HOLLOW NANOSTRUCTURED Ni3Fe MICROSPHERES

DOI 10.1007/s11148-024-00906-5
Refractories and Industrial Ceramics
Vol. 64, No. 6, March, 2024
HOLLOW NANOSTRUCTURED Ni3Fe MICROSPHERES
OBTAINED BY SPRAY PYROLYSIS
B. B. Khaidarov,1 A. G. Yudin,1,4 D. S. Suvorov,1 D. V. Kuznetsov,1
D. V. Lysov,1 I. N. Burmistrov,2 and D. Yu. Karpenkov3
Translated from Novye Ogneupory, No. 12, pp. 32 – 37, December, 2023.
Original article submitted November 16, 2023.
A study of a two-stage method for the formation of nanostructured Ni3Fe is presented. Nanostructured Ni3Fe
hollow microspheres were synthesized by ultrasonic spray pyrolysis (URP) from a mixture of aqueous solutions (10 wt.%) of nickel(II) and iron(III) nitrates. In the first stage, hollow microspheres with diameters in the
range 0.5 – 10 mm were formed from a mixture of Ni and Fe oxides. The second stage involved metallization
of a mixture of Ni and Fe oxides in a tube furnace in a hydrogen atmosphere. X-ray diffraction (XRD) data of
the final product showed the presence of the Ni3Al phase and a crystallite size close to 40 nm. Scanning and
transmission electron microscopy revealed the hollow morphology of the studied Ni3Fe microspheres. Their
walls were assembled from crystallites with diameters of 30 – 60 nm.
Keywords: spray-pyrolysis, hollow nanostructured microspheres, Ni3Fe.
cles [23 – 27], and multicomponent systems [28 – 33]. The
spray pyrolysis procedure includes several processes: 1 —
spraying a starting salt solution [34 – 39]; 2 — solvent evaporation [40]; and 3 — product collection. The ability to use
both inorganic and organic salts makes the USP method universal for producing multicomponent and well-mixed systems [41]. The USP method is well suited to producing materials with an ordered chemical composition. The simplicity
of the technical equipment used for USP is one of the advantages of this method.
The present research showed that hollow nanostructured
Ni3Fe microspheres were formed by USP from nickel and
iron nitrate precursors followed by heat treatment in an H2
atmosphere.
INTRODUCTION
Nanostructured materials are attracting heightened interest because of their specific physicochemical properties due
to the transition from the bulk to the nanoscale state. Among
them, magnetic nanoparticles have significant technological
and theoretical interest. In particular, the compound Ni3Fe
has found practical applications in electrical engineering, optics, and electronics. Its magnetically soft behavior demonstrates low coercive force and high magnetic permeability
[1 – 3].
Ni3Fe and other magnetic composites based on Fe, Ni,
Co, etc. are widely synthesized by mechanical milling in a
planetary ball mill [1 – 3]. Crystalline and amorphous materials based on Ni–Fe are commonly molded by the Taylor(Ulitovsky technique [4 – 7] or the sol-gel method followed by metallization [8]. Foils based on Ni–Fe were
formed by electrodeposition [9].
Ultrasonic spray pyrolysis (USP) is widely used to produce thin films [10 – 23], spherical hollow and dense parti-
EXPERIMENTAL
The starting precursors were Ni(NO3)2·6H2O (OOO
Reakhim, AR grade), Fe(NO3)3·9H2O (OOO Reakhim, AR
grade), and distilled H2O. The ratio of the salts was calculated to give an Ni:Fe stoichiometry of 3:1 in the final product.
Figure 1 shows a conceptual diagram of the USP method
[34, 42, 43]. A solution of the metal nitrates was sprayed using a DK 9-36 ultrasound generator at operating frequency
1
National University of Science and Technology MISiS, Moscow,
Russia.
2
Plekhanov Russian University of Economics, Moscow, Russia.
3
Lomonosov Moscow State University, Moscow, Russia.
4
yudin@misis.ru
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1083-4877/24/06406-0648 © 2024 Springer Science+Business Media, LLC
Hollow Nanostructured Ni3Fe Microspheres Obtained by Spray Pyrolysis
Fig. 1. Diagram of spray-pyrolysis system.
1.2 MHz. Aerosol drops were formed by annihilation of ultrasound cavitation bubbles and were transported by a carrier
gas into a quartz reactor of length 500 mm and internal diameter 25 mm inside a Nabertherm 20/250/13 tube furnace. Air
was used as the carrier gas. The carrier-gas flow rate was
maintained by a KNF Neuberger D7911 pump at 16 L/min.
The furnace temperature was held at ~1000°C. The obtained
hollow microspheres were collected on a stainless-steel filter.
The time of flight of the drops through the heated reactor was
~2 sec.
Two parallel-sequential processes occurred in the furnace reactor. The first was solvent evaporation associated
with transformation of the drops into particles. Evaporation
of H2O and crystallization of the Ni and Fe nitrates began at
the drop surface. The salt solution diffused from the bulk to
the drop surface because of the concentration gradient and
high temperature. The second process was thermal decomposition of the nitrate salts to form Ni and Fe oxides, NO2, and
O2 according to the equations:
2Ni(NO3)2 ® 2NiO + 4NO2 + O2;
4Fe(NO3)2 ® 2FeO3 + 12NO2 + 3O2.
The obtained samples were metallized in a Carbolite
HZS 12/600E tube furnace in an H2 atmosphere at 450°C.
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The metallization temperature was selected based on results
of thermogravimetric studies.
The morphology of the obtained samples was studied using a Tescan Vega 3 scanning electron microscope (Czechia)
and a JEM 1400 transmission electron microscope (JEOL,
Japan). The phase composition of the obtained samples was
studied by x-ray phase analysis (XPA) on a Difray 401 instrument (NPK Nauchpribor, Russia) using Cr Ka-radiation
(2.2909 Å). The specific surface area was studied by
low-temperature N2 adsorption according to BET on a
Quantachrome Nova 1200 e instrument (USA). The magnetic properties of the samples were studied using a Lake
Shore VSM 7410 vibrating magnetometer (USA). Samples
of hollow Ni3Fe microspheres were cold pressed beforehand
at a load of 4 t/cm2. The thermogravimetric parameters were
studied on a Thermal Advances SDT Q 600 instrument in the
range 25 – 1000°C in air and H2 at heating rate 20°C/min.
The size distribution of the microspheres was studied using a
Zetasizer Nano ZS Z 3600 laser diffraction analyzer
(Malvern, Great Britain).
RESULTS AND DISCUSSION
The morphology of the powder studied by an SEM
showed microspheres of diameters in the range 0.5 – 10 mm
(Fig. 2a ). This was confirmed by laser diffraction, which
found microsphere diameters in the range 0.5 – 10 mm. A detailed analysis of the microsphere structure using a TEM revealed hollow microspheres of Ni and Fe oxides, the walls of
which were constructed of 20-nm particles (Fig. 2b and 2c).
XPA of the synthesized powders detected NiO and
NiFe2O4 phases (Fig. 3). This phase composition corresponded to the Fe2O3–NiO phase diagram.
The coherent scattering region (CSR) calculated from the
XPA data was ~15 nm. The specific surface area (SSA) of
the samples was 70 m2/g. The average particle size calculated from the SSA data using the equation Dav = 6/(rS) was
15 nm, where r is the theoretical density (kg/m3) and S, the
measured SSA (m2/kg).
Fig. 2. SEM (a) and TEM photomicrographs (b ) of NiO and FeNi2O4 synthesized at 1000°C.
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Fig. 3. XPA of a mixture of oxides after spray pyrolysis at 1000°C.
B. B. Khaidarov, A. G. Yudin, D. S. Suvorov, et al.
Fig. 5. XFA of Ni3Fe after heat treatment in an H2 atmosphere.
Fig. 4. Thermogravimetric data for heat treatment in the range 25 – 1000°C in an
H2 atmosphere.
Fig. 6. TEM images of Ni3Fe microspheres.
Thermogravimetric data showed several transformations upon heating in an H2 atmosphere
(Fig. 4). The first was metallization of NiO at
250°C; the second, which began at 450°C, was related to metallization of NiFe2O4. This temperature
was chosen as the metallization temperature.
The samples were metallized in a tube furnace
in an H2 atmosphere at 450°C followed by
passivation. XPA data for the metallized samples
showed the single phase Ni3Fe (Fig. 5).
The calculated crystallite size was close to
16 nm. The SSA of the samples was 21 m2/g; the
calculated particle size, 33 nm. TEM images
showed particle sizes in the range 40 – 60 nm
(Fig. 6). The particle size calculated from the SSA
data agreed with the TEM data. The thin oxide film
Hollow Nanostructured Ni3Fe Microspheres Obtained by Spray Pyrolysis
651
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Fig. 7. Field dependence of Ni3Fe nanostructured samples.
formed after passivation was clearly visible (Fig. 7a ).
The magnetic properties of Ni3Fe were studied using
pressed powder and a vibrating magnetometer. Figure 7
shows hysteresis loops of Ni3Fe microspheres at room temperature. The measurement of the magnetic properties of the
nanopowders showed a symmetric hysteresis loop with ferromagnetic behavior and coercive force m0Hc = 35 mT and
saturation magnetization Ms = 60 A·m2·kg(1. It is noteworthy
that Ni3Fe showed significantly increased magnetic
coercivity as compared to bulk Ni3Fe (m0Hc = 0.054 mT).
This was related to most alloy nanoparticles reaching the
typical size of a single-domain state (dcr ~ 20 nm), where Hc
reaches a maximum.
The saturation magnetization of the nanostructured
Ni3Fe samples turned out to be less than the corresponding
bulk values. The decrease in the saturation magnetization together with the decrease in the particle size led to an increase
in the fraction of the noncollinear magnetic structure in
which magnetic moments were not equalized along the direction of the external magnetic field. This increase in the
fraction of the noncollinear structure decreased the saturation
magnetization.
CONCLUSION
Hollow Ni3Fe microspheres with diameters in the range
0.5 – 10 mm were synthesized by USP. The Ni3Fe phase was
produced by metallization of the spray-pyrolysis products in
an H2 atmosphere. The microsphere shells were constructed
of nanoscale particles of diameters 40 – 60 nm with a crystallite size of 16 nm. The wall thickness of the microspheres
was close to 100 nm. The magnetic properties of Ni3Fe
showed that the obtained material was magnetically hard.
The results indicated that the synthesis of nanostructured materials based on Ni–Fe with a homogeneous chemical composition and narrow microsphere size distribution was promising.
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