The structure and electrical properties of Ca0.6(Li0.5Bi0.5-xPrx)0.4Bi2Nb2O9 high-temperature piezoelectric ceramics

Ca_0.6(Li_0.5Bi_0.5-xPr_x)_0.4Bi₂Nb₂O₉ ceramics were prepared via a solid-state reaction method. The effect of the Pr content on the structural and electrical properties was systematically investigated. X-ray diffraction (XRD) combined with Rietveld refinement and X-ray photoelectron spectroscopy (XPS) demonstrated that a moderate amount of Pr³⁺ can be incorporated into the NbO₆ octahedra, while excess Pr³⁺ ions probably enter into the (Bi₂O₂)²⁺ layers, thus resulting in an increase in the tetragonality of the crystal structure. The introduction of Pr suppressed the generation of oxygen vacancies and improved the preferential grain growth along the c-axis, which might be responsible for enhancing the resistivity (ρ ~ 10⁶ Ω cm at 600°C). The replacement of Pr³⁺ for A-site Bi³⁺ enhanced the piezoelectric property, and the piezoelectric constant d₃₃ increased from 13.8 pC/N to 16.3 pC/N. The high depolarization temperature (up to 900°C) implied that CBN-LBP100x ceramics are promising candidates for ultrahigh-temperature application.     

Effects of (Li,Ce, Y) co-substitution on the properties of CaBi2Nb2O9 high temperature piezoceramics

High temperature lead-free Bismuth layer-structured (Li, Ce, Y)-substituted CBN piezoelectric ceramics were prepared by the solid-state reaction method. The phase structure, microstructure, piezoelectric property, dielectric property, thermal stability and electric property of the (Li, Ce, Y)-substituted CBN ceramics were studied. X-ray diffraction and SEM revealed the doped ceramics had typical bismuth layer-structure. The piezoelectric coefficient was improved significantly and the maximum value was ~16.1 pC/N.The Curie temperature of all the samples were in the range of 925–941 °C that was close to or even excess the value of pure CBN ceramics. The resistivity were studied deeply and all the samples possessed excellent resistivity at high temperature (500 °C, ~10⁶ Ω cm; 600 °C, ~10⁵ Ω·cm). The thermal depoling behavior of the ceramics was researched in detail and the doped ceramics exhibited outstanding thermal stability. All the results indicate the (Li, Ce, Y)-substituted CBN ceramics possesses preeminent property, making it promising for application especially in high temperature territories.     

Tailoring structure and piezoelectric properties of CaBi2Nb2O9 ceramics by W6+-Doping

Calcium bismuth niobate (CaBi₂Nb₂O₉) is a typical bismuth-layer structured piezoelectrics (BLSPs) with a high Curie temperature (T_C) of ～943 °C, but it has low piezoelectric coefficient and high-temperature resistivity which severely limits signal acquisition in the high-temperature piezoelectric vibration sensors. Ion-doping modification is regarded as an effective way to enhance electrical properties. In this work, W⁶⁺ donor-doping at Nb⁵⁺ site in the CaBi₂Nb_2-xW_xO₉ (x = 0, 0.020, 0.025, 0.030, 0.035 and 0.040) piezoelectric ceramics with T_C of 931 ± 2 °C were fabricated by the conventional solid-state reaction method. The effects of W⁶⁺-doping on crystal structure of CaBi₂Nb_2-xW_xO₉ as well as microscopic morphology and electrical properties of ceramics were investigated systematically. The tetragonality, isotropy and electrical properties of the ceramics were enhanced with the introduction of W⁶⁺ dopant. It was found that x = 0.025 was the optimal W⁶⁺-doping ratio that yielded remnant polarization of 8.0 μC/cm², electrical resistivity of 3.0 × 10⁶ Ω cm at 600 °C, piezoelectric coefficient (d₃₃) of 14.4 pC/N, and good thermal depoling property. Our work has established a feasible approach to tune the structure of CaBi₂Nb₂O₉ to improve piezoelectric properties for potential applications in high-temperature piezoelectric vibration sensors.     

Influence of cobalt and sintering temperature on structure and electrical properties of BaZr0.05Ti0.95O3 ceramics

Pure and Co-modified BaZr_0.05Ti_0.95O₃ ceramics were fabricated by the traditional solid state reaction technique. The influence of cobalt and sintering temperature on structure, dielectric, ferroelectric properties and diffuse phase transition of BZT ceramics were investigated systematically. 1300 °C was the optimal sintering temperature for BZT ceramics. The solid solubility limit of Co ions in BZT matrix was determined to be 0.4 mol%. The introduction of a moderate amount of Co ions was believed to benefit the microstructure development and make the grain size more uniform. Compared with undoped counterparts, 0.4 mol% Co-modified ceramics showed equivalent ferroelectric properties with a high remnant polarization (P_r=9.6 μC/cm²) and a low coercive field (E_c=0.21 kV/mm). Besides these, a relative high dielectric coefficient (ε_r=2030) and a low dielectric loss (tan δ=1.85%) were also obtained on this composition. The degree of diffuse phase transition was enhanced by the addition of Co ions. The related mechanism of the diffused phase transition behavior was discussed.     

Tailoring structural and electrical properties of A-site non-stoichiometric Na0.5Bi0.5TiO3 ceramic at different sintering temperature

Na/Bi stoichiometry plays crucial role in determining various properties of sodium bismuth titanate-based system. In this work, we have synthesised lead free (Na_0.5Bi_0.5)_1+x TiO₃ (x?=?0, 0.02 and 0.05) ceramics by sol-gel method and systematically presented structural, dielectric and ferroelectric properties at different sintering temperature. Single phase perovskite structure with rhombohedral symmetry (R3c) is obtained for all compositions from low (850°C) to maximum (1150°C) sintering temperature. The shifting of x-ray diffraction peaks and characteristic perovskite metal-oxide vibrational band (～627?cm^?1) in Fourier Transform Infra-red spectra suggests compression or expansion of crystal lattice with Na/Bi non-stoichiometry. Excess of Na/Bi comprises dense crystal growth as compared to pure Na_0.5Bi_0.5TiO₃ composition suggesting compensation of volatile elements loss during heat treatment whose impact has also been observed in dielectric as well as ferroelectric properties. It is observed that Na_0.51Bi_0.51TiO₃ sample with x?=?0.02 exhibits better structural, dielectric and ferroelectric properties in whole range of sintering temperature.     

Role of Cu and Y in sintering,phase transition,and electrical properties of BCZT lead-free piezoceramics

Lead-free (Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1)O₃-xwt%CuOywt%Y₂O₃ (BCZT-Cu_xY_y) ceramics with high piezoelectricity were synthesized by the conventional solid-state reaction method. The role of Cu and Y (Cu/Y) in sintering, phase transition, and electrical properties of such ceramics was systematically studied. The results indicated that the sintering temperatures of BCZT-Cu_xY_y decreased by at least 100?°C due to the low melting point of CuO. The promotion effect of Cu/Y on phase transition lied in the improvement of T_C by 5–15?°C and the coexistence of O+T phase near room temperature. The contribution of Cu/Y to electrical properties was mainly ascribed to the grains growth, the formed oxygen vacancies and lattice distortions, and the donor doping effect of Y³⁺. Adding 0.10?wt% Cu²⁺ and 0.06?wt% Y³⁺ into BCZT dramatically improved the electrical properties as following: d₃₃ =?552 pC/N, ε_m =?10175, ε_r =?4546, tanδ =?0.016, T_C =?100?°C, k_p =?0.475, Q_m =?157.2, P_r =?10.82 μC/cm² and E_C =?2.33?kV/cm. A plausible mechanism was obtained to explain the reaction process and the favorable performances of BCZT-Cu_xY_y. Co-doping Cu²⁺ and Y³⁺ into BCZT could be a promising method to improve and balance the sintering, phase transition, and electrical properties for potential practical applications of lead-free piezoceramics.     

Structure and electrical properties of perovskite layer (1−x)Sr2Nb2O7‐x(Na0.5Bi0.5)TiO3 high‐temperature piezoceramics

The structure and electrical properties of perovskite layer structured (PLS) (1?x)Sr₂Nb₂O₇‐x(Na_0.5Bi_0.5)TiO₃ (SNO‐NBT) prepared by solid‐state reaction method are investigated. The addition of NBT is beneficial to speed up mass transfer and particle rearrangement during sintering, leading to better sinterability and higher bulk density up to 96.8%. The solid solution limit x in the SNO‐NBT system is below 0.03, over which Ti⁴⁺ is preferable to aggregate and results in the generation of secondary phase. After the modification by NBT, all SNO‐NBT ceramics have a Curie temperature T_c up to over 1300°C and piezoelectric constant d₃₃ about 1.0 pC/N. The breakthrough of piezoelectricity can mainly be attributed to rotation and distortion of oxygen octahedron as well as higher poling electric field resulting from the improved bulk density. This study not only demonstrates how to improve piezoelectricity by NBT addition, but also opens up a new direction to design PLS piezoceramics by introducing appropriate second phase.     

Enhanced energy storage properties of Bi0.5Na0.5TiO3-based ceramics via regulating the doping content and sintering temperature

Eco-friendly lead-free energy-storage ceramics featuring high energy storage properties and ultra-high stability have been regarded to be one of the most potential materials in the field of energy storage. In this work, a new element system, (1-x)(0.6Bi_0.5Na_0.5TiO₃-0.4SrTiO₃)-xBi[Zn_2/3(Nb_0.5Ta_0.5)_1/3]O₃ ((1-x)BNST-xBZNT) lead-free ceramics, were synthesized via a conventional solid-state sintering technology. And the phase structure, microstructure and energy storage properties of the (1-x)BNST-xBZNT ceramics were comprehensively studied. After the introduction of BZNT, the average grain size of the materials is greatly decreased, thereby enhancing the dielectric breakdown strength (DBS). Additionally, the thermal stability of the ceramics is significantly improved via regulating the doping content and sintering temperature. Furthermore, the ferroelectric long-range order of the ceramics is decomposed into randomly-oriented polar nano-domains (PNRs) after introducing BZNT, leading to strong relaxor behavior and significantly reducing remanent polarization (P_r). As a result, even under a relatively low electric field of 139 kV/cm, the 0.98BNST-0.02BZNT ceramic sintered at 1150 °C possesses high values of energy storage efficiency (η) value of 92.78% and total energy storage density (W_tot) of 1.67 J/cm³ as well as remarkable thermal stability (25–175 °C), frequency stability (20–70 Hz) and fatigue resistant stability (10⁰-10⁵ cycles). This investigation provides a useful reference for developing advanced energy storage ceramics by regulating the doping content and sintering temperature.     

A simple Bi3+ self-doping strategy constructing pseudo-tetragonal phase boundary to enhance electrical properties in CaBi2Nb2O9 high-temperature piezoceramics

Calcium bismuth niobate (CaBi₂Nb₂O₉, CBN)-based ceramics are promising candidates for high temperature application, the electrical properties of which are commonly enhanced by complex ion substitution or texture processes. Here, we report that high piezoelectricity and high resistivity were achieved in Ca_1-xBi_2+xNb₂O₉ by constructing pseudo-tetragonal boundary through a simple strategy of Bi³⁺ self-doping. At the pseudo-tetragonal boundary, Ca_0.96Bi_2.04Nb₂O₉ ceramics maintain high Curie temperature T_c = 942 °C, and show high piezoelectric coefficient d₃₃ = 15.1 pC/N and high resistivity ρ_dc = 2 × 10⁶ Ω cm (@600 °C). It is proved that the good piezoelectric property mainly originates from the increase of domain density. In addition, Ca_0.96Bi_2.04Nb₂O₉ ceramics reveal good thermal depoling performance, remaining 90% of piezoelectricity after thermal depoling at 900 ℃, which is due to small thermal expansion and structural distortion. Our work provides a promising candidate for high temperature applications and an easy way to improve the performance of Aurivillius-type piezoelectric ceramics.     

Enhancement in electrical and magnetic properties of (Li0.5Ga0.5)2+ and (Li0.5Er0.5)2+-Modified BiFeO3-BaTiO3 ceramics

Effects of (Li_0.5Ga_0.5)²⁺ and (Li_0.5Er_0.5)²⁺ doping on the phase structure, electrical, and magnetic properties of 0.75BiFeO₃-0.25BaTiO₃ (BFO-BT) ceramics were investigated and analyzed. X-ray diffraction measurements suggested a rhombohedral distorted perovskite structure and no structural transformation with the increasing doping content. Rietveld refinement results revealed that (Li_0.5Ga_0.5)²⁺ ions were more susceptible to replace the B-sites and (Li_0.5Er_0.5)²⁺ ions tended to substitute the A-sites. A significant improvement in the dielectric loss, ferroelectricity, and magnetization was observed for both (Li_0.5Ga_0.5)²⁺ and (Li_0.5Er_0.5)²⁺-modified BFO–BT ceramics without the addition of MnO₂ compared to undoped ceramic samples. Remnant magnetization (M_r) of 0.35 emu/g was reached for LG6. The enhanced magnetic properties were related to the suppressed cycloidal spin structure, the presences of the local lattice disorder and the magnetic impurities induced by the (Li_0.5Ga_0.5)²⁺ and (Li_0.5Er_0.5)²⁺ substitution.     

Low‐temperature sintering and electrical properties of Sr2Nb2O7 piezoceramics by CuO addition

Effects of 0.5 wt% CuO addition on the sintering, structural and electrical properties of perovskite layer structured (PLS) Sr₂Nb₂O₇ ceramics prepared by solid‐state reaction method are investigated. The addition of CuO is beneficial to the liquid phase bridge formation at sintering process, leading to lower sintering temperature of 1180°C and larger bulk density up to 98%. Meanwhile, CuO modified Sr₂Nb₂O₇ ceramics show a remarkable d₃₃ of (1.1 ± 0.1) pC/N while still with a very high T_c of (1340 ± 2)°C. Raman spectra indicate that the improvement of piezoelectricity could be attributed to the rotation and/or distortion of oxygen octahedron caused by possible Cu²⁺ substitution at the A‐sites of Sr₂Nb₂O₇.     

Effects of Ho2O3 doping and sintering temperature on the core-shell structure of X9R Nb-modified BaTiO3-(Bi0.5Na0.5)TiO3 ceramics

The amphoteric element holmium was used to dope X9R Nb-modified BaTiO₃-(Bi_0.5Na_0.5)TiO₃ ceramics (BTBNT-Nb) by a conventional solid-state reaction method. The effect of Ho₂O₃ doping on the dielectric and electric properties of ceramics were investigated. X-ray diffraction results showed that the rare earth of Ho³⁺ can occupy A- and B-sites of BTBNT-Nb. All samples met X9R specifications and the insulation resistance of the 0.5 mol% Ho₂O₃ doped ceramic was 1.05 × 10¹³ Ω/cm. The sintering temperature strongly influenced the core–shell structure of ceramics Transmission electron microscope images revealed that the size of ferroelectric domain in the core decreased with increasing temperature. Multilayer ceramic capacitor chips with ten active dielectric layers were prepared and characterized.     

Influence of Co/W co-doping on structural and electrical properties of Na0.5Bi2.5Nb2O9 piezoelectric ceramics

Co/W co-doped Na_0.5Bi_2.5Nb_2-x(Co_1/3W_2/3)_xO₉ (NBNCW-x) ceramic samples were prepared by the conventional solid state reaction method. The electrical properties and crystal structure of the NBNCW-x ceramic samples were analyzed in detail. The XRD and Rietveld refinement results showed that the samples lattice distortion decreased with the increment of Co/W doping. The XPS results showed that the number of oxygen vacancies in the Na_0.5Bi_2.5Nb₂O₉ ceramics could be reduced by the substitution of a small amount of Co/W. The weakened lattice distortion and reduced number of oxygen vacancies of the Na_0.5Bi_2.5Nb₂O₉ ceramics synergistically contributed to its improved electrical properties. In particular, the Na_0.5Bi_2.5Nb_1.97(Co_1/3W_2/3)_0.03O₉ ceramic exhibited the best performance, and its T_c, d₃₃ and P_r were 780 °C, 24.9 pC/N and 12.6 μC/cm², respectively. The dielectric loss was only 3.3% at 550 °C. In addition, this ceramic exhibited excellent thermal stability, with the d₃₃ value of the ceramic being 95.2% of its original value when annealed at 750 °C. These properties indicate that the Co/W co-doped Na_0.5Bi_2.5Nb₂O₉-based ceramics have potential application in the high-temperature field.     

Effect of BaCu(B2O5) on the sintering and microwave dielectric properties of Ca0.4Li0.3Sm0.05Nd0.25TiO3 ceramics

The sintering behaviors and microwave dielectric properties of the Ca_0.4Li_0.3Sm_0.05Nd_0.25TiO₃ (abbreviated CLSNT) ceramics with different amounts of BaCu(B₂O₅) addition were investigated in this paper. Adding BaCu(B₂O₅) to CLSNT lowered its sintering temperature from 1300 °C to 925 °C. No secondary phase was observed in the CLSNT ceramics and complete solid solution of the complex perovskite phase was confirmed. The CLSNT ceramics with small amounts of BaCu(B₂O₅) addition could be well sintered at 925 °C without much degradation in the microwave dielectric properties. Especially, the 1.75 wt.% BaCu(B₂O₅)-doped CLSNT ceramic sample sintered at 925 °C for 3 h had optimum microwave dielectric properties of ε_r = 93.5 ± 3.2, Q × f = 6486 ± 434 GHz, and τ_f = 5 ± 1.5 ppm/°C (at 3–4 GHz), enabling it a promising candidate material for LTCC applications. Obviously, BaCu(B₂O₅) could be a suitable sintering aid to facilitate the densification and microwave dielectric properties of the CLSNT ceramics.     

Li0.5Bi2.5Nb2O9: An alkali-metal bismuth layer structured ferroelectric with high TC and small orthorhombic distortion

Bismuth layer structured ferroelectrics (BLSFs) have drawn much attention due to their great potential for high-temperature applications. It is generally accepted that BLSFs with small orthorhombic distortion should have low T_C. In this paper, we report an anomalous example Li_0.5Bi_2.5Nb₂O₉ (LBN), which has small orthorhombic distortion but very high T_C. LBN shows the highest T_C (834°C) among currently reported prototype alkali-metal BLSFs, which is attributed to its small tolerance factor. However, the refinement result reveals that LBN is orthorhombic with the space group of A2₁am, and the orthorhombic distortion of LBN a/b is merely 1.0019. The measurement of piezoelectric coefficient (d₃₃ ∼ 6 pC/N) and observation of striped domain structure confirm the ferroelectricity nature of LBN. This work deepens our understanding of BLSFs and may lead to the finding of more novel BLSFs with high performance.     

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.     

Structure and electrical properties of Ce-modified Ca1-xCexBi2Nb1.75(Cu0.25W0.75)0.25O9 high Curie point piezoelectric ceramics

Ca_1-xCe_xBi₂Nb_1.975(Cu_0.25W_0.75)_0.025O₉ (CBNCW-xCe: x = 0.00, 0.02, 0.04, 0.06, and 0.09) lead-free piezoelectric ceramics with improved piezoelectric properties were prepared by the traditional solid-state reaction method. The effects of CeO₂ doping on the microstructure and electrical properties were investigated in detail. XRD patterns and Rietveld refinement show that the crystal structures of the samples transform from the orthorhombic phase into the pseudotetragonal phase and that the lattice distortion is weakened. Raman and XPS spectra indicate that Ce ions exist with +3 and + 4 valences in the air sintered ceramics, in which Ce⁴⁺ replaces Nb⁵⁺, causing the weakened NbO₆ octahedral vibration of torsional and tensile and an increase in oxygen vacancies in the doped ceramics. When x = 0.04, it shows excellent comprehensive properties with a high d₃₃ value of 18.1 pC/N, a T_c value of 900 °C, and a ρ_dc value of 2.8 × 10⁵ Ω cm at 500 °C. Our results suggest that the CBNCW-0.04Ce ceramic is a promising candidate in high-temperature piezoelectric applications.     

Microstructure and electrical properties of 3-0 type composite of Na0.5Bi2.5Nb2O9-based bismuth-layered piezoceramics

The microstructure and electrical properties of 3-0 type composite of Na_0.5Bi_2.5Nb₂O₉-based bismuth layered piezoceramics modified by Al₂O₃ addition are investigated. The darker and plate-like grains, locating at the grain boundaries, are confirmed to be pure α-Al₂O₃ by high resolution transmission electron microscope, not a Bi₂AlNbO₇ pyrochlore phase. This 3-0 type Na_0.5Bi_2.5Nb₂O₉-Al₂O₃ composite piezoceramics have a large piezoelectric constant d₃₃ of 15.2pC/N with good temperature stability up to 600 °C, and good ferroelectric properties with a relatively large remnant polarization of ~11.6 μC/cm². These demonstrate that designing a 3-0 type composite structure would be an effective approach to tailor the microstructure and improve the electrical properties of bismuth layered piezoceremics for their potential applications at temperature up to 600 °C.     

Phase transition and electrical properties of Bi0.5(Na0.8K0.2)0.5ZrO3 modified (K0.52Na0.48)(Nb0.95Sb0.05)O3 lead-free piezoelectric ceramics

In this work, (1−x)(K_0.52Na_0.48)Nb_0.95Sb_0.05O₃−xBi_0.5(Na_0.8K_0.2)_0.5ZrO₃ [abbreviated as (1−x)KNNS−xBNKZ, x=0–0.06] lead-free ceramics were fabricated using solid-state reaction method. The effects of BNKZ contents on the phase structure, piezoelectric and ferroelectric properties were investigated. The phase boundaries including orthorhombic-tetragonal (O-T) and rhombohedral-tetragonal (R-T) multiphase coexistence were identified by XRD patterns and temperature-dependent dielectric constant by adding different content of BNKZ. A giant field induced strain (~0.25%) along with converse piezoelectric coefficient d₃₃^* (~629.4 pm/V) and enhanced ferroelectricity P_r (~38 μC/cm²) were obtained when x=0.02, while the specimen with x=0.03 presented the optimal piezoelectric coefficient d₃₃ of 215 pC/N, due to the O-T or R-T phase coexistence near room temperature respectively. These results show that the introduction of Bi_0.5(Na_0.8K_0.2)_0.5ZrO₃ is a very effective way to improve the electrical properties of (K_0.52Na_0.48)(Nb_0.95Sb_0.05)O₃ lead-free piezoelectric ceramics.     

Ultra-low temperature sintering and microwave dielectric properties of a novel temperature stable Na2Mo2O7-Na0.5Bi0.5MoO4 ceramic

The novel ultra-low temperature sintering (1-x)Na₂Mo₂O₇-xNa_0.5Bi_0.5MoO₄ ceramics have been obtained via solid-state reaction method for passive integration use. The Na₂Mo₂O₇ and Na_0.5Bi_0.5MoO₄ crystal phases are found to be compatible with each other from the results of XRD and SEM-EDS. With the x value changing from 0.36 to 1.00, the ε_r increases from 16.0 to 32.0 and the τ_f value varies from ?58 to 47 ppm/°C. At x = 0.75, the 0.25Na₂Mo₂O₇-0.75Na_0.5Bi_0.5MoO₄ ceramic sintered at an ultra-low sintering temperature of 580 °C can be densified (>96%) and possesses good microwave dielectric properties of an ε_r of 24.0, a Q × f value of 13,000 GHz (at 6.2 GHz), and a τ_f value of 3 ppm/°C. The theoretical ε_r and τ_f of the (1-x)Na₂Mo₂O₇-xNa_0.5Bi_0.5MoO₄ composites were calculated using the mixing law and in accordance with the measured values.