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1.
Nanomaterials (Basel) ; 11(4)2021 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-33921115

RESUMO

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.

2.
Nanomaterials (Basel) ; 12(1)2021 Dec 23.
Artigo em Inglês | MEDLINE | ID: mdl-35009987

RESUMO

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 average and Dmax maximum diameter of ferromagnetic nanoinclusions were calculated and they were in the range of 40-50 nm and 160-180 nm, respectively. The mechanism of magnetic state formation is discussed in terms of the effects of the A-site cation size and B-site poly-substitution on the indirect superexchange interactions.

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