Microstructure and magnetic properties of nickel-zinc ferrite ceramics fabricated by spark plasma sintering

Dense nickel-zinc (NiZn) ferrite ceramics were successfully fabricated within tens of seconds via spark plasma sintering. The phase composition and microstructure of the sintered samples were characterized by X-ray diffraction and scanning electron microscopy, respectively. The static magnetic properties at room temperature and Curie temperature of the samples were investigated by vibrating sample magnetometry. The results indicated that the main phase of the sintered samples was Ni_0.75Zn_0.25Fe₂O₄ with spinal structure, and the sintering temperature and heating rate observably affected the microstructure and density, then the magnetic properties of the sample. The Joule heat generated by NiZn ferrite during spark plasma sintering was very important for the rapid preparation of the sample with high density and small grain size. The low sintering temperature and heating rate would be helpful to obtain samples with small grain size, high density, and then good magnetic properties. The samples sintered at 900 °C with the heating rate of 5–10 °C/s were characterized of the relative density above 95%, 4πM_s value beyond 4000 Gs and coercivity below 27.7 Oe.     

Anisotropic thermal expansion and ionic conductivity of a crystal-oriented,Mg2+-conducting NASICON-type solid electrolyte

Multivalent ion-conducting ceramics are required for the manufacture of high-safety, high-capacity rechargeable batteries. However, the low ionic conductivity of solid electrolytes and discrepancies in the thermal expansion between the battery components limit their widespread application. Furthermore, anisotropic thermal expansion in crystals during battery manufacturing and the charge-discharge cycles causes the formation of microcracks, which degrade the battery performance. The physical properties of ceramic materials with anisotropic crystal structures can be modified by varying the crystallographic orientation of their grains. In this study, a co-precipitation approach was used to synthesize an Mg²⁺-conducting (Mg_0.1Hf_0.9)_4/3.8Nb(PO₄)₃ solid electrolyte, and the grain orientation in the bulk sample was controlled using strong magnetic fields during the slip casting process. The results showed that inducing an orientation along the c-axis enhanced the apparent ionic conductivity of the bulk sample. It was also observed that (Mg_0.1Hf_0.9)_4/3.8Nb(PO₄)₃ crystal has a negative volumetric thermal expansion despite a positive linear thermal expansion along its c-axis. By adjusting the c-axis orientation of the grains, (Mg_0.1Hf_0.9)_4/3.8Nb(PO₄)₃ electrolytes with negative or positive linear thermal expansion coefficient have been produced. The findings of this study suggest that solid-electrolytes with negative, positive, or zero linear thermal expansion can be produced to create more compatible and higher-performance solid-state devices.     

Effects of Ni2+ concentration on the composition,structure, magnetic properties,and DC-bias superposition characteristics of NiCuZn ferrites

Ni_xCu_0.2Zn_yFe_1.98O₄ (x = 0.16, 0.26, 0.35, 0.43, 0.50; y = 0.8?x) ferrites were prepared via solid-state reaction. The influence of Ni²⁺ concentration on ferrites composition, microstructure, magnetic properties and DC-bias superposition characteristics was studied by XRD, SEM, XPS, and VSM. Then, the effect of magnetic properties on the DC-bias superposition characteristics was analyzed. The results showed that the ferrites sintered at 900 °C for 3 h were all in pure spinel phase with an average grain size of 7.5 μm and a relative density of about 5.15 g cm^?3. With the increase in Ni²⁺ concentration, the saturation magnetization (M_s) and coercivity (H_c) of ferrites increased, but the magnetocrystalline anisotropy constant (K₁) first increased and then decreased. And the M_s, H_c, and K₁ of the specimen with x = 0.43 were 63.62 emu·g^?1, 27.36 Oe, and 1813.17 Oe·emu·g^?1, respectively. In particular, the specimen of x = 0.50 achieved the best DC superposition characteristics, where the H_70% was about 220 A m^?1. The incremental permeability of the specimens decreased rapidly at a bias magnetic field <400 A m^?1. The variation mainly originated from the domain wall displacement, and the rate of decrease was influenced by both M_s and K₁. At a bias magnetic field ≥400 A m^?1, the incremental permeability of the specimens decreased slowly, mainly because the number of domain walls decreased until disappearing, and the specimens tended to become a single domain structure. And the rate of decrease of incremental permeability was mainly affected by K₁.     

Coexistence of antiferro- and ferrimagnetism in the spinel ZnFe2O4 with an inversion degree δ lower than 0.3

Samples with inversion parameter values (δ) ranging from 0.27 to 0.14 while maintaining the crystallite size value have been successfully fabricated from commercially available powders by mechanical grinding and thermal annealing treatments at temperatures ranging between 400 and 600 °C. Detailed characterization studies of these samples using X-ray, neutron diffraction and magnetic measurements have confirmed for the first time the simultaneous coexistence at 2 K of short range antiferromagnetic and ferrimagnetic ordering for a wide range of the inversion parameter. The magnetic phase diagram obtained is different from the one previously reported, which shows at 2 K the coexistence of long range antiferromagnetic order and short range order for values of inversion parameters less than 0.1 and the presence of a ferrimagnetic order only for values of δ > 0.2. At room temperature, the Rietveld analysis of NPD patterns and the magnetization curves showed a paramagnetic behavior in the samples with δ ≤ 0.1. For the samples with higher cationic inversion, typical hysteresis curves of ferrimagnetic materials were observed and the saturation magnetization values obtained agree quite well with the net magnetic moment obtained from the Rietveld refinement of the neutron diffraction patterns.     

Magnetic field-enhanced photocatalytic nitrogen fixation over defect-rich ferroelectric Bi2WO6

Photocatalytic N₂ fixation is a promising and sustainable manufacturing process of ammonia (NH₃); however, the NH₃ production rate by this method is very low, thus severely restricting further application of this sustainable technology. Therefore, developing an efficient photocatalyst for N₂ fixation under mild conditions is urgently required. Herein, ferroelectric Bi₂WO₆ materials with different surface oxygen defects were prepared, and the concentration of corresponding defects was controlled by adjusting the thermal reduction time. The abundant oxygen defects in Bi₂WO₆ can provide more reactive sites to promote the effective adsorption of N₂, and the photogenerated charge carrier can be efficiently separated benefiting from the internal electric field. These would weaken the N₂ triple bond and reduce the activation energy barrier for the conversion of N₂ to NH₃ under mild conditions. In the absence of sacrificial agents and cocatalysts, the optimized Bi₂WO₆ with oxygen defects shows an indigenous NH₃ yield of 132.175 μmol·g^-1·L^-1·h^-1, which is more than two times higher than that of the original Bi₂WO₆. Surprisingly, the Bi₂WO₆ with oxygen defects produced more than eight times NH₃ (471.13 μmol·g^-1·L^-1·h^-1) than that of the original Bi₂WO₆ when assisted by an external magnetic field, thus providing a new perspective for further enhancing the N₂ fixation performance.     

Modulating the structure,vacancy defects,magnetic and dielectric properties in multiferroic GdMnO3 ceramics by alkaline earth ion substitution

This investigation highlights the significant influences of alkaline earth ion substitution for Gd on the structure, vacancy defects, magnetic and dielectric properties in GdMnO₃ (GMO) ceramics synthesized using the solid-state reaction method. The structure measurements indicate that all of the Gd_0.90A_0.10MnO₃ (A = Ca, Sr, Ba) samples show a single phase structure, and the introduction of A²⁺ ion induces structure distortion. A²⁺ ions substitution increases the Mn⁴⁺ ion concentration in GMOs, but has no significant effect on the oxygen vacancy concentration. All samples with irregular grain shapes have dense microstructures, and A²⁺ ion substitution inhibits grain growth. Positron annihilation experimental results indicate that A²⁺ ion substitution can increase the vacancy size and concentration, while the vacancy concentration increases first and then decreases with increasing A²⁺ ion radius. The evolution of the temperature- and magnetic field-dependent magnetization curves shows that A²⁺ ion substitution could obviously affect the magnetic state of GMOs, and improve the magnetic transition temperature and magnetization of Gd_0.90A_0.10MnO₃. The dielectric measurements reveal that the A²⁺ ion substituted samples exhibit giant dielectric constant characteristics over a broad frequency range. It is found that the enhanced magnetization of Gd_0.90A_0.10MnO₃ has a close relationship with the vacancy concentration, and the giant dielectric constant behaviors in Gd_0.90A_0.10MnO₃ ceramics can be associated with the mixed-valent structure of Mn³⁺/Mn⁴⁺.     

Optimization of structural,electrical, and magnetic properties of ytterbium substituted W-type hexaferrite for multi-layer chip inductors

The rare earth (Yb³⁺) substituted W-type hexagonal ferrites with composition CaPb_2-xYb_xFe₁₆O₂₇ (x = 0.0, 0.5, 1.0, 1.5, 2.0) were synthesized by a facile and cost-effective sol-gel auto combustion method with post heat treatment. The synthesized hexagonal ferrites were characterized by a variety of analytical techniques, and an impedance analyzer was used to investigate the effects of Ytterbium on structural, magnetic, spectral and dielectric properties. The relationship between their impedance, structure and dielectric properties was investigated. The X-ray diffraction patterns verify the presence of single-phase W-type hexagonal ferrites. Physical properties such as D_bulk (bulk density), D_xrd (X-ray density), and P (porosity) of the CaPb_2-xYb_xFe₁₆O₂₇ W-type hexagonal ferrites were calculated. The bulk density of all the samples was decreased, and X-ray intensity was increased with the Ytterbium replacement in the W-type hexaferrite. By adding Yb³⁺ ions, the lattice parameters, cell volume and X-ray density were reduced due to the substitution of ytterbium with smaller ionic radii compared to the lead ion with large ionic radii. The AC-conductivity was increased from (1.523 × 10^?5 to 6.699 × 10^?5) Ωcm^?1. The dielectric constant and tangent loss was found to decrease substantially. The magnetic properties were found to enhance by the substitution of Yb³⁺. The low coercivity value of Yb³⁺ substituted W-type hexagonal ferrites are suitable for magnetic recording media operated at a high-frequency regime. The enhancement of electrical, dielectric and magnetic characteristics suggests these materials as promising for multi-layer chip inductors (MLCIs) circuit applications.     

Effect of organic solvent on the cold sintering processing of SrFe12O19 platelet-based permanent magnets

In this work we have investigated the effect of the solvent during the processing of SrFe₁₂O₁₉ platelet-based permanent magnets by cold sintering process (CSP) plus a post-thermal treatment. Several organic solvents: glacial acetic acid, oleic acid and oleylamine have been analyzed, optimizing the CSP temperatures at 190?270 °C, under pressures of 375?670 MPa and 6?50 wt% of solvent. Modifications in the morphological and structural properties are identified depending on the solvent, which impacts on the magnetic response. Independently of the solvent, the mechanical integrity of ferrite magnets obtained by CSP is improved by a post-annealing at 1100 °C for 2 h, resulting in relative densities around 92 % with an average grain size of 1 μm and a fraction of SrFe₁₂O₁₉ phase >91 %. H_C ≥ 2.1 kOe and M_S of 73 emu/g are obtained in the final sintered ceramic magnets, exhibiting the highest H_C value of 2.8 kOe for the magnet sintered using glacial acetic acid.     

Novel Bi4O5Br2/MnxZn1-xFe2O4 magnetic composite with an enhanced photodegradation activity and excellent recyclability

Bi₄O₅Br₂/Mn_xZn_1-xFe₂O₄ nanocomposites with impressive photocatalytic and recyclability properties were synthesised using a microemulsion method. In addition to the photocatalytic effect, the crystal structure and morphology, photoelectrochemical characteristics, magnetic effect and photocatalytic mechanism of Bi₄O₅Br₂/Mn_xZn_1-xFe₂O₄ were also investigated. As the best sample, the removal rate of the Bi₄O₅Br₂/Mn_xZn_1-xFe₂O₄ photocatalyst with 7.5 wt% Mn_xZn_1-xFe₂O₄ to rhodamine B (RhB) reached up to 99.4% within 60 min. The enhanced photocatalyst activity was mainly attributed to the type-II heterojunction formed between Bi₄O₅Br₂ and Mn_xZn_1-xFe₂O₄, which not only optimised the energy band structure, but also led to the building of an interior electromagnetic field within the Bi₄O₅Br₂/Mn_xZn_1-xFe₂O₄ heterojunction. Meanwhile, the constantly producing and migrating h⁺ and ·O₂^? were the main active components. In particular, the results of the saturation magnetization tests and magnetic recovery experiments revealed that the magnetic composite photocatalyst can be recovered effectively. The results of the removal rate of RhB remaining at 85.2% after five uses reflected the advantages of the stability of the Bi₄O₅Br₂/Mn_xZn_1-xFe₂O₄ photocatalyst. In brief, this paper presented an original idea to develop a novel composite magnetic photocatalyst and research the enhancement mechanism of photocatalysis.     

Comparative study of microwave absorption properties of Ni–Zn ferrites obtained from different synthesis technologies

Spinel ferrites are widely used for electromagnetic wave (EMW) absorption applications. In this study, spinel Ni–Zn ferrites with excellent microwave absorption properties were synthesized. Their EMW absorption characteristics and interaction mechanisms were studied to lay the foundation for the study of the role of Ni–Zn ferrite as a magnetic substrate for composites. Herein, Ni_0·5Zn_0·5Fe₂O₄ was prepared by the hydrothermal method (H-NZFO) and the sol–gel auto-combustion method (S-NZFO); both samples exhibited distinct microwave absorption properties. The S-NZFO absorber (thickness = 3.72 mm) demonstrated the best dual-zone microwave absorption with two strong reflection loss peaks at 5.1 and 10.5 GHz. The corresponding effective absorption bandwidth (EAB) reached 9.0 GHz, which covered part of the S-band and all of the C- and X-bands. These results were attributed to the high saturation magnetization, outstanding complex permeability, and multiple magnetic loss channels of S-NZFO. The H-NZFO sample exhibited excellent absorption capability and matching thickness. At a thickness as low as 1.71 mm, the minimum reflection loss (RL_min) of the H-NZFO absorber reached -60.2 dB at 13.1 GHz. The maximum bandwidth corresponding to RL below -10 dB was 4.6 GHz. These results can be attributed to small particle size, high complex permittivity, and multiple dielectric loss channels of H-NZFO. The observed wide effective absorption bandwidth of S-NZFO and strong microwave absorption capability of H-NZFO suggest the potential of both materials as substrates for efficient microwave absorbers in military as well as civilian absorption applications.