MICROEMULSION-BASED METHOD OF SYNTHESIS OF ZINC-NICKEL FERRITE AND THEIR MAGNETIC PROPERTIES
Solid solutions of nickel-zinc ferrites ZnxNi1-xFe2O4 were synthesized by two different methods: synthesis in microemulsions and by stepwise precipitation. The properties of the resulted nano-sized particles synthesized by two different methods were compared. It was found that the increase in zinc c...
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| Дата: | 2022 |
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| Формат: | Стаття |
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V.I.Vernadsky Institute of General and Inorganic Chemistry
2022
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Репозитарії
Ukrainian Chemistry Journal| _version_ | 1871465845492809728 |
|---|---|
| author | Plutenko, Tetiana V'yunov, Oleg Fedorchuk, Oleksandr Solopan, Sergii Plutenko, Maksim Khomenko, Boris |
| author_facet | Plutenko, Tetiana V'yunov, Oleg Fedorchuk, Oleksandr Solopan, Sergii Plutenko, Maksim Khomenko, Boris |
| author_institution_txt_mv | [
{
"author": "Tetiana Plutenko",
"institution": "V.I. Vernadsky Institute of General and Inorganic Chemistry of National Academy of Sciences of Ukraine"
},
{
"author": "Oleg V'yunov",
"institution": "V. I. Vernadsky Institute of General and Inorganic Chemistry"
},
{
"author": "Oleksandr Fedorchuk",
"institution": "V.I. Vernadsky Institute of General and Inorganic Chemistry of National Academy of Sciences of Ukraine"
},
{
"author": "Sergii Solopan",
"institution": "Vernadsky Institute of General and Inorganic Chemistry N.A.S of Ukraine, Kiev, Palladin av., 32\/34,03142 Ukraine"
},
{
"author": "Maksim Plutenko",
"institution": null
},
{
"author": "Boris Khomenko",
"institution": null
}
] |
| author_sort | Plutenko, Tetiana |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:49Z |
| description | Solid solutions of nickel-zinc ferrites ZnxNi1-xFe2O4 were synthesized by two different methods: synthesis in microemulsions and by stepwise precipitation. The properties of the resulted nano-sized particles synthesized by two different methods were compared. It was found that the increase in zinc content leads to an increase in the lattice parameters. During the synthesis by the method of microemulsions, the temperature of a single-phase product formation is 400 °C, while by the method of precipitation, a single-phase product formation begins at 600 °C. It was shown that the materials synthesized by both methods have similar unit cell parameters. The average size of ferrite nanoparticles synthesized in microemulsions is smaller, lattice strain is higher compared to ferrites synthesized by stepwise precipitation. Also, lower treatment temperatures provide higher stoichiometry, and homogeneity of materials while magnetization difference is negligible. The particles of the obtained powders have high saturation magnetization Ms = 45.6 Am2/kg for synthesis from microemulsions and Ms = 44.8 Am2/kg for co-precipitated samples, the low coercive force Hc = 1.3 kA/m and Hc = 3 kA/m, respectively. Changes made make synthesized particles more applicable in film deposition, and manufacturing of high-quality magnetic coatings. |
| doi_str_mv | 10.33609/2708-129X.88.07.2022.16-28 |
| first_indexed | 2025-09-24T17:43:46Z |
| format | Article |
| fulltext |
16 ISSN 2708-129X. Укр. хім. журн., 2022
UDC: 549.731.11; 537.621.2 doi: 10.33609/2708-129X.88.07.2022.16-28
MICROEMULSION-BASED METHOD OF SYNTHESIS OF ZINC-NICKEL
FERRITE AND THEIR MAGNETIC PROPERTIES
T.O. Plutenko1, O.I. V’yunov *1, O.P. Fedorchuk1, M.O. Plutenko2, S.O. Solopan1, B.S. Khomenko1
1V.I. Vernadsky Institute of General and Inorganic Chemistry of National Academy of Sciences of
Ukraine, Akad. Palladin ave, 32/34, Kyiv 03142, Ukraine
2Taras Shevchenko National University of Kyiv, Volodymyrska street, 60, Kyiv 01033, Ukraine
e-mail: vyunov@gmail.com
Solid solutions of nickel-zinc ferrites ZnxNi1-xFe2O4 were synthesized by two different
methods: synthesis in microemulsions and by stepwise precipitation. The properties of the
resulted nano-sized particles synthesized by two different methods were compared. It was
found that the increase in zinc content leads to an increase in the lattice parameters. During
the synthesis by the method of microemulsions, the temperature of a single-phase product
formation is 400 °C, while by the method of precipitation, a single-phase product formation
begins at 600 °C. It was shown that the materials synthesized by both methods have similar
unit cell parameters. The average size of ferrite nanoparticles synthesized in microemulsions
is smaller, lattice strain is higher compared to ferrites synthesized by stepwise precipitation.
Also, lower treatment temperatures provide higher stoichiometry, and homogeneity of ma-
terials while magnetization difference is negligible. The particles of the obtained powders
have high saturation magnetization Ms = 45.6 Am2/kg for synthesis from microemulsions
and Ms = 44.8 Am2/kg for co-precipitated samples, the low coercive force Hc = 1.3 kA/m and
Hc = 3 kA/m, respectively. Changes made make synthesized particles more applicable in film
deposition, and manufacturing of high-quality magnetic coatings.
Keywords: NiFe2O4, ZnFe2O4, magnetic properties, lattice constant, zinc substitution.
INTRODUCTION. Ferrites are a unique
class of materials that combine high magnetic
permeability with dielectric/insulator proper-
ties. Such combination allows their use in mi-
crowave electronics [1], optics [2], and power
electronics as non-reciprocal components, ac-
tive components of memory devices [3], and
magnets. In addition, there are applications for
ferrites in spintronics, self-controlled magne
tic hyperthermia [4], and absorbent coatings.
Moreover, the properties of different ferrites
compositions can vary greatly, while most of
these materials allow the properties to be ad-
justed using dopants [5].
Two types of ferrites are most often used
for microwave applications in the case of small
(from 0 to thousands Oe) magnetic fields: ma-
terials with the garnet and spinel structure.
17https://ucj.org.ua
T.O. Plutenko, O.I. V’yunov, O.P. Fedorchuk, M.O. Plutenko, S.O. Solopan, B.S. Khomenko UCJ № 7 / Vol. 88
Garnets are distinguished by low energy losses,
but only in the monocrystalline form [6]. The
properties of spinels differ.
Spinels based on Cu, Co, Mn, Mg, Ni, Zn
and their solid solutions are used. For micro-
wave applications, spinels based on Ni systems
are the most interesting due to their highest
electrical resistance and low energy loss com-
pared to other materials. The crystalline struc-
ture of Ni ferrite is almost independent of the
annealing temperature [7]. The addition of
Co increases the coercive force of the material
[8]. The addition of Mn and Cu increases the
conductivity. Such changes are harmful in the
microwave range due to increased energy loss.
Ni-Zn solid solutions, on the other hand, make
it possible to increase the saturation magne
tization and reduce the coercive force. And
energy losses at microwaves do not increase
significantly.
Despite the long history of research, the
synthesis of ferrites remains an urgent problem
due to the constant development of communi-
cations and increasing requirements for mate-
rials. Ferrites are often used as ceramic samples
for which the sintering temperature of ceramics
exceeds 1200 °C [9]. Lowering the sintering
temperature and increasing the homogeneity
of ceramics can be achieved by using small
ferrite particles with low agglomeration. Also,
particles' size affects the possibility of their use
in films, the coercive force of the product, and
thus the energy absorption ability (or quality
factor depending on the application).
Solid-state synthesis used in industry can-
not ensure the chemical homogeneity of ma-
terial particles and requires high temperatures.
The essence of this method is the mechanical
mixing of reagents, in the case of ferrites, these
are metal oxides [10]. A product is formed that
is homogeneous at the macro level, but chemi
cally heterogeneous. In addition, additional
heat treatment at high temperatures is re-
quired. Due to this, additional grinding of the
product is required and contamination with
grinding bodies occurs.
Other methods used are thermal decompo-
sition of precursors [11, 12], hydrothermal [13,
14] and sol-gel synthesis [15, 16], high-energy
ball milling, and precipitation from solutions
[17, 18], synthesis from microemulsions. The
decomposition of precursors requires close
decomposition temperatures of different pre-
cursors, which complicates the production
of a single-phase product [19]. In the case of
hydrothermal synthesis, the disadvantage is
the use of very expensive equipment, which is
not always available. The disadvantage of high-
energy ball milling is the contamination of the
product as a result of wear and tear, which oc-
curs mainly from the balls and partially from
the housing.
Precipitation from solutions is a wide-
spread method of synthesis, which allows the
obtaining of large quantities of the product.
Synthesized materials are more chemically
homogeneous compared to solid-phase syn-
thesis, and lower heat treatment temperatures
allow smaller particles to be obtained. Thus,
this method is a candidate to replace the so
lid-state route in industry. But also the pro
perties of the obtained material depend on a
large number of factors (solubility of particles,
the concentration of material and precipitant
in the volume of the reactor, etc., which also
depend on various environmental conditions).
It is difficult to control the processes of nuclea-
tion and growth of crystals, which leads to the
formation of an amorphous precipitate. The
precipitate is poorly filtered and washed, and
18 ISSN 2708-129X. Укр. хім. журн., 2022
MICROEMULSION-BASED METHOD OF SYNTHESIS OF ZINC-NICKEL FERRITE AND THEIR MAGNETIC PROPERTIESINORGANIC CHEMISTRY
after heat treatment, a strongly agglomerated
product is formed, which requires mechanical
grinding [20]. Nanoparticle growth and size
distribution increase with increasing concen-
tration. The choice of precipitator significantly
affects the overall size, purity of the product,
and the agglomeration process. Therefore, cur-
rently, when using synthesis by precipitation
from aqueous solutions, it is difficult to con-
trol the processes of nucleation and growth
of nanocrystallites, which often prevents the
synthesis of nanoparticles with the necessary
properties [21, 22].
On the other hand, the synthesis of nano-
particles using the microemulsion method is
also of great interest. After the discovery of
microemulsions, they become increasingly im-
portant for fundamental research and synthe-
sis of materials of various natures [23, 24]. Due
to its unique characteristics, namely ultra-low
interfacial tension, high reaction surface area,
thermodynamic stability, and ability to dissolve
otherwise immiscible liquids. The use and ap-
plications of microemulsions are numerous in
the chemical and biological fields. The mic
roemulsion technique promises to be one of
the versatile preparation methods that allow
controlling particle properties such as particle
size, geometry, morphology, homogeneity, and
surface area.
This work aims to obtain small and weakly
agglomerated zinc-nickel ferrite nanoparticles
with the use of synthesis in microemulsions, to
compare the temperature of nanoparticle for-
mation during microemulsion synthesis and
the classical synthesis of stepwise precipitation
from aqueous solutions. Study the influence
of the synthesis method on the magnetization
properties.
EXPERIMENT AND DISCUSSION OF
THE RESULTS. Nano-size spinel composites
ZnxNi1-xFe2O4 with x = 0–1 were synthesized by
using microemulsion of cetyltrimethylammo-
nium bromide, cyclohexane, and n-pentanol.
The obtained mixture of cetyltrimethylammo-
nium bromide (1 g), cyclohexane (75 ml), and
n-pentanol (2.5 ml) was stirred for 20 min. The
aqueous solution of oxalic acid H2C2O4 (1.2 M,
3.75 ml) was added to obtained mixture and
was stirred for 1 h. After that aqueous solu-
tions (1.25 ml) containing Zn(NO3)2 (0.4x M),
Ni(NO3)2 (0.4-0.4x M), and Fe(NO3)3 (0.8 M)
were added to the obtained microemulsion
and stirred for 20 h at room temperature. Ob-
tained zinc-nickel-iron oxalate was washed
with methanol, dried, and milled in an agate
mortar. After calcination at 400 °C for 4 h, spi-
nel-type ferrite of ZnxNi1-xFe2O4 was formed.
For comparison, ZnxNi1-xFe2O4 materials
were synthesized by co-precipitation from
aqueous solutions. A route similar to that
described in [25] was used. The solutions of
Ni(NO3)2, Zn(NO3)2, and Fe(NO3)3 were used
as initial reagents. The precipitant was an aque-
ous solution of NaOH.
The precipitation was carried out in several
stages. At each stage determined constant pH
values had been met. Initially, Fe(NO3)3 salt
solutions and precipitant solutions were add-
ed to the reactor dropwise at the pH value of
4 ÷ 4.5 with continuous stirring. After precipi
tation of Fe(OH)3, the pH of the mother li
quor was adjusted to 7.0 ÷ 7.2 and a solution
of Zn(NO3)2 salt and a precipitant were add-
ed. After precipitation of Zn(OH)2, the pH of
the mother liquor was raised to 8.5 ÷ 8.7, and
a solution of Ni(NO3)2 salt and a precipitant
were added dropwise with continuous stirring.
19https://ucj.org.ua
T.O. Plutenko, O.I. V’yunov, O.P. Fedorchuk, M.O. Plutenko, S.O. Solopan, B.S. Khomenko UCJ № 7 / Vol. 88
After precipitation of all the components, the
suspension was heated to 80oC for 1 hour. The
precipitate obtained was filtered off from the
mother liquor and washed on the filter with
double-distilled water. The resulting product
was dried in an oven in a cuvette at the tem-
perature of 110–120 °C. The final product was
obtained after heat treatment of the precipitate
in a muffle furnace with an automatic program
control unit in an air atmosphere at tempera-
tures of 600 °C, 700 °C, 800 °C, and 850 °C for
two hours.
X-ray powder diffraction was performed
using a DRON-4-07 diffractometer (Cu Kα
radiation, 40 kV, 20 mA) for the analysis of
phases formed during the synthesis. The unit
cell parameters of the samples were calculated
using the Le Bail procedure and the FullProf
software [26]. Anisotropic distribution of pow-
der particles was ensured by sieving through
a sieve onto the surface of a quartz substrate
with an applied organic binder. The average
stress coefficient was calculated by the Wil-
liamson-Hall method.
The size and morphology of nanoparticles
were studied by transmission electron micros-
copy (TEM) using Scanning Transmission
Microscope JEM-2100F. To study nanopar-
ticles by the TEM method, powder particles
were deposited on the Agartsсintific copper
mesh. Using the imageJ [27] calculations by
the method of the equivalent circle diameter
were performed [28]. Sampling was performed
in three different regions based on at least
50 grains in each region.
The infrared absorption spectra of the sam-
ple were recorded in the wave number range
390–1800 cm−1 by using an FTIR-650 spect
rometer (using the technique of pressing sam-
ples from KBr where msample/mKBr = 1/50).
The saturation magnetization (Ms), coerci
vity (Hc), remanence (Mr), and squareness
(Mr/Ms) at room temperature were performed
using a commercial VSM-250 vibrating sam-
ple magnetometer in the magnetizing field (H)
range from -10 to 10 kOe.
Mössbauer spectra were obtained with an
MS1101E spectrometer. Its resolution is cha
racterized by a half-width of 0.24 mm/s for
sodium nitroprusside as an absorber. The non-
linearity of the velocity scan was smaller than
0.45 % at the conditions used in measurements.
57Co in chromium with an activity of 25 mC
served as a source of gamma quanta. The spec-
tra were fitted with the Lorentz lineshape, the
linewidth being considered as an iteration pa-
rameter.
The XRD patterns of the Zn–Ni ferrioxalate
precursor and ZnxNi1-xFe2O4 materials, calcined
for 2 h at different temperatures are shown in
Fig. 1. As the air temperature increases, me
tal oxalates decompose with the formation of
metal oxides and carbon dioxide. It was shown
that the single-phase product ZnxNi1-xFe2O4 is
formed after 400 °C (Fig. 1a). The obtained
XRD diffraction patterns for each sample after
400 °C heat treatment contain the diffraction
peaks of Zn0.4Ni0.6Fe2O4 with the spinel struc-
ture. No other diffraction lines were observed.
The sharp peaks indicate well-crystallized
grains after sintering at 600 °C. Also, for com-
parison, XRD data for materials synthesized
by precipitation from aqueous solutions are
shown (Fig. 1b), a single-phase product for-
mation begins at 600 °C. Thus, microemulsion
synthesis of ZnxNi1-xFe2O4 particles provided a
decrease in temperatures of treatment (200 °C
compared with the temperature for co-preci
pitated ferrites).
20 ISSN 2708-129X. Укр. хім. журн., 2022
MICROEMULSION-BASED METHOD OF SYNTHESIS OF ZINC-NICKEL FERRITE AND THEIR MAGNETIC PROPERTIESINORGANIC CHEMISTRY
a b
Fig. 1. a – XRD patterns of the Ni–Zn ferrioxalate precursor at x=0.4 (1) and Zn0.4Ni0.6Fe2O4 material
calcined at 400 °C (2), 600 °C (3), and 800 °C (4) synthesized by the method of microemulsions;
b – XRD patterns of the Zn0.4Ni0.6Fe2O4 ferrite calcined at 120 °C (1), 400 °C (2), 600 °C (3), 800 °C (4),
and 850 °C (5) synthesized by the precipitation from aqueous solutions.
Le Bail method was used to determine lat-
tice parameters of ferrite particles (Fig. 2). It
can be seen, that crystal lattice parameters in
materials synthesized by the method in micro-
emulsions increase with Zn content (Table 1).
For instance, spinel ferrites have the general
formula of AFe2O4 (where A: Fe, Co, Ni, Zn).
The unit cell contains 32 O2- ions in cubic close
packing with 8 tetrahedral and 16 octahedral
occupied sites. Zinc–nickel ferrite is a mixed
spinel in which tetrahedral sites are occupied
by Zn2+ and Fe3+ ions and the octahedral sites
are occupied by Ni2+ and Fe3+ in the cubic spi-
nel lattice. In inverse spinel NiFe2O4 half of
the Fe3+ ions preferentially fill the tetrahedral
sites A sites and the rest occupy the octahedral
B sites. Zinc ferrite ZnFe2O4 is a normal spi-
nel-type where Fe3+ ions occupy B sites, which
allow antiferromagnetic interactions between
B–B ions to dominate in the magnetic pro
perties of zinc ferrite. And the reason for an in-
crease in the lattice parameter is the large Zn2+
ions size, larger than the radius of Ni2+ and O2-.
Therefore, we can conclude that Zn2+ ions en-
ter the lattice and solid solutions of nickel-zinc
ferrites are formed.
Particle size and particle morphology were
estimated by transmission electron microscopy
(TEM). Zn0.4Ni0.6Fe2O4 samples synthesized at
600 °C for the microemulsions synthesis method
and 800 °C for the stepwise precipitation me
thod with well-crystallized grains were select-
ed for TEM studies and to calculate the lattice
parameters (Table 1). The TEM images of the
samples synthesized by both methods (Fig. 3)
show that the Ni–Zn ferrite nanoparticles are of
21https://ucj.org.ua
T.O. Plutenko, O.I. V’yunov, O.P. Fedorchuk, M.O. Plutenko, S.O. Solopan, B.S. Khomenko UCJ № 7 / Vol. 88
uniform size of nano-dimensions and are highly
crystalline. Samples exhibited good dispersion,
spherical morphology and grain boundaries
were well-developed. The average size of the
crystallites changes slightly with the increase
in zinc concentration. The grain size changes
in the range of 29–42 nm (for Ni1-xZnxFe2O4
synthesized in microemulsions at 600 °C),
48–60 nm (at 800 °C) and 52–66 nm (for
Ni1-xZnxFe2O4 synthesized by precipitation from
aqueous solutions at 800°C) (Table 1). As can be
seen (Fig. 3a, b), an increase in synthesis tem-
perature leads to an increase in particles size.
a
b
Fig. 2. Le Bail refinement of X-ray data for Zn0.4Ni0.6Fe2O4 ferrite synthesized by the method in micro-
emulsions (a) and synthesized by the precipitation from aqueous solutions (b).
22 ISSN 2708-129X. Укр. хім. журн., 2022
MICROEMULSION-BASED METHOD OF SYNTHESIS OF ZINC-NICKEL FERRITE AND THEIR MAGNETIC PROPERTIESINORGANIC CHEMISTRY
There was no significant change in the lattice
parameter for ZnxNi1-xFe2O4 ferrite synthesized
by both methods, as shown in Table 1. Vari-
ation in the lattice parameter with increasing
the calcination temperature suggests a change
in the cations distribution between tetrahedral
A and octahedral B sites due to thermal fluc-
tuation [29]. A change in the cations distribu-
tion causes a change in the mean ionic radii of
A-site (rA) and B-site (rB) [30]. Lattice strain
for particles synthesized by the microemulsion
method is higher compared to ferrites synthe-
sized by stepwise precipitation.
Table 1.
Lattice parameters (a), the average size of crystallites DTEM of Ni1-xZnxFe2O4 particles synthe-
sized by the method in microemulsions at 600 °C and synthesized by the precipitation from
aqueous solutions 800 °C. Rb is the Bragg coefficient, Rf is the form conformity factor and the
lattice strain η.
Ni1-xZnxFe2O4 synthesized by the method in microemulsions at 600 °C
x 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
a, Å 8.331 8.341 8.351 8.362 8.375 8.391 8.410 8.418 8.431 8.444 8.452
DTEM, nm 32 37 29 36 31 35 30 36 39 42 37
η, ×10-3 0.90 1.05 1.78 1.99 2.37 2.58 3.05 3.16 3.06 2.89 2.74
R𝑓, % 6.5 4.4 5.2 4.7 5.3 5.1 5.1 4.7 4.7 4.5 5.3
RBragg, % 3.7 3.8 3.5 3.1 3.2 2.9 4.2 8.7 4.1 3.7 4.2
Ni1-xZnxFe2O4 synthesized by the precipitation from aqueous solutions at 800 °C
x 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
a, Å 8.387 8.393 8.399 8.407 8.426 8.430 8.433 8.447 8.454 8.472 8.483
DTEM, nm 52 54 58 63 55 52 62 58 64 66 60
η, ×10-3 0.64 0.68 0.71 0.83 0.85 0.87 0.90 0.94 1.14 0.98 0.97
R𝑓 5.8 5.4 5.4 4.5 5.7 4.6 5.6 4.4 5.3 5.2 4.8
RBragg 4.2 4.7 4.2 3.6 4.2 3.5 4.6 3.7 4.5 4.4 3.7
23https://ucj.org.ua
T.O. Plutenko, O.I. V’yunov, O.P. Fedorchuk, M.O. Plutenko, S.O. Solopan, B.S. Khomenko UCJ № 7 / Vol. 88
a b
c
Fig. 3. TEM image of Zn0.4Ni0.6Fe2O4 ferrite synthesized from microemulsions after heat treatment at
600 °C (a), at 800 °C (b) and by co-precipitation after heat treatment at 800 °C (c).
The Zn0.4Ni0.6Fe2O4 materials’ characteriza-
tion was also carried out by FTIR within the
wavelength range of 400–2000 cm−1 (Fig. 4).
Strong vibration in curve 1 at 1632 cm-1 is as-
signed to asymmetric νa(CO) vibration and
the strong vibration at 1310 cm-1 is assigned
as symmetric νs(CO) vibration of the oxa-
late group [31–33]. The observed spectral re-
gion at 1357 cm−1 is attributed to C–C sym-
metrical stretching in zinc-nickel ferrioxalate
(Fig. 4, curve 1). These regions are absent in
Zn0.4Ni0.6Fe2O4 (Fig. 4, curve 2). The peak at
823 cm−1 was assigned to the C–C bending vi-
bration absorption in curve 1 and disappeared
in curve 2 indicating that oxalate was decom-
posed in heat treatment, which can be verified
by XRD data. The other low energy vibration
at 740 cm−1 in curve 1 can be related to mixed
vibrations arising from stretching and bending
mode including water in the lattice. Bending
vibrations of Zn–O, Ni–O, and the vibration
of Fe–O in the tetrahedron may be related to
the two absorption peaks in the 550–670 cm−1
in curve 1. After calcination these peaks are
absent but a single peak of metal oxides at
583 cm−1 in curve 2 has appeared.
24 ISSN 2708-129X. Укр. хім. журн., 2022
MICROEMULSION-BASED METHOD OF SYNTHESIS OF ZINC-NICKEL FERRITE AND THEIR MAGNETIC PROPERTIESINORGANIC CHEMISTRY
Fig. 4. Infrared spectra of zinc-nickel ferrioxa-
late (1) and Zn0.4Ni0.6Fe2O4 (2) obtained by calcin-
ing at 600 °C for 2 h.
Fig. 5. 57 Fe Mössbauer spectra of Zn0.4Ni0.6Fe2O4
spinel nanoparticles at room temperature. The ex-
perimental data are represented as a bold red line
(1), while two components corresponding to the
octahedral and tetrahedral sites in the spinel struc-
ture are represented as green (2) and blue (3) lines,
respectively.
In Fig. 5 the MÖssbauer spectrum of the
Zn0.4Ni0.6Fe2O4 ferrite at room temperature
is shown. Fe3+ ions occupy lattice sites in two
sub-lattices of spinel, thus two sextets are ob-
served in the spectrum. Sextet lines broaden
with increasing zinc content, which occupies
tetrahedral positions in the structure.
It was found that the cations in the sub-lat-
tice are distributed randomly. The Fe3+ ions in
the tetrahedral position give a less ultrafine
field and isomeric shift compared to the Fe3+
ions in the octahedral field of ligands. Fe3+ ion
has a high spin compared with Zn2+, as the Zn
concentration increases, the ultrafine values
decrease due to the presence of Zn as the near-
est neighbour of Fe.
Magnetic characteristics of powders of all
compositions, synthesized at 800 °C (and at
600 °C for the synthesis from microemulsions),
were determined using a vibrating magneto-
meter. Samples demonstrate the magnetically
soft behaviour (Fig. 6).
Fig. 6. Hysteresis loops at room temperature
of Zn0.4Ni0.6Fe2O4 ferrites synthesized from mic
roemulsions after heat treatment at 600 °C (1), at
800 °C (2) and by co-precipitation after heat treat-
ment at 800 °C (3).
25https://ucj.org.ua
T.O. Plutenko, O.I. V’yunov, O.P. Fedorchuk, M.O. Plutenko, S.O. Solopan, B.S. Khomenko UCJ № 7 / Vol. 88
Magnetic properties change with increas-
ing Zn concentration. The highest value of
saturation magnetization was observed for
Zn0.4Ni0.6Fe2O4 ferrite synthesized by the me
thod of microemulsions after the heat treat-
ment at 800 °C. The particles of the obtained
powders have high saturation magnetization
Ms = 45.6 Am2/kg for synthesis from micro-
emulsions and Ms = 44.8 Am2/kg for co-pre-
cipitated samples, the low coercive force Hc =
1.3 kA/m and Hc = 3 kA/m, respectively. Al-
though the characteristics of particles syn-
thesized from microemulsions appear to be
slightly better, the difference for magnetization
is within the margin of error.
CONCLUSIONS. The formation tempera-
tures of single-phase spinels synthesized from
microemulsions and precipitation from aque-
ous solutions were determined by X-ray analy-
sis. It was found that the materials synthesized
by the microemulsion method have lower par-
ticle formation temperatures (the difference is
200 °C). The parameters of the elementary cell
and the average size of nanoparticles were cal-
culated by the method of full profile analysis.
It was found that with an increase in zinc, the
parameter of the unit cell increases uniformly
by Vegard's law. The average size of nanopar-
ticles also increases with increasing zinc. The
formation of the spinel structure was proved
by the method of IR spectroscopy. Mössbau-
er spectroscopy showed that the cations in the
sub-lattice are distributed randomly. The study
of magnetic properties confirmed that the ma-
terials are magnetically soft and have a high
saturation magnetization. The magnetization
of materials synthesized from emulsions and
precipitation from aqueous solutions differ
little while coercive force differs near 3 times
(1.3 and 3 kA/m) and is lower for the parti-
cles synthesized from microemulsions. At the
same time, lower treatment temperatures allow
the formation of smaller particles, higher stoi
chiometry, and homogeneity of the resulting
product, making it more applicable in films
and high-quality coating deposition.
ACKNOWLEDGEMENTS. The authors
express their gratitude to the Armed
Forces of Ukraine for providing securi-
ty to perform this work. This work has become
possible only because of the resilience and
courage of the Ukrainian Army.
This work was supported by the NAS of
Ukraine in the framework of the Target Pro-
gram of Scientific Researches of the NAS of
Ukraine “Grants of the NAS of Ukraine to
research laboratories/groups of young scien-
tists of the NAS of Ukraine” No 0121U110363
(2021–2022).
The authors are grateful to the Center of
MÖssbauer spectroscopy in G. V. Kurdyumov
Institute for metal physics of the National
academy of sciences of Ukraine.
МІКРОЕМУЛЬСІЙНИЙ МЕТОД СИНТЕЗУ ЦИНК-
НІКЕЛЕВИХ ФЕРИТІВ ТА ЇХНІ МАГНІТНІ ВЛАС
ТИВОСТІ
T. O. Плутенко1, O. I. В’юнов*1,
O. П. Федорчук1, M. O. Плутенко 2,
С. O. Солопан1, Б. С. Хоменко1
1Інститут загальної та неорганічної хімії
ім. В. І. Вернадського НАН України, просп.
Акад. Палладіна 32/34, Київ 03142, Україна
2Київський національний університет імені
Тараса Шевченка, вул. Володимирська, 60,
Київ 01033, Україна
e-mail: vyunov@gmail.com
26 ISSN 2708-129X. Укр. хім. журн., 2022
MICROEMULSION-BASED METHOD OF SYNTHESIS OF ZINC-NICKEL FERRITE AND THEIR MAGNETIC PROPERTIESINORGANIC CHEMISTRY
Ферити – магнітні діелектрики, виріз-
няються серед інших матеріалів поєднан-
ням високих магнітних характеристик та
низькою електричною провідністю. Тому
їх широко використовують у виробництві
електронних пристроїв, різних типів не-
взаємних надвисокочастотних компонен-
тів, магнітних рідин, поглиначів, в оптиці,
а також у самоконтрольованій магнітній
гіпертермії. Незважаючи на давню історію
досліджень, триває удосконалення методів
отримання феритів та їхніх характеристик,
вивчення окремо об’ємних матеріалів та
нанорозмірних часток.
У роботі синтезовано тверді розчини
нікель-цинкових феритів ZnxNi1‑xFe2O4 з
мікроемульсій та осадженням із водних
розчинів. Проведено РФА-дослідження
часток, ІЧ-спектроскопію, мессбаурівську
спектроскопію, дослідження магнітних
властивостей часток із використанням
вібраційного магнітометра. Було порівня-
но властивості отриманих нанорозмірних
частинок феритів, синтезованих двома ме-
тодами.
Використання синтезу з мікроемульсій
дозволило знизити температуру формуван-
ня однофазного продукту на 200 °С порів-
няно з осадженням із розчинів. Це також
дає можливість отримання часток меншого
розміру, забезпечити більшу однорідність
матеріалу, краще витримати стехіометрію
складу у об’ємі.
Встановлено, що збільшення вмісту цин-
ку призводить до збільшення параметрів
елементарної комірки. ІЧ-спектроскопія
підтвердила повне розкладання й виведен-
ня оксалату при синтезі феритів із мікро-
емульсій. Мессбауерівські спектри матеріа-
лів підтвердили присутність йонів заліза в
обох ґратках фериту й формування твердо-
го розчину. Намагніченість частинок, син-
тезованих різними методами, відрізняється
несуттєво, тоді як коерцитивна сила відріз-
няється в рази (1,3 і 3 кА/м) і є меншою для
зразків, синтезованих із мікроемульсій.
Вказані параметри дозволяють ствер-
джувати, що отримані частинки можна
використовувати при створенні магнітних
плівок, добротних магнітних покриттів та
компонентів на їхній основі.
Ключові слова: NiFe2O4, ZnFe2O4, магніт-
ні властивості, постійна ґратки, заміщення
цинку.
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Стаття надійшла 15.08.2022.
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-465 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:08:30Z |
| publishDate | 2022 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/c6/59e1d2665b7c77f0493410c7d84c2fc6.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-4652026-07-22T08:23:49Z MICROEMULSION-BASED METHOD OF SYNTHESIS OF ZINC-NICKEL FERRITE AND THEIR MAGNETIC PROPERTIES Plutenko, Tetiana V'yunov, Oleg Fedorchuk, Oleksandr Solopan, Sergii Plutenko, Maksim Khomenko, Boris NiFe2O4, ZnFe2O4, magnetic properties, lattice constant, zinc substitution. Solid solutions of nickel-zinc ferrites ZnxNi1-xFe2O4 were synthesized by two different methods: synthesis in microemulsions and by stepwise precipitation. The properties of the resulted nano-sized particles synthesized by two different methods were compared. It was found that the increase in zinc content leads to an increase in the lattice parameters. During the synthesis by the method of microemulsions, the temperature of a single-phase product formation is 400 °C, while by the method of precipitation, a single-phase product formation begins at 600 °C. It was shown that the materials synthesized by both methods have similar unit cell parameters. The average size of ferrite nanoparticles synthesized in microemulsions is smaller, lattice strain is higher compared to ferrites synthesized by stepwise precipitation. Also, lower treatment temperatures provide higher stoichiometry, and homogeneity of materials while magnetization difference is negligible. The particles of the obtained powders have high saturation magnetization Ms = 45.6 Am2/kg for synthesis from microemulsions and Ms = 44.8 Am2/kg for co-precipitated samples, the low coercive force Hc = 1.3 kA/m and Hc = 3 kA/m, respectively. Changes made make synthesized particles more applicable in film deposition, and manufacturing of high-quality magnetic coatings. V.I.Vernadsky Institute of General and Inorganic Chemistry 2022-08-26 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/465 10.33609/2708-129X.88.07.2022.16-28 Ukrainian Chemistry Journal; Vol. 88 No. 7 (2022): Ukrainian Chemistry Journal; 16-28 Украинский химический журнал; ##issue.vol## 88 ##issue.no## 7 (2022): Ukrainian Chemistry Journal; 16-28 Український хімічний журнал; Том 88 № 7 (2022): Український хімічний журнал; 16-28 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/465/238 Copyright (c) 2022 Tetiana Plutenko, Oleg V'yunov, Oleksandr Fedorchuk, Sergii Solopan, Maksim Plutenko, Boris Khomenko https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Plutenko, Tetiana V'yunov, Oleg Fedorchuk, Oleksandr Solopan, Sergii Plutenko, Maksim Khomenko, Boris MICROEMULSION-BASED METHOD OF SYNTHESIS OF ZINC-NICKEL FERRITE AND THEIR MAGNETIC PROPERTIES |
| title | MICROEMULSION-BASED METHOD OF SYNTHESIS OF ZINC-NICKEL FERRITE AND THEIR MAGNETIC PROPERTIES |
| title_full | MICROEMULSION-BASED METHOD OF SYNTHESIS OF ZINC-NICKEL FERRITE AND THEIR MAGNETIC PROPERTIES |
| title_fullStr | MICROEMULSION-BASED METHOD OF SYNTHESIS OF ZINC-NICKEL FERRITE AND THEIR MAGNETIC PROPERTIES |
| title_full_unstemmed | MICROEMULSION-BASED METHOD OF SYNTHESIS OF ZINC-NICKEL FERRITE AND THEIR MAGNETIC PROPERTIES |
| title_short | MICROEMULSION-BASED METHOD OF SYNTHESIS OF ZINC-NICKEL FERRITE AND THEIR MAGNETIC PROPERTIES |
| title_sort | microemulsion-based method of synthesis of zinc-nickel ferrite and their magnetic properties |
| topic_facet | NiFe2O4 ZnFe2O4 magnetic properties lattice constant zinc substitution. |
| url | https://ucj.org.ua/index.php/journal/article/view/465 |
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