Enhanced piezoelectric strain response in 〈100〉 grain-oriented lead-free bismuth ferrite–based piezoelectric ceramics

The 〈100〉 grain-oriented 0.11(Bi_0.5K_0.5)TiO₃–0.23BaTiO₃–0.02Bi(Mg_0.5Ti_0.5)O₃–0.64BiFeO₃ piezoelectric ceramics were prepared by a reactive templated grain growth method using a platelike H_1.08Ti_1.73O₄·nH₂O (HTO) template and Bi₂O₃–KHCO₃–MgO–Fe₂O₃–BaCO₃ matrix particles. The high degree of texturing (a Lotgering orientation factor of 80%) and high density (95%) were achieved by employing weight-pressing treatment during the binder-removal and sintering treatment along with optimizing the sintering temperature. The water-quenching treatment has a significant impact on the enhancement of dielectric, ferroelectric, and piezoelectric properties with the increase of dielectric constant, remanent polarization, and piezoelectric strain constant from 764, 13.6 μC/cm², and 384 pm/V for the as-sintered ceramics to 812, 29.9 μC/cm², and 526 pm/V after the water-quenching treatment at 850°C, respectively. The obtained piezoelectric strain constant with a 1.8 times enhancement compared to that of the ceramics with randomly oriented grains is significantly higher than those reported for other lead-free piezoelectric ceramics with Curie temperature >300°C. This study suggested the strong potentiality of this material system for high-temperature actuator application.     

Formation mechanism and microstructure evolution of Ba2Ti9O20 ceramics by reaction sintering method

Ba₂Ti₉O₂₀ single-phase ceramics were prepared by reaction sintering method using TiO₂ and BaCO₃ as raw materials after heat treating at 1150°C for 10 hours. Furthermore, the formation mechanism and microstructure evolution of Ba₂Ti₉O₂₀ ceramics prepared by reaction sintering method were investigated. The formation behavior of Ba₂Ti₉O₂₀ phase was analyzed from the perspective of diffusion, where the reaction activation energy required for the process was calculated to be about 386.17 kJ/mol. Combined with the scanning electron microscopy and the energy dispersive spectrometer, it was revealed that the pores on Ba₂Ti₉O₂₀ grains in the process of reaction sintering might be caused by the absence of oxygen element. Meanwhile, the reason for the roughness of ceramic surface was that the local inhomogeneous distribution of barium on the surface of Ba₂Ti₉O₂₀ grain leaded to the enrichment of titanium.     

Processing of 0.55(Ba0.9Ca0.1)TiO3-0.45Ba(Sn0.2Ti0.8)O3 lead-free ceramics with high piezoelectricity

We report a large piezoelectric constant (d₃₃), 720 pC/N and converse piezoelectric constant (d₃₃^*), 2215 pm/V for 0.55(Ba_0.9Ca_0.1)TiO₃-0.45Ba(Sn_0.2Ti_0.8)O₃ ceramics; the biggest value achieved for lead-free piezoceramics so far. The ceramic powders were calcined between 1050°C-1350°C and sintered at 1480°C. The best properties were obtained at a calcination temperature (CT) of 1350°C. The fitting combination of processing and microstructural parameters for example, initial powder particle size >2 µm, ceramics density ~95%, and grain size ~40 µm led to a formation of orthorhombic-tetragonal-pseudo-cubic (O-T-PC) mixed phase boundary near room temperature, supported by Raman spectra, pointed to the extremely high piezoelectric activity. These conditions significantly increase piezoelectric constants, together with high relative permittivity (ε_r) >5000 and a low loss tangent (tan δ) of 0.029. In addition, the d₃₃ value stabilizes in the range of 400-500 pC/N for all samples calcined between 1050°C and 1250°C. The results entail that the (Ba,Ca)(Sn,Ti)O₃ ceramics are strong contenders to be a substitute for lead-based materials for room temperature applications.     

Inhibition of abnormal grain growth in BaTiO3 by addition of Al2O3

The effect of additions of up to 1 mol% Al₂O₃ on abnormal grain growth in BaTiO₃ samples sintered at 1200 and 1250 °C has been studied. Samples with and without additions of 0.4 mol% TiO₂ were prepared. For the samples without added TiO₂, addition of 0.1 mol% Al₂O₃ increases the number density of abnormal grains, with further additions reducing the number density. The initial increase in number density is caused by Al₂O₃ forming a solid solution with BaTiO₃ and releasing TiO₂ to the grain boundaries. This excess TiO₂ then reacts with BaTiO₃ to form Ba₆Ti₁₇O₄₀, which promotes {1 1 1} twin formation and abnormal grain growth. Further additions of Al₂O₃ react with BaTiO₃, Ba₆Ti₁₇O₄₀ and excess TiO₂ to form Ba₄Al₂Ti₁₀O₂₇ and BaAl₂O₄ second phases, neither of which are growth sites for abnormal grains. For the samples with added TiO₂, addition of Al₂O₃ decreases the number of abnormal grains due to the Al₂O₃ reacting with the excess TiO₂ and BaTiO₃ to form Ba₄Al₂Ti₁₀O₂₇ and BaAl₂O₄ instead of Ba₆Ti₁₇O₄₀.     

Effects of cerium on structures and electrical properties of (Nb,Ta) modified Bi4Ti3O12 piezoelectric ceramics

Bi₄Ti₃O₁₂ high-temperature piezoelectric ceramics composed of 0.03 mol (Nb, Ta)⁵⁺ substituting B site and x mol CeO₂ (x = 0–0.05, abbreviated as BCTNT100x) substituting A site were synthesized by the conventional solid-state reaction method. The effects of Ce additive on the structures and electrical properties of resulting Bi₄Ti₃O₁₂-based ceramics were systematically investigated. In-situ temperature-dependent X-ray diffraction (XRD) confirmed that the phase structure of BCTNT100x ceramics change from orthorhombic structure to tetragonal structure as temperature increased. The ceramics at Ce content x = 0.03 illustrated optimal performances with superior piezoelectric constant (d₃₃ = 36.5 pC/N), high Curie temperature (T_C = 649 °C), and large remanent polarization (2P_r = 21.6 μC/cm²). BCTNT3 ceramics also possessed high d₃₃ of 32.5 pC/N at an annealing temperature of 600°C, with electrical resistivity preserved at 10⁶ Ω cm at 500 °C. These results demonstrate that BCTNT100x ceramics can be used as high-temperature piezoelectric devices.     

Enhanced thermal stability of piezoelectricity in lead-free (Ba,Ca)(Ti,Zr)O3 systems through tailoring phase transition behavior

Good thermal stability in lead-free BaTiO₃ ceramics is important for their applications above room temperature. In this study, thermal stable piezoelectricity in lead-free (Ba,Ca)(Ti,Zr)O₃ ceramics was enhanced by tailoring their phase transition behaviors. Comparison between (1-x)Ba(Ti_0.8Zr_0.2)O₃-x(Ba_0.65Ca_0.35)TiO₃ and (1-y)Ba(Ti_0.8Zr_0.2)O₃-y(Ba_0.95Ca_0.05)TiO₃ revealed that latter system at y?=?0.80 had much better thermal stable piezoelectric coefficient than the former at x?=?0.45. Both systems crystalized in tetragonal to orthorhombic phase boundary at room temperature. The phase transition temperature and degree of diffusion were adjusted by Ca and Zr ions contents and demonstrated great influence on temperature dependent dielectric permittivity, hysteresis loops, and in-situ domain structures. The improved thermal stability of (1-y)Ba(Ti_0.8Zr_0.2)O₃-y(Ba_0.95Ca_0.05)TiO₃ prepared at y?=?0.80 was linked to its higher paraelectric to ferroelectric phase transition temperature (T_m?=?115.7?°C) and less degree of diffusion (degree of diffusion constant γ?=?1.35). By comparison, (1-x)Ba(Ti_0.8Zr_0.2)O₃-x(Ba_0.65Ca_0.35)TiO₃ prepared at x?=?0.45 revealed T_m?=?81.3?°C and γ?=?1.65. Overall, these findings look promising for future stimulation of phase transition behaviors and design of piezoelectric materials with good thermal stabilities.     

High‐temperature piezoelectric properties of 0‐3 type CaBi4Ti4O15:x wt%BiFeO3 composites

The 0‐3 type CaBi₄Ti₄O₁₅:30 wt%BiFeO₃ composite shows much better high‐temperature piezoelectric properties than the single‐phase CaBi₄Ti₄O₁₅ or BiFeO₃ ceramics. The composite with 0‐3 type connectivity exhibits a high density of 7.01 g/cm³, a saturated polarization of 21.5 μC/cm² and an enhanced piezoelectric d₃₃ of 25 pC/N. After the poled composite was annealed at 600°C, its d₃₃ is 21 pC/N at room temperature. Resistance of the composite decreases slowly from 10⁹ ohm at 20°C to ~10⁵ ohm at 500°C. Furthermore, the poled composite shows strong radial and thickness dielectric resonances at 20°C‐500°C.     

Structure Evolution and Electrical Properties of Y3+‐Doped Ba1−xCaxZr0.07Ti0.93O3 Ceramics

Lead free piezoelectric ceramics of Y³⁺‐doped Ba_1?xCa_xZr_0.07Ti_0.93O₃ with x = 0.05, 0.10, and 0.15 were prepared. Composition and temperature‐dependent structural phase evolution and electrical properties of as‐prepared ceramics were studied systematically by X‐ray diffraction, Raman spectroscopy, impedance analyzer, ferroelectric test system, and unipolar strain measurement. Composition with x = 0.10 performs a good piezoelectric constant d₃₃ of 363 pC/N, coercive field E_c of 257 V/mm, remanent polarization P_r of 14.5 μC/cm², and a Curie temperature T_m of 109°C. High‐resolution X‐ray diffraction was introduced to indicate presence of orthorhombic phase. Converse piezoelectric constant d₃₃* of x = 0.10 composition performed better temperature stability in the range from 50°C to 110°C. That means decreasing orthorhombic–tetragonal phase transition temperature could be an effective way to enlarge its operating temperature range.     

Abnormal reoxidation effects in Ba‐excess La‐doped BaTiO3 ceramics prepared by the reduction‐reoxidation method

Ba‐excess La‐doped BaTiO₃ ceramics have been successfully applied to prepare laminated chip thermistor. Ceramics were firstly fired in a high‐purity N₂ flow and then reoxidized in air to obtain positive temperature coefficient of resistivity effect. However, an abnormal reduction trend of room‐temperature (RT) resistivity was found to be always beginning at ~800°C during reoxidation. This anomaly was found closely correlated with the insulating second phase (Ba₂TiO₄) at grain boundary, which destroyed conducting pathways between semiconducting BaTiO₃ grains. When reoxidation temperature was up to ~800°C, the insulating Ba₂TiO₄ could be gradually consumed and then conducting pathways reestablished leading to RT resistivity reduction. To further prove the proposed explanation, the reoxidation effects of TiO₂‐added ceramics were also studied, in which no Ba₂TiO₄ existed and certainly the abnormal RT resistivity reduction disappeared.     

Dielectric Properties and Low‐Temperature Sintering of the Ba0.6Sr0.4TiO3 Ceramics with B2O3/CuO Additions

The sintering behaviors and dielectric properties of Ba_0.6Sr_0.4TiO₃ ceramics were investigated as a function of B₂O₃ and CuO content. The addition of both B₂O₃ and CuO reduced the sintering temperature of Ba_0.6Sr_0.4TiO₃ about 500°C. It was suggested that a liquid phase BaCu(B₂O₅) was formed and assisted the densification of Ba_0.6Sr_0.4TiO₃ ceramics. Ba_0.6Sr_0.4TiO₃ ceramics co‐doped with 3.0 mol% B₂O₃, and 2.0 mol% CuO, sintered at 950°C for 5 h, had a dense microstructure and showed good microwave dielectric properties of a moderate dielectric constant (ε = 1048), low dielectric loss (0.0090) and high tunability (42.2%) at dc electric field of 30 kV/cm.     

Pyroelectric energy harvesting using low–TC (1–x)(Ba0.7Ca0.3)TiO3–xBa(Zr0.2Ti0.8)O3 bulk ceramics

Lead‐free ferroelectric ceramics (1–x)(Ba_0.7Ca_0.3)TiO₃–xBa(Zr_0.2Ti_0.8)O₃ (BCTZ100x) with x = 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, and 0.80 were evaluated for their pyroelectric energy harvesting performance, using the Olsen cycle. As the composition ratio x increased, the crystal phase changed to tetragonal, orthorhombic, rhombohedral, and cubic; the phase boundaries crossed each other in the vicinity of BCTZ70. The crossover phase transition behavior between first‐order and diffuse phase transition changed to only the diffusion phase transition with increasing x. A pinching effect occurred because an increase in dielectric constant was also observed. Energy densities N_D of 229 mJ/cm³ and 256 mJ/cm³ for BCTZ50 and BCTZ80 were obtained, respectively, in temperature of 30°C‐100°C and an electric field of 0‐30 kV/cm. These N_D values are over two times higher than that of soft–Pb(Ti,Zr)O₃ (PZT), which exhibits piezoelectric performance equivalent to BCTZ50 at room temperature. Compared with soft–PZT, BCTZ50 and BCTZ80 exhibited larger N_D values owing to their lower Curie temperatures (T_C ~ 50°C‐110°C). We conclude that low–T_C ferroelectrics are useful for pyroelectric energy conversion based on the Olsen cycle even if they are unsuitable for piezoelectric applications at high temperatures.     

Composition-dependent microstructure and electrical property of (1−x)SBN-xBNBT solid solutions

In this study, (1−x)Sr_0.75Ba_0.25Nb₂O₆-x[0.94Bi_0.5Na_0.5TiO₃-0.06BaTiO₃] solid solution ceramics were prepared and investigated. The length-diameter ratio of pillar-like grain increased with increase in x, reaching maximum value of 10.5 at average length of 1.36 μm and diameter of 0.13 μm for x = 0.20. The maximum dielectric constant, temperature corresponding to the maximum dielectric constant, and saturated polarization decreased, respectively, from 507, 36°C, and 3.2 μC/cm² for x = 0 to 365, −61°C, and 2.0 μC/cm² fort x = 0.10, and then increased to 1167, 43°C, and 5.5 μC/cm² for x = 0.20. These results indicate the competitive effects of B-site Ti⁴⁺ and A-site Ba²⁺ on ferroelectricity.     

Stability of High‐Temperature Dielectric Properties for (1 − x)Ba0.8Ca0.2TiO3–xBi(Mg0.5Ti0.5)O3 Ceramics

Ceramics in the solid solution system, (1 ? x)Ba_0.8Ca_0.2TiO₃–xBi(Mg_0.5Ti_0.5)O₃, were prepared by a conventional mixed oxide route. Single‐phase perovskite‐type X‐ray diffraction patterns were observed for compositions x < 0.6. A change from tetragonal to single‐phase cubic X‐ray patterns occurred at x ≥ 0.1. Dielectric measurements indicated relaxor behavior for x ≥ 0.1. Increasing the Bi(Mg_0.5Ti_0.5)O₃ content improved the temperature sensitivity of relative permittivity ?_r at high temperatures. At x = 0.5, a near‐plateau relative permittivity, 835 ± 40, extended across the temperature range, 65°C–550°C; the permittivity increased at x = 0.6 to 2170 ± 100 for temperatures 160°C–400°C (1 kHz). The corresponding loss tangent, tanδ, was ≤0.025 for temperatures between 100°C and 430°C for composition x = 0.5; at x = 0.6, losses increased sharply at >300°C. Comparisons of dielectric properties with other materials proposed for high‐temperature capacitor applications suggest that (1 ? x)Ba_0.8Ca_0.2TiO₃–xBi(Mg_0.5Ti_0.5)O₃ ceramics are a promising base material for further development.     

Microstructure and Dielectric Properties of Nickel‐Doped Ba0.7Sr0.3TiO3 Ceramics Fabricated by Solgel Method

A study of phase transition, microstructure, and dielectric properties of Ba_0.7Sr_0.3Ti_1–xNi_xO₃ (BSTN) ceramics prepared by slow‐injection solgel technique with x ranging from 0 to 1 mol% is reported in this article. The as‐prepared BSTN material was calcined at 800 and 1000°C and subsequently sintered at 1100 and 1200°C, respectively. The optimized condition was found to be Ba_0.7Sr_0.3TiO₃ doped with 1 mol% nickel calcined at 1000°C and sintered at 1200°C having the lowest dielectric loss of 0.02 with a dielectric constant of 1603 which was measured at a frequency of 1 kHz at room temperature.     

On the formation of an oxycarbonate intermediate phase in the synthesis of BaTiO3 from (Ba,Ti)-polymeric organic precursors

The study of BaTiO₃ crystallization from X-ray amorphous (Ba,Ti) polymeric organic powders has been carried out on a (Ba,Ti)–citrate polymeric resin heat-treated in air at 250 °C. From thermal analysis, X-ray diffraction, infrared and Raman spectroscopies, and ¹³C NMR spectroscopy, it has been concluded that an intermediate oxycarbonate phase was formed prior to the formation of BaTiO₃ above 550 °C. Although not well crystallized, thermoanalytical measurements, the unique XRD pattern, and new IR, Raman, and ¹³C NMR structural features revealed that such a metastable intermediate oxycarbonate phase has a stoichiometry close to Ba₂Ti₂O₅CO₃, which is characterized by having CO₃^2- groups different to those of pure BaCO₃ located, probably, in an open interlayer BaTiO₃ metastable structure. A tentative structure for the oxycarbonate phase is proposed. From the XRD crystal size measurements and Raman spectra, it was suggested that the thermal decomposition of the (Ba, Ti) citrate polymeric organic precursor above 550 °C led to the formation of a mixture of tetragonal and hexagonal BaTiO₃ polymorphs rather than cubic. Despite the specific surface of the synthesized BaTiO₃ powders up to 700 °C, higher than 40 m²/g and an equivalent particle size smaller than 25 nm, Raman spectra indicated asymmetry inside the TiO₆ octahedra of the BaTiO₃ structure.     

Enhanced dielectric properties of La-doped 0.75BaTiO3-0.25Bi(Mg0.5Ti0.5)O3 ceramics for X9R-MLCC application

A series of 0.75Ba_(1?x)La_2x/3TiO₃-0.25Bi(Mg_0.5Ti_0.5)O₃ (x = 0–0.2) ceramics have been synthesized by doping La₂O₃ into 0.75BaTiO₃-0.25Bi(Mg_0.5Ti_0.5)O₃ (0.75BT-0.25BMT), and their structure and dielectric properties investigated. Upon characterizing the structural properties, the single-phase perovskite structure is identified for all the samples and the long-range order of 0.75BT-0.25BMT is verified to be further destroyed with the addition of La₂O₃. Moreover, it is found that the density of 0.75BT-0.25BMT can be improved by doping with La₂O₃, which also promotes the grain growth. Regarding the dielectric properties, the peak shifting effect induced by La³⁺ improves the permittivity-temperature stability of 0.75BT-0.25BMT remarkably by strengthening its relaxation behavior. Among all the samples, 0.75Ba_0.8La_0.4/3TiO₃-0.25Bi(Mg_0.5Ti_0.5)O₃ shows the most outstanding permittivity-temperature stability with ε_r = 572 ± 15% (compared with ε_r at 25 °C) over the temperature range ?70°C–238 °C at 1 kHz, which is notably better than that of 0.75BT-0.25BMT (?4°C–58 °C) and satisfies the specification of the X9R multilayer ceramic capacitor (MLCC). Our work provides one promising option for selecting an alternative dielectric material in terms of permittivity-temperature stability, which advances the development of the X9R MLCC.     

Low temperature sintering of the Ba2Ti9O20 ceramics using B2O3/CuO and BaCu(B2O5) additives

The effects of B₂O₃/CuO and BaCu(B₂O₅) additives on the sintering temperature and microwave dielectric properties of Ba₂Ti₉O₂₀ ceramics were investigated. The B₂O₃ added Ba₂Ti₉O₂₀ ceramics were not able to be sintered below 1000 °C. However, when both CuO and B₂O₃ were added, they were sintered below 900 °C and had the good microwave dielectric properties. It was suggested that a liquid phase with the composition of BaCu(B₂O₅) was formed during the sintering and assisted the densification of the Ba₂Ti₉O₂₀ ceramics at low temperature. BaCu(B₂O₅) powders were produced and used to reduce the sintering temperature of the Ba₂Ti₉O₂₀ ceramics. Good microwave dielectric properties of Qxf = 16,000 GHz, ɛ_r = 36.0 and τ_f = 9.11 ppm/°C were obtained for the Ba₂Ti₉O₂₀ ceramics containing 10.0 mol% BaCu(B₂O₅) sintered at 875 °C for 2 h.     

Significantly enhanced pyroelectric performance in novel sodium niobate-based lead-free ceramics by compositional tuning

In this study, (1 − x)NaNbO₃–xBa_0.6(Bi_0.5K_0.5)_0.4TiO₃ (abbreviated as NN-xBBKT, x = 0.05, 0.10, 0.15, and 0.20) lead-free pyroelectric ceramics were synthesized by conventional solid-state reaction method. Moreover, their microstructure, phase structure, dielectric, ferroelectric, piezoelectric, and pyroelectric characteristics were studied systematically. The X-ray diffraction result showed that the phase structure of NN-xBBKT ceramics changed from orthorhombic to tetragonal and finally became pseudocubic symmetry. The ferroelectric-paraelectric phase transition temperature and depolarization temperature shifted to lower temperature with the increase in BBKT content. Furthermore, with increasing BBKT content, piezoelectric coefficient, figures of merit, and pyroelectric coefficient first increased and then decreased. The optimum pyroelectric properties (eg F_d = 0.81 × 10⁻⁵ Pa^−1/2, F_v = 1.02 × 10⁻² m² C⁻¹, F_i = 1.04 × 10⁻¹⁰ m V⁻¹, and p = 3.11 × 10⁻⁸ C cm⁻² K⁻¹) were observed in sample composition with x = 0.15. More importantly, the pyroelectric coefficient of ceramic with x = 0.15 also displayed relatively high thermal stability because of high depolarization temperature (~110°C). These parameters demonstrate that the novel Pb-free NaNbO₃-based ceramics form an important class of pyroelectric material with broad range of application prospect.     

High piezoelectricity in CuO-modified Ba(Ti0.90Sn0.10)O3 lead-free ceramics with modulated phase structure

High piezoelectricity was achieved in Ba(Ti_0.90Sn_0.10)O₃ lead-free ceramics by optimizing CuO addition and sintering temperature. The phase structure of 1.0 mol% CuO-doped Ba(Ti_0.90Sn_0.10)O₃ ceramic is coexisting rhombohedral and tetragonal phases as sintered at 1300 °C. The coexistence of rhombohedral, tetragonal and orthorhombic phases appears in 1.0 mol% CuO-doped Ba(Ti_0.90Sn_0.10)O₃ ceramics as sintered at 1350–1450 °C, which leads to highly enhanced d₃₃ up to 650pC/N. This work demonstrates that high piezoelectric property (d₃₃ = 650pC/N) can be obtained in BaTiO₃-based lead-free piezoceramics with a simple composition modification by modulating phase structures, which also indicates that Ba(Ti,Sn)O₃ is a promising candidate to replace the lead-based piezoceramics.     

Ultra‐Broad Temperature Stability Obtained with Ce‐Doped BaTiO3‐Based Ceramics

Ce‐doped BaTiO₃‐based ceramics were prepared and studied to satisfy ultra‐broad temperature stability (from ?55°C to 300°C, capacitance variation rate based on C_20°C is within ±15%). The sample with 0.6 mol% CeO₂ succeeds to achieve this performance with a remarkably high ceiling temperature of 300°C. Meanwhile, the sample has good dielectric and electrical properties at room temperature (ε_r = 1667, tanδ = 1.478%, ρ_V = 5.9 × 10¹² Ω·cm). Ce ion can substitute for Ti ion as Ce⁴⁺ or Ba ion as Ce³⁺. The substitution decreases the spontaneous polarization of BaTiO₃, and then weakens the ferroelectricity of BaTiO₃. As a result, the temperature stability of samples is improved obviously. Besides, CeO₂ addition promotes the formation of exaggerated grains, which are consisting of Ba₆Ti₁₇O₄₀.