetic applications. These materials have very low eddy
current loss and relatively low total core loss at medium to high
frequencies [1]. Consequently, approaching the optimum electro-
magnetic loss characteristics is one of the principal goals in the
SMC designs [14]. The relatively high hysteresis loss of the SMCs
at low frequencies is an important problem and should be consid-
ered in fabrication of these materials. The hysteresis loss results
from the internal stresses introduced during the compaction pro-
cess, which leads to some cold work in the ferromagnetic particles
and therefore increases the density of defects, especially disloca-
tions. This fact hinders the movement of the magnetic domain
walls and consequently increases the hysteresis loss which is the
dominant part of the total core loss at low and medium frequency
ranges. Heat treatment at high temperatures and warm compac-
tion are two effective methods to suppress the residual stresses,
imperfections and therefore decrease the hysteresis loss of the
SMCs [2,4,5]. The reduced inner distortion of the particles by heat
treatment could signicantly decrease the coercive force and en-
hance the magnetic permeability [2]. On the other hand, high tem-
perature annealing can destroy the insulating layer and increase
the eddy current loss especially at high frequencies. Accordingly,
the insulating material should have a high thermal stability specif-
ically between 823 and 1048 K range, which is the temperature
range for stress relieving of pure iron [4]. Most of the organic coat-
ings could be decomposed or burned at these temperatures. As a
result, the inorganic coatings with high thermal resistance can be
used to keep the insulation intact upon the heat treatment and
consequently minimize the eddy current loss. Iron phosphate as
a well-known insulating material has been widely used due to its
good adhesiveness to iron and high electrical resistivity [2,5]. Nev-
ertheless, it has been shown in several researches that the iron
phosphate exhibits a low thermal stability and decomposes during
the heat treatment through the diffusion of oxygen and phospho-
rous from the coating to the iron substrate [2,5].
In this research, new kind of SMCs with alumina insulating
layer with high thermal stability were produced by solgel process.
In addition, the effect of heat treatment at different temperatures
on their microstructure and magnetic properties was investigated.
Furthermore, different components of the core loss factor were cal-
culated for the as-prepared and annealed SMCs.
0925-8388/$ - see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jallcom.2013.07.008

Corresponding author. Tel.: +98 9171046058.

E-mail address: maryamyaghtin@gmail.com (M. Yaghtin).
Journal of Alloys and Compounds 581 (2013) 293297
Contents lists available at SciVerse ScienceDirect
Journal of Alloys and Compounds
j our nal homepage: www. el sevi er . com/ l ocat e/ j al com
2. Experimental procedure
The solgel method at room temperature was used for coating the iron powders
with Al
2
O
3
insulating layer. Iron powders with an average particle size of 10 lm
were supplied by Merck. Aluminumisopropoxide (AIP, Merck), acetylacetone (AcAc,
Merck), nitric acid (Merck) and absolute ethanol were used as the precursor, stabi-
lizer, catalyst and solvent, respectively. Alumina sol was prepared by dissolving
8 wt.% aluminum isopropoxide in 100 ml ethanol. The hydrolysis of the alkoxides
is very fast, leading to the formation ne particles in the sol. This effect can be sup-
pressed by using the stabilizer in order to form a clear solution [6]. The mixture of
alumina sol and stabilizer was mixed with a magnetic stirrer for 1 hour. The iron
powders (12.4 g) were then dispersed in the freshly prepared solution using a
spiral mixer for 5 min. Then a mixture of demineralized water and ethanol (1:5
(V/V)) was added dropwise to the suspension with vigorous stirring over a period
of 15 min. The molar ratio of water to the alkoxide for the hydrolysis was 2:1. Nitric
acid was used to adjust the pH value around 4. The mixture was stirred for 1 h after
the addition of water and ethanol mixture. Subsequently, the suspension was
standing for 1 h before separation and washing with ethanol. After ve cycles of
separation/washing/redispersion with ethanol, the coated powders were dried at
348 K in air. For the calcination process, the coated powders were encapsulated
in a quartz tube under nitrogen atmosphere and heated at 773 K for 3 h.
The alumina insulated powders were pressed at 800 MPa into cylindrical shape
with diameter of 10 mm and height of 20 mm. The compaction of the powders was
performed using graphite as a die wall lubricant. Finally, the prepared composites
were annealed in air at 673 K and 873 K for 30 min.
The coated powders were characterized by scanning electron microscopy (SEM,
HITACHI-SU 70) coupled with energy dispersive X-ray spectrometer (EDS), X-ray
diffraction (XRD, Shimadzu 6000 using Cu Ka radiation) and Fourier transform
infrared spectroscopy (FTIR, Shimadzu 8000). To investigate the thermal stability
of the alumina insulating layer after heat treatment, compositional maps of alumi-
num and oxygen from the cross section of a sample annealed at 873 K were pre-
pared EDS analysis. The magnetic properties of the compacts were measured by
an inductance/ capacitance/resistance meter (LCR meter, KC-605, KDK Co. Ltd.) at
room temperature. The magnetic permeability was calculated from L/L
0
, where L
and L
0
are the inductance of the solenoid with and without core, respectively [7].
Density of the samples was measured three times using the principle of Archimedes
and the average value was reported.
3. Result and discussion
The EDS analysis of the iron powders after the coating process is
shown in Fig. 1. As the gure shows, the presence of iron, alumi-
num and oxygen peaks indicates the formation of the alumina
coating on the surface of iron particles. In addition, the comparison
between the intensity of the aluminumand oxygen peaks with that
of iron, conrms that the produced coating is thin.
In order to study the uniformity of the insulation coating, the
EDS mapping of iron, aluminum and oxygen at the cross section
of the composites was carried out (Fig. 2). As can be observed,
the aluminum and oxygen elements are distributed homoge-
neously along the particles boundary. This result conrms that a
uniform coverage of the iron powders with alumina insulating
layer is obtained by the solgel method.
Fig. 3 represents the XRD pattern of the alumina coated pow-
ders. According to JCPDS Card No. 11-0661, formation of the Bragg
peak of low intensity near two Theta of 68 can be assigned to the
(300) plane of the a-alumina coating [8]. The low intensity of this
peak indicates that the iron powders are coated with a thin layer of
alumina insulation, as previously conrmed by the EDS analysis. In
addition, the produced composites exhibit a density of 6.64 g/cm
3
which is slightly lower than that of pure iron compacts (6.85 g/
cm
3
), demonstrating that the thin alumina insulation has a negligi-
ble inuence on compressibility of the iron powders.
Furthermore, the formation of an alumina insulating layer on
the iron particles surface can be conrmed by the FTIR analysis.
The spectra of the coated powders before and after the calcination
process are shown in Fig. 4(a and b), respectively. The broad
absorption band around 3430 cm
1
is due to solgel products de-
rived from aluminum alkoxide hydrolysis and the hydroxyl groups
present on the surface of pseudo-boehmite and boehmite [911].
The bands at 3020 cm
1
and 2930 cm
1
are assigned to the asym-
metric and symmetric stretching vibrations of CH
3
and CH
2
groups
[12]. The absorption peak around 1484 cm
1
corresponds to the
bending mode of CH
2
groups. The bands at 1638 cm
1
and
1445 cm
1
are due to the asymmetric COO and symmetric COO
stretching vibrations, respectively [13]. The bands around
1100 cm
1
are related to the stretching modes of AlO
4
tetrahedra,
whereas those near 680 cm
1
are assigned to the stretching vibra-
tions of AlO
6
octahedra [12,14]. After calcination at 773 K, the
broad band of the hydroxyl groups vanished and the newband cor-
responding to the stretching vibration of the Al@O bond appeared
at 1350 cm
1
[15]. The bands found near 803 cm
-1
and 619 cm
-1
are attributed to the AlAOAAl and AlAO bonds, respectively [16].
The observed effects imply that the large thermal conversion of
the aluminum hydroxide to the alumina happened after calcina-
tion. Hence, according to the FTIR analysis, the solgel method suc-
cessfully produced an alumina insulating layer on the surface of
iron particles.
Fig. 5 shows the variations of the magnetic permeability of the
as-prepared and annealed samples versus frequency. As can be
seen, both the coating process and heat treatment have noticeable
effects on the magnetic permeability. At low frequencies, addition
of the alumina insulation slightly decreases the magnetic perme-
ability of the composites compared to that of compacts made by
the uncoated powders. The alumina coating as a non-magnetic
phase could act as the distributed air gap and enhance the internal
stray eld and consequently decreases the magnetic permeability
at low frequencies [5]. On the other hand, the composite samples
exhibit a higher permeability at higher frequencies (see Fig. 5)
due to the reduction of the demagnetizing eld corresponding to
the eddy currents. Hence, addition of the alumina insulation layer
could enhance the electrical resistivity and decrease the eddy cur-
rent loss. Fig. 5 shows also the inuence of the annealing on the
magnetic permeability of the compacts made by pure iron and
coated powders. As can be inferred, annealing increases the mag-
netic permeability of the composites at low frequency range. In
addition, the low frequency permeability of the composites in-
creases with increasing the annealing temperature. During the
compaction of the powders, plastic deformation increases the
residual stress, dislocation density and other defects in the parti-
cles microstructure. Such imperfections as the main sources of
the domain wall pinning could hinder the movement of the mag-
netic domain walls and consequently decreases the permeability.
Heat treatment at high enough temperatures can provide the
low-volume fraction of defects, reduce the dislocation density, re-
lief the residual stresses and result in the increasing of the mag-
netic permeability [2]. In contrast, according to Fig. 5, the Fig. 1. EDS analysis of the alumina coated iron powders.
294 M. Yaghtin et al. / Journal of Alloys and Compounds 581 (2013) 293297
annealed SMCs represent a lower magnetic permeability at higher
frequencies and a faster rate of permeability reduction is seen for
the higher annealing temperature. Annealing can signicantly de-
cline the electrical resistivity through decreasing the distortion,
dislocation density and residual stresses in the iron particles and
therefore increases the eddy current loss [5,17]. Hence, the an-
nealed SMCs show a lower magnetic permeability at higher fre-
quencies. As Fig. 5 shows, the annealed SMCs indicate drastically
a higher magnetic permeability almost at the whole frequency
range compared to the annealed pure iron compacts. This fact orig-
inates from the lower eddy current loss of the annealed SMCs as a
result of the stability of the alumina insulation after the annealing
which can be furthermore conrmed by the EDS analysis.
Fig. 2. The SEM image of the cross section of the composites (a) and the corresponding EDS maps of iron (b) and aluminum (c) and oxygen (d).
Fig. 3. XRD pattern of the iron powders after the coating process.
Fig. 4. FTIR spectra of the alumina coated powders: (a) before calcination and (b)
after calcination at 773 K for 3 h.
Fig. 5. Variations of the magnetic permeability versus frequency for the as-
prepared and annealed compacts.
M. Yaghtin et al. / Journal of Alloys and Compounds 581 (2013) 293297 295
Fig. 6 represents the EDS maps of aluminum and oxygen at the
cross section of the composites after annealing at 873 K for 30 min.
A homogenous distribution of the aluminum and oxygen elements
along the particles boundaries shows that the continuous alumina
insulating layer was not degraded upon annealing. This effect
proves that the new insulation coating has signicantly a higher
thermal stability compared to the other conventional coatings such
as iron phosphate insulation [8].
The magnetic losses of a core can be separated into three types
including hysteresis, eddy current and residual losses. For a circuit
with a ferromagnetic core, the total loss resistance (R
s
) can be con-
sidered as a combination of winding (R
c
), hysteresis (R
h
), eddy cur-
rent (R
e
) and residual (R
r
) components according to the series
equivalent circuit [3]. Hence, the total loss tangent can be formu-
lated as follows [7]:
tand
t

R
c
xL

R
h
xL

R
e
xL

R
r
xL
1
The loss tangent due to the winding resistance is:
tand
dc

q
c
l
w
10
9
xA
w
F
w
F
q
A
l

k
1
f
2
where q
c
is the copper resistivity, l
w
is the mean turn length, A
w
is
the cross sectional area of the winding space in the coil former, F
w
is
the copper space factor of the winding, A
l
is the inductance factor in
lH for 1 turn, f is the frequency and k
1
is the winding loss coef-
cient [7].
The hysteresis loss tangent is usually calculated by the Rayleigh
model at a weak magnetic eld as follows:
tand
h

4m
^
b
3pl
0
l
2
a
g
b
^
b k
2
3
where m is the Rayleigh coefcient, l
0
is the permeability of vac-
uum, l
a
is the amplitude permeability at a low applied eld and
k
2
is the hysteresis loss coefcient [7,18]. Hence, for a constant
maximum induction
^
b, the hysteresis loss factor is a constant inde-
pendent of the frequency.
The loss factor corresponding to the eddy currents without con-
sideration of the magnetic domain structure is:
tand
e

l
0
lD
2
x
2qb
k
3
f 4
where D is core diameter, b is the shape factor, k
3
is the eddy cur-
rent loss coefcient and q is the specic electrical resistivity [7].
As the equation indicates, the eddy current loss factor has a linear
relationship by frequency with the slope corresponding to the eddy
current loss coefcient.
The residual or excess contribution of the total loss factor can be
determined by the extrapolation of the maximum induction to
zero and subtraction of the eddy current loss from the total core
loss [3]. The excess loss has different contributions depending on
the working frequency. At high frequency range, the main contri-
butions to the excess loss factor arise from the ferromagnetic res-
onance and domain wall resonance [3]. However, at lower
frequencies, the main contribution of the excess loss originates
from the micro eddy currents produced at the domain walls which
could be neglected compared to the eddy current loss factor (Eq.
(4)) [7].
The total loss factor is obtained by adding the mentioned com-
ponents as [7]:
tand
tot
tand
dc
tand
h
tand
e
tand
r
5
or
tand
tot

k
1
f
k
2
k
3
f k
4
f 6
Fig. 7 shows the variations of the total loss factor of the as-pre-
pared and annealed samples versus frequency. It is obviously seen
that the total loss factor suddenly decreases to a minimum value at
low frequencies and then increases gradually by increasing the fre-
quency. At low frequencies, the winding loss which is proportional
to reciprocal of the frequency is dominant (Eq. (6)). However, this
part of the total loss factor is the same for all samples because of
the same winding parameters used in all of the measurements.
At higher frequencies, the total loss is dominated by one or more
of the other components.
Fig. 8 depicts the variations of core loss factors of the as-pre-
pared and heat treated compacts with frequency. To calculate the
core loss factor, the winding loss factor which is prevailing at very
low frequencies can be subtracted from the total loss factor.
According to Fig. 8, the core loss factor exhibits nearly a linear rela-
Fig. 6. The SEM image of the composites after annealing at 873 K for 30 min (a) and the X-ray maps of aluminum (b) and oxygen (c) at the cross section.
Fig. 7. Total loss factors of the as-prepared and annealed samples at different
frequencies.
296 M. Yaghtin et al. / Journal of Alloys and Compounds 581 (2013) 293297
tion with frequency for all samples. Regarding to this fact and the
linear relationship of the eddy current loss factor with frequency
(Eq. (6)), the slope of each line in Fig. 8 may indicate the eddy cur-
rent loss coefcient (k
3
). In addition, by extrapolation of the men-
tioned lines to zero frequency, the hysteresis part of the core loss
can be determined.
Table 1 lists the loss coefcients of the as-prepared and an-
nealed samples at different temperatures. According to Table 1,
the hysteresis loss coefcient is lower for the annealed SMCs and
its value decreases with increase of the annealing temperature.
The suppression of the hysteresis loss coefcient results from the
stress relieving and decreasing the dislocation density by the
annealing process [5]. From Table 1, the annealed pure iron com-
pacts exhibit a lower hysteresis loss coefcient compared to the
SMCs annealed at the same temperature. The existence of the alu-
mina insulation even after annealing at 873 K (see Fig. 6) as a non-
magnetic phase increases the internal stray eld and consequently
the hysteresis loss coefcient. The results are in a good agreement
with the permeability variations at very low frequencies (Fig. 5). As
can be seen, the pure iron compact after annealing at 873 K has the
highest permeability besides its lowest hysteresis loss coefcient.
In contrast, the annealing process increases the core loss factor at
higher frequencies (Fig. 8) and the core loss factor enhancement in-
creases with increase of the annealing temperature. At high fre-
quencies, the core loss factor can be described by the eddy
current loss factor which has an inverse relation with electrical
resistivity (Eq. (4)). The increase of the core loss by annealing at
high frequencies results in increasing the eddy current loss
coefcient according to Table 1. As explained before, the annealing
treatment can decrease the particles distortion produced during
the compaction step and consequently decrease the electrical
resistivity. This effect leads to increasing the eddy loss coefcient
of the SMCs after the heat treatment. Table 1 shows that the an-
nealed SMCs exhibit a lower eddy current loss coefcient in com-
parison with the heat treated pure iron compacts. This
additionally proves that the alumina insulation remains intact
upon the annealing (see Fig. 6) and contributes effectively to
decreasing the eddy current loss factor of the composites.
4. Conclusion
In this work, effect of heat treatment on the microstructure and
magnetic properties of the soft magnetic composites (SMCs) with
the alumina insulation was investigated. Furthermore, different
components of the magnetic loss factor were calculated by a loss
separation method for the as-prepared and annealed samples.
The following conclusions could be drawn:
1. Coating of the iron particles was carried out successfully by the
solgel method. The EDS, XRD, and FTIR spectra proved that the
iron particles were uniformly covered with alumina insulation.
2. Results of the FTIR and EDS analyses showed that alumina insu-
lation had a high thermal stability and the SMCs produced with
this insulation could be annealed at high temperatures without
any considerable degradation of the insulating layer.
3. Annealing treatment increased the permeability of the compos-
ites at low and medium frequency ranges. The annealed com-
posites exhibited signicantly higher frequency stability of the
magnetic permeability compared to the heat treated pure iron
compacts.
4. The results of the loss separation indicated that the annealing
treatment decreased the hysteresis loss coefcient while it
enhanced the eddy current loss coefcient of the SMCs.
5. The preservation of the alumina insulation upon the heat treat-
ment resulted in lower eddy current loss and higher hysteresis
loss coefcients of the annealed SMCs in comparison with the
heat treated pure iron compacts.
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Fig. 8. The variations of the core loss factor with frequency for the as-prepared and
annealed samples.
Table 1
The hysteresis and eddy current loss coefcients of the as-prepared and annealed
compacts at different annealing temperatures.
SMCs Hysteresis loss
coefcient, K
2
Eddy current loss
coefcient, K
3
Pure Fe, annealed at
873 K
0.0012 4.16 10
6
Coated Fe, without
annealing
0.0026 1.95 10
6
Coated Fe, annealed at
673 K
0.0019 3.47 10
6
Coated Fe, annealed at
873 K
0.0016 3.66 10
6
M. Yaghtin et al. / Journal of Alloys and Compounds 581 (2013) 293297 297