Preparation and characterization of magnesium aluminate (MgAl2O4) spinel ceramic foams via direct foam-gelcasting

Lightweight MgAl₂O₄ spinel ceramic foams with high mechanical strength and good dielectric properties were prepared with a direct foam-gelcasting method using MgAl₂O₄ and TiO₂ (rutile phase, as sintering aid) powders. The effects of calcination temperature and foam volume on bulk density, apparent porosity, and on the mechanical and dielectric properties of the ceramic foams were investigated. Tailored porosity (75.14–82.46%), pore size (10–200 μm), dielectric constant (1.66–2.05), and compressive strength (4.0–14.3 MPa), were obtained based on the change of the foam volume in the foamed slurries, and the calcination temperature of porous ceramics. The compressive strength and dielectric constant of the as-manufactured spinel foam with a porosity of ~75.14% was as high as 14.3 MPa and 2.05, respectively. The spinel ceramic foam which had a porosity of 81.84% was prepared with a foam volume of 350 mL and a sintering temperature of 1500 °C, and exhibited heterogeneous pore structures, whereby large and open spherical cells involved in small circular windows on the internal walls with a mean pore size of ~66.26 μm and a grain size of ~8 μm. The experimental dielectric constant matches well with that calculated by the modified Bruggeman model. The dependence of the mechanical strength on the relative density can be represented by the Gibson and Ashby model. The fitted index values of the power relationship were 3.504 and 3.533, compared to the theoretical value of 1.5. The ceramic foam can potentially become a new type of electromagnetic wave-transmitting radome material due to its low dielectric constant (1.66–2.05) and dielectric loss (0.0026–0.006) values.     

Ion beam assisted electron beam vacuum deposition of antireflective SiO2 coating on MgAl2O4 spinel

In this paper, the electron beam vacuum coating method was used to coat a SiO₂ film on an MgAl₂O₄ spinel substrate. The thickness of the coating was aimed to be 925 nm based on the physics of the antireflection coatings. Atomic force microscope images revealed that the coated silica was 880 nm thick, which is close to the aimed theoretical thickness and had 2.11 nm roughness. It could enhance the transparency of the spinel substrate by being coated on it. The infrared transmittance of the sample coated with SiO₂ film in the range of 3700 nm-4800 nm was measured by a Fourier transform infrared spectrometer and reached 92.5% to 78.5%, which was about 2%–4% higher than that of MgAl₂O₄ spinel. In addition, it was discovered that the bonding force between the coating and the substrate is determined to be about 200 MPa. The results of this study can be used for further precise design and production of antireflection coatings on the transparent materials that need more transparency.     

Enhanced dielectric characteristics of Ba0.94Bi0.04(Fe0.5Nb0.5)O3 coated with SiO2 and SiO2/Al2O3 over a broad frequency and temperature range

Pure phase of Ba_0.94Bi_0.04(Fe_0.5Nb_0.5)O₃ (BBFN) nano-particles were obtained by chemical co-precipitation method. The core-shell structure of BBFN@SiO₂ and BBFN@SiO₂/Al₂O₃ particles and the target ceramics were successfully prepared by aqueous chemical coating approach. The microstructures and dielectric properties of BBFN@SiO₂ and BBFN@SiO₂/Al₂O₃ were studied. Both the BBFN@SiO₂ and BBFN@SiO₂/Al₂O₃ samples show significantly decreased dielectric loss and good frequency and temperature stability on relative permittivity. Compared to the rapid decline of relative permittivity of BBFN@SiO₂, the synergistic effect of SiO₂ and Al₂O₃ in BBFN@SiO₂/Al₂O₃ ceramics made the relative permittivity of which remains a relatively high level with very low dielectric loss, making it more suitable in colossal permittivity applications. Based on the impedance analysis, the grain boundary effect and IBLC models play the important role for the improvement of dielectric properties of BBFN@SiO₂/Al₂O₃ samples.     

Phase evolution,dielectric and impedance spectroscopic study of SrNb2O6 columbite phase

Strontium niobate SrNb₂O₆ has been synthesized by columbite solid-state reaction method and characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and temperature as well as frequency dependence of dielectric and impedance study. XRD analysis indicates single phase formation of the compound with ∼180 nm crystallite size. Study of SEM micrographs pointed out that prepared material has good sinterability and enough density with homogeneous grain distribution. It was found that the magnitude of relative dielectric constant (?_r) was relatively high with low dielectric loss compared with reported columbite compounds. Impedance spectroscopy was used to characterize the electrical behavior of the compound. AC impedance spectrum results indicate that the relaxation mechanism of the material is temperature dependent and has bulk and grain boundary contribution in different temperature ranges.     

Experimental phase relations between MgO-saturated magnesium-aluminate spinel (MgAl2O4) and CuOx-rich liquid

Experimental phase equilibrium data for the Cu-O-Al₂O₃-MgO system is required to improve the performance of MgAl₂O₄-containing refractories and slagging in non-ferrous smelting. In this work, the phase relations of MgAl₂O₄ in the Cu-O-Al₂O₃-MgO system were studied experimentally in air within a temperature range of 1100–1400 °C using the equilibration and quenching method. The chemical compositions of the phases in the quenched samples were determined using electron probe microanalysis (EPMA). Less than 1 wt% of Al₂O₃ or MgO were found in the oxide liquid phase, whereas the solid MgAl₂O₄ and MgO phases contained up to 23 wt% and 30 wt% of ‘Cu₂O’, respectively. Discrepancies between these results and the corresponding calculated values generated by the MTDATA 6.0 software and Mtox database Version 8.2 ranged from 3 wt% to 19 wt%. The results of this work indicate that the MgAl₂O₄ spinel is chemically stable in the presence of a CuO_x-rich liquid under the conditions studied.     

Low cost foam-gelcasting preparation and characterization of porous magnesium aluminate spinel (MgAl2O4) ceramics

Porous MgAl₂O₄ ceramics were prepared via a low cost foam-gelcasting route using MgAl₂O₄ powders as the main raw material, ammonium polyacrylate as a dispersant, a small amount of modified carboxymethyl cellulose as a gelling agent, and TH-IV polymer as a foaming agent. The effects of additive's content, solid loading and gelling temperature on slurry's rheological behavior were investigated, and microstructures and properties of as-prepared porous MgAl₂O₄ ceramics examined. Based on the results, the roles played by the foaming agent in the cases of porosity, pore structure, pore size, mechanical properties and thermal conductivity were clarified. Porosity and pore sizes of as-prepared porous MgAl₂O₄ ceramics increased with increasing the foaming agent from 0.05 to 0.6 vol%. Porous MgAl₂O₄ ceramics with porosity of 75.1% and average pore size of 266 µm exhibited a compressive strength as high as 12.5±0.8 MPa and thermal conductivity as low as 0.24 W/(m K) (at 473 K).     

Flash‐sintering of magnesium aluminate spinel (MgAl2O4) ceramics

The sintering behavior of commercially available MgAl₂O₄ spinel was investigated under DC electric field in a range of 0 and 1000 V/cm. Flash‐sintering results in densification close to theoretical density at 1410°C under the DC field of 1000 V/cm, in comparison to the higher sintering temperature of 1650°C in case of conventional sintering. It was observed that the fields less than 750 V/cm had no significant effect on the densification behavior. An abrupt increase in power dissipation was observed corresponding to the occurrence of the flash event. A significant enhancement in grain size was observed in case of flash‐sintered dense spinel samples. The gradual increase in the specimen conductivity observed in the electric field‐assisted sintering (FAST) regime led to Joule heating within the specimen. The increased specimen temperature triggered further increment of current and Joule heating, resulting in the immediate densification.     

Ionic conduction and dielectric properties of yttrium doped LiZr2(PO4)3 obtained by a Pechini-type polymerizable complex route

We report on the ion transport properties of Li_1+xZr_2-xY_x(PO₄)₃ (0.05?≤ x?≤?0.2) NASICON type nanocrystalline compounds prepared through a Pechini-type polymerizable complex method. Structural properties were characterized by means of powder X-ray diffraction, Raman spectroscopy and electron microscopy with selected area electron diffraction. Impedance spectroscopy was utilised to investigate the lithium ion transport properties. Y³⁺ doped LiZr₂(PO₄)₃ compounds showed stabilized rhombohedral structure with enhanced total ionic conductivity at 30?°C from 2.87?×?10^?7 S?cm^?1 to 0.65?×?10^?5 S?cm^?1 for x=0.05 to 0.20 respectively. The activation energies of Li_1+xZr_2-xY_x(PO₄)₃ show a decreasing trend from 0.45?eV to 0.35?eV with increasing x from 0.05 to 0.20. The total conductivity of these compounds is thermally activated, with activation energies and pre-exponential factors following the Meyer-Neldel rule. The tanδ peak position shifts to the high-frequency side with increasing yttrium content. Scaling in AC conductivity spectra shows that the electrical relaxation mechanisms are independent of temperature.     

Dielectric and impedance spectroscopy of Bi(Ca0.5Ti0.5)O3 ceramic

Bismuth calcium titanate (BiCa_0.5Ti_0.5O₃) ceramic, fabricated by a ceramic processing technique, has been characterized using a variety of experimental techniques. Analysis of basic crystal structure using X-ray diffraction data exhibits the orthorhombic system. Measurements and detailed analysis of some electrical parameters (i.e.,dielectric constant, loss tangent (energy loss), electrical impedance and modulus, conductivity, etc.) of Bi(Ca_0.5Ti_0.5)O₃ in a wide range of frequency (10³–10⁶ Hz) and temperature (30–500 °C) have provided some interesting and useful data and results on structure–properties relationship, conduction mechanism, etc.The role of interface, space charge polarization and Maxwell–Wagner dielectric relaxation in getting high dielectric constant of the material at low frequencies and high temperatures has been discussed. Study of temperature dependence of Nyquist plots clearly shows the contributions of grains in resistive and capacitive properties of the material. The frequency of the applied electric field and temperature strongly affect the dielectric (permittivity and dissipation of energy) and electrical (impedance, electrical modulus and conductivity) characteristics of the material.     

The structure evolution and microwave dielectric properties of MgAl2-x(Mg0·5Ti0.5)xO4 solid solutions

In the present work, MgAl_2-x(Mg_0·5Ti_0.5)_xO₄ (x = 0.02, 0.04, 0.06, 0.08, 0.10) solid solutions were synthesized via the traditional solid-state reaction route. The valence state of Ti ions, crystal structural characteristics, and microwave dielectric properties were discussed. A solid solution with spinel structure was revealed by the Rietveld refinement results. The partial substitution of (Mg_0·5Ti_0.5)³⁺ for Al³⁺ lowered the sintering temperature and improved the Q × f value of MgAl₂O₄ ceramic. The MgAl_2-x(Mg_0·5Ti_0.5)_xO₄ solid solutions with x = 0.06 can be well sintered at 1425 °C in an oxygen atmosphere for 8 h and exhibits excellent microwave dielectric properties with ε_r = 9.1, Q × f = 98,000 GHz, τ_f = −61.36 ppm/°C. The sintering temperature of MgAl_1·94(Mg_0·5Ti_0.5)_0.06O₄ microwave dielectric ceramics was approximately 200 °C lower than that of conventional MgAl₂O₄ ceramics.     

Effect of grain size on the static and dynamic mechanical properties of magnesium aluminate spinel (MgAl2O4)

Samples of transparent polycrystalline spinel with average grain size varying from 0.14 to 170 μm were prepared by different sintering approaches. The effect of grain size on the flexural strength, hardness and Hugoniot elastic limit (impact loading) was investigated. It was found that values of hardness divided by three for samples with grain size in the 0.14–15 μm range were almost equal to the dynamic yield strength values, estimated based on the Hugoniot elastic limit. This led to the assumption that the onset of inelastic deformation at the Hugoniot elastic limit was brittle rather than ductile. The observed departure of the dynamic yield strength from the hardness divided by three value for ceramics with grain size >15 μm was associated with either impact-induced shear banding or twinning. The feasibility of such banding/twinning intervention in initiating inelastic deformation in the spinel is supported by the values of apparent Hall-Petch coefficients in the corresponding grain size domains.     

铜（Ⅱ）掺杂Li3V2（PO4）3/C的结构与性能

用一步碳热还原法制备了Li3V2-xCux(PO4)3/C(x=0.00、0.02、0.05、0.08、0.10、0.15)复合正极材料,并研究了掺杂对材料结构、微观形貌、充放电性能的影响。结果表明掺杂少量铜(Ⅱ)不会影响材料Li3V2(PO4)3的基本结构,但会在Li3V2(PO4)3中形成电子缺陷,提高晶体内部原子的无序化程度,降低极化和电荷转移电阻。从而改善材料的电化学性能。Li3V1.98Cu0.02(PO4)3/C的10 C放电容量比Li3V2(PO4)3/C提高了20 mA.h/g,具有较好的倍率性能。     

Surface barrier layer effect in (In + Nb) co‐doped TiO2 ceramics: An alternative route to design low dielectric loss

Giant dielectric permittivity (ε′) with low loss tangent (tanδ) was reported in (In + Nb) co‐doped TiO₂ ceramics. Either of electron‐pinned defect‐dipole or internal barrier layer capacitor model was proposed to be the origin of this high dielectric performance. Here, we proposed an effectively alternative route for designing low‐tanδ in co‐doped TiO₂ ceramics by creating a resistive outer surface layer. A pure rutile‐TiO₂ phase with a dense microstructure and homogeneous dispersion of dopants was achieved in (In + Nb) co‐doped TiO₂ ceramics prepared by a simple sol‐gel method. Two giant dielectric responses were observed in low‐ and high‐frequency ranges, corresponding to extremely high ε′≈10⁶‐10⁷ and large ε′≈10⁴‐10⁵, respectively. After annealing in air, a low‐frequency dielectric response disappeared and could be restored by removing the outer surface of the annealed sample, indicating the dominant electrode effect in the initial sample. Annealing can cause improved dielectric properties with a temperature‐ and frequency‐independent ε′ value of ≈1.9 × 10⁴ and cause a decrease in tanδ from 0.1 to 0.035. High dielectric performance in (In_0.5Nb_0.5)_xTi_1?xO₂ ceramics can be achieved by eliminating the electrode effect and forming a resistive outer surface layer.     

Broad sintering temperature range and stable microwave dielectric properties of Mg2TiO4–CeO2 composite ceramics

There has been extensive research on microwave dielectric materials considering their application in 5G and 6G communication technologies. In this study, the sintering temperature range of Mg₂TiO₄–CeO₂ (MT-C) ceramics was broadened using a composite of CeO₂ and Mg₂TiO₄ ceramics, and their microwave dielectric performance was stabilized. Low-loss MT-C composite ceramics were prepared using the solid-phase reaction method, and their microwave dielectric properties, microscopic morphologies, and phase structures were investigated. The proposed MT-C ceramics contained Mg₂TiO₄ and CeO₂ phases; their average grain size was maintained at 2–4 μm in the sintering temperature range of 1275–1425 °C, and the samples were uniformly dense without porosity. The cross-distribution of Mg₂TiO₄ and CeO₂ grains in the samples inhibited the growth of ceramic grains, providing uniform and dense surfaces. The dielectric loss of MT-C ceramics remained constant in the temperature range of 1300–1425 °C at 9 × 10^?4 (8.45 ≤ f ≤ 8.75 GHz). As opposed to the base material, MT-C ceramics are advantageous owing to their wide sintering temperature range and the stable microwave dielectric properties, and there are suitable substrate materials for further industrial applications.     

Development of mechanical and visible transparency properties of spark plasma sintered spinel fabricated by powder injection molding of MgAl2O4 nanoparticles

This research aims to investigate the density, hardness, fracture toughness, and infrared and visible transmittance of spark plasma sintered (SPS) spinel discs fabricated through the powder injection molding (PIM) method. These properties were compared with the sample directly SPSed without the PIM process. For this purpose, initially, a feedstock was prepared with 80 wt% spinel nanopowder and 20 wt% binder. The results revealed that the hardness and fracture toughness of the SPSed spinel disc sintered at 1400 °C were greater than those of the spinel sample without PIM treatment. Also, for the PIMed sample and then SPSed sample, the level of infrared and visible transmittance was ~10% greater than for the SPSed spinel nanopowders.     

Analysis of complex impedance and electrical conductivity of YCr0.5Mn0.5O3–CaCu3Ti4O12 negative temperature coefficient ceramics

YCr_0.5Mn_0.5O₃(YCM)-CaCu₃Ti₄O₁₂(CCTO) ceramics were prepared using a solid processing method, and their properties were studied. XRD measurements showed that all prepared ceramics had pure perovskite structures. With increasing YCM content, grain size in ceramics decreased, and the resistivity of materials was found to be very sensitive to grain size and grain size distribution. Moreover, ceramics had NTC characteristics, and values of ρ₂₅, B_25/75, and E_a ranged from 2.21 × 10⁶–7.30 × 10⁶ Ω cm, 5797–6300 K, and 0.5390–0.5800 eV, respectively. The presence of heterovalent ion pairs in samples suggested that conduction mechanism may have been related to electron hopping. Impedance spectroscopy results showed that excessive doping with YCM resulted in greater contribution from grains to overall resistance of the material. Temperature-dependent electrical relaxation behavior was dominated by short-range movement of charge carriers.     

Optimization of dielectric phenomenon in 0.8[(1-x)SrCoO2.29 + xCr2FeO4] + 0.2PZT tri-phase composites

Composite materials are emerging and have potential to revolutionize the modern technology. In this work, a series of tri-phase composite materials having the chemical formula; 0.8[(1-x) SrCoO_2.29+xCr₂FeO₄] + 0.2PZT, is synthesized to explore their energy storage capability. In this series, SrCoO_2.29 and Cr₂FeO₄ ceramics are synthesized by using a sol-gel auto-combustion process while PZT is prepared by the solid-state method. The XRD analysis confirmed the formation of cubic crystal structure of the SrCoO_2.29 and Cr₂FeO₄ and the rhombohedral phase of PZT. The SEM images exhibited an increase in average grain size with the incorporation and increasing contents of Cr₂FeO₄. The presence of all constituting elements with the exact stoichiometric ratio is validated through EDX analysis. Wide-range frequency-dependent dielectric behavior showed a dramatic fall in dielectric constant with increasing frequency. A same frequency dependent behaviour of ε'' and tanδ is witnessed as that of ε'. The investigation of electric modulus reveals that in the low-frequency region it possesses a trivial value which became significantly large with the increase of frequency. The presence of a relaxation peak in the plot of the imaginary part of the electric modulus plays a decisive role to distinguish the small and large range hopping mechanism. The complex impedance analysis revealed different electroactivity of composite material in the different frequency domains which made them viable for advanced energy storage devices working in the vast frequency range.     

Effect of the Liquid-Phase Characteristic on the Microstructures and Dielectric Properties of Donor- (Niobium) and Acceptor- (Magnesium) Doped Barium Titanate

Changes in the microstructure and dielectric properties with the variation of the donor/acceptor ratio in BaTiO₃ ceramics were investigated. In donor-rich specimens, a liquid that appeared during sintering did not penetrate into grain boundaries. However, in the acceptor-rich specimens, the grains were separated by a liquid film during sintering. The much higher mobility of the liquid film than that of the grain boundaries was suggested to cause extensive grain growth in acceptor-rich BaTiO₃. The macroscopic homogenization of dopants because of grain growth in acceptor-rich specimens resulted in changes in the dielectric properties.     

Structure and microwave dielectric properties of Li2Mg3Ti1-x(Al1/2Nb1/2)xO6 ceramics

Aiming to establish relationships between intrinsic structure factors and dielectric characteristics, a series of Li₂Mg₃Ti_1-x(Al_1/2Nb_1/2)_xO₆ (x = 0.0, 0.04, 0.08, 0.12, 0.16, 0.20) ceramics were synthesized to investigate the influences of (Al_1/2Nb_1/2)⁴⁺ substitution on the dielectric properties of Li₂Mg₃TiO₆ ceramics. The XRD and SEM results revealed that the pure rock salt phase (space group: Fm-3m) with a dense microstructure could be obtained with increasing the (Al_1/2Nb_1/2)⁴⁺ concentration, which is accompanied by an increase in the grain size from 11.69 to 22.81 μm. Meanwhile, some intrinsic factors, such as the average ionic polarizability, bond energy, packing fraction and lattice energy were calculated according to the complex chemical bond theory and refinement results. The unusual change in the dielectric constant (ε_r) was explained by the combined effects of the average ionic polarizability and relative density. The variation in the quality factor (Q × f) was ascribed to the packing fraction and lattice energy. The temperature coefficient of the resonant frequency (|τ_f|) reduced gradually with the increase in the octahedral bond energy, which enhanced the system thermal stability. Particularly, the Li₂Mg₃Ti_0.92(Al_1/2Nb_1/2)_0.08O₆ sample exhibited outstanding dielectric characteristics:ε_r = 15.256, Q × f = 174,300 GHz and τ_f = −19.97 ppm/°C.