Influence of inverse spinel structured CuGa2O4 on microwave dielectric properties of normal spinel ZnGa2O4 ceramics

Spinel Zn_1‐xCu_xGa₂O₄ (x = 0‐0.15) ceramics were prepared by the conventional solid‐state method. Only a single phase was indexed in all samples. The continuous lattice contraction of ZnGa₂O₄ unit cell was caused by Cu²⁺ substitution, and the lattice parameter shows a linear correlation with the content of Cu. The refined crystal structure parameters suggest that Cu²⁺ preferentially occupies the octahedron site, and the degree of inversion of Zn_1‐xCu_xGa₂O₄ (x = 0‐0.15) ceramics almost equals to the content of Cu²⁺. The relative intensity of A*_1g mode in Raman spectra confirm that the degree of inversion climbed with the growing content of Cu²⁺. The experimental and theoretical dielectric constant of Zn_1‐xCu_xGa₂O₄ ceramics fit well. Zn_1‐xCu_xGa₂O₄ (x = 0.01) ceramics sintered at 1400°C for 2 h exhibited good microwave dielectric properties, with ε_r = 9.88, Q × f = 131,445 GHz, tanδ = 6.85 × 10^?5, and τ_f = ?60 ppm/°C.     

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.     

Influence of inversion level on the optical absorption spectra of Ti-doped transparent MgGa2O4 ceramics

Ti-doped (0.08, 0.30, and 1.00 atomic% [at.%]) transparent MgGa₂O₄ ceramics (possessing a high inversion level; i up to 0.8) were fabricated by pulsed electric current sintering, at 950°C, under vacuum for 30–90 min. Optical transmission, emission, and electron paramagnetic resonance spectra were recorded. The maximal transmission level was ∼70% (820 nm), for a thickness of ∼1 mm, which, while not very high, permitted the observation of the optical absorption bands location and profile. Interpretation of the fluorescence spectra suggests that some Ti⁴⁺ cations (mostly hexacoordinated) were accommodated by the host despite the scarcity of oxygen in the atmosphere during the sintering process. The Ti³⁺ cations substitute native ions located in tetrahedral sites, distorting the original T_d symmetry toward a D_2d symmetry. Comparing the Ti-doped MgGa₂O₄ (high inversion) and MgAl₂O₄ (low inversion) spinels, spectral characteristics revealed that a significant increase in the inversion level drives Ti³⁺ cations from octahedral toward tetrahedral sites. This is reflected in the optical absorption spectra by the disappearance of the band at ∼20 000 cm⁻¹ (detectable in MgAl₂O₄) in MgGa₂O₄; the two d–d bands, of MgA₂O₄, in MgGa₂O₄ are reduced to a single one, located at 11 800 cm⁻¹. These results, for MgGa₂O₄, strongly support a similar assignment—of the strong band at 12 800 cm⁻¹, in Ti-doped MgAl₂O₄—to a tetracoordinated Ti³⁺. Thus, while in MgAl₂O₄, Ti³⁺ appears in both octahedral and tetrahedral coordination and in MgGa₂O₄ only the latter state is stable. In both spinels, Ti dopant speciates into Ti³⁺ and Ti⁴⁺ cations.     

Ultra-rapid microwave sintering of pure and Y2O3-doped MgAl2O4

MgAl₂O₄ samples were microwave sintered to near-full density in rapid processes with heating rates on the order of 100°C/min and zero isothermal hold. The experiments were carried out using a gyrotron system for microwave processing of materials operating at a frequency of 24 GHz with a maximum power of 6 kW. In the regimes with a preset heating rate sustained by the automatically regulated microwave power, the maximum achieved density was about 95% of the theoretical value in pristine MgAl₂O₄ samples (maximum sintering temperature 1650°C) and about 97% in 1 wt.% Y₂O₃-doped samples (1700°C). In the regimes with a fixed microwave power (about 3.5 kW), translucent spinel samples with a relative density above 99% were obtained at 1700°C. The duration of the high-temperature stage of sintering was 1.5-10 minutes. The suggested mechanism responsible for the enhanced densification involves development of a thermal instability and formation of transient liquid phases at grain boundaries. The estimated specific absorbed power in the samples during the high-temperature stage of ultra-rapid microwave sintering was 27-80 W/cm³, similar to the values observed in dc field-assisted flash sintering experiments.     

Radiation heating test and development of porous MgAl2O4 ceramics with high thermal shielding effect based on Mie theory

Porous MgAl₂O₄ ceramics designated as THERMOSCATT^TM have diffuse reflectance based on the Mie theory. The reflectance greatly suppresses radiation heat transfer and has low emissivity at 1–5 μm wavelengths. Their thermal conductivity has been measured as less than 0.3 W/(m K) at 1500°C. Furthermore, porous MgAl₂O₄ ceramics have near-zero hemispherical spectral emissivity values at 0.35–5 μm wavelengths. High heat resistance and low emissivity materials in the atmosphere are useful for the innermost layer of industrial furnaces to confine energy efficiently. Additionally, this material is useful as a radiation reflectors, such as in stand-off thermal protection systems. This study elucidated the suppression of radiation transfer in porous MgAl₂O₄ ceramics attributable to low thermal emissivity. Therefore, the thermal insulation performance under radiation heating in vacuum, the emissivity validity evaluation of low-emissivity porous materials using finite element analysis, and microstructure effects on radiation heating performance and mechanical properties were investigated.     

Aqueous slip casting and hydrolysis assisted solidification of MgAl2O4 spinel ceramics

Abstract

Abstract

This paper reports on synthesis of MgAl₂O₄ spinel (MAS) powders with six different chemical compositions and the consolidation of the synthesised MAS powders following an aqueous slip casting and hydrolysis assisted solidification (HAS) routes. The synthesised MAS powders were surface passivated against hydrolysis before being dispersed in distilled water to obtain suspensions with 41–45?vol.‐% solid loading using suitable dispersing agents. In the case of the HAS process, the consolidation of suspensions was achieved in non‐porous moulds under ambient conditions by the incorporation of AlN equivalent to 1–5?wt‐%Al₂O₃ into the suspension. The stoichiometric MAS powder consolidated by slip casting and dry pressing routes was sintered along with those consolidated by HAS route at 1550–1650°C for 1?h. Various characterisation techniques were utilised to evaluate the effect of composition and consolidation technique on slurry characteristics and sintered properties of MAS ceramics.     

Photocatalytic performance of Fe-substituted ZnAl2O4 powders under sunlight irradiation on degradation of industrial dyes

Using the sol–gel auto combustion method with diethanolamine (DEA) as fuel, a sequence of iron-substituted zinc aluminates, ZnFe_xAl_2-xO₄ powders, including variable Fe³⁺ ion concentrations (0 ≤ x ≤ 2) were effectively prepared. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), the Brunauer–Emmett–Teller (BET) method, UV–visible diffuse reflectance spectroscopy (UV-DRS), and vibrating sample magnetometer (VSM) were employed to examine the structures, chemical bonds, morphologies, composition, surface area, and optical properties as well as the magnetic behavior of the obtained samples. A single-phase spinel structure was obtained for the calcined aluminate powders with different interplanar spacing and crystallite sizes, as revealed by the classification results. The bandgap energy (E_g) of adapted aluminates was in the range of 2.04-3.14 eV, identified as being much lower compared to the pure sample (5.60 eV). Thus, Fe³⁺-substituted ZnAl₂O₄ samples could be successfully photoexcited using both ultraviolet and visible light, as suggested by the results. Examination of how the four main pollutant types decay when irradiated by sunlight was carried out to assess the samples and establish photocatalytic activity. These contaminants included rhodamine B (RhB), methylene blue (MB), methyl orange (MO), and methyl red (MR). The performance of photocatalytic degradation reached 98% after 150 min for all optimal samples of organic dyes. Besides, each of the altered photocatalysts could be recycled and displayed high stability. The S-shaped curve of ferrimagnetism can result in those samples as found by the magnetic measurements, though pure ZnAl₂O₄ displays diamagnetic characteristics. The adapted samples show intense improvement in the remanent magnetization (M_r) when compared to pure ZnAl₂O₄, signifying that magnetic photocatalyst recovery by applying an external magnetic field is easy. Thus, these results offer a convincing sign that ZnAl₂O₄ powders replaced by Fe³⁺ could provide the ability to aid in the ecologically friendly collection of solar energy.     

Li2O-doped MgAl2O4 nanopowders: Energetics of interface segregation

Manufacturing nanoceramics is challenging owing to the instability of the grain size resulting from the high driving force toward growth associated with the interfaces. Nanometric ceramics of some oxides have exceptional mechanical and optical properties, eg, magnesium aluminate spinel (MgAl₂O₄). The production of these fully conformed ceramics requires a precursor powder, which generally contains sintering-promoting additives. Li salts are typically used as sintering promoters for MgAl₂O₄, but the interface stability associated with the segregation of the additive is poorly understood. In this study, MgAl₂O₄ samples containing 0-2.86 mol% Li ions were synthesized via a simultaneous-precipitation method in an ethylic medium and subsequently calcined at 800°C in air. The nanopowders exhibited only the MgAl₂O₄ phase, and the crystallite size was determined by the Li₂O concentration. The crystallite size was changed via the chemical modification of the interfaces by the segregation of Li ions. The solubility in the bulk material was very low at the fabrication temperature, and small amounts of Li ions saturated the bulk material and segregated to the grain boundaries (GBs), significantly stabilizing the grain–grain interface compared with the surface. The resulting powder was then aggregated further owing to the initial stage of sintering. The surface excess obtained via the selective lixiviation method confirmed that the segregation to the GBs was greater than that to the surface. Energetics calculations confirmed these results, indicating a high enthalpy of segregation at the GBs () compared with that at the surfaces (). The enthalpy of segregation together with the interface excess allowed us to estimate the reduction in the interface energy with Li⁺ segregation of 0.8% to the surface and 11.2% to the GBs. The Li⁺ segregation to the surfaces started by Al³⁺ substitution, and for powders with ≥1.8 mol% Li ions, Mg⁺² was preferentially substituted at the surfaces.     

Full reoxidation of CuMn2O4 spinel catalyst triggered by epitaxial Mn3O4 surface nanocrystals

Transmission electron microscopy was performed on a model system of a novel CuMn₂O₄ spinel catalyst in order to study the effects of reduction by carbon monoxide and subsequent reoxidation by oxygen both processed at 600°C. A phase transition from CuMn₂O₄ spinel into separated MnO and Cu‐rich phases, which are CuO or Cu depending on the reduction period, was observed in the reduced samples. Furthermore, a surface coverage of the MnO grains by epitaxially grown, nanocrystalline Mn₃O₄ was found in all reduced samples. These Mn₃O₄ nanocrystals are assumed to act as seed crystals in the subsequent reoxidation step completely reversing the phase transitions and reconstituting single‐phase CuMn₂O₄ spinel. In addition, superlattice reflections due to cation ordering occurred as a typical feature in the as‐prepared spinel. In the reoxidized spinel, the superlattice reflections were absent, hence indicating a disordered cation distribution.     

Gel-casting of MgAl2O4 transparent ceramics using a common dispersant

The ethanolaminic salt of citric acid (commercial name Dolapix CE 64) has commonly been used as a dispersant for colloidal based ceramic forming process. In this paper, a surprise was presented that MgAl₂O₄ spinel slurries consisting of MgAl₂O₄ spinel nanoparticles and Dolapix CE 64 gelled in air at room temperature spontaneously. The MgAl₂O₄ spinel slurries with high solid loading (54 vol%) were prepared with Dolapix CE 64 and the green body with up to 57% relative density was obtained. MgAl₂O₄ transparent ceramics with small grain size (0.92 μm) and high transmittance (81.7% at 600 nm) were fabricated after pre-sintering at 1500°C and hot-isostatic sintering at 1550°C.     

Gelling behavior of MgAl2O4 slurries with a common dispersant

MgAl₂O₄ transparent ceramics were shaped by a commonly used polyacrylic acid (PAA), which acted as both dispersant and gelling agent. The spinel slurries were prepared by ball-milling MgAl₂O₄ powder, PAA, and water in an attrition mill. The gelling of slurries happened at room temperature in air atmosphere without any other organic additive. The gelling mechanism was the formation of chelates between Mg²⁺ and carboxyl groups (-COO⁻) of PAA. The frequency-based testing method was applied to investigate the gelling process of the as-prepared slurry. In addition, a novel in situ characterization method based on a modified indentation testing was invented to better understand the strengthening of the wet green body with time and to guide when demolding could be carried out. After sintering, transparent MgAl₂O₄ ceramics with high in-line transmittance were resulted.     

DC conductivity and AC impedance of Mn doped magnesia alumina spinel (MgAl2-2xMn2xO4) over a large temperature range

MgAl_2-2xMn_2xO₄ (MAMO) with x = 0-0.12 was synthesized in a single-phase form by solid-state reaction. XRD analysis showed that the samples had the cubic center structure of the Fd-3 m space group. Electrical properties of the samples were studied over the temperature range of 300 K∼1073 K. The results showed that the DC conductivity (σ_DC) increased from 10⁻¹¹S/cm at 300 K (MAMO, x = 0) to 10^-3S/cm at 1073 K (MAMO, x = 0.12). The equivalent circuit of the complex impedance spectra suggested that the relaxation of charge carriers was of non-Debye type. The conduction was mainly caused by grain boundaries and the capacitance was mainly attributed to polarization. The complex permittivity values (ε’ and ε’’) were increased by two orders of magnitude with the increase in Mn content and temperature over the measured frequency range (1 Hz-1 MHz). Therefore, doping with Mn could be applied to modify the electrical properties of MAMO at high temperature.     

Fabrication of Translucent Magnesium Aluminum Spinel Ceramics

A precursor for magnesium aluminum spinel powder, composed of crystalline ammonium dawsonite hydrate (NH₄Al(OH)₂CO₃·H₂O) and hydrotalcite (Mg₆Al₂(CO₃)(OH)₁₆·4H₂O) phases, was synthesized via precipitation, using ammonium bicarbonate as the precipitant. The precursor was characterized by differential thermal analysis/thermogravimetry, X-ray diffractometry, and scanning electron microscopy. Reactive spinel powder, which could be densified to translucency under vacuum at 1750°C in 2 h without additives, was obtained by calcining the precursor at 1100°C for 2 h.     

Effect of micro-sized MgCO3 addition on properties of MgAl2O4 spinel containing castables

Micro-sized MgCO₃ was used in castables as the MgO-precursor for generating sub-micro sized MgO and for producing subsequent in-situ magnesium aluminate (MgAl₂O₄, MA) spinel. The influence of 0–2.0 wt% micro-sized MgCO₃ addition on the volumetric stability and thermo-mechanical properties of castables after firing at 1000 °C and 1550 °C was investigated. The in-situ spinel formation and its influence on the microstructure evolution in castable matrices with different micro-sized MgCO₃ contents after heat-treatment were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The dependence of the volume stability and thermo-mechanical properties of castables on the micro-sized MgCO₃ addition was discussed with respect to the in-situ spinel formation.     

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.     

Thermal and optical properties of La2O3–Ga2O3– (Nb2O5 or Ta2O5) ternary glasses

La₂O₃–Ga₂O₃–M₂O₅ (M = Nb or Ta) ternary glasses were fabricated using an aerodynamic levitation technique, and their glass‐forming regions and thermal and optical properties were investigated. Incorporation of adequate amounts of Nb₂O₅ and Ta₂O₅ drastically improved the thermal stabilities of the glasses against crystallization. Optical transmittance measurements revealed that all the glasses were transparent over a wide wavelength range from the ultraviolet to the mid‐infrared. The refractive indices of the glasses increased and the Abbe number decreased upon substituting Ga₂O₃ with Nb₂O₅, and the decrease in the Abbe number was significantly suppressed when Ta₂O₅ was incorporated into the glass. As a result, excellent compatibility between high refractive index and lower wavelength dispersion was realized in La₂O₃–Ga₂O₃–Ta₂O₅ glasses. Analysis based on the single‐oscillator Drude–Voigt model provided more systematical information and revealed that this compatibility was due to an increase in the electron density of the glass.     

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.     

Influence of fabrication conditions on the structural characteristics and the magnetic properties of FeAl2O4

We report a systematic evaluation of the magnetic properties of FeAl₂O₄ focusing on the relationship between the fabrication conditions and its structural characteristics, in order to improve ceramics processing in applications of this material. For this purpose, the most important factor to control is the inversion parameter, expressed as y in the (Fe_1−yAl_y)(Al_1−y/2Fe_y/2)₂O₄ composition, which is relatively high for the spinel aluminate of a transition metal. The magnetic properties of these samples all show the spin glass phenomenon at low temperatures, and the cusp temperature depends systematically on this y value. This means that the evaluation of these magnetic properties will be an effective way to predict some characteristics of product FeAl₂O₄. Additionally, this study found an anomaly in the structural and magnetic characteristics of FeAl₂O₄ fabricated at a low temperature. This is thought to originate in a tiny and a small amount of impurity. It will be key for discussing the quality of chemically synthesized FeAl₂O₄, which is typically produced at low temperatures.     

Room-temperature multiferroicity in NiFe2O4 and its magnetoelectric coupling intensified through defect engineering

The well-known ferromagnetic oxide, NiFe₂O₄, was studied as a potential candidate for room-temperature Type II magnetoelectrics. A spin canting as one of the essential requirements for Type II multiferroics was induced by breaking the stoichiometry, that is, intentionally subtracting Fe ions. We observed that Fe ions were first subtracted exclusively from the tetrahedral sites, leading to an increase in the magnetoelectric coupling owing to an increasing degree of spin canting. The enhancement in the magnetoelectric coupling culminated beyond the subtraction level of ~30 at.%, at which Fe ions started to be removed from the octahedral sites. Alongside, we observed that the subtraction of Fe ions gives rise to a ferroelectricity due to the formation of defect complexes that establish an internal bias field.     

Nano-structured MgAl2O4 spinel consolidated by high pressure spark plasma sintering (HPSPS)

Nano-structured transparent polycrystalline magnesium aluminate spinel (PMAS) was fabricated using a high pressure (up to 1000 MPa) spark plasma sintering (HPSPS) apparatus and various properties of the spinel, such as transparency, micro-structure and mechanical properties (specifically, hardness and fracture toughness), were tested. Using a creep densification model, it was concluded that densification in the final stage of HPSPS is controlled by grain boundary sliding (GBS), rather than by oxygen diffusion. The average grain size of PMAS fabricated under 400 MPa pressure at 1200 °C was about 170 nm, while for samples fabricated under 1000 MPa at 1000 °C the average grain size was remarkably smaller (about 50 nm). HRTEM analysis clearly demonstrated clean grain boundaries and triple points with no evidence for the existence of amorphous regions. Fully dense specimens displayed in-line transmittance higher than 80%. It was moreover established that hardness and fracture toughness values did not depend on the indentation load applied. Finally, hardness values for grains sized between tens of microns and tens of nm strictly followed the Hall-Petch relationship.