Materials Chemistry and Physics 130 (2011) 13001306

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Materials Chemistry and Physics

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High temperature stability of surfactant capped CoFe2 O4 nanoparticles

S. Ayyappan, G. Panneerselvam, M.P. Antony, John Philip
SMARTS, NDED, MMG, Indira Gandhi Centre for Atomic Research, Kalpalkkam 603 102, Tamil Nadu, India

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

Article history: We investigate the effect of adsorbed surfactant on the structural stability of CoFe2 O4 nanoparticles
Received 29 March 2011 during vacuum thermal annealing. In-situ high temperature X-ray diffraction studies show a reduction
Received in revised form 12 August 2011 of oleic acid coated CoFe2 O4 nanoparticles into -Fe and CoO under annealing at 800 C. On the contrary,
Accepted 9 September 2011
the uncoated CoFe2 O4 nanoparticles remains stable, with its cubic phase intact, even at 1000 C. Thermo-
gravimetric analysis coupled mass spectra reveals that the evolved carbon from the surfactant aids the
Keywords:
removal of oxygen atom from CoFe2 O4 lattice thereby reducing it to -Fe and CoO phases. These results
Cobalt ferrite
are important in tailoring stable CoFe2 O4 nanostructures for various applications.
-Fe
Surfactant 2011 Elsevier B.V. All rights reserved.
Reduction

1. Introduction we follow a simple co-precipitation method to synthesis oleic acid

Surfactant molecules are used to control the particle size and to
protect the surface of the nanoparticles from reactive atmospheres.
Transition metal oxide ferrite nanoparticles, MFe2 O4 (M = Mn, Fe,
Co, Ni and Zn) have been a subject of intense research during
the last few decades due to their interesting physical properties
and technological applications [110]. CoFe2 O4 nanoparticles (CF
nps) exhibit several interesting magnetic properties [6]. They are
tunable coercivity, large anisotropy, moderate saturation magne-
tization, site specic and strong binding to the serum albumin
proteins etc. [1114]. By exploiting the unique magnetic properties
of ferrite nanoparticles, many innovative applications have been
developed [1517], e.g. DNA-based magnetic nanoparticle assem-
bly based on nanoswitch for screening of DNA-cleaving agents [18],
novel drug delivery systems [19], microwave absorption [20,21],
humidity sensors [22], magnetic recording media, photo detector,
and spintronics.
In recent years, several synthesis protocols have been estab-
lished to produce monodisperse nanoparticles of size ranging
from single domain to superparamagnetic limits [2330]. This
include solvothermal [31], hydrothermal [32], micellar method
[33], mechanical milling [34,35], solgel method [36,37], com-
bustion method, miniemulsion [38], bacterial synthesis [39], and
co-precipitation method [4042]. Further, CoFe2 O4 phase with var-
ious morphologies including thin lms, nanoribbons, nanowires,
nanorods, nanoring, nanocube, etc. are obtained using advanced
synthesis methods [10,4349]. Among these synthesis methods,
Corresponding author. Tel.: +91 94 431 51 536; fax: +91 44 27480356.
E-mail addresses: philip@igcar.gov.in, philipj 2000@yahoo.com (J. Philip).
coated (OC-CF) and uncoated CoFe2 O4 (U-CF) using NaOH as an
alkali [50].
High temperature stability and proper understanding of the
reduction kinetics of surface functionalized ferrite nanoparticles
during annealing process are important to assess their suitabil-
ity for high temperature applications [32,5156]. The mechanism
and kinetics of the reduction of powdered iron oxide samples have
been investigated under nonisothermal conditions [57]. They have
shown that the mechanism of pre-reduction step of Fe2 O3 to Fe3 O4
follow an nth order expression where nucleation or diffusion was
not the rate-controlling factor while the main reduction to metallic
phase was described by a model involving the random forma-
tion and growth of nuclei. A novel route of phase transformation
induced by reduction of -Fe2 O3 nanocubes in solution is reported
recently [51]. Magnetization studies of nanosized cobalt ferrite
above room temperature show that the magnetization decreases
with increasing temperature approaching to zero at 830 K [58].
High temperature stable monodisperse superparamagnetic SnO2 -
coated iron-oxide nanoparticles have been synthesized via thermal
decomposition [55]. It was proposed that the SnO2 shell acts as a
barrier to the growth of -Fe2 O3 and consequently, avoiding the
-Fe2 O3 -to--Fe2 O3 phase transition at high temperatures [55].
Attempts have been made to understand the reduction kinetics
of metal oxide nanoparticles during annealing under air, inert,
vacuum, H2 , and CO. Factors inuencing the phase transition of
ferrite nanoparticles during annealing are preparation methods,
size, metal ion doping, reaction media, heating rate, etc. However,
there are only a few systematic high temperature studies on CF nps.
Jeppson et al. [59] prepared CoFe2 O4 by normal micelle precipita-
tion method using SDS as a surfactant and compared the structural
changes during annealing under inert (N2 ) and oxidative (O2 )

0254-0584/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2011.09.021
 S. Ayyappan et al. / Materials Chemistry and Physics 130 (2011) 13001306
atmospheres. They have found that the surfactant causes the reduc-
tion of cobalt ferrite into metallic CoFe alloys, FeS, and -Fe
phases at 600 C. It exhibits superparamagnetic behavior under
inert annealing condition, whereas nonmagnetic hematite and
CoSO4 6H2 O together with CoFe2 O4 are observed as end products
under O2 atmosphere. Wu et al. studied pressure induced electrical
properties of CoFe2 O4 nanoparticles, where they found size depen-
dent phase transition from spinel to tetragonal structure at 7.5 and
12.5 GPa for 6 and 80 nm size particles [60]. Further, the reduc-
tion mechanism of carbon nanotube (CNT) encapsulated magnetic
materials such as Fe, Ni, Co, Fe3 O4 , and CoFe2 O4 have been suc-
cessfully demonstrated [6163]. Our earlier studies show that the
phase transformation of Fe3 O4 involves dehydration followed by
immediate oxidative decomposition to hematite during anneal-
ing under O2 or air [50]. However, studies show that CoFe2 O4 is
stable up to 1000 C and preserve the cubic phase under differ-
ent annealing atmospheres [46,6466]. In this paper, we provide
the rst experimental evidence for surfactant assisted reduction of
CoFe2 O4 nanoparticles under vacuum.
2. Experimental details
2.1. Chemicals
For the synthesis of CoFe2 O4 nanoparticles, FeCl3 6H2 O, CoCl2 6H2 O, NaOH,
oleic acid, 35% HCl, H2 SO4 , ethanol, acetone, and hexane are purchased from E-
Merck. All the chemicals are GR grade (except hexane) and used without any further
purication. Water used in all the experiments (Elga, UK) has a resistivity value of
815 M cm.
2.2. Synthesis details
Oleic acid coated and uncoated CoFe2 O4 nanoparticles are prepared by precipita-
tion method. 2 M FeCl3 6H2 O and 1 M CoCl2 6H2 O salt solutions are freshly prepared
in water medium. These salt solutions are mixed at 1:1 ratio under continuous stir-
ring speed of 1000 rpm at 90 C. CoFe2 O4 nanoparticles are precipitated by adding
NaOH in the salt solution, at the rate of 10 ml s1 . After the addition of alkali, the
pH reaches a value of 12. At this stage, the solution turned to black indicating the
formation of CoFe2 O4 nanoparticles. Further steps to produce uncoated and coated
CoFe2 O4 nanoparticles are given below.
(1) Uncoated CoFe2 O4 nanoparticles. After 10 min digestion time, temperature is
reduced to 60 C and water wash is carried out to remove the salt impurities.
The washing procedure is repeated several times till the pH reaches 7. CoFe2 O4
particles were dried at 35 C for 24 h in inert atmosphere. These dried powders
were used for further characterization.
(2) Oleic acid coated CoFe2 O4 nanoparticles. After a digestion time of 10 min, 6 ml
oleic acid is added to the above solution to coat the particles to restrict the par-
ticle growth. The top water layer with salt impurities is discarded. The above
Fig. 1. (a) HRTEM image of pristine OC-CF. The periodic fringe spacing of 0.28 nm corresponds to the (2 2 0) plane of cubic CoFe2 O4 . Inset shows TEM image of a pristine OC-CF
sample. (b) Selected area electron diffraction (SAED) of OC-CF nanoparticles where the diffused rings have been indexed to reections from (2 2 0), (3 1 1), (4 0 0), (5 1 1), and
(4 4 0) planes.
1301
obtained surfactant coated particles are washed with Elga water at 60 C, until
the pH reaches a value of 7, to remove ionic salt impurities trapped or adhered
to the particles coagulum. Later, the water-washed particles are dispersed in
hexane. The hexane dispersion is treated with acetone to induce the parti-
cle aggregation. The aggregated particles are separated by centrifugation at
2500 rpm for 30 min. The washing procedure is repeated two times to elimi-
nate excess surfactant molecules. Oleic acid coated CoFe2 O4 particles are dried
at 35 C for 24 h in inert atmosphere. These dried powders are used for further
characterization.
2.3. Characterization techniques
Tecnai F30 transmission electron microscope, operating at an acceleration volt-
age of 200 kV, is used to record TEM images and the selected area electron diffraction
(SAED) patterns. High resolution transmission electron microscopy (HRTEM) is
obtained using a JEOL 2000 EX II (T) operated at 200 kV. A drop of nanocrystal sus-
pension in acetone is placed over an amorphous carbon-coated copper grid and
dried under lamp for 10 min.
Philips-Xpert MPD system equipped with the Buhler high vacuum heating stage
is used for in situ high temperature studies under vacuum. 2 value is varied from
25 to 67 using CuK radiation in the BraggBrentano geometry. The heating stage
consisted of a thin (80 m) tantalum foil and the temperature is measured by a
WRe thermocouple, which is spot welded at the bottom of the tantalum heater.
The temperature is controlled by resistance heating mechanism with an accuracy
of 1 C. Initially the heating chamber is pumped down to 105 mbar vacuum and
then the sample temperature is raised at the rate of 2 C min1 . A holding time of
30 min before each measurement and a vacuum level of 105 mbar are maintained
throughout the measurement. After the nal temperature, sample is cooled down
rapidly from 1000 C to room temperature and the XRD pattern is taken. Acquisition
and preliminary analysis of the data are performed by Philips Xpert Pro software
and the phases are veried by comparing with the JCPDS data.
Thermo gravimetric analysis is carried out using Setsys Evolution-1750. Weight
loss measurements are taken from 50 to 1000 C under inert (argon) and air atmo-
spheres. The efuents gases are observed using mass spectroscopy by measuring
the iron current. Heating rate of 5 C min1 is maintained for the entire measure-
ment. BOMEM MB 100 FTIR spectrometer is operated in the spectral range of
4000400 cm1 at a resolution of 1 cm1 to identify the binding of oleic acid on
CoFe2 O4 nanoparticle surface. Vibrating sample magnetometer (VSM) Lake Shore
Model: 7404 and ADE make, model EV9 are employed for room temperature
MH loops up to a maximum eld of 15 kOe and 20 kOe respectively. A Mss-
bauer spectrum is recorded on CoFe2 O4 nanoparticle using electromechanical
type spectrometer with constant acceleration mode. A source of 57 Co(Rh) held at
room temperature is used. The Mssbauer spectra of the samples were tted with
Lorentzian-shaped line by the method of least squares. The isomer shift values
reported in this paper is with respect to -Fe at room temperature.
3. Results and discussion
Fig. 1a shows the high resolution transmission electron
microscopy (HRTEM) image and inset shows the representative
TEM image of pristine OC-CF. The average diameter obtained
from TEM image analysis is 13.8 nm, against the value of 14.4 nm
1302 S. Ayyappan et al. / Materials Chemistry and Physics 130 (2011) 13001306

Fig. 3. In situ XRD pattern of OC-CF nps at different annealing temperature in vac-
Fig. 2. FTIR spectra of oleic acid, OC-CF and U-CF nanoparticles. uum. Solid line: CoFe2 O4 ; open triangular: CoO; solid diamond: -Fe; solid circle:
-Fe phase.

obtained by XRD. The periodic fringe spacing of 0.28 nm corre-

sponds to the (2 2 0) plane of cubic CoFe2 O4 and illustrates the high and 8.383 to 8.441 A respectively in the temperature range of RT
crystallinity of pristine CoFe2 O4 . Fig. 1b shows the SAED pattern of to 700 C. From 600 to 900 C, the d and a values of -Fe phase
OC-CF nanoparticles. The diffuse rings with less intensity have been increase signicantly from 25.3 to 41 nm and 2.89 to 2.897 A respec-
indexed to (2 2 0), (3 1 1), (4 0 0), (5 1 1), and (4 4 0) plane reections tively. At 1000 C, d and a values of -Fe phase are 22.3 nm and
of CoFe2 O4 . 3.797 A respectively. When the sample is cooled to RT, d and a val-
The binding of oleic acid (OA) on CoFe2 O4 surface was examined ues of -Fe phase are 22 nm and 2.874 A respectively. Surprisingly,
by FTIR and is shown in Fig. 2. The FTIR spectra of OA show charac- in situ HTXRD pattern of U-CF under same annealing protocols show
teristic peaks at 1288 and 1465 cm1 is due to the OH bonding and no phase transformation up to 1000 C (Fig. 5). The d and a values
CO stretching respectively. A peak at 1708 cm1 corresponds to of U-CF nps increase from 14 to 20 nm and 8.34 to 8.39 A respec-
C O stretching of carboxylic head group. The characteristic vibra- tively in the temperature range 6001000 C (Fig. 6). Systematic
tions at 2926 and 2853 cm1 are attributed to the stretching of shift in major crystalline phase is attributed to the increase in the
asymmetric and symmetric vibrations of (CH2 ) group of oleic particle size due to coalescence of particles by solid state diffusion
acid respectively [67]. The spectra of OA coated CoFe2 O4 nanopar- where the system reduces its free energy by reducing the surface
ticles consist of characteristic peaks at 594, 1413, 1583, 2924, and area of the nanoparticles. In a crystal supersaturated with vacan-
3471 cm1 [68]. The peak at 594 cm1 corresponds to stretching of cies cluster together to form cavities [70]. For a crystal with free
FeO bond and a broad peak at 3460 cm1 is attributed to hydroxide surface two competing processes can take place during annealing.
ion stretching that originates from moisture content in the sample. Far from the surface, cavities can grow and coalesce whereas near
Two distinct vibrations at 1413 and 1583 cm1 are attributed to the border the cavities tend to dissolve and the vacancies diffuse to
symmetric and asymmetric vibrations of COO receptively [69]. the surface. The increase in the lattice parameter (a) with temper-
The disappearance of COOH characteristic peaks at 1288 and ature or particle size (d) can be understood in terms of the surface
1708 cm1 suggests that nonexistence of physically absorbed oleic effects [71]. For an elastically-isotropic sphere of compressibility
acid in the samples and the formation of monolayer of oleic acid on and radius r, the surface tension  produces an effective pres-
CoFe2 O4 nanoparticles. sure 2/r which gives rise to a fractional volume change 2/r.
Fig. 3 shows the observed in situ high temperature X-ray diffrac- This leads to a change in the lattice spacing by a = 2a/3r. The
tion (HTXRD) pattern of OC-CF heated from room temperature (RT)
to 1000 C in steps of 100 C and cooling it back to RT. The diffrac-
tion peaks from (2 2 0), (3 1 1), (4 0 0), (5 1 1), and (4 4 0) crystalline
planes are observed at 30500 C and can be indexed to cubic spinel
structure with CoFe2 O4 phase (JCPDS no. 22-1086). In the tem-
perature range of 600700 C, the formation of -Fe [additional
reections from (1 1 0) and (2 0 0) planes] is observed together
with CoFe2 O4 phase. At 800 C, CoFe2 O4 phase is fully decom-
posed into -Fe with a trace of CoO phases. On further heating
(9001000 C), -Fe is converted to high temperature phase of -Fe,
which is associated with -Fe and CoO. After cooling back to RT, -
Fe phase is converted to the thermodynamically stable -Fe phase
along with anti-ferromagnetic CoO phase. The average particle size
of each phases are determined from the broadening of the most
intense peak of (3 1 1) for CoFe2 O4 phase and (1 1 0) for -Fe phase.
DebyeScherrer formula is employed to calculate the average size
of each phase. The peak position and full width half maximum are
determined by tting the major peaks with voigt function using
the PEAKFIT program. Fig. 4 shows the size (d) and lattice parame- Fig. 4. Variations in particle size (solid symbols) and lattice constant (open symbols)
ter (a) values of as-synthesized OC-CF increase from 14.4 to 17 nm of available phases of OC-CF during vacuum annealing.
 S. Ayyappan et al. / Materials Chemistry and Physics 130 (2011) 13001306
Fig. 5. In situ XRD pattern of U-CF nps at different annealing temperatures in vac-
uum. Solid lines show the systematic shift in CoFe2 O4 phase with temperature.
reduction of highly stable CoFe2 O4 under vacuum annealing in
presence of surfactant is quite surprising. To understand the exact
reason behind the reduction, we have carried out simultaneous
measurement of thermo gravimetric analysis (TGA), differential
scanning colorimeter (DSC) and mass spectra (MS) of OC-CF in the
temperature range from RT to 1000 C during heating (Fig. 7a and
b) and cooling (Fig. 7c and d) back to RT under argon atmosphere
at the heating rate of 5 C min1 . OC-CF shows a two-step weight
loss with an initial 2% loss along with endothermic peak in DSC
curve in the temperature range of RT to 200 C is attributed to the
removal of moisture content. The rst weight loss of 10% occurs
with a strong endothermic peak at 360 C is due to the decompo-
sition of weakly bound functional group (COOH) from surfactant
layer. The mass spectra reveal the evolution of H2 (m/z: 2), CO (m/z:
28) and CO2 (m/z: 44) with small amount of H2 O (m/z: 18) from
the oleic acid, in the temperature range of 220420 C. On further
heating (550670 C range), the second weight loss of 10% along
with multiple endothermic peak in DSC is observed, which could
be possibly due to the removal of oxygen atoms from the CF lattice
by residual carbon from the oleic acid. The multiple endothermic
peaks are due to the formation of -Fe and CoO, which is consis-
tent with HTXRD patterns where the -Fe and CoO are formed at
600 and 800 C respectively. Shin et al. [72] observed 20% weight
loss in CuFe2 O4 during annealing at 1073 K under the reduction
atmosphere of H2 and Ar mixture. The observed 20% reduction is
Fig. 6. Variations in particle size (solid symbols) and lattice constant (open symbols)
of available phases of U-CF during vacuum annealing.
1303
Fig. 7. (a) Thermo gravimetric analysis (TGA), differential scanning colorimetery
(DSC) and (b) mass spectra (MS) of OC-CF during heating from RT to 1000 C at the
heating rate of 5 C min1 . (c) TGA-DSC and (d) MS of OC-CF during cooling under
argon atmosphere.
assigned to the elimination of three oxygen from CuFe2 O4 . Fur-
ther it is observed that efuents like CO (m/z: 28) and CO2 (m/z:
44) at this temperature range of 500700 C conrm that carbon
from oleic acid act as a reducing agent and favor the removal of
oxygen atom from the CoFe2 O4 lattice. On further heating, there
is no considerable change in weight loss and gas evolution except
an endothermic peak observed at 885 C in DSC (Fig. 7a) which is
due to the structural transition of -Fe-Fe observed at 900 C
(Fig. 3). This observation is in good agreement with the FeC phase
diagram, where at 0% carbon, -Fe is converted into -Fe at 912 C.
The TGADSCMS spectra during cooling cycle (Fig. 7c and d) show
negligible changes except an exothermic peak around 775 C, which
is assigned to the Curie temperature of -Fe phase. Further, to con-
rm the nal phases, the XRD pattern of air exposed sample (OC-CF
annealed to 1000 C under vacuum and cooling back to RT) is taken
again. The XRD patterns (Fig. 8a) match with -Fe, CoO and -Fe2 O3
phases. Interestingly, the in situ HTXRD pattern of OC-CF with tan-
talum (Fig. 3) and without tantalum (Fig. 8a) shows no additional
impurity phases. This means that the efuent carbon from oleic
acid comes out in the form of CO (m/z: 28) and CO2 (m/z: 44) by
Fig. 8. Room temperature XRD pattern of (a) vacuum annealed (at 1000 C) (b) Room
temperature XRD pattern of argon annealed (at 1000 C) OC-CF nps exposed to air.
Solid diamond: -Fe2 O3 , open triangular: CoO, star: Co and solid circle: -Fe phase.
1304 S. Ayyappan et al. / Materials Chemistry and Physics 130 (2011) 13001306
reacting with oxygen of CoFe2 O4 rather than reacting with Fe and
forming Fe3 C phase. This observation is in sharp contrast with the
Fe3 C impurity phase observed in CNT encapsulated Fe3 O4 [62,63].
The room temperature XRD (Fig. 8b) on argon annealed sample
shows the presence of -Fe2 O3 , Co metallic phase, trace of -Fe
and CoO phases. However, the vacuum annealed sample does not
show the presence of Co phase. This shows that the nal product
under vacuum and argon annealing are quite different.
Studies show that oxygen vacancies can be formed during
vacuum annealing [7375]. During reduction of metal oxides,
nucleation-controlled processes involve uniform internal reduc-
tion and occur by the initial random removal of lattice oxygen
atoms until a critical concentration of vacancies is reached. It
has been elegantly demonstrated that such vacancies are annihi-
lated by lattice rearrangement and produce metal nuclei [57]. The
reduction mechanism is generally described by complex kinetics
equation, Rate = Af()exp(E/RT) , where T is the absolute tempera-
ture, A is the preexponential factor, t is the time, is the fraction
of sample reacted, E is the activation energy, R is the gas con-
stant, and f() governs the reaction mechanism. In general kinetic
models are described by diffusion-controlled processes, boundary-
controlled, and a process of random nucleation and subsequent
growth of nuclei. The rate determining process in the above three
processes are gas diffusion through the product layer, shrinking
core or contracting sphere chemical reaction and uniform internal
reduction by the initial random removal of lattice oxygen atoms
until a critical concentration of vacancies is reached respectively.
The vacancies are later annihilated by lattice rearrangement. Dur-
ing nuclei growth, the reduction process accelerates due to the
increasing metalmetal oxide interface and the merging of product
nuclei leads to a decrease in the product interfacial area.
To understand the role of surfactant under air annealing, OC-
CF and U-CF nanoparticles are annealed in air atmosphere up to
1000 C at regular intervals of 200 C. We maintain the heating
rate of 5 C min1 and the holding time of 2 h at each interval.
RT XRD patterns of U-CF and OC-CF annealed in air medium are
shown in Fig. 9a and b respectively. In both cases, XRD patterns are
well matched with the characteristics peaks of CoFe2 O4 (JCPDS no.
22-1086) with spinel structure for the entire temperature range.
These results show that no phase transformation occurs in both
oleic acid coated and uncoated CF during air annealing. Further to
Fig. 9. XRD patterns of (a) U-CF and (b) OC-CF annealed at different temperature in
air for 2 h.
Fig. 10. (a) Thermo gravimetric analysis (TGA) differential scanning colorimetery
(DSC) of OC-CF and (b) mass spectra (MS) of OC-CF during heating under air from
RT to 1000 C. (c) TGADSC and (d) MS of pure oleic acid during heating from RT to
1000 C under air atmosphere at the heating rate of 5 C min1 .
conrm the structural stability of CoFe2 O4 phase, we have done the
simultaneous TGADSCMS on OC-CF under air medium (Fig. 10a
and b), where a single step weight loss of 13% could be observed
compared to two step loss that was observed in argon atmosphere
(Fig. 7a). The strong exothermic peak and evolved gases conrm the
removal of oleic acid during air annealing, where O2 acts as a cat-
alyst for the burn up. In this temperature range (200400 C), CO2
(m/z: 44), H2 (m/z: 2), and H2 O (m/z: 18) are evolved from the oleic
acid (Fig. 10b). On further heating no considerable changes in the
weight loss, heat ow and gas evaluation are observed. This clearly
illustrates that in oxidative medium too, both C and H2 are released
from the oleic acid at the temperature around 300 C. The evolved C
from oleic acid will react with oxygen from the reactive oxygen gas
rather than reacting with oxygen in the CF lattice, as the former is
more energetically favorable at atmosphere pressure. The heating
cycle (Fig. 10a and b) shows no considerable change beyond 300 C
in TGADSCMS curves that reafrms that the cubic phase of the
CoFe2 O4 remains unchanged in OC-CF under air annealing. Further,
to understand the decomposition behavior of pure oleic acid, we
carried out TGADSC (Fig. 10c) and MS (Fig. 10d) of oleic acid up to
1000 C under air annealing. TGA results show a weight loss of more
than 85%, with a strong exothermic peak and the evaluation of CO2
(m/z: 44) and H2 (m/z: 2) in the temperature range of 160500 C,
which conrm the decomposition of oleic acid. On further heating,
there was no signicant weight loss or evolved gases, suggesting
the complete decomposition of oleic acid. TGADSC coupled MS of
pure oleic acid under air annealing clearly demonstrates that at the
temperature beyond 600 C, the carbon is not evolved (in the form
of CO or CO2 ) during air annealing. On contrary, carbon is evolved
in the form of CO and CO2 during argon annealing (Fig. 7) where
the CoFe2 O4 is reduced into metallic Fe and CoO phases.
Mssbauer spectra of OC-CF (Fig. 11) could be well tted with
2 sextets, which are attributed to Fe3+ ions in the two sub lattices
of tetrahedral (A) and octahedral (B) sites representing ferromag-
netic behavior. The outer sextet with larger isomer shift value of
0.33 mm s1 , corresponds to the octahedral B-site Fe3+ ions, while
the other one with a smaller isomer shift value of 0.22 mm s1 cor-
responds to the tetrahedral A-site Fe3+ ions. Further, the hysteresis
behavior of OC-CF and U-CF nanoparticle is shown in Fig. 12a and b
respectively. The observed magnetization loops are consistent with
the observed structural changes after annealing. This is also consis-
tent with the reported instability of pure Fe nanocrystals at room
temperature [7678]. Room temperature MH loop (Fig. 12a) for
 S. Ayyappan et al. / Materials Chemistry and Physics 130 (2011) 13001306
Fig. 11. Room temperature Mssbauer spectra of OC-CF nanoparticles. Open circles
are raw data and solid lines are ts to the spectra.
OC-CF nps before and after vacuum annealing up to 1000 C show
ferromagnetic and superparamagnetic (zero coercivity and zero
remanance) with a saturation magnetization (MS ) of 46 emu g1
(at 15 kOe) and 127 emu g1 (at 20 kOe) respectively. Saturation
magnetization values correspond to the initial and nal products
and these values are in good agreement with the reported values
of CoFe2 O4 [64] and -Fe [79]. The MS value for bulk -Fe phase
is 210 emu g1 and is ferromagnetic in nature. Fig. 12b shows the
MH loops of U-CF nanoparticles, which illustrate a sharp transition
from ferromagnetic to supeparamagnetic after vacuum annealing,
where MS increase from 61 to 70 emu g1 and coercivity decreases
from 0.6 to 0 kOe. As synthesized nanocrystallites, there exist large
amount of uncoordinated surface atoms that can lead to a reduc-
tion in saturation magnetization, a value considerably lower than
its bulk counterparts. The linear dependence of saturation magne-
tization (MS ) with inverse of particles size (d1 ) or surface area (S
in m2 g1 ) can be understood by assuming the core shell structure
of the nanoparticles where the shell layer has a thickness of d and
has a lower saturation magnetization. This is represented as [80]
 MS 2

MS (S) = MS (0) 1 dS
MS (0)
Where MS (0) is the bulk saturation magnetization, MS is the dif-
ference in magnetization between the core and shell, and 2 is the
density of the shell. Studies show that the magnetic nature of the
Fig. 12. Room temperature MH loops for both before (solid circle) and after (open
circle) annealed at 1000 C in vacuum (a) OC-CF and (b) U-CF. Inset show the zoomed
view of MH loops.
1305
Fig. 13. Schematic illustrations of the reduction of OC-CF in vacuum. At the boiling
point of oleic acid (360 C), H2 , O2 , CO, and CO2 gases are evolved. Above 600 C,
the residual carbon from the oleic acid interacts with the oxygen of cobalt ferrite,
which leads to evolution of CO and CO2 . Above 800 C CoFe2 O4 is reduced to metallic
Fe and CoO phases.
rst crystalline layer on the particle is destroyed by the adsorbed
shell layer.
In case of OC-CF (after annealing), the reduction in saturation
magnetization values compared to the bulk value of -Fe could
be due to the coexistence of ferrimagnetic phase of -Fe2 O3 (that
is formed after exposure to air) and an antiferromagnetic phase
of CoO at room temperature. Oxygen vacancies induced cation
migration and subsequent room temperature ferromagnetism is
observed in a paramagnetic ZnFe2 O4 [81]. Similarly, in case of
CoFe2 O4 , oxygen vacancies can lead to cation migration between A-
and B-interstitials and exhibits superparamagnetic behavior with
zero coercivity and zero remanance at room temperature which
need to be proved using Mssbauer spectroscopy. The schematic
illustration of the reduction mechanism is shown in Fig. 13. Gas
efuents such as H2 , O2 , CO, and CO2 , from OC-CF lattice are
observed at the boiling point of oleic acid during heating. At high
temperatures, the residual carbon from the oleic acid interact with
the oxygen of cobalt ferrite (which is evident from the evolved CO
and CO2 at high temperatures) leading to the reduction of CoFe2 O4
(1)
phase to metallic Fe and CoO phases under vacuum annealing.
4. Conclusions
In conclusion, we provide the rst direct experimental evi-
dence for surfactant assisted facile reduction of highly stable
oleic acid coated CoFe2 O4 to metallic Fe under vacuum annealing.
The TGADSCMS shows that efuent carbon from the surfac-
tant removes the oxygen atoms from the cubic lattice leading to
the reduction of CoFe2 O4 into metallic iron and CoO. The room
temperature MH loops for OC-CF nanoparticles before and after
vacuum annealing, up to 1000 C, show ferromagnetic and super-
paramagnetic nature (with a saturation magnetization of 46 and
127 emu g1 ) respectively. The MH loops of U-CF nanoparticles
show a sharp transition from ferromagnetic to supeparamagnetic
after vacuum annealing, where MS increase from 61 to 70 emu g1
and coercivity decreases from 0.6 to 0 kOe. Our results demonstrate
the important role of surfactant monolayer on the reduction of
surface functionalized CoFe2 O4 nanoparticles.
Acknowledgements
Authors would like to thank Dr. R. Divakar and Dr. E. Mohandas
for HRTEM and Dr. R. Sridharan for TGADSCMS spectra. We thank
Dr. T. Jayakumar for useful discussions.
1306 S. Ayyappan et al. / Materials Chemistry and Physics 130 (2011) 13001306
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