Crystal structure and electrical properties of CaNaBi<Subscript>2</Subscript>Nb<Subscript>3</Subscript>O<Subscript>12</Subscript> ceramics

Monophasic CaNaBi₂Nb₃O₁₂ powders were synthesized via the conventional solid-state reaction route. Rietveld refinement of the X-ray powder diffraction (XRD) data and selected area electron diffraction (SAED) studies confirmed the phase to be a three-layer Aurivillius oxide associated with an orthorhombic B2cb space group. The dielectric properties of the ceramics have been studied in the 300–800 K temperature range at various frequencies (1 kHz to 1 MHz). A dielectric anomaly was observed at 676 K for all the frequencies corresponding to the ferroelectric to paraelectric phase transition as it was also corroborated by the high temperature X-ray diffraction studies. The incidence of the polarization–electric field (P vs. E) hysteresis loop demonstrated CaNaBi₂Nb₃O₁₂ to be ferroelectric.     

Effect of CeO<Subscript>2</Subscript> on dielectric,ferroelectric and piezoelectric properties of PMN–PT (67/33) compositions

Lead magnesium niobate–lead titanate [Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃] powders doped with different mole % of CeO₂ were prepared by a modified columbite route with compositions corresponding to morphotropic phase boundary (MPB) region. These powders were calcined at 800 °C for 4 h and circular test specimens were prepared by uniaxial pressing. The specimens were sintered at 1150 °C/2 h, poled at 2 kV/mm d.c. voltage and were characterized for dielectric, ferroelectric and piezoelectric properties. It was observed that the piezoelectric and ferroelectric properties initially increase up to 2 mol% of ceria addition and then decrease with increase in ceria concentration. The diffusivity of the dielectric curves increases with increase in ceria concentration. The decrease in Curie temperature was observed from 173 °C corresponding to pure PMN–PT to a temperature of 138 °C for 10 mol% of ceria addition.     

Preparation of Pb(Zr,Ti)O<Subscript>3</Subscript>–Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> piezoelectric ceramics by dry–dry method

Ternary perovskite ceramics of Pb[(Zr_0.5Ti_0.5)_0.8−x (Mg_1/3Nb_2/3)_0.2+x]_0.98Nb_0.02O_3.01 (PZTMN, x = −0.075, −0.05, −0.025, 0, 0.025, 0.05, and 0.075 ), are synthesized via dry–dry method. B-site precursors of PZTMN ([(Zr_0.5Ti_0.5)_0.8−x (Mg_1/3Nb_2/3)_0.2+x ]_0.98Nb_0.02O_2.01, ZTMN) can be synthesized via a two-step solid state reaction method. The first calcination temperature is 1,300 °C, and the second is not higher than 1,360 °C. Incorporation of magnesium and niobium ions promotes the formation of the single phase solid solution with ZrTiO₄ structure. Single phase perovskite PZTMN is formed at 780 °C, much lower than that in conventional process. Dense ceramics can be sintered at about 1,260 °C with dielectric and piezoelectric properties comparable to that of wet–dry method and higher than that of conventional method. It seems that B-site precursor method is cost effective in preparation of ternary piezoelectric ceramics.     

Effect of La substitution on structural and electrical properties of Ba(Fe<Subscript>2/3</Subscript>W<Subscript>1/3</Subscript>)O<Subscript>3</Subscript> nanoceramics

The nanocrystalline fine powders (∼80 nm) of (Ba_1−x La _x )(Fe_2/3W_1/3)_1−x/4O₃, (BLFW) (x = 0.0, 0.05, 0.10 and 0.15) were synthesized with a combined mechanical activation and conventional high-temperature solid-state reaction methods. Preliminary X-ray structural analysis of pellet samples (prepared from fine powders) showed formation of a single-phase tetragonal system. Detailed studies of dielectric properties (ε_r and tan δ) exhibit that these parameters are strongly dependent on frequency, temperature and La composition. The La-substitution increases the dielectric constant and decreases the tan δ up to 10% substitutions of La at the Ba-site, and then reversed the variation, and hence this composition is considered as a critical composition. This observation was found valid for structure, microstructures, dielectric constant, electrical conductivity, J–E characteristics and impedance parameters also. Like in other perovskites (PZT, BZT), La substitution plays an important role in tailoring the properties of Ba(Fe_2/3W_1/3)O₃ ceramics.     

Properties of fluorine-doped PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript> ceramics

We report the first fluorine doping of lead magnesium niobate in the PbMg _{(1 + x)/3}Nb_{(2 ? x)/3}O_{3 ? x} F _x system in a wide composition range, x = 0.025 to 0.625. The fluorine content of the samples is shown to be substantially lower than the intended one because of the fluorine volatilization in the form of HF during synthesis and sintering in air. The ceramics consist of magnesium and lead oxides undetectable by x-ray diffraction, and a perovskite phase whose composition can be represented by the formula PbMg_{(1 + m)/3}Nb_{(2 ? m)/3}O_{3 ? m} F _m , where the fluorine content after sintering is m ≤ 0.12. The PbO and MgO contents of the ceramics depend on the starting mixture composition (x) and heat-treatment conditions (hydrogen fluoride and lead oxide volatilization). As a result of the low fluorine content, the diffraction patterns of the samples show no superlattice reflections, and their lattice parameter varies insignificantly with x. Data are presented on the temperaturedependent dielectric permittivity of ceramic samples sintered and annealed under different conditions.     

Effect of substitution of titanium by magnesium and niobium on structure and piezoelectric properties in (Bi<Subscript>1/2</Subscript>Na<Subscript>1/2</Subscript>)TiO<Subscript>3</Subscript> ceramics

To develop new (Bi_1/2Na_1/2)TiO₃-based ceramics with excellent piezoelectric properties, the similarities and the differences between PZT and (Bi_1/2Na_1/2)TiO₃ ceramics were analysed. Based on the analysis, a new (Bi_1/2Na_1/2)TiO₃-based piezoelectric ceramic of B-site substitution of complex ions (Mg_1/3Nb_2/3)⁴⁺ for Ti⁴⁺ was prepared by a conventional ceramic technique, and effect of complex ions (Mg_1/3Nb_2/3)⁴⁺ addition on the microstructure, dielectric and piezoelectric properties was investigated. The results show that all compositions are mono-perovskite phase and the grain size increases with increasing content of (Mg_1/3Nb_2/3)⁴⁺. The piezoelectric constant, d ₃₃, first increases and then decreases, and electromechanical coupling factor, k _p, varies insignificantly with increasing content of (Mg_1/3Nb_2/3)⁴⁺.     

Dielectric properties of (1 − <Emphasis Type="Italic">x</Emphasis>)KNbO3 · <Emphasis Type="Italic">x</Emphasis>BiMg<Subscript>2/3</Subscript>Nb<Subscript>1/3</Subscript>O<Subscript>3</Subscript> perovskite solid solutions

(1 − x) KNbO₃ · xBiMg_2/3Nb_1/3O₃ ceramic materials have been prepared by solid-state reactions. The materials with x < 0.3 have been shown to be perovskite solid solutions. Their average lattice parameter increases linearly with x. Like undoped KNbO₃, the solid solutions undergo a low-temperature (rhombohedral → orthorhombic) ferroelectric phase transition. The transition temperature increases almost linearly with x. The dc electrical conductivity of the ceramics exhibits Arrhenius behavior. The activation energy for conduction rises sharply near the phase transition temperature.     

Effect of Pb(Fe1/2Nb1/2)O3 modification on dielectric and piezoelectric properties of Pb(Mg1/3Nb2/3)O3-PbZr0.52Ti0.48O3 ceramics

10 mol% Pb(Fe_1/2Nb_1/2)O₃ (PFN) modified Pb(Mg_1/3Nb_2/3)O₃-PbZr_0.52Ti_0.48O₃ (PMN-PZT) relaxor ferroelectric ceramics with compositions of (0.9 − x)PMN-0.1PFN-xPZT (x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 and 0.9) were prepared. X-ray diffraction investigations indicated that as-prepared ceramics were of pure perovskite phase and the sample with composition of x = 0.8 was close to morphotropic phase boundary (MPB) between rhombohedral and tetragonal phase. Dielectric properties of the as-prepared ceramics were measured, and the Curie temperature (T_c) increased sharply with increasing PZT content and could be higher than 300 °C around morphotropic phase boundary (MPB) area. At 1 kHz, the sample with composition of x = 0.1 had the largest room temperature dielectric constant ?_r = 3519 and maximum dielectric constant ?_m = 20,475 at T_m, while the sample with composition of x = 0.3 possessed the maximum dielectric relaxor factor of γ = 1.94. The largest d₃₃ = 318 pC/N could be obtained from as-prepared ceramics at x = 0.9. The maximum remnant polarization (P_r = 28.3 μC/cm²) was obtained from as-prepared ceramics at x = 0.4.     

Structural and electrical properties of Ba(Sb<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>)O<Subscript>3</Subscript> ceramic

Lead-free perovskite Ba(Sb_1/2Nb_1/2)O₃ was prepared by conventional ceramic fabrication technique at 1200 °C/5 h in air atmosphere. The crystal symmetry, space group and unit cell dimensions were determined from the experimental results using FullProf software whereas crystallite size and lattice strain were estimated from Williamson–Hall approach. XRD analysis of the compound indicated the formation of a single-phase monoclinic structure with the space group P2/m. EDAX and SEM studies were carried out to evaluate the quality and purity of the compound. Dielectric study revealed the frequency-dependent dielectric anomaly. To find a correlation between the response of the real system and idealized model circuit composed of discrete electrical components, the model fittings were presented using the impedance data. Complex impedance analyses suggested the dielectric relaxation to be of non-Debye type. The correlated barrier hopping model was employed to successfully explain the mechanism of charge transport in Ba(Sb_1/2Nb_1/2)O₃. The ac conductivity data were used to evaluate the density of states at Fermi level, minimum hopping length and apparent activation energy of the compound.     

Dielectric and piezoelectric properties of MnO<Subscript>2</Subscript>-doped K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>Nb<Subscript>0.92</Subscript>Sb<Subscript>0.08</Subscript>O<Subscript>3</Subscript> lead-free ceramics

Lead-free MnO₂-doped K_0.5Na_0.5Nb_0.92Sb_0.08O₃ ceramics have been fabricated by a conventional ceramic technique and their dielectric and piezoelectric properties have been studied. Our results show that a small amount of MnO₂ (0.5–1.0 mol%) is enough to improve the densification of the ceramics and decrease the sintering temperature of the ceramics. The co-effects of MnO₂ doping and Sb-substitution lead to significant improvements in the ferroelectric and piezoelectric properties. The K_0.5Na_0.5Nb_0.92Sb_0.08O₃ ceramic with 0.5 mol%MnO₂ doping possesses optimum propeties: d ₃₃ = 187 pC/N, k _P = 47.2%, ε _r = 980, tanδ = 2.71% and T _c = 287 °C. Due to high tetragonal-orthorhombic phase transition temperature (T _O-T ~ 150 °C), the K_0.5Na_0.5Nb_0.92Sb_0.08O₃ ceramic with 0.5 mol%MnO₂ doping exhibits a good thermal stability of piezoelectric properties.     

Preparation and phase formation of perovskite Pb(Ni<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> by a reaction-sintering process

Pyrochlore-free Pb(Ni_1/3Nb_2/3)O₃ perovskite ceramics produced by a simple and effective reaction-sintering process were investigated. Without any calcination, the mixture of PbO, Ni(NO₃)₂ and Nb₂O₅ was pressed and sintered directly into PNN ceramics. Density of 98.5% of theoretical value was obtained after sintered at 1230 °C for 2 h in air. 99.3% of theoretical density was obtained after sintered at 1,200 °C for 2 h in PbO compensated atmosphere. PNN ceramic with dielectric constant 1,680 at 25 °C and 1 kHz has been obtained.     

Effect of nonstoichiometry on the structure and microwave dielectric properties of Ba(Co<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>

Polycrystalline nonstoichiometric Ba(Co_1/3Nb_2/3)O₃ (BCN) materials have been synthesized and investigated. Deviations from stoichiometry have been shown to lead to the formation of crystalline Ba₆CoNb₉O₃₀ (barium deficiency) and Ba₈CoNb₆O₂₄ (cobalt deficiency). The effect of phase composition on the microwave dielectric properties of BCN has been studied. The results demonstrate that the dielectric properties of BCN-based materials can be tuned by varying cobalt content. The materials obtained are high-Q microwave dielectrics with temperature-stable properties.     

Dielectric responses in Mg<Subscript>1/3</Subscript>Ta<Subscript>2/3</Subscript>-replaced Pb[(Zn<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>),Ti]O<Subscript>3</Subscript> ceramics

Octahedral lattice sites of Pb[(Zn_1/3Nb_2/3),Ti]O₃ were replaced by 20 at.% Mg_1/3Ta_2/3 complex to enhance perovskite development, especially at Pb(Zn_1/3Nb_2/3)O₃-rich compositions. Resultant changes in the perovskite formation and associated dielectric responses were investigated. A perovskite structure was identified at Pb(Zn_1/3Nb_2/3)O₃-rich compositions by X-ray diffraction, although the development was rather incomplete. Phase transition modes in the dielectric constant spectra changed from diffuse to sharp ones, regardless of the introduction of Mg_1/3Ta_2/3. Dielectric maximum temperatures of the ceramics shifted linearly with the compositional change.     

Optical properties of (1−<Emphasis Type="Italic">x</Emphasis>)PbZn<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript>−<Emphasis Type="Italic">x</Emphasis>PbTiO<Subscript>3</Subscript> single crystals

The temperature dependence of the optical transmission and small-angle light scattering with and without applied constant electric field was studied in relaxor single crystals of 0.91PbZn_1/3Nb_2/3O₃-0.09PbTiO₃ (PZN-PT 91/9) and 0.93PbZn_1/3Nb_2/3O₃-0.07PbTiO₃ (PZN-PT 93/7) solid solutions in the region of two phase transitions: (i) from cubic paraelectric to tetragonal ferroelectric phase at T=T _c and (ii) from tetragonal ferroelectric to rhombohedral ferroelectric phase at T=T _rt. In the absence of external electric field, only the phase transition at T _c proceeds in both PZN-PT 91/9 and PZN-PT 93/7 crystals according to a percolation mechanism and is accompanied by the appearance of a sharp maximum in the small-angle light scattering intensity curve. In PZN-PT 93/7 crystals, the application of a relatively weak electric field induces an additional percolation type phase transition at T _rt.     

Ferroelectric and dielectric properties of ferroelectromagnet Pb(Fe1/2Nb1/2)O3 ceramics and thin films

The ferroelectric and dielectric properties of ferroelectromagnet Pb(Fe_1/2Nb_1/2)O₃ (PFN) ceramics and thin films prepared by pulsed laser deposition (PLD) have been investigated systematically. PFN ceramics experienced a para-ferroelectric transition and a para-antiferromagnetic transition at 380 K and 145 K, respectively. At room temperature, it has an electrical remnant polarization of 11.5 C/cm² and a coercive field of 4.04 kV/cm. The dielectric behaviors show characteristics of diffusive phase transition at a wide temperature range around 380 K. Anomalies in the dielectric constant and loss tangent have been observed near the Neel temperature of 145 K, indicating a coupling between the ferroelectric and antiferromagnetic orders in PFN ceramics. At room temperature, the PFN films exhibited a remnant electric polarization of 7.4 C/cm², a coercive field of 10.5 kV/cm, and a dielectric constant of 486 at frequency of 10 kHz, indicating their potential applications in memory devices.     

Effects of manganese additive on piezoelectric properties of (Bi<Subscript>1/2</Subscript>Na<Subscript>1/2</Subscript>)TiO<Subscript>3</Subscript>–BaTiO<Subscript>3</Subscript> ferroelectric ceramics

The microstructure, piezoelectric and dielectric properties of piezoelectric ceramics (Bi_1/2Na_1/2)_0.94Ba_0.06TiO₃+xwt%MnCO₃ (BNBT6–xMn) with x ranging from 0 to 1.5 were studied. X-ray diffraction patterns showed the samples exhibited perovskite structure and Mn additive turned the structure from tetragonal phase to rhombohedral phase. The results of SEM indicated the Mn additive promoted the sintering which was beneficial to the synthesis of the perovskite. With the amount of Mn additive up to 0.1 wt.%, the value of d ₃₃, k _p ,and ε were improved; While Q _m also was increased until 0.8 wt%. The Mn additive acted on the “soft” and “hard” function simultaneously; When the amount of Mn additive more than 0.8 wt%, the performance drops.     

Structural and dielectric properties of PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript>-PbZrO<Subscript>3</Subscript> solid solutions synthesized at high pressures and temperatures

(1 ? x)PbMg_1/3Nb_2/3O₃ · xPbZrO₃ (1 ? x)PMN · xPZ) solid solutions have been synthesized at a pressure of 5 GPa and temperatures from 1300 to 1700 K, and their structural and dielectric properties have been studied. The composition dependences of the average unit-cell parameter and dielectric permittivity for the solid solutions indicate that the PMN-PZ system has a morphotropic phase boundary near x = 0.65. The solid solutions have a cubic structure for x < 0.65, a rhombohedral structure in the range 0.65 < x < 0.9, and an orthorhombic structure (similar to that of PbZrO₃) for x > 0.9. The temperature and frequency dependences of dielectric permittivity suggest that the (1 ? x)PMN · xPZ samples with x < 0.65 consist of two ferroelectric phases: a relaxor with antipolar dipole order and a normal ferroelectric with a diffuse phase transition. The effect of annealing temperature on the ferroelectric state of the samples with x < 0.65 is examined. In the composition range 0.65 < x < 0.9, the samples have normal ferroelectric properties, independent of annealing temperature.     

Temperature-stable and low loss Fe-containing dielectrics in BaO-Ln<Subscript>2</Subscript>O<Subscript>3</Subscript>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> system

Polycrystalline samples of Ba₄Ln₂Fe₂Ta₈O₃₀ (Ln = La and Nd) were prepared by a high temperature solid-state reaction technique. The formation, structure, dielectric and ferroelectric properties of the compounds were studied. Both compounds are found to be paraelectrics with filled tetragonal tungsten bronze (TB) structure at room temperature. Dielectric measurements revealed that the present ceramics have exceptional temperature stability, a relatively small temperature coefficient of dielectric constant (τ _ε ) of −25 and −58 ppm/°C, with a high dielectric constant of 118 and 96 together with a low dielectric loss of 1.2 × 10⁻³ and 2.8 × 10⁻³ (at 1 MHz) for Ba₄La₂Fe₂Ta₈O₃₀ and Ba₄Nd₂Fe₂Ta₈O₃₀, respectively. The measured dielectric properties indicate that both materials are possible candidates for the fabrication of discrete multilayer capacitors in microelectronic technology.     

Dielectric properties of Pb[(1?x)(Zr1/2Ti1/2)?x(Zn1/3Ta2/3)]O3 ceramics prepared by columbite and wolframite methods

Polycrystalline samples of Pb[(1 − x)(Zr_1/2Ti_1/2) − x(Zn_1/3Ta_2/3)]O ₃ , where x = 0.1–0.5 were prepared by the columbite and wolframite methods. The crystal structure, microstructure, and dielectric properties of the sintered ceramics were investigated as a function of composition via X-ray diffraction (XRD), scanning electron microscopy (SEM), and dielectric spectroscopy. The results indicated that the presence of Pb(Zn_1/3Ta_2/3)O₃ (PZnTa) in the solid solution decreased the structural stability of overall perovskite phase. A transition from tetragonal to pseudo-cubic symmetry was observed as the PZnTa content increased and a co-existence of tetragonal and pseudo-cubic phases was observed at a composition close to x = 0.1. Examination of the dielectric spectra indicated that PZT–PZnTa exhibited an extremely high relative permittivity at the MPB composition. The permittivity showed a ferroelectric to paraelectric phase transition at 330 °C with a maximum value of 19,600 at 100 Hz at the MPB composition.     

Synthesis,dielectric, and hysteresis behaviour of Ba(Nb<Subscript>0.2</Subscript>Ti<Subscript>0.8</Subscript>)O<Subscript>3</Subscript> ceramics and their solid solutions with BaZrO<Subscript>3</Subscript>

Solid state reaction technique was employed to synthesize Ba(Nb_0.2Ti_0.8)O₃ [BNT], and 0.9Ba(Nb_0.2Ti_0.8)O₃ + 0.1BaZrO₃ [BNT + BZ] samples. Sintered pellets were investigated for its dielectric (ε_r and tanδ) properties in the temperature range 100 K–380 K and in the frequency range of 100 Hz–1 MHz. The variation of ε_r and tan δ may be attributed to hopping of trapped charge carriers, which resulted in an extra dielectric response in addition to the dipole response. Hysteresis loop measurements were studied in the temperature regime 295 K–423 K. Loop area shrunk with the increase of temperature that may be due to phase transition from ferroelectric to paraelectric state.