Influence of sintering temperatures on the electrical property of bismuth sodium titanate based piezoelectric ceramics

A systematic investigation of cerium and stannum doped 0.94(Bi_0.5Na_0.5)TiO₃−0.06BaTiO₃ (Sn&Ce-BNT6BT) based lead-free piezoelectric ceramics is undertaken to understand the influence of sintering temperature on electrical properties. The X-ray diffraction patterns showed that all of the Sn&Ce-BNT6BT ceramics exhibited a single perovskite structure with the co-existence of the rhombohedral and tetragonal phase. The smaller grain size of Sn&Ce-BNT6BT ceramics was obtained at lower sintering temperature, and more cubical grains of Sn&Ce-BNT6BT ceramics were obtained at higher sintering temperature. The temperature dependence of dielectric permittivity of the compositions exhibited strong dispersion with the increasing temperature, and the dielectric loss tangent increased dramatically while the temperature over 225^∘C. The depolarization temperature T _d of Sn&Ce-BNT6BT ceramics sintered at 1160^∘C was 92.6^∘C. The remnant polarizations P _r for Sn&Ce-BNT6BT ceramics sintered at 1120 and 1200^∘C were found to be 28.8 and 33.4 μC/cm² at room temperature, respectively.     

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.     

Fabrication and operation limit of lead-free PTCR ceramics using BaTiO3–(Bi1/2Na1/2)TiO3 system

The electric properties of BaTiO₃–(Bi_1/2Na_1/2)TiO₃ (BT–BNT) solid solution ceramics were studied as a lead-free PTCR (positive temperature coefficient of resistivity) thermistor material usable over 130°C. For determining the maximum switching temperature T _s, the phase diagram of BT–BNT binary system was clarified. Two semiconductorization processes and their electric properties are described. The lanthanum(La)-doped BBNT ceramics sintered in air still showed dielectric behaviors, but the niobium(Nb)-doped ones had a low resistivity at room temperature, ρ _RT, on the order of 10³ Ωcm and showed a PTC behavior. Sintering under a low O₂ atmosphere produces BT–BNT ceramics with less than 10² Ωcm compared to those prepared in air. Our current research produced the BBNT ceramics with T _s values around 210°C by increasing the (Bi_1/2Na_1/2) content in the ceramics.     

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.     

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.     

Low-temperature sintering and microwave dielectric properties of ZnTiO3-based LTCC materials

The low-temperature sintered microwave dielectric ceramics with composition of ZnTiO₃-0.25TiO₂ were prepared by adding a small amount of low-melting compounds CuO-V₂O₅-Bi₂O₃ (CVB). The phase relationship and dielectric properties as a function of sintering temperature and the additional amount were studied. It is demonstrated that the addition of low-melting CVB can suppress the formation of Zn₂TiO₄ at low temperature, but decrease the decomposition temperature of ZnTiO₃. The sintering temperature has a significant effect on the stability of ZnTiO₃ and dielectric properties of sintered ceramics. CVB addition can promote the densification of ceramics through liquid-phase sintering. The dense 2wt% CVB-doped ZnTiO₃-0.25TiO₂ ceramics prepared at 850 °C have excellent dielectric properties of ??=?30, Q×f?=?32,000 GHz, and τ _f ?=?+12 ppm/ °C.     

Sintering and dielectric properties of Bi1.5ZnNb1.5O7 cubic pyrochlore ceramics via high-energy milling technology

The dense Bi_1.5ZnNb_1.5O₇ cubic pyrochlore ceramics is synthesized by high-energy milling technology from the coarse Bi_1.5ZnNb_1.5O₇ cubic pyrochlore powders prepared by solid state route. The sintering and dielectric properties of the Bi_1.5ZnNb_1.5O₇ cubic pyrochlore ceramics are investigated, which show that the sintering temperature of the prepared ceramics could be effectively lowered to 800°C and the bulk density reach 6.889 g/cm³ approximately 97% of the theoretical density of Bi_1.5ZnNb_1.5O₇ cubic pyrochlore ceramics. The excellent dielectric properties of the ceramics sintered at 850°C has been obtained with the relative permittivity of 160 and the dielectric loss of 10^?4. This route would be a low-cost and mass production for lowering the sintering temperature of the Bi_1.5ZnNb_1.5O₇ cubic pyrochlore ceramics without sintering aids.     

Phase compositions and microwave dielectric properties of MgTiO<Subscript>3</Subscript>-based ceramics obtained by reaction-sintering method

MgTiO₃-based microwave dielectric ceramics were prepared successfully by reaction sintering method. The X-ray diffraction patterns of the sintered samples revealed a major phase of MgTiO₃-based and CaTiO₃ phases, accompanied with Mg₂TiO₄ or MgTi₂O₅ determined by the sintering temperature and time. The microwave dielectric properties had a strong dependence of sintering condition due to the different phase compositions and the microstructure characteristics. The ceramics sintered at 1360 °C for 4 h exhibited good microwave dielectric properties: a dielectric constant of 20.3, a high quality factor of 48,723 GHz (at 9GHz), and a temperature coefficient of resonant frequency of ?1.8 ppm/^oC. The obtained results demonstrated that the reaction-sintering process is a simple and effective method to prepare the MgTiO₃-based ceramics for microwave applications.     

Effect of sintering temperature on piezoelectric and dielectric properties of 0.98(Na0.5K0.5)NbO3-0.02Li(Sb0.17Ta0.83)O3+0.01wt%ZnO ceramics

We studied sintering temperature to enhance the piezoelectric and dielectric properties of 0.98(Na_0.5?K_0.5)NbO₃-0.02Li(Sb_0.17Ta_0.83)O₃?+?0.01wt%ZnO (hereafter NKN-LST+ZnO) lead free piezoelectric ceramics. The synthesis and sintering method were the conventional ceramic technique and sintering was executed at 1080?～?1120°C. We found that optimal sintering temperature and NKN-LST+ZnO ceramics showed the highest piezoelectric properties and dielectric properties at the optimal sintering temperature. The NKN-LST+ZnO ceramics sintered at 1090°C show a superior performance with piezoelectric constant d ₃₃?=?185 pC/N, k _p?=?0.36, ε ₃₃ ^T /ε₀?=?491 respectively. These results reveal that NKN-LST+ZnO ceramics are promising candidate materials for lead-free piezoelectric application.     

Low temperature sintering of lead–free (Bi<Subscript>1/2</Subscript>Na<Subscript>1/2</Subscript>)TiO<Subscript>3</Subscript>-SrTiO<Subscript>3</Subscript>-BiFeO<Subscript>3</Subscript> piezoelectric ceramics by adding excess CuO

This study examined the microstructures, crystal structures, and electrical properties of 0.01 mol CuO–added (1–x)(Bi_1/2Na_1/2)TiO₃–xSrTiO₃–2BiFeO₃ (BNST100x–2BF, x?=?0.20 ~ 0.28) ceramics synthesized at two different sintering temperatures. The sintering temperature of the BNST100x–2BF ceramics could be decreased from 1175 °C to 1000 °C by adding a 0.01 mol CuO excess. Low–temperature sintering led to a decrease in average grain size. The dielectrics, polarization hysteresis (P–E), switching current, and electric–field induced strain (S–E) curves changed with increasing SrTiO₃ content and decreasing sintering temperature. Interestingly, the highest reduction ratio of d₃₃^* was calculated to be somewhere in between the high–temperature sintered and low–temperature sintered BNST26–2BF ceramics. These results were attributed to the difference in the stabilized relaxor state and closely related to the electric field–induced reversible phase transition from the relaxor and ferroelectrics.     

Fabrication and electrical properties of textured Na1/2Bi1/2TiO3-BaTiO3 ceramics by reactive-templated grain growth

The <001> fiber-textured Na_1/2 Bi_1/2TiO₃-BaTiO₃ (6 mol% BaTiO₃) ceramics were fabricated by reactive-templated grain growth (RTGG), using plate-like Bi₄Ti₃O₁₄ (BiT) particles prepared by a molten salt method as templates. The effects of sintering conditions on texture development and microstructure evolvement were both studied, and the mechanisms of grain orientation and densification were discussed. High Lotgering factor (≥96%) and high density (≥96% theoretic density) textured Na_1/2 Bi_1/2TiO₃-6BaTiO₃ ceramics were prepared by using the max templates concentration supplying 100% Bi in the final product, and sintering at 1200 °C for 10 h. The NBT-6BT obtained exhibited good piezoelectric performance with piezoelectric coefficient d ₃₃ ?=?241pC/N, and electromechanical coupling factor k _p ?=?41.2%, k _t ?=?66.5% at room temperature.     

Thermoelectric properties of Bi3+ substituted Co-based misfit-layered oxides

Highly densified (Ca_1?x Bi _x )₃Co₄O₉ thermoelectric ceramics with a layered structure were prepared by a sol–gel method followed by spark plasma sintering (SPS). Thermoelectric (TE) properties of the complex oxide ceramics were measured from room temperature to 700 °C. The results show that Bi³⁺ substitution leads to an increase in both electrical conductivity and Seebeck coefficient simultaneously. Bi³⁺ doped samples also show a lower thermal conductivity than undoped samples. The dimensional figure of merit ZT value of (Ca_0.95 Bi_0.05)₃Co₄O₉ samples is 0.25 at 700 °C.     

Normal sintering and electric properties of (K,Na,Li)(Nb,Sb)O3 lead-free piezoelectric ceramics

0.94(K₀₅Na_0.5)NbO₃?0.03LiNbO₃?0.03LiSbO₃ (KNLNS) lead-free piezoelectric ceramics were prepared by conventional mixed oxide route with normal sintering method. The samples were sintered at different temperatures with KNLNS powder atmosphere to prevent volatilization of alkali metal oxides at high temperature. The effects of sintering temperature on the density, structure and electric properties of KNLNS ceramics were studied. X-ray diffraction (XRD) results showed that the crystal structure of the crushed KNLNS ceramic powders were pure perovskite phase with tetragonal phase structure when sintered at T????1080°C. However a K₃Li₂Nb₅O₁₅ phase with tetragonal tungsten bronze structure began to appear when the sintering temperature was higher than 1080°C. The optimum sintering temperature was 1080°C which was determined by measuring the density of the samples. Scanning electron microscope (SEM) observation indicated that the sintering temperature had a great effect on the microstructure of the samples. The KNLNS ceramics under the optimum sintering temperature showed excellent electric properties: ???=?4.29 g/cm³, ?? _r?=?826, tan???=?0.049, d ₃₃?=?190 pC/N, k _p?=?0.30, and T _c?=?385°C. The results show that the KNLNS ceramics are promising candidate for lead-free piezoelectric ceramics.     

Synthesis and characterization of novel Ca2Zn4Ti15O36 microwave ceramics derived from sol-gel powder

A novel microwave dielectric ceramics with composition of Ca₂Zn₄Ti₁₅O₃₆ (CZT) have been synthesized at different sintering temperatures, using citrate sol-gel derived powder. The sintering behavior and the phase identification of the powders were evaluated using differential thermal analysis-thermo gravimetric analysis and X-ray powder diffraction analysis techniques. The phase of CZT can be observed in the powder calcined at 900 °C. The single-phase of CZT, however, can only be obtained at sintering temperature of 1,000 °C or above. The single-phase CZT ceramics can be sintered into dense at 1,100 °C, exhibiting excellent microwave dielectric properties of ? _r?=?48.1, Q?×?f?=?27,000 GHz, and τ _f?=?+53.5 ppm/°C. The effects of sintering temperature on the density, microstructure, and dielectric properties of the sintered ceramics were investigated. The mechanism responsible for the change of dielectric properties with sintering temperature was also discussed.     

Synthesis and piezoelectric properties of [Bi1-z(Na1-x-y-zKxLiy)]0.5BazTiO3 lead-free piezoelectric ceramics

[Bi_1-z(Na_1-x-y-zK_xLi_y)]_0.5Ba_zTiO₃ lead-free piezoelectric ceramics were fabricated by ordinary ceramic technique and the piezoelectric and ferroelectric properties of the ceramics were studied. The ceramics can be well sintered at 1,100–1,150 °C for 2 h. X-ray diffraction (XRD) analysis shows that K⁺, Li⁺ and Ba²⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a solid solution with a single-phase perovskite structure. The introduction of K⁺, Li⁺ and Ba²⁺ into Bi_0.5Na_0.5TiO₃ significantly decreases the coercive field E _c but maintains the large remanent polarization P _r of the materials. The ceramics provide piezoelectric constant d ₃₃ of 205 pC/N, electromechanical coupling factor k _p of 0.346, remanent polarization P _r of 31.7–38.5 μC/cm², and coercive field E _c of 3.18–5.16 kV/mm.     

Microwave dielectric properties of B2O3-added Li2MgTiO4 ceramics for LTCC applications

Li₂MgTiO₄ (LMT) ceramics which are synthesized using a conventional solid-state reaction route. The LMT ceramic sintered at 1250°C for 4 h had good microwave dielectric properties. However, this sintering temperature is too high to meet the requirement of low-temperature co-fired ceramics (LTCC). In this study, the effects of B₂O₃ additives and sintering temperature on the microstructure and microwave dielectric properties of LMT ceramics were investigated. The B₂O₃ additive forms a liquid phase during sintering, which decreases the sintering temperature from 1250°C to 925°C. The LMT ceramic with 8 wt% B₂O₃ sintered at 925°C for 4 h was found to exhibit optimum microwave dielectric properties: dielectric constant 15.16, quality factor 64,164 GHz, and temperature coefficient of resonant frequency -28.07 ppm/°C. Moreover, co-firing of the LMT ceramic with 8 wt% B₂O₃ and 20 wt% Ag powder demonstrated good chemical compatibility. Therefore, the LMT ceramics with 8 wt% B₂O₃ sintered at 925°C for 4 h is suitable for LTCC applications.     

Effect of sintering temperature on microstructure and piezoelectric properties of Pb-free BiFeO3–BaTiO3 ceramics in the composition range of large BiFeO3 concentrations

Lead-free (1-x)BiFeO₃–xBaTiO₃ [(1-x)BF-xBT] piezoelectric ceramics in the range of large BF concentrations were prepared by conventional oxide-mixed method at various sintering temperatures. The sintering temperatures have a significant effect on the microstructure of the ceramics, and the composition has a remarkable effect on optimal sintering temperature of the ceramics, which are closely related with piezoelectric properties. The grain size increased with increasing sintering temperature and the optimal sintering temperature increased with increasing BT content. The ceramics with x?=?0.275 sintered at 990 °C exhibit enhanced electrical properties of d ₃₃?=?136pC/N and k _p?=?0.312 due to the polarization rotation mechanisms at MPB and desired microstructure. These results show that the ceramic with x?=?0.275 is a promising lead-free high-temperature piezoelectric material.     

Piezoelectric and dielectric properties of low temperature sintering Pb(Mn1/3Nb2/3)O3–Pb(Zn1/3Nb2/3)O3–Pb(Zr0.48Ti0.52)O3 ceramics with variation of sintering time

Pb(Mn_1/3Nb_2/3)O₃–Pb(Zn_1/3Nb_2/3)O₃–Pb(Zr_0.48Ti_0.52)O₃ (abbreviated as PMN–PZN–PZT) ceramics containing Li₂CO₃, Bi₂O₃ and CuO as sintering aids were fabricated using two-stage calcinations method in order to develop low temperature sintering ceramics for multilayer piezoelectric actuators. Their dielectric and piezoelectric properties were investigated according to the variation of sintering time. All the specimens sintered at 930°C for 60~150 min showed tetragonal phases without secondary phases. Electromechanical coupling factor (kp), dielectric constant (ε _r) and piezoelectric constant (d ₃₃) increased with the increase of the sintering time. The mechanical quality factor (Qm) exhibited maximum of 1,815 with the increase of sintering time for 120 min and then slightly decreased. At the sintering temperature of 930°C and the sintering time of 120 min, the optimal values such as the density of 7.69 g/cm³, kp of 0.516, ε _r of 1158, Qm of 1815, and d ₃₃ of 287 pC/N were found for multilayer piezoelectric actuators.     

Thermal Expansion Behavior of (Bi0.5Na0.5)Zr1-x Ti x O3 Ceramics

(Bi_0.5Na_0.5)Zr_1-xTi_xO₃ with x = 0, 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6 ceramics were fabricated by a conventional sintering technique at 850–950°C for 2 h. From X-ray diffraction study, three regions of different phases were observed in the ceramic system; i.e., orthorhombic phase region (0 ≤ x ≤ 0.2), mixed-phase region (0.3 ≤ x ≤ 0.4), and rhombohedral phase region (0.5 ≤ x ≤ 0.6). The thermal expansion coefficient data indicated the phase transition in the temperature range from 100°C–150°C of the ceramics. The thermal strain curve of all compositions suggested a decrease of local polarization with temperature increment up to the Burns temperature.