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Synthesis of Magnetite Hydrosols in Inert Atmosphere

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DOI: 10.13140/RG.2.1.4510.1600

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ISSN 1061933X, Colloid Journal, 2013, Vol. 75, No. 4, pp. 483–486. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © S.V. German, O.A. Inozemtseva, A.V. Markin, Kh. Metvalli, G.B. Khomutov, D.A. Gorin, 2013, published in Kolloidnyi Zhurnal, 2013, Vol. 75, No. 4,
pp. 534–537.

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COMMUNICATIONS

Synthesis of Magnetite Hydrosols in Inert Atmosphere

S. V. Germana, O. A. Inozemtsevaa, A. V. Markina, Kh. Metvallia, G. B. Khomutovb, and D. A. Gorina
a
Chernyshevskii Saratov State University, Astrakhanskaya ul. 83, Saratov, 410012 Russia
b
Moscow State University, Moscow, 119899 Russia
Received October 30, 2012

Abstract—A setup is described for magnetite hydrosol synthesis in inert atmosphere via coprecipitation of bi
and trivalent iron salts in the presence of a base with the formation of nanoparticles having desired sizes and
chemical composition. The size of nanoparticles is estimated based on analysis of lightscattering and trans
missionelectronmicroscopy data. The chemical composition of magnetite nanoparticles is monitored by
Raman spectroscopy.
DOI: 10.1134/S1061933X13040042

INTRODUCTION problem of contemporary colloid chemistry. The

Today, the synthesis of magnetic nanostructures
with reproducible parameters is a pressing problem,
solution of which is of importance for biomedicine
and electronics [1, 2]. Nanoparticles of iron oxides are
widely used for creation of planar nanocomposite
coatings [3–6] and hollow polyelectrolyte microcap
sules [7–9]. The introduction of iron oxide nanoparti
cles into polymer matrices allows directionally chang
ing the physical properties of nanocomposites includ
ing providing their sensitivity to electromagnetic fields
[10–13].
The physical properties of the resulting nanocom
posites are determined by the volume fraction [10, 12],
size, and chemical composition of magnetic nanopar
ticles [11].
Different chemical methods can be used for pro
ducing magnetic nanoparticles, including synthesis in
microemulsions [14], sol–gel synthesis [15],
sonochemical reactions [16], hydrothermal reactions
[17], hydrolysis and thermolysis of precursors [18],
etc. The synthesis of such systems is a quite compli
cated process that involves many factors.
Chemical precipitation from solutions of bi and
trivalent iron salts in the presence of a base [19–25] is
the simplest method for synthesis of magnetic nano
particles. The primary problem is the choice of a
reproducible synthesis procedure that could be easily
automated and adapted for largescale production.
Another problem of no less importance is the determi
nation of experimental conditions that would ensure
the synthesis of the monodisperse nanoparticles of a
required size. Although precipitation of iron oxides
from solution is quite simple to realize, what it results
in is affected by a number of factors; therefore, the
development of a procedure for the production of iron
oxide nanoparticles with reproducible parameters,
such as size and chemical composition, is an urgent
results of detailed investigation of magnetite hydrosols
obtained by coprecipitation of bi and trivalent iron
salts in the presence of a base are presented in this
work.
EXPERIMENTAL
Synthesis of Aqueous Solution of Colloidal Magnetite
Stabilized with Citrate Ions
Iron(III) chloride hexahydrate (99.8%, Aldrich),
iron(II) chloride tetrahydrate (99.8%, Aldrich),
sodium hydroxide (99.8%, Fluka), and citric acid
(99.8%, Aldrich) were used to produce magnetite
nanoparticles. All reagents were used as received.
Magnetite nanoparticles were synthesized in the reac
tion setup presented in Fig. 1.
Magnetite nanoparticles were obtained by chemi
cal precipitation from a mixed solution of bi and
trivalent iron salts. An initial solution of reagents was
prepared by dissolving FeCl3 ⋅ 6H2O (0.65 g) and
FeCl2 ⋅ 4H2O (0.24 g) in water (12 mL) under stirring
with a magnetic stirrer at room temperature. A 0.1 M
NaOH solution (100 mL) was placed into the
reaction chamber. For subsequent colloid stabiliza
tion, a 20mg/mL solution (100 mL) of citric acid
was preliminarily prepared. Nitrogen was bubbled
through the chambers with the solution of the salts,
stabilizing solution, and the reaction chamber con
taining sodium hydroxide for 10 min to remove dis
solved oxygen (Fig. 1, channel 1). Then, the solution
of iron salts was injected under nitrogen pressure for
several seconds into the sodium hydroxide solution
under rigorous stirring (Fig. 1, channel 2) and the mix
ture was stirred for 30 min under nitrogen. The result
ing black precipitate of magnetite nanoparticles was
deposited with the use of a permanent magnet, and the
supernatant was poured out by displacing it with nitro
gen into a dump chamber (Fig. 1, channel 4). Then, a

483
484 GERMAN et al.

Nitrogen
1
3
4 2

5 5 5

Reaction Washing Salt

Discharge
chamber solution solution

Fig. 1. Fourchamber setup for synthesis of magnetite hydrosols: (1) channel of nitrogen supply into chambers, (2) channel of
iron salt solution supply into sodium hydroxide solution, (3) channel of washing solution supply, (4) discharge channel, and (5)
valves connected with the atmosphere to develop pressure gradients.

20mg/mL citric acid solution (25 mL) was added to
the precipitate under pressure of nitrogen under stir
ring (Fig. 1, channel 3) and stirred once again. The
procedure was repeated four times (until the citric acid
solution was consumed). Note that, due to the stabi
lizing effect of citrate ions, the particle size and colloid
sedimentation rate decrease in the course of washing.
In the last washing cycle, 5–10 mL of the liquid was
kept and the system was intensely stirred. The resulting
colloidal solution of magnetic nanoparticles was
placed into a dialysis bag, immersed in a vessel with
water (1–1.5 L), and dialyzed for 4 days under gentle
stirring. All processes of reagent mixing and washing
were performed under nitrogen at a pressure regulated
in the channels with a system of valves. The concentra
tion of the resulting magnetic colloid determined by
the dry residue method was 5 mg/mL.
Measurement of ζ Potential
The ζ potential and sizes of magnetite hydrosol
particles were measured with a Zetasizer NanoZ ana
lyzer (Malvern Instruments Ltd, United Kingdom).
Transmission Electron Microscopy (TEM)
Droplets of an aqueous colloidal solution of mag
netite were placed onto carbon filmcoated copper
grids. The measurements were performed with a Zeiss
EM 912 Omega transmission electron microscope
(Zeiss, Germany). Nanoparticle size distributions in
the samples were determined by analyzing TEM
images using the Image J software package [26].
Raman Spectroscopy
Raman spectra were recorded with an NTEGRA
Spectra combined system (NTMDT, Russia) using a
solidstate laser operating at a wavelength of 473 nm
and a point power of 3.5 mW. The measurements were
carried out using a ×100 objective with a numerical
aperture of 0.90 and a spatial resolution of ~1 µm. The
exposure time was 60 s.
RESULTS AND DISCUSSION
Synthesis of Magnetite Nanoparticles
Chemical precipitation of iron oxides from mixed
solutions of bi and trivalent iron salts in the presence
of a base yields rather large amounts of nanoparticles
[27, 28]. Magnetite nanoparticles are formed by the
following chemical reaction [29–31]:
Fe2+ + 2Fe3+ + 8OH– = Fe3O4 + 4H2O.
Magnetite nanoparticles were obtained in a pH
range of 9–14 at a molar concentration ratio of Fe3+ :
Fe2+ = 2 : 1 in the absence of oxygen. To prevent nano
particles from aggregation, their surface was coated
with citric acid molecules. The ζ potential of magne
tite nanoparticles was –30 ± 2 mV at pH 6.5 ± 0.1.
The size distribution of nanoparticles was studied
by the methods of dynamic light scattering (Fig. 2) and
TEM (Fig. 3), which yielded average nanoparticle
sizes of 12 ± 3 and 6 ± 2 nm, respectively. The nanopar
ticle size determined by dynamic light scattering was
larger than that obtained from analysis of TEM
images. This is explained by the fact that, in the former
case the nanoparticle sizes are measured in an aqueous
medium; therefore, the result obtained corresponds to
the particle hydrodynamic radius. Analysis of TEM
images (Fig. 3) showed that nanoparticles are quite
monodisperse and almost spherical.
Raman spectra of magnetite samples were recorded
with a spectrometer of the Probe Nanolaboratory
NTEGRA Spectra. The spectra presented in Fig. 4
exhibit two main peaks at 670 and about 700 cm–1
attributed to magnetite [32] and maghemite [33],
respectively. Magnetite alone is present in sample 1
synthesized under nitrogen, while sample 2 is a mix
ture of magnetite and maghemite, which is formed
during magnetite oxidation in air.
CONCLUSIONS
Magnetic nanoparticles have been synthesized by
coprecipitation of bi and trivalent iron salts in the
presence of a base in a setup that allows one to main

COLLOID JOURNAL Vol. 75 No. 4 2013

 SYNTHESIS OF MAGNETITE HYDROSOLS IN INERT ATMOSPHERE 485

Particle fraction, % Intensity

670
700
30 1.0
1
20 0.8

0.6
10 2
0.4
0
0.1 1 10 100 1000 10000 0.2
Size, nm
0
Fig. 2. Nanoparticle size distribution obtained by dynamic 200 300 400 500 600 700 800
light scattering. Wavenumber, cm–1
Fig. 4. Raman spectra of colloidal solutions: (1) magnetite
(670 cm–1) and (2) mixture of magnetite (670 cm–1) and
maghemite (700 cm–1).

tain an inert atmosphere and use the pressure of a

nitrogen flow for controlling transport of liquids
between chambers.
It has been shown that it is preferable to synthesize
magnetite nanoparticles under nitrogen, because, in
this case, the samples contain only magnetite and are
free of maghemite, which results from oxidation of
Fe(II) ions in solution and in magnetite nanoparticles
in air.

ACKNOWLEDGMENTS
This work was supported by the Russian Founda
tion for Basic Research, project no. 110812058
OFIM2011.

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Translated by K. Aleksanyan
COLLOID JOURNAL Vol. 75 No. 4 2013