Role of structural changes in dielectric,ferroelectric properties of Sr2KxNa1−xNb5O15 lead-free ceramics

Lead-free Sr₂K_xNa_1−xNb₅O₁₅ (0.00 ≤ x ≤ 0.20) piezoelectric ceramics were prepared by two-step solid state reaction method. Pure tungsten bronze structure could be obtained in all ceramics and K substitution could accelerate the phase formation at lower temperatures. The lattice constant calculation indicated expansion of the unit cell and reduced distortion of the crystal structure with K substitution due to the bigger ionic size of K⁺ (1.64 Å) compared to that of Na⁺ (1.39 Å). Electrical properties of Sr₂K_xNa_1−xNb₅O₁₅ ceramics greatly depended on the K content. Curie temperature T_c shifted downward, whereas the maximum dielectric constant ?_m and the degree of diffusion phase transition all increased initially and then decreased as K content increased, indicating that proper amount of K substitution with x between 0.05 and 0.10 could enhance the dielectric properties. All the ceramics showed an intermediate relaxor-like behavior between normal and ideal relaxor ferroelectrics according to the modified Curie–Weiss law. With increasing K content, the remnant polarization (P_r) decreased gradually and the coercive field (E_c) decreased initially and then increased. But normal ferroelectric hysteresis loops could be observed in all compositions. Besides, the underlying mechanism for variations of the electrical properties due to K substitution was explained in this work.     

Structural and dielectric properties of ferroelectric Sr1−xBaxBi2(Nb0.5Ta0.5)2O9 and Sr0.5Ba0.5Bi2(Nb1−yTay)2O9 ceramics

Ferroelectric Sr_1−xBa_xBi₂(Nb_0.5Ta_0.5)₂O₉ and Sr_0.5Ba_0.5Bi₂(Nb_1−yTa_y)₂O₉ were synthesized by solid state reaction route. X-ray diffraction studies confirm the formation of single phase layered perovskite solid solutions over a wide range of compositions (x=y=0.0, 0.25, 0.50, 0.75 and 1). The lattice parameters and the Curie temperature (T_c) have been found to have linear dependence on x and y. Transmission electron microscopy (TEM) suggest the lowering of orthorhombic distortion with increasing Ba²⁺ substitution. Variations in microstructural features as a function of x and y were monitored by scanning electron microscopy (SEM). The dielectric constant at room temperature increases with increase in both x and y. Interestingly Ba²⁺ substitution on Sr²⁺ site induces diffused phase transition and diffuseness increases with increasing Ba²⁺ concentration.     

Structure, dielectric and ferroelectric anisotropy of Sr2−xCaxBi4Ti5O18 ceramics

Sr_2−xCa_xBi₄Ti₅O₁₈(x = 0, 0.05) powders synthesized by solid state route were uniaxially pressed and sintered at 1225 °C for 2 h. The obtained dense ceramics exhibited crystallographic anisotropy with a dominant c axis parallel to the uniaxial pressing direction which was quantified in terms of the Lotgering factor. Microstructure anisotropy of both compositions (x = 0, 0.05) consisted of plate like grains exhibiting their larger surfaces mostly perpendicular to the uniaxial pressing direction. Dielectric and ferroelectric properties of Sr_2−xCa_xBi₄Ti₅O₁₈ ceramics were measured under an electric field (E) applied parallel and perpendicularly to uniaxial pressing direction. The obtained dielectric ?_R(T) and polarization (P-E) curves depended strongly on E direction thus denoting a significant effect from microstructure and crystallographic texture. Sr_2−xCa_xBi₄Ti₅O₁₈ properties were also significantly affected by Ca content (x): Curie temperature increased from 280 °C (x = 0) to 310 °C (x = 0.05) while ?_R and remnant polarization decreased for x = 0.05. The present results are discussed within the framework of the processing and crystal structure-properties relationships of Aurivillius oxides ceramics.     

Dielectric relaxation related to single-ionized oxygen vacancies in (Pb1−xLax)(Zr0.90Ti0.10)1−x/4O3 ceramics

The dielectric relaxation phenomenon has been studied in lanthanum modified lead zirconate titanate ceramics in the high temperature paraelectric phase. The high temperature dielectric response revealed an anomalous behavior, which is characterized by an increase of the real component of the dielectric permittivity with the increase of the temperature. At the same time, a similar behavior, with very high values, has been observed in the imaginary component of the dielectric permittivity, which can be associated with conduction effects related to the conductivity losses. The frequency and temperature behavior of the complex dielectric permittivity has been analyzed considering the semi-empirical complex Cole-Cole equation. The activation energy value, obtained from the Arrhenius’ dependence for the relaxation time, was found to decreases with the increase of the lanthanum concentration and has been associated with single-ionized oxygen vacancies. The short-range hopping of oxygen vacancies is discussed as the main cause of the dielectric relaxation.     

Microgeometry effect on the properties of Pb0.99(Zr0.95Ti0.05)0.98Nb0.02O3 ferroelectric ceramics

Porous Pb_0.99(Zr_0.95Ti_0.05)_0.98Nb_0.02O₃ ferroelectric ceramics with different pore size were prepared by solid-state sintering in air. The microstructural effect on the properties has been systematically investigated by SEM, ferroelectric hysteresis, strain-electric field curves and breakdown strength measurements. The results demonstrate that the microgeometry has a subtle effect on the ferroelectric and dielectric properties. However, the results also demonstrate that the electric field induced strain and the dielectric breakdown strength decreases with the increase of pore size.     

Characterization of Bi4−xRxTi3O12 (Rx = Pr, Nd, Gd, Dy, x = 0.8) layered electroceramics by a photoacoustic method

We have carried out photoacoustic experiments to study the layered electroceramics Bi_4−xR_xTi₃O₁₂ (R_x=Pr, Nd, Gd, Dy), with x=0.8. Results are shown in terms of successive analyses performed on functions, PA(t, T_i), which result from the interaction of the laser beam with the crystalline lattice. Previous permittivity experiments performed in the materials suggested anomalous ferroelectric behavior. Using a pulsed Nd:YAG laser (10 Hz, 5 ns pulse width), photoacoustic experiments were run from room temperature up to 800 °C. Perturbations in the resultant correlation curves can be interpreted as the existence of a wide set of different transition temperatures in the material, such as are believed to occur in relaxors. From these experiments, we conclude that the temperature dependence of non-classical ferroelectrics can be more closely monitored.     

Structural, magnetic and dielectric properties of Bi1−ySryFe(1−y)(1−x)Sc(1−y)xTiyO3 (x = 0-0.2, y = 0.1-0.3) ceramics

In this study, bulk ceramics with general formula Bi_1−ySr_yFe_{(1−y)(1−x)}Sc_(1−y)xTi_yO₃ (x = 0-0.2, y = 0.1-0.3 mol%) were prepared by traditional solid-state reaction method. As a comparison, bulk BiFeO₃ (BF) was also sintered by rapid sintering method. Their structural, magnetic, dielectric properties were investigated. X-ray diffraction analysis indicated that apart from a small amount of secondary phase detected in BF, all other samples crystallized in pure perovskite structure and maintained original R3c space group. The room temperature M-H curves were obtained. While BF had a coercive magnetic field (H_c) of 150 Oe, Bi_1−ySr_yFe_1−yTi_yO₃ solid solutions had a much larger value (for y = 0.1, 0.2, 0.3, H_c were 4537, 5230 and 3578 Oe, respectively). Sc³⁺ substitution decreased the H_c values of these solid solutions remarkably, and resulted in soft magnetic properties, as well as a decrease of the dielectric loss. At 1 MHz, the tan δ of Bi_0.7Sr_0.3Fe_0.7(1−x)Sc_0.7xTi_0.3O₃ with x = 0.05, 0.1, 0.15, 0.2 were 0.1545, 0.1078, 0.1046 and 0.1701, respectively.     

Low loss Sr1−xCaxLa4Ti5O17 microwave dielectric ceramics

Microwave dielectric ceramics in the Sr_1−xCa_xLa₄Ti₅O₁₇ (0 ≤ x ≤ 1) composition series were prepared through a solid state mixed oxide route. All the compositions formed single phase ceramics within the detection limit of in-house X-ray diffraction when sintered in the temperature range 1450-1580 °C. Theoretical density and molar volume decreased due to the substitution of Ca²⁺ for Sr²⁺ which was associated with a decrease in the dielectric constant (?_r) and temperature coefficient of resonant frequency (τ_f) but an increase in quality factor, Qf_o. Optimum properties were achieved for Sr_0.4Ca_0.6La₄Ti₅O₁₇ which exhibited, ?_r ∼ 53.7, Qf_o ∼ 11,532 GHz and τ_f ∼ −1.4 ppm/°C.     

Quantitative dependence of the properties of Pb0.99(Zr0.95Ti0.05)0.98Nb0.02O3 ferroelectric ceramics on porosity

Porous Pb_0.99(Zr_0.95Ti_0.05)_0.98Nb_0.02O₃ ferroelectric ceramics with a pore size of the order of the crystalline grain size were prepared and the microstructure and the properties were investigated. Based on this microstructure, the net porosity of the ceramics can be attributed to the intentionally introduced extrinsic porosity and thus the quantitative dependence of ferroelectric and dielectric properties of the ceramics on the porosity can be established respectively. A good agreement with experimental measurements was obtained. Our work represents the first attempt to tailor the properties of ferroelectric ceramics via varying the porosity from the viewpoint of application.     

Dielectric and pyroelectric anisotropy in melt-quenched BaBi2(Nb1 − xVx)2O9 ceramics

The (0 0 l) textured BaBi₂(Nb_1 − xV_x)₂O₉ (where x = 0, 0.03, 0.07, 0.1 and 0.13) ceramics were fabricated via the conventional melt-quenching technique followed by high temperature heat-treatment (800-1000 °C range). The influence of vanadium content and sintering temperature on the texture development and relative density were investigated. The samples corresponding to the composition x = 0.1 sintered at 1000 °C for 10 h exhibited the maximum orientation of about 67%. The Scanning electron microscopic studies revealed the presence of platy grains having the a-b planes perpendicular the pressing axis. The dielectric constant and the pyroelectric co-efficient values in the direction perpendicular to the pressing axis were higher. The anisotropy in the dielectric constant is about 100 (at 100 kHz) at the dielectric maximum temperature and anisotropy in the pyroelectric co-efficient is about 50 μC cm⁻² °C⁻¹ in the vicinity of pyroelectric anomaly for the sample corresponding to the composition x = 0.1 sintered at 1000 °C. Higher values of the dielectric loss and electrical conductivity were observed in the direction perpendicular to the pressing axis which is attributed to the high oxygen ion conduction in the a-b planes.     

Synthesis, structure and dielectric characterization of Ln2Ti2−2xM2xO7(Ln=Gd, Er; M=Zr, Sn, Si)

The progress in wireless communications and information access has demanded the use of electronic ceramics exhibiting desired properties. To further our understanding of these properties, compounds in the Ln₂Ti_2-2xM_2xO₇ (Ln=Gd, Er; M=Zr, Sn, Si) systems were synthesized by ceramic methods and characterized by powder X-ray diffraction. The ZrO₂-doped Gd₂Ti_2−2xZr_2xO₇ compounds adopt the pyrochlore structure type and form a complete solid solution. Er₂Ti_2−2xZr_2xO₇ forms a pyrochlore solid solution for x<0.1. However, stoichiometric Er₂Zr₂O₇ does not form; instead Er₄Zr₃O₁₂ forms a with defect fluorite structure. The Sn-doped Ln₂Ti_2−2xSn_2xO₇ (Ln=Gd, Er) compounds form complete solid solutions, and the Si compounds adopt the pyrochlore structure up to x=0.05. At ambient temperature, dielectric constants range from 10 to 61 for Er₂Ti_2−2xZr_2xO₇ and 16-31 for Gd₂Ti_2−2xZr_2xO₇ with low dielectric loss (1×10⁻³) at 1 GHz.     

Effect of sintering time on crystal structure and microwave dielectric properties in aeschynite-structured (Sm1−xYx)(Ti1.5W0.5)O6 (x = 0 and 0.5) ceramics

The crystal structure and microwave dielectric properties of the (Sm_1−xY_x)(Ti_1.5W_0.5)O₆ (x = 0 and 0.5) ceramics sintered at 1375 °C for 2-50 h were investigated in this study. No secondary phase was observed in the samples sintered for various sintering times, whereas a secondary phase was formed in the (Sm_0.5Y_0.5)(Ti_1.5W_0.5)O₆ ceramic sintered at 1400 °C for 50 h. As for the microstructure analysis, the formation of the liquid phase was observed in the both of the samples sintered for 20 and 50 h. The formation of the liquid phase is related to the compositional change of Ti and W from the stoichiometric composition of the samples caused by the instability of crystal structure. The dielectric constants were increased with increased sintering time in the both of the samples, though variations in the temperature coefficient of resonant frequency of the samples were not recognized with the variation in the sintering time. Moreover, although the quality factors of the each sample increased with increasing the sintering time from 2 to 10 h, decreases in the quality factors were recognized when the sintering time was over 10 h.     

Structure and electrical properties of (1 − x)Bi0.5Na0.5TiO3-xBi0.5K0.5TiO3 ceramics near morphotropic phase boundary

The binary lead-free piezoelectric ceramics with the composition of (1 − x)Bi_0.5Na_0.5TiO₃-xBi_0.5K_0.5TiO₃ were synthesized by conventional mixed-oxide method. The phase structure transformed from rhombohedral to tetragonal phase in the range of 0.16 ≤ x ≤ 0.20. The grain sizes varied with increasing the Bi_0.5K_0.5TiO₃ content. Electrical properties of ceramics are significantly influenced by the Bi_0.5K_0.5TiO₃ content. Two phase transitions at T_t (the temperature at which the phase transition from rhombohedral to tetragonal occurs) and T_c (the Curie temperature) were observed in all the ceramics. Adding Bi_0.5K_0.5TiO₃ content caused the variations of T_t and T_c. A diffuse character was proved by the linear fitting of the modified Curie-Weiss law. Besides, the ceramics with homogeneous microstructure and excellent electrical properties were obtained at x = 0.18 and sintered at 1170 °C. The piezoelectric constant d₃₃, the electromechanical coupling factor K_p and the dielectric constant ?_r reached 144 pC/N, 0.29 and 893, respectively. The dissipation factor tan δ was 0.037.     

Lattice vibrations and dielectric functions of ferroelectric SrBi2−xNdxNb2O9 bismuth layer-structured ceramics determined by infrared reflectance spectra

Infrared optical properties of SrBi_2−xNd_xNb₂O₉ (SBNN) ceramics with different Nd compositions (from 0 to 0.2) have been investigated by near-normal incident reflectance technique. The experimental spectra in the wavenumbers range of 350-1500 cm⁻¹ were analyzed using the Lorentz oscillator model for five infrared-active phonon mode observed. It is found that the frequencies of the NbO₆ tilting and symmetric stretching modes linearly decrease with the Nd composition due to the octahedra distortion. The high-frequency dielectric constant varies in the range from 4.55 ± 0.04 to 4.80 ± 0.04. Owing to the contribution from the stronger electronic transitions, the real part of dielectric function Re(?) is estimated to about 4.0 in the high-frequency transparent region.     

Structure and ferroelectric properties in (K0.5Bi0.5)TiO3-BiScO3-PbTiO3 piezoelectric ceramic system

(K_0.5Bi_0.5)TiO₃-BiScO₃-PbTiO₃ ceramics were synthesized by conventional solid-state method. A morphotropic phase boundary (MPB) was confirmed with the aid of structural analysis. Two dielectric anomalous peaks were observed, the one around dielectric maximum temperature (T_m) due to phase transformation from ferroelectric to paraelectric while the second one could be ascribed to space charges. Furthermore, the existence of space charges also resulted in the independence of T_m with frequency at low lead composition. A new high temperature piezoelectric ceramic, 0.30(K_0.5Bi_0.5)TiO₃-0.30BiScO₃-0.40PbTiO₃ close to MPB exhibited excellent electrical properties with T_m of 384 °C, d₃₃ of 247 pC/N, k_p of 38.9%, P_r of 19.41 μC/cm², and E_c of 2.25 kV/mm, indicative of a candidate for high temperature application.     

Synthesis of low loss, thermally stable CexY1−xTiTaO6 microwave ceramics

Ce_xY_1−xTiTaO₆ ceramics were prepared through the solid-state ceramic route. The materials were sintered in the range 1520-1580 °C. The structure of the system was analyzed by X-ray diffraction and Raman spectroscopic methods. The cell parameters of solid solutions were calculated using the least square method. The microstructure was analyzed using scanning electron microscopy. The dielectric constant (?_r), temperature coefficient of resonant frequency (τ_f) and the unloaded quality factor (Q_u) are measured in the microwave frequency region using cavity resonator method. The dielectric constant increases with higher concentrations of Ce in the solid solutions. Nearly zero temperature coefficient of resonant frequency (τ_f) was obtained for Ce_0.24Y_0.76TiTaO₆. The samples are of high quality factor and are useful electronic materials for microwave applications.     

Lead substitutions for promoted critical current density Jc and mechanical properties of Mg1−xPbxB2 regime

Lead was used as softener dopant element to replace on magnesium sites in Mg_1−xPb_xB₂ regime (where x = 0.0, 0.05, 0.1 and 0.2 mole). Samples were prepared via high temperature solid-state reaction technique depending upon diffusion mechanism of Mg/Pb-vapour ions through boron-matrix. The maximum solubility limit of lead n was found to be ∼0.2 mole, which emphasises that substitution on MgB₂ system is stilling too limited and needs many precautions to be successful.The crystalline lattice constants were evaluated and exhibit noticeable length elongation in case of c-axis as x increases while a, b-axes were nearly constant. Furthermore, effect of Pb-doping was investigated carefully on microstructure and superconducting properties of MgB₂ system. SE-microscopic analysis indicated that lead ions diffuse regularly through surface and bulk in case of (x = 0.05 and 0.1 mole) and grain size was estimated and found in between 0.43 and 1.6 μm. Critical current densities (J_c's values) recorded an reasonable increase as Pb-content increase (from x = 0 to 0.1 mole) while recorded a slight decrease for sample with maximum lead content (x = 0.2 mole). The mechanical tensile strength of the samples was clearly improved linearly as Pb-content increase recording maximum tensile 31.7 MPa for sample with x = 0.2 mole.     

Synthesis, characterization, and dielectric properties of Ba(Ti1−xSnx)O3 nanopowders and ceramics

We prepared Ba(Ti_1−xSn_x)O₃ powders and ceramics by means of the sol-gel process, with dibutyltin dilaurate as the Sn precursor. The samples were characterized by means of Fourier-transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, and scanning electron microscopy, and also determined the dielectric properties of the ceramics. The powders synthesized by means of the sol-gel process had a grain size on the nanometer scale, with the grains mainly composed of a cubic BaTiO₃ phase. Sn can disperse into BaTiO₃ more uniformly in the sol-gel technique using dibutyltin dilaurate as the Sn precursor. With increasing Sn concentration, the grain size of the Ba(Ti_1-xSn_x)O₃ ceramics increased and the maximum dielectric constant (?_max) first increased and then decreased. At a Sn concentration of 5 mol%, ?_max reached its maximum value (19,235).     

Dielectric properties of (1−x)(Mg0.95Co0.05)TiO3-xCaTiO3 ceramic system at microwave frequency

The microwave dielectric properties and the microstructures of the (1−x)MgTiO₃-xCaTiO₃ ceramic system were investigated. With partial replacement of Mg by Co, dielectric properties of the (1−x)(Mg_0.95Co_0.05)TiO₃-xCaTiO₃ ceramics can be promoted. The microwave dielectric properties are strongly correlated with the sintering temperature. At 1275°C, the 0.95(Mg_0.95Co_0.05)TiO₃-0.05CaTiO₃ ceramics possesses excellent microwave dielectric properties: a dielectric constant ε_r of 20.3, a Q×f value of 107 000 ( at 7 GHz) and a τ_f value of −22.8 ppm/°C. By appropriately adjusting the x value in the (1−x)(Mg_0.95Co_0.05)TiO₃-xCaTiO₃ ceramic system, zero τ_f value can be achieved. With x=0.07, a dielectric constant ε_γ of 21.6, a Q×f value of 92 000 (at 7 GHz) and a τ_f value of −1.8 ppm/°C was obtained for 0.93(Mg_0.95Co_0.05)TiO₃-0.07CaTiO₃ ceramics sintered at 1275°C for 4 h.     

Combustion synthesis of Sr0.5Ba0.5Nb2O6 and effect of fuel on its microstructure and dielectric properties

Nano-sized Sr_0.5Ba_0.5Nb₂O₆ (SBN50) powder has been synthesized, at very short reaction time, for the first time by a novel combustion method. Ba(NO₃)₂ and Sr(NO₃)₂ were used as source of Sr and Ba, respectively, while Nb-oxalate was used as the source of niobium. Urea, hexamethyltetramine (HMT) and glycine were used as fuel. The crystallite sizes in the powder ranged between 14-125 nm. X-ray diffraction analysis showed complete SBN50 phase formation at 700 °C, when urea/HMT was used as fuel, and at 800 °C when glycine was used as fuel. Ferroelectric-paraelectric phase transition temperature (T_c) close to 40 °C was observed when urea and HMT were used and the T_c was −49 °C when glycine was used. When urea was used as fuel highest dielectric constant was observed for the pellets sintered at 1250 °C for 4 h. Low dielectric loss was observed when HMT was used as fuel. Larger grain sizes in the sintered pellets were observed when glycine was used as fuel.