Journal of Alloys and Compounds 792 (2019) 599e609

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Hydrothermal synthesis of hematite (a-Fe2O3) nanoparticle forms:

Synthesis conditions, structure, particle shape analysis, cytotoxicity
and magnetic properties
Marin Tadic a, *, Djordje Trpkov b, Lazar Kopanja c, d, Sandra Vojnovic e, Matjaz Panjan f
a
Condensed Matter Physics Laboratory, Vinca Institute, University of Belgrade, POB 522, 11001 Belgrade, Serbia
b
Vinca Institute of Nuclear Sciences, University of Belgrade, Mike Petrovica Alasa 12-14, 11001 Belgrade, Serbia
c
Faculty of Technology and Metallurgy, University of Belgrade, Belgrade, Serbia
d
Faculty of Mathematics and Computer Science, Alfa BK University, Palmira Toljatija, 3, 11070, Belgrade, Serbia
e
Institute of Molecular Genetics and Genetic Engineering, University of Belgrade, Vojvode Stepe 444a, 11000, Belgrade, Serbia
f
Jo
zef Stefan Institute, Jamova 39, 1000, Ljubljana, Slovenia

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

Article history: In this work, we present the magnetic and structural properties of a-Fe2O3 nanoparticles synthesized by
Received 4 November 2018 the hydrothermal synthesis method. XRD, FTIR and Raman spectroscopy indicate that the samples
Received in revised form consist of single-phase a-Fe2O3 nanoparticles. A microstructural analysis by TEM and SEM shows: (i)
14 March 2019
irregular nanoparticles (~50 nm), (ii) plate-like nanoparticles (with thickness t~10 nm and diameter d~50
Accepted 31 March 2019
Available online 4 April 2019
e80 nm) and (iii) microsized ellipsoid 3D superstructures (with length l~3.5 and diameter d~1.5 mm)
composed of nanosized building blocks (~50 nm). We used circularity, elongation and convexity mea-
sures to quantitatively analyze the shape of the particles. Irregular hematite nanoparticles were syn-
Keywords:
Hydrothermal synthesis
thesized using a water solution of ferric precursor and sodium acetate during the hydrothermal reaction
Iron oxide (reaction conditions: T ¼ 180  C, t ¼ 12 h). The same hydrothermal reaction temperature, reaction
Hematite (a-Fe2O3) duration and ferric precursor (without sodium acetate) were used for synthesizing hematite ellipsoid 3D
TEM image analysis superstructures. Addition of urea and glycine surfactants in hydrothermal reaction resulted in the for-
Magnetic properties mation of nanoplate hematite particles. The role of these surfactants on the structure and morphology of
Self-assembly the particles was also investigated. Magnetic measurements at the room temperature displayed a wide
range of coercivities, from HC ¼ 73 Oe for irregular nanoparticles, HC ¼ 689 Oe for nanoplates to
HC ¼ 2688 Oe for hematite ellipsoid 3D superstructures. The measured coercivity for the ellipsoid su-
perstructure was about 35 times higher than in the case of irregular hematite nanoparticles and about 4
times than the coercivity of hematite nanoplates. Magnetic properties of synthesized samples were
related to their structure and morphology. We conclude that shape anisotropy influenced enhancement
of the coercivity in hematite nanoplates whereas hematite ellipsoid 3D superstructure (nanoparticle
clusters) induced the formation of multidomain magnetic structure and highest coercivity revealing its
superior structure for enhanced magnetic properties. The synthesized hematite nanoparticle structures
exhibit low cytotoxicity levels on the human lung fibroblasts (MRC5) cell line demonstrating a safe use of
these nanoparticles for practical applications.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction and z-Fe2O3 [1e16]. Nanostructured iron oxides are used in

Iron (III) oxide nanoparticle crystal structures exist in five crystal
phases: a-Fe2O3 (hematite), b-Fe2O3, g-Fe2O3 (maghemite), ε-Fe2O3
* Corresponding author. Condensed Matter Physics Laboratory, Vinca Institute,
P.O. Box 522, 11001, Belgrade, Serbia.
E-mail address: marint@vinca.rs (M. Tadic).
different technological areas, such as microwave absorption,
catalysis, environment protection, gas sensors, magnetic storage,
clinical diagnosis and treatment, etc. [17e27]. Hematite is the most
stable form of iron oxide polymorphs and it is important in many
applications [28e41].
Hematite in the bulk form is paramagnetic at temperatures
above its Curie temperature TC z 956 K [41]. Below TC it is weakly
ferromagnetic material and undergoes a phase transition at

https://doi.org/10.1016/j.jallcom.2019.03.414
0925-8388/© 2019 Elsevier B.V. All rights reserved.
600 M. Tadic et al. / Journal of Alloys and Compounds 792 (2019) 599e609
TM~260 K (the Morin temperature) to an antiferromagnetic state
[41]. The magnetic behavior of hematite depends on the crystal-
linity, particle size, subparticle structure, cation substitution,
morphology, dipole-dipole and exchange interactions [41e46].
Hematite has demonstrated very interesting magnetic properties in
nanoparticle forms such as superparamagnetism, spin glass,
memory effects, high coercivity, high magnetization and a decrease
of the Morin and Curie temperatures [41,47e51].
The preparation method is a key factor for the morphology,
particle size distribution, subparticle structures, surface effects as
well as physical properties of the final products [41,52]. Various
synthesis methods of hematite nanoparticles have been reported in
the literature, such as hydrolysis method, hydrothermal method,
precipitation method, solvothermal process, a combustion method,
facile solution route, a sol-gel method, microemulsion method etc.
[41,52e58]. Among these methods, the hydrothermal method is
one of the most common and the least expensive routes of syn-
thesizing nanoparticles with different morphologies. Changing the
hydrothermal reaction conditions by tuning temperature, reaction
time, precursors and solvents may improve properties of the pro-
duced materials [41,59e67]. Surfactants containing amino groups
such as urea and glycine suppress nanocrystal nucleation and
crystal growth having a direct impact on the particle size, structure
and morphology [68,69]. In our previous works, we reported on a
study of hematite nanostructures with hierarchical hematite su-
perstructures, nanoparticles and core-shell nanoplates by the hy-
drothermal method [6,9]. The results revealed strong effects of
synthesis conditions on the structure and morphology of nano-
particles. We found that glycine surfactant induces a more spherical
shape of superstructures, smaller particle sizes and enhance the
coercivity [6]. In this work, we present a continuation of our pre-
vious investigations by exploring different hydrothermal condi-
tions, surfactants and properties of the synthesized nanoparticles.
An important property of hematite nanoparticles for practical ap-
plications is their cytotoxicity. It has been reported that cytotoxicity
depends on the nanoparticle size, its structure and morphology
[9,70e77]. Since the cytotoxicity is crucially dependent on the
particle shape, we employed a mathematical method of the shape
descriptors for quantification analysis of nanoparticles [8].
In this work, we report on tuned hydrothermal synthesis con-
ditions to obtain specific nanoparticle forms of hematite: irregular
nanoparticles (50 nm and HC ¼ 73 Oe), nanoplates (thickness
~10 nm, diameter ~50e80 nm and HC ¼ 689 Oe) and microsized
ellipsoid 3D superstructures (length ~2.5, diameter ~1 mm and
HC ¼ 2688 Oe) composed of nanosized building blocks ~50 nm. We
also demonstrate that the morphology and the substructure of
particles have strong effects on the magnetic properties. Crystal
structure and phase purity of obtained samples were analyzed by
X-ray powder diffraction (XRD), Raman spectroscopy and Fourier
transform infrared (FTIR) spectroscopy. Scanning electron micro-
scopy (SEM) and transmission electron microscopy (TEM) were
used for morphology investigations and quantitative analysis of the
particle shapes (circularity, elongation and convexity) whereas the
magnetic properties at room temperature were recorded by
vibrating sample magnetometer (VSM). The synthesized hematite
Table 1
The chemicals used in the synthesis and reaction conditions.
Sample Precursors, solvents, additives
3þ
S1 2 mmol Fe , 40 mmol NaAc, 15 ml EtOH/DI H2O (v/v 3:1)
S2 3.7 mmol Fe3þ, 26.7 mmol glycine, 15 mmol urea, 20 ml DI H2O
S2.0 3.7 mmol Fe3þ, 20 ml DI H2O
S2.05 3.7 mmol Fe3þ, 13.35 mmol glycine, 7.5 mmol urea, 20 ml DI H2O
S2.2 3.7 mmol Fe3þ, 53.4 mmol glycine, 30 mmol urea, 20 ml DI H2O
S3 20 mmol Fe3þ, 9.5 ml DI H2O, 0.5 ml NH4OH (25%)
nanostructures presented in this study exhibited low cytotoxicity
levels indicating safe use of these nanoparticles in medical treat-
ment and diagnosis.
2. Experimental
Hematite samples were synthesized by hydrothermal method.
For the synthesis we used: ferric chloride hexahydrate (FeCl3$6H2O,
99%, Sigma-Aldrich, USA), ammonium hydroxide (NH4OH, min
25%, Centrohem, Serbia), glycine (99.4%, Merck-Alkaloid,
Macedonia), urea (99%, Sigma-Aldrich, USA), absolute ethanol
(EtOH, min 95%, Zorka pharma), sodium acetate trihydrate (NaAc,
>99%, Centrohem Serbia) and deionized water (Purite Ltd. UK,
18.2 MU).
Table 1 summarizes reaction conditions applied during the hy-
drothermal synthesis. The solvents, surfactants and precursors
were mixed in proportion as presented in Table 1 and stirred until
the reagents were completely dissolved. The measured pH values
were in range 3e4 for all samples. Afterward, the obtained solu-
tions were transferred into Teflon-lined stainless steel autoclaves of
33 ml capacity, firmly sealed and heated (see Table 1). After the
hydrothermal reaction was completed, autoclaves were cooled
naturally to the room temperature. The resulting slurry was
transferred into 10 ml plastic tubes, centrifuged and rinsed four
times with absolute ethanol and DI water. The products were ob-
tained after drying at 60  C for 24 h. Finally, powders were obtained
and used for further analysis.
Crystal structure of the samples was analyzed by X-ray powder
diffraction (XRD) on a Rigaku RINT-TTRIII diffractometer operating
with Cu Ka radiation. Measurements were performed in range
2q ¼ 10 e80 . The Raman spectra of the samples were measured
with a Horiba Jobin Yvon LabRAM HR spectrometer using the
632.81 nm excitation line of a He-Ne laser. Fourier Transform
Infrared (FTIR) spectra of samples were recorded on a Nicolet FTIR
spectrometer (IS 50) at room temperature in the wavenumber
range of 4000e400 cm 1 with a resolution of 4 cm1. Samples
morphologies were investigated using SEM microscope (JEOL JSM-
7600F) and TEM microscopy (JEOL JEM-2100). The vibrating sample
magnetometer (VSM, LakeShore 7400 Series) was used to record
magnetic properties at the room temperature.
Cytotoxicity (anti-proliferative effect) of nanoparticles was
assessed on human lung fibroblasts (MRC5) cell line obtained from
the ATCC culture collection using a standard MTT assay as previ-
ously described [9]. Nanoparticles were resuspended in deionized
water (50 mg/ml) and the highest concentration tested was 500 mg/
mL. Morphological appearance of the treated cells was done using
DM IL LED Inverted Microscope (Leica Microsystems, Wetzlar,
Germany) under 20 magnification.
3. Results and discussion
3.1. XRD, SEM, TEM, Raman and FTIR measurements
Diffraction patterns of the samples S1, S2 and S3 measured by
XRD are shown in Fig. 1. Comparison of the patterns to the hematite
Temperature [ C] Time [h]
180 12
160 10
160 10
160 10
160 10
180 12
 M. Tadic et al. / Journal of Alloys and Compounds 792 (2019) 599e609
Fig. 1. X-ray diffraction patterns of the samples: (a) sample S1 with irregular shaped
particles, (b) sample S2 with plate-shaped particles and (c) sample S3 with ellipsoid-
shaped 3D hematite superstructures.
database (JCPDS card 33-0664) shows the formation of a-Fe2O3
(hematite). The presence of any other iron oxide phases was not
detected. All peaks were indexed to a rhombohedral crystal struc-
ture (space group R-3c). The broad XRD peaks indicate the forma-
tion of small nanoparticles, as later confirmed by the SEM and TEM
images. Crystallite sizes (D) were estimated by Scherrer formula


Kl
D ¼ bcos on the (104) peak. Where K ¼ 0.9, l ¼ 1.5406 Å, b is
q
FWHM (full width at half maximum) of (104) peak and q is
diffraction angle corresponding to peak maximum. The calculated
crystallite sizes were D(S1) ¼ 30.6 nm, D(S2) ¼ 41.9 nm and
D(S3) ¼ 26.8 nm.
The morphology and particle sizes of the samples were inves-
tigated by scanning electron microscopy (SEM) and transmission
electron microscopy (TEM). The electron microscopy images of the
sample S1 (Fig. 2) show irregular nanoparticles with sizes around
(50 ± 20) nm. From the SEM micrographs shown in Fig. 3 (sample
S2), we observed plate-like nanoparticles with a thickness of about
601
10 nm and a diameter ranging from 50 to 80 nm. We also investi-
gated the role of the surfactants (glycine and urea) on the formation
of hematite particles by XRD, SEM and TEM (Fig. 4). Samples ob-
tained with different ratios of the surfactants and the same hy-
drothermal conditions (Table 1) have been investigated to reveal
the relationship between the structure, morphology and surfac-
tants. As shown in Fig. 4aec, rhombohedral shaped superstructures
of hematite are prepared with surfactants-free hydrothermal re-
action (sample S2.0). The surfactants in the hydrothermal reaction
with half of the quantity (sample S2.05) compared with sample S2
produced hematite particles of similar morphology as in S2 but
with wider size distribution (Fig. 4def). However, the products
(sample S2.2) prepared with a double concentration of surfactants
(compared to S2) possess some irregular morphology and have
additional diffraction peaks of spinel structure as observed in the
XRD pattern (Fig. 4gei). The sample S3 (Fig. 5) shows uniform
ellipsoid-like 3D superstructures with diameters of
DSEM~1.5 ± 0.3 mm and lengths about L~3.5 ± 0.5 mm composed of
self-assembled nanoparticles as building blocks with sizes around
50 nm. The Raman spectrums of the samples are shown in Fig. 6.
The spectrums are similar and typical of the a-Fe2O3 (hematite)
phase, showing peaks at around 220, 285, 400, 490, 600, 655 and
1300 cm1. These peaks match well with the previously reported
Raman data for hematite [78e80]. The Raman peaks that appear at
around 220 cm1 and 490 cm1 have been assigned to the A1g
mode, and those at around 285 cm 1, 400 cm 1, and 600 cm 1
have been assigned to the Eg modes [78e80]. The peak located at
around 655 cm 1 has been attributed to disorder effects and/or the
presence of a-Fe2O3 nanocrystals, whereas the peak observed at
around 1300 cm 1 has been assigned to hematite two-magnon
scattering. The FTIR spectrums of the samples were illustrated in
Fig. 7. Two absorption peaks at about 515 and 430 cm 1 are
observed for all samples. These peaks are corresponding to
stretching and bending modes of the FeeO bond in hematite
[80e82]. No peaks corresponding to other phases (organic or
inorganic compounds) were observed, indicating pure hematite
phase.
3.2. Circularity
The shape of particles is a critical factor for the magnetic
properties of nanoparticle materials [67e70]. In order to compare
the shapes, it is necessary to assign them the corresponding nu-
merical values. For the quantitative analysis of the shapes, we used
different shape descriptors including, circularity, elongation and
convexity.
The circularity measure, as one of the most standard shape
descriptors, defines the degree to which a shape differs from a
perfect sphere [83e86]. Circularity values range from 0 to 1. The
circularity measure reaches a value of 1 only in the case of a perfect
circle and approaches 0 when the shapes are highly non-circular,
such as a line. Circularity is usually regarded as the ratio between
shape‘s area and its perimeter: C1 ðSÞ ¼ 4$p$A=P 2 where A repre-
sents the shape's area and P is the shape's perimeter.
In order to avoid disadvantages of the standard measure C1,
which is usually considered in the literature [87,88], we use the
circularity measure C2 based only on an area of the considered
shape, thus avoiding the computation of the perimeter [89]:
AreaðSÞ2
C2 ðSÞ ¼  
2$p$ min ∬ SðqÞ x2 þ y2 dxdy
q2ð0;2p
where S(q) denotes the shape S rotated for q around the origin,
whilst Area(S) represents an area of the considered shape S.
602 M. Tadic et al. / Journal of Alloys and Compounds 792 (2019) 599e609

Fig. 2. Typical SEM micrographs of the sample S1 with irregular shaped particles: a)-b) low-magnification and c)-d) high-magnification.

Fig. 3. Typical SEM and TEM micrographs of the sample S2 with plate-shaped particles: a)-b) low-magnification and c)-d) high-magnification.
 M. Tadic et al. / Journal of Alloys and Compounds 792 (2019) 599e609 603

Fig. 4. Structural and morphological characterization of the particles synthesized with different quantities of surfactants (samples S2.0, S2.05 and S2.2): X-ray diffraction patterns,
SEM micrographs and TEM images.

Fig. 5. Typical SEM and TEM micrographs of the sample S3 with ellipsoid-shaped 3D hematite superstructures: a)-b) low-magnification and c)-d) high-magnification.
604 M. Tadic et al. / Journal of Alloys and Compounds 792 (2019) 599e609

Fig. 6. Raman spectrums of hematite superstructures: a) sample S1 with irregular

shaped particles, b) sample S2 with plate-shaped particles and c) sample S3 with
ellipsoid-shaped 3D hematite superstructures.

Both of these circularity measures C1 and C2 has several Fig. 7. FTIR spectrums of hematite superstructures: a) sample S1 with irregular shaped
particles, b) sample S2 with plate-shaped particles and c) sample S3 with ellipsoid-
following desirable properties:
shaped 3D hematite superstructures.
(a) C1,2(S) 2 (0, 1] for all shape S,
(b) C1,2(S) ¼ 1 ⇔ S is a circle,
(c) C1,2(S) is invariant with respect to similarity transformations
(translation, rotation, scaling).
 M. Tadic et al. / Journal of Alloys and Compounds 792 (2019) 599e609 605

3.3. Elongation 3.4. Convexity (solidity)

For all the shapes S the measured elongation ε(S) is in the range
[1, ∞). A circle has the minimum possible measured elongation, i.e.
ε(circle) ¼ 1. The usual approach for calculating the elongation
arises from the standard definition of orientation [86,89]. The
orientation is a line minimizing an integral of square distances
between shape's points and axes. The integral is
A planar shape S is convex if it has the following property: when
points A and B belong to S, then all points from the line segment AB
belong to S as well. The convexity (solidity) measure defines the
degree to which a shape differs from a convex shape. Convexity
values are numbers in the range (0, 1).
Convexity is usually regarded as the ratio between shape‘s area
and area of its convex hull [90]:

IðS; f; rÞ ¼ ∬ r 2 ðx; y; f; rÞ dxdy

S AreaðSÞ
CðSÞ ¼
AreaðCHðSÞÞ
where rðx; y; f; rÞ is the distance from the point ðx; yÞ to the line
defined as x,cos f  y,sin f ¼ r.
where Area(S) represents the shape's area and Area(CH(S)) is an
If we suppose that the centroid coincides with the origin, and
area of the convex hull of S.
also that the line minimizing IðS; f; rÞ goes through the origin, we
The convexity (solidity) measure has the following desirable
can use r ¼ 0. Therefore, the problem of the shape orientation can
properties:
then be reformulated to determine f for which Iðf; SÞ is defined as
RR
Iðf; SÞ ¼ IðS; f; r ¼ 0Þ ¼ ðx,sin f  y,cos fÞ2 dxdy when it rea- (a) C(S) 2 (0, 1] for all shape S,
ches its minimum. Central geometric moments mp;q ðSÞ are gener- (b) C(S) ¼ 1 ⇔ S is a convex shape,
ally defined as: (c) C(S) is invariant with respect to similarity transformations
(translation, rotation, scaling).

qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 
1  2
maxf IðS; fÞ j f2½0; 2p g ¼ m2;0 ðSÞ þ m0;2 ðSÞ þ 4m1;1 ðSÞ þ m2;0 ðSÞ  m0;2 ðSÞ minf IðS; fÞ j f2½0; 2p g
2

qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 
1  2
¼ m2;0 ðSÞ þ m0;2 ðSÞ  4m1;1 ðSÞ þ m2;0 ðSÞ  m0;2 ðSÞ
2

3.5. Shape analysis

mp;q ðSÞ ¼ ∬ ðx  xc ðSÞÞp ,ðy  yc ðSÞÞq dxdy
S
The shape distribution of S1, S2 and S3 nanoparticles (Fig. 8a, b
and since we suppose ðxc ðSÞ; yc ðSÞÞ ¼ ð0; 0Þ, we have and c) was obtained from an image analysis of the TEM micro-
graphs measuring (circularity, elongation and convexity) about 180
nanoparticles in random fields of view. In order to quantify the
Iðf; SÞ ¼ ðsin fÞ2 ,m2;0 ðSÞ  sin 2 f, m1;1 ðSÞ shapes, it is necessary to segment the appropriate TEM images in
order to obtain isolated nanoparticles, and then measure the
þ ðcos fÞ2 ,m0;2 ðSÞ: shapes using the above descriptors. The obtained results are shown
The maximum and minimum of Iðf; SÞ can be computed from: in the histograms in Fig. 8. Because of their characteristic shape, the
nanoparticles from the sample S3 have the smallest circularity
values and the largest elongation values. In terms of convexity, the
This leads to a standard formula to computing the elongation of nanoparticles of the sample S2 have the most compact shape,
the shape S: whereas the sample S3 consists of nanoparticles whose shape is at
least compact.

maxfIðd; SÞ j d2ð0; 2pg

εðSÞ ¼ 3.6. Magnetic measurements
minfIðd; SÞ j d2ð0; 2pg
When working with digital objects representing digitization of The magnetic measurements have been performed at the room
real objects, then it is natural to approximate mp;q ðSÞ with central temperature (300 K) using VSM magnetometer (Fig. 9). The mea-
discrete moment Mp;q ðSÞ: surement of M(H) for the sample S1 is shown in Fig. 9a. Recorded
magnetic parameters (HC ¼ 73 Oe, Mr ¼ 0.016 emu/g, MS ¼ 0.54
emu/g) indicate the properties of soft magnetic materials. The
X
Mp;q ðSÞ ¼ ði  xcd ðSÞÞp ,ðj  ycd ðSÞÞq observed value of coercivity (HC ¼ 73 Oe) is very close to coercivity
ði;jÞ 2S∩Ζ 2 of irregular nanoparticles (HC ¼ 68 Oe, D¼(380 ± 50) nm) as re-
ported by Jing et al. [91]. Can et al. obtained irregular hematite
0P P 1 nanoparticles with higher coercivity Hc ¼ 286 Oe (d~200 nm) [92].
x y
B ðx;yÞ 2S∩Ζ 2 C Plate-like particles observed in the sample S2 exhibited weak-
where ðxcd ðSÞ; ycd ðSÞÞ ¼ B P P C is a centroid of
ðx;yÞ 2S∩Ζ 2
@ ; 1A
1 ferromagnetism with larger coercivity HC ¼ 689 Oe, Mr ¼ 0.01 and
ðx;yÞ 2S∩Ζ 2 ðx;yÞ 2S∩Ζ 2
MS ¼ 0.372 emu/g (Fig. 9b). The particles in the sample S2 with
a discrete shape. regard to the shape anisotropy increases coercivity in comparison
606 M. Tadic et al. / Journal of Alloys and Compounds 792 (2019) 599e609
Fig. 8. The shape distribution of nanoparticles of the S1 (a), S2 (b) and S3 (c) samples from an image analysis of the TEM micrographs measuring by circularity, elongation and
convexity.
to the sample S1. The small thickness of the synthesized nanoplates
(~10 nm) compared to their diameter (d~50e80 nm) introduces
additional anisotropy effects (shape anisotropy), which increases
coercivity. Some literature reports present lower values of coer-
civity in hematite particles with similar morphology (HC ¼ 22 Oe
for D ¼ 78e92 nm, HC ¼ 75 Oe for D ¼ 91e112 nm and HC ¼ 215 Oe
for D ¼ 132e150 nm [93]). Jiang et al. achieved similar coercivity in
comparison to sample S2 (Hc ¼ 758 Oe) for nanodiscs with the
diameter of 50 ± 10 nm and thickness of ~6.5 nm [94]. Sun et al.
employed double anion mediation hydrothermal method for the
synthesis of hematite nanoplatelets with diameters of 100e140 nm
and heights of 40e70 nm (saturation magnetization Ms ¼ 7.36
emu/g and a coercivity Hc ¼ 485 Oe [95]. Hao et al. reported he-
matite nanoplates (diameter of 180 nm and thickness of ~30 nm)
with Hc ¼ 711.66 Oe and Mr ¼ 0.142 emu/g [61]. It can be concluded
that the shape anisotropy plays a crucial role in the development of
the magnetic properties in the sample S2.
The M(H) magnetization measurement of the sample S3 is
shown in Fig. 9c. Recorded magnetic parameters (HC ¼ 2688 Oe,
Mr ¼ 0.232 emu/g and MS ¼ 0.587 emu/g) indicate weak ferro-
magnetic behavior and the largest coercivity among the investi-
gated samples. The observed coercivity of the sample S3 is 1.5 times
higher than the coercivity of the bulk hematite (HC ¼ 1670 Oe) [96].
Moreover, the coercivity of the sample S3 is much larger than the
coercivity reported for irregular nanoparticles synthesized in this
work (~35 times) and individual a-Fe2O3 particles in the literature
[97].
Magnetic properties of hematite show large changes in the
values of the coercivity. The magnetism of the superstructures has
generated substantial interest in the research community due to
the possibility to enhance the coercivity. The influence of the par-
ticle size, crystal shape, morphology, dipolar and exchange in-
teractions, defects and microstructure of hematite particles on the
€
coercivity have been widely discussed. Ozdemir and Dunlop re-
ported detailed research, concerning magnetic hysteresis proper-
ties (coercivity) of natural and synthetic hematites, with a wide
range of grain sizes [98]. They proposed that high coercivity mainly
originates from the magnetoelastic anisotropy. The magnetoelastic
anisotropy is caused in a fine particles by internal strains whereas
in a large crystals by defects [98]. The crystal growth of the nano-
crystals in the superstructure can be suppressed and may produce
high internal strains. Authors also discuss the grain size depen-
dence of coercivity and conclude that HC reaches a maximum be-
tween 0.1 and 3 mm [98]. Estroff et al. reported mosaic anisotropy in
mesostructured materials with high coercivity whose crystalline
order falls between the perfect order of a single crystal and the
random order of the polycrystalline material [99]. It has been
shown that crystallographic alignment of grains and grain bound-
aries between them contribute to the high coercivity [99]. On the
one hand, the single particles reverse their magnetization indi-
vidually without influencing the neighboring magnetic particles
while the effect of alignment and exchange interactions of particles
in the superstructure on coercivity is evident [99]. It is reported in
the literature that the assembly of the small and oriented sub-
particles into the superstructure results in the change of the single
domain to the multidomain-like structure, leading to the higher
remanent magnetization and coercivity [100e103]. Elongated
shape of the microparticles (Fig. 5) most probably introduced a
shape anisotropy effect and additionally increased overall coer-
civity of the sample S3. Literature reports also suggest a high
 M. Tadic et al. / Journal of Alloys and Compounds 792 (2019) 599e609 607

[105].
The sizes of nanoparticles and building units (which is higher
than the critical size for superparamagnetism) are the main reason
for weak-ferromagnetism and non-zero coercivity at the room
temperature. Due to different nanostructures which we observed in
this work, coercivity is most probably influenced by some other
factors apart from the magneto-crystalline anisotropy: shape
anisotropy, strain, defects and interface exchange coupling. As the
particle transforms from irregular to plate-like shape, its shape
anisotropy increases significantly, leading to an increase in the
coercivity (Fig. 9.). The ellipsoid-shaped 3D hematite superstruc-
ture was composed of nanoparticles and each nanoparticle might
act as a single magnetic domain with its own spin. The coupling of
the magnetic domains in the internal microstructure of the 3D
hematite superstructures is in our opinion the origin of higher
coercivity. Therefore, the exchange coupling of nanoparticles may
increase the effective anisotropy of the particles in the super-
structure, leading to a “harder” reversal of the magnetization and
an enhancement of the coercivity (Fig. 9.). Summary of observed
magnetic properties, particle sizes and shapes in this work is given
in Table 2.

3.7. Cytotoxicity

The cytotoxicity is an important property of nanoparticles when

considering them for biomedical applications [92e99]. Nano-
particles tested in this work were not cytotoxic on MRC5 cells when
they were exposed to doses up to 500 mg/mL (Fig. 10). Only S1
inhibited proliferation of 10% of cell proliferation at this dose
(Fig. 10a). Good internalization within cells was observed for all
nanoparticles (Fig. 10b). These nanoparticles were comparable but
even less cytotoxic in comparison to recently described ones [9,70].

4. Conclusions

This work demonstrates that changes in the conditions of the

Fig. 9. Magnetization vs. magnetic field M(H) measured at 300 K for (a) S1 sample
with irregular shaped particles, (b) S2 sample with plate-shaped particles and (c) S3
sample with ellipsoid-shaped 3D hematite superstructures.
coercivity values for 3D superstructures. An et al. reported
Hc ¼ 3248 Oe for elliptic superstructures [104]. Chaudari et al. re-
ported four different hematite microparticle 3D superstructures
with high HC values: microspheres HC ¼ 2510 Oe, dumbbells
HC ¼ 6000 Oe, grapes HC ¼ 6250 Oe and microcubes HC ¼ 7375 Oe
hydrothermal synthesis lead to substantial changes in the struc-
ture, morphology and magnetic properties of the hematite nano-
particles. We synthesized three different forms of a-Fe2O3
(hematite) particles: irregular nanoparticles (50 nm), nanoplates
(with thickness t~10 nm and diameter d~50e80 nm) and micro-
sized ellipsoid superstructures (with length l~3.5 mm and diameter
d~1.5 mm) composed of nanosized building blocks (~50 nm). The
role of the surfactants (glycine and urea) in the synthesis was also
presented. Structure, morphology and magnetic properties were
characterized by XRD, SEM, TEM, FTIR, Raman spectroscopy, EDS
and VSM. The magnetic properties were in the range from the low
coercivity (HC ¼ 73 Oe for irregular nanoparticles and HC ¼ 689 Oe
for nanoplates) to the high coercivity of HC ¼ 2688 Oe as observed
for the 3D superstructures. The increase of the coercivity in the
~6)
nanoplates can be attributed to the shape anisotropy (aspect ratio
whereas the highest coercivity of ellipsoid superstructures prob-
ably originates from the induced formation of the multidomains.
Elliptic morphology of microparticles is also an important effect,
which contributes to the overall anisotropy and coercivity. The

Table 2
Recorded magnetic parameters, morphology, particle sizes and estimated (calculated) crystallite sizes for samples S1, S2 and S3.

Sample Morphology dXRPD [nm] dSEM HC [Oe] Mr [emu/g]

S1 Irregular particles 30.6 50 nm 73 0.016

S2 Plate-like particles 41.9 t~10 nm 689 0.1
d~60 nm
S3 Ellipsoidal superstructure 26.8 l~3.5 mm 2688 0.232
d~1.5 mm
608 M. Tadic et al. / Journal of Alloys and Compounds 792 (2019) 599e609
Fig. 10. Cytotoxicity of the nanoparticles on MRC5 cell line: a) dose response and b) morphological cell appearance after 48 h treatment at 125 mg/mL.
hematite superstructure shows the highest coercivity, therefore, it
is superior morphology for improving the magnetic properties of
hematite. Low cytotoxicity and good cell internalization indicate
that the synthesized nanoparticles could be utilized as drug
carriers.
Acknowledgment
The Ministry of Education, Science and Technology of the Re-
public of Serbia supported this work financially (Grants nos. III
45015 and III 044006). The support by the Ministry of Higher Ed-
ucation, Science and Technology of the Republic of Slovenia within
the National Research Program is acknowledged. We would also
like to acknowledge Serbian-Slovenian bilateral project BI-RS/16-
17-030.
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