Formation and properties of high entropy oxides in Co-Cr-Fe-Mg-Mn-Ni-O system: Novel (Cr,Fe,Mg,Mn,Ni)3O4 and (Co,Cr,Fe,Mg,Mn)3O4 high entropy spinels

Possibility of formation of quinary and senary equimolar high entropy oxides from the Co-Cr-Fe-Mg-Mn-Ni-O system is presented. Different proposed compositions are synthesized using the solid-state reaction route at high temperatures (900−1100 °C) and quenched to room temperature. Phase composition of the samples is studied, showing tendency toward formation of two main phases: rock salt-structured Fm-3 m and spinel-structured Fd-3 m. It is documented that the annealing temperature has a profound effect on stability of both structures, and at 1100 °C usually the highest content of Fm-3 m phase is usually observed. Three different oxides, namely, (Co,Cr,Fe,Mn,Ni)₃O₄, (Co,Cr,Fe,Mg,Mn)₃O₄ and (Cr,Fe,Mg,Mn,Ni)₃O₄ are obtained as single-phase materials, which structure can be described as the high entropy Fd-3 m spinel one. The latter two compounds have not been previously reported in the literature. Activated character of the electrical conductivity dependence on temperature is observed, with relatively high total conductivity at high temperatures and corresponding high absolute values of Seebeck coefficient.     

Structural,electrical, magnetic and magnetoelectric properties of Fe doped BaTiO3 ceramics

In the present work structural, electrical, magnetic and magnetodielectric properties of BaTi_1−xFe_xO₃ (0%≤x≤10%) ceramics have been investigated. X-ray diffraction (XRD) study reveals that the coexistence of tetragonal and hexagonal phases is strongly influenced by Fe doping concentration. The increase in Fe-doping content leads to the development of hexagonal phase along with an increase in average grain size. A reduction in the dielectric properties is also observed. All BaTi_1−xFe_xO₃ (BTFO) compositions exhibit ferroelectric behavior at room temperature. Remnant polarization (P_r) for pure BaTiO₃ (BTO) has been found to be 7.50 µC/cm² and further decreases with an increase in the Fe concentration. All Fe doped samples exhibit ferromagnetic ordering with saturation magnetization (M_s) being 26 memu/g for x=2.5%. Further, at x=5%, it decreases and thereafter again increases with Fe concentration. The magnetodielectric coefficient increases with Fe doping concentration and highest value found to be 2.80 at x=2.5%.     

Rapid microwave-assisted synthesis and magnetic properties of high-entropy spinel (Cr0.2Mn0.2Fe0.2Co0.2-xNi0.2Znx)3O4 nanoparticles

High-entropy oxide (HEO) has recently become popular because of its unique multifunctional performance. In this study, we developed a novel microwave-assisted method for the production of HEO nanoparticles with the composition (Cr_0.2Fe_0.2Mn_0.2Co_0.2-xNi_0.2Zn_x)₃O₄ (x = 0, 0.05, 0.1, and 0.2). The results revealed that all metallic elements were uniformly distributed throughout the single-phase cubic spinel structure of the HEO nanoparticles. The particle size distributions of four fabricated samples ranged from 10 to 50 nm. Because of its numerous advantages such as the ultrafast and low-temperature fabrication of nanoscale and high-purity products at a relatively low cost, the suggested methodology is an excellent synthesis method. The original HEO spinel (x = 0) achieved saturated magnetization (M_s) and coercivity (H_c) values of 24.3 emu/g and 160 Oe, respectively, at room temperature. Zinc substitution in the HEO composition indicated that M_s and H_c decreased with increasing zinc concentration owing to its non-magnetic nature.     

Synthesis and magnetic properties of complex oxides La0.67Sr0.33MnO3 nanowire arrays

As a new approach of melt-injection-decomposition method, it has been successfully adopted for the synthesis of the complex oxides La_0.67Sr_0.33MnO₃ nanowire arrays. X-ray diffraction studies confirmed the formation of perovskite manganite phase of the sample. Transmission electron microscope and scanning electron microscope characterizations showed a large quantity of one-dimensional nanowires is obtained and the nanowires are continuous, concrete, oriented and rather uniform with an average diameter of 170 nm and length of several tens of micrometers. Magnetic measurements exhibited good ferromagnetic properties at the temperature of 10 K and 300 K respectively. The transition temperature of the complex oxides La_0.67Sr_0.33MnO₃ nanowire arrays is about 350 K, which will endow their great potential applications in magnetoresistance, spintronics or sensor fields at room temperature.     

Structural,morphological, and magnetic properties of sol-gel derived La0.7Ca0.3MnO3 manganite nanoparticles

La_0.7Ca_0.3MnO₃ (LCMO) manganite nanoparticles are synthesized via a sol-gel route at different annealed temperatures. Their structural, morphological, and magnetic properties are investigated. The X-ray diffraction patterns coupled with electron diffraction confirm that all the LCMO samples are single phase and crystallize in the orthorhombic perovskite structure (Pnma space group). The morphology of the samples observed by TEM, reveals a spherical shape with an average grain size lower than 50 nm. The resolved lattice fringes in high-resolution TEM images also reveal the single crystalline nature of the LCMO nanoparticles. Magnetization measurements versus temperature under low magnetic field (0.01 T) show a paramagnetic - ferromagnetic transition for all the samples. The Curie temperature (T_c) is found to be decreased with increasing the annealed temperature. A bifurcation is observed in the zero field-cooled and field-cooled magnetizations, indicating a competition between ferromagnetic and antiferromagnetic interactions in the nanoparticles at low temperatures. Field-cooled hysteresis measurements suggest a cluster glasslike behavior of the nanoparticles. Room temperature and low temperature M - H loops demonstrate that all the samples exhibit ferromagnetic behavior at 5 K, whereas a paramagnetic behavior at room temperature. Resistivity behavior of the LCMO samples shows that they exhibit a metal - insulator transition. Magnetoresistance of ~ 50% at the field up to 8 T was observed at 2 K in the LSCO samples annealed at 600 °C.     

Ferroelectric,dielectric, magnetic,structural and photocatalytic properties of Co and Fe doped LaCrO3 perovskite synthesized via micro-emulsion route

In the present investigation, La_1-xCo_xCr_1-yFe_yO₃ (x,y = 0.0, 0.12, 0.36, 0.60) perovskite was fabricated via a facile micro-emulsion route. The synthesized perovskites were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) techniques to examine the effect of Co and Fe ions on the physico-chemical properties. The ferroelectric, dielectric, and magnetic properties of La_1-xCo_xCr_1-yFe_yO₃ were changed significantly as a function of dopants contents (Co and Fe ions). Outcomes revealed that the dielectric, ferroelectric and magnetic properties of LaCrO₃ perovskite can be tuned significantly via Co and Fe doping and La_0.40Co_0.60Cr_0.40Fe_0.60O₃ have potential for photocatalytic dye removal under (visible) light expoure. The photocatalytic activity (PCA) of the pristine LaCrO₃ and La_0.40Co_0.60Cr_0.40Fe_0.60O₃ photocatalyst was evaluated under (visible) light irradiation for crystal violet (CV) dye. Experimental results revealed that La_0.40Co_0.60Cr_0.40Fe_0.60O₃ photocatalyst degrdae almost 77.21% CV dye with the rate constant value of 0.01475 min^?1. In the presence of isopropyl alcohol (IPA) scavenger, the PCA of the La_0.40Co_0.60Cr_0.40Fe_0.60O₃ photocatalyst and rate constant value of the photocatalytic reaction decreased to 32.5% and 0.00491 min^?1, suggesting the superoxide as main active specie. Results revealed that Co and Fe doping doped material is efficient for photocatalytic presentations under solar light expoure.     

Exchange-coupling effect in hard/soft SrTb0.01Tm0.01Fe11.98O19/AFe2O4 (where A = Co,Ni, Zn,Cu and Mn) composites

In this study, series of hard/soft SrTb_0.01Tm_0.01Fe_11.98O₁₉/AFe₂O₄ (where A = Co, Ni, Zn, Cu and Mn) composites were fabricated via a single-pot citrate sol-gel approach. The structure, morphology and magnetic properties of prepared composite samples were investigated via X-ray diffraction (XRD), scanning and transmission electron microscopes (SEM - TEM) and vibrating sample magnetometer (VSM). The XRD analysis of all composite samples showed the co-existence of both hard (Sr hexaferrite) and soft (spinel ferrites) ferrite phases with minor impurity. TEM micrographs displayed well-distinguished particles of SrM and AFe₂O₄ with different symmetry. The magnetic M − H hysteresis loops were performed at room temperature (RT; T = 300 K) and low temperature (T = 10 K) using VSM instrument. The magnitudes of various magnetic parameters including saturation magnetization (M_s), squareness ratio (SQR = M_r/M_s), remanence (M_r) and coercivity (H_c) were determined. M − H loops revealed smoothed curves and the dM/dH versus H curves exposed only a single peak, indicating that the exchange-coupling effect was accomplished in one-step. Moreover, the various composites showed relatively high M_s, M_r, and H_c values. The obtained results revealed the occurrence of exchange-coupling effect among soft and hard magnetic phases. The magnetic properties of various hard/soft SrTb_0.01Tm_0.01Fe_11.98O₁₉/AFe₂O₄ composites (where A = Co, Ni, Zn, Cu and Mn) were evaluated also by ZFC-FC magnetization measurements with respect to different soft phases. A peak temperature in ZFC curves occurred for various prepared composites. This peak is attributed to competition of the movement of magnetic domain walls and thermal activation. The present study offers a simple but efficient route for the fabrication of exchange-coupled nanocomposites with the chemical formula SrFe_11.98Tb_0.01Tm_0.01O₁₉/AFe₂O₄ (where A = Co, Ni, Zn, Cu and Mn) having controllable magnetic properties. It was found that the SrTb_0.01Tm_0.01Fe_11.98O₁₉/CoFe₂O₄ composite sample displayed the strongest exchange-coupling behavior among the different prepared composite products.     

Design,fabrication, and magnetic properties of novel (Ni,Cr,Zr)-co-doped M-type barium ferrite ceramics

Multicomponent co-doping is an effective method to balance the counteracting magnetic properties of ferrite ceramics. In this work, novel (Ni,Cr,Zr)-co-doped M-type barium hexaferrites (BaFe_12-3xNi_xCr_xZr_xO₁₉, x = 0–0.8) were designed and synthesized by traditional solid-state reaction. Thermogravimetric analysis indicated that NiO would participate in the formation of secondary phase NiFe₂O₄ in the as-synthesized powder. Through traditional solid-state sintering, by using the synthesized pure-phase magnetic powders, almost full-dense ceramics were fabricated. Visual high-temperature deformation analysis revealed that there was no obvious difference in the sintering behavior and densification temperature of the ceramics with different compositional x, due to the low sintering activity of the as-synthesized magnetic powders. And X-ray diffraction analysis indicated that all the fabricated ceramics are of pure-phase M-type barium ferrite, and the lattice parameter c/a firstly increased as x raised up to 0.4 and then remained almost unchanged with further increased x, even if the lattice distortion became heavier. Microstructure examination revealed that the grain size monotonously decreased as the quantity of the substituent ions increased. The remnant magnetization and coercivity of the fabricated ceramics decreased monotonously as x increased, while the saturated magnetization could be maintained till the samples with x ≤ 0.4. Taking all the parameters into consideration, the samples with x = 0.4 might be a good candidate for transformer cores.     

Microstructure evolution and magnetic properties of Eu doped CuFeO2 multiferroic ceramics studied by positron annihilation

A series of multiferroic ceramics CuFe_1-xEu_xO₂ (x?=?0–0.10) are prepared by traditional solid-state reaction. The effects of Eu doping on the microstructure, vacancy-type defects, and magnetic properties of CuFeO₂ ceramics are investigated systematically by means of X-ray diffraction, Raman spectroscopy, scanning electron microscope, positron annihilation lifetime and physical property measurement system. The results show that no phase transition occurs in the entire range of doping content (x?=?0–0.10), but the single phase structure is damaged by high Eu content (x?=?0.04–0.10). Positron annihilation measurements indicate that the local electron density and the vacancy-type defect concentration increase gradually with the increase in Eu content from 0 to 0.08. Furthermore, abnormal changes in lifetime parameters can be found in x?=?0.10 sample induced by the existence of impurity phase in the system. The magnetic measurements reveal that all the samples exhibit two successive magnetic transitions at T?=?15 and 11?K. In x?=?0.02 sample, the coexistence of ferromagnetism and antiferromagnetism can be found, and a maximum saturation magnetization of 11.548?emu/g at 5?kOe is achieved. The possible reasons for the above observations are discussed in detail.     

纳米LaMO3(M＝Cr,Mn,Fe,Co)化合物的光催化氧化活性分析

采用柠檬酸络合法制备了纳米钙钛矿型LaMO3(M =Cr,Mn ,Fe ,Co)化合物 ,并对其进行XRD和TEM分析 ,发现所制样品具有单一晶相结构 ,粒径在 1～ 10 0nm之间。在纳米LaMO3(M =Cr,Mn ,Fe ,Co)悬浮体系中进行了水溶性染料酸性红 3B光催化降解实验 ,其光催化氧化活性变化趋势为LaCrO3相似文献   

Structural,optical and magnetic behavior of (Pr,Fe) co-doped ZnO based dilute magnetic semiconducting nanocrystals

The development of ZnO-based dilute magnetic semiconductor nanostructures co-doped with rare-earth and transition metals has attracted substantial attention for spintronics application. In this work, Pr (1%) and Fe (1%, 3%, and 5%) co-doped ZnO nanoparticles (NPs) were synthesized via co-precipitation method, and their structural, morphological, optical, photoluminescence, and magnetic properties were investigated. The single-phase wurtzite hexagonal crystal structure of all samples was detected via X-ray diffraction. Morphological analysis revealed spherical shape of the NPs with an average size in 20–50 nm range. The ultraviolet (UV)–visible measurements showed a redshift in the UV band and a slight change in the bandgap of the co-doped NPs. Fourier transform infrared analysis proved the existence of different functional groups in all synthesized NPs. X-ray photoelectron spectroscopy confirmed that Pr and Fe ions incorporated in the host ZnO lattice exhibit Pr³⁺ and Fe³⁺ oxidation states, respectively. Photoluminescence analysis showed that incorporated ions induce characteristic emission bands and structural defects in the synthesized NPs. Magnetic characterization indicated that the ZnO NPs exhibit a diamagnetic nature. However, the (Pr, Fe) co-doped NPs exhibit ferromagnetism at room temperature because of the interactions between Pr³⁺ and Fe³⁺ ions and trapped electrons mediated by bound magnetic polarons. Excellent optical and magnetic properties of synthesized samples may render them promising candidates for spintronics applications.     

Structural,magnetic and electronic structure properties of pure and Ti doped Mg0.95Mn0.05Fe2O4 nanocrystalline thin films

Thin films of pure and Ti doped Mg_0.95Mn_0.05Fe₂O₄ deposited using pulsed laser deposition technique, have been characterized using X-ray diffraction, Raman spectroscopy, dc magnetization, atomic force microscopy, magnetic force microscopy and near edge X-ray absorption fine structure spectroscopy measurements. X-ray diffraction and Raman spectroscopy measurements indicate that both the films have single phase and the polycrystalline behavior with FCC structure. The grain size calculated using XRD data was 18 and 27 nm for pure and Ti doped films, respectively. Magnetic measurements reflect that pure film has superparamagnetic behavior while Ti doped film has soft ferrimagnetic behavior at room temperature. Atomic force microscopy measurements indicate that both the films are nanocrystalline in nature. Near edge X-ray absorption fine structure spectroscopy measurements clearly infer that Fe ions are in mixed valence state.     

Solution combustion synthesis of new metal borophosphates (Fe1-xCrx)2B(PO4)3: Structural,thermal, surface,and magnetic properties

The new borophosphates were successfully synthesized by solution combustion synthesis assisted with glycine. The obtained materials were systematically characterized by Fourier-transform infrared spectroscopy, X-ray powder diffraction, UV–visible spectroscopy, thermogravimetric analysis, scanning electron microscopy, Brauner-Emmett-Teller surface area, and magnetometry. The Rietveld refinements indicated that Fe₂B(PO₄)₃ is a hexagonal, space group P63/m with a = b = 8.029 and c = 7.408. As Cr substitutes the Fe atoms, there is a significant decrease in the lattice parameters. When all Fe atoms are replaced by Cr, Cr₂B(PO₄)₃ is formed and the structure turns out to be a trigonal, space group P3 with a = b = 7.950 and c = 7.360. The materials are thermally stable and demonstrate paramagnetic behavior at room temperature. The magnetization increases as the iron content increases because of the high magnetic moment of the iron ion. Temperature-dependent magnetic measurements reveal that Fe₂B(PO₄)₃ has a Néel transition at 30 K and the Néel temperature decreases with Cr substitution.     

Structural,magnetic and photocatalytic properties of Sr2+ doped BiFeO3 nanofibres fabricated by electrospinning

Sr²⁺ doped BiFeO₃ (Bi_1-xSr_xFeO₃, 0?≤x?≤?0.35) nanofibres were fabricated by a sol-gel based electrospinning method. The as-spun BiFeO₃ (BFO) nanofibres consist of fine grained particles with high crystallinity. With Sr²⁺ doping, both the magnetic and photocatalytic properties of BFO are effectively improved. The best photocatalytic property for degradation of the methylene blue (MB) is obtained in Bi_0.75Sr_0.25FeO₃ nanofibres due to their weakest photoluminescence (PL) intensity. Meanwhile, the photocatalytic property of Bi_0.75Sr_0.25FeO₃ nanofibres is much higher than that of nanoparticles with the same constituent, which is attributed to the unique one-dimension fibrous structure benefiting the separation and decreased recombination of e^-/h⁺ pairs. This work proposes an effective approach for the degradation of organic pollutes.     

Sol gel derived MnTi doped Co2 W-type hexagonal ferrites: Structural,physical, spectral and magnetic evaluations

W-type BaSr Co₂ hexaferrites doped with Mn and Ti of the following composition Ba_0.5Sr_0.5Co₂Mn_xTi_xFe_16-2xO₂₇ (x = 0.00, 0.50, 1.00, 1.50, 2.00, 2.50) were synthesized by sol-gel auto ignition method. The structure, phase, spectral bands, microstructure, and magnetic behaviors of the MnTi doped BaSr Co₂ W-type ferrites were determined using XRD, FTIR, FESEM, and VSM respectively. Structural and physical parameters such as lattice parameters ‘a’ and ‘c’, crystallite size, cell volume, micro strain, porosity, bulk and X-ray density of the MnTi doped BaSr Co₂ W-type hexaferrites were evaluated. The detailed and refined structural properties were determined using the Rietveld refinement of the MnTi doped BaSr Co₂ W-type hexagonal ferrites. MAUD software was used for the refinement of the MnTi doped BaSr Co₂ W-type hexagonal ferrites patterns. Rb, Rwp and Rexp values were found in the range of 10–19 for MnTi doped BaSr Co₂ W-type hexagonal ferrites. The force constants at respective sites were also investigated through FTIR studies. FESEM images showed the hexagonal shape of the MnTi doped hexaferrites. Magnetic properties were estimated from the hysteresis loops recorded by VSM. The magnetic properties were decreased with the MnTi doping. However, anisotropic field was also found to be decreased with MnTi doping. This might be due to the ionic radii and nonmagnetic substitution of Ti in BaSr Co₂ W-type hexagonal ferrites. The low coercivity values of these ferrites suggest the use of MnTi doped BaSr Co₂ W-type ferrites for microwave absorption, memory devices and magnetic radar absorbing materials (MRAMs) in high frequency regime.     

Structural,magnetic and electrical properties of K0.5Na0.5NbO3 doped NiZnCo ferrite for high frequency device

Ni_0.6Zn_0.4Co_0.2Fe_1.8O₄ ferrites doped with x wt.% K_0.5Na_0.5NbO₃ (0.00≤x≤1.00) were successfully prepared by solid-state reaction method. The lattice parameters a decreased and the diffraction peak of (311) shifted to higher angle with the increase of K_0.5Na_0.5NbO₃ (KNN) content. The grain size D initially increased to 3.12 μm (x = 0.50) and then reduced to 2.66 μm (x=1.00). The study also showed the addition of KNN effectively improved magnetic and electrical properties of NiZnCo ferrites. The saturation magnetization Ms decreased from 60.59 to 46.11 emu/g and the coercivity Hc overall showed a decreasing trend from 84.64–67.00 Oe. The dielectric constant ε´ of prepared samples increased when x≤0.75, then decreased when x>0.75, and all prepared samples had low loss tangent tanδ at high frequency. In addition, all samples exhibited high resistivity ρ and activation energy E_ρ.     

Analysis of structural,optical and magnetic properties of Fe/Co co-doped ZnO nanocrystals

In this paper, the structural, optical and magnetic properties of pure ZnO and Fe/Co co-doped ZnO nanoparticles are presented. Rietveld refinement of XRD pattern revealed the single phase wurtzite structure for prepared samples. FTIR study confirmed the formation of tetrahedral coordination between zinc and oxygen ions. SEM and TEM techniques were used to examine the morphology of samples. The absorption spectra showed the decrease in optical energy band gap with Fe/Co co-doping in ZnO. PL spectra demonstrated five peaks correspond to the ultraviolet region, violet, violet-blue, blue-green and green in the visible region. Emission peak in the UV region is attributed to near band-edge excitonic emission. Other four emission peaks in PL spectra are related to different defect states. M-H curve showed room temperature ferromagnetic (RTFM) behaviour of doped ZnO sample. This paper enhances the understanding of structural, optical and magnetic properties of Fe/Co co-doped ZnO nanocrystals for application in spintronics, solar cells, and ceramics.     

Structural,dielectric, and magnetic properties of reduced graphene oxide-wrapped MnFe2O4 composites synthesized by in-situ sol-gel autocombustion method

Herein, the reduced graphene oxide (rGO) wrapped MnFe₂O₄ (MFO@rGO) composites with different rGO content of 10, 20, 30, and 40 wt% have been synthesized by a one-step in-situ sol-gel autocombustion method. The synthesized composites have been tested for their structural, electrical, dielectric, and magnetic characteristics. The composites are characterized by using standard techniques (XRD, HR-TEM, FTIR, and Raman spectroscopy). The composite having 20 wt% of rGO exhibits the highest value of dielectric constant (ε′～1.32 × 10⁴ at 100 Hz, ε′～143 at 1 MHz) and dc conductivity (σ_dc = 4.31 × 10^?6 Ω^?1-cm^?1) among the investigated composites. The dipole polarization contribution to the dielectric relaxation behavior of MFO@rGO composites is observed, which arises from the increased vacancy defect dipoles in rGO sheets. The impedance studies show the existence of two different time relaxation phenomena in MFO@rGO composites. The magnetic measurements reveal the superparamagnetic behavior of composites. The saturation magnetization of composites decreases first with the increase in rGO content up to 20 wt% and then increases with a further increase in rGO content. The findings of this research make these composites a potential candidate for various applications such as EMI shielding and energy storage devices.