nanomaterials

Article
Synthesis of Ferrofluids Made of Iron Oxide
Nanoflowers: Interplay between Carrier Fluid and
Magnetic Properties
Federico Spizzo 1 ID , Paolo Sgarbossa 2 ID , Elisabetta Sieni 2 ID , Alessandra Semenzato 3 ID
,
Fabrizio Dughiero 2 , Michele Forzan 2 , Roberta Bertani 2 and Lucia Del Bianco 1, * ID
1 Dipartimento di Fisica e Scienze della Terra, Università di Ferrara, I- 44122 Ferrara, Italy;
federico.spizzo@unife.it
2 Dipartimento di Ingegneria Industriale, Università di Padova, I- 35131 Padova, Italy;
paolo.sgarbossa@unipd.it (P.S.); elisabetta.sieni@unipd.it (E.S.); fabrizio.dughiero@unipd.it (F.D.);
michele.forzan@unipd.it (M.F.); roberta.bertani@unipd.it (R.B.)
3 Dipartimento di Scienze del Farmaco, Università di Padova, I- 35131 Padova, Italy;
alessandra.semenzato@unipd.it
* Correspondence: lucia.delbianco@unife.it; Tel.: +39-0532-974225

Received: 2 October 2017; Accepted: 1 November 2017; Published: 5 November 2017

Abstract: Ferrofluids are nanomaterials consisting of magnetic nanoparticles that are dispersed in
a carrier fluid. Their physical properties, and hence their field of application are determined by
intertwined compositional, structural, and magnetic characteristics, including interparticle magnetic
interactions. Magnetic nanoparticles were prepared by thermal decomposition of iron(III) chloride
hexahydrate (FeCl3 ·6H2 O) in 2-pyrrolidone, and were then dispersed in two different fluids, water
and polyethylene glycol 400 (PEG). A number of experimental techniques (especially, transmission
electron microscopy, Mössbauer spectroscopy and superconducting quantum interference device
(SQUID) magnetometry) were employed to study both the as-prepared nanoparticles and the
ferrofluids. We show that, with the adopted synthesis parameters of temperature and FeCl3 relative
concentration, nanoparticles are obtained that mainly consist of maghemite and present a high
degree of structural disorder and strong spin canting, resulting in a low saturation magnetization
(~45 emu/g). A remarkable feature is that the nanoparticles, ultimately due to the presence of
2-pyrrolidone at their surface, are arranged in nanoflower-shape structures, which are substantially
stable in water and tend to disaggregate in PEG. The different arrangement of the nanoparticles
in the two fluids implies a different strength of dipolar magnetic interactions, as revealed by the
analysis of their magnetothermal behavior. The comparison between the magnetic heating capacities
of the two ferrofluids demonstrates the possibility of tailoring the performances of the produced
nanoparticles by exploiting the interplay with the carrier fluid.

Keywords: magnetic nanoparticles; ferrofluids; thermal decomposition; nanoflower structure;

spinel iron oxides; magnetic interactions; Mössbauer spectroscopy; magnetic heating; spin canting;
superparamagnetism

1. Intruduction
Magnetic nanofluids, also indicated as ferrofluids, consist of colloidal magnetic nanoparticles
(with size between 1 and 100 nm) that are dispersed in a carrier fluid. They are extremely versatile
nanomaterials, showing both liquid and magnetic properties, with a huge potential in a large number
of technological sectors, such as electric and thermal engineering, electronics, magneto-optics, catalysis,
waste water treatment [1–5]. Moreover, ferrofluids have been attracting an increasing interest for

Nanomaterials 2017, 7, 373; doi:10.3390/nano7110373 www.mdpi.com/journal/nanomaterials

Nanomaterials 2017, 7, 373 2 of 15

biomedical applications since the magnetic nanoparticles may act as contrast media in magnetic
resonance imaging, tags for magnetic biosensing, drug delivery carriers, magnetic hyperthermia
agents for cancer therapy or/and thermally activated drug release [6–11]. The properties of the
ferrofluids, and, hence, their field of application strictly depend on the features of the magnetic
nanoparticles, such as the chemical composition (metallic ferromagnets and their oxides), the size,
the shape and the crystallinity. In turn, these characteristics are strictly connected to the saturation
magnetization and the magnetic anisotropy. Moreover, the concentration and the colloidal stability of
the nanoparticles in the carrier fluid are crucial.
Strong research efforts have been carried out during the last decade to develop novel synthetic
routes that are aimed at controlling these different parameters [12–15]. Particular attention has
been directed to the synthesis of nanoparticles of spinel iron oxides (i.e., magnetite and maghemite),
which are very suitable materials for biomedical applications due to their high biocompatibility.
For this purpose, the alkaline co-precipitation of ferrous and ferric salts in aqueous media and the
thermal decomposition of organometallic compounds are among the most widely used methods [12].
Generally, the latter route includes the use of high boiling point organic solvents, which can also act as
surfactants. The surfactants stabilize the colloidal nanoparticles and impede the direct contact among
the nanoparticles and, hence, the magnetic exchange interaction. However, they cannot completely
hinder the onset of dipolar interparticle magnetic interactions, which, as it is now quite well established,
may markedly modify the magnetothermal behavior of an assembly of nanoparticles, as compared
to the case of non-interacting particles. In fact, isolated nanoparticles can show superparamagnetic
relaxation when their thermal energy is comparable to the anisotropy energy barrier for moment
reversal [16], a parameter proportional to the particle volume. Magnetic interactions lead to an increase
of the anisotropy energy barriers, which become interdependent, so that the particle moments do
not relax independently any longer [16,17]. Hence, dipolar interactions may represent an additional
degree of freedom in order to govern the properties of ferrofluids, even if, in turn, they depend on
the particle magnetization, the size of the nanoparticles and their interdistance. Hence, the synthesis
route, the compositional, structural, and magnetic properties of the nanoparticles, as well as their
local spatial arrangement and the degree of magnetic coupling are all strictly intertwined factors. In
order to modify just the strength of the magnetic dipolar interactions of an assembly of a given type of
nanoparticles, their concentration in the dispersing medium is usually varied [16,18].
In this context, we report about the production and the compositional, structural, and magnetic
characterization of iron oxide nanoparticles, subsequently used in the preparation of ferrofluids.
The synthesis was accomplished by thermal decomposition using hydrated ferric chloride as
iron precursor and strong polar 2-pyrrolidone [19], which acted both as surfactant and solvent.
The predicted advantage of this method is that 2-pyrrolidone allows the nanoparticles to be dispersed
in polar fluids without the need of any further functionalization [20,21]. In our case, the produced
nanoparticles were dispersed in two different carrier fluids, water and polyethylene glycol 400 (PEG),
which are commonly used to prepare isotonic solutions for in vitro biological experiments. We will
show that the produced nanoparticles are arranged in compact structures, resembling the shape of a
nanoflower, which are substantially stable in water, whereas in PEG they tend to disaggregate. Hence,
the interplay with the carrier fluid can be used as a tool to modulate the aggregation state of the
nanoparticles and, hence, the strength of the interparticle magnetic interactions, thus conferring to the
ferrofluids different properties, as shown with regard to the magnetic heating capacity.

2. Experiment

2.1. Synthesis of the Nanoparticles and of the Ferrofluids

Iron oxide nanoparticles were prepared by thermal decomposition of iron(III) chloride, according
to the method proposed by Li et al. [19]; FeCl3 ·6H2 O, 2-pyrrolidone and all of the solvents that were
used in the synthesis were purchased from Sigma-Aldrich and were used without further purification.
that were used in the synthesis were purchased from Sigma-Aldrich and were used without further
purification.
In detail, a solution of iron(III) chloride hexahydrate was prepared by dissolving 2.70 g of iron
Nanomaterials 2017, 7, 373 3 of 15
salt in 50 mL of 2-pyrrolidone (relative concentration 5.40 × 10−2 g/mL) in a round bottomed flask
mounted with a reflux condenser. The solution was purged with nitrogen in a Schlenk line and
In detail, a solution of iron(III) chloride hexahydrate was prepared by dissolving 2.70 g of iron
heated by mean of a heating mantle from 25 to 315 °C at 10 °C/min and was kept at 315 °C for 24 h
salt in 50 mL of 2-pyrrolidone (relative concentration 5.40 × 10−2 g/mL) in a round bottomed flask
under vigorous
mounted magnetic
with a reflux stirring in reflux
condenser. conditions.
The solution After with
was purged the solution
nitrogen inwas cooledline
a Schlenk down and to room
temperature,
heated 10 mL of
by mean of methanol werefrom
a heating mantle added25 toand
315 the
◦ C atproduced
◦
10 C/min and nanoparticles
was kept at 315precipitated
◦ C for in a
threefold volume of diethyl ether. The precipitate was separated by means of a permanent magnet
24 h under vigorous magnetic stirring in reflux conditions. After the solution was cooled down to
room temperature,
and purified by repeated10(four mL oftimes)
methanol were added
dispersion inand the produced
methanol nanoparticles
(10 mL) precipitatedwith
and precipitation in a acetone
threefold volume of diethyl ether. The precipitate was separated by means of a permanent magnet
(200 mL). The nanoparticles were recovered by centrifugation (8000 rpm for 15 min) and dried under
and purified by repeated (four times) dispersion in methanol (10 mL) and precipitation with acetone
vacuum(200at 60 °CThe
mL). fornanoparticles
8 h, resulting wereinrecovered
a dark powder. They were
by centrifugation (8000labeled asmin)
rpm for 15 sample S. under
and dried
Thevacuum
employed at 60 synthesis
◦ starts from
C for 8 h, resulting iron(III)
in a dark powder.ions
Theywhich
were can be as
labeled converted
sample S. to FeOOH by reaction
with the hydration watersynthesis
The employed moleculesstartscatalyzed
from iron(III)byions
thewhich
azetidine
can be generated
converted to in situ as
FeOOH schematized in
by reaction
with the hydration water molecules catalyzed by the azetidine generated
Figure 1 (reactions a and b) [19]. The ferric oxide hydroxide can subsequently undergo dehydration in situ as schematized in
Figure 1 (reactions a and b) [19]. The ferric oxide hydroxide can subsequently undergo dehydration to
to form γ-Fe2O3 (maghemite) and/or dehydration and partial reduction by carbon monoxide to form
form γ-Fe2 O3 (maghemite) and/or dehydration and partial reduction by carbon monoxide to form
Fe3O4 (magnetite) (Figure
Fe3 O4 (magnetite) 1, reactions
(Figure 1, reactions c cand
and d).
d). The relative
The relative amount
amount oftwo
of the thespecies
two species
probablyprobably
dependsdepends
on the on reaction temperature.
the reaction temperature.

Figure 1.Figure
Chemical reactions
1. Chemical involved
reactions in in
involved thethesynthesis
synthesis of the iron
of the ironoxide
oxide nanoparticles.
nanoparticles. See text for
See text
for explanation.
explanation.

The presence
The presence of 2-pyrrolidone in
of 2-pyrrolidone insample
sample S was
S assessed by performing
was assessed a Fourier transform
by performing infrared
a Fourier transform
spectroscopy (FT-IR) analysis, as shown in Figure 2. The spectrum shows several absorptions in the
infrared spectroscopy (FT-IR) analysis, as shown in Figure 2. The spectrum shows several
investigated 4000–250 cm−1 range, corresponding to the vibrational modes of 2-pyrrolidone [20,22].
absorptions in the investigated
In particular, the bands related 4000–250
to the cm
−1 range, corresponding to the vibrational modes of
N–H bond stretching (3164 cm−1 ), to the asymmetric
2-pyrrolidone [20,22]. CH
and symmetric In 2particular, the bands
stretching (2968 and 2888related
cm−1 ,torespectively),
the N–H bond to thestretching
C=O bond(3164 cm−1), to the
stretching
asymmetric
(1676–1640 cm−1 ), to CH CH
and symmetric 2 stretching
deformation (2968
(1463 and 1377 cm−2888
and 1 ), to CCN
cm−1stretching
, respectively),
(1302 cmto−1 ), and to
the C=O bond
the N–H bond bending (722 cm − 1 ) are all shifted to lower frequencies as compared to those of free
stretching (1676–1640 cm−1), to CH deformation (1463 and 1377 cm−1), to CCN stretching (1302 cm−1),
2-pyrrolidone [22]. The effect is ascribable
and to the N–H bond bending (722 cm−1) are to allthe coordination to iron centers at the surface of the
shifted to lower frequencies as compared to those of
nanoparticles, as observed in the case of poly[N-vinyl-2-pyrrolidone] coated nanoparticles [23] and
free 2-pyrrolidone
confirms the [22]. Theofeffect
presence is ascribable
2-pyrrolidone to the
as capping coordination
agent. The absorption to iron centers
visible at ~580atcm
the
−1 surface
is not of the
nanoparticles, as observed
characteristic in the case
of 2-pyrollidone, but it of poly[N-vinyl-2-pyrrolidone]
is due to the iron oxide Fe–O bond (Figure coated
2). nanoparticles [23] and
confirms theMoreover,
presencea thermogravimetric
of 2-pyrrolidoneanalysis as capping
(TGA)agent. The absorption
was conducted on sample visible at ~580
S, in nitrogen purgecm−1 is not
gas from ◦ ◦
characteristic of 50 to 700 C (heating
2-pyrollidone, butrate
it is=due
10 C/min). The oxide
to the iron mass loss, ascribed
Fe–O bondto(Figure
the decomposition
2). of
2-pyrrolidone and the subsequent desorption of the decomposition residues, was of ~38% (Figure 3).
 Nanomaterials 2017, 7, 373 4 of 15
Nanomaterials 2017, 7, 373 4 of 15

Figure 2. Fourier transform infrared spectroscopy (FT-IR) spectrum of the as-prepared nanoparticles
(sample S). The tagged bands are discussed in the text.

Moreover, a thermogravimetric analysis (TGA) was conducted on sample S, in nitrogen purge

gas from 50 to 700 °C (heating rate = 10 °C/min). The mass loss, ascribed to the decomposition of
Figure 2. 2.Fourier
Figure Fouriertransform
transforminfrared
infraredspectroscopy (FT-IR)spectrum
spectroscopy (FT-IR) spectrumofofthe
theas-prepared
as-prepared nanoparticles
nanoparticles
2-pyrrolidone(sample
and the subsequent desorption of the decomposition residues, was of ~38% (Figure 3).
S). The tagged bands are discussed in the text.
(sample S). The tagged bands are discussed in the text.

Moreover, a thermogravimetric
100 analysis (TGA) was conducted on sample S, in nitrogen purge
gas from 50 to 700 °C (heating rate = 10 °C/min). The mass loss, ascribed to the decomposition of
2-pyrrolidone and the subsequent desorption of the decomposition residues, was of ~38% (Figure 3).
80
Mass (%)

60100

80
40
Mass (%)

60
20 sample S
40
0
020 100 200 300 400 500 600S 700
sample
T (oC)
0
0 (T)
Figure 3. Mass loss vs. temperature 100for200
the 300 400 500
as-prepared 600
iron 700nanoparticles (sample S).
oxide
Figure 3. Mass loss vs. temperature (T) for the as-prepared T ( C) iron oxide nanoparticles (sample
o
S).

Then, the as-prepared

Then, nanoparticles
the as-prepared nanoparticleswere dispersed
were dispersed in water
in water (sample
(sample SW) and SW) and(sample
in PEG in PEGSP)(sample
Figure 3. Mass loss vs. temperature (T) for the as-prepared iron oxide nanoparticles (sample S).
SP) with a 10 mg/mL concentration.
with a 10 mg/mL concentration.
Then, the as-prepared nanoparticles were dispersed in water (sample SW) and in PEG (sample
2.2. Characterization Techniques
2.2. Characterization Techniques
SP) with a 10 mg/mL concentration.
The infrared spectra were taken on a Perkin-Elmer Spectrum 100 FT-IR spectrophotometer; solid
The infrared
2.2. spectra
Characterization
samples were were
Techniques
dispersed taken
in Nujol on whereas
mull, a Perkin-Elmer Spectrum
fluid samples 100 FT-IR
were analyzed spectrophotometer;
as prepared; all of the
solid samples Thewere
samples weredispersed
spectra in
cast between
infrared Nujol
KBr
were mull,
windows
taken on awhereas fluid samples
for the measurement.
Perkin-Elmer Spectrum were analyzed
100 FT-IR as prepared; all of
spectrophotometer;
The morphology of the samples was investigated by transmission electron microscopy (TEM)
the samples were cast
solid samples were between
dispersed KBr windows
in Nujol for the measurement.
mull, whereas fluid samples were analyzed as prepared; all of
analysis using a TECNAI FEI G2 microscope. Usually, in order to perform TEM analysis on dried
The morphology
thenanoparticles,
samples werethey of
castthe samples
between
must KBr was investigated
windows
be dispersed in for themedium
a liquid by transmission
measurement.
and then a drop electron microscopy
of the suspension is (TEM)
analysis usingThe a TECNAI
morphology
deposited FEI G2
of
on a TEM grid. the microscope.
samples
In our was Usually, in
investigated
case, TEM observations by order to out
transmission
were carried perform
directlyTEM
electron on theanalysis
microscopy on dried
(TEM)
ferrofluids,
analysis using a TECNAI FEI G2 microscope. Usually, in order to
nanoparticles, they must be dispersed in a liquid medium and then a drop of the suspension is
namely on samples SW and SP after being diluted with deionized perform
water. TEM analysis on dried
nanoparticles, they spectroscopy
must be dispersed in a carried
liquid out
medium and then ananoparticles
drop of the suspension in is
deposited onAaMössbauer
TEM grid. In our case, TEMwas
analysis observations onwere carried out directly (sample
the as-prepared on the S)ferrofluids,
deposited
a standardontransmission
a TEM grid.geometry
In our case, TEM
using 57
a Co observations
source in a were carried
Rh matrix. out
The directly onwas
spectrometer the equipped
ferrofluids,
namelynamely
on samples
on SW and
samples SW SP after
and SP being
after beingdiluted
diluted with
with deionizedwater.
deionized water.
with a superconducting magnet. A high-purity iron foil was used for calibration and isomer shifts
A Mössbauer
A Mössbauer
were spectroscopy
calculated respect analysis
spectroscopy
with analysis
to this waswascarried
reference carried out
sample. out ononthetheas-prepared
as-prepared nanoparticles
nanoparticles (sample
(sample
S) in a S)
standard transmission
in a standard transmissiongeometry
geometry using
usingaa 57Co
57
Co source
source inina aRh Rhmatrix.
matrix.TheThe spectrometer
spectrometer was was
equipped with awith
equipped superconducting
a superconducting magnet.
magnet.AAhigh-purity
high-purity iron ironfoilfoilwas
was used
used for for calibration
calibration and and
isomer shifts were calculated with respect to this reference sample.
isomer shifts were calculated with respect to this reference sample.
The magnetic
The magnetic properties
properties of the
of the sampleswere
samples werestudied
studied with
withaaQuantum
Quantum Design superconducting
Design superconducting
quantum interference device (SQUID) magnetometer, operating in the 5–300 K temperature range
quantum interference device (SQUID) magnetometer, operating in the 5–300 K temperature range
Nanomaterials 2017, 7, 373 5 of 15

The magnetic properties of the samples were studied with a Quantum Design superconducting
quantum interference device (SQUID) magnetometer, operating in the 5–300 K temperature range
(maximum applied field 50 kOe). The magnetic moment of the samples was measured as a function of
field Nanomaterials
and of temperature.
2017, 7, 373 5 of 15

Viscosity measurements were performed at room temperature with an Anton Paar Dynamic shear
(maximum applied field 50 kOe). The magnetic moment of the samples was measured as a function
rheometer, model MCR101.
of field and of temperature.
The Viscosity
heating measurements
capacity of SW and SP in a time-varying magnetic field was tested using a
were performed at room temperature with an Anton Paar Dynamic
custom-made apparatus
shear rheometer, modelequipped
MCR101. with a 7-turns inductor supplied by an EASYHEAT 10.0 kW
(Ambrell)The generator,
heating capacity of SWelsewhere
as described and SP in[24]; the temperature
a time-varying wasfield
magnetic measured by means
was tested using aof an
Optocom OPT-2 fiber optic thermometer.
custom-made apparatus equipped with a 7-turns inductor supplied by an EASYHEAT 10.0 kW
(Ambrell) generator, as described elsewhere [24]; the temperature was measured by means of an
3. Results andOPT-2
Optocom Discussion
fiber optic thermometer.

3.1. Morphology andDiscussion

3. Results and Composition
Figure 4a,b are TEM images of sample SW. The magnetic nanoparticles exhibit a rounded profile
3.1. Morphology and Composition
and are arranged in characteristic flower-shaped aggregates, which we indicate as nanoflowers (NFs).
Figure
Several TEM 4a,b are
images TEM images
of sample of sample
SW were SW. and
recorded The analyzed
magnetic nanoparticles
with the ImageJexhibit a rounded
software, so as to
profile and are arranged in characteristic flower-shaped aggregates, which we indicate as
compute the NFs size distribution that is presented in Figure 4c (about 300 NFs were considered).
nanoflowers (NFs). Several TEM images of sample SW were recorded and analyzed with the ImageJ
Thesesoftware,
data were then fitted to a lognormal distribution function, and the calculation yielded a mean
so as to compute the NFs size distribution that is presented in Figure 4c (about 300 NFs
valuewere
d ~25considered).
nm and a standard
These data deviation
were thenof ~5 nm.to a lognormal distribution function, and the
fitted
TEM images of sample SP are shown in Figure
calculation yielded a mean value d ~25 nm and a standard 4d,e.deviation
The arrangement
of ~5 nm. of the nanoparticles is
strongly different
TEM images of sample SP are shown in Figure 4d,e. The arrangementofofnanoparticles
when compared to that observed in SW. Isolated groups are visible,
the nanoparticles is
whichstrongly different
very likely when compared
correspond to that observed
to the starting in SW. Isolated
NFs. However, groups of nanoparticles
the nanoparticles now appear arequite
visible,
separated sowhich veryconfiguration
that their likely correspond
can to the starting
hardly be still NFs. However,
described as a the
NF.nanoparticles now appear
One can distinguish different
quite separated so that their configuration can hardly be still described as a NF.
black elements with a size ranging between 5 and 10 nm, presumably corresponding to individual One can distinguish
different black elements with a size ranging between 5 and 10 nm, presumably corresponding to
nanoparticles or small clusters of 2–3 nanoparticles.
individual nanoparticles or small clusters of 2–3 nanoparticles.

Figure
Figure 4. (a,b)
4. (a,b) Transmissionelectron
Transmission electron microscopy
microscopy (TEM)
(TEM)images
images of of
thethe
as-prepared magnetic
as-prepared magnetic
nanoparticles
nanoparticles dispersedininwater
dispersed water (sample
(sampleSW);
SW);in (b) the white
in (b) circle highlights
the white one nanoflower
circle highlights (NF)
one nanoflower
(NF) structure
structureand
andinin(c)
(c)the
thesize
sizedistribution
distributionof of
thethe
NFsNFsis shown (the(the
is shown straight line line
straight represents a besta fit
represents best fit
performed with a lognormal distribution function; d is the mean value of the distribution). (d,e) TEM
performed with a lognormal distribution function; d is the mean value of the distribution). (d,e) TEM
images of the magnetic nanoparticles dispersed in polyethylene glycol 400 (PEG) (sample SP).
images of the magnetic nanoparticles dispersed in polyethylene glycol 400 (PEG) (sample SP).
Nanomaterials 2017, 7, 373 6 of 15

We propose that the NFs form during the synthesis process since the nanoparticles are held
together by strong hydrogen bonding interaction between the 2-pyrrolidone molecules bound
Nanomaterials 2017, 7, 373
to their
6 of 15
surface. In fact, it is known that pure primary or secondary amides, such as 2-pyrrolidone, tend
to self-associate
We propose formingthat thedimers and higher
NFs form during oligomers
the synthesis [25]. The since
process abilitytheofnanoparticles
the solvent are oligomers
held to
together
coordinate moreby strong
nucleationhydrogen centersbonding
in close interaction
proximity, between
duringthe the2-pyrrolidone
development molecules bound tophase,
of the magnetic
couldtheir surface.
favor In fact, it isof
the formation known
the NFs.that pure primary or secondary amides, such as 2-pyrrolidone, tend
to
The fact that the NF structure and
self-associate forming dimers higher
is less stableoligomers
in PEG [25].thanThe abilitycan
in water of the
be solvent
ascribed oligomers to
to the presence
coordinate more nucleation centers in close proximity, during the development of the magnetic
of the cyclic amide ligands as binders. In fact, 2-pyrrolidone is a polar molecule that coats the
phase, could favor the formation of the NFs.
external surface of the nanoparticles—as suggested by the FT-IR analysis (Figure 2)—thus favoring
The fact that the NF structure is less stable in PEG than in water can be ascribed to the presence
theirofdispersion
the cyclic in amidepolar fluids.
ligands as Water
binders.and PEG 2-pyrrolidone
In fact, are polar fluids, but the
is a polar steric hindrance
molecule that coats the of their
molecules
external issurface
markedly of thedifferent because water
nanoparticles—as suggestedis a bysmall molecule,
the FT-IR whilst
analysis PEG
(Figure is a linear
2)—thus polymer,
favoring
H–(O–CH –CH
their dispersion
2 2 )n –OH
in (in
polar this case
fluids. n
Water ~ 9),
and which
PEG is
are expected
polar to
fluids, fold
but and
the reach
steric a size
hindrance in the
of 2–3 nm
their
range [26]. Weispropose
molecules markedly that, in sample
different because SP,water
the large PEGmolecule,
is a small molecules permeate
whilst PEG isthe NFs,polymer,
a linear thus causing
theirH–(O–CH
expansion. 2–CH 2)n–OH
On the (in this caseinn sample
contrary, ~ 9), which SW,is the
expected
smalltowaterfold and reach a size
molecules canininteract
the 2–3 with
nm the
range [26]. molecules
2-pyrrolidone We proposeon that,
theindifferent
sample SP, the large PEG
nanoparticles molecules
without permeatetheir
disrupting the NFs, thus causing
aggregated form.
their expansion.
To confirm On theofcontrary,
the effect PEG as in sampleand
solvent SW,dismiss
the smallits water
possible molecules can interact
involvement with theon the
as a ligand
2-pyrrolidone molecules on the different nanoparticles without disrupting their aggregated form.
surface of the nanoparticles, we performed a FT-IR analysis on sample SP and, for comparison, on pure
To confirm the effect of PEG as solvent and dismiss its possible involvement as a ligand on the
2-pyrrolidone in PEG (Figure 5). As previously stated (Section 2.1), the shift in the C=O bond stretching
surface of the nanoparticles, we performed a FT-IR analysis on sample SP and, for comparison, on
can give
pure information
2-pyrrolidoneon the coordination
in PEG (Figure 5). As of 2-pyrrolidone
previously to the nanoparticles.
stated (Section 2.1), the shift in The
the C=Ospectra
bondreveal
that in sample SP no free 2-pyrrolidone is present (the C=O stretching is shifted to 1641 cm −1 , and the
stretching can give information on the coordination of 2-pyrrolidone to the nanoparticles. The
bandspectra
at 1682revealcm−1that of free ligand
in sample SPisnonot observed),
free 2-pyrrolidone indicating
is presentthat noC=O
(the substitution
stretchingof is the ligands
shifted to on
the surface
1641 cmof, the
−1 and nanoparticles
the band at 1682by cmPEG has ligand
−1 of free occurred is notupon the dispersion
observed), indicatingin thenofluid.
that This confirms
substitution of
the ligands on
the hypothesis thatthe2-pyrrolidone
surface of the nanoparticles
is strongly by PEG has
bound occurred
to the surface uponof the
thedispersion
nanoparticles,in the fluid.
even after
This confirms
dispersion in the the hypothesis
liquid medium, that and
2-pyrrolidone is strongly bound
that the expansion of thetoNFs the surface
can beofmainly
the nanoparticles,
ascribed to the
even after dispersion in the liquid
disruption of hydrogen bonds between the nanoparticles. medium, and that the expansion of the NFs can be mainly
ascribed to the disruption of hydrogen bonds between the nanoparticles.
Hence, the particular aggregation state of the nanoparticles as well as the possibility of
Hence, the particular aggregation state of the nanoparticles as well as the possibility of
disaggregating the NFs, through the interaction with the carrier fluid, are inherent to the employed
disaggregating the NFs, through the interaction with the carrier fluid, are inherent to the employed
synthesis method.
synthesis For instance,
method. the maghemite
For instance, flower-like
the maghemite nanoparticles,
flower-like producedproduced
nanoparticles, by coprecipitation
by
in form of single crystals
coprecipitation in formby ofHugounenq
single crystals etbyal. Hugounenq
[27], certainly are[27],
et al. not certainly
expectedare to not
break up into
expected tosmall
components
break up whatever is the fluid in
into small components which is
whatever they
the are
fluiddispersed.
in which they are dispersed.

Figure 5. FT-IR spectra of sample SP (bottom) and pure 2-pyrrolidone in PEG (top). The tagged
Figure 5. FT-IR spectra of sample SP (bottom) and pure 2-pyrrolidone in PEG (top). The tagged bands
bands are discussed in the text.
are discussed in the text.
In order to gain further structural and compositional information, the as-prepared
nanoparticles (sample
In order to gain S) structural
further were investigated by Mössbauer
and compositional spectroscopy.
information, To reduce thermally
the as-prepared nanoparticles
(sample S) were investigated by Mössbauer spectroscopy. To reduce thermally inducedout
induced magnetic relaxation effects due to the small nanoparticle size, the analysis was carried at
magnetic
Nanomaterials 2017, 7, 373 7 of 15

Nanomaterials 2017, 7, 373 7 of 15

relaxation effects due to the small nanoparticle size, the analysis was carried out at T = 4.2 K. Spectra
were
T = 4.2collected both
K. Spectra in zero
were field and
collected bothinina zero
staticfield
magnetic
and ininduction field Bappl
a static magnetic = 8 T applied
induction field Balong the
appl = 8 T
propagation
applied alongdirection of the γ-rays.
the propagation Theyofare
direction theshown
γ-rays.inThey
Figure
are6.shown in Figure 6.

Figure 6.
Figure Mössbauerspectra
6. Mössbauer spectra(full
(fullsymbols) recordedatatTT= =4.2
symbols)recorded 4.2KK
onon sample
sample S in
S in (a)(a) Bappl
Bappl = 0 =T 0and
T and
(b)
(b) B appl = 8 T. The black line is the fitting curve; blue and red lines are the A and B sextets, respectively.
Bappl = 8T. The black line is the fitting curve; blue and red lines are the A and B sextets, respectively.

It is worth
worth recalling
recalling that
that stoichiometric
stoichiometric magnetite
magnetite (Fe (Fe33O
O44) and
and maghemite
maghemite (γ-Fe (γ-Fe22O33)) are
ferrimagnetic
ferrimagnetic materials
materials with
with spinel
spinel structure,
structure, which
which implies
implies that
that the
the iron ions occupy two different
crystallographic positions,usually
crystallographic positions, usually identified
identified as tetrahedral
as tetrahedral (A) and (A) and octahedral
octahedral (B) interaction
(B) sites. The sites. The
interaction
between A andbetween A isand
B sites B sites is antiferromagnetic
antiferromagnetic in nature. magnetite
in nature. In particular, In particular,is anmagnetite is an
inverse spinel,
inverse
being thespinel, being
divalent Fe2+
ionsthe divalent
placedions
in theFeB2+ sites
placed
andinthethetrivalent
B sites ions
and theFe3+trivalent ions Fe3+ equally
equally distributed in the
distributed in One
the A and B sites. One magnetite cell [Fe3+ ] [Fe
contains 3+ Feunits
2+ ] O
A eight B [Fe
4 . A]Anet
[Femagnetic
A and B sites. magnetite cell contains eight units 3+ 3+ Fe2+]B Omoment
4. A net

magnetic
arises frommoment 2+
the Fe arises fromthe
ions since thecontributions
Fe ions since
2+ fromthe 3+
thecontributions
Fe ions annihilatefrom the Fe ions annihilate
3+
reciprocally.
In maghemite, only Fe3+ ions are present and ferrimagnetism arises from an unequal distribution
reciprocally.
In ions
of these maghemite,
in A andonly FeThe
B sites. 3+ ions are present
maghemite and ferrimagnetism
cell contains arises from
eight units, as described anformula:
by the unequal
distribution of these ions in A and B sites. The maghemite cell contains eight units, as described by
the formula: [Fe3+ ]A [Fe3+ 5/3 Υ1/3 ]B O4 (1)

where Υ is the cation vacancy. [Fe3+]A [Fe3+5/3 Υ1/3]B O4 (1)

where The zero-field
Υ is the cation Mössbauer
vacancy. spectrum exhibits six broad lines (Figure 6a). On the contrary, in the
in-field spectrum, one
The zero-field Mössbauercan distinguish
spectrumthe presence
exhibits six of two
broad different sextets 6a).
lines (Figure (Figure
On 6b). This reveals
the contrary, the
in the
ferrimagnetic character of the nanoparticles. In fact, as expected, an increase
in-field spectrum, one can distinguish the presence of two different sextets (Figure 6b). This reveals of the hyperfine field of
A
thesites and a decrease
ferrimagnetic of thatofofthe
character B sites is observedIn
nanoparticles. under
fact, anas applied
expected, field,
an so that theoflines
increase 1 and 6 of
the hyperfine
the two sextets appear well resolved [28].
field of A sites and a decrease of that of B sites is observed under an applied field, so that the lines 1
and 6Hence,
of the both spectraappear
two sextets were least-squared
well resolvedfitted
[28].with two sextets of Lorentzian-shaped lines, which
are also
Hence, both spectra were least-squared the
displayed in Figure 6 together with resulting
fitted with two fitting curves.
sextets The sextets have a lines,
of Lorentzian-shaped large
linewidth. For the zero-field spectrum, the linewidth is 0.4 mm/s and
which are also displayed in Figure 6 together with the resulting fitting curves. The sextets have 0.92 mm/s for the A and a
B sextets,
large respectively
linewidth. For the(the linewidth
zero-field of thethe
spectrum, calibration
linewidthFeisfoil pattern
0.4 mm/s andwas 0.16
0.92 mm/smm/s).
for theAAsimilar
and B
broadening
sextets, of the spectral
respectively (the lines is observed
linewidth of theincalibration
the in-fieldFe spectrum.
foil patternThis effect is to mm/s).
was 0.16 be connected with
A similar
a high degree of structural disorder since it indicates that not all of the Fe
broadening of the spectral lines is observed in the in-field spectrum. This effect is to be connected ions located in both the A
and Basites
with highare surrounded
degree by andisorder
of structural identicalsince
atomic environment,
it indicates actually
that not all of[29–31].
the Fe ions located in both
The fitting parameters are reported in Table 1: isomer shift
the A and B sites are surrounded by an identical atomic environment, actually [29–31]. IS, hyperfine field Bhf (measured
without
The applied field) and effective
fitting parameters hyperfine
are reported in Table 1: Bisomer
field eff (measured
shift IS,in the presence
hyperfine BhfB(measured
field of appl ), ratio
relative resonant area of each sextet X A /X B (equal f
without applied field) and effective hyperfine field Beff (measured in the presence of Bappl),forratio
between the factors have been assumed the
between the relative resonant area of each sextet XA/XB (equal f factors have been assumed for the
resonant atoms that are located in the two different configurations). The quadrupolar shift is not
reported in Table 1 as it remains close to zero for both sites.
Nanomaterials 2017, 7, 373 8 of 15

resonant atoms that are located in the two different configurations). The quadrupolar shift is not
reported in Table 1 as it remains close to zero for both sites.

Table 1. Parameters deduced from Mössbauer spectra measured in Bappl = 0 and 8 T: isomer shift (IS),
hyperfine field in no applied field (Bhf ), hyperfine field in applied field (Beff ); canting angle θ for A and
B sites, ratio between the relative resonant area of the A and B sextets (XA /XB ).

Bappl (T) Site IS (mm/s) Bhf (T) Beff (T) θ (◦ ) X A /X B

Fe(A) 0.40 ± 0.02 50.7 ± 0.1 - -
0 0.57 ± 0.03
Fe(B) 0.57 ± 0.03 50.0 ± 0.1 - -
Fe(A) 0.41 ± 0.01 - 57.4 ± 0.1 36 ± 2
8 0.57 ± 0.02
Fe(B) 0.51 ± 0.03 - 44.7 ± 0.1 45 ± 2

As maghemite can result from the oxidation of magnetite, ferrimagnetic iron oxide nanoparticles
are often reported to consist of a mix of these two phases, which are very difficult to distinguish. In our
case too, the Mössbauer analysis is not able to assess unambiguously the chemical composition of
the nanoparticles. The values of Bhf for A and B sites are almost equal, as expected for γ-Fe2 O3 [28].
However, since the hyperfine field in nanostructured spinel oxides may be somewhat altered as
compared to the bulk phases [31–34], we cannot precisely discriminate between γ-Fe2 O3 and Fe3 O4 on
the basis of Bhf .
However, the quite low IS values, varying between 0.40 and 0.57 mm/s, support a prevalent
presence of Fe3+ ions [35–37]. Moreover, the XA /XB ratio is ~0.57, which is very close to the theoretical
value for γ-Fe2 O3 (0.6). Hence, based on the hyperfine parameters, we are inclined to think that the
nanoparticles consist mainly of maghemite even if the presence of magnetite, namely of Fe2+ ions,
cannot be totally excluded.
With reference to Figure 1, it appears that, with the adopted synthesis parameters of temperature
and FeCl3 relative concentration, the reaction d, which would have led to the formation of magnetite,
was partially inhibited. This demonstrates the versatility of the synthesis method designed by
Li et al. [19] and, on the other hand, the need of carefully characterizing the nanoparticles produced in
that way.
In the presence of an external magnetic field, the spins of the Fe ions are to some degree aligned
by the field. In bulk maghemite the magnetization of the A sublattice is antiparallel to that of the
B sublattice—i.e., the structure is collinear—and when a saturating magnetic field is applied parallel to
the γ-ray direction, the area of lines 2 and 5 of the sextets reduces to zero [28]. If this does not occur,
the evidence is obtained that the structure is not collinear, and, hence, even a very strong magnetic
field is unable to attain a complete spin alignment. Usually, iron oxide nanoparticles show such a spin
canting phenomenon, and a long-debated issue is whether it is a surface effect, involving only the
spins located in a surface layer [33,38], or a finite size effect, involving also core spins [39,40].
In this respect, it should be considered that different synthesis methods and even small
differences in the preparation procedures of the nanoparticles could result in a variety of sizes, shapes,
and crystallinity degrees [12]. For this reason, in our opinion, the matter depends on the characteristics
of the nanoparticles. In any case, spin canting is the hint of structural disorder at the surface and/or in
the core of the nanoparticles, since it generally arises because of modified atomic coordination and
altered superexchange bonds. The value of the effective field Beff results from the vectorial sum of Bhf
with Bappl , according to the relation:

Beff 2 = Bhf 2 + Bappl 2 + 2 Bhf Bappl cosδ (2)

where δ is the angle between the directions of Bhf and Bappl [28].
Applying the relation (2) to the Fe ions in the A and B sites, one can calculate δa and δb ; the
canting angles that A and B spins form with the applied field are θa = δa and θb = (180◦ − δb ) (Table 1).
Nanomaterials 2017, 7, 373 9 of 15

3.2. Magnetic Properties and Heating Capacity

Magnetic hysteresis loops measured on sample S at T = 5 and 300 K are shown in Figure 7.
In particular, the specific magnetization (M) is reported, obtained by dividing the magnetic moment,
Nanomaterials
as measured by2017, 7, 373 for the whole sample mass, which also includes the mass of 2-pyrrolidone.
SQUID, 9 of 15

The saturation magnetization, extrapolated from the loop at T = 5 K for 1/H tending to zero, is
emu/g. To obtain MS of the iron oxide phase only, we must subtract the mass of 2-pyrrolidone,
MS ~estimated
28 emu/g. byToTGAobtain MS 3),
(Figure of from
the iron
the oxide phase mass.
total sample only, we must
Hence MSsubtract thesubstantially
~ 45 emu/g, mass of 2-pyrrolidone,
lower
estimated
than bytheTGA (Figuremagnetization
saturation 3), from the total sample
value mass.for
expected bulk Mmaghemite
Hence S ~ 45 emu/g, (~83substantially
emu/g). Thislower
than the saturation magnetization
magnetization value expected
reduction is certainly connected forto
bulk
themaghemite (~83
spin canting emu/g).
effect, This magnetization
as revealed by the
reduction is certainly
Mössbauer analysis. connected to the spin canting effect, as revealed by the Mössbauer analysis.
Based Based
on the on the values
values of of
θa θand
a andθbθb(Table
(Table1), 1), we
we can
can calculate
calculatethe
theexpected
expected value of M
value ofS for
MSour for our
nanoparticles,
nanoparticles, assuming
assuming that
that they
they aretotally
are totallymade
made ofof maghemite.
maghemite.WithWithreference to formula
reference (1), it(1),
to formula is it is
known that the filled A site has moment μ a = 4.18 μB (μB = Bohr magneton) and the 5/3 filled B sites
known that the filled A site has moment µa = 4.18 µB (µB = Bohr magneton) and the 5/3 filled B sites
have moments μb = 4.41 μB [41]. Hence, the effective moment per unit (1) can be calculated through
have moments µb = 4.41 µB [41]. Hence, the effective moment per unit (1) can be calculated through
the relation:
the relation:
µeffμ=eff−=µ−μ a cosθa + 5/3 μb cosθb
a cosθa + 5/3 µb cosθb
(3) (3)
We obtain that μeff ~ 1.83 μB. In the case of collinear maghemite (i.e., θa = θb = 0°), the moment
We obtain that µeff ~ 1.83 µB . In the case of collinear maghemite (i.e., θa = θb = 0◦ ), the moment
per unit is 3.17 μB. Therefore, the spin canting effect produces a magnetization reduction of ~42%.
per unit is 3.17 µB . Therefore, the spin canting effect produces a magnetization reduction of ~42%.
Accordingly, the specific magnetization MS is expected to decrease from the nominal value of ~83
Accordingly,
down tothe ~48specific
emu/g,magnetization MS is expected
in excellent agreement with the to decrease fromvalue.
experimental the nominal
It is to value of ~83
be noted thatdown
to ~48Equation
emu/g,(3) in implies
excellent
that all the maghemite spins are canted. The good agreement between the (3)
agreement with the experimental value. It is to be noted that Equation
implies that all the maghemite
experimental and calculated spins
MS are canted.
values The good
indicates agreement
that indeed this between
must be thetheexperimental
case of our and
calculated MS values indicates that indeed this must be the case of our nanoparticles.
nanoparticles.
In sample
In sample S, the
S, the coercivity
coercivity HCHC~170
~ 170Oe
Oeatat TT = 55 KK and
andititdecreases
decreases down
downto ~6
to Oe
~6 atOeT at
= 300
T =K300 K
(Figure
(Figure 7).remanent
7). The The remanent magnetization
magnetization Mr shows
Mr also also shows a strong
a strong thermal
thermal dependence:
dependence: the ratio
the ratio between
between the remanence and the magnetization at H = 40 kOe is ~0.2 at
the remanence and the magnetization at H = 40 kOe is ~0.2 at 5 K and ~0.01 at 300 K. 5 K and ~0.01 at 300 K.

Figure 7. Magnetic hysteresis loops recorded on the as-prepared nanoparticles (sample S) at T = 5 K (black
Figure 7. Magnetic hysteresis loops recorded on the as-prepared nanoparticles (sample S) at T = 5 K
symbols)
(blackand T = 300
symbols) K T(red
and symbols).
= 300 The specific
K (red symbols). magnetization
The specific M, relative
magnetization to the
M, relative to whole sample
the whole
mass sample
(including 2-pyrrolidone), is reported on the y-axis. The inset is an enlarged view of the central
mass (including 2-pyrrolidone), is reported on the y-axis. The inset is an enlarged view of the
region of the loops.
central region of the loops.

Assamples
As for for samples
SWSW andand
SP,SP,
in in ordertotoobtain
order obtain M
MS,, the measured hysteresis loops were corrected
S the measured hysteresis loops were corrected
by subtracting the diamagnetic signals deriving from the carrier fluid and from the special holder for
by subtracting the diamagnetic signals deriving from the carrier fluid and from the special holder for
liquids. In both of the samples, the value of MS was consistent with that expected when considering
liquids. In both of the samples, the value of MS was consistent with that expected when considering
the saturation magnetization of the as-prepared nanoparticles and their concentration; at T = 250 K,
the saturation magnetization
no hysteresis was observed,ofnamely
the as-prepared nanoparticles
HC and Mr were and
equal to zero (totheir concentration;
impede any movement T=
at of the250 K,
no hysteresis wasduring
nanoparticles observed,
the SQUID HC andthe
namelyanalysis, Mrmeasurements
were equal to onzero
SW (to
andimpede
SP wereany movement
performed at of
temperature lower than 250 K, at which the carrier fluids were in the frozen solid state).
Nanomaterials 2017, 7, 373 10 of 15

the nanoparticles
Nanomaterials during the SQUID analysis, the measurements on SW and SP were performed
2017, 7, 373 10 ofat
15
temperature lower than 250 K, at which the carrier fluids were in the frozen solid state).
The magnetothermal
The magnetothermal behavior behavior of of samples
samples S, S, SW
SW andand SPSP waswas investigated
investigated by by performing
performing
magnetizationmeasurement
magnetization measurementas asaafunction
functionof ofincreasing
increasingtemperature
temperature(heating
(heatingrate rate22K/min)
K/min) in in aa static
static
magneticfield
magnetic fieldHH appl==10
appl
10 Oe,
Oe, after
after cooling
cooling the the
samplesample
from from
room room temperature
temperature down down
to T = 5toK T =
without5 K
without applied field (zero-field-cooling, ZFC) and in the presence of H
applied field (zero-field-cooling, ZFC) and in the presence of Happl (field-cooling, FC). The results are appl (field-cooling, FC). The
results in
shown areFigure
shown in Figure 8a,b.
8a,b.
Magnetic irreversibility
Magnetic irreversibility (difference(difference betweenbetween M MFC and M
FC and MZFC
ZFC)) is observed in
is observed in the
the as-prepared
as-prepared
nanoparticles in all the spanned temperature range. This indicates that
nanoparticles in all the spanned temperature range. This indicates that thermally induced magnetic thermally induced magnetic
relaxation processes
relaxation processes occur,
occur, butbut that
that the
the full
full superparamagnetic
superparamagneticstate stateofofthe
thenanoparticles
nanoparticlesassemblyassembly is
is not achieved up to T = 300 K. This behavior is consistent with the strong reduction of HC and Mrr,,
not achieved up to T = 300 K. This behavior is consistent with the strong reduction of H C and M
passing from
passing fromTT == 55 K K toto TT =
= 300 K, where
300 K, where smallsmall butbut non-zero
non-zero values
values are
are measured
measured (Figure(Figure 7). 7). AA quite
quite
similar magnetic
similar magnetic irreversibility
irreversibility effect
effect isis found
found in in SW,
SW, whereas
whereas in in SP
SP the
the ZFCZFC and and FC
FC branches
branches are are
superposed for T
superposed for T > 200 K.> 200 K.
For an
For an assembly
assembly of of non-interacting
non-interacting magneticmagnetic nanoparticles,
nanoparticles, the the temperature
temperature derivative
derivative of of the
the
difference (M − M ) is a figure of the distribution of anisotropy
difference (MFC − MZFC ) is a figure of the distribution of anisotropy energy barriers for magnetic
FC ZFC energy barriers for magnetic
moment reversal,
moment reversal, which
which substantially
substantially reflects
reflectsthe thesize
size distribution
distribution [16].
[16]. In
In fact,
fact, the
the anisotropy
anisotropy energy energy
barrier associated
barrier associated to to one
one nanoparticle
nanoparticle is is given
given by by KV,
KV, where
where K K is
is the
the magnetic
magnetic anisotropy
anisotropy coefficient
coefficient
and V is the volume. In our case, it is to be expected that
and V is the volume. In our case, it is to be expected that the magnetothermal behavior ofthe magnetothermal behavior of the
the
nanoparticles is affected by magnetic interactions, mainly dipolar in type
nanoparticles is affected by magnetic interactions, mainly dipolar in type because of the presence of because of the presence of
the surfactant
the surfactant that
thatprevents
preventsaadirect directexchange
exchangecoupling.
coupling.InInthis thiscase,
case,the
thederivative
derivativeofof (M(M FC − MZFC)
FC − MZFC )
provides qualitative though valuable information on the distribution
provides qualitative though valuable information on the distribution of effective anisotropy energy of effective anisotropy energy
barriers [42,43],
barriers [42,43], which
which can canbe be associated
associatedto toaadistribution
distributionof ofeffective
effectivemagnetic
magneticsizes. sizes.
For our samples, the curves of [−d(MFC −MZFC )/dT] are shown in Figure 8c (normalized
For our samples, the curves of [−d(M FC −M ZFC )/dT] are shown in Figure 8c (normalized to to their
their
area). The distribution of the as-prepared nanoparticles (sample S)
area). The distribution of the as-prepared nanoparticles (sample S) extends over the whole investigated extends over the whole
investigated range
temperature temperature rangeaand
and features features
narrow peakaat narrow
T ~ 10 peak
K andataTsecond
~ 10 Kone andata Tsecond
~ 220 K. one at T ~ 220
K.

Figure 8.8.(a,b)
Figure Magnetization
(a,b) Magnetizationmeasured in ZFC
measured in mode
ZFC mode(lower(lower
branches) and FC mode
branches) and FC(upper
modebranches)
(upper
for increasing
branches) temperature
for increasing (T) in Happl(T)
temperature = 10
in Oe on=samples
Happl 10 Oe onS,samples
SW and S,
SP.SW
(c) and
Temperature derivative
SP. (c) Temperature
−d(MFC −M[−d(M
[derivative ZFC )/dT] of the difference between field-cooled and zero-field-cooled magnetizations for
FC−MZFC)/dT] of the difference between field-cooled and zero-field-cooled
samples
magnetizations for samplescurves
S, SW, and SP (the S, SW,are normalized
and to their
SP (the curves are area).
normalized to their area).

Passing to the distributions of SW and SP, the peak at ~10 K is still well visible, whereas a very
different profile is observed at higher temperature. In fact, regarding SW, a very broad peak at T ~
100 K is visible; as for SP, just a shoulder, followed by a broad tail, appears on the right side of the
low-temperature peak.
Nanomaterials 2017, 7, 373 11 of 15

Passing to the distributions of SW and SP, the peak at ~10 K is still well visible, whereas a
very different
Nanomaterials profile
2017, 7, 373 is observed at higher temperature. In fact, regarding SW, a very broad peak 11 ofat15
T ~ 100 K is visible; as for SP, just a shoulder, followed by a broad tail, appears on the right side of the
If we describe
low-temperature the relaxation process using the Néel expression for the relaxation time, a rough
peak.
estimation of the magnetic
If we describe size that
the relaxation is associated
process using the to Néel
the two peaks in for
expression thethedistribution
relaxationoftime, sample S can
a rough
be done through
estimation the well-known
of the magnetic size that isrelation
associated KVto= the 25 two
kBTppeaks
, where K distribution
in the is the magnetic anisotropy
of sample S can
coefficient
be done through of the thenanoparticle,
well-known relation V is the KVvolume,
= 25 kB Tpk,Bwhereis theK Boltzmann
is the magnetic constant,
anisotropy and coefficient
Tp is the
temperature
of of the V
the nanoparticle, peak [16,43,44].
is the volume, In kBour case,
is the the anisotropy
Boltzmann constant, is unknown,
and Tp is the buttemperature
we can tentatively
of the
assign
peak to K the value
[16,43,44]. In ourof bulk
case, themaghemite
anisotropy(5 is ×unknown,
10 erg/cm
4
but). we
3 Hence, we obtain assign
can tentatively ~11 nmtoand K the~30value
nm for of
the first
bulk and second
maghemite 4 erg/cm
(5 × 10peak, 3 ). Hence,These
respectively. we obtain values~11arenm close
and ~30 to nmthe for
sizes
theof theand
first separated
second
nanoparticles
peak, respectively.and of the NFs,
These values as are
indicted
close by TEM
to the (Figure
sizes of the4).separated
Hence, wenanoparticles
infer that the and peakofatthe~10NFs,
K is
to indicted
as be associated
by TEM to(Figure
a fraction of almost
4). Hence, isolated
we infer that ortheweakly
peak at interacting
~10 K is to be nanoparticles,
associated to whereas
a fractionthe of
energyisolated
almost barriersoratweakly
higherinteracting
temperature, and in particular
nanoparticles, whereas the peak atbarriers
the energy ~220 K,atarisehigher because of the
temperature,
tendency
and of the nanoparticles
in particular the peak at ~220 to arrange
K, ariseinbecause
form ofofNFs. the tendency of the nanoparticles to arrange in
form Theof NFs.fact that, passing from sample S to SW and to SP, the distribution shrinks and shifts
towards low that,
The fact temperature values
passing from indicates
sample S to that
SW and the topresence
SP, the of the fluid reduces
distribution shrinks and the strength of the
shifts towards
interparticle
low temperature magnetic
values interactions,
indicates thatwhich resultsofinthe
the presence magnetic
fluid reducesaggregates with aofsmaller
the strength effective
the interparticle
magnetic interactions,
magnetic size. This effect is especially
which results inremarkable in sample SP,
magnetic aggregates within aagreement with themagnetic
smaller effective TEM analysissize.
that indicates a substantial disaggregation of the NF structures (Figure
This effect is especially remarkable in sample SP, in agreement with the TEM analysis that indicates 4d,e). As for sample SW, the
abroad peak centered
substantial at T~100ofKthe
disaggregation (Figure 8c) corresponds
NF structures (Figureto4d,e).
an average
As foreffective
sample SW, magnetic size of
the broad ~24
peak
nm, consistent with the dimension of the aggregates in Figure 4a,b. The
centered at T ~ 100 K (Figure 8c) corresponds to an average effective magnetic size of ~24 nm, consistent fact that the first peak at T~
10 K the
with is visible
dimensionin theofthree distributions
the aggregates in and
Figure that4a,b.
its intensity
The fact is larger
that the in SPpeak
first thanat inTthe~ 10other
K issamples
visible
supports
in the three thisdistributions
description. and that its intensity is larger in SP than in the other samples supports
A significant example, demonstrating to what extent the different arrangement of the
this description.
nanoparticles
A significant in the carrierdemonstrating
example, fluids may affect the physical
to what extent theproperties, is providedof
different arrangement bythe
thenanoparticles
study of the
magnetic
in the carrier heating
fluidscapacity,
may affect tested by exposing
the physical 2 mL is
properties, of provided
SW and SP bytotheanstudy
alternating
of the magnetic field heatingfor
300 s.
capacity, tested by exposing 2 mL of SW and SP to an alternating magnetic field for 300 s.
The field
The field amplitude
amplitude was was of of 170
170Oe Oeandandthe thefrequency
frequency177 177kHz.
kHz. These
These parameters
parameters were were chosen
chosen
because, for prospective in-vivo biomedical applications,
because, for prospective in-vivo biomedical applications, their product (~3 × 10 their product (~3 × 1077 Oe Hz) follows the
Hz) follows the
safety guideline
safety guideline to to avoid
avoid detrimental
detrimental effectseffects ofof eddy
eddy currents
currentson onhealthy
healthytissues
tissues[45].
[45]. The
The results
results are
are
shownin
shown inFigure
Figure9:9: thethetemperature
temperatureincreaseincrease∆T ~11 ◦°C
ΔTisis~11 for sample
C for sample SW SW and ~1.5 ◦°C
and ~1.5 C for sample SP. SP.

Figure9.9.Heating
Figure Heatingcurves for for
curves samples SW and
samples SW SP in an
and SP alternating magneticmagnetic
in an alternating field (170 field
Oe in(170
amplitude
Oe in
at frequency 177 kHz).
amplitude at frequency 177 kHz).

It is worth remarking that the same amount of nanoparticles was present in the two measured
samples and that the density and specific heat values for water and PEG are 1 g/cm3 and 1 cal/g·°C
for the first one and 1.1 g/cm3 and 0.51 cal/g·°C for the second one. As for the viscosity η —which is
also a crucial parameter for the heating efficiency [46]—measurements carried out on SW and SP at
room temperature revealed that it was similar in the two samples (η ~ 33 × 10−2 P) and close to that of
PEG (reference viscosity values at 20 °C of PEG and water are η ~ 32 × 10−2 P and η ~ 1 × 10−2 P,
Nanomaterials 2017, 7, 373 12 of 15

It is worth remarking that the same amount of nanoparticles was present in the two measured
samples and that the density and specific heat values for water and PEG are 1 g/cm3 and 1 cal/g·◦ C
for the first one and 1.1 g/cm3 and 0.51 cal/g·◦ C for the second one. As for the viscosity η —which
is also a crucial parameter for the heating efficiency [46]—measurements carried out on SW and
SP at room temperature revealed that it was similar in the two samples (η ~ 33 × 10−2 P) and
close to that of PEG (reference viscosity values at 20 ◦ C of PEG and water are η ~ 32 × 10−2 P and
η ~ 1 × 10−2 P, respectively), and that it did not depend on the applied shear rate (i.e., the ferrofluids
showed a Newtonian behavior). It is worth noticing that this result appears to be consistent with our
picture regarding the arrangment of the nanoparticles in the two fluids. In SP, the nanoparticles are
separated and do not offer resistance to the flow strong enough to substantially alter the viscosity
of PEG. On the contrary, the remarkable increase of η passing from water to SW indicates that the
large NFs offer a strong resistance to the flow, although the Newtonian character of the ferrofluid is
preserved. This interesting effect may be tentatively related to the presence of ordered and tightly
bound 2-pyrrolidone molecules on the NFs structure, which interact strongly with the aqueous medium
by hydrogen bonding, whereas, in PEG, the interaction is of lower extent and is partially disrupted.
The phenomenon will deserve further attention.
Coming back to the heating capacity, based on the above considerations, the result in Figure 9 is
to be entirely ascribed to the different arrangement of the nanoparticles in the two fluids.
It is well known that the amount of heat released by magnetic nanoparticles subjected to the
varying magnetic field is determined by different parameters, e.g., the saturation magnetization,
the magnetic anisotropy and the size [46,47]. A crucial role is also played by interparticle dipolar
interactions, although their effects on the heating efficiency are still a controversial issue. Dipolar
interactions are reported to have a detrimental effect because they diminish the effective field acting
on each particle [48]. Moreover, in the case of aggregates, large hydrodynamic sizes slow down the
Brownian relaxation, thus reducing the heating efficiency [49].
On the other hand, several studies predict [50,51] and experimentally demonstrate [52] that dipolar
interactions result in a substantial increase of the magneto-thermal stability of the nanoparticles and in
enhanced hysteresis losses, and, hence, in improved heating performances. The results in Figure 9
support this last scenario, namely indicate that, in the adopted experimental conditions, a larger
amount of heat is released by the nanoparticles in form of NFs.
The noteworthy conclusion is that the heating capacity of the produced iron oxide nanoparticles
can be tuned by properly selecting the fluid in which they are dispersed, which determines their
aggregation state.

4. Conclusions
Magnetic nanoparticles, with mean size between 5 and 10 nm, were produced by thermal
decomposition of iron(III) chloride hexahydrate (FeCl3 ·6H2 O) in 2-pyrrolidone and successively
dispersed in water and PEG. Experimental techniques for chemical, structural, and magnetic
characterization were synergically employed to study the nanoparticles in the as-prepared state
and in the form of ferrofluids.
With the reported synthesis, parameters of temperature and FeCl3 relative concentration,
nanoparticles made of spinel iron oxides are obtained, maghemite being the predominant phase,
as indicated by the Mössbauer spectroscopy analysis. The Mössbauer results for sample S are also
consistent with a strong structural disorder and a marked spin canting effect, resulting in a low
saturation magnetization, about half of the expected one for bulk γ-Fe2 O3 .
The peculiarity of the produced nanoparticles is that they form NF aggregates—having a mean
size of ~25 nm, as shown by TEM—which are substantially stable in water and tend to disaggregate
in PEG. The particular aggregation state of the nanoparticles and their behavior in the carrier
fluids can be ultimately connected to the presence of the strong polar 2-pyrrolidone at their surface,
as revealed by FT-IR and TGA measurements. Hence, although one may object that the structural
Nanomaterials 2017, 7, 373 13 of 15

and magnetic properties of the nanoparticles prepared by the adopted synthesis method are not
optimal for applications, it should be considered that it is just the synthesis method that determines
the NF configuration of the nanoparticles and the interesting way they re-arrange in the carrier fluids.
As indicated by the analysis of the magnetothermal behavior of samples SW and SP, the different
state of aggregation of the nanoparticles in water and PEG directly affects the strength of interparticle
magnetic interactions, which can be crucial in determining the final performances of the ferrofluids.
As a support to this last statement, we have compared the magnetic heating capacity of SW and SP,
definitely higher for the former.
Our study paves the way to the possibility of tailoring the properties of ferrofluids by controlling
the aggregation state, and hence the degree of magnetic coupling, of properly engineered nanoparticles
through their interplay with the carrier fluid.

Acknowledgments: Lucia Del Bianco acknowledges Ferrara University for financial support provided through
‘Fondo per l’Incentivazione alla Ricerca—FIR 2016’. The work was also partially supported by a grant “Progetto
di Ateneo” of the Padova University (CPDA114144). Federico Caicci and Francesco Boldrin (Electron Microscopy
Service, University of Padova) are acknowledged for their assistance for the TEM analysis. The Mössbauer
spectroscopy measurements were performed at the National High Magnetic Field Laboratory (NHMFL) which is
supported by the NSF (DMR-1157490) and the State of Florida. S.A.S. (NHMFL Jack E. Crow postdoctoral fellow)
is acknowledged for his assistance in collecting the spectra and for discussion. The Mössbauer instrument was
funded by the UCGP Project 5064 granted to A. Ozarowski at the NHMFL.
Author Contributions: Federico Spizzo and Lucia Del Bianco (affiliation 1) carried out the magnetic study by
SQUID, the TGA investigation and the analysis of the Mössbauer spectra. Paolo Sgarbossa and Roberta Bertani
(affiliation 2) prepared the samples and performed the FT-IR and TEM analyses. Elisabetta Sieni, Fabrizio Dughiero
and Michele Forzan (affiliation 2) carried out the magnetic heating analysis. Alessandra Semenzato (affiliation 3)
carried out the viscosity measurements. Lucia Del Bianco wrote the paper that was discussed and revised by
Federico Spizzo , Paolo Sgarbossa and Elisabetta Sieni.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Shulman, Z. Magnetorheological systems and their application. In Magnetic Fluids and Applications Handbook,
1st ed.; Berkovsky, B.M., Bashtovoi, V.G., Eds.; Begell House: New York, NY, USA, 1996; Volume 1,
pp. 188–229. ISBN 1-57600-062-2.
2. Pîslaru-Dănescu, L.; Morega, A.M.; Telipan, G.; Morega, M.; Dumitru, J.B.; Marinescu, V. Magnetic nanofluid
applications in electrical engineering. IEEE Trans. Magn. 2013, 49, 5489–5497. [CrossRef]
3. Bahiraei, M.; Hangi, M. Flow and heat transfer characteristics of magnetic nanofluids: A review. J. Magn.
Magn. Mater. 2015, 374, 125–138. [CrossRef]
4. Shylesh, S.; Schünemann, V.; Thiel, W.R. Magnetically separable nanocatalysts: Bridges between homogeneous
and heterogeneous catalysis. Angew. Chem. Int. Ed. 2010, 49, 3428–3459. [CrossRef] [PubMed]
5. Wan, T.-J.; Shen, S.-M.; Siao, S.-H.; Huang, C.-F.; Cheng, C.-Y. Using magnetic seeds to improve the
aggregation and precipitation of nanoparticles from backside grinding wastewater. Water Res. 2011, 45,
6301–6307. [CrossRef] [PubMed]
6. Qiao, R.; Yang, C.; Gao, M. Superparamagnetic iron oxide nanoparticles: From preparations to in vivo MRI
applications. J. Mater. Chem. 2009, 19, 6274–6293. [CrossRef]
7. Furlani, E.P. Magnetic biotransport: Analysis and applications. Materials 2010, 3, 2412–2446. [CrossRef]
8. Kumar, C.S.S.R.; Mohammad, F. Magnetic nanomaterials for hyperthermia-based therapy and controlled
drug delivery. Adv. Drug Deliv. Rev. 2011, 63, 789–808. [CrossRef] [PubMed]
9. Kurlyandskaya, G.V.; Portnov, D.S.; Beketov, I.V.; Larrañaga, A.; Safronov, A.P.; Orue, I.; Medvedev, A.I.;
Chlenova, A.A.; Sanchez-Ilarduya, M.B.; Martinez-Amesti, A.; et al. Nanostructured materials for magnetic
biosensing. Biochim. Biophys. Acta Gen. Subj. 2017, 1861, 1494–1506. [CrossRef] [PubMed]
10. Li, C.H.; Hodgins, P.; Peterson, G.P. Experimental study of fundamental mechanisms in inductive heating
of ferromagnetic nanoparticles suspension (Fe3 O4 Iron Oxide Ferrofluid). J. Appl. Phys. 2011, 110, 54303.
[CrossRef]
Nanomaterials 2017, 7, 373 14 of 15

11. Attaluri, A.; Seshadri, M.; Mirpour, S.; Wabler, M.; Marinho, T.; Furqan, M.; Zhou, H.; De Paoli, S.;
Gruettner, C.; Gilson, W.; et al. Image-guided thermal therapy with a dual-contrast magnetic nanoparticle
formulation: A feasibility study. Int. J. Hyperth. 2016, 32, 543–557. [CrossRef] [PubMed]
12. Roca, A.G.; Costo, R.; Rebolledo, A.F.; Veintemillas-Verdaguer, S.; Tartaj, P.; González-Carreño, T.;
Morales, M.P.; Serna, C.J. Progress in the preparation of magnetic nanoparticles for applications in
biomedicine. J. Phys. D Appl. Phys. 2009, 42, 224002. [CrossRef]
13. Kurlyandskaya, G.V.; Bhagat, S.M.; Safronov, A.P.; Beketov, I.V.; Larrañaga, A. Spherical magnetic
nanoparticles fabricated by electric explosion of wire. AIP Adv. 2011, 1, 42122. [CrossRef]
14. Laureti, S.; Peddis, D.; Del Bianco, L.; Testa, A.M.; Varvaro, G.; Agostinelli, E.; Binns, C.; Baker, S.; Qureshi, M.;
Fiorani, D. Exchange bias and magnetothermal properties in Fe@Mn nanocomposites. J. Magn. Magn. Mater.
2012, 324, 3503–3507. [CrossRef]
15. Osipov, V.V.; Platonov, V.V.; Uimin, M.A.; Podkin, A.V. Laser synthesis of magnetic iron oxide nanopowders.
Tech. Phys. 2012, 57, 543–549. [CrossRef]
16. Dormann, J.L.; Fiorani, D.; Tronc, E. Magnetic Relaxation in Fine-Particle Systems. In Advances in Chemical
Physics; Prigogine, I., Stuart, A.R., Eds.; J. Wiley & Sons, Inc.: New York, NY, USA, 1997; Volume XCVIII,
pp. 283–494.
17. Allia, P.; Coisson, M.; Tiberto, P.; Vinai, F.; Knobel, M.; Novak, M.; Nunes, W. Granular Cu-Co alloys as
interacting superparamagnets. Phys. Rev. B 2001, 64, 144420. [CrossRef]
18. Tronc, E.; Ezzir, A.; Cherkaoui, R.; Chanéac, C.; Noguès, M.; Kachkachi, H.; Fiorani, D.; Testa, A.M.;
Grenèche, J.M.; Jolivet, J.P. Surface-related properties of γ-Fe2 O3 nanoparticles. J. Magn. Magn. Mater. 2000,
221, 63–79. [CrossRef]
19. Li, Z.; Sun, Q.; Gao, M. Preparation of water-soluble magnetite nanocrystals from hydrated ferric salts in
2-Pyrrolidone: mechanism leading to Fe3 O4 . Angew. Chem. Int. Ed. 2005, 44, 123–126. [CrossRef] [PubMed]
20. Özkaya, T.; Baykal, A.; Toprak, M. 2-pyrrolidone-capped Mn3 O4 nanocrystals. Open Chem. 2008, 6, 465–469.
[CrossRef]
21. Topkaya, R.; Kurtan, U.; Junejo, Y.; Baykal, A. Sol–gel auto combustion synthesis of CoFe2 O4 /1-methyl-
2-pyrrolidone nanocomposite with ethylene glycol: Its magnetic characterization. Mater. Res. Bull. 2013, 48,
3247–3253. [CrossRef]
22. National Institute of Advanced Industrial Science and Technology. Available online: http://sdbs.db.aist.go.jp
(accessed on 30 September 2017).
23. Zhang, Y.; Liu, J.-Y.; Ma, S.; Zhang, Y.-J.; Zhao, X.; Zhang, X.-D.; Zhang, Z.-D. Synthesis of PVP-coated
ultra-small Fe3 O4 nanoparticles as a MRI contrast agent. J. Mater. Sci. Mater. Med. 2010, 21, 1205–1210.
[CrossRef] [PubMed]
24. Di Barba, P.; Dughiero, F.; Sieni, E. Magnetic field synthesis in the design of inductors for magnetic fluid
hyperthermia. IEEE Trans. Magn. 2010, 46, 2931–2934. [CrossRef]
25. Garcia, B.; Alcalde, R.; Leal, J.M.; Matos, J.S. Solute-solvent interactions in amide-water mixed solvents.
J. Phys. Chem. B 1997, 101, 7991–7997. [CrossRef]
26. Heymann, B.; Grubmüller, H. Elastic properties of poly(ethylene-glycol) studied by molecular dynamics
stretching simulations. Chem. Phys. Lett. 1999, 307, 425–432. [CrossRef]
27. Hugounenq, P.; Levy, M.; Alloyeau, D.; Lartigue, L.; Dubois, E.; Cabuil, V.; Ricolleau, C.; Roux, S.; Wilhelm, C.;
Gazeau, F.; et al. Iron oxide monocrystalline nanoflowers for highly efficient magnetic hyperthermia. J. Phys.
Chem. C 2012, 116, 15702–15712. [CrossRef]
28. Morrish, A.H.; Haneda, K. Surface magnetic properties of fine particles. J. Magn. Magn. Mater. 1983, 35,
105–113. [CrossRef]
29. Del Bianco, L.; Hernando, A.; Bonetti, E.; Navarro, E. Grain-boundary structure and magnetic behavior in
nanocrystalline ball-milled iron. Phys. Rev. B 1997, 56, 8894–8901. [CrossRef]
30. Herr, U.; Jing, J.; Birringer, R.; Gonser, U.; Gleiter, H. Investigation of nanocrystalline iron materials by
Mössbauer spectroscopy. Appl. Phys. Lett. 1987, 50, 472–474. [CrossRef]
31. Bonetti, E.; Del Bianco, L.; Signoretti, S.; Tiberto, P. Synthesis by ball milling and characterization of
nanocrystalline Fe3 O4 and Fe/Fe3 O4 composite system. J. Appl. Phys. 2001, 89, 1806–1815. [CrossRef]
32. Goya, G.F.; Berquó, T.S.; Fonseca, F.C.; Morales, M.P. Static and dynamic magnetic properties of spherical
magnetite nanoparticles. J. Appl. Phys. 2003, 94, 3520–3528. [CrossRef]
Nanomaterials 2017, 7, 373 15 of 15

33. Pereira, A.M.; Pereira, C.; Silva, A.S.; Schmool, D.S.; Freire, C.; Grenèche, J.M.; Araùjo, J.P. Unravelling
the effect of interparticle interactions and surface spin canting in γ-Fe2 O3 @SiO2 superparamagnetic
nanoparticles. J. Appl. Phys. 2011, 109, 114319. [CrossRef]
34. Rebbouh, L.; Hermann, R.P.; Grandjean, F.; Hyeon, T.; An, K.; Amato, A.; Long, G.J. 57Fe Mössbauer
spectral and muon spin relaxation study of the magnetodynamics of monodispersed γ-Fe2 O3 nanoparticles.
Phys. Rev. B 2007, 76, 174422. [CrossRef]
35. Randrianantoandro, N.; Mercier, A.M.; Hervieu, M.; Grenèche, J.M. Direct phase transformation from
hematite to maghemite during high energy ball milling. Mater. Lett. 2001, 47, 150–158. [CrossRef]
36. Helgason, O.; Rasmussen, H.K.; Mørup, S. Spin-canting and transverse relaxation in maghemite nanoparticles
and in tin-doped maghemite. J. Magn. Magn. Mater. 2006, 302, 413–420. [CrossRef]
37. Gorski, C.A.; Scherer, M.M. Determination of nanoparticulate magnetite stoichiometry by Mössbauer
spectroscopy, acidic dissolution, and powder X-ray diffraction: A critical review. Am. Mineral. 2010, 95,
1017–1026. [CrossRef]
38. Coey, J.M.D. Noncollinear spin arrangement in ultrafine ferrimagnetic crystallites. Phys. Rev. Lett. 1971, 27,
1140–1142. [CrossRef]
39. Parker, F.T.; Foster, M.W.; Margulies, D.T.; Berkowitz, A.E. Spin canting, surface magnetization, and finite-size
effects in γ-Fe2 O3 particles. Phys. Rev. B 1993, 47, 7885–7891. [CrossRef]
40. Morales, M.P.; Serna, C.J.; Bødker, F.; Mørup, S. Spin canting due to structural disorder in maghemite. J. Phys.
Condens. Matter 1997, 9, 5461–5467. [CrossRef]
41. Greaves, C. A powder neutron diffraction investigation of vacancy ordering and covalence in γ-Fe2 O3 .
J. Solid State Chem. 1983, 49, 325–333. [CrossRef]
42. Del Bianco, L.; Fiorani, D.; Testa, A.M.; Bonetti, E.; Savini, L.; Signoretti, S. Magnetothermal behavior of a
nanoscale Fe/Fe oxide granular system. Phys. Rev. B 2002, 66, 174418. [CrossRef]
43. Del Bianco, L.; Lesci, I.G.; Fracasso, G.; Barucca, G.; Spizzo, F.; Tamisari, M.; Scotti, R.; Ciocca, L. Synthesis of
nanogranular Fe3 O4 /biomimetic hydroxyapatite for potential applications in nanomedicine: structural and
magnetic characterization. Mater. Res. Express 2015, 2, 065002. [CrossRef]
44. El-Gendy, A.A.; Khavrus, V.O.; Hampel, S.; Leonhardt, A.; Büchner, B.; Klingeler, R. Morphology, structural
control, and magnetic properties of carbon-coated nanoscaled niru alloys. J. Phys. Chem. C 2010, 114,
10745–10749. [CrossRef]
45. Hergt, R.; Andrä, W. Magnetic Hyperthermia and Thermoablation. In Magnetism in Medicine, 2nd ed.;
Andrä, W., Nowak, H., Eds.; Wiley: Hoboken, NJ, USA, 2006; Volume 1, pp. 550–567. ISBN 978-3-527-40558-9.
46. Périgo, E.A.; Hemery, G.; Sandre, O.; Ortega, D.; Garaio, E.; Plazaola, F.; Teran, F.J. Fundamentals and
advances in magnetic hyperthermia. Appl. Phys. Rev. 2015, 2, 041302. [CrossRef]
47. Carrey, J.; Mehdaoui, B.; Respaud, M. Simple models for dynamic hysteresis loop calculations of magnetic
single-domain nanoparticles: Application to magnetic hyperthermia optimization. J. Appl. Phys. 2011, 109,
083921. [CrossRef]
48. Serantes, D.; Baldomir, D.; Martinez-Boubeta, C.; Simeonidis, K.; Angelakeris, M.; Natividad, E.; Castro, M.;
Mediano, A.; Chen, D.-X.; Sanchez, A.; et al. Influence of dipolar interactions on hyperthermia properties of
ferromagnetic particles. J. Appl. Phys. 2010, 108, 073918. [CrossRef]
49. Arteaga-Cardona, F.; Rojas-Rojas, K.; Costo, R.; Mendez-Rojas, M.A.; Hernando, A.; de la Presa, P. Improving
the magnetic heating by disaggregating nanoparticles. J. Alloy. Compd. 2016, 663, 636–644. [CrossRef]
50. Landi, G.T. Role of dipolar interaction in magnetic hyperthermia. Phys. Rev. B 2014, 89, 014403. [CrossRef]
51. Mehdaoui, B.; Tan, R.P.; Meffre, A.; Carrey, J.; Lachaize, S.; Chaudret, B.; Respaud, M. Increase of magnetic
hyperthermia efficiency due to dipolar interactions in low-anisotropy magnetic nanoparticles: Theoretical
and experimental results. Phys. Rev. B 2013, 87, 174419. [CrossRef]
52. Jeun, M.; Bae, S.; Tomitaka, A.; Takemura, Y.; Park, K.H.; Paek, S.H.; Chung, K.-W. Effects of particle dipole
interaction on the ac magnetically induced heating characteristics of ferrite nanoparticles for hyperthermia.
Appl. Phys. Lett. 2009, 95, 082501. [CrossRef]

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