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Complex permittivity, permeability and wide

band microwave absorbing property of La3+
substituted U-type hexaferrite
Article in Journal of Magnetism and Magnetic Materials July 2010
DOI: 10.1016/j.jmmm.2010.01.008

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Contents lists available at ScienceDirect

Journal of Magnetism and Magnetic Materials

journal homepage: www.elsevier.com/locate/jmmm

Complex permittivity, permeability and wide band microwave absorbing

property of La3 + substituted U-type hexaferrite
R.S. Meena, Sudeshna Bhattachrya 1, Ratnamala Chatterjee n
Department of Physics, Indian Institute of Technology Delhi, Hauz Khas, New Delhi-110016, India

a r t i c l e in fo

abstract

Article history:
Received 31 August 2009
Received in revised form
16 December 2009
Available online 21 January 2010

Polycrystalline samples of U-type hexaferrite series: (Ba1  3xLa2x)4Co2Fe36O60 with 0.10 r xr 0.20 in
step of 0.05, are prepared by conventional solid state reaction route. Partial substitution of Ba2 + ions
with La3 + ions enhances the electron hopping and reduces the magnetic interaction in the samples over
the entire X-band frequencies; leading to wide band microwave absorption in all sample. Relative
complex permittivity (er = e0  je00 ) and permeability (mr = m0  jm00 ) of the prepared samples were
measured using Vector Network Analyzer (VNA, Agilent PNA-L N5230A) for X-band (8.212.4 GHz)
frequency range. The maximum absorption of 99.8% was obtained for x= 0.10 sample for thickness
tm =1.8 mm and all sample showed absorption Z 96%. The reection loss (RL) calculated using the
measured parameter (er = e0  je00 and mr = m0  jm00 ) shows good agreement when compared with the
return loss measured directly using VNA for sample x= 0.20. The material can be expected to nd
relevance in suppression of electromagnetic interference (EMI) shielding and reduction of radar
signatures.
& 2010 Elsevier B.V. All rights reserved.

Keywords:
Complex permittivity
Complex permeability
Microwave absorption
U-type hexaferrite

1. Introduction
Electromagnetic interference (EMI) refers to any unwanted,
spurious, conducted, or radiated signal of electric or magnetic origin
that can cause unacceptable degradation of system performance.
With the rapid advances and broad implementation of computer
and telecommunications technology, and with the ongoing
miniaturization of electronic equipments, there is an increased
functionality of microwave absorbing materials [1] that can provide
effective shielding of EMI, especially in microwave (MW) frequency
range. Electromagnetic (EM) wave absorbers are rapidly increasing
in visibility because of their two-fold applications in EMI shielding
and counter measure to radar detection, i.e., stealth technology. Out
of various types of materials, the magnetic absorber is considered to
be the preeminent one. These materials show higher losses due to
the co-existence of dielectric and magnetic loss simultaneously
[14]. The magnetic materials exist in different structures, like
spinel-ferrite, hexaferrite, garnet and orthoferrites. Out of these, the
hexaferrites, which are soft magnetic materials with planar
magnetic anisotropy, are of great interest for use.
The hexaferrites are ferrites with complex crystal structure of
AOFe2O3MeO, known as magnetoplumbite structure, where
A= Ba, Sr, Ca, or La and Me= a bivalent transition metal. The

Corresponding author. Tel.: + 91 11 2659 1354; fax: + 91 11 2658 1114.

E-mail address: ratnamalac@gmail.com (R. Chatterjee).
1
Present address: Department of Astrophysics, Delhi University, Delhi, India.

0304-8853/$ - see front matter & 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmmm.2010.01.008

different stable phases of hexaferrites, in the increasing order of

complexity are M, Y, W, Z, X and U [46]. Out of these, the U-type
hexaferrite Ba4Me2Fe36O60 has most complex crystal structure
and largest unit cell size, and is least studied. A systematic study
of this class of hexaferrite, regarding proper phase formation,
thermal stability and MW properties was carried by Lisjak et al.
[713]. The higher complexity and larger unit cell size helps to
achieve higher MW absorption over wide band frequencies.
Ferromagnetic resonance frequency in hexaferrites is increased
by their anisotropic properties and thus these can be tailored to
dissipate electromagnetic energy in MW frequencies.
The EM properties of magnetic materials can be tailored very
easily and widely by doping different transition and rare earth
metals. The variation of EM as well as MW absorbing properties
with different metallic ions have been studied extensively in
spinel-ferrites and hexaferrites [414], but variation of these
properties with varying base ions (Ba in barium hexaferrite) has
been rarely reported [1517]. In the current work, we substitute
the base ion Ba2 + by La3 + keeping the metallic ion constant, in a
series of U-type hexaferrite: (Ba1  3xLa2x)4Co2Fe36O60, where
x= 0.10, 0.15 and 0.20. Here, we present the results of EM
properties and MW absorption studies on this series with low
La substitution. Literature on La substituted M-barium hexaferrites [17] and Co2Z-type hexaferrites [15] indicate that the
addition of higher content of Lanthanum (x 40.20) results in the
formation of a secondary phase of Lanthanum orthoferrites.
The fascinating feature of this composition lies in the large
difference between ionic radii of base ions Ba2 + (149 pm) and

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La3 + (117 pm). This difference may result in a change in both

strength and direction of the dipole moment (resulting between
the cations Ba2 + , La3 + , Co2 + , Fe2 + and Fe3 + and anion O2  ). The
atomic distances between the magnetic moment producing ions
Fe2 + , Fe3 + and Co2 + can also be anticipated to change as a
consequence of this base ion radii difference. As a result, the
amount of exchange interaction between different magnetic
moments changes and this may vary the total magnetization. In
this work, we demonstrate that wide band microwave absorption
that is tunable over entire X-band frequency range can be
achieved by partial substitution of Ba2 + ions with La3 + ions.

so as to t exactly into a rectangular waveguide of X-band

(WR90). The thickness of the pellets varied from 2 to 4 mm. The
pellets were nally sintered at 1260 1C for 4 h with a slow heating
and cooling rate (r0.0138 1C/s.).
The complex permittivity (er = e0  je00 ) and permeability
(mr = m0 jm00 ) were measured using Vector Network Analyzer
(VNA, Agilent PNA-L N5230A). The EM parameters (e0 , e00 , m0 and
m00 ) were then calculated by a material measurement software
(Agilent software module 85071 loaded in the VNA) [4,18]. Using
these EM parameters, the reection loss (RL) was calculated and
MW absorbing properties were determined.

2. Experimentation

3. Results and discussion

The U-type Bahexaferrite compositions: (Ba1  3xLa2x)4Co2Fe36O60, with x varying from 0.10 to 0.20 in step of 0.05 have
been prepared by conventional solid state reaction route [813].
The raw materials used were barium carbonate (99% Aldrich USA),
ferric oxide (99.4% CDH India), cobalt oxide (98.5% CDH India) and
Lanthanum oxide (99% Aldrich USA). The powders were weighed
in stoichiometric proportions and were mixed in acetone medium
for 20 h using wet ball milling technique. This mixture was then
dried and grinded, and was followed by subsequent calcination at
1250 1C for 4 h, resulting in the formation of hexaferrite phase.
Phase formation was established by X-ray diffraction (XRD)
technique. The calcined powder was further grinded and mixed
with 3% of poly vinyl alcohol (PVA). This dry mixture of calcined
powder with PVA was grinded again and sieved through a mesh to
acquire particle size r50 mm. The resulting powder was
compressed in a piston cylinder assembly under a pressure of
20 kPa and cast into rectangular pellets of size 10.26  22.86 mm2,

Fig. 1 shows the X-ray diffractograms (XRD) of sintered pellets

for all compositions of the series. All the peaks in the diffraction
pattern have been indexed and the renement of lattice
parameter was done using Xpowder software [14]. The peaks
and Miller indices {h k l} are matched with those of previously
reported XRD patterns of U-type hexaferrites [712]. No extra
peaks belonging to any other phase could be identied. For the
indexed planes, the difference between observed and calculated
values of d, i.e., dobs and dcal is minimum (i.e. SDd = D(dobs  dcal)
and is o0.001 A for all shown indices). The value of lattice
parameters a and c of hexagonal structure, as determined from
X-ray analysis are shown in Table 1. These values match well with
the previously reported values of a = 5.88 A and c =113 A for
U-type hexaferrite [812]. As some of the Ba2 + ions are replaced
with La3 + ions in the compositions designated in Table 1 by
x= 0.10, 0.15 and 0.20; a reduction in lattice parameters a & c are
observed with increasing x. However, the c/a ratios are seen to

Fig. 1. X-ray diffractogram for all samples.

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Table 1
Values of lattice parameters (a and c) and density for all compositions.
x

a (A)

c (A)

c/a

Density d (g/cm3)

X-ray density dx (g/cm3)

Porosity P (%)

0.10
0.15
0.20

5.8815
5.8796
5.8756

112.9943
112.9930
112.9442

19.2118
19.2178
19.2225

4.74
4.43
4.37

5.27
5.23
5.20

10.05
15.29
15.96

Fig. 2. Scanning electron micrograph (SEM) for x =0.20.

increase with increasing x; possibly caused by the partial

replacement of Ba2 + (149 pm) ion with the smaller La3 + (ionic
radius 117 pm) ions.
The X-ray density dx was calculated using the known formula
for hexagonal structure:
2nM
dx p
3Na a2 c

Here n (3 for U-type phase [812]) is the number of molecules per

unit cell, Na is Avogadros number per gram mole, a and c are the
lattice constants obtained from X-ray diffraction analysis and M is
the molecular weight of the sample. As evident from Table 1, the
calculated X-ray density closely matches the theoretical density
(  5.3 g/cm3) reported previously for hexagonal structure [812].
The porosities of the samples were calculated using the relation:


dx d
 100%
2
P
dx
The compositional dependence of the apparent density d,
X-ray density dx and porosity P for the prepared compositions are
also tabulated in Table 1. The apparent density d, as measured by
Archimedes principle, is obtained to be maximum in sample with
x =0.10, i.e., 91.69% and minimum in x = 0.20, i.e., 82.45% of the
theoretical density (  5.3 g/cm3).
Fig. 2 shows a representative scanning electron micrograph
(SEM) for sample with x= 0.20. The micrograph clearly illustrates
hexagonal platelet structure. The average grain size varies from 8
to 20 mm as revealed from the micrograph. The micrographs taken
for other samples also show similar features and no
microstructure change is seen with La3 + substitution.
Figs. 3(a) and (b) show the variation of real and imaginary parts
of complex permittivity (er = e0 je00 ) in X-band frequencies for
different compositions of U-type hexaferrite. The average value of

Fig. 3. Complex permittivity spectra: (a) real part e0 and (b) imaginary part e00 .

electric polarization e0 and dielectric loss e00 rises continuously with

La3 + addition. The addition of Lanthanum in Barium hexaferrites
results into partial replacement of Ba2 + ion sites by La3 + ions,
which further results into partial conversion of Fe3 + ions into Fe2 +
ions, governed by the charge balancing in the form of Ba2 + +Fe3 + La3 + +Fe2 + . As a consequence of this phenomenon, every La3 + ion
introduced in the U-type hexaferrite structure, in turn introduces
one Fe2 + ion in place of Fe3 + ion. This leads to hopping conduction
resulting from hopping of electrons between Fe2 + and Fe3 + in these
lattice sites. As evident from Fig. 3, this hopping mechanism results

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into increment of both dielectric polarization and dielectric loss

[15,16] with x. An important feature to note is that both dielectric
polarization (e0 ) and dielectric loss (e00 ) spectra are almost at in the
complete X-band frequency range in all compositions (x=0.10, 0.15
and 0.20).
The real (m0 ) and imaginary (m00 ) parts of complex permeability
mr = m0  jm00 for different compositions are shown in Figs. 4(a) and
(b), respectively. A small ferromagnetic resonance peak is
observed around 8.7 GHz. However, this peak is very small in
the sample x =0.20. Both magnetic permeability m0 and magnetic
loss m00 decrease with La3 + addition and also with frequency; but
the fall in magnetization with frequency is very steep. The
decrease in magnetic permeability m0 is ascribed to the partial
conversion of Fe3 + to Fe2 + with increase in La3 + content; the
contribution of Fe2 + (4 mB) ion to the total magnetic moment is
lower than that of Fe3 + (5 mB) ion [15,16]. Thus, the overall
magnetic interaction weakens in our samples with increasing
La3 + content and due to the weakening of magnetic interactions
in the samples with increasing x, the values of m0 and m00 evidently
decrease with increase of La3 + content.

4. Microwave absorption
Measured values of e0 , e00 ,m0 and m00 are used to determine the
reection loss (RL) based on a model of single-layered plane wave
absorber, proposed by Naito and Sutake [19]. In this model, the
wave impedance (Z) at airabsorber interface is given as
r



mr
j2p p
3
Zm Z0
mr er ft
tanh

er
c
where mr = m0  jm00 and er = e0  je00 are, respectively, the relative
complex permeability and permittivity of the absorber medium.
Z0( =377 O) and f are wave impedance and frequency, respectively, in free space. c is the speed of light and t is the sample
thickness. The reection loss (RL) in decibels (dB) is then
determined as


Zm Z0
4
RL 20 log10
Zm Z0
The impedance matching condition is given by Z= Z0, where the
incident wave is perfectly absorbed. This condition is satised at a
particular matching thickness (tm) and matching frequency (fm),
where minimum reection loss occurs. When the thickness of
absorber is equal to one quarter of wavelength, as given by Eq. (5),
the wave reected at the airabsorber interface is out of phase
with the wave reected at absorbermetal interface:
tm

Fig. 4. Complex permeability spectra: (a) real part m0 and (b) imaginary part m00 .

la
4

c
p
4f0 mr er

where la is the wavelength distance inside the absorber, f0 the

free space frequency of incident wave.
The reection loss spectra RL for different compositions are
shown in Figs. 5(a)(c). The loss was calculated for different
thicknesses to obtain the optimum thickness (tm), which shows the
maximum absorption. The most interesting feature in these gures
is that the wide band absorption is observed for all compositions
and the peak of absorption curves shift to higher frequency with
decreasing sample thickness. As shown in Fig. 5(a), minimum
reection loss of RL =  27 dB (99.8% absorption) was observed for
sample with x=0.10 with a thickness of 1.8 mm. For x=0.15 and
0.20, the corresponding values are RL =  14 dB (96% absorption) for
tm =1.6 mm and RL =  16 dB (97%, absorption) for tm =1.4 mm,
respectively. Table 2 lists the values of peak absorption and
absorption bandwidth for all samples at different thicknesses.
The dominating factor for large absorption in sample with
x= 0.10 is magnetic loss whereas, in x =0.20, it is due to high
dielectric loss. In all samples, the EM parameters are
nearly constant throughout the X-band and hence the interface
impedance Zm does not change with frequency. As a result, the
impedance matching condition remains constant and similar
absorption behavior is obtained for measured compositions over a
wide range. In these samples, the peak of absorption exists at a
sample thickness t = la/4 and shifts on thickness variation such
that the product (tmnfm) remains constant.
The values of bandwidth shown in Table 2 are for  10 dB
absorption. The maximum value of bandwidth is 3.54 GHz in
sample x =0.10 when the sample thickness is 1.5 mm. For  10 dB
reference the absorption is more than 90% (or RL r 10 dB) over
the entire bandwidth. This sample is most suitable for MW
absorption in X-band frequency range.
The calculated reection loss was compared with the actual
loss incurred in a sample, by measuring the return loss (given by
the S11 parameter when the short circuited single port set up
used) in the representative sample x= 0.20. The results of loss
measurements performed on this sample for varying thicknesses
are shown in Fig. 6. The peak of absorption can be seen to shift
towards higher frequency as the sample thickness is decreased

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1927

Table 2
Values of peak absorption (RL) and bandwidths for all compositions.
x

t (mm)

0.10
0.10
0.10
0.15
0.20
0.20

1.5
1.6
1.8
1.6
1.4
1.5

Peak value

 10 dB Bandwidth (GHz)

RL (dB)

fm (GHz)

 21.03
 23.17
 27.8
 13.68
 16.25
 15.68

10.63
9.79
8.53
10.63
10.97
10.20

3.54
2.36

2.10
2.30

Fig. 6. Measured reection loss for different thicknesses in sample x= 0.20.

maximum in sample with x= 0.10. The absorption is tunable and

it shifts towards lower frequency in the X-band with increasing
thickness of the sample. The results of calculated and experimentally observed absorption curves match very well in the X-band
frequency range.

References

Fig. 5. Reection loss spectra RL for composition (a) x= 0.10, (b) x = 0.15 and
(c) x = 0.20.

from 2.0 to 1.45 mm as expected from the calculated absorption

spectra for the same sample, shown in Fig. 5c.

5. Conclusions
This work demonstrates wide-band absorption of microwaves
over the X-band frequency range on Lanthanum substituted
Barium U-type hexaferrite. The results show that the replacement
of Barium ion with Lanthanum in U-type hexaferrite increases the
number of Fe2 + ion and enhances the electron hopping, which
in turn increases the microwave absorption over the complete
X-band frequencies. The  10 dB bandwidth of 3.54 GHz is

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