Structure and Properties of Hot-Pressed Pb(Lu1/2Nb1/2)O3-PbTiO3 Binary System Ceramics*

Solid solution series of the (1 - x)Pb(Lu_1/2Nb_1/2)O₃ - x PbTiO₃ binary system ceramics (PLuNT) were synthesized and hot-pressed (temperature 950°C to 1130°C, pressure 25 MPa); its structure, dielectric and piezoelectric properties were studied. Pure lutecium niobate PLuN (x = 0) has a pronounced long-range order in the B-sublattice and an antiferroelectric to paraelectric phase transition at ～258°C. The phase structure of the PLuNT system, at room temperature, changes from a pseudomonoclinic (psd-M, space group Bmm2) to tetragonal (T, space group P4mm). The pseudomonoclinic phase extends over the 0 ≤ x ≤ 0.38 interval within which the monoclinic angle β proceeds a minimum near to 90° at x ? 0.2. The morphotropic region covers the interval x = 0.38 - 0.49, the concentration ratio psd-M:T? 1 (the morphotropic phase boundary—MPB) corresponds to x = 0.41. Within the morphotropic region, a rather strong distortion of the unit cell—(c/a - 1)≥ 0.02, β ≥ 90.37º, characteristic of “hard” piezoelectrics is maintained. Dielectric dispersion and broadening of the phase transition, features typical to relaxors, are observed within the concentration interval of 0.1 ≤ x ≤ 0.3. The highest electromechanical coupling coefficients: k_p = 0.66, k_t = 0.48, k₃₁ = 0.34 of (1 - x) PLuN?xPT ceramics are attained in compositions near the MPB at x ≈ 0.41. Non-isovalent doping of PLuNT with La³⁺ in Pb sublattice shifts the MPB to lower values of x.     

Electro-caloric behaviors of lead-free Bi0.5Na0.5TiO3-BaTiO3 ceramics

Electro-caloric (EC) properties of lead-free Ba_0.5Na_0.5TiO₃-xBaTiO₃ (BNT-xBT) ceramics prepared by citrate method are investigated at temperatures of 30–250°C. Based on thermodynamics calculations, BNT-xBT (x = 0, 0.05, 0.06, 0.1, 0.25, 0.3) are found to show EC effects different with other lead-based or lead-free ferroelectric ceramics, i.e., they absorb heats (refrigeration effect) during the processes of field application while other ferroelectric ceramics show refrigeration effect during the processes of field removal. The EC temperature change of BNT-xBT can be as large as 2.1°C under an electric field of 60 kV/cm, which is larger than most of the lead-free ferroelectric bulk ceramics. When x is close to the morphotropic phase boundary (x ~ 0.06–0.1), the EC temperature change of BNT-xBT shows a maximum near the ferroelectric to anti-ferroelectric transition temperature, which is characterized by dynamic mechanical analysis. This study suggests that these lead-free ferroelectric materials are promising in the practical application as EC coolers.     

Structural, Thermal and Electrical Properties of Ce-Doped SrMnO3

The Sr_1-xCe_xMnO_1-α system (0≤ x ≤ 0.5) was investigated with respect to its structural, thermal and electrical properties. Although un-doped SrMnO₃ has the perovskite structure above 1400°C, the structure is unstable at room temperature. However, partial substitution of Ce for Sr in SrMnO₃ stabilizes the perovskite structure down to room temperature. Single phase perovskite is obtained for 0.1≤ x ≤ 0.3 in Sr_1-xCe_xMnO_1-α, and it remains stable even following heat treatment at 800°C for 100 h. The dependence of the electrical conductivity on temperature was measured from room temperature to 1000°C in air. Ce doping dramatically enhanced the electrical conductivity of SrMnO₃. Sr_0.7Ce_0.3MnO_1-α exhibits a higher conductivity (290 S · cm^-1 at 1000°C) than that of La_0.8Sr_0.2MnO₃ (LSM, about 175 S · cm^-1) and remains n-type over the whole range of temperature examined. The thermal expansion coefficients in the system were nearly constant with values ranging between 1.24 × 10^-6 and 1.01 × 10^-6 cm/cm · K for temperatures of 50°C to 1000°C.     

Ferroelectric Bi4Ti3O12 and Bi4−x La x Ti3O12 ceramics prepared by a new sol-gel route

Ceramics of bismuth titanate, Bi₄Ti₃O₁₂ (BIT) and the La-doped series, Bi_4?x La _x Ti₃O₁₂ (xBLT) with x?=?0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, and 0.75, have been synthesized by a new sol-gel process based on ethylene glycol. La-doping is found to reduce the temperature of the formation of pure Bi-layer-structured phase from 600 °C in BIT and low La-doped xBLT (x?=?0.1–0.3) to 500 °C in high La-doped xBLT (x?=?0.4–0.75). Increasing the La-content in the xBLT ceramics decreases the contribution of the space charge polarization to the apparent dielectric permittivity. The ceramics of xBLT prepared by this sol-gel route exhibit improved dielectric properties, with a higher room temperature dielectric constant and lower losses up to high temperatures.     

Characteristics improvement of Li0.058(K0.480Na0.535)0.966(Nb0.9Ta0.1)O3 lead-free piezoelectric ceramics by LiF additions

In this study, a series of Li_0.058(K_0.480Na_0.535)_0.966(Nb_0.90Ta_0.10)O₃ + (x)LiF (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5 wt%) lead-free piezoelectric ceramics were fabricated by a conventional solid-state reaction method. The incorporation of LiF could significantly improve the sintering ability of LKNNT ceramics by reducing the optimal sintering temperature from 1090°C to 1020°C. The crystal phases and micro-structures were analyzed by means of the X-ray diffraction and scanning electronic microscopy, respectively. The impedance analyzer was used to measure the Curie temperature, phase transition point, and electro-mechanical coupling factor. And the d₃₃ meter was used to measure the piezoelectric constants.

From the results, due to the addition of 0.2 wt% LiF, uniform and condensed grains can be obtained and hence the sintering temperature can be lowered down. As the contents of LiF increased, the orthorhombic to tetragonal phase transition points T_O-T were almost no changed, but the Curie temperature T_C decreased from 425°C (x = 0) to 405°C (x = 0.5). And furthermore, the electro-mechanical coupling factor k_p and piezoelectric constant d₃₃ were all decreased with increases of LiF contents. Hence, even though the reducing of little amount of piezoelectric characteristics, the LiF addition can improve the sintering ability of the LKNNT ceramics effectively.     

Microstructure and electrical properties of the rare-earth doped 0.94Na0.5Bi0.5TiO3-0.06BaTiO3 piezoelectric ceramics

Phase structure, microstructure, piezoelectric and dielectric properties of the 0.4 wt% Ce doped 0.94Bi_0.5Na_0.5TiO₃-0.06BaTiO₃ (Ce-BNT6BT) ceramics sintered at different temperatures have been investigated. The powder X-ray diffraction patterns showed that all of the Ce-BNT6BT ceramics exhibited a single perovskite structure with the co-existence of the rhombohedral and tetragonal phase. The morphologies of inside and outside of the bulk indicated that the different sintering temperatures did not cause the second phase on the inside of bulk. However, the TiO₂ existed on the outside of the bulk due to the Bi₂O₃ and Na₂O volatilizing at higher temperature. The ceramics sintered at 1,200 °C showed a relatively large remnant polarization (P _r) of about 34.2 μC/cm², and a coercive field (E _c) of about 22.6 kV/cm at room temperature. The permittivity ? _r of the ceramics increased with the increasing of sintering temperature in antiferroelectric region, the depolarization temperature (T _d) increased below 1,160 °C then decreased at higher sintering temperature. The resistivity (ρ) of the Ce-BNT6BT ceramics increased linearly as the sintering temperature increased below 1,180 °C, but reduced as the sintering temperature increased further. A maximum value of the ρ was 3.125?×?10¹⁰ ohm m for the Ce-BNT6BT ceramics sintered at 1,180 °C at room temperature.     

SYNTHESIS AND CHARACTERIZATION OF SB-SUBSTITUTED (K0.5Na0.5)NbO3 PIEZOELECTRIC CERAMICS

ABSTRACT

Lead-free piezoelectric ceramics (K_0.5Na_0.5)(Nb_1-xSb_x)O₃+0.5 mol.%MnO₂, where x = 0 ÷ 0.10, with single phase structure and rhombohedral symmetry at room temperature were prepared by conventional ceramic technology. The optimal sintering temperatures of compositions were within 1100°–1140°C. MnO₂ functions as a sintering aid and effectively improves the densification. The samples reached density from 4.26 g/cm³ for undoped (K_0.5Na_0.5)NbO₃ to 4.40 g/cm³ for Mn/Sb⁵⁺ co-doped ceramics. The co-effects of MnO₂ doping and Sb⁵⁺ substitution lead to significant improvement in dielectric and piezoelectric properties: ε at the T_c increased from 6000 (KNN) to 12400 (x = 0.04), d₃₃ = 92 ÷ 192 pC/N, k_p = 0.32 ÷ 0.46, k_t = 0.34 ÷ 0.48.     

The inferences of ZnO additions for LKNNT lead-free piezoelectric ceramics

By the conventional solid-state liquid-phase sintering technique, Li_0.058(K_0.480Na_0.535)_0.966(Nb_0.9Ta_0.1)O₃ + x wt% ZnO (x = 0, 0.2, 0.4, 0.6, 0.8, 1, 3) lead-free piezoelectric ceramics were fabricated. The addition of ZnO liquid-phase sintering promoters could improve the grain-growth of LKNNT ceramics significantly and its inferences were investigated detailed in this paper. The crystal phases and micro-structures were analyzed by means of the X-ray diffraction and scanning electronic microscopy, respectively. Using the impedance analyzer, the dielectric constant, loss tangent, Curie temperature, phase transition point, and electromechanical coupling factor were measured. And the piezoelectric constants were measured by the d₃₃ meter. Compared to pure LKNNT ceramic (sintered at 1090°C, d₃₃ = 279 pC/N, and k_p = 0.46), for x = 0.6 specimen, even though the optimal d₃₃ and k_p values were only 272 pC/N and k_p = 0.44, but the optimal sintering temperature have been improved from 1090°C to 1020°C successfully.     

EFFECT OF ADDITION OF BT ON RELAXOR BEHAVIOR OF PIN-PT CERAMICS

ABSTRACT

Ferroelectric ceramics with chemical formula (1-x)Pb(In_0.5Nb_0.5)O₃-(x)PbTiO₃ and (1-x)Pb(In_0.5Nb_0.5)O₃-(x)PbTiO₃ with 20%mol of BT (x = 0.0, 0.1, 0.2 and 0.3) were prepared via the wolframite method. The relaxor behavior was analyzed from the dielectric properties and thermal expansion measurements. The dielectric properties were measured at frequencies between 100 Hz and 100 kHz whereas the thermal expansion was measured in the temperature range between ?145°C and 500°C. It is found that the addition of BT effects the relaxor behavior of PIN-PT system. The broad and diffused dielectric constant maxima and essentially no change in Burns temperature were measured and thus suggesting the glassy polarization and relaxor behavior in the PIN-PT-BT compositions.     

Low-temperature sintering of Li2O-doped BaTiO3 lead-free piezoelectric ceramics

Low-temperature sintering of BaTiO₃ ceramics using Li₂O as sintering aids was investigated with a special influences of Li₂O content (0–4?mol%) and sintering temperature (1000–1100°C) on crystalline structure and electrical properties. The sinterability of BaTiO₃ ceramics significantly improved by adding Li₂O, whose densification sintering temperature reduced from 1300°C to 1000°C. XRD pattern indicated that BaTiO₃-xLi₂O samples were single phase with a tetragonal symmetry as x?=?0–0.3?mol%, while the samples became an orthorhombic symmetry as x?=?0.5–4?mol%. The densification sintering temperature in which samples showed relative density higher than 90?% decreased with increasing Li₂O content. A maximum d ₃₃ value (200 pC/N) was obtained for the BaTiO₃-0.5?mol%Li₂O sample sintered at 1050°C, which is attributed to a vicinity of the phase transition and the high density. Adding Li₂O not only reduced the sintering temperature but also obtained the acceptable piezoelectric properties, which will make BaTiO₃ become a kind of promising and practical lead-free piezoelectric ceramics.     

High-temperature stable dielectrics in Mn-modified (1-x) Bi0.5Na0.5TiO3-xCaTiO3 ceramics

In the current work, the bulk (1-x) Bi_0.5Na_0.5TiO₃-xCaTiO₃ [BNCT100x] system was synthesized via solid-state route. CaTiO₃ in solid solution with Bi_0.5Na_0.5TiO₃ was observed to decrease the dielectric constant at higher temperature and raise the dielectric constant at lower temperature. Polarization hysteresis measurements indicated that the ferroelectricity of Bi_0.5Na_0.5TiO₃ was weakened with an increase of CaTiO₃, resulted in the shift of the depolarization temperature (T _d) toward lower temperatures. X-ray diffraction analysis revealed that TiO₂ was produced as a secondary phase due to the losses of Bi and Na during milling and sintering processes. Moreover, the addition of Ca promoted the segregation of Ti out of BNT grains. Dielectric properties of BNCT12 ceramics with different dopant levels of Mn were characterized as a function of temperature for potential use of high-temperature capacitors. Modification of BNCT12 materials with Mn improved the temperature characteristic of capacitance (?55°C to 250°C, △C/C_25°C ≤ ±15%). Finally, by doping 1.5 wt% Mn, the dielectric constant at room temperature could reach over 900, with a low dielectric loss below 1% and a high insulation resistivity about 10¹² Ω?cm. Furthermore, a small amount of Mn influenced the microstructure in the way to inhibit the long grains and grain growth of BNCT solution ceramics. However, excess Mn caused abnormal grain growth, and therefore, rectangle grains appeared again.     

Electrical and mechanical properties of MgO added 0.5Ba(Zr<Subscript>0.2</Subscript>Ti<Subscript>0.8</Subscript>)O<Subscript>3</Subscript>–0.5(Ba<Subscript>0.7</Subscript>Ca<Subscript>0.3</Subscript>)TiO<Subscript>3</Subscript> (BZT–0.5BCT) composite ceramics

MgO (0–2.0 vol%) added Ba(Zr_0.2Ti_0.8)O₃–0.5(Ba_0.7Ca_0.3)TiO₃ (BZT-0.5BCT) ceramics have been prepared by the conventional solid-state reaction method. The effects of MgO powder on the phase formation, densification, dielectric, piezoelectric and mechanical properties (flexural strength, hardness) of the BZT-0.5BCT ceramics have been studied systematically. The synthesized powder could be densified to 97 % of true density at a temperature of 1350 °C. The MgO addition also provided materials with better mechanical properties. The most interesting aspect of MgO added samples is their relative permittivity vs. temperature response. MgO additions effectively suppress the relative permittivity around phase transition temperature. The aging rate of d₃₃ observed for BZT-0.5BCT is 14 %/decade. MgO addition reduces the ageing rate and for 1 vol% MgO added, BZT-0.5BCT shows aging rate of 3 %/decade. BZT-0.5BCT/MgO ceramics possesses good mechanical properties viz., flexural strength 93 MPa, which is almost 25 % higher than that of monolithic BZT-0.5BCT (73 MPa).     

Preparation,characterisation, and electrical properties of (K0.5Na0.5)NbO3 lead-free piezoelectric ceramics

Na_0.5?K_0.5NbO₃ (KNN) ceramics were sintered at different temperatures (970 °C, 1000 °C, 1030 °C, 1060 °C, and 1090 °C) for 3 h by a pressureless sintering method. The powders had been synthesised by sol–gel method, using citric acid as a coordination agent and ethylene glycol as an esterifying agent. The effects of temperature on the phase, microstructure, dielectric, ferroelectric, and piezoelectric properties of the as-prepared ceramics were analysed. The results revealed that all of the ceramics had a pure perovskite phase with orthorhombic symmetry. The piezoelectric constant (d ₃₃), the relative dielectric constant (ε _r), the planar electromechanical coupling coefficient (K _p), and the remnant polarization (P _r) initially increased and then decreased with increasing of temperature in such KNN ceramics. The volatilization of sodium and potassium increased with increasing sintering temperature. Over the range of temperatures studied, those ceramics sintered at 1060 °C had the following optimal properties: (ρ?=?3.97 g/cm³, d ₃₃?=?119 pC/N, ε _r?=?362.46, tan δ?=?0.05, K _p?=?0.23, P _r?=?11.97 μC/cm², E _c?=?10.35 kV/cm, and T _c?=?408 °C).     

Fabrication and dielectric properties of Na0.5Bi0.5Cu3Ti4O12 from co-precipitation method

High dielectric Na_0.5Bi_0.5Cu₃Ti₄O₁₂ (NBCTO) ceramics were firstly prepared by co-precipitation method at low temperature. X-ray diffraction results revealed that pure phase of NBCTO was achieved by calcination at 950 °C for 2 h. Thermo-gravimetric analysis on a dried NBCTO precursor was carried out to study the thermal decomposition process. The microstructure and dielectric properties of NBCTO ceramics sintered at different temperatures were investigated. The results indicate that the sintering temperature has a sensitive influence on the microstructure and dielectric properties. Higher sintering temperature gave rise to increased dielectric constant and dielectric loss of NBCTO samples, and the sample sintered at 975 °C for 8 h exhibits high dielectric constant of 8.3?×?10³ and low dielectric loss of 0.069 at 10 kHz. The dielectric properties were further discussed by the impedance spectroscopy.     

Dielectric and pyroelectric properties of Li2CO3 doped 0.2Pb(Mg1/3Nb2/3)O3–0.5Pb(Zr0.48Ti0.52)O3–0.3Pb(Fe1/3Nb2/3)O3 ceramics

Relaxor ferroelectric compositions of 0.2Pb(Mg_1/3Nb_2/3)O₃–0.5Pb(Zr_0.48Ti_0.52)O₃–0.3Pb(Fe_1/3Nb_2/3)O₃ (0.2PMN–0.5PZT–0.3PFN) ceramics were doped with different concentrations of Li₂CO₃ and were prepared by a columbite precursor process. Their structural, dielectric and pyroelectric properties were studied. A phase analysis was performed using the X-ray diffraction patterns from 2θ?=?44° to 46°, over which the tetragonal phase displays two peaks, (002)_T and (200)_T, while the rhombohedral phase displays one peak, (200)_R. A well saturated P–E hysteresis loop was obtained for the 0.2PMN–0.5PZT–0.3PFN ceramic doped with 0.2 wt.% Li₂CO₃, and the values for the remnant polarization (P _r) and coercive field (E _c) were 30 μC/cm² and 5.4 kV/cm, respectively. A maximum value of the pyroelectric coefficient, 518 μC/m²K, was obtained for the 0.2PMN–0.5PZT–0.3PFN ceramic doped with 0.3 wt.% Li₂CO₃ at the maximum temperature (T _max) due to the decrease of the binding energy for the polarization charge which in formed at the surface.     

Structural and Dielectric Properties of Ca Doped Barium Iron Niobate

Ceramic materials with high dielectric constant are being used in many electric and electro-optics applications. Ca substituted barium iron niobate with general formula (Ba_1-xCa_x) (Fe_0.5Nb_0.5)O₃ with x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0 were prepared by conventional solid state reaction method. Structural properties were investigated using X-ray diffraction and scanning electron microscope. Two types of phases were observed for 0.4 ≤ x ≤ 08. Dielectric constant and loss tangent were measured using impedance analyzer in the frequency range of 20 Hz–1 MHz at room temperature. Dielectric constant and loss tangent were found to decrease with increasing the frequency. A relatively good combination of dielectric constant and loss tangent was obtained for x = 0.2 (?_r = 1441 and tan δ = 0.19) at 10 KHz.     

Effect of reoxidation on positive temperature coefficient of resistance behavior for BaTiO3-K0.5Bi0.5TiO3 ceramics

As a positive temperature coefficient of resistivity (PTCR) material, (1-x)BaTiO₃-xK_0.5Bi_0.5TiO₃ (BT-KBT, 0.05≦ x ≦0.15) ceramics without any donor doping were prepared by a conventional oxide mixing method. All samples were sintered in an Ar atmosphere at 1280?~?1350°C, subsequently, reoxidized at 800?~?1100°C in a gas mixture (99 %Ar–1 %O₂). The PTCR behavior of BT-KBT ceramics were investigated in terms of KBT content, reoxidation temperature and time. The results showed that the BT-KBT ceramics exhibited an abrupt increase in their resistivity near the Curie temperature (Tc) after annealing in gas mixture, Tc of 0.9BT-0.1KBT ceramic was shifted to a higher temperature (~150°C). Furthermore, the room-temperature resistivity (ρ_RT) of ceramic samples sintered in Ar and reoxidized in a gas mixture decreased to 10² Ω·cm. The jump in resistivity (maximum resistivity [ρ_max]/minimum resistivity [ρ_min]) was enhanced by three orders of magnitude through a suitable reduction–reoxidation method without sacrificing the ρ_RT.     

Structure and properties of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> doped Bi(Mg<Subscript>1/2</Subscript>Ti<Subscript>1/2</Subscript>)O<Subscript>3</Subscript>-0.38PbTiO<Subscript>3</Subscript> ceramics with MPB composition

0.62Bi(Mg_1/2Ti_1/2)O₃-0.38PbTiO₃-xwt%Bi₂O₃ (BMT-0.38PT-xBi₂O₃) ceramics were prepared by conventional powder-processing method. It indicated that the morphotropic phase boundary (MPB) region located in 0.0?≤?x?≤?0.3. For x?=?0.3, it exhibited good piezoelectric properties, d₃₃ ~245pC/N and k_p ~40 %. With the increase of Bi₂O₃ content, the Curie temperature (T_c) was found to increase, and the dielectric loss was found to decrease above 200 °C compared with BMT-0.38PT sample. Finally, it can be found that depolarization temperature was around 350 °C by thermal depoling method.     

Effect of Ca substitution on microwave dielectric properties of BaV<Subscript>2</Subscript>O<Subscript>6</Subscript> ceramics

Effects of Ca substitution for Ba on the phase composition, microstructure, sintering behavior and microwave dielectric properties of nominal ceramics Ba_1-xCa_xV₂O₆ (0.2?≤?x?≤?0.5) were investigated. The XRD, Raman and SEM results revealed that BaV₂O₆ and CaV₂O₆ composite ceramics were formed. Nominal ceramics Ba_1-xCa_xV₂O₆ could be well densified at about 550 °C via a solid-state reaction method. The microwave dielectric properties exhibited strong dependence on the composition and microstructure. Typically, the Ba_0.7Ca_0.3V₂O₆ ceramics sintered at 550 °C exhibited excellent microwave dielectric properties: ε_r?=?10.9, Qxf?=?17,100 GHz (at 9.9 GHz), and τ_f?=?4 ppm/°C. Meanwhile, Ba_0.7Ca_0.3V₂O₆ ceramics also showed good chemical compatibility with Al electrode. These results indicated that the Ba_0.7Ca_0.3V₂O₆ ceramics could be a promising candidate for the ULTCC technology.     

Structure and piezoelectric properties of K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>NbO<Subscript>3</Subscript> based lead-free piezoceramics with slight deviation from A-site K or Na stoichiometry

The dependence of structure and piezoelectric response d₃₃ on individual excess A-site K or Na in K_0.5Na_0.5NbO₃ based lead-free piezoceramics is reported. The coexistence of orthorhombic, tetragonal, and monoclinic phases at room temperature is observed in the investigated 0.94K_0.5+xNa_0.5NbO₃–0.06LiNbO₃ and 0.94K_0.5Na_0.5+yNbO₃–0.06LiNbO₃ ceramics (x, y = 0–0.025). The weight ratio of three phases, orthorhombic-tetragonal phase transition temperature, and d₃₃ value are highly sensitive to A-site K or Na nonstoichiometry. A-site Na nonstiochiometry plays a dominant role in enhancing the electrical properties of KNN by significantly reducing the weight ratio percentage of monoclinic phase and shifting the orthorhombic-tetragonal phase transition temperature to lower temperatures.