ARTICLE IN PRESS

Journal of Magnetism and Magnetic Materials 314 (2007) 128–134

www.elsevier.com/locate/jmmm

The role of Mg substitution on the microstructure and magnetic

properties of Ba Co Zn W-type hexagonal ferrites
M.A. Ahmeda,, N. Okashab, M. Oafa, R.M. Kershic
a
Faculty of Science, Physics Department, Material Science Laboratory (1) Cairo University, Giza, Egypt
b
Physics Department, Faculty of Girls, Ain Shams University, Cairo, Egypt
c
Physics Department, Faculty of Science, Ibb University, Ibb, Yemen
Received 2 August 2006; received in revised form 18 November 2006
Available online 4 January 2007

Abstract

A series of W-type hexagonal ferrites with the composition BaCoZn1xMgxFe16O27 (0pxp0.6) were prepared by the conventional
ceramic method to study their structural and magnetic properties as a function of temperature and composition. The characterization
using X-ray diffraction indicated that a hexagonal W-type single-phase structure and the effect of composition on the unit cell
parameters, density and porosity was studied. The variation of the magnetic susceptibility (wM) with temperature for all the investigated
samples in the temperature range (300–800 K) shows three regions of behavior that was explained on the basis of the distribution of Zn2+
and Mg2+ ions in the lattice and leads to the anomalous behavior of the effective magnetic moment meff. The Curie temperature indicated
that the critical concentration is at x ¼ 0.5. Paramagnetic nature of the samples above the Curie temperature is observed. The Curie
Weiss constant y calculated from the plot of 1/wM vs. T (K) is in agreement with the expected value. The effective magnetic moment meff
decreases with increasing the intensity of magnetic field. The possible mechanisms contributing to these properties are discussed in the
text.
r 2007 Published by Elsevier B.V.

Keywords: Hexagonal ferrite; X-ray analyses; Microstructure SEM; Magnetic susceptibility; Curie temperature

1. Introduction microstructure and magnetic properties of M-type [12] and

Recently, ceramic magnetic materials are distinguished
by their high resistivity and high permeability, so a
numerous products of them are used in industry, technol-
ogy, electronic devices, communication equipments and
military, high-density magnetic recording media, material
for permanent magnets and microwave devices [1–6]. The
interest of hexaferrites comes from their specific magnetic
behavior and electronic conduction [7,8].
Many studies focused on modifying the magnetic
parameters based on substitution of Fe3+ ions with other
ions in barium ferrites [9–11]. Meanwhile, it was found that
a small amount of additive with low melting point could
have a great influence on the magnetic and electrical
properties of ferrites. With the addition of Ba2O3, the
Corresponding author. Tel.: 002025676742.
E-mail address: Moala47@hotmail.com (M.A. Ahmed).
Z-type [13] hexagonal ferrites can be changed significantly.
The magnetic properties of hexagonal ferrites were
extensively studied [14–18]. Mamalui and Murakhowskii
[17,18] studied the temperature and composition depen-
dence of the equilibrium of BaCoNiFeO27 W-type hex-
agonal ferrite. It was found that the equilibrium
orientation of the magnetization vector Is is along the c-
axis (easy direction). Shorfa et al. [19] studied the effect of
replacement of Fe3+ ions by Co2+ and Ti4+ ions in M-
type hexagonal ferrites. They found that at a certain
temperature and concentration of the substituted ions, the
magnetization changes its direction to the easy plane. The
structure of this hexagonal system consists of six possible
different types designated as M, W, Y, Z, X, and U. The
crystal structure of the investigated W-type hexagonal
ferrites (Ba–M), BaM2Fe16O27 (M is any divalent metal
ion) is built up of stacking spinel and hexagonal blocks,
containing Fe3+ ions allocated in five different sublattices,

0304-8853/$ - see front matter r 2007 Published by Elsevier B.V.

doi:10.1016/j.jmmm.2006.11.212
 ARTICLE IN PRESS
M.A. Ahmed et al. / Journal of Magnetism and Magnetic Materials 314 (2007) 128–134 129

namely 12k, 4f2(4fVI), 2a, 4f1(4fIV) and 2b, which are
distributed in both blocks [20]. One Ba2+ ion is found in
the hexagonal block replacing oxygen. The first three
positions (12k, 4f2 and 2a) have octahedral coordination,
while 4f1 shows tetrahedral and 2b occupies a bypiramidal
(pseudo-tetrahedral) site. Besides, 4f1 and 4f2 have spin
down configurations, whereas the other three sites con-
tribute positively to the magnetization. Therefore, each
magnetic sublattice has a specific contribution to the total
magnetic moment and to the crystalline anisotropy of
Ba–M. However, the substitution of paramagnetic or
diamagnetic cations instead of Fe3+ ions has a great effect
on the magnetic and transport properties [21,22]. In other
words, the crystal structure and chemistry of W-type
hexaferrite are closely related to BaFe12O19 (M-type). The
crystal structure of M- and W-type hexaferrite can be
understood as an alternating stacking of spinel and R
blocks in the direction of the hexagonal c-axis. The spinel
blocks in W-type structure are twice as thick as the M-
structure [23].
The aim of the present work is to study how to prepare
and improve the properties of W-type hexaferrite to be
more efficient and applicable. Also, one of our galls is to
focus a light on the magneto—transport properties of the
samples in order to find a correlation between the Mg
substitute and the microstructure of the investigated
samples.
2. Experimental
A series of polycrystalline W-type hexagonal ferrite with
the formula BaCoZn1xMgxFe19O27, 0pxp0.6 was pre-
pared by the conventional ceramic method using high-
purity (BDH) BaCo3, Fe2O3, MgO, ZnO and Co3O4, were

200
x=0.5
(201)

100 (2114)

(0012) (2111)
(209) (216)
(110) (219) (222)

0
150
x=0.4

100

50

0
150
x=0.3
Intensity %

100

50

0
150
x=0.1
100

50

0
150
x=0

100

50

0
20 30 40 50 60 70 80
2θ

Fig. 1. X-ray diffraction patterns for BaCoZn1xMgxFe16O27 system.

 ARTICLE IN PRESS
130 M.A. Ahmed et al. / Journal of Magnetism and Magnetic Materials 314 (2007) 128–134

thoroughly stoichiometric from pure oxides, weighted, uniaxial pressure a press of 1.9  108 N m2 and presintered
mixed, and well grounded in a planetary agate mortar for in air at 900 1C for 8 h with heating rate 4 1C/min in the
3 h. The mixture was pressed into pellets form using electrical Lenton furnace 16/5 UAF (England) then
slow cooled to room temperature with the same rate as
that of heating. After that, the samples were groun-
a ded again and pressed into pellets, then finally sintered in
5.956 air at 1200 1C for 5 h with the same rate of heating and
cooling.
Lattice parameter a (A)

5.952
X-ray diffraction analyses was carried out using Scintag
(USA) X-ray diffractometer equipped with CuKa radiation
5.948
(l ¼ 1.5418 Å), confirmed the presence of single-phase W-
type hexagonal ferrite for all prepared percentage porosity
5.944
P of each sample was calculated using the relation
P ¼ (1D/Dx)%. The microstructure of the samples was
5.94 carried out using the scanning electron microscope (SEM)
0 0.2 0.4 0.6 0.8 (model JEM-100S).
Mg content (x) Some of the samples were crushed again in an agate
b mortar to fine powder for DC magnetic susceptibility
32.9 measurements. The magnetic susceptibility of the investi-
gated samples was measured using Faraday’s method
Lattice parameter c (A)

32.88 where a very small quantity of sample was inserted at the

point of maximum gradient (maximum force) in a Pyrex
32.86
tube. The measurement of magnetic susceptibility was
32.84 performed at different temperatures ranging from 300 to
800 K and different magnetic field intensities of (1280,
32.82 1733, 2160, 2557, and 3000 Oe). The temperature of the
samples was measured using T-type thermo-couple with
32.8
0 0.2 0.4 0.6 0.8 junction near the sample to avoid the temperature gradient.
Mg content (x) The accuracy of magnetic susceptibility measurements was
71% where the data were reproducible.
Fig. 2. (a) The variation of lattice parameter (a) as a function of Mg
content (x). (b) The variation of lattice parameter (c) as a function of Mg
content (x). 3. Results and discussion

Table 1 3.1. Structural properties

The values of the lattice parameters (a), (c), X-ray density (Dx), and
porosity P% at different Mg content (x)
Fig. 1 shows the X-ray diffraction patterns at room
x a (Å) C (Å) Dx (g/cm3) P% temperature for the investigated samples. The patterns
show that all samples have a single-phase W-type
0 5.953 32.814 4.532 6.04
0.1 5.95 32.816 4.525 2.46
hexagonal ferrite without notable residuals of the original
0.2 5.948 32.826 4.515 2.56 constituent oxides. The average values of the lattice
0.3 5.947 32.826 4.506 2.88 parameters were calculated from the diffractograms and
0.4 5.945 32.826 4.496 2.77 it was found that W-type structure has average lattice
0.5 5.944 32.859 4.481 3.41 parameter (a ¼ 5.94 Å) that agree well with other author
0.6 5.942 32.891 4.468 4.06
[24] for Ba W-type hexaferrites.

Table 2
The values of the effective magnetic moment meff at different Mg content as a function of different magnetic field

meff meff meff meff meff H ¼ 3000 (Oe)

X 1280 Oe 1733 Oe 2160 Oe 2557 Oe 3000 Oe TC (K) y

0 18.86 13.24 10.11 8.35 7.09 790 710
0.1 15.09 12.16 8.06 7.74 5.98 722 684
0.2 13.71 10.56 7.24 5.91 5.59 737 678
0.3 13.15 10.46 7.41 5.41 5.2 753 665
0.4 12.74 10.12 7.35 5.32 4.99 765 681
0.5 12.14 9.64 6.85 4.13 4.76 800 780
0.6 15.39 9.95 9.41 8.02 6.67 783 762
 ARTICLE IN PRESS
M.A. Ahmed et al. / Journal of Magnetism and Magnetic Materials 314 (2007) 128–134 131

The decrease in the lattice parameter (a) with Mg content

(Fig. 2a) is attributed to the cation radius ratio on
tetrahedral sites. The parameter (c) is slightly increased
with the increase of Mg content as in Fig. 2b. Previously it
was reported that [25–27] Zn ions prefer the tetrahedral
sites, while Mg2+ ions have a statistical distribution over
tetrahedral and octahedral sites, but mainly prefer to
occupy octahedral sites [28]. In addition, for W-type
hexaferrites, Fe ions have three different kinds of sites
(A, B and the five-fold coordination site [29]. Accordingly,
we may suggest that, the replacement of Zn2+ by Mg2+
ions takes place on tetrahedral sites and at the same time,
Mg2+ ions remains on octahedral sites followed by the
migration of some Fe3+ ions from octahedral sites to
tetrahedral sites. In other words, it was reported that the
unit cell of W-type phase is closely related to M-type phase;
the only difference is that the successive R-blocks are
interspaced by two S-blocks instead of one as in the M-
phase [30]. Lotgering and Vromans [31] found that W-type
hexagonal ferrite is chemically unstable, though that some
of W-type phase decomposed to M-type phase and a-
Fe2O3 [32,33]. Therefore, the presence of S- and M-type
phases in the investigated samples may be attributed to the
decomposition process of W-type phase at high sintering
temperature. The experimental density (D) was calculated
using Archimedes principle, X-ray density (Dx) was
calculated using the equation Dx ¼ ZM/NV, where M is
the molecular weight, N is Avogadro’s number, Z is the
number of molecules for W-type hexagonal unit cell and V
is the volume of the unit cell and the results of calculations
were reported in Tables 1and 2. The data in the table show
that, the experimental density D (the bulk density) values
were found to be in general less than those of Dx (the
theoretical density) which was expected due to the presence
of unavoidable pores created during sintering processes.
Besides, a relatively significant decrease in the bulk density
and a corresponding increase in porosity can be explained
on the assumption that most of Mg2+ ions occupy
octahedral sites and partially occupy tetrahedral sites
whereas Zn2+ ions occupy tetrahedral sites, therefore, if
we take into consideration that Mg2+ ion has an ionic
radius of 0.65 Å and Zn2+ ion is 0.74 Å, we can expect the
decrease in bulk density and a corresponding increase in
porosity is obtained.
Fig. 3 shows typical SEM micrograms of the bulk
material. It is found that the W-type ferrite grains are
homogeneous hexagonal-shaped crystals. It was found that
the average grain size estimated from the SEM is about 3
and 6 mm and it was almost dependent of the composition
(x).

3.2. Magnetic properties

Fig. 3. Images for a typical SEM of BaCoZn1xMgxFe16O27 composition
at x ¼ 0, 0.1, 0.5.
Fig. 4 illustrates the variation of the molar magnetic
susceptibility (wM) with the absolute temperature as a
function of the magnetic field intensity for all investigated
samples. Three different and distinct regions are observed
 ARTICLE IN PRESS
132 M.A. Ahmed et al. / Journal of Magnetism and Magnetic Materials 314 (2007) 128–134

20 20
x=0.3 x=0.4

15 15

10
10

5
5

0
0 30
30 x=0.5
x=0.2

20

χM
20

10

10
0
χM

12
x=0.6
0
9
18
x=0.1
6

12 …
3

6 0
300 500 700 900
T(K)
0
25
x=0
1280 Oe
1733 Oe
20 2160 Oe
2557 Oe
15 3000 Oe

10

0
300 500 700 900
T(K)

Fig. 4. The variation of molar magnetic susceptibility (wm) at different temperature T(K) at different concentration of Mg content (x).

for each sample. In the first one, a slight increase of wM
with temperature is obtained giving a broad hump for all
samples that is designated as an isotropic hump [34]. Its
appearance takes place when the magnetic material is in
multidomain state (MD) and it occurs when the magneto-
crystalline anisotropy is zero. Beyond the temperature at
which the isotropic hump occurs, the sample exists in a
single domain state (SD) and the coercive force due to the
sample anisotropy still dominant with the same value if the
temperature of such a single domain particle is further
increased. In this case, the thermal energy given to the
sample becomes comparable to the effective magnetic
anisotropy. In such a state, a particle is said to exhibit
superparamagnetism. After the hump, the values of wM
decrease sharply to Curie temperature where the magnetic
susceptibility is nearly independent of temperature
although still slightly dependent on composition. This
can be explained according to the preference of the Mg2+
 ARTICLE IN PRESS
M.A. Ahmed et al. / Journal of Magnetism and Magnetic Materials 314 (2007) 128–134 133

a
840

Curie temperature TC (K)

800

760

720

680
0 0.2 0.4 0.6 0.8
Mg content (x)

b
20

15
x=0
μeff

x=0.1
10

5
1000 1500 2000 2500 3000 3500
H Oe
c
8
H= 3000 Oe
7
μeff

4
0 0.2 0.4 0.6 0.8
Mg content (x)

Fig. 5. (a) The variation of Curie temperature (TC) as a function of Mg content (x). (b) The variation of effective magnetic moment (meff) at different
magnetic field intensity as a function of Mg content (x). (c) The variation of effective magnetic moment (meff) as a function of Mg content (x) at a selected
magnetic field intensity (H ¼ 3000 Oe).

with Zn2+ ions for tetrahedral sites. It is known that [35]
that the only available tetrahedral sites (4f1, 4f2) belong to
the spin down oriented sublattice.
Fig. 5a shows the increases of TC with increasing Mg
content. The data give a hump at x ¼ 0.5 which is
considered as a critical concentration after which TC
decreases again. This means that the substitution of
Mg2+ instead of Zn2+ ions with ratio of more than
50%; a weakening of the total distance or angle due to the
superexchange interaction Fe–O–Fe takes place. In other
words, some of Mg2+ ions migrate to occupy octahedral
(B) sites in S blocks [26]. The ferric (Fe3+) ions transferred
from octahedral sites to tetrahedral (A) sites in blocks S
instead of Zn2+ ions, this leads to an increase in the
magnetic moment AA interactions. Thus the thermal
energy required to offset the spin alignment increases as
well as TC. Further increases in Mg2+ after x ¼ 0.5 leads to
the migration of ferric ions which decreases the AA
magnetic moment as well as a decrease in TC.
Fig. 5b shows the relation between the effective magnetic
moment meff and the magnetic field intensity (H) as a
function of Mg content (x). The data clarify that meff
decreases with increasing both H and x due to presence of
diamagnetic Mg2+ ions on the octahedral sites on the
expense of Fe3+ ions which migrate to tetrahedral sites in a
form of Fe2+ ions. The presence of Fe2+ ions reduces meff,
and its atomic fraction can be calculated by the following
equation:
 ARTICLE IN PRESS
134 M.A. Ahmed et al. / Journal of Magnetism and Magnetic Materials 314 (2007) 128–134
m2effðxÞ ¼ am2effðFe3þ Þ þ ð1 þ aÞm2effðFe2þ Þ , where a is the frac-
3+
tion of Fe atoms. The character of interatomic interac-
tions between Fe2+and Fe3+ ions should be ferromagnetic
because the susceptibility increases as Mg content increase
up to x ¼ 0.5.
Fig. 5c illustrates the relation between the effective
magnetic moment meff and Mg content (x) at a certain
magnetic field intensity (H ¼ 3000 Oe). From the figure,
the decreasing of meff up to the critical concentration
x ¼ 0.5 is due to created Fe2+ in octahedral sites leads to
increase in the magnetic moment (AB) interaction and this
cause an increase in of meff.
4. Conclusion
The conventional ceramic technique is used to prepare
W-type hexaferrites as it was used in preparing the soft
ferrites to yield the required properties. The experimental
results show that improving the magnetic properties is
achieved by adding a small amount of the nonmagnetic
substituent. The substitution of Mg2+ ions on the
tetrahedral sites in the W-type structure could enhance
the magnetic properties. The values of the magnetic
susceptibility decrease with increasing Mg concentration
as well as the magnetic field intensity. The effective
magnetic moment decreases with increasing the magnetic
field intensity. The paramagnetic study above Curie
temperature indicates no change has occurred in the
valency distribution because of the high Curie temperature
and magnetization with the result of opening a new area of
applications in permanent magnets and electromagnetic
microwave absorbers. This can be obtained at the critical
concentration of Mg2+ ions.
References
[1] B. Viswanathan, V.R.K. Murthy, Ferrite Materials; Science
and Technology, Narosa publishing house, New Delhi, 1990, p. 429.
[2] E.C. Snelling, Soft Ferrites/Properties and Application, second ed,
Butter worths, London, 1988, 1.
[3] J. Smith, H.P.J. Wijn, Ferrite, Philips Technical Library, Eindhoven,
1959, p. 195.
[4] T.L. Hylton, M.A. Parker, M. Ullah, K.R. Coffey, R. Umphress,
J.K. Haward, J. Appl. Phys. 75 (1994) 5960.
[5] A. Morisako, M. Matsumoto, M. Naoe, IEEE Trans. Magn. 24
(1988) 3024.
[6] T.P. Niesen, M.R. de Guire, J. Electroceram. 6 (2001) 169.
[7] H. Graetsch, F. Haberey, R. Leckebusch, M. Rosenberg, K. Sahl,
IEEE Trans. Magn. Magn. 20 (1984) 495.
[8] M.N. Deschizeaux, M. Regi, J.C. Joubert, J. Solid State Chem. 57
(1985) 234.
[9] Z. Haijun, L. Zhichao, M. Chenliang, Y. Xi, Z. Liangying, W.
Mingzhong, Mater. Chem. Phys. 80 (2003) 129.
[10] E. Brando, H. Vincent, O. Dubrinfaut, A. Fourrier-Lamer, R.
Lebourgeois, J. Phys. IV 7CL (1997).
[11] H.S. Cho, S.S. Kim, IEEE Trans. Magn. 35 (1999) 3151.
[12] C. Wang, L. Li, J. Zhou, X. Qi, Z. Yue, X. Wang, J. Magn. Magn.
Mater. 257 (2003) 100.
[13] H. Zhang, J. Zhou, Y. Wang, L. Li, Z. Yue, Z. Gui, IEEE Trans.
Magn. 38 (2002) 1797.
[14] N.E. Fuchi, J. Phys. Soc. Jpn. 20 (1965) 760.
[15] X.Z. Zhou, A.H. Morrish, Z. Yang, H. Zang, J. Appl. Phys. 75 (1994)
5556.
[16] F.K. Lotgering, P.R. Van Staple, J. Phys. Chem. Solids 41 (1980)
481.
[17] Yu.A. Mamalui, A.A. Murakhowskii, FJ 173 (1972) 391.
[18] Yu.A. Mamalui, A.A. Murakhowskii, Crystallographia 20 (1975)
351.
[19] A.D. Shorfa, T.M. Perekalina, B.P. Sheparin, JETF 55 (44) (1968)
1197.
[20] Z. Haijun, L. Zhichao, M. Chenliang, Y. Xi, Z. Liangying, W.
Mingzhong, J. Mater. Chem. Phys. 80 (2003) 129.
[21] E. Brando, H. Vincent, O. Dubrinfaut, A. Fourrier-Lamer, R.
Lebourgeois, J. Phys. IV 7CI (1997).
[22] C. Wang, L. Li, J. Zhou, X. Qi, Z. Yue, X. Wang, J. Magn. Magn.
Mater. 257 (2003) 100.
[23] P.B. Broun, Philips Res. Rep. 12 (1957) 491.
[24] H.C. Frang, Z. Yang, C.K. Ong, Y. Li. C. S. Wang, J. Magn. Magn.
Mater. 187 (1998) 129.
[25] F.L. Wei, H.C. Fang, C.K. Ong, C.S. Wang, Z. Yang, J. Appl. Phys.
87 (2000) 8636.
[26] Sung Yang An, In.-Bo. Shim, Chul Sung Kim, J. Appl. Phys. 91
(2002) 8465.
[27] R.D. Shannon, Acta Crystallogr. A 32 (1976) 751.
[28] D. El Kony, S.A. Saafan, J. Magn. Magn. Mater. 276 (2003) 46.
[29] K.J. Standly, Oxide Magnetic Materials, Clarendon Press, Oxford,
1962.
[30] H. Kojima, in: E.P. Wohlfahrt (Ed.), Fundamental properties of
Hexagonal Ferrites, In Ferromagnetic Materials, vol. 3, North-
Holland, Amsterdam, 1982, p. 305.
[31] F.K. Lotgering, P.H.G.M. Vromans, J. Am. Ceram. Soc. 60 (1977)
416.
[32] B.R. Karche, B.V. Khasbardar, A.A. Vaingankar, J. Magn. Magn.
Mater. 168 (1997) 292.
[33] J. Smit, H.P. Wijn, Ferrites, Cleaver- Hume Press, 1959.
[34] K. Jisheng, L. Huaixian, D. Youwei, J. Magn. Magn. Mater. 31
(1983) 801.
[35] C.R.K. Murthy, S.D. Likhite, Earth Planet. Sci. Lett. 7 (1970)
389.