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http://dx.doi.org/10.1016/j.jmmm.2015.05.003
MAGMA60178
Abstract
Nano crystalline NiFe2-xGdxO4 (0.0x0.4) ferrite was prepared by citrate method. The samples were
characterized with X-ray diffraction, FT-IR spectroscopy, TEM and magnetic measurements. The
effect of Gd3+ cations substitution on structural, microstructural and magnetic properties of prepared
nanoparticles was investigated. From Rietveld analysis, the system was found to be inverse spinel
structure with Gd3+ residing on octahedral B-site 16 c and the grain boundary, while Ni2+ occupying
the B-site at both 16c and 16d. The lattice parameter (a) changes nonmonotonically, first increases then
decreases with Gd doping content. The MH and MT relations had demonstrated a change in the
magnetic moment and a ferrimagnetic superparamagnetic transition in the ferrite system. For low
temperature measurements, an increase in gadolinium content resulted in increasing the coercive field
while the saturation of magnetization (Ms), first deceases then increases with Gd doping content. At
room temperature Ms decreases with increasing Gd substitution.
Keywords: Nickel
Microstructure.
nanoferrite,
Gadolinium,
Rietveld,
magnetic,
cations
distribution,
1. Introduction
Beside the versatile applications taking advantages of their upgrading properties, spinel ferrites
show physical phenomena of fundamental interest in physics. For instance, magnetic and electric
properties are tunable with a small change in chemical stoichiometry or particle size [15].
Moreover, different cationic distribution, between the two crystallographically nonequivalent
sites 8b and 24d, and oxygen vacancies yield unusual magnetic properties especially for
nanoferrites [610].
Ferrimagnetic nickel ferrite has attracted growing attention due to its remarkable properties:
large permeability, high saturation magnetization, high resistivity, so low eddy currents, and
accordingly potential applications in versatile fields. Substitution of magnetic or nonmagnetic
ions at Fe site on either A or B site may result in changes in the magnetic and electric properties
suitable for special functions. Due to their high resistivity, rare earth oxides are good candidate
for doping spinel ferrites. By the proper choice of rare element for doping, the electric and
magnetic properties can be tailored for especial application.
Doping with large ions like rare-earth ones, leads to structural disorder; change in grain size and
lattice strain. Also rare-earth (RE) atoms play an important role in determining the magnetic
crystalline anisotropy in the 4f3d intermetallic compounds [11]. So, introducing trivalent rare
earth (RE) cations into the inverse ferrite lattice will induce RE3-Fe3 interactions and hence
modify the magnetic properties [1214]. Many publications handled the substitution of rare earth
ions at Fe site in spinel ferrites.
Bharathi et. al. investigated ferroelectric and ferromagnetic properties of Gd [15], Dy [16], Sm
and Ho [17] substituted nickel ferrite. Kahn et.al. investigated magnetic properties of cobalt
spinel ferrite nanoparticles doped with lanthanide ions and found a dramatic increase in the
blocking temperature and coercivity in case of Gd3+ or Dy3+ ions [18]. Dixit et. al. studied the
temperature-dependent electron paramagnetic resonance spectra of Ce- and Gd- doped nickel
ferrite nanoparticles [19].
The distribution of cations among the lattice sites depends on method of preparation [20-22]. The
spinel ferrite crystallizes in the space group 3 with a unit cell containing 32 oxygen atoms.
The unit cell contains 32 octahedral holes (16c and 16d) and 64 tetrahedral holes (8a, 8b, and
48f). In the spinel structure only one eighth of the available tetrahedral sites and half of the
octahedral ones are occupied. Taking the center of symmetry at (), cations may occupy the
tetrahedral sites 8a at (000) (A-site) and/or the octahedral sites 16d at ( 3 8 3 8 3 8 ) (B-site). For
nickel ferrite, NiFe2O4, Ni ions has a strong preference for octahedral B-sites, forming inverse
spinel, despite partial inverse distribution was reported [23, 24]. Also, abnormal cation
distribution with Ni ions occupying octahedral 16c sites was reported for nonstoichiometric
ferrites obtained from -NaFeO2 via molten media reactions [25].
In the present study, X-ray powder diffraction (XRD) with Rietveld analysis, IR, TEM and
magnetic measurements at room and low temperatures, have been performed to find out the
effect of Gd doping in nanocrystalline NiFe2-xGdxO4, (x=0, 0.1, 0.2, 0.3, 0.4) on the
microstructural parameters, cations distribution among A and B sites and the magnetic
parameters of the system.
2. Experimental
NiFe2-xGdxO4 (0x0.4) samples were synthesized using stoichiometric amounts of iron, nickel,
and gadolinium nitrates and citric acid. Deionized water was as a solvent.
The solution was heated under stirring to evaporate the solvent water. The gel was dried at 180
C for 1 h then heated at 400 oC for an hour then cooled to room temperature [24-28]. X-ray
diffraction patterns were collected using Panalytical diffractometer (Xpert MPD) with Cu-K
radiation. The MAUD program [29] was used for crystal structure and microstructure refinement
applying Rietveld profile method. In this program, the U, V, W parameters of the instrumental
broadening, the instrumental asymmetry and the Gaussianty of reflections were estimated for the
present setting of the diffractometer using a LaB6 standard sample. These instrumental
parameters were kept fixed during the successive profile refinements of the samples. Anisotropic
crystallite size and lattice microstrain were obtained from subsequent refinement. Infrared (IR)
spectroscopy (Bruker Tensor 27 FTIR Spectrometer) was used in the range of 4004000 cm-1,
for this purpose, quantities of 0.2 mg ferrite per 200 mg KBr were mixed and pressed into
pellets. The powder morphology was recorded by transmission electron microscope (TEM,
JEOL JEM-100CX) with accelerating voltage up to 100 kV. Magnetic measurements were
carried out with the Quantum. Design Model 6000 Vibrating Sample Magnetometer (VSM)
option for the physical properties measurement system (PPMS) in the temperature interval from
5 to 300 K under a magnetic field up to 6 T
for the two cases; the weighted profile residual factor is reduced from 13.6 to 11.2 %.Moran et.
al. reported similar results for nickel [31] and magnesium [25] ferrites obtained from -NaFeO2
via molten media reactions, applying neutron and x-ray diffraction for structural analysis. It is
interesting to note that Mg enter both the tetrahedral and the octahedral positions, while Ni enter
only octahedral ones. For the ideal value of u = 0.375, the arrangement of O2- ions fits exactly a
cubic closed packing, but in actual spinel lattice, this ideal pattern is slightly deformed. Values of
u > 0.375 mean that O2- ions move away from the cations in tetrahedral A-site along the 111
directions due to the expansion of the tetrahedral interstices; correspondingly the octahedral Bsites become smaller. Inspecting Table 1, one notices that the occupancy values of Gd ions are
less than the values intended during the preparation. This is make us assume that some Gd ions
may reside at grain boundary as the ionic radii of the Gd3+ ions are larger than that of Fe3+ ions.
This is manifested in the diffraction patterns by the saddle appeared in the low 2 region
resulting in bad fitting during Rietveld analysis, Fig. 1. Also, the presence of Gd ions at the grain
boundaries yields a pressure on the grains and hinders the growth of grains, so the grain size
decreases as the Gd content increases and the diffraction peaks become broader, Fig. 1.
Inspecting table 1, the crystallite size for all samples is in the nano range and, to some extent; it
may be considered as quantum dots. The lattice microstarin increases markedly upon insertion of
Gd ions due to the large difference in ionic radii of Gd3+ and Fe3+.The lattice parameter (a) first
increases then decreases with increasing Gd doping concentration, Fig.2. These results confirm that
Gd content with x0.1 can enter the lattice while for x > 0.1, the decreases in the lattice parameter
could be attributed to that some Gd ions reside at the grain boundaries, as mentioned above,
obstructing the grain growth and exerting a pressure on the grains leading the lattice parameter to
decrease.
The bond lengths between cations (Me-Me) (b, c, d, e, and f), cations -anion (Me-O) (p, q, r, and s)
and the bond angles (1, 2, 3, 4, and 5) between the cations and cation-anion, Fig.3, are given by
following relations [32]:
Me-O:
Me-Me:
p =a(5/8-u)
= 2(/4)
= 3( 1/4)
= 11(/8)
= 11( 1/8)
= 3(/4)
= 3( + 1/8)
3
= 3(3/8)
+
=
(
)
2
+
=
(
)
2
2
! =
(
)
2
+
#
" =
(
)
2
+
$ =
(
)
2
# = 6(/4)
The values of the interatomic distances between cationanion (Me-O) and cation-cation (MeMe) for NiFe2-xGdxO4 nano system are p (2.1002.076 ), q (2.0751.950 ), r (3.4393.511
), s (3.7603.777 ), b (3.0083.024 ), c (3.5273.546 ), d (3.6793.639 ), e (5.422
5.427 ), and f (5.1125.118 ) varies with increasing Gd3+ substitution. This variation in bond
lengths is related to the higher ionic radius of Gd3+ ions. This can lead to the change in the superexchange strength (wave-function overlapping) [32]. The bond angles vary such as 1 (125.79
4
amount of Gd increases; similar results was obtain with Gd doped CoFe2O4 [34]. Neel theory
explains the dependency of the blocking temperature on K (the magnetocrystalline anisotropy
constant), and/or V (the average particle volume) and is given by the following equation [35]:
25 kBTB= KV
In our case, the particle size decreases with Gd substitution, Table 1, this leads to a decrease in
the average particle volume and hence decreases in TB with Gd substitution amount increases
[34].
The magnetization measurements (M-H) for NiFe2-xGdxO4 nanoparticles with different Gd
contents (0x0.4) at 300 K and 10 K are shown in Fig.7. There is a considerable enhance in
magnetic properties as temperature decreases.
The increase in these values may be because of the proper ordering of the magnetic moments
along the direction of the magnetic field which in turn is disturbed at elevated temperatures (at
300 K) due to the randomization of the magnetic moment by the thermal vibrations. The
hysteresis loops, Fig.7, showed that the value of magnetization increases with the applied
magnetic field and it does not attain saturation due to the smallest average crystallite size of the
samples, Table 1. These nano size particles are much smaller than the magnetic domain and
accordingly saturation does not achieved. The insets of Fig.7 show the presence of coercivity for
nano NiFe2O4 sample at 10 and 300 K, while the doped samples have coercivity only at 10 K.
This indicates that pure nickel ferrite exhibit ferrimagnetic behavior while all doped samples are
superparamagnetic at room temperature.
The saturation magnetizations (Ms) at 10 K are obtained from the extrapolation of M vs 1/H
curve to1/H0 and are plot in Fig. 8a. The degree of magnetic saturation and the corresponding
magnetization values were strongly dependent on the composition of the ferrites. The magnetic
moments in the case of the rare-earth ions generally originates from the localized 4f electrons
and they are characterized by lower ordering temperatures, i.e. less than 40 K [36], so its effect
should appear in our case (10 K). Other reports measured the hysteresis loops for Gd substituted
CoFe2O4 or NiFe2O4 [37, 38] at room temperature where the Gd is treated as diamagnetic
element with no magnetic moment. In our case, at 10 K the saturation magnetization generally
increases as the amount of Gd substitute Ni-ferrite increases except for x=0.1 it decreases. The
increasing in magnetization is due to the substitution of Fe3+ ions at the octahedral site (B-site)
by Gd3+ ions, which have the high spin magnetic moment (7.9 B) compared to that of Fe3+ ion
(5 B). The decrease of saturation magnetization for x=0.1 may be do to present Gd in A-site as
indicated by IR spectrum, which may be decreasing the number of magnetic linkages occurring
between tetrahedral and octahedral cations and hence weakening of exchange interactions.
Inspecting Fig. 7a for M-H at room temperature, one can find out that Ms is decreasing with the
Gd content, Fig.8b. a result consistent with the cation distribution obtained from X-ray analysis.
Table1. Substituting Fe3+ magnetic ions by Gd3+ ion in the B-site reduces the net magnetic
moment, where Gd ions are treated as diamagnetic ions as mentioned above. By introducing rare
earth ions, the interaction Gd3+-Fe3+ takes place with the 3d-4f electron coupling and, as a
consequence, the magnetic exchange interaction between the cations in the A-site and B-site is
reduced. Moreover, the exchange interactions Fe-Gd and Gd-Gd (indirect 4f5d5d4f
mechanism) are much weaker than Fe-Fe interaction.
The change of coercivity at 10 K with increase the amount of Gd doped Ni ferrite is shown in
Fig.8c; the coercivity increases as the amount of gadolinium substitution increases. This result
was obtained previously in other ferrite CoFe2-xGdxO4 [39] and it can explain as follows: Gd3+
and Ni2+ ions have stronger s-l coupling and weaker crystal field, so they have stronger
magnetocrystalline anisotropy [40-41]. Moreover, the radii of Gd3+ ions are larger than that of
Fe3+ ions, the symmetry of crystal will be decreased after the sample was substituted by Gd3+
ions, hence there is a distort in lattice field, and generate an internal stress [42], Table1.
Furthermore, the crystallite size decreases as the amount of Gd increases, Table1, hence the grain
boundary increases. So, the area of disordered arrangement for ions on grain boundaries may fix
and hinder the domain walls motion, thus the coercivity of the samples increases with
Gd3+substitution ions. In addition the values of the coercivity for Gadolinium substituted Nickel
ferrite are very large, because Gadolinium has got a ferromagnetic at low temperature as mention
above, and also strongly paramagnetic at high temperature temperature and has magnetocaloric
effect [43]. Thus, when it enters a magnetic field its temperature increases. Therefore, when Gd
is added to any system, the magnetic behavior (as coercive field) of the system can increase.
Conclusion
NiFe2-xGdxO4 (0.0 x 0.4) nano ferrites have been prepared by citrate-precursor method. TEM
micrograph confirmed the nanoscale nature of the prepared powders. A rather unusual cation
distribution is found for Ni2+ residing at the two octahedral sites 16c and 16d. Rietveld analysis
revealed that Gd3+ is accommodated at the octahedral sites 16c with a part on the grain boundary,
nevertheless FT-IR spectrum indicated that, for the sample x=0.1, part of Gd3+ is residing at
tetrahedral site 8a. The lattice parameter (a) changed nonlinearly with Gd doping content. MH
magnetic measurements indicated that all the doped samples exhibit superparamagnetic behavior
at room temperature while pure nickel ferrite exhibit ferrimagnetic behavior. The saturation of
magnetization(Ms) at 10 K first decreases due to the present of Gd ions in A site then it increases
as the amount of Gd substitution increases due to substitution of Fe3+ ions by Gd3+ ions which
have larger magnetic moment. Ms at room temperature decreases with increasing the amount of
Gd substitution due to substitution of magnetic ions (Fe3+) by nonmagnetic ions (Gd3+). The
coercive field increased with the Gd content due to the decrease in crystallite size.
References
[1] Alex Goldman, Modem Ferrite Technology, 2nd Ed., 2006 Springer Science+Business
Media, Inc.
[2] K. Szymaski, L. Dobrzyski, M. Bakr, D. Satua, W. Olszewski, G. Parzych, H. Fuess,
Phase Transit., 83(2010)824.
[3] Mohamed Bakr Mohamed, Adel Maher Wahba, M. Yehia, Mater. Sci. Eng. B 90(2014)52.
[4] Adel Maher Wahba, Mohamed Bakr Mohamed, Ceram. Int. 40 (2014) 6127.
[5] Mohamed Bakr Mohamed, M. Yehia, J. Alloy. Comp. 615 (2014) 181.
[6] A.H. Ashour, O.M. Hemeda, Z. K. Heiba, S.M. Al-Zahrani, J. Magn. Magn.Mater. 369
(2014) 260.
[7] Ge-Liang Sun, Jian-Bao Li, Jing Jing Sun, Xiao Zhan Yang, J. Magn. Magn.Mater.281
(2004) 173.
[8] Z. K. Heiba, N.Y. Mostafa, O.H.Abd-Elkader, J. Magn. Magn.Mater. 68 (2014) 246.
[9] Adel Maher Wahba, Mohamed Bakr Mohamed, J. Magn. Magn.Mater.378 (2015) 246.
[10] N. Y.Mostafa, Z.I. Zaki, Z.K. Heiba, J. Magn. Magn. Mater. 329 (2013) 71.
[11] G.-L. Sun, J.-B. Li, J.-J. Sun, and X.-Z. Yang, J. Magn. Magn. Mater. 281 (2004) 173.
[12] J. Jensen and A. Mackintosh, Rare Earth Magnetism Structures and Excitations (Clarendon,
Oxford, 1991).
[13] M. H. Mahmoud and A. A. Sattar, J. Magn. Magn. Mater. 277 (2004) 101.
[14] S. Urcia-Romero, O. Perales-Perez, and G. Gutierrez, J. Appl. Phys. 107 (2010) 09A508.
[15] K.K. Bharathi and G. Markandeyulu, J. Appl. Phys. 103 (2008) 07E309.
[16] K.K. Bharathi, K. Balamurugan, P. N. Santhosh, M. Pattabiraman and G. Markandeyulu,
Phys. Rev. B 77 (2008) 172401.
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[18] M. L. Kahn, Z. J. Zhang, Appl. Phys. Lett., Vol. 78 (2001) 3651.
[19] G. Dixit, J.P. Singh, R.C.Srivastava, H.M.Agrawal, J. Magn. Magn.Mater. 324 (2012) 479.
[20] Zein K. Heiba,
3750.
NiFe2-xGdxO4
(a)
x=0.4
x=0.3
x=0.2
x=0.1
x=0.0
(b)
(c)
8.360
NiFe2-xGdxO4
8.355
a ()
8.350
8.345
8.340
8.335
8.330
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
11
p
3
p
1 Oxygen
2
e
c
q
Fig. 3. Configuration of the ion pairs in spinel ferrites with favorable distances and
angles.
12
T%
NiFe2-xGdxO4
x
0.4
0.3
0.2
0.1
0
500
-1
Wavenumber (cm )
13
14
2.0
3.0
NiFe1.8Gd0.1O4
NiFe2O4
2.5
1.5
M(emu/g)
1.5
1.0
0.5
1.0
0.5
50 Oe
50 Oe
0.0
0.0
ZFC
FC
-0.5
-50
-0.5
-50
ZFC
FC
0
T (K)
2.5
3.6
NiFe1.8Gd0.2O4
3.3
2.0
3.0
1.5
2.7
M(emu/g)
M(emu/g)
2.4
2.1
50 Oe
1.8
1.5
ZFC
FC
1.2
-50
NiFe1.7Gd0.3O4
1.0
0.5
0.0
50 Oe
ZFC
FC
-0.5
-1.0
-50
T(K)
1.5
NiFe1.6Gd0.4O4
1.2
0.9
M(emu/g)
M(emu/g)
2.0
0.6
0.3
50 Oe
0.0
ZFC
FC
-0.3
-50
30
20
20
M (emu/g)
10
(a)
-20
-1.3
0.0
1.3
0
NiFe2-xGdxO4
-10
-20
300 K
-30
-30
-20
-10
10
20
x=0.0
x=0.1
x=0.2
x=0.3
x=0.4
30
H (kOe)
50
40
(b)
30
30
10
0
-10
NiFe2-xGdxO4
10 K
M(emu/g)
M(emu/g)
20
x=0.0
x=0.1
x=0.2
x=0.3
x=0.4
-20
-30
-40
0
NiFe2-xGdxO4
10 K
x=0.0
x=0.1
x=0.2
x=0.3
x=0.4
-30
-50
-40
-30
-20
-10
10
20
30
40
-4
H(kOe)
-2
H(kOe)
Fig.7. Magnetization as function of applied magnetic field (M vs. H) hysteresis loop at (a) 300 and (b) 10
K with magnified part of hystersies loops for CoFe2-xGdxO4 (0x0.4).
16
32
NiFe2-xGdxO4
55
30
50
MS(emu/g)
28
(a)
45
40
26
(b)
24
22
300 K
20
35
18
10 K
30
16
0.0
0.1
0.2
0.3
0.4
0.0
0.1
0.2
x
0.3
0.65
NiFe2-xGdxO4
0.60
0.55
Hc(KOe)
MS(emu/g)
NiFe2-xGdxO4
0.50
(c)
0.45
0.40
10 K
0.35
0.0
0.1
0.2
x
0.3
0.4
17
0.4
Table1
x = 0.1
x = 0.2
x = 0.3
x = 0.4
Cell parameter
8.348(2)
8.356(3)
8.348(3)
8.338(4)
8.333(8)
O (u-parameter)
0.3777
0.3803
0.3804
0.3803
0.3603
[100]
10.2
9.3
8.5
8.6
8.8
[111]
18.4
15.4
8.1
7.5
5.5
Strain [100]
x10-4 [111]
2.0
27.2
41.4
27.0
60.6
2.1
33.4
40.8
19.1
34.9
Size nm
Atom
position
Ni
16d
16c
0.894
0.106
0.667
0.333
0.743
0.257
0.542
0.458
0.444
0.556
8a
1.0
1.0
1.0
1.0
1.0
16d
1.0
0.9
0.8
0.7
0.6
16d
0.0
0.108
0.111
0.253
0.269
550.83
548.85
556.2
564.9
Fe
Gd
1(cm-1)
Occupancy factors
551.03
Highlights
18