Ceramics International 45 (2019) 11226–11232

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Improvement in magnetic parameters of polycrystalline barium hexaferrite T

by nonmagnetic cation substitution and microwave processing
Manju Sharma∗,1, Subhash C. Kashyap2
Department of Physics, Indian Institute of Technology Delhi, New Delhi, 110016, India

A R T I C LE I N FO A B S T R A C T

Keywords: Polycrystalline ZneZr substituted barium hexaferrite (BaFe12-xZnx/2Zrx/2O19 where x = 0.3, 0.5, 0.7 and 1.0)
Barium hexaferrite specimen have been synthesized by two different methods, namely conventional and microwave sintering. The
Microwave sintering latter has resulted in magnetoplumbite phase in 5 min at a lower temperature (1000 °C). The values of magnetic
Cation substitution parameters of different samples are extracted from the corresponding M − H loops using law of approach to
Raman spectroscopy
saturation magnetization. A high value of saturation magnetization (Ms = 76 emu/g) is obtained for a con-
Saturation magnetization
Coercivity
ventionally sintered sample. Still higher value of saturation magnetization (Ms = 104 emu/g) has been obtained
for the microwave sintered cation substituted sample. The increase in the magnetization has been attributed to
the magnetic reordering of iron cations in the non-magnetic Zn2+-Zr4+ substituted samples. The coercivity of
the microwave processed substituted samples has been drastically reduced to 163 Oe (from 2961 Oe for con-
ventionally sintered pristine sample). The observed decrement can be ascribed to the increase in particle size and
reduction in magnetocrystalline anisotropy (2.58 × 106 erg/cc). Raman spectra of the substituted samples have
shown a shift in the vibrational frequencies (characteristic of magnetoplumbite phase) with cation substitution.
This suggests that the non-magnetic ZneZr cations replace Fe3+ from certain interstitial sites (4f1, 4f2, 2b and
12k).

1. Introduction
Hexaferrites are known to be very promising candidates for their
technical use in magnetic recording, permanent magnets, microwave
devices, etc. [1,2]. The importance of these materials lies in their
striking properties like high saturation magnetization, high coercivity,
high anisotropy field, high resistivity, chemical inertness, etc. The
properties in turn depend on their preparation method, particle size,
sintering technique, and most importantly on their composition/struc-
ture. The structure of barium hexaferrite is same as that of magneto-
plumbite, and hence it is known as M-Barium hexaferrite (M-BHF or
simply BaM). The crystal structure of diamagnetically doped barium
hexaferrites may be described by two space groups. One of them is
classical P63/mmc (No.194). Second of them is P63/mc (No.186) space
group. Second space group has been used for describing the crystal
structure to explain the existence of non-zero spontaneous polarization.
This is a polar non-centrosymmetric space group [3,4]. A unit cell of
BaM consists of two formula units of BaFe12O19, i.e. a total of 64 ions.
Oxygen ions form the closed packed arrangement (as in hcp and fcc)
and iron ions occupy the interstitial sites. The interstitial sites are oc-
tahedral (2a, 12k, 4f2), tetrahedral 4f1, and trigonal bipyramidal (2b).
The M-hexaferrites substituted in Fe-positions with Al or In are pro-
mising for practical uses [5–8].
The properties of pristine and cation substituted BHF samples can be
modified by the method of preparation and processing conditions [9]. A
number of preparation techniques, including crystallization of glass
ceramic [10], low temperature cofiring of ceramics [11], salt melt
technique [12], hydrothermal synthesis [13], ammonium nitrate melt
method [14], water-in-oil micro-emulsion procedure [15], chemical co-
precipitation [16], one step solvent free gel synthesis technique [17],
and citrate precursor method [18] have been employed to prepare
pristine and substituted BaM samples. New techniques such as micro-
wave sintering, thin film formation, ion irradiation etc. are being ap-
plied to modify the structure and hence magnetic properties of hex-
aferrites [19–21]. Microwave sintering is a new, rapid, green, economic
technique of heating/modifying the materials including nonmetals and
alloys [22].
The large spontaneous polarization and multiferroic properties at

∗
Corresponding author.
E-mail address: phz118138@physics.iitd.ac.in (M. Sharma).
1
Present Address: Department of Physics, Government College for Women Jind, Jind-126102, India.
2
Former Professor, Department of Physics, Indian Institute of Technology Delhi.

https://doi.org/10.1016/j.ceramint.2019.02.136
Received 25 June 2018; Received in revised form 19 February 2019; Accepted 19 February 2019
Available online 20 February 2019
0272-8842/ © 2019 Published by Elsevier Ltd.
M. Sharma and S.C. Kashyap
Fig. 1. X-ray diffractograms of (a) Conventionally Sintered (CS) and (b) microwave sintered (MS) polycrystalline BaFe(12-x)Znx/2Zrx/2O19 samples.
room temperature have been recently discovered in diamagnetic ca-
tions substituted barium hexaferrites. Herewith the magnetoelectric
characteristics of M-type hexaferrites fabricated by a modified ceramic
technique are more advanced than those for the well-known room
temperature BiFeO3 orthoferrite multiferroics [23–26]. The magnetic
properties of BaM can also be altered simply by the spin imbalance
induced either by cation substitution or by cation rearrangement in the
unit cell. It may be noted that the double cation pairs like ZneZr,
ZneSn, MgeTi, CoeTi, LaePr, NieZr substitute iron cations in BHF
from spin up/down sites and hence modify the magnetic properties
[27–32]. It is reported that by varying the concentration of ZneSn,
optimal magnetic properties are achieved for high density magnetic
recording applications [28]. The high value of Hc in NieZr substituted
BHF is attributed to the single domain particles. Further reduction in
coercivity has been reported in NieZr substituted BHF with increase in
the concentration of substituents because of decrease in magnetocrys-
talline anisotropy [33]. It is found that the crystallinity of triple cation
substituted BHF decreases with increase in substituent concentration.
The perfect hexagonal particles with improved magnetic parameters
were formed at lower temperature and even at lower concentration of
triple ions e.g CoeZneSn which can make it suitable for different uses
[34].
In our laboratory the Fe3+ cations are successfully substituted in
bulk barium hexaferrite specimen by either one cation (Zn), two cation
pair (MgeZr) or three cations (MgeZneZr) in either conventionally
sintered (CS) and/or microwave sintered samples [22]. In this paper, a
brief account of modification of magnetic properties of M-BHF realized
by both, substitution of ZneZr ions for iron ions and by microwave
sintering (MS), is presented.
2. Experimental
Powders of BaFe12-xZnx/2Zrx/2O19 (where x = 0.3, 0.5, 0.7 and 1.0)
were prepared by solid state reaction technique. A mixture of stoi-
chiometric amounts of BaCO3, Fe2O3, ZnO and ZrO2 powders was ball
milled for 24 h. The mixed powder was dried and subjected to calci-
nation at 1000 °C for 10 h. Thereafter 2 wt % binder (Polyvinyl alcohol)
was added to the calcined powder. The pellets of this powder were
sintered separately in a conventional furnace at 1200 °C for 5 h and in a
single mode (H-field) microwave cavity at 1000 °C for 5 min. The
emissivity of pyrometer was set at 0.64. The samples of different
composition synthesized either by conventional sintering (CS) or mi-
crowave sintering (MS) have been named as CSBHFZZ03, CSBHFZZ05,
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Ceramics International 45 (2019) 11226–11232
CSBHFZZ07, CSBHFZZ10, and MSBHFZZ03, MSBHFZZ05 and
MSBHFZZ07, where ZZ represent zinc and zirconium, and the numbers
following the alphabets are 10x values (represented in 2 digits) in
BaFe12-xZnx/2Zrx/2O19.
The structural characterization of the prepared samples was carried
out using x-ray diffraction (X-Pert PRO Philips) technique in θ–2θ
geometry using Cu Kα radiation (λ = 1.54060 Å) with a step size Δ (2θ)
of 0.05°. The morphology and particle size were investigated by em-
ploying a scanning electron microscope (Zeiss EVO 50). The magnetic
parameters like magnetization (M) and coercivity (Hc) of the samples
were estimated from the room temperature hysteresis measurements
(M − H curves) which were carried out by using VSM option of 14-T
PPMS (Quantum Design) at a maximum field of 50 kOe. Raman spectra
of the samples were recorded using Renishaw Invia Raman microscope
equipped with a 10 mW HeeNe laser of wavelength 632.8 nm and a
Leica microscope.
3. Results and discussion
3.1. Structural characterization
Oxygen excess or deficit in a sample can increase and decrease the
oxidation degree of 3d-metals. The changing of charge state of 3d-
metals as a consequence of changing of oxygen content changes the
magnetic parameters such as the Curie temperature and magnetic mo-
ment and electrical parameters such as the resistivity and value of band
gap which either increase or decrease [35]. The oxidation degree of 3d
metals may change the unit cell parameters also [36]. The cation or-
dering is reported to enhance the Curie temperature (Tc) by two times
the Tc of cation disordered compounds [37]. The magnetic parameters
are assumed to be unchanged because of the oxygen deficiency because
of sintering in oxygen atmosphere.
Fig. 1(a) and (b) illustrate the x-ray diffractograms of all the con-
ventionally- and microwave-sintered samples of BaFe12-xZnx/2Zrx/2O19.
Single magnetoplumbite phase (JCPDS#39–1433) formation is con-
firmed in all the conventionally sintered samples. However in case of
MSBHFZZ05 sample, an impurity peak is observed near 33° in the dif-
fractogram. A shift of all the peaks in the diffractograms to lower angle
side indicates an increase in the lattice parameters. The lattice para-
meters are calculated using the following relation:
1 4(h2 + hk + k 2 ) l2
2
= 2
+ 2
d 3a c
M. Sharma and S.C. Kashyap Ceramics International 45 (2019) 11226–11232

Table 1 ratio of c/a, in CS as well as MS samples, is lower than 3.98 (Table 1),
Lattice parameters (a and c), c/a ratio, unit cell volume, average crystallite size, and hence supports the formation of the M-type hexagonal structure
and average particle size of conventionally sintered (CS) and microwave sin- [38]. It may be noted from the Table that the lattice parameter a in-
tered (MS) pristine and cation substituted BHF specimen. creases marginally (up to a maximum of 0.34%) whereas c shows a
Sample a (Å) c (Å) c/a Unit cell Average Average higher increment (up to a maximum of 0.75%) with an increase in the
volume Crystallite Particle concentration of substituents (ZneZr cations) upto 8.33% of iron ca-
(Å3) Size (D) (nm) Size (nm) tions in CS samples. The lattice parameters may change with oxygen
a
CSBHF00 5.888 23.210 3.942 696.83 52 598
stoichiometery [36], however, the variation in the same has been stu-
CSBHFZZ03 5.897 23.279 3.947 701.04 24 412 died with concentration of the substituted ions and plotted with non-
CSBHFZZ05 5.901 23.315 3.951 703.08 27 474 linear interpolation in Fig. 2. In MS samples, the value of a increases
CSBHFZZ07 5.907 23.362 3.955 705.93 24 579 from 5.885 to 5.919 (0.58%) and c increases from 23.261 to 23.429 Å
CSBHFZZ10 5.908 23.384 3.960 706.83 23 627
b (0.72%) as concentration of ZneZr cations is increased up to 6.19% of
MSBHF00 5.885 23.261 3.953 697.65 46 650
MSBHFZZ03 5.905 23.314 3.948 704.00 46 880 Fe cations. This is because of larger ionic radii of the zinc and zirconium
MSBHFZZ05 5.913 23.392 3.956 708.27 51 – cations as compared to that of iron cations. The ionic radii of iron
MSBHFZZ07 5.919 23.429 3.958 710.83 37 2000 (Fe3+), zinc (Zn2+) and zirconium (Zr4+) cations in tetrahedral co-
a
ordination are 0.49 Å, 0.60 Å, and 0.59 Å; whereas in octahedral co-
Reference [15]. ordination the corresponding values are 0.55 Å, 0.74 Å and 0.72 Å re-
b
Reference [16].
spectively [39].
The crystallite size (Dhkl) is calculated using Scherrer equation:

0.89λ
Dhkl =
β cos θ hkl

where λ is the wavelength of X-rays, β is full width at half maximum

Fig. 2. Nonlinear fitting of lattice parameters ‘a’ and ‘c’.
where d is interplanar spacing between (h k l) planes; and a and c are
lattice parameters.
The lattice parameters (a and c) and crystallite size (D) for the
pristine and substituted samples are listed in Table 1. The observed
(FWHM) of the diffraction peaks, θhkl is angle of diffraction from (hkl).
The average crystallite size is estimated from the two Dhkl values cal-
culated from the most intense peaks.
The average crystallite size ranges from 23 nm to 27 nm with in-
crease in concentration of substituents in CS samples. The crystallite
size of MS samples is, in general, higher than that of CS samples and
ranges from 37 to 46 nm. The nanocrystallites can promote the spin
dependent current and to the increase in the electrical resistivity due to
the significant contribution of the surface layer to the spin tunneling
[40].
The Scanning electron micrographs of all the substituted samples
are shown in Fig. 3. Well faceted particles are clearly visible in the
micrographs. The average particle size, estimated by using Image J
software, for MW sintered samples is larger than CS samples. The
average particle sizes for the CS samples are found to range from 0.41 to
0.63 μm whereas a maximum average particle size for MSBHFZZ07
sample has been estimated to be 2 μm. The variation in the morphology
of the particles is because of higher heating rate, lower activation en-
ergy and hence enhanced diffusion kinetics.

Fig. 3. Scanning electron micrographs of BaFe(12-x)Znx/2Zrx/2O19 samples: (a),(b),(c), and (d) correspond to CS samples; (e) and (f) correspond to microwave sintered
at 1000 °C for 5 min. In addition to size distribution, average particle size is also depicted in the histograms.

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M. Sharma and S.C. Kashyap
Fig. 4. (a): Raman spectra of conventionally sintered pristine and substituted
polycrystalline BaFe(12-x)Znx/2Zrx/2O19 samples. (b): Deconvoluted Raman
spectra of polycrystalline BaFe(12-x)Znx/2Zrx/2O19 samples.
3.2. Raman studies
There are 64 atoms in a unit cell of barium hexaferrite which give
rise to 189 modes of vibration. Forty two of these modes are Raman
active (11A1g+ 14E1g + 17E2g); 30 are IR active (13A2u +17E1u) and
the remaining modes i.e. 3A1u + 4A2g+ 13B1g + 4B1u + 3B2g + 12B2u
+ 15E2u are silent. Out of the 42 Raman active modes, 32 frequencies
(A1g, E1g, and E2g) were observed at room temperature in the range of
173–713 cm−1 and assigned to various polyhedra in the unit cell
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Ceramics International 45 (2019) 11226–11232
[41,42]. However a few peaks were observed in polycrystalline BHF
[43]. The structure of barium hexaferrite can also be assumed to be
made up of the cation centered polyhedra stacked together and sharing
the faces with anions at the corners: FeO4 (four imaginary triangular
faces) tetrahedra, FeO6 (eight imaginary triangular faces) octahedra,
FeO5 bipyramid and dodeca-coordinated (12 faces) barium cations
[44]. The Fe2+ cations in tetrahedral coordination like the Mn3+ ca-
tions in octahedral coordination are Jahn-Teller ones. For example, the
Mn3+ trivalent manganese cation is a Jahn-Teller cation and its pre-
sence in the octahedral position is expressed in the specific distortion of
the MnO6 octahedron due to the static cooperative Jahn-Teller effect
and the formation of the so-called orthorhombic symmetry of the unit
cell. One can understand the presence of divalent iron in tetrahedral
positions by the presence of such symmetry [45].
The frequency and intensity of characteristic Raman peaks of a
compound are affected by the substitution of cations in it. The shift in a
peak is due to mass effect and/or variation in force constant resulting
from the substitutions, whereas the intensity of a peak depends upon
the concentration of cation(s) in the vibrating polyhedra. Two types of
models have been proposed to account for the shifting of bands: virtual
ion model, which is observed when changes in force constant and mass
are small and two-mode behavior, when masses and force constant
involved are quite different [42].
Room temperature Raman spectra of the conventionally sintered
pristine and substituted samples are shown in Fig. 4(a) and their de-
convoluted versions are presented in Fig. 4(b). The peaks are numbered
as 1, 2, 3, 4, 5, 6, and 7. The exact positions of peaks, along with
corresponding modes, are listed in Table 2. It may be noted from the
table that the prominent Raman bands in the spectrum of pristine BHF
appear very close to 338, 412, 469, 526, 615, 685, and 720 cm−1. The
strongest band (# 6), characteristic of M-hexaferrite, is observed at
685 cm−1 and is accompanied by a shoulder at 721 cm−1 (band 7). The
two bands belong to A1g mode of Fe(2)O5 bipyramid and Fe(3)O4 tetra-
hedra, centered at 2b and 4f1, respectively. The band (5) at 615 cm−1
corresponds to A1g mode of Fe(4)O6 octahedra centered at 4f2. Bands
5–7 are dominated by the displacement of oxygen atoms.
Band 1 is obtained as the superposition of an A1g and E2g modes
appearing at 340 and 335 cm−1 (12k) respectively, and is shifted to
lower wavenumber side with substitution. Band 2 is resulted from the
superposition of A1g mode at 409 and E2g mode at 420 cm−1, and is also
shifted to the lower wavenumber side due to heavy zirconium ion.
Therefore, both the bands can be interpreted by applying virtual ion
model [42] with an average mass and the force constant remaining
nearly the same. Band 3 (octahedra 2a and 12k dominated) is domi-
nated by the A1g symmetry of motions of Fe(1)O6 and Fe(5)O6 (2a and
12k) octahedra and is continuously shifted to lower wavenumber side.
Band 4 is of E1g symmetry and is also continuously shifted to lower
wavenumber. It may be pointed out that a significant shift is observed
in the peak at 527 cm−1 (band 4, corresponding to E1g mode) with an
increase in Zr4+ concentration confirming its substitution at Fe3+ site
(s) in CSBHFZZ samples. Since the maximum atomic fraction of 0.091
(1.0 ZneZr and 11.0 Fe cations) can occupy any one or more of five
types of 12 interstitial sites (initially occupied by Fe cations) in a unit
cell, it is difficult to identify the precise location or concentration of Zn
and Zr cations.
3.3. Magnetic characterization
The magnetic moment of pure BHF is only because of magnetic
cations i.e. Fe3+. At absolute zero, the spin direction of magnetic ca-
tions at 2a, 2b and 12k (a total of 16) is in one direction (upward di-
rection) whereas spin of cations at 4f1 and 4f2 (a total of 8) is in another
(downward) direction [46]. Thus net magnetization per formula unit of
BaFe12O19 is given by M = M2a (↑) + M2b (↑) + 6M12k (↑) – 2M4f1 (↓) –
2M4f2 (↓) which is equal to 20 μB.
The M − H loops of ZneZr substituted BHF samples, sintered
M. Sharma and S.C. Kashyap Ceramics International 45 (2019) 11226–11232

Table 2
Raman frequencies and area under the peaks (shown inside the bracket) in the spectra of conventionally sintered pristine and substituted BHF specimen.
Mode (1) A1g, E2g (2) A1g, E2g (3) A1g (4) E1g (5) A1g (6) A1g (7) A1g

(5) (1) (4) (2)

Site Occupation by Octahedra 2a, 12k or 4f2 Fe O6 2a and 12 k Fe O6 and 12k Octahedra 4f2 Fe O6 2b Fe O5 4f1 Fe(3)O4
ZneZr cations (mixed) Octahedra Fe(5)O6 Octahedra Octahedra Bipyramid Tetrahedra

CSBHF 338 (5.1) 412 (7.0) 469 (3.0) 526 (6.93) 615 (10.3) 685 (28.3) 721 (6.3)
CSBHFZZ03 337 (5.0) 412 (4.1) 466 (3.0) 523 (5.45) 614 (9.2) 684 (33.5) 718 (4.2)
CSBHFZZ05 337 (6.1) 412 (3.6) 466 (2.2) 522 (4.74) 615 (8.0) 685 (32.6) 718 (3.8)
CSBHFZZ07 335 (7.6) 410 (4.2) 463 (2.9) 519 (6.38) 613 (8.1) 683 (34.7) 717 (3.2)
CSBHFZZ10 336 (8.3) 409 (4.9) 463 (2.5) 518 (6.17) 614 (8.8) 683 (32.5) 717 (2.9)

Fig. 5. The M − H loops of polycrystalline BaFe(12-x)Znx/2Zrx/2O19 samples: (a) Conventionally sintered (CS) at 1200 °C for 5 h and (b) its expanded M − H loops (c)
microwave sintered (MS) at 1000 °C for 5 min (d) its expanded M − H loops. Figures (b) and (d) clearly depict the changes in magnetic parameters with composition
and processing techniques.

Table 3 conventionally (CS) and by microwave technique (MS) are presented in

Saturation magnetization (Ms), Coercivity (Hc), anisotropy field (Ha) and ani- Fig. 5(a)–(d). The values of coercivity (Hc) and magnetization (Ms) of
sotropy constant (K1) of polycrystalline cation substituted barium hexaferrite these samples have been extracted from the expanded M − H loops
specimen. (Fig. 5 (b) and 5 (d)). The values of zero field saturation magnetization
Parameters Ms (emu/g) Hc (Oe) Ha (Oe) K1 ( × 106 erg/cc) (Ms) and anisotropy field (Ha) are calculated from the law of approach
to saturation magnetization (LAS) [47]:
a
CSBHF 67.4 2961 20365 3.63
CSBHFZZ03 75.6 1653 14343 2.87 A B C
CSBHFZZ05 70.8 1066 13299 2.49 M (H ) = Ms ⎛1 + + 2 + 3 ⎞ + Xd H
CSBHFZZ07 70.3 606 11623 2.16 ⎝ H H H ⎠
CSBHFZZ10 68.3 250 9204 1.66
b
MSBHF 58.7 956 10415 1.62 where Xd is high field differential susceptibility, A/H pertains to the
MSBHFZZ03 78.0 1000 15951 3.30 existence of inhomogeneities (vanishes at high fields), and B/H2 and C/
MSBHFZZ05 104.9 490 12402 3.45 H3 refer to the magnetocrystalline anisotropy. For a uniaxial hexagonal
MSBHFZZ07 86.0 163 11334 2.58
compound, with anisotropy constants K2 ≪ K1, the constants B, C and
a
Reference [15]. Ha can be written as:
b
Reference [16].
1 2
B=− Ha
15

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M. Sharma and S.C. Kashyap
Fig. 6. Variation of first anisotropy constant (K1) and anisotropy field (Ha) with
concentration (x) of ZneZr cations in polycrystalline BaFe(12-x)Znx/2Zrx/2O19
samples.
2 3
C=− Ha
105
2K1
Ha =
Ms
It may be noted from Table 3 that, the saturation magnetization (Ms)
varies marginally whereas the coercivity (Hc) decreases drastically with
an increase in concentration of ZneZr cations in the conventionally
sintered samples. A high value of Ms (76 emu/g), even higher than the
reported values [48–50], is observed for CSBHFZZ03 sample. With
further increase in concentration of ZneZr ions in BaFe12-xZnx/2Zrx/
2O19 (from x = 0.5 to x = 1.0) the magnetization, however decreases
marginally. The observed variation in Ms can be explained on the basis
of modified superexchange interactions. Four main super-exchange
interactions are expected to arise in BHF between pairs of iron cations
i.e. 12k and 4fl, 12k and 4f2, 2b and 4f2, 2a and 4f1, the extent of which
can be decided by the concentration of magnetic ions at these sites. It
may be noted that there is no complete agreement regarding the oc-
cupation of substituted ZneZr cations in the hexaferrite unit cell. It is
reported that Zn cations occupy 4f1 (spin down) site while Ti cations are
found equally distributed between 4f2 (spin down) and 12k (spin up)
sites in ZneTi substituted BHF [51]. In another study on ZneZr BHF,
ZneZr cations prefer to occupy 2b (spin up) and 4f2 sites [27]. In NieZr
system, Zr cations at low concentration occupy 2b site and at high
concentration the ions go to 4f1 site [33]. Assuming that in the present
case also the substitution of iron ions by zinc ions takes place at 4f1/4f2
(spin down) sites which reduces the effective downward spin and hence
leads to net higher magnetic moment/saturation magnetization. The
zirconium cations are expected to substitute iron cations from 2b and
12k sites (spin up) as revealed by Raman study (Table 2). The observed
decrease in Ms in the present case may therefore be accounted for by the
decrease in super-exchange interaction among 4f1-12k and 4f1-2a sites
due to nonmagnetic cation substitution and reduced magnetic colli-
nearity.
The value of Ms for MSBHFZZ03 is found to be nearly same as that of
corresponding CS sample. However, an increased Ms (86 and 104 emu/
g) is observed in case of MSBHFZZ07 and MSBHFZZ05 samples. Such a
large increase in Ms could be accounted for by the following reasons:
One reason could be the presence of some ferromagnetic impurity phase
in the sample and another reason could be the flipping of spins of Fe3+.
The ferromagnetic phase could not be detected by X-ray diffraction
analysis. So the increased magnetization may be attributed to the
flipping of spins of cations at tetrahedral sites.
It may be noted from Table 3 that the coercivity (Hc) of pristine
CSBHF and MSBHF are reported to be 2961 Oe [21] and 956 Oe [22]
whereas the observed values for CSBHFZZ03 and MSBHFZZ03 samples
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Ceramics International 45 (2019) 11226–11232
are 1653 Oe and 1000 Oe. The observed high value of coercivity of
pristine samples is expected to result from the strong uniaxial aniso-
tropy along c-axis. The non magnetic cation substitution disrupts the
uniaxial anisotropy, as evidenced by the decrease in anisotropy field
(Table 3), and results in drastic decrease in coercivity (by nearly 92% in
CS samples and by 83% in MS samples). In addition the variation in
particle size also contributes to the change in Hc.
The variation in estimated anisotropy field (Ha) and effective ani-
sotropy constant (K1) due to addition of substituents is shown in Fig. 6.
It can be clearly seen from the figure that the effective anisotropy
constant decreases rapidly with increase in the concentration of sub-
stituents. It is reported that the maximum contribution to the aniso-
tropy comes from 2b site (1.40 cm−1/ion) and minimum contribution
from 4f1 site (0.18 cm−1/ion) whereas contribution from 12k site is
negative (−0.18 cm−1/ion). The contributions from the other sites 2a
and 4f2 are reported to be 0.23 and 0.51 respectively [52]. The aniso-
tropy constant (K1) is expected to decrease when Zn2+ ions substitute
Fe3+ ions at 4f1/4f2 sites and Zr4+ ions occupy the bipyramid (2b) or
octahedral sites in BHF samples.
4. Conclusions
Polycrystalline BaFe(12-x)Znx/2Zrx/2O19 samples were successfully
prepared from the precursor powders obtained after calcination of
stoichiometric mixtures of appropriate compositions at 1000 °C for 10 h
followed either by conventional sintering (CS) at 1200 °C for 5 h or by
microwave sintering (MS) at 1000 °C for 5 min. While the CS took
longer time of 5 h for the phase formation, the same was achieved in a
smaller duration of 5 min by MS technique. The observed marginal
increase in cell parameters of ZneZr substituted barium hexaferrite
specimen has been explained on the basis of ionic radii of the sub-
stituents. The observed characteristic Raman frequencies in CS samples
confirm the M-phase formation. The understandable shift of Raman
bands to lower wavenumber side supports the substitution of iron ions,
residing at various interstitial sites (4f1, 4f2, 2b and 12k), by ZneZr
cations. The saturation magnetization (Ms) is increased to 76 emu/g in
CS samples and further enhanced to 104 emu/g in MS samples by the
controlled non-magnetic cation pair substitution for iron cations. The
observed higher Ms values are attributed to the redistribution of mag-
netic Fe3+ ions due to substituted nonmagnetic cation-pair (Zn2+-
Zr4+). The observed drastic decrease in coercivity from 2961 to 163 Oe
in MS samples may be attributed to the change in particle size and
decrease in magnetocrystalline anisotropy. The high value of MS and
low value of Hc could be advantageous for magnetic recording appli-
cations.
Acknowledgement
The authors are thankful to Prof. G. V. Prakash of the Department
for arranging Raman measurements.
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