Magnetic characteristics of MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles obtained by glycine–nitrate synthesis

The magnetic properties of magnesium–iron spinel (MgFe₂O₄) powdered nanoparticles obtained by glycine–nitrate synthesis are investigated by X-ray phase analysis and the NMR method. According to the results of X-ray phase analysis, the average size of the crystalline part of nanoparticles of the powder under investigation is 45 ± 4 nm. Magnetization J is determined using the formula J = (B/μ0)–H, where B and H are the induction and strength of the magnetic field in the sample, which are measured by the NMR method. The magnetic characteristics of MgFe₂O₄ are as follows: specific saturation magnetization J_sat = 17.52 A m²/kg, specific residual magnetization J_r = 5.73 A m2/kg, coercive force H_c = 4600 A/m, and magnetic moment P_sat = 371 × 10^–20 A m² in the magnetic saturation state and P_r = 121 × 10^–20 A m² in the residual magnetization state.     

Formation of nickel magnetic nanoparticles and modification of nickel phthalocyanine matrix by sodium doping

Data for the vapor-phase doping (300°C) of nickel phthalocyanine (NiPc) by sodium taken in different concentrations (x), as well as structural analysis data for Na _{x = 0.2}NiPc, Na _{x = 1}NiPc, and Na _{x = 3}NiPc samples, have been reported. The structure of the samples and their atomic configuration versus the doping level have been studied by transmission electron microscopy, Raman scattering, X-ray diffraction, X-ray absorption spectroscopy, and extended X-ray absorption fine structure (EXAFS) spectroscopy. The structural parameters of Ni–N, Ni–C, and Ni–Ni bonds have been determined, and it has been found that, at a low level of doping by sodium, local structural distortions are observed in some molecules of the NiPc matrix near nickel atoms. The fraction of these molecules grows as the doping level rises from x = 0.2 to x = 1.0. It has been shown that doping changes the oscillation mode of light atoms, which indicates a rise in the electron concentration on five- and six-membered rings. At a high level of sodium doping (x = 3.0), nickel nanoparticles with a mean size of 20 nm and molecule decomposition products have been observed in the NiPc matrix. It has been found that the fraction of nickel atoms in the Na _{x = 3}NiPc nanoparticles as estimated from EXAFS data is sufficient for the room-temperature magnetic properties of the samples to persist for a long time.     

Ferrimagnetic nanoparticles for self-controlled magnetic hyperthermia

Based on the Heisenberg model including single-site uniaxial anisotropy and using aGreen’s function technique we studied the influence of size and composition effects on theCurie temperature T _C , saturationmagnetization M _S and coercivityH _C of spherical nanoparticles with astructural formulaM e _1?x Zn _x Fe₂O₄,Me = Ni, Cu, Co, Mn. It is shown that for x = 0.4–0.5and d = 10–20 nm these nanoparticles have aT _C  = 315 K and are suitable for aself-controlled magnetic hyperthermia.     

Mössbauer Spectroscopy Study of the Superparamagnetism of Ultrasmall ϵ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> Nanoparticles

The superparamagnetism of an ensemble of ?-Fe₂O₃ nanoparticles with a mean size of 3.9 nm dispersed in a xerogel SiO₂ matrix is studied by the Mössbauer spectroscopy method. It is shown that most nanoparticles at room temperature are in the superparamagnetic (unblocked) state. As the temperature decreases, the progressive blocking of the magnetic moments of the particles occurs, which is manifested in the Mössbauer spectra as the transformation of the quadrupole doublet into a Zeeman sextet. The analysis of the relative intensity of the superparamagnetic (quadrupole doublet) and magnetically split (sextets) spectral components in the range of 4–300 K provides the particle size distribution, which is in agreement with the transmission electron microscopy data. The values of the effective magnetic anisotropy constants (K_eff) are determined, and the contribution of surface anisotropy (K_S) is estimated for particles of various sizes. It is shown that the quantity K_eff is inversely proportional to the particle size, which indicates the significant contribution of the surface to the magnetic state of the ?-Fe₂O₃ nanoparticles with the size of several nanometers.     

Magnetic M<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>@N-C as heterogeneous catalysts for the catalytic oxidation of aniline solution with sulfate radicals

Metal nanoparticles have been combined with magnet metal–organic frameworks (MOFs) to afford new materials that demonstrate an efficient catalytic degradation, high stability, and excellent reusability in areas of catalysis because of their exceptionally high surface areas and structural diversity. Magnetic M _x O _y @N-C (M = Fe, Co, Mn) nanocrystals were formed on nitrogen-doped carbon surface by using 8-hydroxyquinoline as a C/N precursor. The Co@N-C, MnO@N-C, and Fe/Fe₂O₃@N-C catalysts were characterized by X-ray diffraction (XRD), Raman, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), N₂ adsorption/desorption, and X-ray photoelectron spectroscopy (XPS). The catalytic performances of catalysts were thoroughly investigated in the oxidation of aniline solution based on sulfate radicals (SO₄ ^?.) toward Fenton-like reaction. Magnetic M _x O _y @N-C exhibits an unexpectedly high catalytic activity in the degradation of aniline in water. A high magnetic M _x O _y @N-C catalytic activity was observed after the evaluation by aniline degradation in water. Aniline degradation was found to follow the first-order kinetics, and as a result, various metals significantly affected the structures and performances of the catalysts, and their catalytic activity followed the order of Co > Mn > Fe. The nanoparticles displayed good magnetic separation under the magnetic field.

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Spectroscopy of optical centers of Eu<Superscript>3+</Superscript> ions in partially stabilized and stabilized zirconium crystals

The structure of the optical centers of Eu³⁺ ions in tetragonal (ZrO₂)_1–x–y (Y₂O₃) _x (Eu₂O₃) _y (х = 2.7–3.6; y = 0.1) and cubic (ZrO₂)_1–x–y (Y₂O₃) _x (Eu₂O₃) _y (х = 8–38; y = 0.1–0.5) crystals of solid solutions on the basis of zirconium dioxide is studied using the methods of optical and Raman-scattering spectroscopy. Characteristic optical centers of Eu³⁺ ions with different crystalline environments are revealed in the above compounds.     

Composition of <Emphasis Type="Italic">α</Emphasis>−<Emphasis Type="Italic">F</Emphasis><Emphasis Type="Italic">e</Emphasis> nanoparticles precipitated from CuFe alloy studied by hyperfine interactions

Iron-based nanoparticles prepared by precipitation from solid solution of saturated binary Cu-Fe alloy were studied by transmission electron microscopy, high-energy X-ray diffraction and Mössbauer spectroscopy. The results showed that the investigated as-prepared nanoparticles contained two phases. The major phase was determined as α?F e and the minor phase as γ?F e ₂ O ₃. Furthermore, additionally annealed samples in Ar protective atmosphere were investigated. Results showed clear decrease in contribution of α?F e phase and also revealed the presence of various iron oxides (maghemite, magnetite, hematite and w?stite).     

Multiferroic properties and structural features of <Emphasis Type="Italic">M</Emphasis>-type Al-substituted barium hexaferrites

Precise studies of the crystal and magnetic structures of M-type substituted barium hexaferrites BaFe_12–x Al _x O₁₉ (0.1 ≤ x ≤ 1.2) have been performed by powder neutron diffraction in the temperature range 300–730 K. The electric polarization and the magnetization, and also the magnetoelectric effect of the compositions under study have been studied in electric (to 110 kV/m) and magnetic (to 14 T) fields at room temperature. The spontaneous polarization and significant correlation between the dielectric and magnetic subsystems have been observed at room temperature. The magnetoelectric effect value is, on average, about 5%, and it increases slightly with the aluminum cation concentration. The precise structural studies made it possible to reveal the cause and the mechanism of formation of the spontaneous polarization in M-type substituted barium hexaferrites BaFe_12–x Al _x O₁₉ (x ≤ 1.2) with a collinear ferromagnetic structure.     

Sodium–cesium molybdenum-oxide bronzes

The region of the electrolytic deposition of bialkaline sodium–cesium molybdenum-oxide bronzes is established. A correlation between the nonstoichiometry of bronzes and Mo_nO_3n–x oxides with respect to molybdenum charge density, crystal structure, and type of electrical conduction is found. The importance of the Mo_nO_3n–x homologous series in the formation of the nonstoichiometry of bronzes and their physical properties is shown. The electrophoretic deposition of coatings with binary bronzes for the anticorrosion protection of metals is investigated.     

Effect of structural defects on the magnetic properties of the EuBaCo<Subscript>1.90</Subscript>O<Subscript>5.36</Subscript> single crystal

The effect of structural defects in cobalt and oxygen sublattices with the constant average oxidation level 3+ of all cobalt ions on the magnetic properties of the EuBaCo_1.90O_5.36 single crystal has been studied. The magnetic properties of the single crystal and the polycrystalline sample of the corresponding composition are compared in the range T = 200–650 K. The results show that the cobalt-deficient EuBaCo_2–xO_5.5–δ samples demonstrate a three-dimensional XY ferromagnetic ordering of magnetic sublattices. The values of the effective magnetic moment at T > 480 K indicate the existence of the IS and HS states of Co³⁺ ions. The large difference of values of μ_eff of the EuBaCo_1.90O_5.36 single crystal and polycrystal can be due to that the magnetic ion spins lie in plane ab. The magnetic field directed along plane ab substantially influences the magnetic ordering at T < 300 K.     

Apparently enhanced magnetization of Cu(I)-modified <Emphasis Type="Italic">γ</Emphasis>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> based nanoparticles

Using a chemically induced transition method in FeCl₂ solution, γ-Fe₂O₃ based magnetic nanoparticles, in which γ-Fe₂O₃ crystallites were coated with FeCl₃?6H₂O, were prepared. During the synthesis of the γ-Fe₂O₃ nanoparticles Cu(I) modification of the particles was attempted. According to the results from both magnetization measurements and structural characterization, it was judged that a magnetic silent “dead layer”, which can be attributed to spin disorder in the surface of the γ-Fe₂O₃ crystallites due to breaking of the crystal symmetry, existed in the unmodified particles. For the Cu(I)-modified sample, the CuCl thin layer on the γ-Fe₂O₃ crystallites incurred the crystal symmetry to reduce the spin disorder, which “awakened” the “dead layer” on the surface of the γ-Fe₂O₃ crystallites, enhancing the apparent magnetization of the Cu(I)-modified nanoparticles. It was determined that the surface spin disorder of the magnetic crystallite could be related to the coating layer on the crystallite, and can be modified by altering the coating layer to enhance the effective magnetization of the magnetic nanoparticles.     

Finite size and surface effects on the magnetic properties of cobalt ferrite nanoparticles

Cobalt ferrite, CoFe₂O₄, nanoparticles in the size range 2–15 nm have been prepared using a non-aqueous solvothermal method. The magnetic studies indicate a superparamagnetic behavior, showing an increase in the blocking temperatures (ranging from 215 to more than 340 K) with the particle size, D _TEM. Fitting M versus H isotherms to the saturation approach law, the anisotropy constant, K, and the saturation magnetization, M _S, are obtained. For all the samples, it is observed that decreasing the temperature gives rise to an increase in both magnetic properties. These increases are enhanced at low temperatures (below ~160 K) and they are related to surface effects (disordered magnetic moments at the surface). The fit of the saturation magnetization to the T ² law gives larger values of the Bloch constant than expected for the bulk, increasing with decreasing the particle size (larger specific surface area). The saturation magnetization shows a linear dependence with the reciprocal particle size, 1/D _TEM, and a thickness of 3.7 to 5.1 Å was obtained for the non-magnetic or disordered layer at the surface using the dead layer theory. The hysteresis loops show a complex behavior at low temperatures (T ≤ 160 K), observing a large hysteresis at magnetic fields H > ~1000 Oe compared to smaller ones (H ≤ ~1000 Oe). From the temperature dependence of the ac magnetic susceptibility, it can be concluded that the nanoparticles are in magnetic interaction with large values of the interaction parameter T ₀, as deduced by assuming a Vogel–Fulcher dependence of the superparamagnetic relaxation time. Another evidence of the presence of magnetic interactions is the almost nearly constant value below certain temperatures, lower than the blocking temperature T _b, observed in the FC magnetization curves.     

Magnetic properties of single crystals of a new cobaltite TbBaCo<Subscript>4</Subscript>O<Subscript>7+<Emphasis Type="Italic">x</Emphasis></Subscript>

The temperature and field dependences of the magnetization of a single crystal of a new class of layered cobaltites, TbBaCo₄O_7+x , with a structure containing a Kagomé lattice and a triangular lattice were measured. The measurements were performed on a SQUID magnetometer at temperatures in the range 2–300 K and in magnetic fields of up to 55 kOe for two field orientations. The anisotropy of the magnetization was studied, and the presence of antiferromagnetic ordering in fields H < H _c and a weak magnetic-field-induced (H > H _c ) ferromagnetic component in the low-temperature range was demonstrated. The magnetic characteristics of the initial TbBaCo₄O_7+x single crystal and the single crystal annealed in an O₂ atmosphere were compared.     

Magnetic Resonance in Gadolinium Nanoparticles near the Curie Point

The Influence of temperature in the range from 275 to 320 K on ESR spectra and magnetization m of ensembles of spherical gadolinium nanoparticles with the diameter from 89 to 18 nm was studied. The particles with d = 18 nm had a cubic face centered structure and no magnetic transition. At T > T_C all particles were paramagnetic, and their g factors were g = 1.98 ± 0.02 irrespective of their size and structure. At T = T_C the particles having 28 to 89 nm in size experienced a magnetic and orientation transition; at T < T_C their m(H) dependences were described by the Langevin function, and the FMR lines broadened and shifted towards H = 0. FMR lines of the Gd particle ensembles showed a hysteresis behavior during magnetization reversal, which did not correlate with the coercivity of the particles. Dependences of the Gd nanoparticles FMR linewidth ΔH(T) changed proportionally to |T–T_C|.     

Nonstoichiometric high-pressure phase of Tm<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>3</Subscript>V<Subscript>4</Subscript>O<Subscript>12</Subscript>

Tm _x Cu₃V₄O₁₂, a perovskite-like oxide (space group, Im-3; Z = 2; a = 7.279–7.293 Å) containing vacancies in its cationic sublattice, was obtained barothermally (P = 7.0–9.0 GPa, t = 1000–1100°C) for the first time. The temperature dependences on the electrical resistivity (10–300 K) and the magnetic susceptibility (0–300 K) were investigated. It was shown that the oxide Tm _x Cu₃V₄O₁₂ is characterized by metal-type conductivity and paramagnetic properties.     

Surface and volume superconductivity of Pb embedded in nanopores

The heat capacity of lead embedded in glass nanopores (7 nm in diameter) and bulk lead was studied in the temperature range 2–40 K without a magnetic field and in magnetic fields of 1–8 T. The properties of lead nanoparticles and bulk lead were compared. The results obtained allowed us to separate the surface superconductivity from the volume superconductivity. The temperature dependence of the heat capacity of lead nanoparticles was shown to exhibit two superconducting transitions above and below the transition temperature for bulk lead (T _c = 7.2 K), which are associated with the surface and volume superconductivity. The upper critical fields H _c3 for the surface superconductivity and H _c2 for the volume superconductivity were determined. It turned out that these fields for Pb nanoparticles are two orders of magnitude higher than those for bulk lead. The “superconductor-normal metal” phase diagrams were constructed for lead nanoparticles. The study established an increase in the density of low-frequency excitations in Pb nanocrystals as compared to bulk Pb and a difference in the electronic heat capacity of Pb nanoparticles as compared to bulk Pb.     

Magnetization and Static Magnetic Susceptibility of Fine-Crystalline High-Temperature YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> Superconductors Synthesized by the Sol–Gel Method

A comparative study of the magnetization and static magnetic susceptibility of high-temperature superconductors (HTSC) YBa₂Cu₃O_y synthesized by two variants of the sol–gel method with different average sizes of crystallites 〈 D〉 ranging 0.4–2 μm has been performed in constant magnetic fields (Н ≤ 6 kOe). It has been shown that the different annealing temperatures and times, at which their crystal structure is formed, change both the average sizes of crystallites 〈D〉 and the sizes of the structural homogeneity regions 〈l〉 and, at the same time, the magnetic field penetration depth (λ) and the coherence length (ξ). As a result, such parameters as 〈D〉 ~ λ and 〈l〉 ~ ξ become comparable, leading to a change in the physical characteristics of HTSCs. It has also been shown that the superconducting transition temperature T_c determined from the measurements of magnetic characteristics in constant magnetic fields remains within values optimal for superconductivity (T_c ≈ 92 K) in the case of an optimal number (y) of oxygen atoms, which determine the levels of charge doping for a given compound.     

Phase diagrams of stratified bismuth–praseodymium-containing iron garnet films in an external magnetic field

The form of phase diagrams has been determined for epitaxial magnetic films of the composition Y_3–x–y Bi _x Pr _y Fe₅O₁₂ on the plane (H _‖ H _⊥), where H _‖ and H _⊥ are the external magnetic field components parallel and orthogonal, respectively, to the direction of the normal n to the surface of the film. The specific features have been revealed in the magnetization reversal of the objects under investigation, which are associated with their structural stratification.     

Magnetic and structural properties of Fe–Co nanowires fabricated by matrix synthesis in the pores of track membranes

Fe_1-x Co _x nanowires are obtained by electrochemical deposition into the pores of track-etched membranes. The characteristics of the growth process that allow controlling the length and aspect ratio of the nanowires are established. The elemental composition and magnetic properties of the nanowires depend on the diameter of the track-etched pores, which varies from 30 to 200 nm, and the electrochemical potential U (650–850 mV), which determines the nanowire growth rate. According to the results of elemental analysis and the Mössbauer spectroscopy data, the Co content in Fe_1-x Co _x lies in the range of x=0.20?0.25. It is found that the orientation of the magnetic moment of Fe–Co nanoparticles in the wires depends both on the track pore size d and on the nanowire growth rate. Thus, the magnetic moments in nanowires grown in 50-nm-diameter pores are oriented within 0°–40° with respect to the nanowire axis. The magnetic properties of the nanowires are explained in the framework of a theoretical model describing the magnetic dynamics of nanocomposites, which was extended to include the relaxation of the magnetization vector and to take into account interaction between the particles. The key physical parameters important for the technological applications of the nanowires are determined, their dependence on the nanowire growth conditions is traced, and the possibility of controlling them is established.     

Synthesis,structure, and optical and photocatalytic properties of quasi-one-dimensional ZnO doped with Со<Subscript>3</Subscript>O<Subscript>4</Subscript> and carbon

One-dimensional nanocomposites Zn_1–x Co _x O_1–y С _у :nCo₃O₄ and solid solutions Zn_1–x Co _x O_1–y С _у , which are promising photocatalysts for the oxidation of toxic organic compounds in visible light, are obtained via the thermolysis of Zn_1–x Co _x (HCOO)(OCH₂CH₂O)_1/2 (0.1 ≤ x ≤ 0.5) precursor in a controlled gaseous atmosphere.