Dielectric characteristics of donor-acceptor modified BaTiO3 ceramics

Sm/Mn codoped BaTiO₃ ceramics were investigated for their microstructure and dielectric characteristics. The powders were prepared by the conventional solid state procedure. The concentration of Sm₂O₃ as a donor dopant has been kept from 0.1 up to 5.0 at%. The content of MnO₂ as acceptor was kept constant at 0.05 at% Mn in all samples. The specimens were sintered at 1290 °C, 1320 °C and 1350 °C in an air atmosphere for two hours.A mainly uniform and homogeneous microstructure with average grain size ranging from 0.3 µm to 2.0 µm was observed in low doped samples. In highly doped samples, apart from the fine grained matrix, the appearance of local area with secondary abnormal grains was observed.The dielectric properties were investigated as a function of frequency and temperature. The low doped samples exhibit the high value of dielectric permittivity at room temperature and the greatest change at the Curie temperature. The highest value of dielectric constant (ε_r=6800) was measured for 0.1Sm/BaTiO₃ samples sintered at 1350 °C. A nearly flat permittivity-temperature response and lower values of ε_r were obtained in specimens with 2.0 and 5.0 at% additive content. The dielectric constant increases with the increase of sintering temperature. The dissipation factor ranged from 0.01 to 0.22 and decreases with the increase of sintering temperature. The Curie constant (C), Curie-Weiss temperature (T₀) and critical exponent of nonlinearity (γ ) were calculated using a Curie-Weiss and modified Curie-Weiss law. The highest value of Curie constant (C=9.06·10⁵ K) was measured in 0.1 at% doped samples. The Curie constant decreased with increasing dopant content. The γ values, ranging from 1.001 to 1.58, point out the sharp phase transition in low doped samples, and the diffuse phase transition in heavily doped BaTiO₃ samples.     

Study of physical properties of cobalt substituted Pr0.7Ca0.3MnO3 ceramics

An investigation on single phase semiconducting polycrystalline Pr_0.7Ca_0.3MnO₃ and Pr_0.7Ca_0.3MnCo_0.1O₃ crystallized in the orthorhombic system with Pnma space group is reported. We found that σ_DC increases when introducing Co for T<110 K but for T>110 K, it decreases. Also, the contribution of hopping process in conduction mechanism was in agreement with the Jonscher law and Mott theory. Capacitance was extensively dependent on temperature and frequency. A dielectric transition was observed at T=150 K for the doped compound. The temperature dependence of dielectric permittivity is well described by Curie–Weiss law. The parameter of deviation from Curie–Weiss behavior to modified Curie–Weiss law is found to be ΔT_m=30 K. The substitution of Mn by Co was found to destroy the charge order state observed in the parent compound and to induce a ferromagnetic phase at low temperature. The cobalt-substituted sample exhibits a maximum value of magnetic entropy change |∆S^max|=3.2 J kg⁻¹ K⁻¹and a large relative cooling power with a maximum value of 301 J/kg under an applied field of 5 T. Technically, these large values make the prepared material very promising for magnetic refrigeration.     

Induced anisotropic behavior and enhanced electrical properties on hot-pressed strontium barium niobate ceramics

Sr_0.30Ba_0.70Nb₂O₆ (SBN30) ferroelectric ceramics were fabricated by conventional sintering (CS) and by hot-pressing sintering (HP) and their crystal structure, microstructure, dielectric, ferroelectric and pyroelectric properties were studied and compared. Preferred orientation of the HP ceramics was detected through X-ray diffraction. Dense microstructure virtually free of pores has been achieved in HP samples. Moreover, the HP samples manifested prominent anisotropy in electrical properties. Besides, the relative permittivity (ε_r), saturated polarization (P_s), pyroelectric coefficient (p) in the direction perpendicular to the pressing axis were much higher than those of the randomly oriented CS samples. The HP samples sintered under 200 MPa show excellent pyroelectric properties in the direction perpendicular to the pressing axis, with pyroelectric coefficient of 2.38×10⁻⁸C/cm²K and pyroelectric figure of merit of F_i=1.13 pm/V, F_v=1.89 m²/C and F_d=0.63 μPa^−1/2,which roughly triple the values obtained in CS samples. These results indicate that hot-pressing is a viable option for accessing single-crystal-like anisotropy as well as enhanced electrical properties in polycrystalline ceramics, thus unveiling the distinctive potential of HP SBN30 ceramics for infrared detector applications.     

Pyroelectric,ferroelectric, piezoelectric and dielectric properties of Na0.5Bi0.5TiO3 ceramic prepared by sol-gel method

Sodium bismuth titanate (BNT) nanopowder of molar composition 50/50 (Na_0.5Bi_0.5TiO₃) was prepared by a sol-gel processing method. The structure and microstructure of the precursor gel as well as the ferroelectric, pyroelectric, dielectric and piezoelectric properties of the BNT were studied. BNT crystallized in the rhombohedra perovskites structure Na_0.5Bi_0.5TiO₃ was obtained from the precursor gel by heating at 700 °C for 2 h in air. The BNT ceramic at 1100 °C sintering temperature present high crystallinity, good dielectric properties at 1 kHz (ε′=885, tan δ=0.03, T_c=370 °C), piezoelectric properties (k₃₃=0.39, c₃₃=105 GPa, e₃₃=12.6 C/m², d₃₃=120 pC/N), high remnant polarization (P_r=47 μC/cm²) and pyroelectric coefficient ($p$=707 μC/m² K) and low coercive field (E_c=55 kV/cm). Hence, the BNT prepared by sol-gel method could be used for silicon based memory device application where a low synthesis temperature is a key requirement.     

Preparation and electrical properties of (1−x)SrBi2Nb2O9−xBiFeO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics, (1−x)SrBi₂Nb₂O₉−xBiFeO₃ [(1−x)SBN−xBFO] (x=0.0, 0.03, 0.05, 0.07, 0.10) were prepared by a conventional solid-state reaction method. The crystal structure, microstructure and electrical properties were systematically investigated. All compositions formed layered perovskite structure without any detectable secondary phases. Plate-like morphology of the grains which is characteristic for layer-structure Aurivillius compounds was clearly observed. The excellent electrical properties (e.g., d₃₃~19 pC/N, 2P_r~18.8 μC/cm²) and a high Curie temperature (e.g., T_c~449 °C) were simultaneously obtained in the ceramics with x=0.05. Additionally, thermal annealing studies indicated that the BFO modified SBN ceramics system possessed stable piezoelectric properties, demonstrating that the modified SBN-based ceramics are the promising candidates for high-temperature applications.     

Improvement on the phase stability,mechanical properties and thermal insulation of Y2O3-stabilized ZrO2 by Gd2O3 and Yb2O3 co-doping

Gd₂O₃ and Yb₂O₃ co-doped 3.5 mol% Y₂O₃–ZrO₂ and conventional 3.5 mol% Y₂O₃–ZrO₂ (YSZ) powders were synthesized by solid state reaction. The objective of this study was to improve the phase stability, mechanical properties and thermal insulation of YSZ. After heat treatment at 1500 °C for 10 h, 1 mol% Gd₂O₃–1 mol% Yb₂O₃ co-doped YSZ (1Gd1Yb-YSZ) had higher resistance to destabilization of metastable tetragonal phase than YSZ. The hardness of 5 mol% Gd₂O₃–1 mol% Yb₂O₃ co-doped YSZ (5Gd1Yb-YSZ) was higher than that of YSZ. Compared with YSZ, 1Gd1Yb-YSZ and 5Gd1Yb-YSZ exhibited lower thermal conductivity and shorter phonon mean free path. At 1300 °C, the thermal conductivity of 5Gd1Yb-YSZ was 1.23 W/m K, nearly 25% lower than that of YSZ (1.62 W/m K). Gd₂O₃ and Yb₂O₃ co-doped YSZ can be explored as a candidate material for thermal barrier coating applications.     

Control of coring effect in BaTi4O9 microwave dielectric ceramics by doping with Mn4+

In the present work, we have attempted to reduce the effect of coring effect in the titanate ceramic system BaTi₄O₉ (BT4) by doping it with Mn⁴⁺. The microwave dielectric BaTi₄O₉ ceramics doped with 0, 0.5 and 1.0 mol% Mn⁴⁺ were synthesized by conventional ceramic processing route. The XRD studies confirmed a single phase crystalline structure for all the ceramic samples studied. The SEM micrographs of the ceramics reveal a microstructural change leading towards a more uniform grain size distribution as the Mn⁴⁺ content increases to 1.0 mol%. In the low frequency region (100 Hz to 1 MHz), the temperature stability of dielectric properties exhibits a marked improvement with the increasing amount of Mn⁴⁺ in the ceramic system. In the microwave frequency region (9.3 GHz), Q-factor increases from 11,625 GHz to 46,500 GHz for BaTi₄O₉ ceramic doped with 1.0 mol% Mn⁴⁺. The present paper reveals that the commonly observed degradation of dielectric properties due to coring effect in the BaTi₄O₉ ceramic system can be controlled by doping it with an appropriate quantity of Mn⁴⁺.     

Dy3+ doped LiCl–CaO–Bi2O3–B2O3 glasses for WLED applications

Dy³⁺ doped calcium bismuth borate glasses were synthesized in the composition range of xLiCl-(30 − x)CaO-20Bi₂O₃-50B₂O₃ + 1 mol% Dy₂O₃ (x = 0, 2, 5, 7, 10 and 15 mol%, LC0, LC2, LC5, LC7, LC10 and LC15 respectively) using conventional melt-quench technique. Broad XRD profiles confirmed non-crystalline nature of synthesized compositions. The compositional dependencies of structural changes (using FTIR spectra), thermal behavior (using DSC thermographs) and optical band gap (using UV–Vis–NIR spectra) were discussed. Photoluminescence (PL) excitation spectra recorded at 577 nm yielded six different excitation peaks belonging to Dy³⁺ ions. The PL emission spectra recorded at 451 nm were analyzed to extract different light emission parameters viz. Y/B ratio, color coordinates, correlated color temperature (CCT) following CIE 1931 chromaticity diagram. The emission colors were found to lie in white light region and lies very close to standard white light emission. The CCT of sample LC10 (5335 K) is closest to CCT of standard white light (5615 K) which depicted the optimized concentration of LiCl for application of these glasses in WLED application.     

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.     

Structural,electrical, dielectric and magnetic behavior of Gd1−xBixFe1−yZryO3 nanoparticles for advanced technological applications

Gd_1−xBi_xFe_1−yZr_yO₃ nanoparticles were synthesized via micro-emulsion route with different molar concentrations of Bi⁺³ (x) and Zr⁺⁴ (y). The values of x and y were kept in the range 0.00, 0.15, 0.30, 0.45 and 0.60. The characterizations were done by the thermo-gravimetric analysis (TGA), X-ray Diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The average particle size was ~50 nm. The effect of Bi³⁺ and Zr⁴⁺ contents on electrical, dielectric and magnetic parameters were studied. The DC resistivity measurements showed at certain Bi³⁺ and Zr⁴⁺ contents, more than two fold increase in electrical resistivity from 68×10⁸ Ω cm to 150×10⁸ Ω cm. The magnetic measurements showed the paramagnetic nature of Gd_1−xBi_xFe_1−yZr_yO₃ nanoparticles. The electrical and magnetic properties of these nanoparticles suggested that these materials are potential candidates for the fabrication of telecommunication and switching devices.     

Investigation of dielectric and piezoelectric properties in Pb(Ni1/3Nb2/3)O3–PbHfO3–PbTiO3 ternary system

The dielectric and piezoelectric properties were investigated in the (1 ? x)Pb(Hf_1?yTi_y)O₃–xPb(Ni_1/3Nb_2/3)O₃ (PNN–PHT, x = 0.05–0.50, y = 0.55–0.70) ternary system. The morphotropic phase boundary (MPB) was determined by X-ray powder diffraction analysis. Isothermal map of Curie temperature (T_C) related to the compositions in the phase diagram was obtained. The optimum dielectric and piezoelectric properties were achieved in ceramics with the MPB compositions, with the maxima values being on the order of 6000 and 970pC/N, respectively. Rayleigh analysis was used to study the extrinsic contribution (domain wall motion) in PNN–PHT system, where the extrinsic contribution was found to be ～30% for composition 0.49PNN–0.51PHT(30/70), showing a high nonlinearity.     

Preparation,sintering and electrical properties of nano-grained multidoped ceria

Multiply doped ceria nanopowders were synthesized by applying MGNP (modified glycine/nitrate procedure). The overall concentration of dopants was kept constant (x = 0.2) whereby Gd ion as the main dopant was gradually substituted by Sm and by Sm + Y. The compositions of solid solutions were calculated by applying defect model introducing anion vacancy radius. Characterization of powders involved BET, TEM, XRD and chemical analyses. Densification was performed at 1500 °C, in an oxygen atmosphere for 1 h. The results showed that with increasing number of dopants, specific surface area of powders increased, followed by decrease of crystallite and grain sizes. Densification degree was also found to rise with increasing number of dopants. According to impedance measurements it was found that ionic conductivity was the highest 1.14 × 10^?3 S cm^?1 at 450 °C in sample doped with Gd, Sm and Y simultaneously.     

Structural,electromagnetic, and dielectric properties of lithium-zinc ferrite ceramics sintered by pulsed electron beam heating

Structural, electromagnetic, and dielectric properties of Li_0.4Fe_2.4Zn_0.2O₄ lithium-zinc ferrite sintered by 2.4 MeV pulsed electron beam heating at 1050 °С for 2 h were investigated. The formation of ferrite with a single-phase cubic spinel structure was confirmed by X-ray diffraction analysis. The average grain size of ferrite ceramic was determined by SEM analysis and its value was 1.7 µm. The radiation-thermal sintered samples are characterized by a saturation magnetization of 67.8 emu/g, the Curie temperature of 508 °C, AC electrical resistivity of 2.4×10⁴ Ω cm (at 25 °C). The frequency dependences of permittivity and the loss tangent were obtained in (20 – 2×10⁶) Hz frequency range. The behavior of ε′ is characterized by high dispersion caused by relaxation polarization in the investigated frequency range. The results were compared to the LiZn ferrite characteristics sintered by traditional thermal heating.     

Enhanced electrocaloric,pyroelectric and energy storage performance of BaCexTi1−xO3 ceramics

BaCe_xTi_1−xO₃ (BCT) ceramics with compositions x = 0, 0.1, 0.12 and 0.15 were synthesized using conventional solid state reaction route. Systematic exploration of enhancing electrocaloric effect (ECE) in BaTiO₃ by rare earth dopant Ce is presented. BaCe_0.12Ti_0.88O₃ exhibited an electrocaloric strength of ∼0.35 K m/MV at 351 K, which caters the need for a series of high-level ECE material. Further, the temperature dependence of pyroelectric coefficient is established for all compositions. The pyroelectric figure of merits (FOMs) for current responsivity (F_i), voltage responsivity (F_v), detectivity (F_d) and energy harvesting (F_e and F_e^*) are calculated and the results reveal that x = 0.1 could be a technologically superior candidate for pyroelectric devices. Further, BaCe_0.15Ti_0.85O₃ exhibited highest electrical energy storage performance of 115 kJ/m³ compared with 71 kJ/m³ in BaTiO₃. Our findings in this work may provide a better understanding for developing high ECE materials combined with pyroelectric and energy storage performance of Ce substituted BaTiO₃ ceramics.     

Composition design,phase transitions and electrical properties of Sr2+-substituted xPZN–0.1PNN–(0.9−x)PZT piezoelectric ceramics

The influences of PZN content and Sr²⁺ substitution on the structure and electrical properties of Pb(Zn_1/3Nb_2/3)O₃–Pb(Ni_1/3Nb_2/3)O₃–Pb(Zr_0.52Ti_0.48)O₃ (abbreviated as PZN–PNN–PZT) piezoelectric ceramics were studied. All as-prepared PZN–PNN–PZT ceramics presented single phase of perovskite structure, while higher PZN contents favored rhombohedral symmetry and larger grain size. Meanwhile, with the increase in Sr²⁺ content, the phase structure changed from a mix of tetragonal and rhombohedral symmetries to a pure rhombohedral symmetry. Although the ferroelectric Curie temperature (T_C) was decreased with increasing the PZN and Sr²⁺ contents, the piezoelectric constant (d₃₃) exhibited the opposite trend. As a result, optimum comprehensive electrical properties were obtained in the 0.1PZN–0.1PNN–0.8PZT composition with 10 mol% Sr²⁺ substitution: d₃₃~800 pC/N, k_p ~0.65, ɛ_r~4081, T_C~176 °C, P_r~30.92 µC/cm². Thus, the 10 mol% Sr²⁺-substituted 0.1PZN–0.1PNN–0.8PZT ceramic is a promising candidate for high performance applications.     

Structural and optical characterization of Zn0.95−xMg0.05AlxO nanoparticles

The structural and optical properties of ZnO nanoparticles doped simultaneously with Mg and Al were investigated. XRD results revealed the hexagonal wurtzite crystalline structure of ZnO. The FE-SEM study confirmed the formation of nano-sized homogeneous grains whose sizes decreased monotonously with increasing doping concentrations of Mg and Al. The absorption spectra showed that band gap increased from 3.20 to 3.31 eV with Mg doping. As the Al concentration changed from x=0.01 to x=0.06 mol% at constant Mg concentration the band gap observed to be decreased. Particle sizes estimated from effective mass approximation using absorption data and these values are in good agreement with the crystallite sizes calculated from XRD data. Raman spectra of ZnO showed a characteristic peak at 436 cm⁻¹ correspond to a non-polar optical phonon E₂ (high). With increase of the Al doping concentrations, E₂ (high) phonon frequency shifted to 439 cm⁻¹ from to 436 cm⁻¹. The origin of E₂ (high) peak shift in ZnO nanoparticles is attributed to optical phonon confinement effects or the presence of intrinsic defects on the nanoparticles. PL spectra indicated that with increase of Al co-doping along with Mg into ZnO, intensity of the peak positioned at 395 nm was initially increased at x=0 and then decreased with increase of the Al concentrations from x=0.01 to x=0.06 mol%.     

A comparative study of the magnetic and microwave properties of Al3+ and In3+ substituted Mg–Mn ferrites

The effect of substitution of diamagnetic Al³⁺ and In³⁺ ions for partial Fe³⁺ ions in a spinel lattice on the magnetic and microwave properties of magnesium–manganese (Mg–Mn) ferrites has been studied. Three kinds of Mg–Mn based ferrites with compositions of Mg_0.9Mn_0.1Fe₂O₄, Mg_0.9Mn_0.1Al_0.1Fe_1.9O₄, and Mg_0.9Mn_0.1In_0.1Fe_1.9O₄ were prepared by the solid-state reaction route. Each mixture of high-purity starting materials (oxide powders) in stoichiometric amounts was calcined at 1100 °C for 4 h, and the debinded green compacts were sintered at 1350 °C for 4 h. XRD examination confirmed that the sintered ferrite samples had a single-phase cubic spinel structure. The incorporation of Al³⁺ or In³⁺ ions in place of Fe³⁺ ions in Mg–Mn ferrites increased the average particle size, decreased the Curie temperature, and resulted in a broader resonance linewidth as compared to un-substituted Mg–Mn ferrites in the X-band. In this study, the In³⁺ substituted Mg–Mn ferrites exhibited the highest saturation magnetization of 35.7 emu/g, the lowest coercivity of 4.1 Oe, and the highest Q×f value of 1050 GHz at a frequency of 6.5 GHz.     

Influence of MnO2 and Co3O4 dopants on dielectric properties of Pb(Fe2/3W1/3)O3 ceramics

Dielectric properties of Pb(Fe_2/3W_1/3)O₃ ceramic doped with 0.05–1 mol% of MnO₂ or Co₃O₄ were investigated in a wide temperature range from −160 to 450 °C at frequencies 10 Hz–1 MHz. Besides the maxima corresponding to the ferroelectric–paraelectric transition, at higher temperatures other peaks in temperature dependencies of relative electrical permittivity and dissipation factor were observed, attributed to dielectric relaxation. The location and height of these peaks are strongly related to frequency and the dopant level. Both MnO₂ and Co₃O₄ addition caused a significant increase in the resistivity of PFW ceramic—from 10⁶ Ω cm for undoped samples to 10¹¹ Ω cm for those with 1 mol% of a dopant. The activation energies of relaxation calculated on the basis of dielectric measurements are very close to the conduction activation energies determined in similar temperature range.     

Densification behavior and electrical properties of CuO-doped Pb(In1/2Nb1/2)O3–Pb(Mg1/3Nb2/3)O3–PbTiO3 ternary ceramics

CuO modified Pb(In_1/2Nb_1/2)O₃–Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PIN–PMN–PT) ternary relaxor based ferroelectrics with the composition near the morphotropic phase boundary were synthesized by two-step columbite precursor method. The introduction of CuO significantly improved the sinterability of PIN–PMN–PT ceramics, resulting in the full densification of samples at lower sintering temperatures. It also profoundly modified the crystal structure and fracture mode of the ceramics. Properly increasing CuO content led to the disappearance of rhombohedral-tetragonal phase transition, remarkably improved the Curie temperature (T_c), and made the ceramics more relaxorlike. The ternary ceramics doped with 0.25 wt% CuO possessed optimum piezoelectric properties (d₃₃=584 pC/N, d₃₃^*=948 pC/N, and k_p=0.68), high ferroelectric properties (E_c=9.9 kV/cm, and P_r=33.1 μC/cm²), low dielectric loss (tan δ=0.9%), and wider temperature usage range (T_c=225 °C). The obtained properties are much higher than those of previously reported PIN–PMN–PT based ceramics, indicating that CuO doped PIN–PMN–PT is a promising candidate for electromechanical applications with high performance and wide temperature/electric field usage ranges.     

Influence of the composition-induced structure evolution on the electrocaloric effect in Bi0.5Na0.5TiO3-based solid solution

The present work investigated the influence of the composition induced structure evolution on the electrocaloric effect in lead-free (0.935−x)Bi_0.5Na_0.5TiO₃–0.065BaTiO₃–xSrTiO₃ (BNBST, BNBSTx) ceramics. It was found that broad ∆T peak could be observed for all compositions and the electrocaloric strength α (α=ΔT_max/ΔE) in BNBST0.02 could reach as high as 0.27 K mm/kV. The increase of the SrTiO₃ concentration led to a shift of ∆T_max to a lower temperature, resulting in a large near room-temperature electrocaloric strength α of 0.17 K mm/kV in BNBST0.22.