Journal of Alloys and Compounds 486 (2009) 759–767

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jallcom

Structure and magnetic properties of Nix Zn1−x Fe2 O4 nanoparticles prepared

through co-precipitation method
M.M. Rashad a,∗ , E.M. Elsayed a , M.M. Moharam a , R.M. Abou-Shahba b , A.E. Saba a
a
Central Metallurgical Research and Development Institute (CMRDI), P.O. Box 87, Helwan 11421, Egypt
b
Chemistry Department, Faculty of Science (Girls), Al-Azhar University, Cairo, Egypt

a r t i c l e i n f o a b s t r a c t

Article history: Nickel zinc ferrites, Nix Zn1−x Fe2 O4 , nanoparticles have been synthesized using the chemical co-
Received 7 April 2009 precipitation technique. Effects of synthesis conditions on the crystal structure, crystallite size, lattice
Received in revised form 8 July 2009 parameter, microstructure and magnetic properties of the produced spinel ferrites were investigated by
Accepted 8 July 2009
X-ray diffraction analysis (XRD), scanning electron microscope (SEM) and vibrating sample magnetome-
Available online 16 July 2009
ter (VSM). The results showed that a well crystalline single cubic structure of Ni0.5 Zn0.5 Fe2 O4 phase was
formed through precipitation precursors at pH 10 and annealed for 2 h at 1000 ◦ C, using sodium carbonate
Keywords:
to adjust the pH. With the use of NaOH to adjust the pH, mixture of Ni0.5 Zn0.5 Fe2 O4 and Fe2 O3 phases
Nickel zinc ferrites
Nanoparticles
were obtained. However, the addition of hydrogen peroxide, to the sodium hydroxide during precipitation,
Synthesis improved the formation of the single phase of Ni–Zn spinel ferrites. Moreover, the addition of two types
Microstructure of surfactants found to enhance the formation of the spinel crystal structure of the ferrites. The change of
Magnetic properties the Ni molar ratio content (x) from 0.2 to 0.9 had strongly affected the properties of the formed ferrites
powders. The lattice parameters found to decline gradually with increasing nickel content and the crys-
tallite size was in the range between 27 and 155 nm. Maximum saturation magnetization (85.4 emu/g)
was achieved for the prepared Ni0.5 Zn0.5 Fe2 O4 phase; annealed at 1200 ◦ C for 2 h using Na2 CO3 as alkali.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction
Nickel zinc ferrites with spinel crystal structure posses a unique
combination of desirable properties such as large magnetic per-
meability at high frequencies, electrical resistively, mechanical
hardness, chemical stability and reasonable cost [1]. Accordingly,
they have a wide range of applications in microwave absorbance,
number of electronic devices as, radio, TV sets, integrated non-
reciprocal circuits, high frequency transformers, memory cores
devices, rod antennas, read-write heads for high-speed digital tape
or disk recording [1–5], telecommunication applications [6] and
excellent catalyst for alkylation of aromatics [7]. Furthermore, they
are used for gas and ethanol sensors [8]. The crystal structure of
Ni–Zn ferrites spinel configuration is based on a face centered cubic
lattice of oxygen ions. The unit cell consists of eight formula units of
the type [ZnFe1−x ]A [Ni1−x Fe1+x ]B O4 , where A represents tetrahedral
site and B octahedral site [9].
The conventional method for the synthesis of the ferrites
is solid-state reaction method in which, Ni–Zn ferrite is pre-
pared by mixing the desired equivalent weights of either the
oxides or carbonates followed by annealing at high tempera-
∗ Corresponding author.
E-mail address: rashad133@yahoo.com (M.M. Rashad).
tures (>1200 ◦ C). The procedure has some inherent disadvantages.
These disadvantages include chemical non-homogeneity, coarser
particle size and contamination of some impurities during ball
milling [10]. Thus, the preparation of Ni–Zn ferrites powder with
fine and narrow particle size distribution with minimum parti-
cles agglomeration has received considerable attention in order
to improve the material properties. To obtain nano-crystalline
powders with high homogeneity and uniform structure, many
techniques have been provided for the synthesis of the fer-
rites spinel powders. These methods are sol–gel [11–14], organic
precursors [3,15], hydrothermal [6,16], co-precipitation [17–20],
cathodic electrophoretic deposition (EPD) [21], mechanochemical
synthesis [22], reverse micelle [23], and electrochemical deposi-
tion [24,25]. The chemical co-precipitation method ensures proper
distribution of the various metals ions resulting to stoichiomet-
ric and smaller particles size product, compared to some of
the other procedures. Moreover, the chemical co-precipitation
method is a low-cost technique suitable for mass production.
Furthermore, the molecular level mixing and the tendency of par-
tially hydrolyzed species to form extended networks, facilitate
the structure evolution and thereby lowering the crystalliza-
tion temperature of the prepared ferrite. The main drawback is
that the particle size is not, relatively, small and monodispersed
enough for specific applications like recording media applications
[26,27].

0925-8388/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2009.07.051
760 M.M. Rashad et al. / Journal of Alloys and Compounds 486 (2009) 759–767

The properties of Ni–Zn ferrites are strongly depending on their

chemical composition and microstructure. This, in turn is sensitive
on the processing method used. Selection of the appropriate pro-
cess is, therefore, a key factor to obtain the desired ferrite quality
especially for low loss and high frequency [6]. In this article, the
preparation of nanostructure nickel–zinc ferrites, Nix Zn1−x Fe2 O4 ,
powders using co-precipitation process was reported. The effect
of the type of precipitating agents, pH, annealing time (1–4 h), the
addition of surfactants (cetyltrimethyl ammonium bromide (CTAB
as cationic) or sodium dodeceyl sulphate (SDS as anionic)) and
annealing temperature (800–1200 ◦ C), on the formation, crystal-
lite size, microstructure and magnetic properties of the prepared
ferrites was systematically studied. Moreover, the effect of nickel
substitution on the formation, microstructure and magnetic prop-
erties of Nix Zn1−x Fe2 O4 particles (with x varying from 0.2 to 0.9)
was also investigated.

2. Experimental
Fig. 1. Effect of pH on the XRD patterns of Ni0.5 Zn0.5 Fe2 O4 powders using NaOH
All the chemicals and reagents used were of high purity. To obtain the desired
annealed at 1000 ◦ C for 2 h.
ferrites composition, stoichiometric amounts of nickel sulphate NiSO4 ·6H2 O, zinc
sulphate ZnSO4 ·7H2 O, and ferrous sulphate FeSO4 ·7H2 O were dissolved in bidistilled
water with magnetic stirring. The precipitants (2 M Na2 CO3 or NaOH,) were added
gradually until the required pH (8–10) for the carbonate, and (8–12) when using
NaOH, as alkali precipitating agent. Sulphuric acid, H2 SO4 , and hydrogen peroxide,
H2 O2 , as oxidizer, were added to the starting solution, when NaOH was used as
precipitants, to accelerate the reaction and avoid the formation of other phases. The
reaction can be expressed as follows:

(1 − x)ZnSO4 ·7H2 O + xNiSO4 ·6H2 O + 2FeSO4 ·7H2 O + (CO3 −2 , OH− )

→ Nix Zn1−x Fe2 O4 + SO4 −2 + H2 O + CO2

The precipitate was filtered, washed thoroughly with distilled water until free
from sodium and sulphate ions. The precipitate was dried overnight at 100 ◦ C. The
dried precursor powder was annealed at different temperatures from 800 to 1200 ◦ C
at a heating rate of 10 ◦ C/min in open air. The composition Ni0.5 Zn0.5 Fe2 O4 was
selected to study the effect of the preparations variables and additives. The fer-
rite phases were identified through X-ray diffraction (XRD) using a Brucker axis D8
diffractometer and Cu K␣ ( = 1.5406 Å) radiation. Secondary monochromator, in the
range 2 from 20◦ to 80◦ , was used. The morphology of the prepared ferrites was
examined by scanning electron microscope (SEM JSM-5400). The magnetic proper-
ties were measured at room temperature using a vibrating sample magnetometer
VSM (9600-1 LDJ, USA) in a maximum applied field of 15 kOe. From the obtained
hysteresis loops, the saturation magnetization Ms , remanence magnetization ratio
Mr and coercivity Hc were determined.

3. Results and discussion Fig. 2. Effect of pH on the XRD patterns of Ni0.5 Zn0.5 Fe2 O4 powders using Na2 CO3
annealed at 1000 ◦ C for 2 h.
XRD patterns of Ni0.5 Zn0.5 Fe2 O4 powders prepared at different
pH values from 8 to 12 using NaOH or Na2 CO3 as alkali and annealed
at 1000 ◦ C for 2 h are shown in Figs. 1 and 2.
The XRD patterns in Fig. 1 indicated that a secondary phase
of hematite Fe2 O3 (JCPDS#72-0469) was formed with the spinel
ferrite phase when prepared at pH 8 and 10 using sodium hydrox-
ide as alkali. Peaks at 2 of 30.07◦ , 35.60◦ , 43.06◦ , 49.45◦ , 56.93◦ ,
63.95◦ and 74.0◦ corresponding to the planes (1 0 4), (1 1 0), (1 1 3),
(0 2 4), (2 1 1), (3 0 0), (2 0 0) of the iron oxide were determined.
Increasing the pH to 12 led to the formation of the single phase
of Ni0.5 Zn0.5 Fe2 O4 . Peaks at 2 of 30.07◦ , 35.42◦ , 37.05◦ , 43.09◦ ,
63.42◦ , 56.94◦ , 62.56◦ , 71.02◦ , 74.02◦ related to XRD diffraction
planes (2 2 0), (3 1 1), (2 2 2), (4 0 0), (4 2 2), (5 1 1), (4 4 0), (6 2 0)
and (5 3 3) were present. These peaks confirmed that cubic spinel
nickel–zinc ferrite (JCPDS# 08-0234) was formed in a well crys-
talline form. The crystallite size, determined from the most intense
diffraction peaks (3 1 1) for the different prepared ferrite com-
positions, applying Debye–Scherrer equation, showed that the
crystallite size was increased with the pH value. It increased
from 69.8 nm at pH 8 to 111.5 nm at pH 12. XRD patterns of the
formed nickel–zinc ferrite precursors using sodium hydroxide (pH
values 10 and 12) in the presence of hydrogen peroxide H2 O2 Fig. 3. Effect of pH on the XRD patterns of Ni0.5 Zn0.5 Fe2 O4 powders using
as oxidizer annealed at 1000 ◦ C for 2 h are given in Fig. 3. The NaOH + H2 O2 annealed at 1000 ◦ C for 2 h.
 M.M. Rashad et al. / Journal of Alloys and Compounds 486 (2009) 759–767 761

Fig. 4. Effect of alkali’s type on the SEM microstructure of Ni0.5 Zn0.5 Fe2 O4 powders using (a) NaOH, (b) NaOH + H2 O2 and (C) Na2 CO3 at pH 10 annealed at 1000 ◦ C for 2 h.

results illustrated that the well-defined crystalline spinel cubic
Ni–Zn ferrite phase formed at both pH values. The crystallite
size was also increased with the pH. It increased from 81.6 nm
at pH 10 to 86.4 nm at pH 12. XRD patterns of the ferrites pre-
pared using sodium carbonate as alkali (pH 8 and 10) by using
the similar conditions applied with sodium hydroxide (Fig. 2)
showed that a single phase of Ni0.5 Zn0.5 Fe2 O4 crystalline powder
obtained. The crystallite size of the produced ferrite increased from
90.9 to 92.4 nm when preparing at pH values 8 and 10, respec-
tively.

Fig. 5. M–H hysteresis loops of Ni0.5 Zn0.5 Fe2 O4 powders annealed at 1000 ◦ C for 2 h at different (a) type of alkali at pH 10, (b) pH values using NaOH, (c) pH values using
NaOH + H2 O2 and (d) pH values using Na2 CO3 .
762 M.M. Rashad et al. / Journal of Alloys and Compounds 486 (2009) 759–767

Table 1
Effect of pH on magnetic properties of Ni0.5 Zn0.5 Fe2 O4 powders using NaOH,
NaOH/H2 O2 , Na2 CO3 annealed at 1000 ◦ C for 2 h.

Type of alkali pH Magnetic properties

Ms Mr Hc

NaOH 8 54.25 7.257 54.15

10 69.75 11.69 54.48
12 75.57 10.9 60.88

NaOH + H2 O2 10 77.19 19.61 79.17

12 70.7 12.64 61.48

Na2 CO3 8 74.96 11.54 90.7

10 76.78 14.53 79.3

SEM micrographs (Figs. 4a–c) of the produced nickel zinc ferrite

showed that most of the nickel–zinc ferrites particles were fine,
homogeneous with narrow particle distributions. These particles
were fine agglomerated with soft characteristics (produced by Van
der Waals’ forces). Fig. 6. Effect of annealing time on the XRD patterns of Ni0.5 Zn0.5 Fe2 O4 powders using
NaOH + H2 O2 at pH 10 annealed at 1000 ◦ C.
The magnetization of the produced Ni0.5 Zn0.5 Fe2 O4 powders
was measured at room temperature under an applied field of 15 kOe
and the hysteresis loops were determined. Plots of magnetization
(M) as a function of the magnetic field (H) for the two used alka-
lies and annealed for 2 h at 1000 ◦ C were plotted in Fig. 5(a–d). The
magnetic parameters of the formed nickel–zinc ferrites powders
were given in Table 1.
The results obtained indicate that the increase in the pH led to
increase the saturation magnetization (Ms ) in the presence of both
NaOH and Na2 CO3 . The saturation magnetization increased from
54.25 to 75.57 emu/g in the presence of NaOH whereas it increased
from 74.96 to 76.78 emu/g in the presence of Na2 CO3 . The increase
of saturation magnetization was attributed to the well crystalline
formation of Ni0.5 Zn0.5 Fe2 O4 phase and increasing grain size. More-
over, the coercivity (Hc ) was increased by increasing the grain
size, which attributed to the magnetization mechanism, which is
a domain rotation process. The Hc is in direct proportion to the vol-
ume single-domain grains. Therefore, Hc becomes gradually larger
as the single-domain particle size increases [13]. When the grain
size arrives to a critical diameter of 30 nm (below which the parti-
Fig. 7. Effect of annealing time on the XRD patterns of Ni0.5 Zn0.5 Fe2 O4 powders using
cle is of a single-domain grain), the coercivity starts increasing. This Na2 CO3 at pH 10 annealed at 1000 ◦ C.
is because that the domain–wall displacement in the magnetization
process is the multi-domain grains. Thus, the coercivity decreases
The magnetic parameters, measured from M–H hysteresis loop
with the growing of multi-domain grain [13]. The decrease in sat-
of the nickel–zinc ferrites produced at different annealing times
uration magnetization from 77.19 to 70.70 emu/g can be related to
ranging from 1 to 4 h using NaOH/H2 O2 mixture and Na2 CO3 were
the increase of lattice parameter. This take place when the d values
given in Figs. 8–9 and Table 2. The loops showed that the saturation
increased from 2.528 to 2.531 Å, which is attributed to the reduc-
magnetization was slightly increased from 76.63 to 78.98 emu/g
tion of Fe3+ to Fe2+ ions with a larger ionic radius, which probably
when the annealing time increased from 1 to 4 h using NaOH/H2 O2
dissolve in the spinel lattice [15].
mixtures. Furthermore, the Ms values were increased from 71.05
The influence of annealing time on the crystal structure, crystal-
to 78.01 emu/g when using Na2 CO3 and at similar annealing peri-
lite size, microstructure and magnetic properties were measured at
ods. On the other hand, the coercivity was increased by annealing
different annealing periods ranging from 1 to 4 h at pH 10. Anneal-
up to 2 h and then decreased again by increasing the annealing
ing was performed at 1000 ◦ C using NaOH/H2 O2 and Na2 CO3 , which
is given in Figs. 6 and 7. The results show that a single well crys-
talline phase of the Ni0.5 Zn0.5 Fe2 O4 can be achieved at the studied Table 2
annealing periods. The crystallite size of the most intense peak indi- Effect of annealing time on magnetic properties of Ni0.5 Zn0.5 Fe2 O4 powders using
NaOH/H2 O2 , Na2 CO3 at pH 10 annealed at 1000 ◦ C.
cated was found to be increased with the samples annealed for
1–2 h, after which it decreased up to 4 h. The crystallite size was Type of alkali Time (h) Crystal size Magnetic properties
found to be increased from 68.4 to 81.6 nm then decreased to 62 nm (nm)
by using NaOH and H2 O2 as alkali, whereas, it decreases from 95.5 Hc (Oe) Mr (emu/g) Ms (emu/g)

for 1 h annealing time to 92.4 and 85.3 nm when using Na2 CO3 and NaOH + H2 O2 1 68.4 76.63 15.81 27.7
annealed for 1, 2 and 4 h, respectively. The change in crystallite size 2 81.6 77.19 19.61 79.17
4 62.0 78.98 16.28 43.58
was discussed on the basis of Zn and O2 losses from the ferrite sam-
ple leading to lattice shrinkage. Moreover, ZnO could not be ruled Na2 CO3 1 95.5 71.05 12.75 41.8
out from the XRD pattern as its d values are close to those for ferrites 2 92.4 76.78 14.53 79.3
4 85.3 78.01 16.97 49.54
[15], which explained the change of magnetic properties.
 M.M. Rashad et al. / Journal of Alloys and Compounds 486 (2009) 759–767
Fig. 8. Effect of annealing time on M–H hysteresis loop of Ni0.5 Zn0.5 Fe2 O4 powders
using NaOH + H2 O2 at pH 10 annealed at 1000 ◦ C.
Fig. 9. Effect of annealing time on M–H hysteresis loop of Ni0.5 Zn0.5 Fe2 O4 powders
using Na2 CO3 at pH 10 annealed at 1000 ◦ C.
time to 4 h. The change in magnetic properties can be attributed
to increasing of the crystallinity and the formation of single phase
of Ni0.5 Zn0.5 Fe2 O4 [13]. However, the decrease in Hc at annealing
time 4 h was due to the decrease in grain size [13,18].
The effect of surfactants additions on the different param-
eters characterizing the (Ni0.5 Zn0.5 Fe2 O4 ) powders, when
using NaOH/H2 O2 mixtures was studied by adding 1000-ppm
Fig. 11. Effect of surfactants addition (a) SDS and (b) CTAB on the SEM microstructure of Ni0.5 Zn0.5 Fe2 O4 powders using NaOH + H2 O2 at pH 10 annealed at 1000 ◦ C for 2 h.
763
Fig. 10. XRD patterns of Ni0.5 Zn0.5 Fe2 O4 powders at pH 10 annealed at 1000 ◦ C for
2 h using NaOH + H2 O2 as alkali when CTAB and SDS used as surfactants.
cetyltrimethyl ammonium bromide (CTAB) as cationic and sodium
dodecyl sulfate SDS as anionic surfactants; added during the
precipitating process. The produced precursors were annealed for
2 h at 1000 ◦ C. The changes in crystal structure, investigated by XRD
patterns, were given in Fig. 10. The results show a well-defined
crystal phase of Ni0.5 Zn0.5 Fe2 O4 spinel structure. The crystallite
size of the produced powder ferrite was increased by the addition
of the two studied surfactants. It increased to 89.8 nm with CTAB
and to 102.1 nm with SDS surfactants compared with 81.6 nm in
their absence of surfactant.
SEM micrographs of the ferrite powders obtained by the addi-
tion of each surfactant are given in Fig. 11(a–b). It can observed that
addition of the anionic surfactant SDS, before the co-precipitation
step forms, spherical particles agglomerated with small and large
grains sizes (Fig. 11a). This may be due to some kind of attraction
forces between negative surfactant anions and the positive charges
molecules of Ni, Zn, Fe hydroxides leading to agglomerate of parti-
cles during the heating step. Fig. 11b shows the SEM micrographs of
the produced particles with 1000 ppm CTAB. The microstructure of
the powders appeared as small spherical-like structure in compar-
ison with SDS. Furthermore, the particles were more homogeneous
and the grains are in narrow size distribution.
The magnetic properties of the produced powders were illus-
trated by M–H hysteresis loop in Fig. 12 and Table 3. The results
showed that the saturation magnetization was increased by the
addition of 1000 ppm SDS. This may be attributed to the increase
of the crystallite size from 89.8 nm with CTAB to 102.1 nm with
SDS. Furthermore, the addition of CTAB has insignificant effect on
the saturation magnetization. The reduction in coercivity with the
addition of surfactant compared with the precursor surfactant free
is attributed to the fall in the magnetic anisotropy behaviors and
the multidomain behavior [17].
764 M.M. Rashad et al. / Journal of Alloys and Compounds 486 (2009) 759–767

Fig. 14. Effect of Ni concentration on the lattice parameter and crystallite size of
Nix Zn1−x Fe2 O4 powders with x varying from 0.2 to 0.9 at pH 10 annealed at 1000 ◦ C
for 2 h.

Fig. 12. Effect of surfactants addition on M–H hysteresis loop of Ni0.5 Zn0.5 Fe2 O4
decrease in lattice parameter (a) with increasing nickel content
powders using NaOH + H2 O2 at pH 10 annealed at 1000 ◦ C for 2 h.
[13]. Therefore, the crystallite size of the produced Ni–Zn ferrite
was Ni content dependent. Higher crystallite size (113.4 nm) can be
Table 3
Effect of surfactants addition on magnetic properties of Ni0.5 Zn0.5 Fe2 O4 powders obtained at Ni (x of 0.9) whereas lower crystallite size (54.4 nm)
using NaOH/H2 O2 at pH 10 annealed at 1000 ◦ C for 2 h. can be achieved at x equal 0.6. Pryidyaharsini et al. [28] showed
that the small amount of Fe2+ ions in the B-site may be attributed as
Type of surfactants CTAB SDS Baseline (surfactant free)
the result of some intermediary physiochemical processes occurred
Ms (emu/g) 73.58 80.46 77.19 during the synthesis. Moreover, it showed that the lattice param-
Mr (emu/g) 16.89 18.83 19.61
Hc (Oe) 43.88 44.33 79.17
eter decreased with increasing Ni2+ substitution. Furthermore, it
Mr /Ms 0.2 0.2 0.2 showed that the cation distribution in B (octahedral) site appeared
as Zn0.15 2+ Ni0.16 2+ Fe1.3 3+ 5Fe0.34 2+ at Ni substitution ratio 0.2 which
changed to Zn0.06 2+ Ni0.61 2+ Fe1.255 3+ 5Fe0.075 2+ at Ni substitution
The effect of variation of nickel substitution and its impact on ratio 0.8 which deals with our data and our conclusions. Moreover,
the properties of the ferrite powders were studied. XRD patterns the nickel ions have high octahedral preference energy and there-
of the produced powders with nickel ratios ranging from x = 0.2 fore they are supposed to be predominantly present in the surface
to 0.9 were given in Fig. 13. The results revealed that the peaks of the nanoparticles. In addition, the surface moments of the nickel
ascribed to single phase of cubic structure of Nix Zn1−x Fe2 O4 were ions exist as canted structure. Thus, the contribution of the mag-
observed. The lattice parameter of the produced spinel was varied netic moment is been weakened with the further addition of nickel
by substitution of nickel as shown in Fig. 14. It gradually decline ions, which has, ultimately lead to a fall in the magnetization.
with increasing nickel content from 0.2 to 0.9. This behavior is The microstructures of the produced powders investigated
in agreement with the experimental results of bulk Ni–Zn ferrite by SEM micrographs are given in Fig. 15. The micrographs of
[13]. It is well known that both Zn ionic radius (0.082 nm) and Ni0.5 Zn0.5 Fe2 O4 (Fig. 15a) show that they have agglomerated mor-
Ni ionic radius (0.078 nm) are larger than the interstices of A site phologies consist of nanosized spherical particles. In comparison
(0.058 nm) and B-site (0.073 nm) in the spinel cubic structure of with those of the ferrites with x of 0.6 (Fig. 15b) and 0.7 (Fig. 15c),
the ferrite [13]. This leads to expansion of the lattice with dop- the grains appeared as fine agglomerated particles. Furthermore,
ing Zn or Ni ions into the interstices. Thus, the lattice expansion the grain size increased again with increasing Ni content to 0.8
is weakened if Zn ions are replaced by nickel ions with a smaller and 0.9 (Fig. 15a–d) which deals with the data obtained from XRD
radius. The weakening of the lattice expansion results in slight patterns applying Scherrer’s formula.
The magnetic properties of the produced ferrites powders
of the different nickel contents are illustrated in Fig. 16 and
Table 4. The results indicated that the high saturation magnetiza-
tion (77.19 emu/g) and coercivity Hc (79.17 Oe) were achieved with
Ni0.5 Zn0.5 Fe2 O4 powders. The value was smaller than that observed
in the bulk (65–115 emu/g) and the Hc was much larger than the
bulk (Hc < 10 Oe). In addition, the saturation magnetization and the
coercive force of the obtained Ni–Zn ferrites were size dependent.
The increase of the crystallite size increased the saturation mag-
netization. Furthermore, the mechanism has also been explained
in terms of spin-disorder, spin canting, and spin–glass like state
in the surface layers of the nanoparticles due to the local chem-
ical disorder, broken exchange interaction, and a dissimilar local
symmetry for those atoms near the surface [13]. Because both diva-
lent cations can occupy both sites, so they can form the mixed
spinel between inverse and normal spinel structures. Mixed spinel
configurations are characterized by the degree of inversion, which
Fig. 13. Effect of Ni concentration on the XRD patterns of Nix Zn1−x Fe2 O4 powders depends strongly on the preparation procedures. Moreover, the sur-
annealed at 1000 ◦ C for 2 h NaOH/H2 O2 face barrier potential is an enhanced because of the distortion of the
 M.M. Rashad et al. / Journal of Alloys and Compounds 486 (2009) 759–767 765

Fig. 15. SEM images of Nix Zn1−x Fe2 O4 powders with x varying from 0.2 to 0.9 at pH 10 annealed at 1000 ◦ C for 2 h.

crystal lattice caused by the atoms deviate from the normal posi-
tions in the surface layers [13,29]. On the other hand, the decrease
on the saturation magnetization of Ni0.9 Zn0.1 Fe2O4 which may be
attributed the similar to the bulk value of 55 emu g−1 reported for
NiFe2 O4 [30].
A typical effect of annealing temperature (800, 1000 and
1200 ◦ C) on the crystal structure of the produced spinel

Table 4
Effect of Ni concentration on crystallite size, magnetic properties of Nix Zn1−x Fe2 O4
powders with x varying from 0.2 to 0.9 using NaOH/H2 O2 as alkali at pH 10 annealed
at 1000 ◦ C for 2 h.

Composition x Crystallite Magnetic properties

size (nm)
Ms (emu/g) Mr (emu/g) Hc (Oe)

Ni0.2 Zn0.8 Fe2 O4 0.2 97.5 34.53 7.33 18.38

Ni0.4 Zn0.6 Fe2 O4 0.4 67.7 63.21 13.95 40.77
Ni0.5 Zn0.5 Fe2 O4 0.5 81.6 77.19 19.61 79.17
Ni0.6 Zn0.4 Fe2 O4 0.6 54.4 75.4 12.64 65
Ni0.7 Zn0.3 Fe2 O4 0.7 58.3 74.33 18.35 79.79
Fig. 16. Effect of Ni concentration on M–H hysteresis loop of Nix Zn1−x Fe2 O4 powders
Ni0.8 Zn0.2 Fe2 O4 0.8 99.4 74.35 18.03 73.4
with x varying from 0.2 to 0.9 using NaOH/H2 O2 as alkali at pH 10 annealed at 1000 ◦ C
Ni0.9 Zn0.1 Fe2 O4 0.9 113.4 59.6 14.76 76
for 2 h.
766 M.M. Rashad et al. / Journal of Alloys and Compounds 486 (2009) 759–767

Fig. 17. Effect of annealing temperature on the XRD patterns of Ni0.5 Zn0.5 Fe2 O4
powders using NaOH/H2 O2 at pH 10 annealed for 2 h.

Ni0.5 Zn0.5 Fe2 O4 powders using NaOH with H2 O2 and Na2 CO3 , pre-
cipitated at pH 10 annealed at 2 h was shown in Figs. 17–18. The
results indicated that single phase of the spinel nickel zinc powders
was formed at different annealing temperatures. The crystallite size
of the ferrite powders was increased by increasing the annealing
temperature. It increased from 30.6 to 155.0 nm using NaOH with
H2 O2 and from 27.6 to 139.6 nm using Na2 CO3 at 800 and 1200 ◦ C,
respectively.
Fig. 19 shows the SEM microstructures of Ni0.5 Zn0.5 Fe2 O4
annealed at 1200 ◦ C for 2 h using NaOH + H2 O2 and Na2 CO3 , respec-
tively. The SEM images of the sample with NaOH (Fig. 19a) showed
microstructures with a grain growth with a large well-clear cubic-
like crystal structure. It was found that Ni–Zn ferrite powder
Fig. 18. Effect of annealing temperature on the XRD patterns of Ni0.5 Zn0.5 Fe2 O4
powders using Na2 CO3 at pH 10 annealed for 2 h.
granules were made up of overall crystallite aggregates (1–5 ␮m)
due to the relative higher annealing temperature and interac-
tion between magnetic nanoparticles. With annealing temperature
using Na2 CO3 (Fig. 19b), the ferrite powders possessed a uni-
form coarse structure with a well-clear crystalline microstructure
containing a fewer numbers of spherical small particles with a
little small pores. The average grain sizes for the powder were
about 0.5–2 ␮m with homogeneous and narrow size distribution
microstructure. TEM micrographs (Fig. 20) showed that the pro-
duced Ni–Zn ferrite using NaOH and H2 O2 annealed at 1200 ◦ C for

Fig. 19. Effect of annealing temperature on SEM of microstructure of Ni0.5 Zn0.5 Fe2 O4 powders using (a) NaOH + H2 O2 and (b) Na2 CO3 at pH 10 annealed for 2 h.

Fig. 20. Effect of annealing temperature on TEM micrographs of Ni0.5 Zn0.5 Fe2 O4 powders using (a) NaOH + H2 O2 and (b) Na2 CO3 at pH 10 annealed for 2 h.
 M.M. Rashad et al. / Journal of Alloys and Compounds 486 (2009) 759–767 767

2. A well crystalline single cubic structure of Ni0.5 Zn0.5 Fe2 O4 phase

Fig. 21. Effect of annealing temperature on M–H hysteresis loop of Ni0.5 Zn0.5 Fe2 O4
powders using NaOH/H2 O2 at pH 10 annealed for 2 h.
Table 5
Effect of annealing temperature on magnetic properties of Ni0.5 Zn0.5 Fe2 O4 powders
using NaOH/H2 O2 , Na2 CO3 at pH 10 annealed for 2 h.
was formed at pH 10 and annealed at 1000 ◦ C for 2 h, using NaOH
with H2 O2 or Na2 CO3 as precipitating agent.
3. Impurity phase of ␣-Fe2 O3 was obtained with the nickel zinc
ferrite spinel using sodium hydroxide as alkali at pH 8 and 10 in
the absence of hydrogen peroxide.
4. Addition of sodium dodecyl sulfate SDS as anionic surfactant
enhanced the formation of the crystal structure and the satu-
ration magnetization of the formed spinel ferrites.
5. The lattice parameter of the produced Ni–Zn ferrite spinel was
gradually decline with increasing nickel content from 0.2 to 0.9.
6. The saturation magnetization of Nix Zn1−x Fe2 O4 powders was
increased by increasing the nickel content x up to 0.5 (Ms
79.17 emu/g) and then decreased by increasing the Ni content
to 0.9 related to the change on the crystallite size and the
microstructure.
7. Increasing the annealing temperature increased the crystallite
size and the saturation magnetization of Ni0.5 Zn0.5 Fe2 O4 parti-
cles.
8. The crystallite size of the produced powders at different synthe-
sis conditions was in the range between 27 and155 nm.
9. Maximum saturation magnetization (85.4 emu/g) was achieved
for the formed Ni0.5 Zn0.5 Fe2 O4 phase at pH 10 annealed at
1200 ◦ C for 2 h using Na2 CO3 as alkali.

Type of alkali Temperature (◦ C) Magnetic properties

References
Ms (emu/g) Mr (emu/g) Hc (Oe)

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