Microwave dielectric characteristics of Mg(Ta1−xNbx)2O6 ceramics

The crystalline phase and the microwave dielectric properties of the Mg(Ta_1−xNb_x)₂O₆ ceramics have been investigated. Combining the positive temperature coefficient of the resonant frequency (τ_f) material (MgTa₂O₆, τ_f = +30 ppm/°C) with the negative one (MgNb₂O₆, τ_f = −70 ppm/°C) can produce the composite with τ_f ∼ 0 ppm/°C. The crystal structure of pure MgTa₂O₆ ceramic is the tetragonal structure. For x = 0.15, the crystal structure of the solid solution was the coexistence of the tetragonal structure and orthorhombic structure. Solid solutions with 0.25 ≦ x ≦ 1 exhibit the orthorhombic structure, which is like the structure of pure MgNb₂O₆ ceramic. The sintered morphologies of Mg(Ta_1−xNb_x)₂O₆ ceramics gradually change from the disk-typed grains (x = 0 and 0.15) to the disk-typed and bar-typed grains coexist (x = 0.35, 0.5, and 0.7), and then reveal the bar-typed grains (x = 0.85 and 1). The densities, dielectric constants (ɛ_r) and τ_f values of Mg(Ta_1−xNb_x)₂O₆ ceramics decrease with the increase of the MgNb₂O₆ content. The quality factor (Q × f) reaches the minimum value at x = 0.15, and then increases with the increase of the MgNb₂O₆ content. The Mg(Ta_1−xNb_x)₂O₆ ceramic with x = 0.25 sintered at 1450 °C exhibits a minimum τ_f value of −0.7 ppm/°C.     

Microwave dielectric properties of Ba3La2Ti2Nb2−xTaxO15 ceramics

High dielectric constant and low loss ceramics in the system Ba₃La₂Ti₂Nb_2−xTa_xO₁₅ (x = 0–2) have been prepared by conventional solid-state ceramic route. Ba₃La₂Ti₂Nb_2−xTa_xO₁₅ solid solutions adopted A₅B₄O₁₅ cation-deficient hexagonal perovskite structure for all compositions. The materials were characterized at microwave frequencies. They show a linear variation of dielectric properties with the value of x. Their dielectric constant varies from 49.8 to 45.1, quality factor Q_u × f from 22,000 to 31,040 GHz and temperature variation of resonant frequency from + 6.9 to − 13.4 ppm/°C as the value of x increases. These low loss ceramics might be used for dielectric resonator (DR) applications.     

New dielectric materials of xSrTiO3–(1 − x)Ca(Mg1/3Nb2/3)O3 ceramic system at microwave frequency

The crystal structures and the microwave dielectric properties of the xSrTiO₃–(1 − x)Ca(Mg_1/3Nb_2/3)O₃ perovskite ceramic system have been investigated. In order to achieve a temperature-stable material, we studied a method of combining a positive temperature coefficient material with a negative one. SrTiO₃ has dielectric properties of dielectric constant ε_r ∼ 205, Q × f value ∼ 4200 GHz and a large positive τ_f value ∼ 1700 ppm/°C. Ca(Mg_1/3Nb_2/3)O₃ possesses high dielectric constant (ε_r ∼ 28), high quality factor (Q × f value ∼ 58,000 at 7 GHz) and negative τ_f value (− 48 ppm/°C). As the x value varies from 0.2 to 0.8, the xSrTiO₃–(1 − x)Ca(Mg_1/3Nb_2/3)O₃ system has the dielectric properties as follows: 40 < ε_r < 123, 4600 < Q × f < 33,400 and − 23 < τ_f < 600. A new microwave dielectric material, 0.3SrTiO₃–0.7Ca(Mg_1/3Nb_2/3)O₃, applicable in microwave devices is suggested and possesses the dielectric properties of a dielectric constant ε_r ∼ 46, a Q × f value ∼ 29,300 GHz (at 6.8 GHz) and a τ_f value ∼− 2 ppm/°C. A near-zero τ_f value can be achieved by adjusting the x value of xSrTiO₃–(1 − x)Ca(Mg_1/3Nb_2/3)O₃ ceramics.     

Microwave dielectric properties of Ba(Mg1/3Ta(2−2x)/3Wx/3Tix/3)O3 ceramics

The microwave dielectric properties of ceramics based on Ba(Mg_1/3Ta_(2−2x)/3W_x/3Ti_x/3)O₃ is investigated as a function of x. The densification as well as dielectric properties deteriorate with increase in the substitution levels of (Ti_1/3W_1/3)^3.33+ at (Ta_2/3)^3.33+ site in Ba(Mg_1/3Ta_2/3)O₃. The τ_f is approaching zero between x = 0.1 and 0.15 in Ba(Mg_1/3Ta_(2−2x)/3W_x/3Ti_x/3)O₃ where quality factor is reasonably good (Q_u × f = 80,000–90,000 GHz). The Ba(Mg_1/3Ta_(2−2x)/3W_x/3Ti_x/3)O₃ with x = 1.0 has ɛ_r = 15.4, τ_f = −25.1 ppm/°C, Q_u × f = 35,400 GHz.     

High dielectric constant and low-loss dielectric ceramics of Ba5LnZnNb9O30 (Ln = La,Nd and Sm)

Polycrystalline Ba₅LnZnNb₉O₃₀ (Ln = La, Nd and Sm) ceramics were prepared as single-phase materials through conventional solid-state ceramics route. The structure was characterized by X-ray diffraction methods and scanning electron microscopy (SEM) and the dielectric properties were measured from − 120 °C to 150 °C. All three compounds are paraelectric phases adopting the filled tetragonal tungsten–bronze (TB) structure at room temperature, and the Curie temperature (at 1 MHz) were − 60, − 25 and − 5 °C for Ba₅LaZnNb₉O₃₀, Ba₅NdZnNb₉O₃₀, and Ba₅SmZnNb₉O₃₀ respectively. At 1 MHz their dielectric constant (ε_r) varies from 258 to 310, dielectric loss (tanδ) from 0.0033 to 0.0068, and the temperature coefficients of the dielectric constant (τ_ε) from − 1220 to − 1390 ppm °C^− 1.     

Electrocaloric properties of (1 − x)Pb(Mg1/3Nb2/3)O3–xPbTiO3 ferroelectric ceramics near room temperature

Electrocaloric effects of (1 − x)Pb(Mg_1/3Nb_2/3)O₃–xPbTiO₃ [abbreviated as (1 − x)PMN–xPT] ferroelectric ceramics with x being, 0.08, 0.10, and 0.25, respectively, were measured near room temperature, and the origins of the electrocaloric effects of these ceramics were discussed. It was found that these ceramics possess large electrocaloric effect with ΔT being, more than 1 K under an electric field of 1.5 kV mm⁻¹ in a wide temperature range (more than 10 K) near room temperature, and this effect is due to both of the electrocaloric effect resulting from the electric field induced first-order phase transition and the linear electrocaloric effect. It is expected that these ceramics could be used for multi-stage cascade ferroelectric refrigeration near room temperature.     

The effect of B-site cations on the properties of KTaxNb1−xO3 [1 0 0] surface: A study of density functional theory

Ferroelectric material and piezoelectric properties are different in potassium tantalite niobate (KTa_xNb_1−xO₃) crystal according to differences in x. Here, we show the results of KTa_xNb_1−xO₃ (x = 0.25, 0.5, 0.75) crystal [1 0 0] surface properties calculated by density functional theory (DFT). Using local density approximation (LDA) and generalized gradient approximation (GGA), DFT has been employed to determine the structural, electronic, and optical properties of chemically ordered ferroelectric KTa_xNb_1−xO₃ crystal [1 0 0] surfaces. Based on the research, comparison and analysis of the results show that all kinds of properties of KTa_xNb_1−xO₃ [1 0 0] surfaces are vary with respect to x. It is found, for instance, that the ordering of B-site cations obviously influences the properties of the KTa_xNb_1−xO₃ surface. At the same time, this allows the experimental studies to be supervised effectively.     

Processing and electrical properties of (1 − x)[(1 − y)(Pb(Mg1/3Nb2/3)O3)–y(Pb(Yb1/2Nb1/2)O3)]–xPbTiO3 ceramics

Ferroelectric ceramics in the vicinity of morphotropic phase boundary (MPB) with compositions represented as (1 ? x)[(1 ? y)(Pb(Mg_1/3Nb_2/3)O₃)–y(Pb(Yb_1/2Nb_1/2)O₃)]–xPbTiO₃ were prepared by solid state reaction. The addition of PYbN to PMN–PT decreased the sintering temperature from 1200 °C (y = 0.25) to 1000 °C (y = 0.75). The PT content, where the MPB was observed, increased with the PYbN addition. A remanent polarization value of 28.5 µC/cm² and a coercive field value of 11 kV/cm were measured from 0.62[0.25PMN–0.75PYbN]–0.38PT ceramics, which were close to the ones measured from PMN–0.32PT ceramics. In addition, the Curie temperature was found to increase with PYbN additions.     

Microwave-induced combustion synthesis and electrical conductivity of Ce1−xGdxO2−1/2x ceramics

Ce_1−xGd_xO_2−1/2x nanopowder were successfully synthesized by microwave-induced combustion process. For the preparation, cerium nitrate, gadolinium nitrate hexahydrate, and urea were used for the microwave-induced combustion process. The process took only 30 min to obtain Ce_1−xGd_xO_2−1/2x powders. The exo-endo temperature, phase identification, and morphology of resultant powders were investigated by TG/DTA, XRD, and SEM. The as-received Ce_1−xGd_xO_2−1/2x powders showed that the average particle size ranged from 18 to 50 nm, crystallite dimension varied from 11 to 20 nm, and the specific surface area was distribution from 16 to 46 m²/g. As for Ce_1−xGd_xO_2−1/2x ceramics sintered at 1450 °C for 3 h, the bulk density of Ce_1−xGd_xO_2−1/2x ceramics were over 91% of the theoretical density, the maximum electrical conductivity, σ_700 °C = 0.017 S/cm with minimum activation energy, E_a = 0.869 eV was found at Ce_0.80Gd_0.20O_1.90 ceramic.     

Preparation,characterization and dielectric properties of Ba3−xSrxM4Ti4O21 (M = Nb,Ta and 0 ≤ x ≤ 3) ceramics

Ba_3−xSr_xM₄Ti₄O₂₁ (M = Nb, Ta and 0 ≤ x ≤ 3) ceramics have been prepared through solid state ceramic route. The structure and microstructure of the compositions have been studied using powder X-ray diffraction and Scanning Electron Microscopic studies. In the present study, both Ba₃Nb₄Ti₄O₂₁ and Ba₃Ta₄Ti₄O₂₁ are obtained as single phase compositions whereas strontium rich compositions exhibit multiphase in nature. Energy dispersive X-ray analysis has been performed to identify the nature of additional phases present in the strontium rich compositions. The dielectric constant, dielectric loss and temperature variation of dielectric constant of the well sintered ceramic specimens have been studied in the low frequency region (< 13 MHz) using an impedance analyzer. The present study reveals that high dielectric compositions can be realized by Sr-substitution in the BaO–TiO₂–Nb₂O₅/Ta₂O₅ ternary systems.     

Perovskite phase stabilization and dielectric properties of Pb(Zn1/3Ta2/3)O3–BaTiO3 ceramics

The phase structure and dielectric properties of (1 − x)Pb(Zn_1/3Ta_2/3)O₃–xBaTiO₃ (x = 0.00–0.40) ceramics were investigated. Pure perovskite is obtained when x ≥ 0.24. With increasing BT content, the diffuse phase transition and frequency dissipation of the dielectric constant increase and the dielectric maxima temperature decreases. It is related to the existing of Ba(Zn_1/3Ta_2/3)O₃ paraelectric microregions and the incomplete solid solution reaction between Pb(Zn_1/3Ta_2/3)O₃ and BaTiO₃.     

On the synthesis and dielectric studies of (1 − x)Bi(Mg1 / 2Zr1 / 2)O3 − xPbTiO3 piezoelectric ceramic system

Scandium free piezoelectric ceramics of the composition (1 − x)Bi(Mg_1 / 2Zr_1 / 2)O₃ − xPbTiO₃ (BMZ − xPT) were fabricated by the solid state reaction method. Dielectric and structural properties were measured and phase diagram was constructed from the temperature dependent dielectric and impedance data. The morphotropic phase boundary (MPB) was found to be located in the range 0.55 < x < 0.60 with paraelectric–ferroelectric phase transition temperature, T_C (∼ 280 °C). The ceramics near the MPB showed high room temperature dielectric constant (∼ 1387). The room temperature values of the remanent polarization (P_r) and coercive filed (E_C), were ∼ 29 μC/cm² and ∼ 23 kV/cm, respectively.     

Low-temperature hydro/solvothermal synthesis of Ta-modified K0.5Na0.5NbO3 powders and piezoelectric properties of corresponding ceramics

K_0.5Na_0.5Nb_1–xTa_xO₃ (KNNTx, x = 0–0.4) powders were synthesized by a novel hydro/solvothermal method at a low reaction temperature (180 °C) and the corresponding ceramics were obtained by normal sintering. Compared with conventional solid-state reaction technique, the optimal sintering temperatures of these ceramics were reduced at least 150 °C. Crystalline structures and surface morphologies were analyzed by X-ray diffraction and scanning electron microscopy. The excellent piezoelectric properties could be obtained by selecting poling temperature near the orthorhombic–tetragonal polymorphic phase transition temperature region. Ta-modified KNN ceramics exhibited better piezoelectric properties than those of pure KNN, and the piezoelectric coefficient d₃₃ showed the maximum value of 156 pC/N for KNNT0.3 ceramics. In addition, the sintering temperature for maximum d₃₃ value differed from that for maximum density. The present hydro/solvothermal method provides a new potential route for preparing KNN-based materials at relatively low temperature.     

Microwave dielectric ceramics in (Ca1− xBax)(Zn1 / 3Nb2 / 3)O3 system

(Ca_1−xBa_x)(Zn_1 / 3Nb_2 / 3)O₃ (x = 0–1.0) microwave dielectric ceramics were prepared and investigated. The Ba(Zn_1 / 3Nb_2 / 3)O₃-based solid solution was observed for x = 0.9, and the compositions with x = 0.1–0.7 resulted in the mixture of two phases. Dielectric constant ε_r and temperature coefficient of resonant frequency τ_f of the present ceramics varied anomalously and reached their maximum at x = 0.7–0.9, and these phenomena were originated from the partial substitution of small Ca²⁺ ions for larger Ba²⁺ at A-site. On the other hand, a good combination of microwave dielectric properties (ε_r = 36, Qf = 16,170 GHz, τ_f = − 12 ppm/°C) were obtained at x = 0.1, while the decreased Qf value was observed in other compositions.     

Effects of SrTiO3 on dielectric and piezoelectric properties of K0.48Na0.48Li0.04Nb0.96Ta0.04O3-based piezoceramics

In this study, (100 ? x) K_0.48Na_0.48Li_0.04Nb_0.96Ta_0.04O₃ ? xSrTiO₃ (0 ≤ x ≤ 10) ceramics were fabricated via normal sintering of synthesized powder by using solid state reaction. All ceramics revealed pure perovskite structure, indicating formation of solid solution between KNNLT and ST up to 10%. With increasing x, the crystal structure of ceramics changed from orthorhombic to tetragonal and finally pseudocubic symmetry when x = 10. Ceramic containing 1% ST had orthorhombic and tetragonal symmetries, simultaneously. Investigation of the variation of dielectric constant of ceramics versus temperature revealed that for ceramic with x = 1, polymorphic phase transition (PPT) temperature between orthorhombic and tetragonal is less than room temperature. Thus coexistence of two different structures in this ceramic is due to vicinity of its composition to morphotropic phase boundary (MPB). As a result, the maximum piezoelectric constant was measured for this ceramic. Ceramics containing 5 and 7.5% ST tend to appear relaxor ferroelectric behavior which is because of chemical inhomogeneities in both A- and B-sites of the ABO₃ perovskite structure.     

Low-temperature sintering and microwave dielectric properties of CaTi1−x(Fe0.5Nb0.5)xO3 ceramics with B2O3 addition

CaTi_1−x(Fe_0.5Nb_0.5)_xO₃ (0 ≤ x ≤ 1) dielectrics were synthesized via the solid state reaction route and structure analysis was performed together with the dielectric characterization. The substitution of Ti⁴⁺ by Fe³⁺/Nb⁵⁺ and developed phase were studied by X-ray diffraction. The dielectric constant and temperature coefficient of resonant frequency decrease rapidly with an increase of x. The influence of 1–5 wt.% B₂O₃ as a sintering additive investigated at CaTi_0.5(Fe_0.5Nb_0.5)_0.5O₃ solid solutions. The dielectric properties were found to strongly depend on the sintering conditions and contents of B₂O₃ additions. ɛ_r = 52.3, Q × f_o = 2930 GHz and T_f = 13 ppm/°C were obtained for CaTi_0.5(Fe_0.5Nb_0.5)_0.5O₃ specimen 3 wt.% B₂O₃ sintered at 900 °C for 2 h.     

Porous high entropy (Zr0.2Hf0.2Ti0.2Nb0.2Ta0.2)B2: A novel strategy towards making ultrahigh temperature ceramics thermal insulating

Transition metal diborides based ultrahigh temperature ceramics (UHTCs) are characterized by high melting point, high strength and hardness, and high electrical and thermal conductivity. The high thermal conductivity arises from both electronic and phonon contributions. Thus electronic and phonon contributions must be controlled simultaneously in reducing the thermal conductivity of transition metal diborides. In high entropy (HE) materials, both electrons and phonons are scattered such that the thermal conductivity can significantly be reduced, which opens a new window to design novel insulating materials. Inspired by the high entropy effect, porous HE (Zr_0.2Hf_0.2Nb_0.2Ta_0.2Ti_0.2)B₂ is designed in this work as a new thermal insulting ultrahigh temperature material and is synthesized by an in-situ thermal borocarbon reduction/partial sintering process. The porous HE (Zr_0.2Hf_0.2Nb_0.2Ta_0.2Ti_0.2)B₂ possesses high porosity of 75.67%, pore size of 0.3–1.2 μm, homogeneous microstructure with small grain size of 400–800 nm, which results in low room temperature thermal diffusivity and thermal conductivity of 0.74 mm² s⁻¹ and 0.51 W m⁻¹ K⁻¹, respectively. In addition, it exhibits high compressive strength of 3.93 MPa. The combination of these properties indicates that exploring porous high entropy ceramics such as porous HE (Zr_0.2Hf_0.2Nb_0.2Ta_0.2Ti_0.2)B₂ is a novel strategy in making UHTCs thermal insulating.     

Synthesis and characterization of Gd3+ and Nd3+ co-doped ceria by using citric acid–nitrate combustion method

A series of Ce_0.8Gd_0.2?xNd_xO_2?δ (x = 0–0.20) compositions have been synthesized by citric acid–nitrate combustion method. XRD measurements indicate that all the obtained materials crystallized in cubic fluorite-type structure. Lattice parameters were calculated by Rietveld method and the parameter a values in Ce_0.8Gd_0.2?xNd_xO_2?δ system obey Vegard's law, a (Å) = 5.4224 + 0.1208x. The obtained powders have good sinterability and the relative density could reach above 95% after being sintered at 1400 °C. Impedance spectroscopy measurements indicated that the conductivity of Ce_0.8Gd_0.2?xNd_xO_2?δ first increased and then decreased with Nd dopant content x. The maximum conductivity, σ_700 °C = 6.26 × 10^?2 S/cm, was found in Ce_0.8Gd_0.12Nd_0.08O_1.9 when sintered at 1300 °C. The corresponding activation energies of conduction had a minimum value E_a = 0.676 eV. The results tested experimentally the validity of the effective atomic number concept of recent density functional theory, which had suggested that co-dopant with effective atomic number between 61 (Pm) and 62 (Sm) was the ideal dopant exhibiting high ionic conductivity and low activation energy.     

Influence of V2O5 additions to Ba(Mg1/3Ta2/3)O3 ceramics on sintering behavior and microwave dielectric properties

The microstructures and the microwave dielectric properties of barium magnesium tantalate ceramics prepared by conventional mixed oxide route have been investigated. The prepared Ba(Mg_1/3Ta_2/3)O₃ exhibited a mixture of cubic perovskite and a hexagonal superstructure with Mg and Ta showing 1:2 order in the B-site. It is found that low level doping of V₂O₅ (up to 0.5 wt.%) can significantly improve densification of the specimens and their microwave dielectric properties. The density of doped Ba(Mg_1/3Ta_2/3)O₃ ceramics can be increased beyond 95% of its theoretical value by 1500 °C-sintering, which is caused by the liquid-phase effect of V₂O₅ addition. The detected second phase Ta₂O₅ was mainly the result of V⁵⁺ substitution in the ceramics. Dielectric constant (ε_r) and temperature coefficient of resonant frequency (τ_f) were not significantly affected, while the unloaded quality factors Q were effectively promoted by V₂O₅ addition due to the increase in B-site ordering. The ε_r value of 24.1, Q×f value of 149,000 (at 10 GHz) and τ_f value of 7.2 ppm/°C were obtained for Ba(Mg_1/3Ta_2/3)O₃ ceramics with 0.25 wt.% V₂O₅ addition sintered at 1500 °C for 3 h.     

Microwave dielectric properties of xNd(Zn1/2Ti1/2)O3–(1 − x)CaTiO3 ceramics

The microwave dielectric properties of xNd(Zn_1/2Ti_1/2)O₃–(1 − x)CaTiO₃ have been investigated. The system has been prepared by a conventional solid state ceramic route. Nd(Zn_1/2Ti_1/2)O₃ (NZT) possesses a dielectric constant (ε_r) of 32, a high quality factor (Q × f) of 170,000 GHz and a temperature coefficient of resonant frequency (τ_f) of − 42 ppm/°C. In order to produce a temperature-stable material, the addition of CaTiO₃ leads to a near-zero temperature variation of resonant frequency. In general, the microwave quality factor (Q × f) decreased as x increased and the temperature coefficient of resonant frequency (τ_f) was approximately linearly proportional to permittivity. The dielectric constant decreases from 77 to 32 as x varies from 0.2 to 1.0. The dielectric constant (ε_r) of 45, Q × f value of 56,000 (at 6 GHz) and temperature coefficient of resonant frequency (τ_f) of 0 ppm/°C were obtained for 0.5Nd(Zn_1/2Ti_1/2)O₃–0.5CaTiO₃ ceramics sintered at 1300 °C for 4 h. As the content of x increases, the highest Q × f value of 136,200 GHz for x = 0.8 is achieved at the sintering temperature 1300 °C.