Spinel Mg(Al,Ga)2O4 Solid Solution as High‐Performance Microwave Dielectric Ceramics

Spinel Mg(Al_1?xGa_x)₂O₄ (x = 0–1) solid solutions were synthesized via solid‐state method. Replacement of Al³⁺ by Ga³⁺ in MgAl₂O₄ gave rise to the expansion of the lattice, as well as blueshifts of FT‐IR and Raman peaks. The homogeneous solid solutions, high relative densities, large grain sizes, and compact microstructures resulted in excellent microwave dielectric properties for spinel Mg(Al_1?xGa_x)₂O₄ (x = 0.6) ceramics sintered at 1485°C: that is, ε_r = 8.87, Q × f = 107 000 GHz (at 14.8 GHz), and τ_f = ?16 ppm/°C. Spinel‐structured Mg(Al_1?xGa_x)₂O₄ (x = 0–1) solid solutions possessed low sintering temperatures, wide temperature regions (~100°C), and small negative τ_f values. These outstanding performance make Mg(Al, Ga)₂O₄ a promising candidate material for millimeter‐wave devices.     

Optical and Microwave Dielectric Properties of Zn‐Doped MgAl2O4 Transparent Ceramics Fabricated by Spark Plasma Sintering

(Mg_1?xZn_x)Al₂O₄ transparent ceramics were fabricated by spark plasma sintering technique at 1325°C for 10 min. A small mount of Zn²⁺ addition to MgAl₂O₄ ceramics was very effective to the performance improvement, while further increase in Zn‐doped content would give rise to the optical transmittance deterioration. The optical and microwave dielectric properties of MgAl₂O₄ transparent ceramics were improved by Zn substitution for Mg. The in‐line transmittance of the (Mg_1?xZn_x)Al₂O₄ (x = 0.02) ceramics can be as high as 70% at λ = 550 nm and 86.5% at λ = 2000 nm, respectively. The dielectric constant ε_r of (Mg_1?xZn_x)Al₂O₄ just varied from 8.32 to 8.54, however, the Q × f value increased significantly up to a maximal value of 66,000 GHz at x = 0.02. Moreover, the τ_f of (Mg_1?xZn_x)Al₂O₄ transparent ceramics changed from ?74 to ?65.5 ppm/°C. With the increasing of Zn‐doped content, the average grain size and the porosity increased, which was the primary reason for the change in optical and microwave dielectric properties.     

Improved sinterability and microwave dielectric properties of [Zn0.5Ti0.5]3+-doped ZnAl2O4 spinel solid solution

Low-permittivity ZnAl_2-x(Zn_0.5Ti_0.5)_xO₄ ceramics were synthesized via conventional solid-state reaction method. A pure ZnAl₂O₄ solid-state solution with an Fd-3m space group was achieved at x ≤ 0.1. Results showed that partial substitution of [Zn_0.5Ti_0.5]³⁺ for Al³⁺ effectively lowered the sintering temperature of the ZnAl₂O₄ ceramics and remarkably increased the quality factor (Q × f) values. Optimum microwave dielectric properties (ε_r = 9.1, Q × f = 115,800 GHz and τ_f = −78 ppm/°C) were obtained in the sample with x = 0.1 sintered at 1400°C in oxygen atmosphere for 10 h. The temperature used for the sample was approximately 250°C lower than the sintering temperature of conventional ZnAl₂O₄ ceramics.     

Structural and dielectric properties,and nonlinear electrical response of the CaCu3-xZnxTi4O12 ceramics: Experimental and computational studies

CaCu_3-xZn_xTi₄O₁₂ ceramics (x = 0, 0.05, 0.10) were successfully prepared by a conventional solid-state reaction method. Their structural and dielectric properties, and nonlinear electrical response were systematically inspected. The X-ray diffraction results indicated that single-phase CaCu₃Ti₄O₁₂ (JCPDS no. 75–2188) was obtained in all sintered ceramics. Changes in the lattice parameter are well-matched with the computational result, indicating an occupation of Zn²⁺ doping ions at Cu²⁺ sites. The overall tendency shows that the average grain size decreases when x increases. Due to a decrease in overall grain size, the dielectric permittivity of CaCu_3-xZn_xTi₄O₁₂ decreases expressively. Despite a decrease in the dielectric permittivity, it remains at a high level in the doped ceramics (~3,406–11,441). Besides retention in high dielectric permittivity, the dielectric loss tangent of x = 0.05 and 0.10 (~0.074–0.076) is lower than that of x = 0 (~0.227). A reduction in the dielectric loss tangent in the CaCu_3-xZn_xTi₄O₁₂ ceramics is closely associated with the enhanced grain boundary response. Increases in grain boundary resistance, breakdown electric field, and conduction activation energy of grain boundary as a result of Zn²⁺ substitution are shown to play a crucial role in improved grain boundary response. Furthermore, the XPS analysis shows the existence of Cu⁺/Cu²⁺ and Ti³⁺/Ti⁴⁺, indicating charge compensation due to the loss of oxygen lattice. Based on all results of this work, enhanced dielectric properties of the Zn-doped CCTO can be explained using the internal barrier layer capacitor model.     

Large enhancement of piezoelectric properties and resistivity in Cu/Ta co-doped Bi4Ti3O12 high-temperature piezoceramics

In this study, the electrical properties of Bi₄Ti₃O₁₂-based Aurivillius-type ceramics were tailored by a B-site co-doping strategy combining high valence Ta⁵⁺ and low valence Cu²⁺. A series of Bi₄Ti_3−x(Cu_1/3Ta_2/3)_xO₁₂ (BTCT) (x = 0, 0.005, 0.01, 0.015, 0.02, 0.025, and 0.03) ceramics were prepared by the conventional solid-state reaction method. The effect of Cu/Ta co-doping on the crystal structure, microstructure, dielectric properties, piezoelectric properties, ferroelectric properties, and electrical conductivity of these ceramics was systematically investigated. Co-doping significantly enhanced the piezoelectric properties and DC electrical resistivity of the resulting composites. The optimized comprehensive performances were obtained at x = 0.015 with a large piezoelectric coefficient (34 pC/N) and a relatively high resistivity of 9.02 × 10⁶ Ω cm at 500°C. Furthermore, the ceramic also exhibited stable thermal annealing behaviors and excellent fatigue resistance. The results of this study demonstrated great potential of the Cu/Ta co-doped Bi₄Ti₃O₁₂ ceramics for high-temperature piezoelectric device applications.     

Relaxor Ferroelectric BaTiO3–Bi(Mg2/3Nb1/3)O3 Ceramics for Energy Storage Application

Perovskite solid solution ceramics of (1 ? x)BaTiO₃–xBi(Mg_2/3Nb_1/3)O₃ (BT–BMN) (x = 0.05–0.2) were synthesized by solid‐state reaction technique. The results show that the BMN addition could lower the sintering temperature of BT‐based ceramics. X‐ray diffraction results reveal a pure perovskite structure for all studied samples. Dielectric measurements exhibit a relaxor‐like characteristic for the BT–BMN ceramics, where broadened phase transition peaks change to a temperature‐stable permittivity plateau (from ?50°C to 300°C) with increasing the BMN content (x = 0.2), and slim polarization–electric field hysteresis loops were observed in samples with x ≥ 0.1. The dielectric breakdown strength and electrical resistivity of BT–BMN ceramics show their maxima of 287.7 kV/cm and 1.53 × 10¹³ Ω cm at x = 0.15, and an energy density of about 1.13 J/cm³ is achieved in the sample of x = 0.1.     

Fabrication and optical properties of transparent fine-grained Zn1.1Ga1.8Ge0.1O4 and Ni2+ (or Cr3+)-doped Zn1.1Ga1.8Ge0.1O4 spinel ceramics

For the first time, a Zn_1.1Ga_1.8Ge_0.1O₄ transparent spinel ceramic has been fully densified by spark plasma sintering. XRD measurements show that this ceramic is composed of a pure cubic spinel phase. SEM analysis revealed a homogeneous and dense microstructure with the average grain size being 200 ± 100 nm. The transmittance of these fine-grained ceramics reached 70 % in the visible range and is very close to 80 % at 2 µm, thus close to the T_max value deduced from the measurement of the refractive index. The ceramics exhibit excellent mechanical properties with a Young modulus of 222 GPa, a Vickers hardness of 14.25 GPa and a thermal conductivity of 7.3 W.m⁻¹. K⁻¹. By doping with Cr³⁺ ions, transparent Zn_1.1Ga_1.8Ge_0.1O₄ ceramics present both a red luminescence and a long-lasting afterglow during several minutes. Moreover, a near infrared broadband emission at 1.3 µm is also achieved with Ni²⁺ ions.     

Copper‐substituted spinel Zn‐Mg ferrite nanoparticles as potential heating agents for hyperthermia

Cu_xZn_0.5‐xMg_0.5Fe₂O₄ (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) ferrite nanoparticles are synthesized via thermal treatment technique using polyvinyl alcohol (PVA) as a capping agent. The effect of Cu²⁺ ions substitution on the magnetic and structural properties of ZnMg ferrite nanoparticles is assessed. X‐ray diffraction (XRD) results prove the formation of spinel cubic ferrite with nanocrystalline structure. It is observed by increasing Cu²⁺ ions content in Cu²⁺‐substituted ZnMg ferrite samples, the lattice constant decreases. The field‐emission scanning electron microscopy (FESEM) micrographs indicate that all samples have sizes in nanometer scale with almost spherical morphology and ZnMg ferrite nanoparticles size is increased as the result of Cu²⁺ substitution. Magnetic data show that by increasing in Cu²⁺ content, the saturation magnetization (Ms) increases up to x = 0.3 and then declines with the addition of more Cu²⁺ ions in the samples. To assess the heat release of Cu²⁺‐substituted ZnMg ferrite nanoparticles, an alternating magnetic (AC) field is applied. The results show an upward trend for the samples in the temperature vs time chart, as a result of increasing in Ms of the samples. The Cu_0.3Zn_0.2Mg_0.5Fe₂O₄ sample exhibits a temperature increase up to 43°C during 510 seconds in the exposure of 125 Oe magnetic field intensity. The cell compatibility of the samples is investigated using osteoblast‐like cells (MG63). Results show that the substitution of Cu²⁺ significantly affects the cell compatibility of the ZnMg ferrite nanoparticles.     

Local Structure Evolution in Ba‐Substituted Pb(Fe1/2Nb1/2)O3 Ceramics

Evolution of crystal structure in Pb_1‐xBa_x(Fe_1/2Nb_1/2)O₃ ceramics has been investigated by X‐ray diffraction and Raman spectra analysis together with the dielectric characterization. The crystal structure for all compositions is cubic and the cell volume indicates a sudden change at x = 0.075. Pb_1‐xBa_x(Fe_1/2Nb_1/2)O₃ ceramics with x > 0.075 are paraelectric, whereas those for x < 0.075 are ferroelectric at room temperature. The evolution of phonon modes indicates that the ferroelectricity of Pb_1‐xBa_x(Fe_1/2Nb_1/2)O₃ solid solution ceramics is caused by the off‐center Nb⁵⁺ in BO₆ octahedron. The ferroelectric‐related distortion is still observed in paraelectric solid solutions with x > 0.075.     

Eu-substitution-induced commensurate phase with enhanced ferroelectric property in Ba4(EuxLa1−x)2Fe2Nb8O30 multiferroics

Effects of Eu-substitution on the crystal structure, dielectric, ferroelectric, and magnetic properties have been systematically studied for Ba₄(Eu_xLa_1−x)₂Fe₂Nb₈O₃₀ (x = 0, 0.3, 0.5, 0.7, 0.9, 0.95, 1) tungsten bronze ceramics. The tetragonal bronze structure is confirmed in all compositions. With the increase of x, Ba₄(Eu_xLa_1−x)₂Fe₂Nb₈O₃₀ ceramics transform from paraelectric to ferroelectric. The compositions of x = 0.9, 0.95, and 1 show first-order ferroelectric phase transitions above room temperature (391 K for x = 0.9, 404 K for x = 0.95, and 425 K for x = 1). The ferroelectric behavior is associated with a commensurate octahedral tilting, which is caused by large A2-A1 ionic-radius difference. Magnetic hysteresis loops for all compositions at room temperature have been obtained, which could be ascribed to both the secondary phase and tungsten bronze structure per se. It is confirmed that the radius difference between A2 and A1 cations plays a critical role on the structure, dielectric, and ferroelectric characteristics.     

New Antiferroelectric Solid Solution of Pb(Mg1/2W1/2)O3–Pb(Zn1/2W1/2)O3 as Dielectric Ceramics

A new solid solution of (1?x)Pb(Mg_1/2W_1/2)O₃–xPb(Zn_1/2W_1/2)O₃ has been prepared in the form of ceramics by solid‐state reaction with composition x up to 30%. It is found that with the substitution of Zn²⁺ for Mg²⁺ on the B site of the of complex perovskite structure the antiferroelectric (AFE) Curie temperature T_C of PMW increases from 40°C (x = 0) to 67°C (x = 30%), indicating an enhancement of antiferroelectric order, whereas, at the same time, the phase transition becomes more diffuse due to a higher degree of chemical inhomogeneity. X‐ray diffraction analysis indicates that the crystal structure adopts an orthorhombic space group (Pmcn) with a decrease in lattice parameter a, but an increase in b and c as the Zn²⁺ concentration increases. The low dielectric constant (~ 10²), low dielectric loss (tanδ ≈ 10^?3), linear‐field‐induced polarization, and significantly high breakdown field (~ 125 kV/cm) at room temperature make this family of dielectric materials a promising candidate for ceramic insulators.     

Enhancement of structural and microwave properties of Zn2+ ion-substituted Li2MgSiO4 ceramics for LTCC applications

In this study, Zn²⁺-substituted Li₂MgSiO₄ ceramics (Li₂(Mg_1-xZn_x)SiO₄, x = 0.00, 0.05, 0.10, 0.15, and 0.20) were synthesized using a traditional solid-state method. A fixed amount of LiF sintering aid (1.5 wt%) was added to the ceramics for decreasing the sintering temperature and adjusting their microwave dielectric properties. X-ray diffraction (XRD) results revealed no secondary phases, and scanning electron microscopy (SEM) data suggest that the Zn²⁺ ion substitution increased the size and uniformity of the grains, thereby affecting the densification of the prepared ceramics. The maximum bulk density (2.94 g/cm³) was found in a Zn²⁺ ion-substituted ceramic with x = 0.10 at a relative density of 94.2% (compared with the XRD theoretical density). Excellent microwave dielectric properties (ε_r = 6.28, Q × f = 50400 GHz, and τ_f = ?145 ppm/°C) can also be obtained at this zirconium content. We believe that the developed ceramics are promising for use as antenna substrates or transmit/receive modules in low-temperature co-firing ceramic applications.     

Extremely high corrosion resistance of ZnxNi1–xCr2O4 spinel as sidewalls in the aluminum electrolyte

The sidewall material is a key component in new electrolytic cell with an inert electrode for the aluminum electrolysis industry. The continuous development of novel sidewall materials with excellent corrosion resistance in molten salts electrolyte is an important topic. Herein, a new system of sidewall material, spinel structured Zn_xNi_1–xCr₂O₄ (x = 0 – 1), is prepared by solid-phase reaction and the corrosion-resistance enhancement is investigated. The results prove that Zn²⁺ plays two roles in the Zn_xNi_1–xCr₂O₄ spinels. Firstly, Zn²⁺ tunes the surface energies of spinels resulting in the octahedral grains, which suppresses the cation diffusion in the corrosion process. Secondly, Zn²⁺ stabilizes the Cr³⁺ in the spinels. As a result, the Zn_0.5Ni_0.5Cr₂O₄ spinel displays an extremely low corrosion rate ～0.007 cm·a^–1 in NaF-KF-AlF₃ bath at 800 °C comparing with other sidewall materials. The as-obtained spinel shows great potential as a novel sidewall material for the new electrolytic cell.     

Effect of Ga2O3 on Sintering and Phase Stability of Sc2O3‐Doped Tetragonal Zirconia Prepared via Aqueous Solution Route

The effects of the presence of Ga₂O₃ on low‐temperature sintering and the phase stability of 4, 5, and 6 mol% Sc₂O₃‐doped tetragonal zirconia ceramics (4ScSZ, 5ScSZ, and 6ScSZ, respectively) were investigated. A series of zirconia sintered bodies with compositions (ZrO₂)_0.99?x(Sc₂O₃)_x(Ga₂O₃)_0.01, x = 0.04, 0.05, and 0.06 was fabricated by sintering at 1000°C to 1500°C for 1 h using fine powders that were prepared via the combination of homogeneous precipitation method and hydrolysis technique using monoclinic zirconia sols synthesized through the forced hydrolysis of an aqueous solution of zirconium oxychloride at 100°C for 168 h. The presence of 1 mol% Ga₂O₃ was effective in reducing sintering temperature necessary to fabricate dense bodies and enabled to obtain dense sintered bodies via sintering at 1100°C for 1 h. The phase stability, that is, low‐temperature degradation behavior of the resultant zirconia ceramics was determined under hydrothermal condition. The zirconia ceramics codoped with 1 mol% Ga₂O₃ and 6 mol% Sc₂O₃ (1Ga6ScZ) fabricated via sintering at 1300°C for 1 h showed high phase stability without the appearance of monoclinic zirconia phase, that is the tetragonal‐to‐monoclinic phase transformation was not observed in the 1Ga6ScZ after treatment under hydrothermal condition at 150°C for 30 h.     

Effect of strontium substitution on the structure and dielectric properties of unfilled tungsten bronze Ba4-xSrxSmFe0.5Nb9.5O30 ceramics

The effects of Sr²⁺ substitution for Ba²⁺ on phase structure, microstructure, dielectric and electric properties for Ba_4-xSr_xSmFe_0.5Nb_9.5O₃₀ (x = 0, 1, 2, 3 and 4) ceramics were systematically researched. X-ray diffraction patterns show that Ba_4-xSr_xSmFe_0.5Nb_9.5O₃₀ (x = 0, 1, 2 and 3) ceramics are tetragonal tungsten bronze compound with a space group of P4bm, while the sample for x = 4 is an orthorhombic structure compound. The result can be corroborated by the analysis of Raman spectroscopy. As the Sr²⁺ contents increase from 0 to 3, the full width at half maximum of Raman lines of all samples increase gradually, indicating that the degree of lattice distortion increase. All tetragonal tungsten bronze ceramics exhibited a broad permittivity peaks, accompanied by frequency dispersion, indicating all samples are relaxor. The electrical properties of BSSFN ceramics were further studied by complex impedance spectroscopy. XPS spectrum shows that Fe²⁺ and Fe³⁺ coexist in Ba_4-xSr_xSmFe_0.5Nb_9.5O₃₀ ceramics, and their proportion varies with the concentration of Sr²⁺.     

Effects of cerium on structures and electrical properties of (Nb,Ta) modified Bi4Ti3O12 piezoelectric ceramics

Bi₄Ti₃O₁₂ high-temperature piezoelectric ceramics composed of 0.03 mol (Nb, Ta)⁵⁺ substituting B site and x mol CeO₂ (x = 0–0.05, abbreviated as BCTNT100x) substituting A site were synthesized by the conventional solid-state reaction method. The effects of Ce additive on the structures and electrical properties of resulting Bi₄Ti₃O₁₂-based ceramics were systematically investigated. In-situ temperature-dependent X-ray diffraction (XRD) confirmed that the phase structure of BCTNT100x ceramics change from orthorhombic structure to tetragonal structure as temperature increased. The ceramics at Ce content x = 0.03 illustrated optimal performances with superior piezoelectric constant (d₃₃ = 36.5 pC/N), high Curie temperature (T_C = 649 °C), and large remanent polarization (2P_r = 21.6 μC/cm²). BCTNT3 ceramics also possessed high d₃₃ of 32.5 pC/N at an annealing temperature of 600°C, with electrical resistivity preserved at 10⁶ Ω cm at 500 °C. These results demonstrate that BCTNT100x ceramics can be used as high-temperature piezoelectric devices.     

Effects of Gd Substitution on Sintering and Optical Properties of Highly Transparent (Y0.95−xGdxEu0.05)2O3 Ceramics

Highly transparent (Y_0.95?xGd_xEu_0.05)₂O₃ (x = 0.15–0.55) ceramics have been fabricated by vacuum sintering at the relatively low temperature of 1700°C for 4 h with the in‐line transmittances of 73.6%–79.5% at the Eu³⁺ emission wavelength of 613 nm (~91.9%–99.3% of the theoretical transmittance of Y_1.34Gd_0.6Eu_0.06O₃ single crystal), whereas the x = 0.65 ceramic undergoes a phase transformation at 1650°C and has a transparency of 53.4% at the lower sintering temperature of 1625°C. The effects of Gd³⁺ substitution for Y³⁺ on the particle characteristics, sintering kinetics, and optical performances of the materials were systematically studied. The results show that (1) calcining the layered rare‐earth hydroxide precursors of the ternary Y–Gd–Eu system yielded rounded oxide particles with greatly reduced hard agglomeration and the particle/crystallite size slightly decreases along with increasing Gd³⁺ incorporation; (2) in the temperature range 1100°C–1480°C, the sintering kinetics of (Y_0.95?xGd_xEu_0.05)₂O₃ is mainly controlled by grain‐boundary diffusion with similar activation energies of ~230 kJ/mol; (3) Gd³⁺ addition promotes grain growth and densification in the temperature range 1100°C–1400°C; (4) the bandgap energies of the (Y_0.95?xGd_xEu_0.05)₂O₃ ceramics generally decrease with increasing x; however, they are much lower than those of the oxide powders; (5) both the oxide powders and the transparent ceramics exhibit the typical red emission of Eu³⁺ at ~613 nm (the ⁵D₀→⁷F₂ transition) under charge transfer (CT) excitation. Gd³⁺ incorporation enhances the photoluminescence and shortens the fluorescence lifetime of Eu³⁺.     

Structure and Microwave Dielectric Characteristics of Ca[(Ga1/2Nb1/2)1−xTix]O3 Ceramics

The microwave dielectric characteristics of Ca[(Ga_1/2Nb_1/2)_1?xTi_x]O₃ ceramics were investigated together with the structure evolution. The excellent microwave dielectric characteristics were achieved by forming solid solution between Ca(Ga_1/2Nb_1/2)O₃ and CaTiO₃ in the present ceramics. The solid solutions in space group Pbnm with antiphase and inphase tilting were determined for all compositions where minor secondary phase was detected for x = 0–0.47, whereas no B‐site ordering was detected. Owing to the structural modification, the dielectric constant (ε_r) increased with increasing x, and the temperature coefficient of resonant frequency (τ_f) could be tuned from negative to positive, while the decrease of Qf value was acceptable. The best combination of microwave dielectric properties was obtained at x = 0.47: ε_r = 51.6, Qf = 34 100 GHz and τ_f = ?0.3 ppm/°C.     

Investigations of Structural and Magnetic Properties of Nanostructured Ni0.5+xZn0.5‐xFe2O4 Magnetic Feeders for CSEM Application

Marine CSEM is a new technique for detection of deep target hydrocarbons. Aluminum EM antenna was developed, and nanostructured NiZn magnetic feeders were used to increase the field strength from EM antenna for deep hydrocarbons. The doping of Ni²⁺ was aimed at the optimization of initial permeability and magnetic losses. Ni_0.5+xZn_0.5‐xFe₂O₄ (x = 0.3) samples sintered at 950°C presented highest initial permeability (106.23) and low magnetic loss (0.0002) as compared to other samples. Due to better magnetic properties, Ni_0.5+xZn_0.5‐xFe₂O₄ (x = 0.3) samples were used as magnetic feeders for EM antenna. Magnitude of EM waves from the antenna increased up to 186%.