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La-, Nd- and La/Nd-based polysubstituted high-entropy oxides (HEOs) were produced by solid-state reactions. Composition of the B-site was fixed for all samples (Cr0.2Mn0.2Fe0.2Co0.2Ni0.2) with varying of A-site cation (La, Nd and La0.5Nd0.5). Nominal chemical composition of the HEOs correlates well with initial calculated stoichiometry. All produced samples are single phase with perovskite-like structure. Average particle size is critically dependent on chemical composition. Minimal average particle size (~400 nm) was observed for the La-based sample and maximal average particle size (5.8 µm) was observed for the Nd-based sample. The values of the configurational entropy of mixing for each sample were calculated. Electrical properties were investigated in the wide range of temperatures (150-450 K) and frequencies (10-1-107 Hz). Results are discussed in terms of the variable range hopping and the small polaron hopping mechanisms. Magnetic properties were analyzed from the temperature and field dependences of the specific magnetization. The frustrated state of the spin subsystem was observed, and it can be a result of the increasing entropy state. From the Zero-Field-Cooling and Field-Cooling regimes (ZFC-FC) curves, we determine the average and Smax maximum size of a ferromagnetic nanocluster in a paramagnetic matrix. The average size of a ferromagnetic cluster is ~100 nm (La-CMFCNO) and ~60 nm (LN-CMFCNO). The Smax maximum size is ~210 nm (La-CMFCNO) and ~205 nm (LN-CMFCNO). For Nd-CMFCNO, spin glass state (ferromagnetic cluster lower than 30 nm) was observed due to f-d exchange at low temperatures.
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Three high-entropy Sm(Eu,Gd)Cr0.2Mn0.2Fe0.2Co0.2Ni0.2O3 perovskite solid solutions were synthesized using the usual ceramic technology. The XRD investigation at room temperature established a single-phase perovskite product. The Rietveld refinement with the FullProf computer program in the frame of the orthorhombic Pnma (No 62) space group was realized. Along with a decrease in the V unit cell volume from ~224.33 Å3 for the Sm-based sample down to ~221.52 Å3 for the Gd-based sample, an opposite tendency was observed for the unit cell parameters as the ordinal number of the rare-earth cation increased. The average grain size was in the range of 5-8 µm. Field magnetization was measured up to 30 kOe at 50 K and 300 K. The law of approach to saturation was used to determine the Ms spontaneous magnetization that nonlinearly increased from ~1.89 emu/g (Sm) up to ~17.49 emu/g (Gd) and from ~0.59 emu/g (Sm) up to ~3.16 emu/g (Gd) at 50 K and 300 K, respectively. The Mr residual magnetization and Hc coercive force were also determined, while the SQR loop squareness, k magnetic crystallographic anisotropy coefficient, and Ha anisotropy field were calculated. Temperature magnetization was measured in a field of 30 kOe. ZFC and FC magnetization curves were fixed in a field of 100 Oe. It was discovered that the Tmo magnetic ordering temperature downward-curve decreased from ~137.98 K (Sm) down to ~133.99 K (Gd). The spin glass state with ferromagnetic nanoinclusions for all the samples was observed. The
RESUMO
The possibility of the formation of high entropy single-phase perovskites using solid-state sintering was investigated. The BaO-SrO-CaO-MgO-PbO-TiO2, BaO-SrO-CaO-MgO-PbO-Fe2O3 and Na2O-K2O-CaO-La2O3-Ce2O3-TiO2 oxide systems were investigated. The optimal synthesis temperature is found between 1150 and 1400 °C, at which the microcrystalline single phase with perovskite structure was produced. The morphology, chemical composition, crystal parameters and dielectric properties were studied and compared with that of pure BaTiO3. According to the EDX data, the single-phase product has a formula of Na0.30K0.07Ca0.24La0.18Ce0.21TiO3 and a cubic structure.
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Crystalline high-entropy single-phase products with a magnetoplumbite structure with grains in the µm range were obtained using solid-state sintering. The synthesis temperature was up to 1400 °C. The morphology, chemical composition, crystal structure, magnetic, and electrodynamic properties were studied and compared with pure barium hexaferrite BaFe12O19 matrix. The polysubstituted high-entropy single-phase product contains five doping elements at a high concentration level. According to the EDX data, the new compound has a formula of Ba(Fe6Ga1.25In1.17Ti1.21Cr1.22Co1.15)O19. The calculated cell parameter values were a = 5.9253(5) Å, c = 23.5257(22) Å, and V = 715.32(9) ų. The increase in the unit cell for the substituted sample was expected due to the different ionic radius of Ti/In/Ga/Cr/Co compared with Fe3+. The electrodynamic measurements were performed. The dielectric and magnetic permeabilities were stable in the frequency range from 2 to 12 GHz. In this frequency range, the dielectric and magnetic losses were -0.2/0.2. Due to these electrodynamic parameters, this material can be used in the design of microwave strip devices.
RESUMO
Barium hexaferrite powder samples with grains in the µm-range were obtained from solid-state sintering, and crystals with sizes up to 5 mm grown from PbO, Na2CO3, and BaB2O4 fluxes, respectively. Carbonate and borate fluxes provide the largest and structurally best crystals at significantly lower growth temperatures of 1533 K compared to flux-free synthesis (1623 K). The maximum synthesis temperature can be further reduced by the application of PbO-containing fluxes (down to 1223 K upon use of 80 at % PbO), however, Pb-substituted crystals Ba1-xPbxFe12O19 with Pb contents in the range of 0.23(2) ≤ x ≤ 0.80(2) form, depending on growth temperature and flux PbO content. The degree of Pb-substitution has only a minor influence on unit cell and magnetic parameters, although the values for Curie temperature, saturation magnetization, as well as the coercivity of these samples are significantly reduced in comparison with those from samples obtained from the other fluxes. Due to the lowest level of impurities, the samples from carbonate flux show superior quality compared to materials obtained using other methods.
RESUMO
The coexistence of three valence states of Mn ions, namely, +2, +3, and +4, in substituted magnetoplumbite-type BaFe12-xMnxO19 was observed by soft X-ray absorption spectroscopy at the Mn-L2,3 edge. We infer that the occurrence of multiple valence states of Mn situated in the pristine purely iron(III) compound BaFe12O19 is made possible by the fact that the charge disproportionation of Mn3+ into Mn2+ and Mn4+ requires less energy than that of Fe3+ into Fe2+ and Fe4+, related to the smaller effective Coulomb interaction of Mn3+ (d4) compared to Fe3+ (d5). The different chemical environments determine the location of the differently charged ions: with Mn3+ occupying positions with (distorted) octahedral local symmetry, Mn4+ ions prefer octahedrally coordinated sites in order to optimize their covalent bonding. Larger and more ionic bonded Mn2+ ions with a spherical charge distribution accumulate at tetrahedrally coordinated sites. Simulations of the experimental Mn-L2,3 XAS spectra of two different samples with x = 1.5 and x = 1.7 led to Mn2+:Mn3+:Mn4+ atomic ratios of 0.16:0.51:0.33 and 0.19:0.57:0.24.