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Mn0.5Zn0.5Fe2O4 nanoparticles

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Journal of Magnetism and Magnetic Materials 324 (2012) 394–402

Contents lists available at SciVerse ScienceDirect

Journal of Magnetism and Magnetic Materials

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

Study of magnetic and structural properties of ferrofluids based

on cobalt–zinc ferrite nanoparticles
J. López a,n, L.F. González-Bahamón b, J. Prado a, J.C. Caicedo a, G. Zambrano a,
M.E. Gómez a, J. Esteve c, P. Prieto d
a
Thin Film Group, Universidad del Valle, A.A. 25360, Cali, Colombia
b
Analytical Chemistry Laboratory, Universidad del Valle, A.A. 25360, Cali, Colombia
c
Department de Fı́sica Aplicada i Óptica, Universitat de Barcelona, Catalunya, Spain
d
Center of Excellence for Novel Materials, Universidad del Valle, Cali, Colombia

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

Article history: Ferrofluids are colloidal systems composed of a single domain of magnetic nanoparticles with a mean
Received 30 May 2011 diameter around 30 nm, dispersed in a liquid carrier. Magnetic Co(1  x)ZnxFe2O4 (x ¼0.25, 0.50, 0.75)
Received in revised form ferrite nanoparticles were prepared via co-precipitation method from aqueous salt solutions in an
15 July 2011
alkaline medium. The composition and structure of the samples were characterized through Energy
Available online 19 August 2011
Dispersive X-ray Spectroscopy and X-ray diffraction, respectively. Transmission Electron Microscopy
Keywords: (TEM) studies permitted determining nanoparticle size; grain size of nanoparticle conglomerates was
Chemical co-precipitation established via Atomic Force Microscopy. The magnetic behavior of ferrofluids was characterized by
Ferrofluid Vibrating Sample Magnetometer (VSM); and finally, a magnetic force microscope was used to visualize
Nanoparticle
the magnetic domains of Co(1  x)ZnxFe2O4 nanoparticles. X-ray diffraction patterns of Co(1  x)ZnxFe2O4
Single domain
show the presence of the most intense peak corresponding to the (311) crystallographic orientation of
Spinel structure
Super-paramagnetism the spinel phase of CoFe2O4. Fourier Transform Infrared Spectroscopy confirmed the presence of the
bonds associated to the spinel structures; particularly for ferrites. The mean size of the crystallite of
nanoparticles determined from the full-width at half maximum of the strongest reflection of the (311)
peak by using the Scherrer approximation diminished from (9.5 7 0.3) nm to (5.4 7 0.2) nm when the
Zn concentration increases from 0.21 to 0.75. The size of the Co–Zn ferrite nanoparticles obtained by
TEM is in good agreement with the crystallite size calculated from X-ray diffraction patterns, using
Scherer’s formula. The magnetic properties investigated with the aid of a VSM at room temperature
presented super-paramagnetic behavior, determined by the shape of the hysteresis loop. In this study,
we established that the coercive field of Co(1  x)ZnxFe2O4 magnetic nanoparticles, the crystal and
nanoparticle sizes determined by X-ray Diffraction and TEM, respectively, decrease with the increase of
the Zn at%. Finally, our magnetic nanoparticles are not very hard magnetic materials given that the
hysteresis loop is small and for this reason Co(1  x)ZnxFe2O4 nanoparticles are considered as soft
magnetic material.
Crown Copyright & 2011 Published by Elsevier B.V. All rights reserved.

1. Introduction the nanoparticles are injected directly into them. When this fluid
is placed in an alternating magnetic field, the nanoparticles
Magnetic nanoparticles offer attractive possibilities in biome- generate heat and destroy the tumor. It should be taken into
dicine. Recently, ferrofluids (FFs) or magnetic fluids have been the consideration that, for medical applications, these materials must
subject of interest because of their unusual optical, electronic, and be biocompatible. Nowadays, FFs are promising materials for
magnetic properties [1–3], which can be changed by applying an cancer diagnosis and therapy. Cobalt–Zinc ferrite nanoparticles
external magnetic field. But the use of nanometer-size magnetic have attracted considerable attention because of their broad
particles has expanded their applications in fields such as biome- applications in several technological fields, including electronic
dicine, which has been proposed, for example, as an alternative devices and ferrofluids, prospective material for biomedical
therapy and localized for treatment of malignant tumors, where applications in diagnostics and cancer therapy, magnetic drug
delivery, microwave devices, crystal photonics, and high-density
information storage systems [4–8]. Ferrofluids are colloidal sys-
n
Corresponding author. tems composed of single domain of magnetic nanoparticles with a
E-mail address: [email protected] (J. López). mean diameter of around 10 nm, dispersed in a liquid carrier.

0304-8853/$ - see front matter Crown Copyright & 2011 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.jmmm.2011.07.040
 Author's personal copy

J. López et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 394–402 395

The special feature of FF is the combination of normal liquid 2.2. Materials

behavior with super-paramagnetic properties, due to the small
particle size. There are various methods to prepare magnetic To prepare the ferrofluid, FeCl3  6H2O (97%), CoCl2  6H2O
nanoparticles at nanometer-size range. Synthesis of Co(1  x)Znx- (97%), ZnSO4  7H2O (99%), and sodium hydroxide (NaOH) from
Fe2O4 nanoparticles has been of great interest, especially in the MerckTM were used. HPLC-grade Oleic acid (C18H34O2) was used
form of ferrofluids. In the present work, magnetic Co(1  x)ZnxFe2O4 as surfactant. All the materials were reagent grade and used
ferrite nanoparticles were prepared by co-precipitation method without further purification. Distilled and de-ionized water was
from aqueous salt solutions in an alkaline medium. We structu- used as a solvent.
rally characterized the samples by X-ray diffraction (XRD) and the
magnetic nanoparticles size was determinate by Transmission
2.3. Procedure
Electron Microscopy (TEM). On the other hand, Atomic Force
Microscopy (AFM) investigation provides a qualitative informa-
Magnetic nanoparticles of Co(1  x)ZnxFe2O4, with nominal
tion of the surface morphology and a quantitative information of
value x¼0.25–0.75, were prepared by co-precipitation technique
the scanned magnetic nanoparticles conglomerates, via statistical
from mixed solutions of CoCl2, ZnSO4, and FeCl3 in their respec-
calculation of their diameter and height, in order to establish the
tive stoichiometry at 80 1C. After dissolving 75 ml of 0.4 M
grain size of conglomerates of nanoparticles. The compositions of
FeCl3  6H2O, 75 ml of 0.1 M CoCl2,  6H2O, and ZnSO4  7H2O solu-
the samples were calculated by Energy Dispersive X-ray Spectro-
tion for Co0.5Zn0.5Fe2O4 sample, 75 ml of 3 M NaOH was added as
scopy (EDS). Fourier Transform Infrared Spectroscopy (FTIR) was
co-precipitating agent. The mixed solution was added to the
used to confirm the presence of bonds associated to the spinel
solution of NaOH drop-wise under constant stirring and then
structures for this ferrite in particular. The magnetic behavior
the precipitation occurred immediately to change the solution to
of Co(1  x)ZnxFe2O4 nanoparticles was studied by Vibrating
a dark color (brown), characteristic of this ferrite. The precipitated
Sample Magnetometer (VSM) method, which allows us to
liquid was brought to a reaction temperature of 80 1C for 1 h and
make the magnetic moment curves as a function of applied field
cooled to room temperature. The pH of the solution was
H, as well as perform magnetization as temperature function
constantly monitored when NaOH solution was added to produce
curves in the FC and ZFC process to find the blocking temperature
the precipitation of Co(1  x)ZnxFe2O4 ferrofluids with magnetic
of the material. Finally, Magnetic Force Microscopy (MFM) was
nanoparticles. The reactants were magnetically stirred during
used to visualize the magnetic domains of Co(1  x)ZnxFe2O4
the precipitation, and the pH level was reduced from approxi-
nanoparticles.
mately 12 to 10.5 by washing with de-ionized water. As a result,
the mixture of NaOH added slowly to the solution of salts
promotes the formation of the respective metal hydroxide that
2. Experimental details subsequently becomes ferrites under temperature conditions.
The reaction for the precipitation of Fe3 þ , Zn2 þ , and Co2 þ
To prepare Co(1  x)ZnxFe2O4 magnetic nanoparticles, chemical nanoparticles to obtain the Co0.5Zn0.5Fe2O4 sample, is described
co-precipitation is probably the most-common and the most-used as follows:
method for synthesis of ferrofluids or magnetic fluids based on
magnetic nanoparticles. The preparation of surfacted and ionic 4Fe3 þ þZn2 þ þCo2 þ þ16HO -2Co0:5 Zn0:5 Fe2 O4 þ8H2 O ð1Þ
aqueous ferrofluids based on spinel ferrite nanoparticles has been However, Co(1  x)ZnxFe2O4 nanoparticles synthesized by the
reported by Massart [9,10]. Through this method, it is usually co-precipitation method can easily form particle conglomerates.
necessary to start from a mixture of FeCl3  6H2O, CoCl2  6H2O, To prevent this phenomenon, we added 5 ml of oleic acid to the
and ZnSO4  7H2O salts in an aqueous alkaline medium. Then, solution as a surfactant and coating material and then the
the solution is subjected to different procedures such as decanta- solution was stirred for 2 h at 80 1C. Oleic acid is added when
tion, magnetic separation, centrifugation, and dilution. To avoid the pH of the precipitate has a value between 10 and 11 because
the agglomeration of magnetic nanoparticles, the solution is the solution is completely ionized, permitting to bind the carbox-
usually covered with a shell of an appropriate material (steric ylate group to the ferrite surface, creating an electrostatic repul-
stabilization). sion that prevents the aggregation of particles, and therefore
stabilizing the ferrofluid. To get particles free from sodium and
chlorine compounds, the precipitate was washed twice with de-
2.1. Synthesis of Co(1  x)ZnxFe2O4 nanoparticles
ionized and distilled water as a solvent and with ethanol and
acetone to remove the surfactant excess from the solution. To
The synthesis of Co(1  x)ZnxFe2O4 magnetic nanoparticles in
isolate the supernatant liquid (ethanol, acetone, and water) the
ferrofluids has two steps: the preparation of nano-sized magnetic
beaker content was then centrifuged for 15 min at 4000 rpm.
particles and the respective dispersion—stabilization of the
Thus, the supernatant liquid is decanted and the precipitate
nanoparticles in a carrier liquid (ethanol). The magnetic ferro-
remains. A part of the volume of this precipitate was dried at
fluids based on Co(1  x)ZnxFe2O4 nanoparticles are prepared
100 1C for 10 h and ground into a fine powder to perform the XRD
by co-precipitation technique from aqueous salt solutions
an FTIR analyses. The other part of the colloid was used to carry
FeCl3,  6H2O, CoCl2,  6H2O, and ZnSO4  7H2O in the molar ratio
out the magnetic and AFM measurements [11–16]. Table 1 shows
1:2 [Me2 þ /Fe3 þ ], in an alkaline medium. The magnetic nanopar-
the Co, Zn, and Fe mol concentration for the three different values
ticles obtained are stabilized by a surfactant. Oleic acid is usually
of x (Zn substitution). In all instances, we kept constant stirring
used as a surfactant, which forms the waterproofing shell around
speed and adjusted the volume of the final solution in the
the magnetic nanoparticles. The treatment of the nanoparticles by
reaction vessel to keep the M/OH  -ratio around 0.20.
oleic acid is a very important stage of magnetic ferrofluid
preparation, because it is added to prevent the agglomeration of
nanoparticles. The size and physical properties of the nanoparti- 2.4. Characterization of Co(1  x)ZnxFe2O4 nanoparticles
cles depend on preparation parameters such as, reaction tem-
perature, pH of the suspension, initial molar concentration, and Chemical composition of magnetic nanoparticles obtained via
others. co-precipitation method was performed in a Philips XL30 ESEM
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396 J. López et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 394–402

Table 1 Table 2
Nominal values of zinc substitution in the Co(1 x)ZnxFe2O4 magnetic nanoparticles. Atomic percent and ratios of x ¼Zn/(Znþ Co) and Fe/(Zn þCo) in the Co(1  x)Znx-
Fe2O4 magnetic nanoparticles for the three different values of Zn concentration.
Sample Concentration mol/l
Sample Co at% Zn at% Fe at% Zn=ðZn þ CoÞ FeðZnþ CoÞ
Co Zn Fe
Co0.79Zn0.21Fe2O4 11 3 30 0.21 2.14
Co0.75Zn0.25Fe2O4 0.15 0.05 0.40 Co0.56Zn0.44Fe2O4 9 7 33 0.44 2.06
Co0.5Zn0.5Fe2O4 0.10 0.10 0.40 Co0.25Zn0.75Fe2O4 3 9 26 0.75 2.16
Co0.25Zn0.75Fe2O4 0.05 0.15 0.40

increased monotonically from 0.21 to 0.75; whereas, the

with an EDAX microprobe for chemical analysis (12 KV), equipped Fe/(ZnþCo) ratio was preserved practically close to 1:2 with the
with a window for the detection of light elements. increase of Zn concentration in the Co(1 x)ZnxFe2O4 samples. Note
The crystal structure of Co(1 x)ZnxFe2O4 magnetic nanoparticles that the real x-values are slightly different from the nominal ones.
was recorded in the 2y scale with a RIGAKU (DMAX-2100) From now on, we will use the real values extracted from the EDS
diffractometer using CoKa radiation (l ¼1.78899 Å, 30 kV, and chemical composition analysis. Therefore, EDS elemental concen-
16 mA) radiation at room temperature in the range of 15 to 951, trations were obtained by using the ZAF correction method;
with a scanning speed of 0.021 s  1 and step time of 0.2 s, and at 51 because certain factors related to the sample composition, called
incidence angle to avoid the fluorescence from the Fe and Co matrix effects associated with atomic number (Z), absorption (A),
present in the samples. The peaks of the diffraction pattern were and fluorescence (F) can affect the X-ray spectrum produced
indexed and analyzed by using the International Center for during the analysis of the electron microprobe and, therefore,
Diffraction Data (ICDD-PDF2) database and the WINJADE 8.5 soft- these effects should be corrected to ensure the development of a
ware for identification and compared such with the CoFe2O4 careful analysis. The correction factors for a standard specimen of
standard. Fourier Transform Infrared Spectroscopy (FTIR) spectra known composition were initially determined by the ZAF routine.
were recorded for the dried sample of ferrite with an FTIR— The relative intensity of the K peak was determined by dead time
Shimadsu 8400 spectrophotometer in wave range of 3500– correction and a referent correction for the X-ray measured. Thus,
400 cm  1 with a resolution of 4 cm  1. The dried sample was before each quantitative analysis of an EDS spectrum, a manual
placed on a silicon substrate transparent to the infrared radiation background correction and an automated ZAF correction were
and spectra were recorded according to the transmittance method. carried out.
Magnetic characterization of the nanoparticles was carried out
through magnetic hysteresis loops by using a vibrating sample 3.2. Structural and particle characterization
magnetometer (VSM) in the physical property measurements
system (PPMS) from Quantum DesignTM. Magnetizations vs. Fig. 1 shows the X-ray diffraction spectra for (a) Co(1 x)ZnxFe2O4,
applied field measurements were performed at room temperature (b) Co(1 x)ZnxFe2O4, and (c) Co(1 x)ZnxFe2O4 magnetic nanoparti-
with an applied magnetic field varying within the range of cles. In all cases, the peaks indexed (220), (311), (400), (422), (511),
15,000 Oe–15,000 Oe. Thermal demagnetization curves without and (440) are presented. The strongest reflection coming from the
applied magnetic field (Zero Field Cooling, ZFC) and cooled with (311) plane can also be observed, which denotes the formation of
applied magnetic field (Field Cooling, FC) of H ¼100 Oe were the characteristic cubic spinel structure [17–21]. According to
carried out to study the blocking temperature and also to obtain Fontijn et al., [22,23] the substitution of Co by Zn in the Co(1 x)Znx-
the profile of distribution of particle sizes of the Co(1  x)ZnxFe2O4 Fe2O4 system, causes the Zn ions to begin to take up the sites of Fe
samples. ions found in tetrahedral sites and Fe ions migrate to octahedral
The AFM used to visualize the morphology of nanoparticles sites, displacing Co ions thereby, the Fe ions in octahedral sites
was an Asylum Research MFP-3D Atomic Force Microscope in AC increase. Hence, the system changes from an inverse spinel to a
non-contact mode in air operating at room temperature. For normal spinel structure. This process produces a slight shift of
magnetic imaging, we used an Asylum Research ASYMFM Si peaks in the X-ray diffraction patterns. In our case, this effect has
cantilever with a 50 nm Co–Cr coating, a spring constant between been detected. Thus, we confirm that the crystalline structure of
1–2 N/m, resonant frequency of 55–90 KHz, and tip radius less Co(1 x)ZnxFe2O4 magnetic nanoparticles changes to a normal spinel
than 20 nm. Transmission Electron Microscope (TEM Philips structure when the Zn atomic concentration increases.
CM30) operating at 300 kV was used to determine nanoparticle The lattice parameters of the Co(1  x)ZnxFe2O4 were calculated
size and their morphologies and crystal structure. A drop of the from the position of the strongest reflection, the (311) peak, by
magnetic nanoparticle fluid at room temperature was placed on a fitting the whole pattern of the experimental data, according to
copper grid with a graphite mask to support the magnetic (WPF) X-ray diffraction profiles and Rietveld refinement of crystal
nanoparticles and to reduce their magnetic effect on the TEM structures with Materials Data Jade 8.5 (MDJ) software. Also,
measurements. Scherrer’s formula was used to assess the crystallite size of the
particles from the broadening FWHM of the (311) peak in the XRD
patterns, using the profile fitting and peak decomposition method
3. Results and discussion of the Materials Data Jade 8.5 (MDJ) software. The lattice para-
meter and the crystal size are presented in Table 3.
3.1. Chemical composition Fig. 2 displays the lattice parameter and the crystal size
extracted from the fitted XRD data as functions of the Zn atom
The EDS spectra for Co(1  x)ZnxFe2O4 magnetic nanoparticles concentration. An increase of the Co(1  x)ZnxFe2O4 lattice para-
confirms, in all instances, the presence of Co, Zn, Fe, and O2 in the meter was observed with the inclusion of Zinc; the lattice
samples. In Table 2, we present the atomic percent and relative parameter of CoFe2O4 is (0.838 nm), as expected, because the
ratios of x¼Zn/(Znþ Co) and Fe/(ZnþCo) in the Co(1 x)ZnxFe2O4 atomic radius for Zn is larger than the Co atomic radius. Also, the
magnetic nanoparticles, as functions of the inclusion of zinc in the crystal size decreases with the increase of the Zn concentration, as
ferrite samples. Table 2 reveals that the metal ratio x¼Zn/(ZnþCo) seen in Fig. 2.
 Author's personal copy

J. López et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 394–402 397

Fig. 2. Variation of the lattice parameter and crystal size as functions of Zn

concentration.

Fig. 3. FTIR spectra for Co(1  x)ZnxFe2O4/C18H34O2/ethanol based magnetic

ferrofluids.

bands Fe–O bonds in the crystalline lattice of Co(1  x)ZnxFe2O4

Fig. 1. X-ray diffraction patterns of (a) Co0.79Zn0.21Fe2O4, (b) Co0.56Zn0.44Fe2O4,
[24]. They are characteristically pronounced for all spinel struc-
and (c) Co0.25Zn0.75Fe2O magnetic ferrofluids at different Zn concentrations. tures and for ferrites in particular. This occurs because the
stretching vibration bands related to metal in the octahedral
and tetrahedral sites are in this region. FTIR spectra also show
Table 3
Lattice parameter and crystal size of Co(1  x)ZnxFe2O4 magnetic nanoparticles as an absorption band between 1247 cm  1 and 1650 cm  1, corre-
functions of Zn concentration. sponding to the stretching vibration of the carboxyl group (C¼O),
associated to the oleic acid molecule. In summary, FTIR absorp-
Sample Lattice parameter [nm] Crystal size [nm]
tion spectroscopy allows identifying the spinel structure and
Co0.79Zn0.21Fe2O4 0.839 7 0.003 9.5 7 0.3 confirms the XRD structural characterization, as well as the
Co0.56Zn0.44Fe2O4 0.843 7 0.001 7.07 0.2 presence of certain types of chemical substances adsorbed on
Co0.25Zn0.75Fe2O4 0.844 7 0.002 5.4 7 0.2 the surface of nanoparticles [25,26].

3.4. Magnetic characterization

3.3. FTIR spectral measurements
Fig. 4 shows the M vs. H loops for the Co(1 x)ZnxFe2O4 ferrite
FTIR spectra of the samples exhibit two intense bands between samples based on ethanol-like carrier liquid, at different Zn con-
590 cm  1 and 621 cm  1 (Fig. 3) belonging to the stretching centrations taken at room temperature. From the hysteresis loops,
vibration modes associated to the metal–oxygen absorption one can see that when magnetic nanoparticles are suspended in
 Author's personal copy

398 J. López et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 394–402

Fig. 5. Coercive field (Hc) as a function of crystal size and Zn concentration.

Fig. 4. M vs. H hysteresis loop of Co(1  x)ZnxFe2O4 magnetic ferrofluid as a function

of Zn concentrations at room temperature.

ethanol and coated with oleic acid as surfactant agent, the differ-
ence in the magnetic properties of particles can be attributed to a
weak interaction favored by the combined action of interfacial (Van
der Waals of acid–base) magnetic attractions between the particles
immersed in the carrier liquid and the steric repulsion produced
between particles, which avoids the formation of conglomerates.
Therefore, Co(1 x)ZnxFe2O4 nanoparticles can be considered single
domain, showing the tendency to super-paramagnetic behavior at
room temperature [27,28], characteristic of a soft ferromagnetic
material like a Co(1 x)ZnxFe2O4 ferrite.
The behavior of ferrofluids is mainly determined by their
magnetic properties. Usually, they show super-paramagnetic
behavior considering each particle as a thermally agitated per-
manent magnet in the carrier liquid. In the presence of a magnetic Fig. 6. Zero-field-cooled (ZFC) and field cooled (FC) magnetization curves, ZFC–FC
field, H, the magnetic moment (m) of the particles will try to align curve and the derivative with respect to temperature of the difference between
with the magnetic field direction leading to a macroscopic the FC and ZFC vs. T.
magnetization of the liquid. The magnetization, M, of the liquid
behaves as the magnetization of a paramagnetic system. Further- samples causes a decrease of the surface effects on their magnetic
more, these types of materials present a behavior of the hysteresis properties.
M vs. H loops, which indicates the irreversibility in the magneti- The study of nanoparticle size from measurements of the
zation process related to the pinning of the magnetic domain blocking temperature for FC and ZFC processes is an interesting
walls at impurities or grain boundaries within the material, as research topic [32]. Magnetization as a function of temperature in
well as to the intrinsic effects such as the magnetic anisotropy of the applied field of 100 Oe was performed between 4 K and 300 K.
the crystalline lattice. On the other hand, the shapes of these From the FC and ZFC curves in Fig. 6, we can observe its
loops are determined—in part—by particle size. At even smaller irreversibility, typical of the blocking process assembly of super-
sizes (in order of tens of nanometers or less), one can see super- paramagnetic nanoparticles [33]. Additionally, above the blocking
paramagnetic behavior [29] where the magnetic moment of the temperature, the magnetization decreases as the temperature
particle as a whole is free to fluctuate in response to thermal increases. From the behavior of the ZFC and FC curves, it is
energy, while the individual atomic moments maintain their possible to conclude that these curves are almost overlapped
ordered state relative to each other. This leads to the low an above the blocking temperature, TB, indicating the presence of the
hysteretic behavior shown in Fig. 4. small-sized particles [34]. The measurements without field (ZFC)
Finally, the coercive field (Hc) behavior obtained as a function allow obtaining parameters such as blocking temperature, aniso-
of crystal size and Zn concentration at room temperature is tropy constant, critical volume, and critical diameter of the
presented in Fig. 5. The results related to the particle size and nanoparticles by adjusting the dependence of magnetization with
magnetic behavior of our Co(1  x)ZnxFe2O4 magnetic nanoparti- the temperature in the ZFC process. The expression used for
cles, agree well with the results previously reported for similar adjustment by assuming a spherical shape of the particles is given
Fe3O4 and Co–Ni magnetic nanoparticles [30,31]. With respect to by [35]:
the coercive field Hc values reported for other systems, in the case Z
m2 H Vc ðT,tÞ
of particles with similar or smaller particle sizes, it has been MðH,TÞ ¼ 0 f ðvÞv2 dv ð2Þ
2T 0
found Hc values greater than those obtained in this work. Taking
into account the values of crystallite size of our Co (1  x) ZnxFe2O4 where m0 is the magnetization of the nanoparticle, Vc critical
magnetic nanoparticles, probably a higher crystallinity in our volume or blocking and (V) is the volume distribution function.
 Author's personal copy

J. López et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 394–402 399

After the adjustment, the blocking temperature, TB, can be found. 0.0 0.2 0.4 0.6 0.8µm
From the theory of magnetism, we know that for nanostructured
materials the critical volume of super-paramagnetic materials is
directly proportional to temperature. In other words, if the
temperature increases, the critical size of the particles will be 0.8µm 0.8µm
greater, and the particles having a size less than or equal to the
critical can be considered in the super-paramagnetic regime.
Finally, from the critical volume, for a nanoparticle, given by the 0.6 0.6
expression:
25KB T
V¼ ð3Þ
Ka 0.4 0.4
where T is the blocking temperature, KB is Boltznmann’s constant,
and Ka is anisotropy constant it is possible to calculate the critical
diameter for the nanoparticles. 0.2 0.2
Fig. 6 presents the ZFC and FC curves and the difference
between ZFC and FC of Co0.79Zn0.21Fe2O4 magnetic nanoparticles
dispersed in the carrier liquid. Additionally, the irreversibility
temperature, which is the temperature where the ZFC magnetiza- 0.0 0.0
tion curve is separated from the FC curve and the derivative with 0.0 0.2 0.4 0.6 0.8µm
respect to the temperature of the difference between the FC and
ZFC vs. T curves are also presented in Fig. 6. This temperature 0.0 0.2 0.4 0.6 0.8µm
corresponds to the maximum temperature, which gives informa-
tion on the profile of the distribution of sizes and obeys the
lognormal distribution function. In our case, from the distribution
of sizes, the TB and VC were found as 45 K and (151717) nm3, 0.8µm 0.8µm
respectively. By using the critical volume, we obtained a value of
6.6 nm for the critical diameter for the nanoparticles, a value that
is within the expected results and is consistent with the crystal 0.6 0.6
size of the Co0.79Zn0.21Fe2O4 magnetic nanoparticles obtained
from XRD and TEM measurements [36].
0.4 0.4
3.5. SPM measurements

AFM measurements were performed on dried samples depos- 0.2 0.2

ited on mica substrate. They were repeated on different sites of
the deposited sample and prepared under the same conditions of
room temperature and ambient atmosphere. The analysis of
0.0 0.0
magnetic particles consisted of observing the surface of conglom-
erates of Co(1  x)ZnxFe2O4 nanoparticles, Fig. 7. The mean dia- 0.0 0.2 0.4 0.6 0.8µm
meter from the height, measured by AFM, is larger than the
crystal size of the nanoparticles measured by XRD. This can be Fig. 7. (a) 2D AFM topography image of conglomerates of Co56Zn0.44Fe2O4 nano-
explained because the analysis is statistical and some ‘particles’ particles, (b) 2D MFM image of magnetic domains of Co56Zn0.44Fe2O4 nanoparticle
conglomerates.
are actually conglomerates, which may result in particle con-
glomerates with relatively larger height. The existence of such
agglomerates requires improving the preparation of the samples
given that the attractive electric and magnetic forces are not 3.6. Transmission electron microscopy (TEM)
totally balanced by the steric repulsion conferred by the oleic acid
coating molecules. The agglomeration of Co(1  x)ZnxFe2O4 nano- TEM images of Co0.79Zn0.21Fe2O4 nanoparticles at two different
particles is evident in the topography image (Fig. 7a). Fig. 7b scales are shown in Fig. 9. In the HRTEM micrograph on a 10 nm
shows a 2D MFM image, where it is possible to see the magnetic scale (Fig. 9b) it may be observed that the nanoparticles prepared
domains of the Co(1  x)ZnxFe2O4 nanoparticle conglomerates. The by this method are single crystals. On the other hand, the inset in
samples and the tip were magnetized by an external field the figure shows the selected area diffraction pattern (SAED
oriented vertically to the mica substrate plane prior to the pattern) obtained from a single nanoparticle. The lattice fringes
measurement. The interpretation of magnetic domains shows of the image corresponds to a group of atomic planes within
that a dark zone represents a repulsive force of domains, while particles, demonstrating that the nanoparticles are structurally
a bright zone is an attractive force. uniform. In other words, these fringe patterns indicate a highly
Fig. 8 displays the particle-size histogram and the best-fit crystalline structure in the sample, supported by well-pro-
curves using the lognormal distribution function with a most- nounced diffraction rings [42].
probable particle diameter of conglomerates [37–40]. The lognor- Fig. 10 shows the inverse transform selected area (IFFT-SAED)
mal distribution function for the different concentrations of zinc of the image in Fig. 10b of a Co0.79Zn0.21Fe2O4 nanoparticle. The
show that the conglomerate size determined by AFM statistical inverse Fourier transform indicates that the planes are preferen-
analysis decreases with the increasing of at% Zn, (62.970.3) nm tially aligned along the same direction and, thus, we can observe
for x¼0.21, (59.0 70.2) for x¼ 0.56, and (16.670.3) for x ¼0.75; the periodicity of the crystal structure for this spinel ferrite.
similar behavior to that obtained for crystal size from X-ray Fig. 11 shows the size-distribution histogram of the
diffraction [41]. Co0.79Zn0.21Fe2O4 nanoparticles from TEM images, by using a
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400 J. López et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 394–402

Fig. 9. HRTEM images of Co0.79Zn0.21Fe2O4 nanoparticles at two different scales:

(a) 50 nm and (b) 10 nm. The inset shows the selected area diffraction pattern
(SAED) of the Co0.79Zn0.21Fe2O4 sample.

Fig. 8. Histogram constructed using the AFM data and the best fit of the lognormal
function (a) Co0.79Zn0.21Fe2O4, (b) Co0.56Zn0.44Fe2O4, and (c) Co0.25Zn0.75Fe2O
nanoparticles.

Gaussian fit of the particle diameter (D), from different parts of

the grid for an average number of particles close to 40. Symmetry
in the Gaussian fit of about 9.0 nm was obtained. This size of the Fig. 10. Inverse Fourier transform (IFFT) of the selected area in the image of
Co–Zn ferrite nanoparticles obtained by TEM is in good agreement Fig. 10b. The inset is the FFT of the selected TEM image of the sample.
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J. López et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 394–402 401

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