Role of (La,Gd) co-doping on the enhanced dielectric and magnetic properties of BiFeO3 ceramics

The effect of the La³⁺ and Gd³⁺ co-doping on the structure, electric and magnetic properties of BiFeO₃ (BFO) ceramics are investigated. For the compositions (x=0 and 0≤y≤0.15) in the perovskite structured La_xGd_yBi_1−(x+y)FeO₃ system, a tiny residual phase of Bi₂Fe₄O₉ is noticed. Such a secondary phase is suppressed with the incorporation of ‘La’ content (x). The magnitude of dielectric constant (ε_r) increases progressively by increasing the ‘La’ content from x=0 to 0.15 with a remarkable decrease of dielectric loss. For x=0.15, the system La_xGd_yBi_1−(x+y)FeO₃ exhibits highest remanent magnetization (M_r) of 0.18 emu/g and coercive magnetic field (H_C) of ~1 T in the presence of external magnetic field of 9 T at 300 K. The origin of enhanced dielectric and magnetic properties of La_xGd_yBi_1−(x+y)FeO₃ and the role of doping elements, La³⁺, Gd³⁺ has been discussed.     

Structure and microwave dielectric properties of La(2−x)/3Nax(Mg1/2W1/2)O3

The structure evolution, sintering behavior and microwave dielectric properties of La_(2−x)/3Na_x(Mg_1/2W_1/2)O₃ (x = 0–0.5) were investigated in this paper. The X-ray diffraction (XRD) results show that all samples exhibit single phase, and the structure changed from orthorhombic when 0 ≤ x < 0.3 to monoclinic phase when 0.3 ≤ x ≤ 0.5. The size and ordering degree of A/B-site domains decrease with the increase in x value. The sintering temperature of the Na-doped samples increased compared to the pure La_2/3(Mg_1/2W_1/2)O₃ (LMW) due to the estimated decrease in the concentration of A-site vacancies. The addition of Na⁺ ion does not affect the dielectric permittivity greatly. The Q × f value decreases with the increase in x value, although the estimated concentration of A-site vacancies decreases with increasing x, which may be ascribed to the decrease of A/B-site ordering and domain size with the increase in x. The temperature coefficient of resonant frequency changed from negative values into positive values with the increase in x value.     

Crystal structure,microstructure and electrical properties of (1−x−y)Bi0.5Na0.5TiO3–xBi0.5K0.5TiO3–yBiFeO3 ceramics near MPB prepared via the combustion technique

(1?x?y)Bi_0.5Na_0.5TiO₃–xBi_0.5K_0.5TiO₃–yBiFeO₃ (BNKFT-x/y with 0.12≤x≤0.24, 0≤y≤0.07) lead-free piezoelectric ceramics have been prepared by the combustion technique. The effects of amounts of x and y on structures and electrical properties were examined. Powders and ceramics can be well calcined and sintered at 750 °C for 2 h and 1025–1050 °C, respectively. The results indicated that the crystalline structure and microstructure changed with the increase of x and y concentrations. XRD results of BNKFT-x/0.03 and BNKFT-0.18/y ceramics with 0.12≤x≤0.24 and 0≤y≤0.07 showed the rhombohedral–tetragonal morphotropic phase boundary (MPB). The addition of y caused a promoted grain growth while the addition of x suppressed the grain growth. The highest density (ρ=5.85 g/cm³), superior dielectric properties at T_c (ε_r=7846 and tan δ=0.02), remnant polarization measured at 40 kV/cm (P_r = 20.1 μC/cm²) and piezoelectric coefficient (d₃₃=213 pC/N) were obtained for x=0.18 and y=0.03.     

High-Qf value and temperature stable Zn2+-Mn4+ cooperated modified cordierite-based microwave and millimeter-wave dielectric ceramics

Cordierite-based dielectric ceramics with a lower dielectric constant would have significant application potential as dielectric resonator and filter materials for future ultra-low-latency 5G/6G millimeter-wave and terahertz communication. In this article, the phase structure, microstructure and microwave dielectric properties of Mg₂Al_4–2x(Mn_0.5Zn_0.5)_2xSi₅O₁₈ (0 ≤ x ≤ 0.3) ceramics are studied by crystal structure refinement, scanning electron microscope (SEM), the theory of complex chemical bonds and infrared reflectance spectrum. Meanwhile, complex double-ions coordinated substitution and two-phase complex methods were used to improve its Q×f value and adjust its temperature coefficient. The Q×f values of Mg₂Al_4–2x(Mn_0.5Zn_0.5)_2xSi₅O₁₈ single-phase ceramics are increased from 45,000 GHz@14.7 GHz (x = 0) to 150,500 GHz@14.5 GHz (x = 0.15) by replacing Al³⁺ with Zn²⁺-Mn⁴⁺. The positive frequency temperature coefficient additive TiO₂ is used to prepare the temperature stable Mg₂Al_3.7(Mn_0.5Zn_0.5)_0.3Si₅O₁₈-ywt%TiO₂ composite ceramic. The composite ceramic of Mg₂Al_3.7(Mn_0.5Zn_0.5)_0.3Si₅O₁₈-ywt%TiO₂ (8.7 wt% ≤ y ≤ 10.6 wt%) presents the near-zero frequency temperature coefficient at 1225 °C sintering temperature: ε_r = 5.68, Q×f = 58,040 GHz, τ_f = ?3.1 ppm/°C (y = 8.7 wt%) and ε_r = 5.82, Q×f = 47,020 GHz, τ_f = +2.4 ppm/°C (y = 10.6 wt%). These findings demonstrate promising application prospects for 5 G and future microwave and millimeter-wave wireless communication technologies.     

A/B-site cosubstituted Ba4Pr28/3Ti18O54 microwave dielectric ceramics with temperature stable and high Q in a wide range

High permittivity Ba₄(Pr_1-xSm_x)_28/3Ti_18-yAl_4y/3O₅₄(0.4≤x ≤ 0.7, 0≤y ≤ 1.5) ceramics were synthesized using a standard solid-state method. The effects of Sm³⁺ substitution into the A-site and Sm³⁺/Al³⁺ cosubstitution into the A/B-sites on the microstructure, crystal structure, Raman spectra, infrared reflectivity (IR) spectra and dielectric characteristics were investigated in a Ba₄Pr_28/3Ti₁₈O₅₄ solid solution. In the ceramic samples of Ba₄(Pr_1-xSm_x)_28/3Ti₁₈O₅₄(0.4≤x ≤ 0.7), Sm³⁺ partial substitution for Pr³⁺ could improve the quality factor (Qf) value and reduce the TCF value. Nevertheless, the quality factor (Qf~10,000GHz) needed further improvement and the TCF values (+12.3~+35.4 ppm/°C) were still too large. Therefore, Al³⁺ was introduced for further optimization of the TCF values and Qf values of the Ba₄(Pr_1-xSm_x)_28/3Ti₁₈O₅₄ ceramics. Sm/Al cosubstitution led to a good combination of high ε_r (ε_r ≥ 70), high Qf (Qf ≥ 12,000 GHz), and near-zero TCF (−10 < TCF < +10 ppm/°C) in a wide range (0.4≤x ≤ 0.7). Infrared reflectivity (IR) spectra indicated that A-TiO₆ vibration modes gave the primary contribution rather than Ti–O bending and stretching modes. The decrease in the degree of B-site cations order could be confirmed by Raman spectra. XPS results demonstrated that the improvement of quality factor (Qf) value was strongly related to the suppression of Ti³⁺. Excellent dielectric properties were achieved in Ba₄(Pr_1-xSm_x)_28/3Ti_18-yAl_4y/3O₅₄ microwave ceramics with x = 0.5 and y = 1.25: ε_r = 72.5, Qf = 13,900GHz, TCF = +1.3 ppm/°C.     

Enhanced energy storage performance in Na(1-3x)BixNb0.85Ta0.15O3 relaxor ferroelectric ceramics

High-performance lead-free dielectric containers have excellent energy storage performance such as higher power density and energy density. While being eco-friendly materials, lead-free dielectric materials are more suitable for pulse power systems than other dielectric materials. In this study, Ta⁵⁺and Bi³⁺ ions were introduced into the A site and B site of the NaNbO₃ matrix. The introduction of Bi³⁺ ions induced the formation of a vacancy in the A site, yielding Na_(1-3x)Bi_xNb_0.85Ta_0.15O₃ (NBNT, x = 0.05, 0.08, 0.11, 0.14) ceramics. The recoverable energy density (W_rec) and the energy storage efficiency (η) were highest for the Na_0.67Bi_0.11Nb_0.85Ta_0.15O₃ ceramic, with values of 3.37 J/cm³ and 89% respectively. Batteries employing the Na_0.67Bi_0.11Nb_0.85Ta_0.15O₃ ceramic achieved a current density of 830.4 A/cm², an energy density of 49.8 MW/cm³ and 60.2 ns discharge time. These results show that the Na_0.67Bi_0.11Nb_0.85Ta_0.15O₃ ceramic is an effective energy storage material with broad application prospects.     

Microwave dielectric properties of (Zn1/3B2/3)0.5(Ti0.8M0.2)0.5O2 (B = Nb5+, Ta5+, M = Sn4+, Ge4+) ceramics

Dielectric properties of (Zn_1/3Nb_(2?x)/3Ta_x/3)_0.5(Ti_0.8Sn_0.1Ge_0.1)_0.5O₂ (x = 0, 1, 2) and/or (Zn_1/3Nb_1/3Ta_l/3)_0.5(Ti_0.8Sn_0.2(l?y)Ge_0.2y)_0.5O₂ (y = 0, 0.5, 1) were investigated at the microwave frequencies. For the compositions with single phase of rutile structure, the dielectric constant (K) of specimens was not only dependent on the dielectric polarizabilities, but also on the bond length ratio of apical bond (d_apical) to equatorial bond (d_equatorial) of oxygen octahedron in the unit cell. Temperature coefficients of the resonant frequencies (TCF) of the specimens with B = Nb⁵⁺ and/or M = Sn⁴⁺ was larger than those with B = Ta⁵⁺ and/or M = Ge⁴⁺. These results could be attributed to the changes of the degree of oxygen octahedral distortion. Quality factors (Qf) of the specimens with B = Ta⁵⁺ and/or M = Sn⁴⁺ were larger than those with B = Nb⁵⁺ and/or M = Ge⁴⁺.     

Structure and microwave dielectric properties of 1:1 ordered Nd[(Mg1-xZnx)1/2Ti1/2]O3 complex perovskite ceramics

Nd[(Mg_1-xZn_x)_1/2Ti_1/2]O₃ perovskite ceramics (x = 0, 0.2, 0.4, 0.6, 0.8) are prepared by the solid-state reaction method. The effects of Zn²⁺ substitution on the structure, microstructure, especially the B-site 1:1 cation ordering and microwave dielectric properties have been investigated. Sintered Nd[(Mg_1-xZn_x)_1/2Ti_1/2]O₃ ceramics all adopt dense microstructure, along with increased dimensional uniformity as Zn²⁺ substitution. All the ceramics are confirmed to have B-site 1:1 ordered monoclinic perovskite structure with P2₁/n space group. Atomic mass difference of B-site elements might be an important factor affecting the B-site 1:1 cation ordering. HRSTEM observation suggest that the doped Zn²⁺ cations have roughly entered the Mg²⁺ sites to promote 1:1 cation ordering. The degree of the 1:1 cation ordering can be negatively reflected by the full width at half maximum (FWHM) of F_2g(B) mode at 372 cm^?1 in Raman spectra. With Zn²⁺ doping, the degree of the 1:1 cation ordering first increases then decreases, and reaches its maximum at x = 0.6. Meanwhile the best combination of microwave dielectric properties is obtained, as ε_r = 31.4, Q × f = 74,000 GHz, τ_f = ?44 ppm/°C. It is found that the long-range ordering not only decreases the dielectric loss but also affects the dielectric constant, providing a theoretical foundation to understand further the correlation between ionic configuration and microwave dielectric properties.     

Impedance spectroscopy,B-site cation ordering and structure–property relations of (1 − x) La[Al0.9(Mg0.5Ti0.5)0.1]O3–x CaTiO3 ceramics for 5G dielectric waveguide filters

Dense (1 ? x) La[Al_0.9(Mg_0.5Ti_0.5)_0.1]O₃–x CaTiO₃ ceramics were synthesized via solid-state reaction. The crystal structure and microwave dielectric properties of the ceramics were systematically investigated. Rietveld refinement revealed that when x ≤ 0.2, the ceramics had a rhombohedral structure with an R-3c space group. When x ≥ 0.5, the ceramics had an orthorhombic structure with a Pbnm space group. Selected area electron diffraction and Raman spectroscopy analyses proved that the microwave dielectric ceramics had a B-site order, which accounted for the great improvement in microwave dielectric properties. The content of oxygen vacancies was identified through X-ray photoelectron spectroscopy, and the change rule of Q × f was closely related to oxygen vacancy content. The perturbation of A-site cations had an important influence on dielectric constant. Specifically, with the increase in Ti⁴⁺ content, the perturbation effect of the A-site cations was enhanced and dielectric constant increased. When x = 0.65, the temperature coefficient of resonant frequency of the (1 ? x) La[Al_0.9(Mg_0.5Ti_0.5)_0.1]O₃–x CaTiO₃ microwave dielectric ceramics was near zero. The optimal microwave dielectric properties of 0.35LaAl_0.9(Mg_0.5Ti_0.5)_0.1O₃–0.65CaTiO₃ were ε_r = 44.6, Q × f = 32,057 GHz, and τ_f = +2 ppm/°C.     

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.     

Dependence of dielectric properties on structural characteristics of (Zn1/3A2/3)0.5 (Ti1−xBx)0.5O2 (A = Nb5+, Ta5+, B = Ge4+, Sn4+) ceramics at microwave frequencies

The effects of structural characteristics on the dielectric properties of (Zn_1/3A_2/3)_0.5(Ti_1?xB_x)_0.5O₂ (A = Nb⁵⁺, Ta⁵⁺, B = Ge⁴⁺, Sn⁴⁺) (0.1 ≤ x ≤ 0.3) ceramics were investigated at microwave frequency. The sintered specimens showed solid solutions with a tetragonal rutile structure within the solid solution range of compositions. With an increase of BO₂, the temperature coefficient of resonant frequency (TCF) and dielectric constant (K) decreased with a decrease of oxygen octahedral distortion and dielectric polarizabilites, respectively. However, the quality factor (Qf) of the sintered specimens was increased with BO₂ due to the reduction of Ti⁴⁺ ions. The Qf value of the specimens with A = Ta was higher than that of the specimens with A = Nb.     

Relationships between crystal structure and electrical properties of Li0.055[Agx(K0.5Na0.5)1−x]0.945(Nb1−yTay)O3 ceramics

Electrical properties of perovskite Li_0.055[Ag_x(K_0.5Na_0.5)_1?x]_0.945(Nb_1?yTa_y)O₃ (0.00 ≤ x ≤ 0.04, 0.01 ≤ y ≤ 0.09) ceramics were investigated based on the structural characteristics. A morphotropic phase boundary (MPB) between orthorhombic and tetragonal phase was detected through the entire range of compositions. With increasing of Ta⁵⁺ content, the dielectric constant (?_r), piezoelectric coefficient (d₃₃) and electromechanical coupling factor (k_p) of Li_0.055(K_0.5Na_0.5)_0.945(Nb_1?yTa_y)O₃ ceramics were increased up to y = 0.07 and then decreased, while mechanical quality factor (Q_m) was increased. However, the ?_r, d₃₃, k_p and Q_m of Li_0.055[Ag_x(K_0.5Na_0.5)_1?x]_0.945(Nb_0.07Ta_0.03)O₃ ceramics were not changed remarkably with Ag⁺ content. The dependence of temperature coefficient of k_p (TCk_p) on the oxygen octahedral distortion was also discussed by Raman-active vibrations modes.     

Dielectric performance of pyrochlore-type Bi2MgNb2-xTaxO9 ceramics: The effects of tantalum doping

The solid solutions based on the pyrochlore-type system Bi₂MgNb_2-xTa_xO₉ were formed in the compositional range х = 0–2.0 (Bi_1·6Mg_0·8Nb_1.6-tTa_tO_7.2, t = 0–1.6). The Rietveld method was used to refine the structure for Bi₂MgNb_2-xTa_xO₉ (x = 0, 1.0, 2.0). The increasing tantalum content led to the slight decrease in the cubic unit cell parameters from 10.56934 (4) Å for x = 0 and 10.54607 (3) Å for x = 2 (sp.gr. Fd-3m:2). At the same time, tantalum additions suppressed grain growth in the pyrochlore ceramics during sintering and made it possible to obtain materials with an average grain size of 1–2 μm (Bi_1·6Mg_0·8Ta_1·6O_7.2). The increase in the Ta⁵⁺ concentration led to the decrease in the dielectric permeability from 104 (Bi_1·6Mg_0·8Nb_1·6O_7.2) to 20 (Bi_1·6Mg_0·8Ta_1·6O_7.2) at room temperature, while the dielectric loss tangent remained lower than 0.002, which is due to the small grain size and the high porosity of the samples. An increase in temperature has practically no effect on the values of the dielectric permittivity in the entire frequency range. The samples have weak through conductivity. The activation energies of electrical conductivity varied in the range of 0.84–1.00 eV, and the less tantalum, the lower the activation energy. The electrical properties of the samples at 200 Hz to 1 MHz are described by the simplest parallel scheme.     

Enhancement of dielectric characteristics in donor doped Aurivillius SrBi2Ta2O9 ferroelectric ceramics

In this study, investigations have been made on the crystal structure, surface morphology, dielectric and electrical properties of tungsten doped SrBi₂(W_xTa_1−x)₂O₉ (0.0 ≤ x ≤ 0.20) ferroelectric ceramics. Dielectric measurements performed as a function of temperature at 1, 10 and 100 kHz show an increase in Curie temperature (T_c) over the composition range of x = 0.05–0.20. W⁶⁺ substitution in perovskite-like units results in a sharp dielectric transition at the ferroelectric Curie temperature with the dielectric constant at their respective Curie temperature increasing with tungsten doping. The dielectric loss reduces significantly with tungsten addition. The temperature dependence of ac and dc conductivity vis-à-vis tungsten content shows a decrease in conductivity, which is attributed to the suppression of oxygen vacancies. The activation energy calculated from the Arrhenius plots is found to increase with tungsten content.     

Extended X-ray absorption fine structure,X-ray diffraction and Raman analysis of nickel-doped Ba(Mg1/3Ta2/3)O3

Raman, X-ray diffraction and extended X-ray absorption fine structure (EXAFS) measurements of xBa(Ni_1/3Ta_2/3)O₃ + (1 − x)Ba(Mg_1/3Ta_2/3)O₃ samples with x = 0–0.03 were performed to reveal the nickel doping effect on the microwave properties. EXAFS result clearly shows that the nickel is located on the Mg lattice site. We also found that, as the nickel concentration increases, microwave dielectric constant decreases with the TaO and NiO bond distances. X-ray diffraction shows that the 1:2 ordered structure is degraded with the increasing of nickel concentration. The stretching phonon of the TaO₆ octahedra, that is A_1g(O) phonon near 800 cm⁻¹, are strongly correlated to the microwave properties of xBa(Ni_1/3Mg_2/3)O₃ + (1 − x)Ba(Mg_1/3Ta_2/3)O₃ samples. The large Raman shift and the large width of the A_1g(O) imply rigid but distorted oxygen octahedral structure, therefore, the effect of nickel doping lowers the dielectric constant and the Q × f value of Ba(Mg_1/3Ta_2/3)O₃ ceramic.     

Abnormal variation of microwave dielectric properties in A/B site co-substituted (Ca1−0.3xLa0.2x)[(Mg1/3Ta2/3)1−xTix]O3 complex perovskite ceramics

A/B site co-substituted (Ca_1?0.3xLa_0.2x)[(Mg_1/3Ta_2/3)_1?xTi_x]O₃ ceramics (0.1 ≤ x ≤ 0.5) were prepared by solid state reaction and the structures, microstructures and dielectric properties were investigated. B site 1:2 cation ordering and oxygen octahedra tilting lead to monoclinic symmetry with space group P2₁/c for x = 0.1. For x above 0.1, the ordering was destroyed and the crystal structure became orthorhombic with space group Pbnm. The B site 1:2 cation ordering tended to be destroyed to form 1:1 ordering by the A site La³⁺ substitution. The dielectric constant increased linearly with increasing content of Ti⁴⁺ as the increasing second Jahn–Teller distortion enhanced the B site cation rattling. The temperature coefficient of resonant frequency and Qf values showed abnormal variations, which were refined to be caused by the increasing A site cation vacancy and diffused distribution of small size ordering domains respectively. Good combination of microwave dielectric properties was obtained at x = 0.5, where ?_r = 48, Qf = 21,000 GHz and τ_f = 2.2 ppm/°C.     

The relationship between crystal structure and modified microwave dielectric properties of Ca3SnSi2-xGexO9 ceramics

Ca₃SnSi_2-xGe_xO₉ (0 ≤ x ≤ 0.8) and (1–y) Ca₃SnSi_1.6Ge_0.4O₉ – y CaSnSiO₅ – 2 wt% LiF (y = 0.4 and 0.5) microwave dielectric ceramics were prepared by traditional solid-state reaction through sintering at 1250°C–1425°C for 5 h and at 875°C for 2 h, respectively. Ge⁴⁺ replaced Si⁴⁺, and Ca₃SnSi_2-xGe_xO₉ (0 ≤ x ≤ 0.4) solid solutions were obtained. At 0.1 ≤ x ≤ 0.4, the Ge⁴⁺ substitution for Si⁴⁺ decreased the sintering temperature of Ca₃SnSi_2-xGe_xO₉ from 1425 to 1300°C, the SnO₆ octahedral distortions, and the average CaO₇ decahedral distortions, which affected the τ_f value. The large average decahedral distortions corresponded with nearer-zero τ_f values at Ca₃SnSi_2-xGe_xO₉ (0.1 ≤ x ≤ 0.4) ceramics. The τ_f value and sintering temperature of Ca₃SnSi_2-xGe_xO₉ (x = 0.4) ceramic were adjusted to near-zero by CaSnSiO₅ and decreased to 875°C upon the addition of 2 wt% LiF. The (1 – y) Ca₃SnSi_1.6Ge_0.4O₉ – y CaSnSiO₅ – 2 wt% LiF (y = 0.5) ceramic sintered at 875°C for 2 h exhibited good microwave dielectric properties: ε_r = 10.3, Q × f = 14 300 GHz (at 12.2 GHz), and τ_f = ‒5.8 ppm/°C.     

Dielectric temperature stability of Nb-modified Bi0.5(Na0.78K0.22)0.5TiO3 lead-free ceramics

In this study, the phase structure, microstructure and dielectric properties of Bi_0.5(Na_0.78K_0.22)_0.5(Ti_1-xNb_x)O₃ lead-free ceramics prepared by traditional solid phase sintering method were studied. The second phase pyrochlore bismuth titanate (Bi₂Ti₂O₇) was produced in the system after introduction of Nb⁵⁺. The dielectric constant of the sample (x = 0.03) sintered at 1130 °C at room temperature reached a maximum of 1841, and the dielectric loss was 0.045 minimum. It had been found that the K⁺ and Nb⁵⁺ co-doped Bi_0.5Na_0.5TiO₃ (BNT) lead-free ceramics exhibited outstanding dielectric-temperature stability within 100–400 °C with T_cc ≤±15%. Result of this research provides a valuable reference for application of BNT based capacitors in high temperature field.     

Structural and chemical bond characteristics of microwave dielectric ceramics Sm3-xBixGa5O12

Herein, the Bi substitution for Sm in garnet Sm_3-xBi_xGa₅O₁₂ (x = 0–0.4) microwave dielectric ceramics is reported. A single garnet-structure phase could be achieved when Bi³⁺ content is in the range of 0 ≤ x ≤ 0.3. The addition of Bi³⁺ effectively reduces the sintering temperature of Sm₃Ga₅O₁₂ ceramics from 1440 °C to 1140 °C. Furthermore, the relationship between the structure and properties of Sm_3-xBi_xGa₅O₁₂ ceramics was investigated by Raman, SEM, TEM, and complex chemical bonding theory. The dielectric constant of Sm_3-xBi_xGa₅O₁₂ (0 ≤ x ≤ 0.3) ceramics increases slightly from 12.68 to 13.35, which is closely related to an increase in the polarizability and the bond susceptibility χ^μ. The Q × f increases from 107,617 GHz to 137,069 GHz, which is related to the lattice energy and the Raman FWHM values. The τ_f value of Sm_3-xBi_xGa₅O₁₂ gradually shifted in the positive direction with the increase of Bi content and the best performance (ε_r = 13.35, Q × f = 137,069 GHz and τ_f = ?15.37 ppm/°C) was obtained at x = 0.3.     

Effects of B-site ion (M) substitution on the ionic conductivity of (Li3xLa2/3−x)1+y/2(MyTi1−y)O3 (M=Al, Cr)

Effect on the ionic conductivity of B-site ion (M) substitution in (Li_3xLa_2/3−x)_1+y/2M_yTi_1−yO₃ (M=Al, Cr) has been investigated. It has been found that partial substitution of smaller Al³⁺ for Ti⁴⁺ is effective to enhance the ionic conductivity of Li_3xLa_2/3−xTiO₃. At 300 K, the maximum bulk conductivity of (1.58±0.01)×10⁻³ S cm⁻¹ is observed from the composition of (Li_0.39La_0.54)_1−y/2Al_yTi_1−yO₃ with y=0.02 (x=0.13), that is the highest yet reported for known perovskite solutions at room temperature. The conductivity enhancement is interpreted as being due to the substitution-induced bond-strength change rather than due to bottleneck size change for Li migration, TiO₆-octahedron tilting or A-site cation ordering.