Journal of Alloys and Compounds 741 (2018) 28e34

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Journal of Alloys and Compounds

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

Synthesis and magnetic properties of magnetite prepared by chemical

reduction from hematite of various particle sizes
V.P. Ponomar*
M.P. Semenenko Institute of Geochemistry, Mineralogy and Ore Formation of NAS of Ukraine, Kyiv, Ukraine

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

Article history: In the process of beneficiating iron ores by the magnetic separation, particles of hematite and quartz
Received 13 July 2017 accumulate, forming tailings that occupy large areas of agricultural lands. Such man-made deposits are
Received in revised form quite common and contain large quantities of iron oxides such as hematite. Therefore the tailings can be
1 December 2017
used as raw material for the production of magnetite. In this work, magnetite was synthesized by he-
Accepted 2 January 2018
matite reduction at a temperature of 500
C in an atmosphere of carbon monoxide. The source hematite
Available online 4 January 2018
was separated initially into ten particle size categories ranging from 0.05 to 2.5 mm. The reduction was
carried out with carbon monoxide, which was synthesized by reaction of air and activated carbon at
Keywords:
Magnetite
750
C. It was determined by X-ray diffraction analysis and magnetometry that, after reduction, samples
Hematite of each particle size consisted mainly of magnetite. In addition, the magnetic properties of the resulting
Gas-solid reactions magnetite were noted to be somewhat different from those of natural magnetite. In particular, rema-
Reduction nence and coercivity are higher for synthetic magnetite than for natural magnetite. The saturation
Tailings magnetization of transformed samples increases to 60e80 Am2/kg, while the source hematite does not
Magnetic measurements have strong magnetic properties. Hematite with a particle size from 0.05 to 0.25 mm is completely
converted into magnetite, but if the size of hematite particles increases to from 0.25 to 2.5 mm,
incomplete conversion of hematite to magnetite is observed. The obtained results are important for the
development of technology for converting hematite to magnetite, which can, in turn, be used to bene-
ficiate iron ores.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction sensors, and for other applications [2,3]. Recently, magnetite has
become very important in the biomedical field, with applications in
Magnetite is one of the most important minerals in the Earth's drug delivery systems, magnetic resonance imaging enhancement,
crust due to peculiarities of its composition, structure, and mag- medical diagnostics, and cancer therapy [4e7].
netic properties. Magnetite (Fe3O4) has an inverse spinel structure The use of magnetite in various fields results from its chemical,
in which cations occupy tetrahedral and octahedral sites in the structural, and physical properties. Because natural magnetite
face-centered cubic lattice [1,2]. The tetrahedral sites (A) occupied varies in particle size and chemical purity, most naturally occurring
by Fe3þ and the octahedral sites (B) occupied by both Fe3þ and Fe2þ magnetite is unsuitable for some uses. Recently, many methods
form the basis for two antiparallel magnetic sublattices. The have been developed for the synthesis of magnetite [5,8e11]
number of spins at sites A and B is unequal, resulting in ferrimag- including co-precipitation [9e12], sol-gel [13,14], thermal decom-
netism in magnetite below the Curie temperature of 580
C [2]. position [15], and hydrothermal synthesis [16,17] to control most of
From the Iron Age to the present day, magnetite has been the its properties. Thus, the connection between the synthesis pro-
main component of both high-grade and low-grade iron ores. cedure and the properties of synthesized magnetite is important e
Magnetite quartzite, for example, is suitable for beneficiation by not only theoretically, but also for practical purposes.
magnetic separation. Magnetite is widely used for pigments, as a The methods listed above have certain disadvantages, however.
catalyst, for magnetic recording media, for magnetic fluids, for gas The particles of magnetite prepared by liquid methods, for instance,
have relatively low crystallinity. Organic solvents used in the syn-
thesis of magnetite are undesirable thereafter and should be
* 34 Palladina Prospect, Kyiv, 03680, Ukraine. removed from the suspension. In addition, the reagents involved in
E-mail address: [email protected].

https://doi.org/10.1016/j.jallcom.2018.01.023
0925-8388/© 2018 Elsevier B.V. All rights reserved.
 V.P. Ponomar / Journal of Alloys and Compounds 741 (2018) 28e34 29

the reactions are quite expensive. Another method for the synthesis hematite to magnetite.
of magnetite is based on the phase transformation of iron oxides, In this paper, the crystalline structure and magnetic properties
carbonates, or sulfides. Note that iron-containing minerals such as were identified for magnetite obtained by chemical reduction of
hematite and goethite form waste (tailings) when magnetite ores natural hematite. Study samples were divided into ten groups by
are beneficiated. Iron ore tailings are promising solid wastes for use particle size. The results obtained for synthetic magnetite were
in industry. The production of magnetite from industrial waste is compared with the results for natural magnetite.
attractive for commercial and environmental purposes.
Hematite has the chemical formula of Fe2O3 and is one of the 2. Materials and methods
most common minerals in iron ore deposits. The spin configuration
of hematite is antiferromagnetic below the Neel temperature of 2.1. Initial materials
680 ± 5
C. Hence, the hematite has a net magnetic moment of close
to zero, because the antiparallel spins completely compensate for The initial sample of hematite was collected from the Kryvyi Rih
each other. Nonetheless, hematite can be converted into highly Basin. The magnetic fraction of the sample was removed by wet
magnetic magnetite. Features of the synthesis of magnetite by low-intensity magnetic separation. The main mineral phases of the
hematite transformation were investigated by several methods, remaining sample were hematite and minor quartz. The initial
including ultrasonic chemical co-precipitation [10] and chemical hematite was divided by sieving and grinding into the following
reduction with carbohydrates [18,19], with hydrogen [20], with particle sizes: <0.05, 0.05e0.1, 0.1e0.16, 0.16e0.25, 0.25e0.4,
carbon monoxide [21], and with other agents. 0.4e0.63, 0.63e1.0, 1.0e1.6, 1.6e2.5, and >2.5 mm.
Chemical reduction of synthetic hematite with starch in air at The magnetite was represented by natural material obtained by
265e580
C was investigated by means of X-ray powder diffraction, wet low-intensity magnetic separation of magnetite quartzite from
FT-IR, and 57Fe Mo € ssbauer spectroscopies [18]. A mixture of he- the Kryvyi Rih Basin. Mineral phases of the sample were magnetite
matite and starch was heated at various temperatures and minor quartz. The particles of magnetite were ground to a size
(265e580
C) for various times (30e120 min). Magnetite and a less than 0.07 mm.
small fraction of hematite were detected in the transformed sam-
ples. Magnetite synthesized at 580
C was highly 2.2. Procedure for magnetite synthesis
substoichiometric.
The authors [20] investigated the transformation of hematite The synthesis process included two main stages. The first stage
into magnetite by heating the sample in a stream of an H2-Ar was the synthesis of carbon monoxide by activated charcoal gasi-
mixture at a temperature range from 260 to 360
C. The starting fication. For this, activated charcoal was heated to 750
C. After that,
material was a pure hematite powder (analytical reagent, Mal- air was fed into the gas generator and passed through the layer of
linckrodt) consisting of nonporous crystalline grains approximately activated charcoal. The reaction between charcoal and oxygen
0.7 mm in size. Reduction of the starting samples at 320
C for contained in the air led to the formation of carbon monoxide (CO).
40 min and 50 min led to complete conversion of hematite to The slow flow of air through the layer of activated charcoal provides
magnetite. Activation energy of 98.74 kJ/mol was calculated for that conditions for the formation of carbon monoxide:
reaction.
The formation of magnetite was investigated in Ref. [22] by O2 þ 2C ¼ 2CO (1)
reduction of hematite by iron in an aqueous solution at 350e570
C
In the second stage, gas containing carbon monoxide was
and a pressure of 1e2 kbar. The starting material was synthetic
delivered to a quartz reactor with the particles of hematite. The
hematite (Koch Light Ltd.). The reaction involved the oxidation of
sample temperature inside the reactor was 600
C. The reduction of
metallic iron with water and the reduction of hematite with
hematite may occur according to the equation:
hydrogen.
The kinetics of hematite ore reduction with hydrogen at low 3Fe2 O3 þ CO ¼ 2Fe3 O4 þ CO2 (2)
temperature were studied for various sizes of particles in Ref. [23]
by thermogravimetric analysis. Australian iron ore, consisting of
hematite and magnetite, was used as the experimental material.
The experiments used particle sizes of 2.0 mm, 6.5 mm, 25.0 mm, and 2.3. Thermomagnetic analysis
107.5 mm. When the particle size of the powder decreased from
107.5 mm to 2.0 mm, the reduction process of hematite accelerated The thermomagnetic analysis was carried out with a custom-
by about eight times, resulting in an increase in the activation en- built facility that measures the magnetic interaction between the
ergy of the reaction from 78.3 kJ/mol to 36.9 kJ/mol. magnet and the specimens when the temperature changes. The
Thermomagnetic analyses of natural and synthetic hematite interaction strength between the sample and the magnet is pro-
were carried out in air and in vacuum [24]. The starting sample portional to the magnetization of the sample. The facility is
consisted of commercial hematite powder (99.999% Fe2O3) with a equipped with a digital balance that has a built-in permanent
grain size of about 10 mm. It has been shown that intense reduction magnet. The steady applied magnetic field that results is 300 mT.
of hematite occurs when the experiment is performed in a vacuum, Such force is great enough to reach the saturation magnetization of
but not while the hematite is heated in air. magnetite. Synthesis and analysis of the investigated samples were
Despite the fact that there have been several studies concerning performed in a quartz mini-reactor at a temperature of 650
C. The
the reduction of hematite to magnetite, research on the issue rate of the sample's heating/cooling was 65
C/minute. Thermo-
cannot be considered sufficient, especially with regard to industrial magnetic data are represented by derivative thermomagnetic
applications such as the processing of tailings. First, the process is curves (DTMC) and integral thermomagnetic curves (TMC).
often complicated because the techniques described above are
economically ineffective through many stages and require expen- 2.4. Magnetometry measurements
sive reagents. Also, because the tailings have quite different iron
oxide particle sizes, there is a need for further in-depth study of the Measurement of magnetization as a function of the applied field
effects of various particle sizes on the process of converting was performed for the starting and transformed samples. The
30 V.P. Ponomar / Journal of Alloys and Compounds 741 (2018) 28e34

analysis was carried out at room temperature by means of a indicate a mixture of both phases.
magnetometer with Hall sensors. The magnetic field of the Although the parameters of magnetite and maghemite lattices
magnetometer varied in the range from 0.45 T to þ0.45 T. are almost the same, the thermal stabilities and Curie temperatures
of those iron oxides are distinctly different. Therefore it is possible
to clearly differentiate magnetite from maghemite with the aid of
2.5. X-ray diffraction
thermomagnetic analysis.
The mineral composition of the initial and transformed samples
3.2. Thermomagnetic analysis
was determined by X-Ray Diffraction (XRD) methods with a DRON-
3M diffractometer in filtered emission of CuKa (l ¼ 0.154184 nm).
Determination of the relationship between temperature and
Diagnostics of crystalline phases were performed by comparing the
magnetization (magnetic force) may be useful for determining the
d-spacings of the studied samples with the standards of the
number of magnetic phases in the sample, their thermal stabilities,
PCPDFWIN (PDF-2) database.
and their Curie temperatures. The thermomagnetic curves of syn-
thetic magnetite obtained by hematite reduction are shown for the
3. Results and discussion size of the particles 0.05e0.1 mm (Fig. 2a), 0.25e0.4 mm (Fig. 2b),
and 1.6e2.5 mm (Fig. 2c). Samples with other particle sizes have
3.1. X-ray diffraction similar thermomagnetic properties (data not shown). For compar-
ison, Fig. 2d shows the thermomagnetic curve of pure natural
Fig. 1 shows the X-Ray diffraction patterns of initial hematite (1) magnetite.
and transformed samples obtained by hematite reduction with the The thermomagnetic behavior of natural magnetite (Fig. 2d) is
particle sizes 0.05e0.1 (2), 0.25e0.4 (3), and 1.6e2.5 mm (4). characterized by a general decrease in magnetization with
The characteristic peaks (d-spacing) of hematite and a small increasing temperature. That is due to the decrease in the energy of
amount of quartz (d011 ¼ 3.329 Å) are identified for the initial exchange of magnetic sublattices because of the intensification of
sample. The main mineral phase of the transformed samples is thermal vibrations of atoms. The Curie temperature of natural
magnetite. Characteristic peaks (d-spacing) of the resulting magnetite, shown as a peak on the DTMC (Fig. 2d), is about 565
C,
magnetite and their comparison with the standard values for which indicates the transition from ferromagnetic to paramagnetic
magnetite and maghemite (PDF 85e1533 and 39e1346, corre- state.
spondingly) are given in Table 1. No significant difference in The thermomagnetic properties of synthetic magnetite ob-
structure was found in the magnetite obtained from hematite with tained by the reduction of hematite are quite similar to the ther-
different particle sizes. Moreover, traces of hematite are found in momagnetic properties of natural magnetite. There are slight
the sample with coarse particles (4) and in the sample with fine differences, however. When the synthetic magnetite is heated, a
particles (2) (d104 ¼ 2.686 Å and d104 ¼ 2.679 Å, respectively). slight increase in magnetization at 200
C and a slight decrease in
Note that the diffraction pattern of magnetite is close to the magnetization in the range of 200e300
C are observed (Fig. 2aec).
patterns of some other minerals with a spinel structure, such as According to literature data [27], such changes in magnetization on
maghemite (g-Fe2O3) or magnesioferrite (MgFe2O4). For instance, heating can be attributed to the effects associated with maghemite.
maghemite and magnetite have lattice parameters of 8.3515 Å and A slight increase in magnetization at 200
C can be explained by
8.397 Å, respectively, which means a slight shift of peaks to higher the transition of maghemite from the trigonal structure to the cubic
values of 2q (from magnetite to maghemite) [25]. However, the structure, which means the transition from ordered to disordered
lattice parameters obtained in our experiments (Table 1) lie be- state. Disordering of cations and vacancies in defective crystalline
tween magnetite and maghemite, making it difficult to identify the structures may lead to an increase in the magnetization of the
product of the reaction. The authors [26] supposed that the lattice mineral. The papers [28,29] showed different types of maghemite
parameter with values between magnetite and maghemite can with different cation distributions and different magnetic
characteristics.
A slight decrease in magnetization at 200e300
C can be
attributed to the transformation of maghemite into hematite.
Literature data [27] confirm that phase transformation of meta-
stable maghemite into hematite commonly occurs at approxi-
mately 350
C. The authors [30] have also proposed the formation
of maghemite without magnetite by thermal treatment of synthetic
goethite in the presence of glucose. After the second run of thermal
treatment, the resulting maghemite transforms into a weakly
magnetic hematite. In our studies, only a small part of the newly
formed magnetic phase was converted into hematite, so we can
assume the presence of a small amount of maghemite in the
transformed samples.
Curie temperatures of the resulting synthetic magnetite range
from 560 to 570
C (Fig. 2aec), which is close to the 565
C for natural
magnetite (Fig. 2d). Curie temperatures of synthetic and natural
magnetite are close to the Curie temperature of the pure stoichio-
metric bulk sample (580
C) [27]. A slight shift in the values obtained
can be explained by chemical impurities [31,32] in magnetite.

Fig. 1. XRD patterns of the initial hematite (1) and the transformed samples obtained
3.3. Magnetization measurement
by hematite reduction with particle sizes of 0.05e0.1 (2), 0.25e0.4 (3), and 1.6e2.5 mm
(4). Numbers correspond to Miller's indexes. Magnetization as a function of the time of synthesis,
 V.P. Ponomar / Journal of Alloys and Compounds 741 (2018) 28e34 31

Table 1
Characteristic peaks (d-spacing in Å) of resulting magnetite and standard d-spacing for magnetite (PDF 85e1533) and maghemite (PDF 39e1346).

hkl Magnetite obtained from Magnetite obtained from Magnetite obtained from Standard d-spacing for magnetite Standard d-spacing for maghemite
hematite 0.05e0.1 mm, Å hematite 0.25e0.4 mm, Å hematite 1.6e2.5 mm, Å (85e1533), Å (39e1346), Å

111 n/d 4.815 4.789 4.8480 4.8220

220 2.950 2.949 2.951 2.9687 2.9530
311 2.526 2.528 2.514 2.5317 2.5177
400 2.092 2.092 2.092 2.0992 2.0886
333 1.613 1.613 1.608 1.6160 1.6073
440 1.481 1.481 1.479 1.4843 1.4758
Lattice 8.370 8.371 8.363 8.397 8.3515
parameter, Å

magnetization as a function of the applied field, and magnetization carbon monoxide. The saturation magnetization values of the
as a function of particle size were measured to characterize the samples obtained by grinding and re-reduction are shown in
process of hematite reduction to magnetite. The magnitudes of the Fig. 3(2).
saturation magnetization of synthetic magnetite obtained by he- Measurement of magnetization as a function of the applied field
matite reduction are shown in Fig. 3(1). After that experiment, the was carried out at room temperature for synthetic magnetite ob-
samples with particle sizes in the range of 0.25e2.5 mm were tained by hematite reduction with particle sizes of 0.05e0.1,
ground to a uniform particle size of less than 0.07 mm. After they 0.25e0.4, and 1.6e2.5 mm (Fig. 4a) and natural magnetite (Fig. 4b).
were ground, the samples were again reduced in an atmosphere of As shown in Fig. 4, synthetic magnetite obtained by hematite

Fig. 2. Thermomagnetic curves of synthetic magnetite obtained by hematite reduction with particle sizes of 0.05e0.1 mm (a), 0.25e0.4 mm (b), and 1.6e2.5 mm (c). The ther-
momagnetic curve of natural magnetite is shown in (d).
32 V.P. Ponomar / Journal of Alloys and Compounds 741 (2018) 28e34

size. Indeed, the variation of the saturation magnetization of

magnetite may decrease due to the pinning effect, which means the
breaking of a large number of bonds of surface atoms. In addition to
the effect of size, it should be considered that the measurement of
magnetization (in the case of mass magnetization) is applied to a
certain mass of the test sample. Consequently, absorbed water,
organic residual materials, and other impurities can significantly
affect the magnitude of mass saturation magnetization.
An increase in particle size of the initial hematite produced a
decrease in saturation magnetization of the resulting samples from
80 to 60 Am2/kg, which indicated incomplete transformation of
hematite into magnetite. That was also confirmed by the XRD
pattern of a transformed sample of grain size 1.6e2.5 mm (Fig. 1),
which contained a small amount of residual hematite.
The incomplete conversion of hematite to magnetite was also
confirmed by an additional experiment. At first, samples with
Fig. 3. Dependence of the saturation magnetization of the resulting samples on the particle sizes greater than 0.25 mm that exhibited incomplete he-
size of the particles of the initial material (1) and the saturation magnetization of the matite transformation into magnetite were ground to a size of less
samples additionally reduced after grinding to 0.07 mm (2). than 0.07 mm. Then the ground samples were again reduced in the
atmosphere of carbon monoxide at 500
C for 40 min. As shown in
Fig. 3(2), the saturation magnetization of the samples increased and
reduction has a higher coercivity and remanence in comparison to
thus corresponded to the complete transformation of hematite into
natural magnetite. Moreover, the parameters of the hysteresis loops
magnetite. Therefore, the reduction of hematite with particle sizes
do not differ significantly in synthetic magnetite with different
from 0.4 to 2.5 mm was incomplete, indicating a deceleration of the
particle sizes.
reaction by the formation of a layer of magnetite on the surfaces of
The saturation magnetization of obtained samples increased to
the hematite particles. The maximum thickness of the magnetite
60e80 Am2/kg in comparison with the initial magnetization of <1
layer formed in that reaction was about 0.2 mm, because only
Am2/kg. That was due to the conversion of hematite to magnetite;
samples with a particle size of less than 0.4 mm had completely
that is, the saturation magnetization in this case was proportional
transformed into magnetite.
to the amount of magnetite in the resulting samples. However, the
Hematite with particle sizes of 0.25e0.4 and 1.6e2.5 mm was
bulk saturation magnetization of pure magnetite is 92 Am2/kg [27].
reduced in the atmosphere of carbon monoxide at 600
C for
Such a value is rarely achieved in the synthesis of magnetite. Miz-
10e60 min. The saturation magnetization of the resulting samples
utani et al. [17] found that magnetite nanoparticles prepared by
increased during the first 30 min for smaller (0.25e0.4 mm) par-
hydrothermal synthesis had a saturation magnetization of 80 Am2/
ticles and for the first 40 min for larger (1.6e2.5 mm) particles
kg. Magnetite nanoparticles obtained from tailings by means of
(Fig. 5).
ultrasonic chemical co-precipitation revealed a saturation magne-
Increasing the reduction time to 60 min did not change the
tization of 75 Am2/kg [10]. The saturation magnetization of
saturation magnetization of the resulting samples. For smaller
magnetite nanoparticles synthesized by microwave-solvothermal
particles, that was due to the complete conversion of hematite to
synthesis in Ref. [33] was 41 Am2/kg. Generally, the authors
magnetite. For larger particles, it can be explained by the deceler-
assumed that the difference between the values obtained in their
ation effect caused by a layer of magnetite forming on the surface of
studies and the corresponding bulk magnetization of magnetite (92
hematite particles. Thus, the optimal reduction time of hematite to
Am2/kg) could have been associated with differences in particle

Fig. 4. The dependence of magnetization on the applied field for synthetic magnetite obtained from hematite with particle sizes of 0.05e0.1 mm (1), 0.25e0.4 mm (2), 1.6e2.5 mm
(3) is shown in (a). The dependence of magnetization on the applied field for natural magnetite is shown in (b).
 V.P. Ponomar / Journal of Alloys and Compounds 741 (2018) 28e34 33

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