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Magnetic study of M-type Ru-Ti doped

strontium hexaferrite nanocrystalline particles
ARTICLE in JOURNAL OF ALLOYS AND COMPOUNDS JULY 2015
Impact Factor: 3 DOI: 10.1016/j.jallcom.2015.06.274

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Journal of Alloys and Compounds 648 (2015) 419e427

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Magnetic study of M-type RueTi doped strontium hexaferrite

nanocrystalline particles
A.M. Alsmadi a, b, *, I. Bsoul c, S.H. Mahmood d, G. Alnawashi b, F.M. Al-Dweri b,
Y. Maswadeh d, U. Welp e
a

Physics Department, Kuwait University, Safat, 13060, Kuwait

Physics Department, The Hashemite University, Zarqa, 13115, Jordan
Physics Department, Al al-Bayt University, Mafraq, 13040, Jordan
d
Physics Department, The University of Jordan, Amman, 11942, Jordan
e
Material Science Division, Argonne National Laboratory, Argonne, IL, 60439, USA
b
c

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 9 June 2015
Received in revised form
29 June 2015
Accepted 30 June 2015
Available online 6 July 2015

We carried out a systematic study on the effect of the substitution of Ti2 and Ru4 ions for Fe3 ions on
the structural and magnetic properties of the strontium ferrite SrFe122xRuxTixO19 nanoparticles with
(0  x  0:3), using x-ray diffraction, Quantum Design PPMS-9 magnetometry, and electrical resistivity. A
clear irreversibility between the zero-eld-cooled and eld-cooled curves was observed below room
temperature and the zero-eld-cooled magnetization curves displayed a broad peak at a temperature TM.
These results were discussed within the framework of random particle assembly model and associated
with the magnetic domain wall motion. The resistivity data showed some kind of a transition from
insulator to perfect insulator around TM . The high-temperature magnetization measurements exhibited
sharp peaks just below Tc indicating a superparamagnetic behavior. With RueTi substitution, the saturation magnetization at 5 K showed small variations were it slightly increased with increasing x up to 0.2,
and then decrease for x 0.3, while the coercivity decreased monotonically, recording a reduction of
about 78% at x 0.3. These results were discussed in light of the cationic distributions based on the
results of the structural renements.
2015 Elsevier B.V. All rights reserved.

Keywords:
Strontium hexaferrite
RueTi substitution
ZFC and FC curves
Magnetic properties
Rietveld renement
Ball milling

1. Introduction
M-type hexaferrites SrFe12O19 (SrM) and BaFe12O19 (BaM) have
been intensively investigated in the past years for their fundamental physical interest, and, additionally for their potential applications in high-density magnetic recording, high frequency
devices, future multiferroics, and as materials for permanent
magnets [1e6]. In addition, these hexaferrite materials are important permanent magnets because of their lower processing cost,
wide availability of raw materials, high coercivity, high Curie temperature, large uniaxial magnetic anisotropy and good chemical
stability [7e10]. Although BaM is already used for high frequency
applications in multilayer chip inductor [1], SrM ferrite can be
another material for such applications as it has slightly better

* Corresponding author. Physics Department, Kuwait University, Safat, 13060,

Kuwait.
E-mail address: abdel.alsmadi@ku.edu.kw (A.M. Alsmadi).
http://dx.doi.org/10.1016/j.jallcom.2015.06.274
0925-8388/ 2015 Elsevier B.V. All rights reserved.

magnetic properties than those of BaM as shown in Table 1 [1]. To

control their magnetic properties to fulll various applications, a
large number of chemistry-based synthesis techniques have been
developed to prepare M-type hexaferrites. Among these are mainly
the conventional solid-state method [11], co-precipitation method
[12], glass crystallization [13], solegel method [14], hydrothermal
process [15,16], ammonium nitrate melt method [17], microwaveinduced combustion [18], mechano-combustion route [19], and
ball milling method [20,21]. Ball milling is a user-friendly and
simple method suitable for the production of powders composed of
ne particles smaller than the single domain size, and has been
recently employed for the preparation of strontium ferrite nanoparticles [22].
While materials possessing large coercivity and high saturation
magnetization are suitable for permanent magnet applications, the
large coercivity prohibits usage of such materials in magnetic
recording and data storage media due to the requirement of large
switching elds. For high density magnetic recording media, materials with high saturation magnetization and coercivities ~1e3 kO

420

A.M. Alsmadi et al. / Journal of Alloys and Compounds 648 (2015) 419e427

Table 1
Comparison of magnetic properties of BaM and SrM ferrites at room temperature
measured in single crystal form [1]. Ms is saturation magnetization, Ha is magnetic
anisotropy eld, K1 is magnetic anisotropy constants, and Tc is Curie temperature.
Ferrite
BaM
SrM

Formula
BaFe12O19
SrFe12O19

Ms (emu/gm)
72
74e92

Ha (kOe)
16.9
19.9

K1 (erg/cm3)
6

3.3  10
3.5  106

TC (K)
723
733

are required [23]. In addition, highly resistive magnetically softer

materials with low eddy currents are required for high frequency
devices, in which case magnetic oxides have an advantage over
metallic materials [2]. The magnetocrystalline anisotropy of uniaxial M-type hexaferrites, in addition to the saturation magnetization and particle morphology, was reported to have an essential
role in determining the coercivity of the material [20]. Further, large
variations in coercivity of BaM hexaferrites ranging from about 1.0
kO to about 5.7 kOe were reported [10,12,23e26], reecting the
sensitivity of this parameter to the fabrication technique and prevailing experimental conditions. Therefore, an interplay between
the saturation magnetization, magnetocrystalline anisotropy, and
particle shape and size can lead to tuning the coercivity of the
material to t the requirements for specic applications. This can be
achieved by suitable ionic substitutions for Fe3 ions in the hexaferrite lattice, where improvement of the performance of the Mtype hexaferrites can be attained. For this purpose, trivalent metal
substitutions for Fe3 ions were used, and substitutions with
metals such as Al, Ga, Cr were reported to result in an increase in
coercivity [20,21,27,28], whereas the substitution with Mn, Co, or Ni
resulted in a signicant drop in coercivity [29,30]. In addition,
substitutions of Fe ions by combinations of tetravalent and divalent
ions were used to modify the coercivity of M-type hexaferrites.
Specically, the substitution for Fe by MgeTi [25], TieCo, TieZn,
TieSn [23], CoeSn [31], and various cationic combination such as
NieTi [32] MneTi, NieRu, ZneRu [33], TieRu [22,34], and CoeTi
[35] were found effective in reducing the coercivity in these hexaferrites. Also, the substitution of La, Sm and Nd rare earth (RE)
metals for Sr in SrM hexaferrites was investigated for different RE/
Sr ratios between 1:16 and 1:2 [1,36]. Up to a ratio of 1:8 the
saturation magnetization stayed constant, but it then decreased
with increasing rear earth element substitution, particularly for Nd.
On the other hand, the substitution of the cations combination
(ZneTi)x for Fe in SrM nanoparticles showed higher values of both
coercive eld strength and saturation magnetization than the
(ZneIr)x substituted phase for 0 < x  0.6 [37]. In a relatively recent
study conducted by Ghasemie et al. [38], it was found that an increase in ZreMg substitution content resulted in a decrease in the
coercivity, but the value of the saturation magnetization increased
in SrFe12x(Zr0.5Mg0.5)xO19 for 0 < x  2.5. On the opposite, it was
found that the coercivity increased while the saturation magnetization decreased with Nd3 substitution for Fe in SrFe12xNdxO19
nanoparticles with 0 < x  0.3 [39]. In our latest report [22], we
found that the substitution of a small amount of Fe3 ions by Ti2
and Ru4 ions in SrFe12_2xTixRuxO19 with (0.0 < x < 0.3) system
induced a substantial reduction in the coercivity, and improved the
saturation magnetization. These properties, in addition to the large
saturation magnetization, good chemical stability, and low
switching eld distribution make these SrM compounds useful in
high-density recording and high frequency applications. Most of
the previous studies on these SrM systems, however, were carried
out at room temperature, where most of the industrial applications
take place. However, studying these materials at lower and higher
temperatures, and investigating the dependence of their electrical
and magnetic properties on the temperature is of fundamental
importance to understand the mechanisms and origin of the

changes in the magnetic behavior of these ferrites.

In this contribution, we study the effect of RueTi substation for
Fe on the magnetic properties of strontium hexaferrites in
SrFe12O19 synthesized by ball milling method. The temperature
dependence of the magnetic and electrical properties of
SrFe122xRuxTixO19 with (0  x  0:3) are investigated in a wide
range of temperature and magnetic elds in an attempt to understand the magnetic behavior of these hexaferrites.
2. Experimental procedures
All samples were prepared by ball milling and extracted from
the same batch we used in our previous study [22]. The starting
materials for synthesis of SrFe122xRuxTixO19 with x 0.0, 0.1, 0.2,
and 0.3 were high purity metallic oxides (Fe2O3 99%, TiO 99% and
RuO2 99%) and strontium carbonate (SrCO3 99%). The molar ratio of
iron to strontium was set at Fe/Sr 11, which is the optimum ratio
for obtaining a single hexaferrite phase. All samples were prepared
in a planetary ball-mill (Fritsch Pulverisette-7) with balls and vials
made of hardened steel. The milling experiment was carried out at
250 rpm for 16 h and the ball to powder ratio was 8:1. The as-milled
powders were annealed in air atmosphere at 1100  C for 2 h.
Further detailed explanation of this treatment was given in
Refs. [22,34]. The phase purity and crystallite sizes in the synthesized samples were checked by x-ray diffraction, and Rietveld renements of the patterns were carried out using FULLPROF
software to determine the rened crystal parameters, relative
abundance of secondary phases, and the cationic distributions in
the lattice. The particle size and morphology was determined from
the scanning electron microscopy (SEM) imaging.
The magnetization measurements were performed at the materials science division of Argonne National Laboratory using a
Quantum Design superconducting quantum interference device
(SQUID). The temperature dependence of magnetization and electrical resistivity measurements were performed using a Quantum
Design 9T Physical Properties Measurements System (PPMS),
which is recently installed at the Hashemite University, Jordan. The
zero-eld-cooled (ZFC) and eld-cooled (FC) processes were
recorded at low magnetic elds in the temperature range from 2 K
to 300 K. Before each run, the sample was demagnetized at 300 K
by applying an oscillatory magnetic eld, and then cooled down in
zero elds to 5 K. At 5 K, a small magnetic eld of the order of
100 Oe was applied, and the magnetization was measured as we
heated the sample to 300 K. This procedure was denoted as the
zero-eld cooled (ZFC) measurements. At 300 K, the small-applied
magnetic eld was kept as is and then samples were cooled again to
5 K, with a subsequent recording of the magnetization as we heated
the sample to 300 K. Such measurements were denoted as eldcooled (FC) measurements. In addition, our thermomagnetic
measurements were extended to higher temperatures ranging
from 300 K to 800 K using the Vibrating Sample Magnetometer
(VSM) to investigate their superparamagnetic behavior.
3. Results and discussion
X-ray diffractions patterns for SrFe122xRuxTixO19 with Rietveld
renement are shown in Fig. 1. The results of the renement
demonstrated that the main phase in all samples was consistent
with the standard pattern for hexagonal strontium ferrite SrFe12O19
with
space
group
P63/mmc
and
lattice
parameters
a 5.881 0.001 and c 23.04 0.007 . In addition, small
amounts of a-Fe2O3 phase were detected in the samples with
x > 0.1. The rened cell parameters, cell volume, and reliability (R)
factors are shown in Table 2, in addition to the phases and their
weight-ratios in each sample. Our values of c2 (goodness of t), Rwp

A.M. Alsmadi et al. / Journal of Alloys and Compounds 648 (2015) 419e427

421

Fig. 1. X-ray diffraction patterns for SrFe122xRuxTixO19 hexaferrites.

(weighted pattern reliability factor), and RB (Bragg-reliability factor) were lower than those reported by Refs. [24,27], indicating
reliable ts and rened parameters. The renement results indicated that the ratio of a-Fe2O3 nonmagnetic oxide phase was 2.23%

in the sample with x 0.2, and 6.88% in the sample with x 0.3.
Since the presence of nonmagnetic phases in the sample is undesirable, our study was limited to the proposed concentrations of the
substituents, which yield relatively low concentration of the non-

422

A.M. Alsmadi et al. / Journal of Alloys and Compounds 648 (2015) 419e427

Table 2
Results of the renement of XRD patterns of SrTixRuxFe122xO19 hexaferrites.
x

0.1
16.8
8.91
1.08

Rp
Rwp

c2

0.2

15.5
8.09
1.02

14.9
8.06
1.08

0.3
16.2
8.75
1.21

Phase 1: SrFe12O19

Space group: P63/mmc (hexagonal)

a ()
c ()
V (3)
RB
RF
Wt. ratio

5.8813
23.037
690.09
2.89
3.77
100%

5.8832
23.0427
690.7
2.34
2.98
100%

5.8832
23.0508
690.94
2.09
2.44
97.77%

Phase 2: Fe2O3

Space group: R3c (trigonal)

a ()
c ()
V (3)
RB
RF
Wt. ratio

5.0467
13.727
302.78
3.38
2.65
2.23%

5.8827
23.0556
690.97
2.25
3.09
93.12%

5.0368
13.7538
302.18
4.44
3.86
6.88%

magnetic phase.
The rened ionic positions in the substituted samples demonstrated small shifts with respect to the un-substituted sample (see
representative data in Tables 3 and 4 for the samples with x 0 and
x 0.3). These shifts resulted in variations of some bod-lengths and
bond angles as demonstrated by the representative data in Table 5,
leading to structural distortions in the various sites as a result of the
metal substitution. Examples of distortions occurring in 2b, and 4f1
and 12k sites are shown in Figs. 2 and 3, respectively.
The rened site occupancies (not shown) indicated that the
TieRu substitution in the sample with x 0.1 occurs at the 4f1, 4f2,
and 2b sites, while for the sample with x 0.2, the substitution
occurs at all crystallographic sites. As x increased up to x 0.3, a
signicant increase in the occupancy of the 12k, 4f1, 4f2, and 2b sites
was observed. This result indicates the onset of random ionic distributions of the substituents as x increase above 0.1. The site occupancies determined by our structural renement are in good
agreement with the preferential site occupations of metal ions
ssbauer spectroscopy [22].
determined from Mo
Fig. 4 shows representative SEM images for the RueTi
substituted hexaferrites. The average particle size in the un-doped
sample was found to be ~150 nm, which is signicantly below the
critical single domain size of 460 nm [40]. The average particle size
for the doped samples, however, was found to be in the range from
200 nm to 450 nm, which is close to the critical single domain size,
and could indicate the presence of multi-domain particles in these
samples. These particle sizes are also comparable to those found in
RueTi substituted BaM samples using TEM measurements [34].
Table 3
Rened atomic positions and R-factors for SrFe12O19 hexaferrite.
Atom

Site

X/a

Y/b

Z/c

Sr
Fe1
Fe2
Fe3
Fe4
Fe5
O1
O2
O3
O4
O5
RB 2.34

2d
2a
2b
4f
4f
12 k
4e
4f
6h
12 k
12 k
RF 2.98

0.66667
0.00000
0.00000
0.33333
0.33333
0.16979
0.00000
0.33333
0.16967
0.15581
0.49030
Rp 16.8

0.33333
0.00000
0.00000
0.66667
0.66667
0.33955
0.00000
0.66667
0.33927
0.31162
0.98058
Rwp 8.91

0.25000
0.00000
0.25000
0.02727
0.19186
0.89130
0.14673
0.94159
0.25000
0.05023
0.14924
c2 1.08

Phase: SrFe12O19, Space-group: P63/mmc (hexagonal).

Table 4
Rened atomic positions and R-factors for SrTi0.3Ru0.3Fe11.4O19 hexaferrite.
Atom

Site

X/a

Y/b

Phase 1: SrFe12O19, Space-group: P63/mmc (hexagonal)

Sr
2d
0.66667
0.33333
Fe1
2a
0.00000
0.00000
Fe2
2b
0.00000
0.00000
Fe3
4f
0.33333
0.66667
Fe4
4f
0.33333
0.66667
Fe5
12 k
0.17177
0.34350
O1
4e
0.00000
0.00000
O2
4f
0.33333
0.66667
O3
6h
0.18290
0.36576
O4
12 k
0.16446
0.32891
O5
12 k
0.49324
0.98638
RF 3.08
Rp 16.2
Rwp 8.75
RB 2.25
Phase 2: a-Fe2O3, Space group: R-3c (trigonal)
Fe
12c
0.00000
0.00000
O
18e
0.31098
0.00000
RF 3.86
RB 4.44

Z/c
0.25000
0.00000
0.25000
0.02841
0.19082
0.89121
0.14936
0.94586
0.25000
0.05186
0.14962
c2 1.21
0.35550
0.25000

a 5.0368 , c 13.7538 , V 302.18(3) 3.

Fig. 5(a)(d) show the ZFC and FC magnetization curves of

SrFe122xRuxTixO19 measured at 100 Oe. Similar measurements
were done even in a smaller magnetic eld of 40 Oe and the results
showed similar magnetization behavior. For each substituted
sample the ZFC magnetization increased from almost the same
value of ~2 emu/g at 5 K to a maximum value at TM, and then
decreased exhibiting a broad peak. Similar magnetization behavior
was reported for BaM doped with both CoeTi and RueTi [41]. The
temperature at peak value increased with increasing x. The occurrence of the peak can be associated with the magnetic domain wall
motion in multi-domain particles, where net magnetization is
established in the sample as a consequence of the 180 domain wall
ip into the direction of the applied eld when the eld is switched
on at 5 K. At this temperature, however, some domain walls are
pinned due to microstructure in the sample, and can be unpinned
by thermal activation [42], and the eld required to unpin the domains (Hcp) decreases with increasing temperature [43]. Consequently, the competition between the tendency to increase the
magnetization due to thermal unpinning of the domain walls, and
the tendency to reduce the magnetization due to thermal agitation
as the temperature increases at constant applied eld, is expected
to result in a peak (at TM). The slight shift of the peak position to
higher temperatures (TM ~ 47, 49, and 53 K for x 0.1, 0.2, and 0.3
respectively) can be associated with the enhancement of the
domain wall pinning by structural distortions as x increased. According to this interpretation, the absence of the peak in the sample
with x 0 is consistent with minimal structural distortions in
single domain particles, which is consistent with the results of the
XRD renement and SEM imaging. The observed behavior of
magnetization is consistent with the results of previous study on
BaM [15] and early studies on BaFe122xTixCoxO19 with x 0.8
[44,45]. The interpretation of the occurrence of the peak in the ZFC
curves as being due to ferromagneticesuperparamagnetic transition in the nano-sized particles was, however, in direct contradiction with the results of a more recent study [46], which concluded
that such transition occurs at ~ 700 K for the Ga substituted hexaferrites, resulting in a large Hopkinson peak just below TC. At
lower temperatures the particle moments are blocked and no
superparamagnetic behavior is anticipated.
In Fig. 6 (a), we extended our magnetization measurements to
higher temperatures for all concentrations to investigate their
superparamagnetic behavior. Indeed, the data shows a typical
behavior for a ferrimagnetic material with a large Hopkinson peak
just below Tc, indicating a superparamagetic behavior in this

A.M. Alsmadi et al. / Journal of Alloys and Compounds 648 (2015) 419e427

423

Table 5
Representative bond angles and bond lengths at different crystallographic site in SrTixRuxFe122xO19 hexaferrites.
site

4f1 e Fe3

Angle

O4eFe3eO2

O4eO2eFe3

12k e Fe5
O1eFe5eO2

O4eFe5eO2

2b e Fe2
O3eO1eFe2

O3eO1eO3

Fe1eFe3eO4

2a e Fe1

X0
X1
X2
X3
Length
X0
X1
X2
X3

106.30
108.10
107.53
107.44
Fe3eO4
1.8847
1.7983
1.8397
1.8037

35.85
34.62
36.05
35.15
Fe3eO2
1.9743
1.9190
1.8556
1.9032

172.05
171.20
169.73
170.70
Fe5eO2
2.0299
2.0463
2.0964
2.0732

89.99
88.70
87.81
88.05
Fe5eO4
2.1407
2.1607
2.1462
2.1589

35.99
39.15
37.62
38.77
Fe2eO1
2.3796
2.3590
2.3491
2.3203

61.19
66.22
63.83
65.68
Fe2eO3
1.7286
1.9202
1.8104
1.8634

26.78
28.48
28.10
28.36
Fe1eO4
1.9648
2.0589
2.0270
2.0585

Fig. 2. Variations of the bond lengths and bond angles of ions in the 2b (Fe2) bi-pyramidal site in the sample with x 0.1 (X1) as compared to those of the un-doped sample (X0).

Fig. 3. Structural distortions in the 4f1 (Fe3) tetrahedral, and 12 k (Fe5) octahedral sites
in the sample with x 0.2 (X2) as compared to the sample with x 0.1 (X1).

temperature regime. The critical temperature at the Hopkinson

peak value decreased with increasing x as a result of the decrease in
Curie temperature due to the reduction of the strength of the
superexchange interaction between spin-up and spin-down sublattices (Fig. 4(b)).
Fig. 5(a)(d) also show a clear irreversibility between the ZFC
and FC measurements. The FC magnetization is always above the
ZFC up to temperatures even above room temperature for higher
RueTi concentrations. This could be attributed to easier unpinning
of the domain walls by the constant eld at higher temperatures.
For all different concentrations, the FC magnetization reaches
almost a constant value below a given temperature, below which
the domain wall motion is saturated and no further increase in
magnetization occurs at lower temperatures.
In order to get more information on the nature of the transition
at TM , we extended our study to electrical resistivity measurements
using the Quantum Design 9 T Physical Properties Measurements
System (PPMS). In Fig. 7, the temperature dependence of the electrical resistivity SrFe122xRuxTixO19 with x 0.2, measured in zero
magnetic eld and in 1 T is shown. Similar behaviors were reported
recently for BaM doped with both RueTi and CoeTi substitutions
[41]. No signicant magnetic eld effects (magnetoresistance) were
observed and the resistivity data show some kind of a transition
from insulator to perfect insulator below TM . The resistivity
behavior could be associated with a perfectly insulating ferroelectric phase below about 50 K, which is destroyed as the conductivity

424

A.M. Alsmadi et al. / Journal of Alloys and Compounds 648 (2015) 419e427

Fig. 4. SEM images for representative samples of SrFe122xRuxTixO19 hexaferrites with a) x 0.0, b) x 0.1, c) x 0.2 and d) x 0.3.

FC

M (emu / g)

3.6

a)
x = 0.0
100 Oe

ZFC

3.2

2.9

substituted sample belong to hard magnetic materials with coercive eld strength of 3.598 kOe at 5 K. This value is in good
agreement with the reported value for a similar samples [1,22]. The
saturation magnetization at 5 K was obtained from the law of
approach to saturation [47]:

2.2

b)
x = 0.1
100 Oe

FC
ZFC

M (emu / g)

rises above this temperature [41].

Fig. 8(a) shows magnetization hysteresis curves of the
SrFe122xRuxTixO19 series for x 0.0 and x 0.2, measured at 5 K.
Similar measurements were done on the other samples with
different concentrations. The magnetization curves for the non-

T
1.8

1.6
1.4

SrFe
2.6

Ru Ti O

12-12x

19

1.2

FC

c)

M (emu / g)

2.6

2.3

M (emu / g)

x = 0.2
100 Oe

ZFC

d)

FC

2.8

x = 0.3
100 Oe

ZFC
2.4

1.6

1.9
0

50

100

150

T (K)

200

250

300

50

100

150

200

250

300

T (K)

Fig. 5. Zero-eld-cooled and eld-cooled magnetizations of SrFe122xRuxTixO19 as a function of temperature measured at 100 Oe for a) x 0.0, b) x 0.1, c) x 0.2, and d) x 0.3.

A.M. Alsmadi et al. / Journal of Alloys and Compounds 648 (2015) 419e427

a)

SrFe

Co Ti O

12-12x

x = 0.0

x = 0.2

0.8

x = 0.1

x = 0.3

760
c

100 Oe

0.6

b)

770

19

T (K)

M (emu / g)

1.2

425

750
0.4
0.2

740
560

600

640

680

720

760

800

0.1

0.2

0.3

Concentration (x)

T (K)

Fig. 6. (a) High temperature magnetizations measurements of SrFe122xRuxTixO19 with different concentrations. (b) The critical temperature at the Hopkinson peak value for
different concentrations.

. 
M MS  1  A=H  B H2 c  H

(1)

where MS is the spontaneous magnetization of the magnetic domains, c  H represents the contribution of the eld-induced increase in the spontaneous magnetization of the domains, A is a
constant associated with sample in homogeneity, and B is a constant related to the magnetocrystalline anisotropy contribution.
Straight lines of M vs 1/H 2 plots in the eld range between about
8 kOe and 12 kOe indicate that in this led range both A and the last
term in Equation (1) are negligible. The saturation magnetizations
for the samples were then determined from the intercepts of the
straight lines. Further, the slopes of these lines were used to
determine the anisotropy eld from the relation:

.
B Ha2 15

(2)

The rst anisotropy constant was then evaluated using the

relation [47]:

Ha 2K1 =MS

(3)

The saturation magnetization obtained from the linear t, and

the coercivity determined from the hysteresis loops are shown in
Fig. 8(b). The saturation magnetization and the coercivity exhibits a
behavior similar to that reported at room temperature [22]. The

SrFe12-12xRuxTixO19

8 10

x = 0.2

m)

6 10

0T
1T

4 10

2 10

0
0

40

80

120 160 200 240 280

saturation magnetization at 5 K was found to range from about

100 emu/g for the non-substituted sample to 93 emu/g for the
sample with x 0.3. The value for the non-substituted sample at
5 K is consistent with the theoretically predicted value at zero
temperature corresponding to a net magnetic moment of 20mB per
formula unit [1,47]. The value of MS 93 emu/g corresponds to a
net magnetic moment of 19:2mB at T 0. With RueTi substitution
at 5 K, the saturation magnetization showed small variations were
it slightly increases up to x 0.2 and then decrease for x 0.3. The
observed increase in the saturation magnetization up to x 0.2 is
consistent with the substitution of Fe3 ions by nonmagnetic Ru4
and Ti2 ions at 4f1 and 4f2 spin-down sites. On the other hand, the
observed drop in the saturation magnetization for higher concentrations can be partially associated with the excessive replacement
of Fe3 ions by Ti2 and Ru4 ions at the 12 k and 2b spin-up sites,
which was conrmed by our structural analyses, and room tem ssbauer spectroscopy results [22]. The observed 7%
perature Mo
reduction in saturation magnetization for the sample with x 0.3 is
also consistent with the presence of 6.88% wt. of nonmagnetic iron
oxide phase in this sample as conrmed by our structural renement. This could lead to the conclusion that the TieRu substitution
in this sample occurs randomly at spin-up and spin-down sites
with almost equal probabilities.
The coercivity, HC , was found to decrease signicantly from
about 3.6 kOe to 0.45 kOe as x increased from 0.0 to 0.3. Thus, the
substitution of a small fraction of Fe by RueTi resulted in a substantial reduction in coercivity, and an improvement in saturation
magnetization at low x. This indicates that this system, especially at
low RueTi substitutions in the range between 0.0 and 0.2, has
potential for magnetic recording applications since one can easily
control HC to meet the requirements of different magnetic
recording systems, while maintaining a relatively high value of MS .
For x 0.1 and x 0.2, the saturation magnetization MS was found
to be around 102 emu/g, while the coercivities were found to be
around 0.98 and 0.61 kOe, respectively. Similar behaviors were
reported on other SrM systems especially at low substitutions
[1,22,48]. The behavior of the coercivity is consistent with the
general behavior of the anisotropy eld shown in Fig. 8(c) and the
saturation magnetization. The initial large drop in coercivity in the
concentration region between 0.0 and 0.2 is associated with the
decrease in anisotropy eld and increase in saturation magnetization according to the relation:

T(K)
Fig. 7. Electrical resistivity of the SrFe122xRuxTixO19 sample with x 0.2 as a function
of temperature measured at different applied magnetic elds.

HC CHa  Nd MS

(5)

0
-40

95

90

Ru Ti O
x

19

1.3 10

0.1

0.3

c)

13

12

0.2

Concentration (x)

Magnetic field (Oe)

11

3
1

2.5

H (KOe)

12-12x

-1.3 10

10
2

9
8

SrFe
4

100

K (10 erg/cm )

-80

x = 0.0
x = 0.2
5K

40

105

b)

Magnetization, M (emu / g)

Coercivity, H (kOe)

M (emu / g)

a)

80

1.5
0

0.1

0.2

0.3

Concentration (x)

a)
Ru Ti O

12-12x

19

60

40

x = 0.0
x = 0.1
x = 0.2
x = 0.3

20

b)

4.8
4
3.2
2.4
1.6
0.8
0

14

c)

d)

3
3

12

x=0
x = 0.1
x = 0.2
x = 0.3

10

H (KOe)

Coercivity, H (kOe)

SrFe

80

x = 0.0
x = 0.1
x = 0.2
x = 0.3

5.6

K (10 erg / cm )

Magnetization, M (emu / g)

Fig. 8. (a) Magnetization loops of the SrFe122xRuxTixO19 samples with x 0.0 and 0.2 as a function of the applied magnetic eld measured at 5 K. (b) Saturation magnetization and
coercivity of SrFe122xRuxTixO19 as a function of RueTi concentration (x). (c) Anisotropy eld and the rst anisotropy constant of SrFe122xRuxTixO19 as a function of RueTi concentration (x).

x = 0.0
x = 0.1
x = 0.2
x = 0.3

2.5
2
1.5
1
0.5
0

200

400

600

Temperature (K)

800

200

400

600

800

Temperature (K)

Fig. 9. (a) Saturation magnetization, (b) Coercivity, (c) Anisotropy eld and (d) The rst anisotropy constant of SrFe122xRuxTixO19 as a function of temperature for different RueTi
concentration (x).

A.M. Alsmadi et al. / Journal of Alloys and Compounds 648 (2015) 419e427

where C is a constant which depends on the nature and degree of

alignment of the magnetic particles, and Nd is the demagnetization
factor which depends on the shape of the particles. Fig. 8(c) also
shows the variation of the rst anisotropy constant with x. The
value of 3.26  106 erg/cm3 is in good agreement with the reported
value for pure SrM hexaferrite [1].
We extended our measurements to evaluate the temperature
dependence of the coercivity, saturation magnetization, anisotropy
eld and anisotropy constant for all other concentrations. The
isothermal magnetization hysteresis curves of the SrFe122xRuxTixO19 were taken at different temperatures ranging from 5 K to
800 K. In Fig. 9 (a), (b), the extracted values for saturation magnetization and coercivity of SrFe122xRuxTixO19 sample with different
concentration are shown as a function temperature. The saturation
magnetization showed a typical behavior of a ferrimagnetic material with TC around 730 K. On the other hand, the value of the
coercivity, HC , showed a broad peak around 580 K. The appreciable
increase in coercivity below 500 K could be a consequence of the
thermally assisted domain wall de-pinning and the transition to
single domain particles at temperatures above TM . Fig. 9(c),(d)
show the variation of the anisotropy eld and the rst anisotropy
constant with temperature for different concentrations. It was
found that the anisotropy constant decreased with temperature,
while a very slight increase in the anisotropy eld was observed.

427

References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]

4. Conclusion

[25]
[26]

In conclusion, RueTi substituted strontium ferrite nanocrystalline particles: SrFe122xRuxTixO19 with (0  x  0:3) were prepared
by ball milling method. Full structural renement was carried out,
and rened ionic positions, cationic distributions, and structural
distortions were discussed. Also, the static magnetic properties of
the powders and their temperature dependencies were studied.
The ZFC and FC curves of all samples below room temperature
displayed behavior consistent with the thermally aided unpinning
of domain walls and the subsequent domain wall motion. The position of the observed peak in ZFC curves at a temperature TM
seems to be sensitive to the microstructure of the prepared samples. We also observed a clear irreversibility between the ZFC and
FC curves, which disappeared as we go above the room temperature region. The resistivity data show some kind of a transition from
insulator to perfect insulator below TM . This is associated with a
transition to a ferroelectric state below TM . TM shifted slightly to
higher values by increasing the RueTi concentration due to the
increased level of crystal imperfections and the consequent
enhancement of the domain wall pinning. The high-temperature
magnetization measurements exhibited sharp peaks at Tc indicating a superparamagnetic behavior just below the Curie temperature. At 5 K, doping strontium ferrite with RueTi resulted in
small variations in their saturation magnetization (slight
improvement at low concentration) and a signicant drop in their
coercivity, recording a reduction of about 78% at x 0.3.

[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]

R.C. Pullar, Prog. Mater. Sci. 57 (2012) 1191.

U. Ozgr,
Y. Alivov, H.J. Morko, Mater. Sci. Mater. Electron 20 (2009) 789.
T. Kimura, Annu. Rev. Condens. Matter Phys. 3 (2012) 93.
P. Novak, J. Rusz, Phys. Rev. B 71 (2005) 184433.
G. Tan, X. Chen, J. Magn. Magn. Mater. 327 (2013) 87.
N. Koga, T. Tsutaoka, J. Magn. Magn. Mater. 313 (2007) 168.
Y.Y. Meng, M.H. He, Q. Zeng, D.L. Jiao, S. Shukla, R.V. Ramanujan, Z.W. Liu,
J. Alloys Compd. 583 (2014) 220.
J. Kreisel, H. Vincent, F. Tasset, P. Wolfers, J. Magn. Magn. Mater. 213 (2000) 262.
G. Li, G. Hu, H. Zhou, X. Fan, X. Li, Mater. Chem. Phys. 75 (2002) 101.
G.-H. An, T.-Y. Hwang, J. Kim, J.B. Kim, N. Kang, S. Kim, Y-m. Choi, Y.-H. Choa,
J. Alloys Compd. 583 (2014) 145.
S.B. Narang, L.S. Huidara, J. Ceram. Process Res. 7 (2006) 113.
M.M. Rashad, I.A. Ibrahim, J. Magn. Magn. Mater. 323 (2011) 2158.
O. Kabo, T. Ido, H. Yokoyama, IEEE Trans. Magn. 18 (1982) 1122.
G.B. Teh, Y.C. Wong, R.D. Tilley, J. Magn. Magn. Mater. 323 (2011) 2318.

si
M. Drofenik, I. Ban, D. Makovec, A. Znidar
c, Z. Jagli
ci
c, D. Han
zel, D. Lisjak,
Mater. Chem. Phys. 127 (2011) 415.
M. Jean, V. Nachbaur, J. Bran, J.-M. Le Breton, J. Alloys Comp. 496 (2010) 306.
U. Topal, H. Ozkan, L. Dorosinskii, J. Alloys Comp. 428 (2007) 17.
Y.P. Fu, C.H. Lin, K.Y. Pan, J. Appl. Phys. 42 (2003) 2681.
A. Ataie, S.E. Zojaji, J. Alloys Compd. 431 (2007) 331.
M. Awawdeh, I. Bsoul, S.H. Mahmood, J. Alloys Compd. 585 (2014) 465.
I. Bsoul, S.H. Mahmood, J. Alloys Compd. 489 (2010) 110.
I. Bsoul, S.H. Mahmood, A.-F. Lelooh, A. Al-Jamel, J. Alloys Comp. 551 (2013)
490.
G. Mendoza-Suarez, L.P. Rivas-Vazquez, J.C. Corral-Huacuz, A.F. Fuentes,
J.I. Escalante-Garcia, Phys. B 339 (2003) 110.
P. Sharma, R.A. Rocha, S.N. Medeiros, B. Hallouche, A. Paesano Jr., J. Magn.
Magn. Mater. 316 (2007) 29.
M. Jazirepour, M.H. Shams, O. Khani, J. Alloys Compd. 545 (2012) 32.
G.H. Dushaq, S.H. Mahmood, I. Bsoul, H.K. Juwhari, B. Lahlouh, M.A. AlDamen,
Acta Metall. Sin. Eng. Lett.) 26 (2013) 509.
S. Ounnunkad, P. Winotai, J. Magn. Magn. Mater. 301 (2006) 292.
D. Chen, Y. Liu, Y. Li, K. Yang, H. Zhang, J. Magn. Magn. Mater. 337e338 (2013)
65.
X. Zhang, Y. Duan, H. Guan, S. Liu, B. Wen, J. Magn. Magn. Mater. 311 (2007)
507.
S. Singhal, A.N. Garg, K. Chandra, J. Magn. Magn. Mater. 285 (2005) 193.
X. Gao, Y. Du, X. Liu, P. Xu, X. Han, Mater. Res. Bull. 46 (2011) 643.
X. Tang, Y. Yang, K. Hu, J. Alloys Compd. 477 (2009) 488.
, J. Lipka, M. Papa
nov
A. Gonz
alez-Angeles, G. Mendoza-Su
arez, A. Gruskova
a,
J. Sl
ama, J. Magn. Magn. Mater. 285 (2005) 450.
I. Bsoul, S.H. Mahmood, J. Abdel-Fatah Lehlooh, Alloys Comp. 498 (2010) 157.
W. Zhang, Y. Bai, X. Han, L. Wang, X. Lu, L. Qiao, J. Alloys Comp. 546 (2013)
234.
R. Grossinger, M. Kupferling, J.C. Tellez Blanco, G. Wiesinger, M. Muller,
G. Hilscher, et al., IEEE Trans. Mag. 39 (2003) 2911.
Q. Fang, Y. Liu, P. Yin, X. Li, J. Magn. Magn. Mater. 234 (2001) 366.
A. Ghasemi, J. Magn. Magn. Mater. 324 (2012) 1375.
J. Luo, Mater. Lett. 80 (2012) 162.
L. Rezlescu, E. Reslescu, P.D. Papo, J. Magn. Magn. Mater. 193 (1999) 288.
A.M. Alsmadi, I. Bsoul, S.H. Mahmood, G. Alnawashi, K. Prokes,
K. Siemensmeyer, B. Klemke, H. Nakotte, J. Appl. Phys. 114 (2013) 243910.
P. Gaunt, IEEE Tans. Magn. 5 (1983) 2030.
rtesy, I. Tomaa
s, Z. Ve
rtesy, J. Phys. D. Appl. Phys. 35 (2002) 625.
G. Ve
rmert, E. Sinn, IEEE
X. Batlle, M. Garca del Muro, J. Tejada, H. Pfeiffer, P. Go
Trans. Magnetics 30 (1994) 708.
rmert, E. Sinn, J. Appl.
X. Batlle, M. Garca del Muro, J. Tejada, H. Pfeiffer, P. Go
Phys. 74 (1993) 3333.
S.H. Mahmood, I. Bsoul, EPJ Web Conf. 29 (2012) 00039.
B.D. Cullity, C.D. Graham, Introduction to Magnetic Materials, second ed.,
Wiley, Hoboken, New Jersy, 2009.
S. Kanagesan, S. Jesurani, R. Velmurugan, T. Kalaivani, J. Mater. Sci. Mater.
Electron 23 (2012) 952.