Materials Science and Engineering B78 (2000) 70 – 74

www.elsevier.com/locate/mseb

Microwave absorption studies of Ca–NiTi hexaferrite composites

in X-band
Praveen Singh a,*, V.K. Babbar b, Archana Razdan b, S.L. Srivastava c, T.C. Goel a
a
Department of Physics, I.I.T, New Delhi, India
b
Department of Applied Physics, G.N.D. Uni6ersity, Amritsar, India
c
Department of Physics, Allahabad Uni6ersity, Allahabad, India

Received 28 June 2000; received in revised form 3 July 2000; accepted 15 August 2000

Abstract

The effect of Ni2 + Ti4 + substitution on complex permeability, permittivity and microwave absorption has been studied for
[Ca(NiTi)x Fe12-2x O19]96.0[La2O3]4.0 ferrite–polymer composites, wherein x varies from 0.0 to 1.0 in steps of 0.2, in frequency range
from 8.0 to 12.4 GHz. The ferrite-composites with x \0.0 exhibit significant dispersion in complex permittivity (o%-jo%%) with
maximum value of o%% observed for x=0.6. The dispersion in complex permeability (m%-jm%%) is not significant and is attributed to
the shielding effect of polymer matrix over the ferrite crystallites. The variation of reflection loss has been studied as a function
of frequency ( f ), Ni2 + Ti4 + content (x) and thickness of the absorber. A minimum reflection loss of −30.0 dB is obtained for
composite with x=0.4 and an absorber thickness of 4.15 mm. The experimental values of the matching frequency and the
matching thickness agree well with the theoretical values obtained by solving the equations numerically. © 2000 Elsevier Science
S.A. All rights reserved.

Keywords: Microwave absorbers; Reflection loss; Hexaferrites

1. Introduction crowave [6] and the influence of the addition of con-

In the development of ferrite based microwave ab-
sorbers, the M-type hexagonal ferrites are of impor-
tance to extend the range of microwave absorbers to a
higher frequency region of X-band [1]. These ferrites
absorb microwaves due to various interactive loss pro-
cesses of magnetization and polarization in the mate-
rial. The complex permeability (m%-jm%%) and permittivity
(o%-jo%%) of the constituent material of the microwave
absorbers determine the reflection and attenuation
characteristics of the investigated material. In case of
ferrite–epoxy composites, a number of investigations
had reported [1– 5] the effect of composition on their
microwave properties. Many studies were carried out to
investigate the effects of ferrite materials and its volume
percentage in the composite on absorption of mi-
* Corresponding author. Present address. Biophysics, EM & I
Section, Indian Veterinary Research Institute, Izatnagar-243122,
U.P., India. Tel.: + 91-581-442313; fax: + 91-851-447284.
E-mail address: psingh@ivri.up.nic.in (P. Singh).
ducting fiber [7] on the microwave absorbing properties.
The present work is aimed at finding the optimum
amount of Ni2 + Ti4 + ions to be substituted in
CaFe12O19 hexaferrite in order to yield a minimum
reflection loss over broad frequencies and also to inves-
tigate the quantitative relationship between magnetic
and dielectric characteristics of ferrite–epoxy composite
and its microwave absorbing properties in the X-band
frequencies. Theoretically determined frequency for
matched impedance was compared with experimental
value of frequency corresponding to minimum loss.
Two important conditions are to be satisfied by lossy
materials. The first is ‘matched characteristics
impedance’ in which the intrinsic impedance of material
is made equal to intrinsic impedance of free space. This
entails making the dielectric constant and magnetic
permeability of the material equal to each other. Sec-
ond, the incident electromagnetic wave must enter and
get attenuated rapidly through the material layer, thus
reducing the emerging wave to an acceptably low
magnitude.

0921-5107/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 9 2 1 - 5 1 0 7 ( 0 0 ) 0 0 5 1 1 - 0
 P. Singh et al. / Materials Science and Engineering B78 (2000) 70–74
2. Experiments
It had been reported that [8] anisotropic calcium
hexaferrite CaO.6Fe2O3 with magnetoplumbite struc-
ture and optimum ferromagnetic properties can be pre-
pared only by substituting 4.0 wt.% of La2O3 to yield
[CaO.6Fe2O3]96.0[La2O3]4.0 composition. A series of
samples was prepared by the conventional solid state
reaction method with composition [Ca(NiTi)x Fe(12-2x)
O19]96.0[La2O3]4.0 wherein x varies from 0.0 to 1.0 in
steps of 0.2. The samples were synthesized from stoi-
chiometric mixtures of Fe2O3, CaCO3, NiO, TiO2 and
La2O3 of 99.9% purity by pulverizing each sample and
heating in the air at 1000°C for 2 h. The presintered
materials were thoroughly ground and cold pressed into
pallets and were finally sintered at 1180°C for 3 h.
X-ray diffraction analyses of few typical samples were
made by using Cu – ka radiation from Rigaku-Denki
X-ray diffractometer which confirmed magneto-
plumbite type of crystal structure for these samples.
The ferrite–epoxy composites were prepared by ho-
mogeneously mixing the ferrite powder with 90% epoxy
resin (EPG 280) and 10% hardener (No. 10). The
hexaferrite composites of thickness 2.0, 3.0 and 4.0
mm were prepared by Perspex dies of rectangular shape
and size so as to fit exactly into the coaxial cavity of the
X-band microwave bench. These samples were cured at
80°C for 2 h and coated on thin aluminium substrate.
The variations of reflection loss versus frequency were
studied by measuring Voltage Standing Wave Ratio in
the X-band on microwave bench.
To measure the complex relative permeability (m%,
m%%) of these ferrite composites, toroidal shaped samples
of 3.5 mm outer diameter and 1.5 mm inner diameter
were prepared. The samples were prepared with 50%
(wt.%) ferrite loading in epoxy resin. The measurements
of o%, o%%, m% and m%% versus frequency were made by
reflection/ transmission technique using a calibrated
Hewlett Packard Network Analyser Model HP 8510B.
The test samples of toroidal shape were tightly inserted
into the standard coaxial line of 15 cm air length and
used to measure reflected and transmitted scattering
parameters (S11, S21). The values of o%, o%%, m% and m%%
parameters were calculated for all these composite sam-
ples [9].
3. Results and discussion
3.1. Dielectric and magnetic parameters
The frequency dependence of o% and o%% for Ca–M
hexaferrite–polymer composites with Ni2 + Ti4 + con-
tent, x = 0.2, 0.4 and 0.6 is shown in Fig. 1. The real
part of permittivity (o%) decreases from 3.5 at 8.0 GHz
to 3.4 at 12.4 GHz for the composite with x=0.0.
71
However, for composites, x= 0.2, 0.4 and 0.6, there is
a significant decrease in the values of the o% with
frequency. The values of o%% increase with frequency for
all three composites. The ferrite–polymer composites
(x=0.2, 0.4, 0.6) show higher values of dielectric loss
(o%%) from 8.0 to 12.4 GHz whereas for composites,
x= 0.0, the dielectric loss (o%%) increases from 11.0 GHz
onwards as shown in Fig. 1. The dielectric properties of
polycrystalline ferrite–polymer composites arise mainly
due to the interfacial polarization along with some
contribution from ionic polarization and intrinsic elec-
tric dipole polarization. The interfacial polarization re-
sults from the heterogeneous structure of ferrites
comprising low conductivity grains separated by the
higher resistivity grain boundaries as proposed by
Koops [10]. The higher values of o% for composites with
x= 0.2, 0.4 and 0.6 may be due to significant contribu-
tions of Fe3 + and as well as Ni2 + Ti4 + complexes to
interfacial polarization. The permittivity (o%-jo%%) shows a
small variation among the different substituted ferrite–
polymer composites. The dielectric loss increases very
slightly for higher values of x where the number of
Fe3 + ions is reduced. The permeability (m%-jm%%) of the
composites shows less variation in the values of m% and
m%% in the X-band. The real part of permeability m%
varies between 1.2 and 1.4 for these composites as
shown in Fig. 2. The imaginary part of m%% shows a
small peak between 11.0 and 11.8 GHz. The magnetic
behaviour of composite primarily depends on the
hexagonal ferrites used as magnetic filler. The variation
in the magnetic spectra is attributed to the mechanism
of natural magnetic resonance and domain wall turn-
ing. In the weak alternative magnetic field, domain wall
turning is the dominant magnetization process. More
over, the crystallites of ferrites are enveloped by non-
magnetic coating of epoxy resin which enhances the
Fig. 1. Variations of o% and o%% as a function of frequency for [Ca
(NiTi)x Fe12-2x O19] 96.0[La2O3]4.0 hexaferrite composites for x =0.2,
0.4, 0.6, respectively.
72 P. Singh et al. / Materials Science and Engineering B78 (2000) 70–74
Fig. 2. Variations of m% and m%% as a function of frequency for [Ca
(NiTi)x Fe12-2x O19]96.0[La2O3]4.0 hexaferrite composites for x =0.2,
0.4, 0.6, respectively.
effective reluctance of the composite thus resulting in
the weak dispersion phenomenon in the spectra of m%%
[11]. The relations expressing the resonance – relaxation
phenomena near the characteristics frequency of spin
rotation or domain wall displacement are given by
Ishino et al. [12]. The effective magnetic spectra of
composites have been described in a model by Slama et
al. [11] which attempts to predict effective permeability,
susceptibility of composites by taking into account the
grain and matrix reluctance’s and their dimension
parameters.
3.2. Microwa6e absorbing properties
The normalized input impedance of a microwave
absorbing layer backed by reflector at the absorber
surface (Zin) is given by [6]:
Zin =Zi/Zo = (mr/or)1/2 tanh [j2p/C (mo)1/2 f.d], (1)
where Zi and Zo are the impedances of absorber and
that of free space respectively, m and o are relative
permeability and permittivity of medium, C is the ve-
locity of light in free space, f is the frequency of the
microwave in free space and d is the thickness of an
absorber. The reflection loss is related to Zin as follows:
Fig. 3. Microwave absorption behaviour of the composites (x= 0.2,
0.4, 0.6) at different matching thickness.
the decrease of anisotropy field with increased substitu-
tion of Ni2 + Ti4 + complex [4].
The comparison of reflection loss measured and cal-
culated for the composites (x= 0.4) with thickness 4.15
mm is shown in Fig. 4. The measured curve is in
accordance with theoretical calculations. The measured
curve does not fit exactly on the theoretical curve. The
difference in the measured values is attributed to the
reflections caused by the mismatch from various com-
ponents of waveguide, the surface irregularity of ab-
sorbing sample, the gap between the sample and
waveguide dimensions and unstabilized frequency
source of microwave bench.
In M-type hexagonal ferrite, the substitution of non-
magnetic ionic complexes lowers the anisotropy field
which results in lowering of natural resonance frequen-
cies [1]. This also results in decrease of matching fre-
Reflection loss [dB]=20 log10 ((Zin – 1)/(Zin +1)) (2)
Thus, surface reflectance of an absorber is a function of
six characteristics parameters, e.g. f, d, m%, m%%, o% and o%%.
It is possible to evaluate the numerical values of the
parameters corresponding to the condition of zero
reflection (Zin = 1.0). The values of reflection loss calcu-
lated by using Eqs. 1 – 2 for various measured values of
m%, m%%, o% and o%% is shown in Fig. 3 for composites with
x =0.2, 0.4 and 0.6, respectively. The minimum reflec-
tion point shifts slightly to lower frequencies with in- Fig. 4. The comparison of theoretical and experimentally measured
crease of Ni2 + Ti4 + content, which is consistent with values of reflection loss with frequency.
 P. Singh et al. / Materials Science and Engineering B78 (2000) 70–74
Fig. 5. The Matching frequency nM as a function of the chemical
composition x of the M-ferrite (CaNix Tix Fe12-2x O19).
quency (nm) as observed for these composites and as
shown in Fig. 5. The values of m%, m%%, o% and o%% for these
composites (x= 0.2, 0.4, 0.6) are almost comparable to
each other in the entire measured frequency region.
Consequently the matching frequency, nm, is observed
in a narrow frequency region between 9.7 and 9.9 GHz.
The relationship between matching layer thickness (dM)
and matching frequency (nm) is depicted in Fig. 6 for
composites Ca(NiTi)0.4Fe11.2O19. The matching thick-
ness decreases linearly with the increase in the matching
frequency. This follows the relationship given by Eq. 1
by assuming the m and o as constant for given region of
frequency.
(a 2 + b 2) (4)
Fig. 6. Correlation between the matching layer thickness dM the
matching frequency nM for CaNi0.4Ti0.4Fe11.2O19 hexaferrite com-
posite.
73
Fig. 7. Variations of attenuation constant as a function of frequency
for [Ca(NiTi)x Fe12-2x O19]96.0[La2O3]4.0 hexaferrite composites with
x =0.0, 0.2, 0.4, 0.6, respectively.
3.2.1. Attenuation constant
The transmission constant, T, has been computed
from scattering parameters S11 and S21 and has been
employed to calculate the values of attenuation con-
stant for all the samples using the relation [13]:
T= e − gd (3)
The transmission coefficient is a complex function
expressed as (a+ ib) where a and b represent the real
and imaginary parts respectively. The propagation con-
stant, g, is also complex and is given by a+ ib where a
and b represent the attenuation constant and phase
constant respectively. The attenuation constant is re-
lated to a and b as:
a= −1/d loge
The variations of attenuation constant with frequency
for Ca–NiTi hexaferrite composites of different compo-
sitions are shown in Fig. 7. It shows a maximum value
of a for composites with x= 0.4 between the 8.0 and
11.0 GHz frequency region. Hence, it corroborates the
minimum reflection loss measured for the same compo-
sition in X-band.
In summary, The complex relative permittivity and
permeability spectra and their relationship with mi-
crowave absorbing properties were investigated in poly-
mer–hexaferrite composites. A matching thickness is
found corresponding to a matching frequency. The
matching thickness decreases with the increase in the
matching frequency for typical composite sample. The
matching frequency decreases slightly with the substitu-
tion of progressively increasing amount of non-mag-
netic (Ni2 + Ti4 + ) ion complexes in place of magnetic
Fe3 + . The attenuation constant (a) shows maximum
value for the composite with x= 0.4 between 8.0 and
11.0 GHz.
74 P. Singh et al. / Materials Science and Engineering B78 (2000) 70–74

Acknowledgements [3] W. Gruberger, B. Spreingman, M. Brusberg, M. Schmit, R.

The authors would like to thank Professor V.K.
Aggarwal, Department of Physics, Allahabad Univer-
sity, Allahabad for developing the computer programs
used in the calculations of dielectric constant and per-
meability.
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