You are on page 1of 8

Please cite this article in press as: T.F. Marinca, et al.

, Synthesis and characterization of the NiFe
2
O
4
/Ni
3
Fe nanocomposite powder and compacts
obtained by mechanical milling and spark plasma sintering, Appl. Surf. Sci. (2013), http://dx.doi.org/10.1016/j.apsusc.2013.07.145
ARTICLE IN PRESS
GModel
APSUSC-26119; No. of Pages 8
Applied Surface Science xxx (2013) xxx–xxx
Contents lists available at ScienceDirect
Applied Surface Science
j our nal homepage: www. el sevi er . com/ l ocat e/ apsusc
Synthesis and characterization of the NiFe
2
O
4
/Ni
3
Fe nanocomposite
powder and compacts obtained by mechanical milling and spark
plasma sintering
T.F. Marinca
a
, B.V. Neamt¸ u
a
, F. Popa
a
, V.F. Tart¸ a
a
, P. Pascuta
b
, A.F. Takacs
c
, I. Chicinas¸
a,∗
a
Materials Sciences and Engineering Department, Technical University of Cluj-Napoca, 103-105, Muncii Avenue, 400641 Cluj-Napoca, Romania
b
Physics and Chemistry Department, Technical University of Cluj-Napoca, 103-105 Muncii Avenue, 400641 Cluj-Napoca, Romania
c
Faculty of Physics, Babes¸ -Bolyai University, 1 Mihail Kog˘ alniceanu, 400084 Cluj-Napoca, Romania
a r t i c l e i n f o
Article history:
Received 16 April 2013
Received in revised form13 July 2013
Accepted 25 July 2013
Available online xxx
Keywords:
Nanocomposite
Nickel ferrite/metal interface
Mechanical milling
Spark plasma sintering
Interdiffusion
a b s t r a c t
Nanocomposite powder and compacts of NiFe
2
O
4
/Ni
3
Fe type were synthesized using mechanical milling
and spark plasma sintering (SPS) techniques. The samples have been investigated by X-ray diffraction
(XRD), laser particles size analysis, differential scanning calorimetry (DSC), scanning electron microscopy
(SEM) and energy dispersive X-ray spectrometry (EDX). The nanocomposite powder was obtained by
mechanical milling in a high planetary ball mill of nanocrystalline NiFe
2
O
4
and nanocrystalline Ni
3
Fe
powders. The nanocomposite powder consists from Ni
3
Fe particles covered at the surface with a layer
of NiFe
2
O
4
fine particles and NiFe
2
O
4
particles. The nanocomposite particles have the median diameter
d
50
of 1.6␮m. The sintering in 400–600

C temperature range preserve the nanocomposite phases but
lead to a high porosity. The nanocomposite compacts consist in Ni
3
Fe clusters surrounded by NiFe
2
O
4
.
A sintering temperature of 800

C leads to a good density for the nanocomposite compacts and to the
new phase formation. The new phase is a wustite type (Fe
1−x
Ni
x
O) and is formed at the metal/ceramic
interface. A change in the Ni/Fe ratio, in the spinel structure, was evidenced during sintering. Sintering at
a temperature of 800

C, leads to the formation of a mixed iron–nickel ferrite with a very small amount
of nickel, Ni
1−x
Fe
x
Fe
2
O
4
.
© 2013 Elsevier B.V. All rights reserved.
1. Introduction
Nowadays, the composites magnetic materials field is one of
the major research themes. The researchers are focusing on sev-
eral topics: the hard/soft magnetic materials for improving the
(BH)
max
energy product [1–3], exchange biased composites [4–6]
and core–shell magnetic composites [7–9]. Also, the magnetic soft
ferrite/metal (especially Fe and Ni) or soft ferrite/soft magnetic
alloy composites have attracted the interest of the researchers in
the last period of time [10–12]. The interest for these types of com-
posites materials derives from the remarkable characteristics of
their components: soft ferrite and soft magnetic metals or alloys;
that could lead to the obtaining of new materials with extraordi-
nary properties. The soft ferrites magnetic materials are used in
many applications due to their versatile characteristics. The spinel
soft ferrites are ferrimagnetic materials and have high electrical
resistivities which allowthemto be used in high frequencies appli-
cations [13]. The general chemical formula for these materials can

Corresponding author. Tel.: +40 264401705; fax: +40 264415054.
E-mail address: Ionel.Chicinas@stm.utcluj.ro (I. Chicinas¸ ).
be written as MeFe
2
O
4
, where Me represents a metallic cation or a
combination of two or more metallic cations. This group of mate-
rials has the cubic spinel structure, which allows two kinds of sites
for the metallic cations (Me
2+
and Fe
3+
): tetrahedral and octahe-
dral. The distributionof the cations betweenthese sites dictates the
electrical and magnetic characteristics of the spinel ferrites [13,14].
The soft ferrites are synthesizedby various methods suchas sol–gel
[15], surfactant assisted hydrothermal [16], self-propagating auto
combustion [17] or mechanosynthesis [18]. The soft magnetic
metals and alloys (such as iron, iron alloys, nickel or nickel alloys)
are very well knownmaterials andhave excellent magnetic proper-
ties whichmake themsuitable for a large number of applications. In
general, these magnetic materials have a large magnetic induction
and a good magnetic permeability [19], but because of their low
electrical resistivity, they cannot be used in high frequency appli-
cations. For both classes of materials, soft ferrites and soft magnetic
alloys, the synthesis in nanocrystallite state has been proved to
lead to the change/enhance of their characteristics [20–23]. A suit-
able method of synthesizing materials in nanocrystalline state is
mechanosynthesis route [24]. This technique was used for synthe-
sizing many nanocrystalline/nanosized soft magnetic ferrites such
as ZnFe
2
O
4
[18], NiFe
2
O
4
[25], Ni
1−x
Zn
x
Fe
2
O
4
[26], Mn
1−x
Zn
x
Fe
2
O
4
0169-4332/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apsusc.2013.07.145
Please cite this article in press as: T.F. Marinca, et al., Synthesis and characterization of the NiFe
2
O
4
/Ni
3
Fe nanocomposite powder and compacts
obtained by mechanical milling and spark plasma sintering, Appl. Surf. Sci. (2013), http://dx.doi.org/10.1016/j.apsusc.2013.07.145
ARTICLE IN PRESS
GModel
APSUSC-26119; No. of Pages 8
2 T.F. Marinca et al. / Applied Surface Science xxx (2013) xxx–xxx
[27], Mg
1−x
Zn
x
Fe
2
O
4
[28], etc. The nanocrystalline soft ferrites can
be obtained by mechanical milling of the polycrystalline ceramic
ferrites which have crystallites size in microns range [25] or by
reactive milling of the ferrites precursors until the spinel phase in
nanocrystalline state is achieved[21]. For nanocrystalline alloys the
mechanosynthesis involves usually mechanical alloying of the ele-
mental powders until the alloy reaches the nanocrystalline state
[22]. It is important to note that the nanocrystalline alloys fromthe
Fe–Si [29], Ni–Fe [23] or Co–Fe and Co–Ni [30] systems have been
produced by mechanosynthesis.
The compaction of the nanocrystalline and compos-
ite/nanocomposite powders is difficult to be realized by
conventional sintering technique due to the high sintering
temperature requirements. The recrystallisation phenomenon
that occurs in materials during classical sintering leads to the loss
of the advantages given by nanocrystalline state and, therefore,
non-conventional routes are necessary to be considered. Also, in
the case of the composites/nanocomposites the reaction between
the phases is encountered during classical sintering. Therefore, a
suitable method for compaction of these kinds of powders was
proved to be the spark plasma sintering technique [31,32]. This
technique involves a short sintering time and a lower sintering
temperature as compared to the classical sintering process.
By combining the soft magnetic ferrites with the soft magnetic
alloys, newmaterials with higher electrical resistivity as compared
to the soft magnetic alloys and a magnetic induction close to the 3d
metal alloys, canbe obtained. This type of nanocomposite magnetic
materials can be suitable for application in mid and high frequen-
cies [10,11].
The paper presents some results regarding the synthesis and
characterization of the nanocomposite NiFe
2
O
4
/Ni
3
Fe powder and
compacts prepared by mechanical milling and spark plasma sinter-
ing.
2. Experimental
Thenanocompositepowder of NiFe
2
O
4
/Ni
3
Fetypewas obtained
by mechanical milling of the nanocrystalline NiFe
2
O
4
with the
20wt.% of the nanocrystalline Ni
3
Fe. A high energy planetary
ball mill Fritsch Pulverisette 4 model was used. The milling time
was 15min, and the milling atmosphere was air. Agate vials and
balls (15mm diameter) and a ball to powder ratio (BPR) of 11:1
were used for milling process. The main disc and vials rotational
speeds were set at ˝=800rpmandω=−400rpm, respectively. The
nanocrystalline nickel ferrite–NiFe
2
O
4
was obtained by mechani-
cal millingfor 120min of ceramic NiFe
2
O
4
obtainedfromequimolar
mixture of nickel and iron oxides (NiO and ␣-Fe
2
O
3
) as described
in ref. [33]. The Ni
3
Fe intermetallic compound was obtained by wet
mechanical alloying (using benzene as surfactant) of the elemental
powder mixture of iron and nickel for 20h [34]. The mean crystal-
lite size for the nanocrystalline nickel ferrite was 23nm [33] and,
respectively 15nmfor the Ni
3
Fe intermetallic compound [34]. The
compactionof thepowder incylindrical shapewas performedusing
home-made spark plasma sintering (SPS) equipment. The sinter-
ing process was carried out using graphite mould and punches in
Ar atmosphere, in 400–800

C temperature range. We used mould
with a diameter of 15 and 30mm, and the sintering pressure was
set at 30MPa.
The evolution of the powder during mechanical milling and of
the nanocomposites during sintering was investigated using X-ray
diffraction (XRD). The X-ray diffraction patterns were recorded in
angular range 2 =20–100

using Bruker D8 and Shimadzu 6000
diffractometers operating with CuK

radiation (=1.5418
˚
A). The
Williamson–Hall method was used for the calculus of mean crys-
tallites size [35].
Fig. 1. X-ray diffraction patterns of the nano-Ni
3
Fe, ceramic NiFe
2
O
4
, nano-NiFe
2
O
4
and NiFe
2
O
4
/Ni
3
Fe samples.
The morphology and the local chemical homogeneity of the
samples were investigated by Jeol-JSM 5600 LV scanning elec-
tron microscope-SEM equipped with an energy dispersive X-ray
spectrometer-EDX (Oxford Instruments, Inca 200 soft).
A Laser Particle Size Analyzer, Fritsch Analysette 22 – Nanotec,
with an analysis range of 10nm to 2000␮m was used for parti-
cles size distribution determinations. Specific area, formfactor and
d
10
, d
50
and d
90
diameters of the particles were determined (the
d
n
diameter represents the particles size diameter for which n%
volume percent of particles are smaller than d
n
).
Differential scanning calorimetry (DSC) analyses were recorded
using a Setaram Labsys apparatus. As reference was used high
purity alumina and the measurements were performed in Ar atmo-
sphere in the temperature range of 25–800

C. A heating/cooling
rate of 10

C/min was used.
3. Results and discussion
Fig. 1 presents the X-ray diffraction patterns of the nano-Ni
3
Fe
(nanocrystalline Ni
3
Fe), ceramic NiFe
2
O
4
, nano-NiFe
2
O
4
(nickel
ferrite samples milled for 120min) and NiFe
2
O
4
/Ni
3
Fe nanocom-
posite. The Bragg reflections of the ceramic nickel ferrite are well
defined in comparison to the ones of milled samples as a result
of larger crystallites size and equilibrium distribution of cations
[33]. The diffraction patterns of the Ni
3
Fe intermetallic compound
and of the nano-NiFe
2
O
4
have broadened Bragg peaks due to the
reducedcrystallites size (15nmand23nm, respectively) anddue to
the second-order internal stresses induced by mechanical milling
[21,34]. Also, the positions of the Bragg peaks are shifted to lower
angles as a result of lattices distortions caused by the first order
internal stresses [22]. Thesephenomenaaretypical for themechan-
ical milling process. In the case of nano-NiFe
2
O
4
beside the internal
stresses, the cations redistribution between tetrahedral and octa-
hedral sites during the milling process can lead to an enlarged
crystal lattice [21]. The mechanical milling of the nano-NiFe
2
O
4
together with the nanocrystalline Ni
3
Fe intermetallic compound
for this short period of time leads to the preservation of phases; no
reaction between these phases is evidenced by X-ray diffraction.
The diffraction pattern consists in the Bragg peaks of both phases,
without the presence of newpeaks. A powder contamination dur-
ing mechanical milling of ceramic nickel ferrite was produced [33],
and the Bragg reflection observed at about 2 =27

is assigned to
SiO
2
(agate). It is assumed that during mechanical milling, due to
the abrasive characteristic of the spinel ferrite, small pieces from
Please cite this article in press as: T.F. Marinca, et al., Synthesis and characterization of the NiFe
2
O
4
/Ni
3
Fe nanocomposite powder and compacts
obtained by mechanical milling and spark plasma sintering, Appl. Surf. Sci. (2013), http://dx.doi.org/10.1016/j.apsusc.2013.07.145
ARTICLE IN PRESS
GModel
APSUSC-26119; No. of Pages 8
T.F. Marinca et al. / Applied Surface Science xxx (2013) xxx–xxx 3
Fig. 2. Heating and cooling DSC curves of nano-Ni
3
Fe, nano-NiFe
2
O
4
and
NiFe
2
O
4
/Ni
3
Fe samples.
vials and balls were detached. The contamination of the powder
duringmechanical millingis a commonphenomenon[33]. As it was
expected, a small amount of SiO
2
is also present in nanocomposite
NiFe
2
O
4
/Ni
3
Fe powder.
Inorder toevaluatethethermal behaviour of themilledsamples,
DSC measurements were performed. The heating and cooling DSC
curves of nano-Ni
3
Fe, nano-NiFe
2
O
4
and NiFe
2
O
4
/Ni
3
Fe samples
are presented in Fig. 2. A large exothermic peak can be observed in
all the heating curves fromabout 150 up to 350

C and is assigned
to the releasing of the internal stresses accumulatedduring milling.
This aspect is in good correlation with the X-ray diffraction. In
the DSC of nano-NiFe
2
O
4
the endothermic peak at about 560

C
is assigned to the Curie temperature, the assignment is confirmed
by the presence of an exothermic peak on the cooling curve [21].
Considering that we can assimilate the DSC measurement with
a heat treatment, the DSC treatment at about 800

C leads also
to the cation reordering close to the equilibrium in spinel struc-
ture (Ni
2+
cations in octahedral sites and the Fe
3+
cations equal
distributed between tetrahedral and octahedral sites). The DSC of
the intermetallic compound presents a large heat release at about
350

C. This heat release is assigned to the removing of the benzene
adsorbed on the surface of the Ni
3
Fe particles during wet mechan-
ical alloying (up to 20h) of the elemental Ni and Fe precursors [36].
At about 500

C an exothermic peak can be noticed in the heat-
ing curve of the nanocrystalline Ni
3
Fe due to its recrystallisation.
The Curie temperature of Ni
3
Fe (∼570

C) is very close to the one of
nickel ferriteandcanberemarkedintheheatingandcoolingcurves.
The DSCheating andcooling curves of NiFe
2
O
4
/Ni
3
Fe nanocompos-
ite sample present a sumof phenomena generated by the presence
of Ni
3
Fe and NiFe
2
O
4
: stresses release, benzene removing, inter-
metallic compound recrystallisation, magnetic transition, spinel
cations reordering.
This DSC investigation did not evidence any reaction between
NiFe
2
O
4
and Ni
3
Fe during the heating up to 800

C in argon atmo-
sphere. Anyway, at the NiFe
2
O
4
/Ni
3
Fe interface it is assumed to
have some diffusion, taken into account the affinity of iron for the
oxygen, evenif the Fe is present inanalloy. The lower Curie temper-
ature as compared to the ones of NiFe
2
O
4
and Ni
3
Fe observed in the
DSC cooling curve of the nanocomposite is assigned to the diffusion
phenomena, which change the both phases stoichiometry.
The particles size distribution of the nano-Ni
3
Fe, nano-NiFe
2
O
4
and NiFe
2
O
4
/Ni
3
Fe powders are presented in Fig. 3. The particles
size distribution of the nano-Ni
3
Fe presents a particles size range
from60␮mdown to nanometric range. The mechanical milling of
the metallic powder with benzene as process control agent (PCA)
Fig. 3. Particles size distribution of the: (a) nano-Ni
3
Fe, (b) nano-NiFe
2
O
4
and (c)
NiFe
2
O
4
/Ni
3
Fe.
has been proved that can be used to obtain controlled particles size
distribution [34]. The addition of the benzene as PCA prevents the
excessive cold welding processes between these ductile particles,
leading to small particles, which are more suitable to obtain a good
homogeneity of the composite mixture.
The particles size distribution of nano-NiFe
2
O
4
shows that 90%
of the nickel ferrite particles have the main diameter less than
10␮m and a significant amount of powder are in nanometric
range due to the fragile characteristics of spinel structure [10].
The particles size distribution correlated with the calculus of the
mean crystallites size revealed that the NiFe
2
O
4
is in a nanocrys-
talline/nanosized state. The NiFe
2
O
4
/Ni
3
Fe powder contains larger
particles as compared to the nano-NiFe
2
O
4
particles (the d
90
diam-
eter is 14.4␮m). The bimodal distribution of the NiFe
2
O
4
/Ni
3
Fe
milled powder particles suggests the presence of two types of par-
ticles: first are the fine NiFe
2
O
4
particles and the second ones the
large nanocomposite NiFe
2
O
4
/Ni
3
Fe particles. The nanocomposite
Please cite this article in press as: T.F. Marinca, et al., Synthesis and characterization of the NiFe
2
O
4
/Ni
3
Fe nanocomposite powder and compacts
obtained by mechanical milling and spark plasma sintering, Appl. Surf. Sci. (2013), http://dx.doi.org/10.1016/j.apsusc.2013.07.145
ARTICLE IN PRESS
GModel
APSUSC-26119; No. of Pages 8
4 T.F. Marinca et al. / Applied Surface Science xxx (2013) xxx–xxx
Table 1
Specific surface area, formfactor and d
10
, d
50
and d
90
diameters of the nano-Ni
3
Fe, nano-NiFe
2
O
4
and NiFe
2
O
4
/Ni
3
Fe.
Specific surface area (cm
2
/g) Formfactor d
10
(␮m) d
50
(␮m) d
90
(␮m)
NiFe
2
O
4
92,860 1.25 0.2 1.6 9.9
Ni
3
Fe 11,711 1.29 3.4 11.6 29.8
NiFe
2
O
4
+Ni
3
Fe 83,999 1.8 0.3 1.6 14.4
particles areformedduringmillingbytheembeddingof thefinefer-
rite particles on the Ni
3
Fe particles surface. The mechanical milling
procedure leads to a slight decrease of the particles diameter. The
nanocomposite particles size is less than 50␮m and it is lower as
compared to the particles size of Ni
3
Fe powder.
The supplementary data obtained from particles size analysis
such as specific surface area, formfactor and d
10
, d
50
and d
90
diam-
eters of nano-Ni
3
Fe, nano-NiFe
2
O
4
and NiFe
2
O
4
/Ni
3
Fe powders are
presented in Table 1. The changes of value for the formfactor of the
particles of the milledmixture as comparedto the nickel ferrite and
intermetallic compound particles can be assigned to the nanocom-
posite particles formation. The covering of the ductile intermetallic
Ni
3
Fe particles by a layer of embedded nickel ferrite fine particles
can lead to such a change.
The value of the d
90
diameter of the particles from the milled
mixture is considerable larger as compared to the one of nickel
ferrite although the amount of intermetallic compound in the
NiFe
2
O
4
/Ni
3
Fe powder is only 20wt.%. This increase of the particles
diameter cannot be explained only by the addition of large Ni
3
Fe
particles. It can be assumed that, in part, this increase is given also
by the nanocomposite particles formation.
In Fig. 4 are presented SEM images at a 20,000× magnification
obtained for the NiFe
2
O
4
, Ni
3
Fe and nanocomposite NiFe
2
O
4
/Ni
3
Fe
powders. The nickel ferrite particles are agglomerated, andit seems
that the large particles are formed by small agglomerated/bonded
particles. The nanometric size of a part of the nickel ferrite particles
is confirmed by the SEM. In the SEM image of the Ni
3
Fe particles
can be observed the larger size of these particles as compared to
the NiFe
2
O
4
ones and their polyhedral shape. The milled composite
mixture presents, on one hand, small particles, which are identified
as nickel ferrite, and large particles identified as nanocomposite
NiFe
2
O
4
/Ni
3
Fe particles. This comes to confirmthe results obtained
by the particles size distribution analysis.
The X-ray diffraction patterns of the NiFe
2
O
4
/Ni
3
Fe nanocom-
posite compacts spark plasma sintered at 400

C for 1min, 600

C
for 2min and 800

C for 2min are presented in Fig. 5. As a ref-
erence, in the same figure, the X-ray diffraction pattern of the
NiFe
2
O
4
/Ni
3
Fe nanocomposite powder was added. After the sin-
tering process at 400

C for 1min in the diffraction pattern are
noticed the same Bragg reflections as for the reference nanocom-
posite powder: Ni
3
Fe, NiFe
2
O
4
together with a reflection of SiO
2
(powder contamination). The Bragg peaks, after this sintering pro-
cedure, for both phases, are much better defined as a result of the
internal stresses removing [34].
The sintering procedure acts like an annealing treatment for the
stressing release for these chosen sintering parameters. This result
is in good agreement with the DSC investigations which showed
that the stresses release take place up to this temperature (400

C).
The mean crystallites size of the Ni
3
Fe and NiFe
2
O
4
after sintering
process at 400

Cpractically remains at the same value as they were
calculated for the homonymous powders. Therefore, after this sin-
tering procedure the nanocomposite compact was obtained, the
both phases remain in nanocrystalline state, and furthermore no
recrystallisation phenomena occurred. By increasing the sintering
temperature at 600

C (2min sintering time), in the compact are
present the same phases as for the compact sintered at 400

C. An
increase of the mean crystallites size for both phases is noticed
after sintering at 600

C: from 15nm to 40nm for Ni
3
Fe and from
23nm to 43nm for NiFe
2
O
4
. The XRD investigation does not indi-
cate any reaction between the intermetallic compound and nickel
ferrite for these sintering conditions. The sintering process carried
out at 800

C/2min leads to some changes in the composition of
the nanocomposite compact, beside the spinel ferrite and inter-
metallic phases a newphaseis noticed: wustitephase. It is expected
that this new phase to be formed at the Ni
3
Fe/NiFe
2
O
4
interface.
Indeed, at the interface an iron–nickel mixed oxide, (Fe, Ni)O, with
wustite structure can be formed. This wustite structure is assumed
that is formed by the reaction and/or interdiffusion of the inter-
metallic phase with the spinel structure leading to the oxidation
Fig. 4. SEMimages of the NiFe
2
O
4
, Ni
3
Fe and nanocomposite NiFe
2
O
4
/Ni
3
Fe pow-
ders at 20,000×.
Please cite this article in press as: T.F. Marinca, et al., Synthesis and characterization of the NiFe
2
O
4
/Ni
3
Fe nanocomposite powder and compacts
obtained by mechanical milling and spark plasma sintering, Appl. Surf. Sci. (2013), http://dx.doi.org/10.1016/j.apsusc.2013.07.145
ARTICLE IN PRESS
GModel
APSUSC-26119; No. of Pages 8
T.F. Marinca et al. / Applied Surface Science xxx (2013) xxx–xxx 5
Fig. 5. X-ray diffraction patterns of the NiFe
2
O
4
/Ni
3
Fe nanocomposite powder and
of the NiFe
2
O
4
/Ni
3
Fe nanocomposite compacts spark plasma sintered at 400

C,
600

C, 800

C.
of the metallic part and to the reduction of the Fe
3+
cations to
Fe
2+
. The supplementary energy induced into the nanocomposite
by increasing the sintering temperature from600 to 800

C seems
to be consumed by the reaction/diffusion processes rather than
the recrystallisation. The mean crystallites size of the intermetallic
phase and of the ferrite are at almost the same value as for the sam-
ple sintered at 600

C: 41nmfor Ni
3
Fe and 43nmfor spinel phase.
The lattice parameters of the spinel phase and the one of the inter-
metallic phase were calculated for a further investigation related to
the structural changes induced by sintering. The lattice parameters
of the intermetallic compound and of the spinel phase in the milled
sample and in the sintered compacts are presented in Table 2.
The lattice parameter of the nano-NiFe
2
O
4
is larger as compared
to the un-milled ceramic ferrite and also as compared to the one
from the JCPDS file 10-0325 (8.333
˚
A and respectively 8.339
˚
A) as
a result of cations reordering and internal stresses induced during
milling. The sintering process at 400

Cand600

Cleads tothe more
compact structure of nickel ferrite, and as consequence a decrease
of the lattice parameter can be observed. The spinel structure after
sintering at 800

C presents a larger lattice parameter as compared
tothespinel structures obtainedafter sinteringat 400

Cand600

C,
respectively. The value of the lattice parameter is very close to the
iron ferrite, FeFe
2
O
4
(8.396
˚
A – JCPDS file 19-0629). This suggests
that the spinel ferrite from the nanocomposite compact does not
respect the initial stoichiometry, Ni to Fe ratio of 1:2 and after
sintering a mixed nickel–iron ferrite Ni
1−x
Fe
x
Fe
2
O
4
with very low
nickel content is formed. The reaction that occurs is assumed to be
of this type [37]:
NiFe
2
O
4
+x · Fe →(Ni
1−x
Fe
x
)Fe
2
O
4
+x · Ni (1)
The lattice parameter of the Ni
3
Fe intermetallic compound
decreases after sintering procedure at 400

C, and 600

C as a con-
sequence of the internal stresses releasing. The increase of the
lattice parameter after sintering at 800

C suggests a change in the
structure and stoichiometry of the Ni
3
Fe intermetallic compound.
Table 2
The lattice parameters of the NiFe
2
O
4
and Ni
3
Fe in the nanocomposite powder and
nanocomposite sintered compacts.
Ceramic Milled sample SPS 400

C SPS 600

C SPS 800

C
NiFe
2
O
4
8.333
˚
A 8.350
˚
A 8.334
˚
A 8.337
˚
A 8.394
˚
A
Ni
3
Fe – 3.583
˚
A 3.525
˚
A 3.527
˚
A 3.548
˚
A
Fig. 6. SEM micrographs of the NiFe
2
O
4
/Ni
3
Fe nanocomposite compacts spark
plasma sintered at: (a) 400

C, (b) 600

C and (c) 800

C.
Indeed, the diffusion of nickel in Ni
3
Fe structure can lead to the
change of the lattice parameter.
The SEM images of the sintered nanocomposite compacts
obtained by SPS at 400

C, 600

C and 800

C, are presented in Fig. 6.
In the compact sintered at 400

C, the particles seemto be welded
together. It can be observed that, analogous with the nanocompos-
ite powder, two types of zones exist in the compact. First zone is
given by the nickel ferrite obtained by welding of homonymous
particles during sintering by SPS. The second zone is given by Ni
3
Fe
clusters. Also, as can be noticed in the image obtained at high
magnification, the sample has a high porosity. This characteristic
is in good agreement with the sintered compacts densities. The
compacts sintered for 1min present a relative density of 73.8%
and the compacts sintered for 2min have a relative density of
75.7%. The relative densities of the nanocomposite sintered com-
pacts were determined using as reference the weighted average
density of nickel ferrite and intermetallic compound densities. The
Please cite this article in press as: T.F. Marinca, et al., Synthesis and characterization of the NiFe
2
O
4
/Ni
3
Fe nanocomposite powder and compacts
obtained by mechanical milling and spark plasma sintering, Appl. Surf. Sci. (2013), http://dx.doi.org/10.1016/j.apsusc.2013.07.145
ARTICLE IN PRESS
GModel
APSUSC-26119; No. of Pages 8
6 T.F. Marinca et al. / Applied Surface Science xxx (2013) xxx–xxx
Fig. 7. X-ray microanalysis of the nanocomposite compact sintered at 600

C: (a) distribution maps of the Ni, Fe and O chemical elements and (b) a line scan of the Ni, Fe and
O chemical elements on a micro-area of the compact.
compacts obtained at 600

C present a better relative density
(81.2%) as compared to the compacts obtained at 400

C. This com-
pact alsoconsists intwotypes of zones as the one sinteredat 400

C.
In Fig. 6b can be observed a zone of NiFe
2
O
4
which binds two
Ni
3
Fe clusters. The compact sintered at 800

C presents also metal-
lic clusters surrounded by ferrite matrix. A high relative density of
93.2% was obtained after sintering at this temperature. The reac-
tion/diffusion at the Ni
3
Fe/NiFe
2
O
4
interface should contribute to
powder consolidation.
In Fig. 7 are shown the X-ray microanalysis of the nanocom-
posite compact sintered at 600

C. In figure are presented the
distribution maps of the Ni, Fe and O chemical elements and a
line scan of the Ni, Fe and O chemical elements on a micro-area
of the compact. The distribution maps evidence a central area (in
this picture) where elemental oxygen is less present. This obser-
vation evidence the central Ni
3
Fe (where oxygen is less present)
zone surrounded by nickel ferrite matrix (containing oxygen).
The EDX analyses confirm the fact that, the nanocomposite com-
pact is formed by two types of zones. The line scan highlights
these two types of zones from the composite compacts. At the
NiFe
2
O
4
/Ni
3
Fe interface, the amount of Ni decreases and in the
meantime the amount of Fe and O increases. This suggest a change
in the stoichiometry of both phases and is associated with a small
interdiffusion processes.
The distribution maps of the Ni, Fe and Ochemical elements and
a line scan of the Ni, Fe and Ochemical elements on a micro-area of
the compact sintered at 800

C are presented in Fig. 8. The distribu-
tionmap of nickel present zones where it seems that this element is
missing. These zones are superposing to the zones where the oxy-
gen and iron also are present. This comes to confirmthe formation
of Ni
1−x
Fe
x
Fe
2
O
4
with a small amount of nickel, in agreement with
the XRD analysis results. The line scan X-ray microanalysis is also
Fig. 8. X-ray microanalysis of the nanocomposite compact sintered at 800

C: (a) distribution maps of the Ni, Fe and O chemical elements and (b) a line scan of the Ni, Fe and
O chemical elements on a micro-area of the compact.
Please cite this article in press as: T.F. Marinca, et al., Synthesis and characterization of the NiFe
2
O
4
/Ni
3
Fe nanocomposite powder and compacts
obtained by mechanical milling and spark plasma sintering, Appl. Surf. Sci. (2013), http://dx.doi.org/10.1016/j.apsusc.2013.07.145
ARTICLE IN PRESS
GModel
APSUSC-26119; No. of Pages 8
T.F. Marinca et al. / Applied Surface Science xxx (2013) xxx–xxx 7
Fig. 9. The elemental chemical analysis obtained by X-ray microanalysis in various
micro-areas of the compact sintered at 800

C.
in good correlation with the XRD and with the distribution maps.
In the line scan one can be observed three zones:
(i) a zone richinnickel –correspondingtothe intermetallic phase.
(ii) a zone with a very small amount of nickel – corresponding to
the Ni
1−x
Fe
x
Fe
2
O
4
.
(iii) a zone where the nickel progressively decrease and the other
two elements, iron and oxygen progressively increase – cor-
responding to the interface of the other two zone above
mentioned – wustite Fe
1−x
Ni
x
O phase.
The interface interdiffusion noticed for the sample sintered
at 600

C is accompanied by reactions between nanocomposite
phases if the sintering temperature is increased at 800

C.
Fig. 9 presents the elemental chemical analysis obtained by X-
ray microanalysis in various micro-areas of the compact sintered at
800

C. Also, in the same figure are indicated zones where the pores
are present. The local chemical composition of the measured zones
is given in Table 3. The first zone, marked as Zone 1, according to
EDX, represents an intermetallic zone of Ni
3
Fe type. In this zone,
the amount of iron is less as compared with mechanically alloyed
nanocrystalline Ni
3
Fe powder (Ni ≈68at.% and Fe =32at.%). This
comes to confirmour supposition regarding the diffusion of some
ironfromthe intermetallic phase inspinel structure. The Zone 2has
a very small amount of nickel and represents the Ni
1−x
Fe
x
Fe
2
O
4
nanocomposite matrix. Zone 3 represents a thick layer at the
metal/ceramic interface formed by the wustite Fe
1−x
Ni
x
O phase.
Zone 4 has also a small amount of nickel and represents some
Fe
1−x
Ni
x
O small clusters formed by reaction of intermetallic phase
with the spinel phase. These local chemical analyses clearly indi-
cated that the interdiffusion processes and reactions take place
during sintering in the nanocomposite compact at 800

C. Also,
it is emphasized that the structure of the nanocomposites con-
sists in metallic clusters in a ferrite matrix. These investigations
reinforce the dates offered by XRD determinations concerning the
Table 3
The local chemical composition of the measured zones of Fig. 9.
Measured zone Ni (at.%) Fe (at.%) O (at.%) Observations
1 79.1 20.9 –
2 1.2 38.0 60.8
3 2.7 47.3 50.0 Oxygen by stoichiometry
(normalized)
4 4.4 45.6 50.0 Oxygen by stoichiometry
(normalized)
transformation of the NiFe
2
O
4
into the Ni
1−x
Fe
x
Fe
2
O
4
(with lowNi
content) and the enrichment of Ni
3
Fe in nickel content, together
with the formation of the Fe
1−x
Ni
x
O interface.
4. Conclusions
NiFe
2
O
4
/Ni
3
Fe nanocomposite powder was synthesized by ball
milling of nanocrystalline NiFe
2
O
4
and nanocrystalline Ni
3
Fe in
a high planetary ball mill. During mechanical milling of the
NiFe
2
O
4
+Ni
3
Fe mixture, no solid state reaction was observed. The
nanocomposite particles are formed during milling by covering
of the surface of large Ni
3
Fe particles by a layer of embedded
NiFe
2
O
4
fine particles. The formation of the nanocomposite par-
ticles was confirmed by SEM, EDX and particles size analysis. The
nanocomposite particles have the d
90
diameter less than 14.4␮m.
The spark plasma sintering of the nanocomposite powder car-
ried out at 400–800

C temperature range leads to the obtaining
of nanocomposite compacts of spinel ferrite/intermetallic com-
pound type. The sintering process preserves the NiFe
2
O
4
and Ni
3
Fe
phases inthecompositecompact, andfurthermorerecrystallisation
phenomena were moderate for 400

C and 600

C sintering tem-
peratures. The sintering process at 800

C leads to the formation of
an interface of wustite Fe
1−x
Ni
x
O type between spinel ferrite and
Ni
3
Fe intermetallic compound. Also, a change in the intermetallic
compound stoichiometry is remarked together with the transfor-
mation of NiFe
2
O
4
into Ni
1−x
Fe
x
Fe
2
O
4
with lownickel content. The
nanocomposite compacts obtained at 800

C has a good relative
density (more than 93%) and consist in two zones; the first is an
iron–nickel ferrite matrix and the second is provided by Ni
3
Fe par-
ticles. The mechanical milling followed by spark plasma sintering
can be considered as suitable route for obtaining nanocomposite
compacts of spinel ferrite/Ni
3
Fe type.
Acknowledgment
This workwas supportedbyCNCSIS –UEFISCSU, project number
PNII – IDEI code 519/2008.
References
[1] H.G. Cha, Y.H. Kim, C.W. Kim, H.W. Kwon, Y.S. Kang, Preparation for exchange-
coupled permanent magnetic composite between ␣-Fe (soft) and Nd
2
Fe
14
B
(hard), Current Applied Physics 7 (2007) 400–403.
[2] K. O‘Donnell, M. Aindow, I.R. Harris, R. Skomski, J.M.D. Coey, Structural imag-
ing of mechanically alloyed remanence-enhanced Sm
2
Fe
17
N
3
/␣–Fe, Journal of
Magnetismand Magnetic Materials 157/158 (1996) 79–80.
[3] Z. Liu, R.J. Chen, D. Lee, A.R. Yan, Influence of milled ␣-Fe powders on struc-
ture and magnetic properties of Sm(Co,Zr)7/␣-(Fe,Co) nanocomposite magnets
made by mechanical alloying, Journal of Applied Physics 109 (2011) 07A752.
[4] J. Nogues, J. Sort, V. Langlais, V. Skumryev, S. Surinach, J.S. Munoz, M.D. Baro,
Exchange bias in nanostructures, Physics Reports 422 (2005) 65–117.
[5] S.R. Mishra, I. Dubenko, J. Griffis, N. Ali, K. Marasinghe, Exchange bias effect
in ball milled Co-Cr
2
O
3
FM–AFMnanocomposites, Journal of Alloys and Com-
pounds 485 (2009) 667–671.
[6] L. DelBianco, F. Spizzo, M. Tamisari, Tailoring the exchange bias of Ni/NiO
nanogranular samples by the structure control, Journal of Magnetismand Mag-
netic Materials 321 (2009) 3071–3076.
[7] J. Wang, S. Zheng, Y. Shao, J. Liu, Z. Xu, D. Zhu, Amino-functionalizedFe
3
O
4
@SiO
2
core–shell magnetic nanomaterial as a novel adsorbent for aqueous heavy
metals removal, Journal of Colloid and Interface Science 349 (2010) 293–299.
[8] X.Q. Xu, H. Shen, J.R. Xu, J. Xu, X.J. Li, X.M. Xiong, Core–shell structure and mag-
netic properties of magnetite magnetic fluids stabilized with dextran, Applied
Surface Science 252 (2005) 494–500.
[9] E. Popovici, F. Dumitrache, I. Morjan, R. Alexandrescu, V. Ciupina, G. Prodan, L.
Vekas, D. Bica, O. Marinica, E. Vasile, Iron/iron oxides core–shell nanoparticles
by laser pyrolysis: structural characterization and enhanced particle disper-
sion, Applied Surface Science 254 (2007) 1048–1052.
[10] V.F. Tart¸ a, T.F. Marinca, I. Chicinas¸ , F. Popa, B.V. Neamt¸ u, P. Pascuta, A.F.
Takacs, Study onstability of phases inball milledZnFe2O4/Fe composite during
processing by spark plasma sintering, Materials and Manufacturing Processes
28 (2013) 993–998.
[11] K. Hirota, M. Obatal, M. Kato, H. Taguchi, Fabrication of full-density Mg-
ferrite/Fe–Ni permalloy nanocomposites witha high-saturationmagnetization
Please cite this article in press as: T.F. Marinca, et al., Synthesis and characterization of the NiFe
2
O
4
/Ni
3
Fe nanocomposite powder and compacts
obtained by mechanical milling and spark plasma sintering, Appl. Surf. Sci. (2013), http://dx.doi.org/10.1016/j.apsusc.2013.07.145
ARTICLE IN PRESS
GModel
APSUSC-26119; No. of Pages 8
8 T.F. Marinca et al. / Applied Surface Science xxx (2013) xxx–xxx
density of 1T, International Journal of Applied Ceramic Technology 8 (2011)
1–13.
[12] J. Xiang, X. Shen, F. Song, M. Liu, G. Zhou, Y. Chu, Fabrication and characteriza-
tion of Fe–Ni alloy/nickel ferrite composite nanofibers by electrospinning and
partial reduction, Materials Research Bulletin 46 (2011) 258–261.
[13] A. Goldman, Modern Ferrite Technology, 2nd ed., Springer, Pittsburgh, 2006.
[14] B.D. Cullity, C.D. Graham, Introduction to Magnetic Materials, 2nd ed., IEEE,
Press & Wiley, NewJersey, 2009.
[15] D. Yang, L.K. Lavoie, Y. Zhang, Z. Zhang, S. Ge, Mössbauer spectroscopic
and x-ray diffraction studies of structural and magnetic properties of heat-
treated (Ni
0.5
Zn
0.5
)Fe
2
O
4
nanoparticles, Journal of Applied Physics 93 (2003)
7492–7494.
[16] X. Xu, L. Zhou, Q. Zhai, C. Luw, Synthesis, properties, and formation mecha-
nism of zinc ferrite hollow spheres, Journal of the American Ceramic Society
90 (2007) 1959–1962.
[17] M.B. Shelar, P.A. Jadhav, S.S. Chougule, M.M. Mallapur, B.K. Chougule, Struc-
tural and electrical properties of nickel cadmium ferrites prepared through
self-propagating auto combustion method, Journal of Alloys and Compounds
476 (2009) 760–764.
[18] T.F. Marinca, I. Chicinas¸ , O. Isnard, V. Pop, Structural and magnetic properties
of nanocrystalline ZnFe
2
O
4
powder synthesized by reactive ball milling, Opto-
electronics and Advanced Materials-Rapid Communications 5 (2011) 39–43.
[19] C.H. Chen, MagnetismandMetallurgyof Soft Magnetic Materials, NorthHolland
Publishing Company, Amsterdam, New-York/Oxford, 1977.
[20] R.H. Kodama, A.E. Berkowitz, E.J. McNiff Jr., S. Foner, Surface spin disorder in
NiFe
2
O
4
nanoparticles, Physical ReviewLetters 77 (1996) 394–397.
[21] T.F. Marinca, I. Chicinas¸ , O. Isnard, V. Pop, F. Popa, Synthesis, Structural and
magnetic characterization of nanocrystalline nickel ferrite–NiFe
2
O
4
obtained
by reactive milling, Journal of Alloys Compounds 509 (2011) 7931–7936.
[22] I. Chicinas¸ , V. Pop, O. Isnard, Magnetic properties of Ni
3
Fe intermetallic com-
pound obtained by mechanical alloying, Journal of Magnetism and Magnetic
Materials 242–245 (2002) 885–887.
[23] R. Hamzaoui, O. Elkedim, E. Gaffet, J.M. Greneche, Structure, magnetic and
Mössbauer studies of mechanically alloyed Fe–20wt.% Ni powders, Journal of
Alloys and Compounds 417 (2006) 32–38.
[24] I. Chicinas¸ , Soft magnetic nanocrystalline powders produced by mechanical
alloying routes, Journal of Optoelectronics and Advanced Materials 8 (2006)
439–448.
[25] V.
ˇ
Sepelák, D. Baabe, K.D. Becker, Mechanically induced cation redistribution
and spin canting in nickel ferrite, Journal of Materials Synthesis and Processing
8 (2000) 333–337.
[26] M. Jalaly, M.H. Enayati, F. Karimzadeh, Investigation of structural and
magnetic properties of nanocrystalline Ni
0.3
Zn
0.7
Fe
2
O
4
prepared by high
energy ball milling, Journal of Alloys and Compounds 480 (2009)
737–740.
[27] S. Dasgupta, K.B. Kim, J. Ellrich, J. Eckert, I. Manna, Mechano-chemical syn-
thesis and characterization of microstructure and magnetic properties of
nanocrystalline Mn
1−x
ZnxFe
2
O
4
, Journal of Alloys and Compounds 424 (2006)
13–20.
[28] H. Dutta, M. Sinha, Y.C. Lee, S.K. Pradhan, Microstructure characterization and
phase transformation kinetics of ball-mill prepared nanocrystalline Mg–Zn-
ferrite by Rietveld’s analysis and electron microscopy, Materials Chemistry and
Physics 105 (2007) 31–37.
[29] S. Kim, Y. Jung, B. Lee, K. Lee, K. Narasimhan, Y.D. Kim, Characteristics of nano-
structured Fe-33at.% Si alloy powders produced by high-energy ball milling,
Journal of Alloys and Compounds 424 (2006) 204–208.
[30] N.E. Fenineche, R. Hamzaoui, O. El Kedim, Structure and magnetic properties
of nanocrystalline Co–Ni and Co–Fe mechanically alloyed, Materials Letters 57
(2003) 4165–4169.
[31] R. Orrú, R. Licheri, A.M. Locci, A. Cincotti, G. Cao, Consolidation/synthesis of
materials by electric current activated/assistedsintering, Materials Science and
Engineering R 63 (2009) 127–287.
[32] B.V. Neamt¸ u, I. Chicinas¸ , O. Isnard, I. Ciascai, H. Chiriac, M. Lostun, Magnetic
properties of nanocrystalline Ni
3
Fe compacts prepared by spark plasma sin-
tering, Intermetallics 35 (2013) 98–103.
[33] V.F. Tart¸ a, I. Chicinas¸ , T.F. Marinca, B.V. Neamt¸ u, F. Popa, C.V. Pric˘ a, Synthe-
sis of the nanocrystalline/nanosized NiFe
2
O
4
powder by ceramic method and
mechanical milling, Solid State Phenomena 188 (2012) 27–30.
[34] B.V. Neamt¸ u, I. Chicinas¸ , O. Isnard, F. Popa, V. Pop, Influence of wet milling
conditions on the structural and magnetic properties of Ni
3
Fe nanocrystalline
intermetallic compound, Intermetallics 19 (2011) 19–25.
[35] G.K. Williamson, W.H. Hall, X-ray line broadening from filed aluminium and
wolfram, Acta Metallurgica 1 (1953) 22–31.
[36] B.V. Neamt¸ u, O. Isnard, I. Chicinas¸ , C. Vagner, N. Jumate, P. Plaindoux,
Influence of benzene on the Ni
3
Fe nanocrystalline compound formation by
wet mechanical alloying: an investigation combining DSC, X-ray diffraction,
mass and IR spectrometries, Materials Chemistry and Physics 125 (2011)
364–369.
[37] T.F. Marinca, I. Chicinas¸ , O. Isnard, V. Popescu, Nanocrystalline/nanosized
Ni
1−␥
Fe
2+␥
O
4
ferrite obtained by contamination with Fe during milling of
NiO–Fe
2
O
3
mixture. Structural and magnetic characterization, Journal of the
American Ceramic Society 96 (2013) 469–475.