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 Thermophysics and Aeromechanics, 2015, Vol. 22, No. 4

Methods of magnetic fluid synthesis (review)*

S.A. Novopashin, M.A. Serebryakova, and S.Ya. Khmel

Kutateladze Institute of Thermophysics SB RAS, Novosibirsk, Russia

E-mail: khmel@itp.nsc.ru

(Received October 4, 2014; in revised form December 15, 2014)

This is a review of the current state of research in the field of the methods of magnetic fluid synthesis. It focuses
on analysis of the methods that use magnetic nanoparticles in an inert coating.

Key words: magnetic fluid, colloid solution, nanoparticles in carbon coating.

Introduction
The magnetic fluid (MF) is a stable colloid solution based on magnetic nanoparticles
in a basic fluid. The magnetic fluid is also called ferromagnetic fluid, magnetic nanofluid,
magnetic liquid or ferrofluid (Joseph, Mathew, 2014; Genc, Derin, 2014; Vekas et al., 2009;
Odenbach, 2009). First MFs were synthesized in the mid 60’s of the 20th century (Papell,
1965; Rosensweig, Kaiser, 1967). Since that time, the intensive study of MFs’ properties
started, as well as a search for the new methods of MF synthesis and areas of their practical
use. Magnetic fluids have a unique combination of fluidity and ability to interact with
the magnetic field; therefore, they are of a great interest for practical applications. MFs
are widely used in the energy sector (intensification of heat transfer, magnetic seals, magnetic
lubricants) (Joseph, Mathew, 2014; Odenbach, 2009; Orlov et al., 1976); for information
storage and processing (Braginsky, Timofeev, 1987); in ecology (collection of oily
contaminants in water, removal of organic waste from water with subsequent catalytic
processing) (Baranov, Gubin, 2009; Kaur et al., 2014); in medicine (targeted drug delivery,
staining for magnetic resonance imaging, hyperthermia) (Joseph, Mathew, 2014; Vekas et al.,
2009; Odenbach, 2009; Baranov, Gubin, 2009; Faraji et al., 2010; Laurent et al. 2011;
Mahmoudi et al., 2011; Sharifi et al., 2012); mineral concentration (Joseph, Mathew, 2014).
The fundamental studies of MF properties are associated with the study of their aggregate
stability, magnetic hydrodynamics, thermal physical properties, dynamics of magnetization and
relaxation of the magnetic moments in the single-domain ferromagnetic or ferrimagnetic
particles. Let us note one of the first studies on the analysis of the physical properties of MF
(Shliomis, 1974).
To date, many physical phenomena in MFs were understood and described, the areas
of their practical use were expanded, and new methods of synthesis were created due to
the development of nanotechnologies, new generation of analytical instruments and
progress in computer technology. An interest in the study and application of magnetic

*
This research was was financially supported by the Russian Ministry of Education and Science. Project Identifier:
RFMEFI60414X0004.

© S.A. Novopashin, M.A. Serebryakova, and S.Ya. Khmel, 2015

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S.A. Novopashin, M.A. Serebryakova, and S.Ya. Khmel

fluids continues growing. Over the past five years, the world's leading journals have
published dozens of review papers (many of them are quoted in this work).
The important objectives in production of MFs are the protection of colloid particles from
oxidation and prevention of their agglomeration and coagulation in both the process
of production and transformation of particles into the colloidal state in the carrier liquid. For some
applications, for instance, in medicine, it requires eliminating the possibility of interaction
between the magnetic particle material and environment. These problems are solved in two
ways. In most methods of MFs production, at the step of nanoparticles synthesis, the surfac-
tants are used. The second method is the synthesis of magnetic nanoparticles in a coating,
which does not allow the particles to approach at the distance, when it is impossible to divide
them by ultrasound treatment.
The methods of synthesis of magnetic nanoparticles in a carbon coating and the use
of these nanoparticles for the synthesis of MF are considered in detail in the present review.
Other methods of the synthesis of nanoparticles in other inert coatings will be distinguished
specially. To complete the picture, the general properties of MFs are presented, and the modern
methods for the synthesis of MF based on the review of recently published papers are considered.

1. General properties of magnetic fluids

The magnetic fluid consists of dispersed solid magnetic phase, dispersion medium,
and stabilizer. The properties of magnetic fluid are determined by a set of characteristics
of constituent components, varying which we can change the properties of MFs in a wide range.
Due to their small size (5−15 nm), the magnetic nanoparticles are in vigorous Brownian
motion, which ensures the sedimentation stability of magnetic colloids and their uniform
distribution in the liquid volume. The aggregate and spatial stability of the colloidal systems
based on magnetic particles requires appearance of repulsive forces between the particles
caused by their convergence. This can be achieved in two ways: either by introducing a certain
amount of stabilizer (surfactant) into the MF or by the use of an ionic liquid as a carrier.
The structure of the magnetic fluid stabilized by surfactant is shown in Fig. 1 (Odenbach, 1998;
Sharifi et al., 2012). Usually, the substances consisting of the polar organic molecules, whose
structure is characterized by a short functional group (alkali, acid, etc.) and long tail chain
(hydrocarbon, fluorocarbon, etc.), are used as the surfactants. Oleic acid is often used as
a classical stabilizer for magnetic fluids.
The stable magnetic fluids contain the particles of 5−15 nm. If the particle size
exceeds 30−40 nm, these are the magnetorheological fluids. Their feature is the sharp increase
in the viscosity under the action of magnetic field, and in the strong fields, they can harden
completely. This property allows us to attribute them to the so-called “smart” materials with non-
linear response to an external stimulus (de Vicente et al., 2011; Lopez-Lopez et al., 2012).
The magnetic particles for MF are single-domain, and for magnetorheological fluids they are
polydomain. The magnetic fluids are classified by the size of magnetic particles in (Joseph,
Mathew, 2014; Lopez-Lopez et al., 2012). It should be noted that the synthesis, investigation, and
use of magnetic fluids began to develop intensively since 1960s, i.e., long before the appearance
of the term “nanotechnology” (Joseph, Mathew, 2014; Genc, Derin, 2014; Vekas et al., 2009;
Odenbach, 2009). Despite the name, the ferromagnetic fluids (MF) do not demonstrate
the ferromagnetic properties because they do not retain residual magnetization, when the external
magnetic field disappears. Therefore, MFs are paramagnetic, and they are often called super-
paramagnetic because of the high magnetic susceptibility.
Since magnetism is a manifestation of the collective interaction of atomic magnetic
dipoles, then it is strongly influenced by the temperature and spatial factors. When the size
of ferromagnetic or ferrimagnetic particle becomes less than the critical value, the particle moves
from the polydomain to the single-domain state. The critical size of a single-domain particle

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Fig. 1. Structure of magnetic fluid stabilized by a surfactant.

depends on its shape, temperature, and crystal magnetic anisotropy. With a further reduction
of the particle size, the thermal energy is sufficient to randomize the magnetic dipoles within
a short period of time (Faraji et al., 2010; Jeong et al., 2007). Such small particles have no
intrinsic magnetic moment without the external field, but in its presence, they enhance
the magnetic field greatly. These particles are similar to the paramagnetic atoms, but with
a very high intrinsic magnetic moment. They are superparamagnetic, and lately they are used
for the synthesis of magnetic fluids (Faraji et al., 2010; Laurent et al., 2011; Mahmoudi et al.,
2011; Jeong et al., 2007). Classification of magnetic fluids by the size of used nanoparticles is
presented in Fig. 2 (Faraji et al., 2010; Jeong et al., 2007).
Efficiency of technologies for the synthesis of MF is estimated by the achievement
of the main physical characteristics: colloidal stability during a long time, saturation magneti-
zation, viscosity, working temperature range. The qualitative magnetic fluids remain stable
during 2−5 years and have good fluidity combined with magnetic properties.
Ferromagnetic or ferrimagnetic metals and metal oxides are most often used as
the dispersed magnetic phase. To synthesize MFs, the following metals are used: Fe, Co, Ni,

Fig. 2. Classification of magnetic fluids by the size of nanoparticles.

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S.A. Novopashin, M.A. Serebryakova, and S.Ya. Khmel

Table 1
Ferruginous magnetic materials (Kaur et al., 2014)

Chemical formula Symbol and name Crystalline structure and magnetic properties
Fe α-Fe Crystalline phase with volumetric-centered cubic
lattice.
γ-Fe Crystalline phase with face-centered cubic lattice.
amorphous No crystalline phase.
3+
Fe2O3 α-Fe2O3 (haematite) All ions Fe have octahedral coordination.
γ-Fe2O3 (maghemite) γ-Fe2O3 has cation-deficit АВ2О4 spinel, atoms of А and
В metals are in tetrahedral and octahedral states,
respectively.
Fe3O4 Magnetite Cubic spinel Fe3O4. Ferrimagnetic at the temperature
below 858 K.
2+
FeO Wustite Cubic Fe oxide. Antiferromagnetic
(Тс = 185 K) in the condensed state.
Fe2O3·H2O α-FeOOH (goethite) Antiferromagnetic (Тс = 393 K) in the condensed state.
β-FeOOH (akaganeit) Paramagnetic at 300 K.
γ-FeOOH (hydrohaematite) Paramagnetic at 300 K.
δ-FeOOH (feroxigite) Ferrimagnetic.

and Gd; nitrides of these metals (such as FexN); metal oxides (especially, magnetite Fe3O4 and
maghemite γ-Fe2O3); bimetallic particles of alloys (Ni-Fe, Fe-Pt, Fe-Co, and Sm-Co). Ferrites,
i.e., chemical compounds of iron oxide Fe2O3 and oxides of other metals with special magnetic
properties (ferrimagnets, see Fig. 3) are also used. Ferrites-spinels with chemical formula
MFe2O4, where letter M indicates metal (MnFe2O4, CoFe2O4, NiFe2O4, ZnFe2O4, and Li2Fe2O4),
and ferrites-garnets with chemical formula MFe5O12 are distinguished (Joseph, Mathew, 2014;
Genc, Derin, 2014; Kaur et al., 2014; Faraji et al., 2010). Although metals have the highest
saturation magnetization, they are very sensitive to oxidation, especially in a highly dispersed
state. Therefore, nanoparticles of ferrites, including magnetite Fe3O4 = FeFe2O4, are most often
used as the dispersed phase, and magnetite is most often used among the ferrites. Table 1
prepared on the basis of materials of (Gubin et al., 2005) presents the data on ferrous materials
used in MF.
The magnetic properties of magnetic fluids are determined by the weight content of solids,
which can be 25 %. The choice of magnetic materials is quite broad, but production of colloidal
suspensions with sufficient stability requires good compatibility of nanoparticles with a surfactant
and carrier liquid, and this reduces the range greatly.
An important component of magnetic fluid is a carrier liquid, which can be polar or non-
polar. The function of the carrier liquid is to provide an environment, where the particles
of magnetic material are “suspended”. The choice of the liquid depends significantly on MF
application. To date, a wide spectrum of carrier liquids is used: water, ethanol, pentanol,
glycols, perfluoropolyethylens, synthetic complex esters, transformer oils, freons, styrene,
methyl ethyl ketone, naphtha, various synthetic
hydrocarbons and organic solvents, such as heptane,
benzene, toluene, mineral and organic-silicone oils,
vegetable oils (sunflower, rapeseed, castor oil) and
silicone oils (Joseph, Mathew, 2014; Genc, Derin,
2014).

Fig. 3. Ferrimagnets. Dark spot in the center ⎯ cobalt ferrite,

coating ⎯ silicon dioxide (Odenbach, 2009).
Picture obtained at the electron microscope.

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The boiling point, vapor pressure at increased temperatures, and freezing point are
the important parameters for the choice of such a liquid. The carrier liquid must not react
chemically with the magnetic phase and materials used in the device.
The last necessary component of MF is a stabilizer of magnetic nanoparticles in
the carrier liquid. In a volume the nanoparticles are subjected to intensive Brownian motion
and can collide. The substance-stabilizer is required to prevent coagulation of magnetic
nanoparticles at collision at the expense of magnetic forces or Van der Waals forces and
prevent this collision in general. Stabilizers also prevent oxidation of the surface of magnetic
nanoparticles. Usually, the stabilizers are surfactants or polymers, adsorbed physically or
chemically on the nanoparticle surface. Oleic acid is the most common surfactant, used
to stabilize the magnetic nanoparticles, obtained by the conventional chemical methods based
on rapid neutralization of salts of di- and trivalent iron by an excess of aqueous solution of alkali.
The wine and citric acids, derivatives of fatty acids, sodium oleate, dodecylamine, sodium
carboxymethylcellulose, and other chemicals are also used for these purposes (Joseph,
Mathew, 2014; Genc, Derin, 2014; Vekas et al., 2009; Sharifi et al., 2012; Barreto, 2012).
The use of certain surfactants is defined by functional properties of MFs. Thus, the chemical
substance used to stabilize nanoparticles in the magnetic fluids for the biological and medical
purposes are shown in Table 2.

2. Classifications of the methods for magnetic nanoparticle synthesis

As was already noted, the process of magnetic fluid preparation consists of two main
stages: preparation of magnetic particles of the desired size and their stabilization
in a carrier liquid. As for the synthesis of magnetic nanoparticles, many articles and
reviews are published now; these particles are widely used not only for MF preparation,
but also in magnetic materials used in the devices for magnetic data recording and storage,
catalysis, electronics, electrical engineering, etc. (Joseph, Mathew, 2014; Baranov, Gubin,
2009; Kaur et al., 2014; Faraji et al., 2010; Mahmoudi et al., 2011; Jeong et al., 2007; Wen,

Table 2
Substances, which can be used for stabilization of magnetic fluid applied for biomedical purposes
(Genc, Derin, 2014)

Polymer/molecule Characteristics
Polyethylene glycol Noncovalent fixation of PEG on the surface increases biological compatibility.
(PEG)
Dextran Stabilizer of colloid solutions.
Polyvinylpyrrolidone Stabilizer of colloid solutions.
(PVP)
Fatty acids Colloid stability, end functional carboxyl groups.

Polyvinyl alcohol (PVA) Prevents particle coagulation exciting monodispersed particles.

Polyacrylic acid Used successfully in cellular biology.
Polypeptide −
Phosphorylcholine Stabilizer of colloid solutions. Fills the surface insufficiently, facilitating particle
coagulation.
Chitosan Natural cation linear polymer, widely used as the system for delivery of nonviral
genes; biologically compatible, hydrophilic, used in agriculture, food industry,
medicine, biotechnologies, textile branch, polymer branch, and for water cleaning.
Gelatine Used as a gelling agent, a hydrophilic emulsifier; biocompatible, natural polymer.

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S.A. Novopashin, M.A. Serebryakova, and S.Ya. Khmel

Krishnan, 2011; Kharisov et al., 2012; Issa et al., 2013; Canfarotta, Piletsky, 2014; Gubin,
2009; Frey et al., 2009; Teja, Koh, 2009).
There are several classifications of the methods for magnetic nanoparticle synthesis.
In some studies (Faraji et al., 2010; Teja, Koh, 2009), classification is made by the phase,
where the magnetic nanoparticles form: liquid-phase, gas-phase and solid-phase synthesis.
In the liquid phase, the magnetic nanoparticles are synthesized by the methods of code-
position, microemulsion, thermal decomposition, chemical reduction, hydrothermal or
solution-thermal methods as well as acoustic-chemical and microwave methods. In the gas
phase, they are produced by the methods of chemical gas-phase deposition, arc discharge, and
laser pyrolysis, and in the solid phase, they are obtained through combustion and annealing
(Faraji et al., 2010). Another classification separates the synthesis methods by scientific
disciplines as physical, chemical, and even biological (Mahmoudi et al., 2011; Kharisov et al.,
2012; Abhilash et al., 2011). In (Mahmoudi et al., 2011), classification is given for
the synthesis of superparamagnetic particles of iron oxide (i.e., magnetite, hematite,
maghemite). However, it is clear that it is suitable for magnetic nanoparticles of different
composition, as they can be synthesized analogously. According to this work, the magnetic
nanoparticles are made mainly by the chemical methods, the physical methods are used ten
times less, and the biological ones are used hundred times less (see Fig. 4). The chemical
methods are used in the liquid phase and include the method of codeposition and
the hydrothermal method, microemulsion, acoustochemical and thermal decomposition.
The physical gas-phase methods include: spraying, gas-phase deposition, laser ablation and
pyrolysis, and the method of ball mill grinding is attributed to the solid-phase methods
(Mahmoudi et al., 2011). In (Kharisov et al., 2012), the condensation method and nano-
dispersion of a compact material are attributed to the physical methods of magnetic
nanoparticle synthesis. Here, ball mill grinding of a volumetric compact material is called
nanodispersion, and the condensation method involves formation of nanoparticles from the gas
(vapor) phase; at that, the method of heating for evaporation is not important: thermal, electric
arc, laser or plasma ones.
The methods for preparing the nanoparticles of magnetic material can also be divided
into two groups. The first group includes the methods based on obtaining nanoparticles by
grinding the solid materials, the second one includes the opposite methods based on
nanoparticle assembly of atoms, ions, and molecules (Baranov, Gubin, 2009). In English these
approaches to the production of magnetic nanoparticles are called the “top-down” and “bottom-
up” (Joseph, Mathew, 2014; Canfarotta, Piletsky, 2014; Gubin, 2009). In comparison with
the methods of magnetic nanoparticles production by the principle of grinding (e.g., crushing
the solid materials in the ball mills), the concept of “bottom-up” assembly has a larger number
of opportunities to control the size, shape, composition, structure, self-organization processes,
and physical properties of nanoparticles. All the above methods apply simultaneous synthesis
and dispersion of nanoparticles in a carrier liquid, and this excludes such processing stages as
drying, storage, transportation and dispersion of magnetic nanoparticles (Joseph, Mathew, 2014).
This process minimizes agglomeration of particles and generates uniformly dispersed
particles in the carrier medium (Li et al., 2009). Its disadvantages are the presence
of impurities, for instance, due to unreacted reagent residues and the products of material
abrasion in the ball mills at grinding (nanodispersion) the compact material.

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Fig. 4. Distribution of publications on the methods of MF synthesis in journals by scientific disciplines

(Mahmoudi et al., 2011).

3. The methods of magnetic fluid synthesis

Historically, the first method for the synthesis of magnetic nanoparticles and simu-
ltaneous synthesis of stable magnetic fluid was the method of grinding the solid materials
in the ball mills. In the mid 60s of the last century, the first stable magnetic fluid was made by
grinding magnetite Fe3O4 in a ball mill with the addition of a mixture of oleic acid and heptane
(US Patent 3215572 A, 1965). This MF was stable for six months. The main disadvantage
of this method is a very long time of MF production: from several days to several months, and
as a result, the low productivity. Other disadvantages are as follows: contamination of magnetic
fluid by the product of ball abrasion and a wide spread of particles by size (Aleksashkin et al.,
2010). However, this method was used for a long time and it was improved, so, despite
the shortcomings, it is still in use. In (Hosseini et al., 2012), the MF was obtained from
the nanoparticles of cobalt oxide, when grinding the initial cobalt oxide powder with a particle
size of 50 nm in a ball mill in the solution of liquid paraffin and oleic acid during five hours.
This MF was stable, and the average particle size was 21 nm. This method of magnetic
nanoparticle synthesis is the one-step physical “top-down” method, carried out in the solid
phase.

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The method of chemical co-deposition is considered the most common and easiest method
for the synthesis of magnetic nanoparticles (Joseph, Mathew, 2014; Baranov, Gubin, 2009; Faraji
et al., 2010; Mahmoudi et al., 2011; Kharisov et al., 2012; Canfarotta, Piletsky, 2014; Teja, Koh,
2009; Aleksashkin et al., 2010). The method of chemical co-deposition usually involves
the deposition of Fe3+ and Fe2+ salts in the ratio of 2 : 1 in the water medium, using a strong alkali
such as NaOH and KOH in the inert atmosphere and at low temperatures (the so-called Massart
method (Baranov, Gubin, 2009; Canfarotta, Piletsky, 2014)). In general, the chemical reaction is
2+ 3+ 2+ 2+ 2+ 2+ 2+
as follows: M + 2Fe + 8OH¯ → MFe2O4+ 4H2O, where M can be Fe , Mn , Co , Cu , Mg ,
2+ 2+
Zn , and Ni . The nanoparticles of iron oxides (magnetite Fe3O4 or maghemite γ-Fe2O3) and
ferrites can be obtained in this way (Faraji et al., 2010). In particular, magnetite is produced
in reaction FeCl2 + 2FeCl3 + 8NaOH → Fe3O 4 + 8NaCl + 4H 2O. Ten-percent solutions
of FeCl2·4H2O and FeCl3·6H2O were mixed at 70 °С, and 10-% solution of sodium hydroxide
was added there in a large excess at constant mixing. To obtain a fine deposit, it is necessary
to limit the growth of particles, which is achieved by intense stirring the solutions. This reaction
3+ 2+
was carried out at salt solution ratio of Fe / Fe = 2/1 in order to obtain magnetite of desired
composition: 31 % of FeO (wustite) and 69 % of γ-Fe2O3 (maghemite). Replacement of sodium
hydroxide (NaOH) by ammonium hydroxide (NH4OH, 25 percent) allowed us to organize
the milder conditions of salt co-deposition, which facilitated the formation of FeO·Fe2O3 deposit
with a certain ratio of oxides in the reaction. As it was turned out later, the experimental
technique of Fe3O4 magnetic nanoparticle production is so simple that now the experiment is
a demonstration, and it is included in some laboratory courses of inorganic chemistry (Baranov,
Gubin, 2009). The advantages of this method are its simplicity, short time of synthesis, relatively
high efficiency, low temperature of the process and, what is important from the point
of environmental perspective, the use of water as a solvent. The method allows the synthesis
of the particles with the size of 3−20 nm. The temperature of solution, pH, and ratio between
the salts of bivalent and trivalent iron affect the particle size. The disadvantages of this method
are the risk of oxidation of Fe3O4 particles to Fe2O3 (therefore, the synthesis process is carried out
in the atmosphere of argon or nitrogen), poor control of the particle shape, and broad size
distribution. To obtain the monodisperser particles, it is suggested to use the following method:
to organize short explosive nucleation followed by the slow and controlled growth of particles.
Sometimes this method of co-deposition is called the method of “chemical condensation”
(Baranov, Gubin, 2009). It is widely used now (Gomes et al., 2011; de Matteis et al., 2012; Wu,
Gao, 2012; Dietricha et al., 2012).
The methods of hydrolysis and condensation of metal alkoxides or alkoxide pre-
cursors, leading to dispersion of oxide particles in the sol are called the sol-gel methods.
Then, this sol is dried or gelled without a solvent. Water is a usual solvent, but
the precursors can be also hydrolyzed with acid or alkali. Alkaline catalysis induces
the formation of a colloidal gel, and acid catalysis produces the polymer form of gel.
The rates of hydrolysis and condensation are the important parameters, which affect
the properties of the final products. The particles are smaller at the slow and better-
controlled rates of hydrolysis. The particle size depends also on the composition of solu-
tion, pH and temperature. The drawbacks of this method are pollution by the reaction
by products and necessity of the post-treatment of products. The sol-gel method is widely
used for the synthesis of nanoparticles, but it is also used for the synthesis of nanoparticles
for MFs (Gubin et al., 2005; Mahmoudi et al., 2011; Kharisov et al., 2012; Canfarotta,
Piletsky, 2014; Gubin, 2009; Teja, Koh, 2009; de Matteis et al., 2012).

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The procedure of synthesis of magnetite nanoparticles coated with silica dioxide by

the sol-gel method is described in (Du et al., 2006). The synthesis occurs in two stages. At the first
stage, the magnetite nanoparticles are produced by co-deposition and dispersing in a water
solution by means of electrostatic interactions in the presence of tetramethylammonium
hydroxide. At the second stage, the magnetite nanoparticles are covered by silica dioxide
obtained by hydrolysis of tetraethyl orthosilicate. The studies have shown that the synthesized
nanoparticles are superparamagnetic and have a size of about 30 nm.
One more method of magnetic nanoparticle synthesis is the hydrothermal or hydro-
thermal/solvothermal synthesis (Joseph, Mathew, 2014; Baranov, Gubin, 2009; Faraji et al.,
2010; Mahmoudi et al., 2011; Kharisov et al., 2012; Canfarotta, Piletsky, 2014; Teja, Koh,
2009). A good version of technology for obtaining soluble magnetite nanoparticles, based on
the Massart method, is reducing hydrolysis of salts in the medium of polyatomic alcohols
(ethylene glycol, di-, tri- and tetraethylene glycol, glycerol) with heating. This method allows
good control of size and morphology of the products. Hydrothermal reaction is generally
performed in an autoclave or high-pressure reactors in an aqueous medium at high temperature.
The pressure can be 140 atm, and the temperature can be 200 °С or higher (Faraji et al., 2010).
Under these supercritical conditions, kinetics of hydrolysis is accelerated, water viscosity
decreases, and as a result, solubility and mobility of the most ionic components increases
(Joseph, Mathew, 2014). Hydrothermal synthesis of nanoferrites is possible either at
neutralization of mixed metal hydroxides (using the iron salt) or at oxidation-hydrolysis
process (using ferrous salts) (de Matteis et al., 2012). The hydrothermal method can be
used for the synthesis of highly crystalline magnetic nanoparticles in the two-stage
synthesis of MF. High-quality nanoparticles of Co-Zn ferrite with the diameter from 5.5
to 9 nm, were synthesized by the hydrothermal method, and then they were coated with
a layer of oleic acid for stabilization and dispersed in kerosene to form a MF (Joseph,
Mathew, 2014). The spherical cobalt ferrite and nickel nanoparticles with a narrow dis-
tribution function (7.91 and 6.87 nm, respectively) were synthesized in solvothermal
process in ethylene glycol followed by heat treatment (Yu, Kwak, 2011). Nanoparticles
of Fe3O4 with the average size from 5 to 32 nm were also synthesized by the hydrothermal
method (Yang et al., 2012). Production of MF with a double electric layer (Joseph, Mathew,
2014) was implemented by the hydrothermal method and the method of hydrothermal co-
deposition of nanoparticles of Co, Cu, Ni, and Zn ferrites. The advantages of hydrothermal
method are the good control of the size and shape of particles and narrow distribution function.
The sizes of particles are determined by the pressure, temperature, and reaction time.
The drawbacks are as follows: high temperature, inability of particle surface to function, and
slow reaction kinetics at the given temperature.
The microwave method for the synthesis of magnetic nanoparticles in a solution has
the advantages of rapid volumetric heating, higher reaction rate, reduced reaction time and
increased productivity as compared with the conventional heating methods (Joseph, Mathew,
2014; Baranov Gubin, 2009; Faraji et al., 2010; Mahmoudi et al., 2011; Kharisov et al., 2012;
Polshettiwar et al., 2009). The microwave method is a fast, simple, and clean approach, saving
time and energy, which yields a high quality product. Currently, the use of microwave reactors
with the automatic control of temperature and pressure increases significantly the efficiency
of synthesis and product quality. In (Bhattacharya et al., 2011), the MF was synthesized by co-
deposition of iron salts in polyvinyl alcohol and by the microwave method. The magnetite
nanoparticles with a larger average size of 9.43 nm and higher crystallinity, magnetization,
and similar stability were obtained by the microwave method.

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Usually, the method of microemulsions or micelle method is used to synthesize

the nanoparticles of ferrites-spinels (Joseph, Mathew, 2014; Baranov, Gubin, 2009; Faraji et al.,
2010; Mahmoudi et al., 2011; Kharisov et al., 2012; Canfarotta, Piletsky, 2014; Teja, Koh,
2009; Sanchez-Dominguez et al., 2009). Microemulsions are divided into oil micelles
dispersed in water, and water reverse micelles dispersed in oil depending on the ratio of oil,
water, and hydrophilic-lipophilic balance of surfactants (Sanchez-Dominguez et al., 2009).
In (Rana et al., 2010), the magnetic nanoparticles of cobalt ferrite with the average size of 4 nm
and narrow size distribution functions were synthesized by the method of reverse micelles
in the presence of dioctyl sodium sulfosuccinate (AOT, surfactant) in the n-heptane non-polar
solvent (oil phase) at low reagent concentration. In (Okoli et al., 2012) the magnetic particles
of iron oxide with the size of 2−10 nm were synthesized by the method of microemulsion
in the oil-water and water-oil systems. If we introduce a polar solvent such as water into
the critical micelle solution, the reverse micelles are formed ⎯ homogeneously dispersed solvent
molecules surrounded by the polar head groups. The small droplets of encapsulated polar
solvents in the reverse micelles act as the reactors (the sites for reactions). A large number of
reverse micelles containing reagents, and precipitating agents diffuse into each other, and this
leads to nucleation and growth of particles. This method is very attractive in terms of control
of the function of particle size distribution during preparation of the MF. The particle size is
controlled by the type and amount of surfactant. The disadvantages of this method are low
productivity, presence of surfactants in MF, and need for an organic solvent. The synthesis
of magnetic nanoparticles coated by silica oxide by the reverse micelles method was imple-
mented in (Vestal, 2003).
Another method for the synthesis of magnetic nanoparticles is the method of thermal
decomposition (thermolysis). The method of thermal decomposition of precursors, containing
corresponding metals, is the simplest way for preparation of magnetic nanoparticles. Currently,
the most flexible and efficient method of obtaining the magnetic nanoparticles in solutions is
thermolysis of metal-bearing compounds in high-boiling non-coordinating solvents in the pre-
sence of stabilizing agents (Joseph, Mathew, 2014; Baranov, Gubin, 2009; Faraji et al., 2010;
Mahmoudi et al., 2011; Jeong et al., 2007; Canfarotta, Piletsky, 2014; Gubin, 2009; Frey et
al., 2009; Teja, Koh, 2009). The method of thermal decomposition does not cause any
difficulties in terms of controlling the particle size and monodispersity. The particles with
narrow distribution function can be obtained at a change in the following factors:
decomposition temperature, metal-bearing precursors, surfactants, solvent type, and reaction
time. Such methods as the selection of alternative metal precursors and change in their relative
ratios are typically used to achieve the desired particle size (Schladt et al., 2011). The synthesis
of spherical nanoparticles of Fe3O4 with dimensions of 4, 6, 8, 9, 10, 11, 12, 13, and 15 nm from
iron oleate with the help of this method is shown in (Baranov, Gubin, 2009).
The method of thermal decomposition, apparently, is the best way to control the mor-
phology and size of nanoparticles. A major advantage of this method over other ones is an ability
to produce in a single experiment the nanoparticles in the amount of up to 40 grams, and this
method allows scaling. The disadvantages include the complicated synthesis processes and
relatively high temperature. There are the techniques similar to thermolysis, but instead of heating
the liquid the reagents are exposed to powerful influences of ultrasound (sonolysis) or powerful
electromagnetic radiation (photolysis) (Marchegiani et al., 2012; Watanabe et al., 2009).
We further consider the group of condensation methods (Faraji et al., 2010; Mahmoudi
et al., 2011; Kharisov et al., 2012; Canfarotta, Piletsky, 2014; Teja, Koh, 2009; Aleksashkin
et al., 2010). The essence of condensation techniques is that, according to the classical theory
of nucleation, the clusters in the form of spherical nanoparticles are formed from supersaturated
metal vapors. The difference of the condensation method is the way of obtaining

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the supersaturated vapor of metal: laser, plasma or thermal evaporation. In the classical method
of thermal evaporation (sometimes it is called the method of gas-phase evaporation), the metal
or alloy is heated in a tungsten boat in the flow of helium or argon. The atoms of evaporated
metal lose kinetic energy in collisions with the atoms of inert gas, combine in clusters, and
condense on a cooled substrate in the form of nanosized powder (Kharisov et al., 2012).
The synthesis of nanoparticles by these methods is carried out in the gas phase, and deposition
occurs into a liquid medium or on the solid matrices. Substrates, filters, etc. can be used as
such matrices. The magnetic particles produced by this method are not protected from
the environment, therefore, the special measures for storage of the obtained particles are
required (e.g., the inert atmosphere). Among the disadvantages of the method, where the par-
ticles are deposited on a solid carrier, is the use of special procedures of particle collection
for the synthesis of MF.
The metal vapor in the gas phase can also be obtained by the chemical methods such as
chemical gas-phase deposition and laser pyrolysis (Teja, Koh, 2009; Faraji et al., 2010).
In the method of chemical gas-phase deposition, the carrier gas flow delivers the precursors to
the reaction chamber, where the vacuum conditions and high temperature (> 900 °C) are
maintained. Chemical reactions occur in the high-temperature reaction chamber, and the reac-
tion products interact there to form the clusters or nanoparticles. The growth and agglo-
meration of particles are suppressed by rapid expansion of the two-phase flow at the outlet
of the reaction chamber. Subsequent thermal treatment of particles in different gas media allows
modification of the composition, morphology, and crystal structure of the synthesized nano-
powders. In particular, the method of chemical gas-phase deposition is to synthesize
the particles of iron oxide in the reaction of ferric trichloride with water at the temperature
of 800−1000 °С. The use of metallorganics reduces this temperature to 300−800 °С,
and the pressure varies starting from 1 Torr (Teja, Koh, 2009).
The method of laser pyrolysis consists in heating the moving mixture of gases by
the continuous CO2-laser for initiating and maintaining the chemical reaction until the achie-
vement of the critical concentration in the reaction zone; then homogeneous nucleation occurs
there, and nanoparticles are formed (Teja, Koh, 2009). Nanoparticles formed during
the reaction are entrained by the gas flow and trapped by the filter at the outlet.
Although the gas-phase methods can produce a high-quality product, their productivity is
low, and equipment scaling is hindered. Varying the concentration of gas, time of heating, and
pressure, the process can be accurately controlled, and the desired product can be obtained
(Canfarotta, Piletsky, 2014; Aleksashkin et al., 2010). An exception is the gas-phase synthesis,
when the metal vapor is obtained by induction heating and vaporization of the molten metal
(Tsurin et al., 2014). Condensation of the metal vapors takes place in the flow of inert gas
containing hydrocarbons (e.g., methane or butane).

4. Magnetic nanoparticles in the inert coating

Achieving the stability of the magnetic fluid for a long time is an important factor for
practical applications. This is particularly applied to the pure metal particles, susceptible
to oxidation and degradation. The magnetite particles can also be oxidized to maghemite
and dissolved in an acid medium. Furthermore, some compounds, which include, for
instance, cobalt, are toxic. Using the inert coating can solve the above problems (Gijs
et al., 2010).
The coating thickness can exceed the size of the magnetic particle so that at their direct
contact, we can neglect the forces of magnetic attraction (the structure of cobalt ferrite

407
S.A. Novopashin, M.A. Serebryakova, and S.Ya. Khmel

nanoparticles coated by silica dioxide is shown in Fig. 3 (Odenbach, 2009)). The van der
Waals forces can be overcome by sonication at production of the MF.
The methods of physical or chemical synthesis of the coated magnetic nanoparticles are
generally more expensive and have lower productivity. However, there are several advantages
at their use in special applications (Yu, Xie, 2012), when chemical inertness is required, as well
as during their storage and transport in the form of a powder. Moreover, at laboratory
investigations, the presence of magnetic powder can quickly change the magnitude of magnetic
properties of fluid and the base fluid itself at application of corresponding surfactants.
The magnetic nanoparticles in the coatings of silica dioxide (Odenbach, 2009), polymers
(Cornell, Schertmann, 1996) and carbon (Majetich, 1993; Brunsman, 1994) are the most
studied for the synthesis and use.
As was noted in the introduction, the range of MF applications is very wide. According to
the number of publications, to date the medical and biological applications of MF are the most
rapidly developing fields. The main criterion for the use of MFs in these areas is the bioco-
mpatibility of the magnetic particle coating together with chemical inertness. Therefore,
depending on the specific problem (targeted drug delivery, staining for magnetic resonance
imaging, hyperthermia), the magnetic nanoparticles in different coatings can be used (Joseph,
Mathew, 2014; Vekas et al., 2009; Odenbach, 2009; Baranov, Gubin, 2009; Faraji et al., 2010;
Laurent et al., 2011; Mahmoudi et al., 2011; Sharifi et al., 2012; Gijs et al., 2010).

5. Synthesis of magnetic nanoparticles in the carbon coating

The studies of the plasma-arc method for the synthesis of magnetic nanoparticles,
encapsulated into the carbon coating, started from the paper of (Kratschmer et al., 1990) on
the fullerene synthesis. The discovery of a possibility to encapsulate the atoms and nanocrystals
by the fullerene structures (Yannoni, 1992; Ruoff, 1993) allowed the start of a study on
the magnetic properties of encapsulated atoms at the example of gadolinium carbide (Majetich,
1993). The plasma-arc synthesis and systematic studies of the magnetic properties of nano-
particles obtained by spraying the composite “graphite-transition metal” electrodes were
performed in the work of (Brunsman, 1994). The works on the synthesis of magnetic
nanoparticles in a carbon coating by the electric arc method are continued. This method uses
the DC electric carbon arc with a hot cathode in the atmosphere of inert gas of the reduced
pressure. Metal precursors are usually put into a cavity drilled in a graphite electrode, and then
they are sprayed together with graphite. Under these conditions, the discharge is maintained by
thermionic emission of electrons from the cathode. The high temperatures in the zone of arc glow
lead to thermal spraying of the anode material. The flow of high-temperature atomic spray
products into the buffer gas medium occurs. Diffusion and turbulent mixing of outflowing
products with the buffer gas results in cooling, processes of heterogeneous condensation,
and chemical reactions of the spray products. As a result, the metal particles “packed” into
the carbon material are formed. The determining parameters of the synthesis are the pressure
and type of the buffer gas, current and discharge voltage, electrode geometry and composition,
and molar content of the precursor in the sprayed electrode. Varying these parameters, we can
control the morphology and chemical composition of the synthesized particles. The pressure
of the buffer gas is one of the most important parameters that determine the rate of cooling and
kinetics of condensation processes and chemical reactions, which allows the control of an average
size of nanoparticles (Maltsev et al., 2007). The scheme of experimental setup is shown in Fig. 5.
Two graphite electrodes, between which the arc glows in the inert gas atmosphere at the pressure
of 5−50 Torr, are located in vacuum chamber 1. Fixed consumable electrode 3 has the composite
compound based on graphite, and it is a rod with the diameter of 6.5 mm; movable electrode 2

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Fig. 5. Scheme of plasma-arc reactor for synthesis

of metal nanoparticles in the carbon coating
(Maltsev et al., 2007).
Symbols see in the text.

is the graphite tablet with the diameter of

20 mm. The design allows variation of the
electrode spacing and maintenance of the arc
glow conditions. The electrode is moved by
means of a bellows assembly of transmission
of forward motion 6. The current is fed to the camera through the heavy-current cerametallic
sealed input 7. Copper water-cooled cylinder 5 is mounted around the electrodes. The constant
voltage of 20−30 V is applied to the electrodes through the varied ballast resistance,
maintaining the arc current of 100 A. Inside the cylinder there is tightly fixed removable
stainless steel screen 4 for collecting the synthesis products. A consumable electrode is made of
the composite metal-graphite material of certain molar composition. Spraying the composite
electrode leads to appearance of atomic carbon and metal components in the zone of the arc.
Diffusion and convection of components in the buffer gas causes cooling and heterogeneous
condensation of the spray products. Subsequently, the condensation products of the nano-
structured material of metal and carbon are deposited on cooled screen 4.
Usually, the synthesis of nanoparticles is implemented in the inert gas atmosphere.
The presence of oxygen in the reactor leads to undesirable oxidation of the graphite electrode.
Therefore, the synthesis of metal oxide nanoparticles is performed in two stages. At the first
stage, the metal nanoparticles are synthesized on the carbon matrix, and at the second stage,
synthesized material is annealed in the oxygen atmosphere. The second stage allows oxidation
of the metal particles and removal of the carbon material in the form of carbon oxides
(Gulyaev, 2014). The disadvantages of this method are low productivity, broad function of
nanoparticles distribution by sizes, and heterogeneity of the carbon coating thickness.
Moreover, as usual, the mixture of various forms of carbon is synthesized, and it is difficult
to separate the product from the impurities (Faraji et al., 2010).
After the pioneering works of the early 90-s, the possibility of application of the plasma-
arc method for the synthesis of magnetic nanoparticles in a carbon coating was studied
in various versions. Thus, in (Chaitoglou, 2014), they used the blowing of the discharge zone
by helium with ferrocene microdroplets. In this case, ferrocene acted as a precursor for
the formation of iron nanoparticles (in the classic method, iron is sprayed together with
a graphite electrode). By changing the parameters of helium injection and ferrocene
concentration, it was managed to establish the control of the process of production
of the medium-sized magnetic nanoparticles and form a carbon coating, which ensured the re-
liable protection of iron nanoparticles from oxidation. In (Sun et al., 2000), the ferromagnetic
nanoparticles of iron, cobalt, and nickel encapsulated into the carbon coating were synthesized
by the modified plasma-arc method. Modification of the method included the use of methane
(instead of the inert gas) and application of pure metal as the anode (cathode was made
of graphite). Methane dissociation gave a sufficient amount of carbon to form a carbon coating
around nanoparticles of the mentioned metals. The gas-phase synthesis method is close by
the physical processes of nanoparticles formation (Tsurin et al., 2014). Metal vapor in this
method is obtained by induction heating and evaporation of the molten metal. Condensation
of metal vapors occurs in the inert gas flow containing hydrocarbons (e.g., methane or butane).
It was noted above that the pressure and type of the buffer gas affect the kinetics
of condensation and chemical reactions at expansion of the sublimation products from the arc
region. Thus, in (Borysiuk et al., 2008), the mixture of hydrogen and argon was used.

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S.A. Novopashin, M.A. Serebryakova, and S.Ya. Khmel

Furthermore, the synthesis products were purified additionally by boiling in hydrochloric acid,
followed by washing and drying. This procedure washed out metal from soot, which was
insufficiently covered by the carbon material. We should note that in this study, the plasma-arc
method for the synthesis of encapsulated magnetic nanoparticles was compared with
the method based on combustion. It is shown that plasma-arc method has significant
advantages. Typically, the composite material consisting of graphite and pure metal is used as
the sprayed anode, but the plasma-arc method synthesizes nanoparticles from the complex
chemical compounds at their spraying and pyrolysis. This ability is demonstrated in expe-
riments of (Filatov et al., 2013) on the synthesis of bimetallic magnetic nanoparticles with
the use of double salts as the precursors.
The electric arc between the graphite electrodes can also be obtained in liquid (Bingshe et al.,
2006). The iron nanoparticles in the carbon coating are synthesized at a discharge in FeSO4
solution.
Summing up the results of plasma-arc synthesis of magnetic nanoparticles in the car-
bon coating for the synthesis of MF, we can emphasize the following important points:
− the carbon coating is non-toxic and compatible with biological objects, and this defines
a wide range of MF applications in biology and medicine based on these nanoparticles;
− variation of determining parameters in the plasma-arc method allows the control
of the synthesis process, depending on the particular purpose;
− to separate the encapsulated magnetic nanoparticles from soot and to modify the carbon
coating, the processing by various physical-chemical methods can be applied;
− the magnetic nanoparticles encapsulated into a carbon coating are protected from
oxidation and other chemical reactions under the normal storage conditions.

Conclusion
This review deals with the modern methods of magnetic fluid synthesis. Their advantages
and disadvantages are identified. The methods allowing the synthesis of magnetic nano-
particles in an inert coating are noted specially. The advantages of using the magnetic
nanoparticles in the inert coatings are described. The method of plasma-arc synthesis
of magnetic nanoparticles encapsulated in carbon coating is considered in detail. This method
is based on high-temperature dispersion of the metal-graphite electrode in the electric arc.
To date, a number of modifications that allow the achievement of the higher quality of carbon
coating, monitoring and control of the size and composition of magnetic nanoparticles have
been implemented.

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