Structure,electrical and dielectric properties of Ca substituted BaTiO3 ceramics

BaTi_1-xCa_xO_3-x [BTC100x] ceramics were synthesized via solid-state reaction method. Effect of Ca substitution on the structure, electrical and dielectric properties of BTC100x ceramics was systematically investigated. Calcined BTC100x powders were in tetragonal phase when x?≤?0.01, whereas transformed to cubic at x?>?0.01. Additionally, the diffraction peak (200) shifted to lower angles with increasing x, indicating increased unit cell volume. Meanwhile, Ba_0.97Ca_0.03TiO₃ [BC3T] ceramic was prepared and studied, to compare with BaTi_0.97Ca_0.03O_2.97 (BTC3). It was found that pure BaTiO₃ [BT] and BC3T ceramics had the similar structural and dielectric properties, whereas BTC3 ceramic showed much difference，XRD patterns, Raman spectrum, impedance spectra and dielectric-temperature spectra provided strong evidence of Ca²⁺ substitution at Ti site in BT lattice. Finally, BTC100x ceramics were produced and dielectric properties were investigated. With increasing x, the Curie temperature decreased from 128?°C (BT) to 42?°C (BTC5).     

Effects of sintering method and BiFeO3 dopant on the dielectric and ferroelectric properties of BaTiO3–BiYbO3 based solid solution ceramics

(0.95–x) BaTiO₃–0.05 BiYbO₃–x BiFeO₃ (x?=?0, 0.01, 0.02, and 0.04) (abbreviated as (0.95–x) BT–0.05 BY–x BFO) ceramics were fabricated by conventional sintering (CS) and microwave sintering (WS) methods. Effects of sintering method and BFO dopant on the microstructure and electric properties of (0.95–x) BT–0.05 BY–x BFO ceramics were comparatively investigated. X-ray diffraction showed that all CS and WS samples presented a single perovskite phase. It was also found that WS ceramics possessed denser microstructure and finer grains compared to CS samples as indicated by the surface morphology characterization. Dielectric measurements revealed that all samples exhibited the weak relaxation behavior; however, the degree of relaxation behavior of BT–BY based ceramic could be strengthened by addition of BFO and by WS method. Moreover, the temperature and frequency stability could be improved with doped BFO. The density of 0.93BT–0.05BY–0.02BFO ceramic was found to be the largest while that of 0.94BT–0.05BY–0.01BFO ceramic was the smallest, thus, the dielectric constant of 0.93BT–0.05BY–0.02BFO was significantly larger than that of 0.94BT–0.05BY–0.01BFO and 0.94BT–0.05BY–0.04 BFO ceramics. minimum dielectric constant of (0.95–x) BT–0.05 BY–x BFO ceramic was obtained at x?=?0.01. Ferroelectric measurements indicated that all samples showed the slim hysteresis loop. The remnant polarization (P_r) and coercive field (E_C) of (0.95–x) BT–0.05 BY–x BFO ceramics first decreased and then increased with increasing x，the minimum values were obtained at x?=?0.01. Moreover, P_r and E_C of WS ceramics were slightly larger than those of CS ceramics, indicating that higher density and larger grain sizes contributed to enhancing the ferroelectric characteristic. These findings indicate that addition of moderate amount of BFO and use of WS technique can strengthen the degree of relaxation behavior and improve the ferroelectric properties of BT–BY based ceramics.     

Investigation of grain boundaries influence on dielectric properties in fine-grained BaTiO3 ceramics without the core–shell structure

Grain boundaries of the Ca-doped and fine-grained BaTiO₃ (BT) ceramics were investigated in order to understand the role of grain boundaries, using a high-resolution transmission electron microscope (TEM) analyses, X-ray diffraction (XRD) and chemical etching analyses. Electrical properties and complex impedance spectroscopy of multilayer ceramic capacitors (MLCs) using Ca-doped BT were also examined to investigate with reference to the roles of grain boundaries. Doped elements were peculiarly enriched at the grain boundaries and tetragonality of the BT ceramics recovered significantly after grain boundaries were etched. It is confirmed that the grain boundaries have a significant influence in stabilizing the temperature dependence of the dielectric properties, and that the residual stress is caused by grain boundaries with the grain growth inhibited during sintering. In addition, the high reliability of BT ceramics without the core–shell structure is considered to be due to the high resistivity of the grain boundaries.     

Densification,microstructure and mechanical properties of Ta4HfC5-based ceramics obtained from synthesized nanoscale powder

Solvothermal treatment was used to synthesize nanoscale 4TaC-HfC (Ta₄HfC₅) powder at a relatively low calcination temperature and in a short period (1400 °C, 2 h). The obtained powder had uniform size distribution and dispersion. Ta₄HfC₅ ceramics were then consolidated via spark plasma sintering at 2100 °C. Ceramics had a better densification and smaller mean grain size at a shorter sintering time compared with that of materials sintered using mechanical ball milling method. The densification behavior of ceramics deriving from synthesized or ball milled powders was analyzed and the mechanical properties of different samples were investigated. To further increase the mechanical properties, a nearly fully dense Ta₄HfC₅-MoSi₂ ceramic was sintered using the synthesized powder. The mechanical properties of the ceramic composite doubled the strength values. This processing route demonstrated to be a viable approach to synthesize nanoscale Ta₄HfC₅ powder with high purity and uniformity, and obtain higher performances ceramics once sintered.     

Remarkable piezoelectricity and stable high‐temperature dielectric properties of quenched BiFeO3–BaTiO3 ceramics

Effects of quenching process on dielectric, ferroelectric, and piezoelectric properties of 0.71BiFeO₃?0.29BaTiO₃ ceramics with Mn modification (BF–BT?xmol%Mn) were investigated. The dielectric, ferroelectric, and piezoelectric properties of BF–BT?xmol%Mn were improved by quenching, especially to the BF–BT?0.3 mol%Mn ceramics. The dielectric loss tanδ of quenched BF–BT?0.3 mol%Mn ceramics was only 0.28 at 500°C, which was half of the slow cooling one. Meanwhile, the remnant polarization P_r of quenched BF–BT?0.3 mol%Mn ceramics increased to 21 μC/cm². It was notable that the piezoelectric constant d₃₃ of quenched BF–BT?0.3 mol%Mn ceramics reached up to 191 pC/N, while the T_C was 530°C, showing excellent compatible properties. The BF–BT?xmol%Mn system ceramics showed to obey the Rayleigh law within suitable field regions. The Rayleigh law results indicated that the extrinsic contributions to the dielectric and piezoelectric responses of quenched BF–BT?xmol%Mn ceramics were larger than the unquenched ceramics. These results presented that the quenched BF–BT?xmol%Mn ceramics were promising candidates for high‐temperature piezoelectric devices.     

Influence of A‐site nonstoichiometry on the electrical properties of BT‐BMT

A stoichiometric and 2 mol% Ba deficient samples in the formulation 0.5BaTiO₃‐0.5BiMg_1/2Ti_1/2O₃ (BT‐BMT) were processed via a mixed oxide solid‐state route. The deficient sample exhibited a high relative permittivity (2100±15%) over the temperature range 90‐450°C and a low dielectric loss (tanδ < 0.01), maintained up to high temperature (430°C). The samples exhibited intrinsic conduction mechanism and showed an n‐type character. By introducing 2 mol% Ba vacancies, a dramatic influence on the dielectric loss was observed which was mainly associated with the trapping of electrons by barium‐oxygen vacancy pair associated with the intentionally produced cation vacancies. Thus, control of composition by creating deficiency allows fine tuning of the dielectric properties of BT‐BMT ceramics for applications in high‐temperature multilayered ceramic capacitors.     

Correlation between grain size and electrical properties of high-temperature lead-free 0.70BiFeO3-0.30BaTiO3 ceramics

0.70BiFeO₃-0.30BaTiO₃ (0.70BF-0.30BT) ceramics have been widely concerned because of their potential applications for high-temperature piezoelectric devices. In this work, a series of dense 0.70BF-0.30BT ceramics with average grain size variation from 0.55 to 6.0 μm were prepared. XRD results indicate that 0.70BF-0.30BT ceramics show the coexistence of rhombohedral and pseudo-cubic phases and the volume fraction of the rhombohedral phase increase with the grain size. The dielectric, ferroelectric and piezoelectric properties increase with the grain size initially from 0.55 to 5.0 μm and then decrease slightly. Values of d₃₃, P_r, and ε_r, of 0.70BF-0.30BT ceramics with the grain size of 5.0 μm are 185 pC/N, 21.2 μC/cm², and 638, respectively, about five times higher than those ceramics with fine-grain of 0.55 μm. Of particular importance is that 0.70BF-0.30BT ceramics with large grain sizes possess better piezoelectric thermal stability due to the much stabler poled domain state with the rising temperature. The detailed structural studies indicate that the enhanced electric properties are owing to the significantly improved domain motion and the increased lattice distortion. This clarifying the relationship between electrical properties and grain size offers a novel way of improving the performances of piezoceramics.     

Defect mechanisms in BaTiO3‐BiMO3 ceramics

Often, addition of BiMO₃ to BaTiO₃ (BT) leads to improvement in resistivity with a simultaneous shift to n‐type conduction from p‐type for BT. In considering one specific BiMO₃ composition, that is, Bi(Zn_1/2Ti_1/2)O₃ (BZT), several prospective candidates for the origin of this n‐type behavior in BT‐BZT were studied—loss of volatile cations, oxygen vacancies, bismuth present in multiple valence states and precipitation of secondary phases. Combined x‐ray and neutron diffraction, prompt gamma neutron activation analysis and electron energy loss spectroscopy suggested much higher oxygen vacancy concentration in BT‐BZT ceramics (>4%) as compared to BT alone. X‐ray photoelectron spectroscopy and x‐ray absorption spectroscopy did not suggest the presence of bismuth in multiple valence states. At the same time, using transmission electron microscopy, some minor secondary phases were observed, whose compositions were such that they could result in effective donor doping in BT‐BZT ceramics. Using experimentally determined thermodynamic parameters for BT and slopes of Kröger‐Vink plots, it has been suggested that an ionic compensation mechanism is prevalent in these ceramics instead of electronic compensation. These ionic defects have an effect of shifting the conductivity minimum in the Kröger‐Vink plots to higher oxygen partial pressure values in BT‐BZT ceramics as compared to BT, resulting in a significantly higher resistivity values in air atmosphere and n‐type behavior. This provides an important tool to tailor transport properties and defects in BT‐BiMO₃ ceramics, to make them better suited for dielectric or other applications.     

3D printing of doped barium-titanate using robocasting - Toward new generation lead-free piezoceramic transducers

Lead-free piezoelectric ceramics, most commonly prepared via conventional process based on a solid-state synthesis, can be used as acoustical transducers or sensors in many application fields. Particularly in some applications where specific geometries are desirable, the need of complex, time consuming, and costly operations could make conventional process inappropriate. This paper proposes an alternative solution based on additive manufacturing (AM), which is of great interest to control and shape the structure in an automatic manner. A formulation of ceramic slurry, consisting of 80%wt doped barium titanate (BT) and organic mixture, was investigated. The synthesized slurry is revealed to be compatible with the robocasting technique while maintaining good mechanical strength after debinding and sintering steps. Empirical measures together with microscopic analysis confirm high densities of the printed BT ceramics (∼ 95% after sintering), which is consistent to those obtained in literatures. To better assess the material and process performances, microstructural, dielectric and piezoelectric characterizations are conducted on both 3D printed and conventional BT ceramics. The results demonstrate that the printed samples give rise to excellent dielectric and piezoelectric properties (d₃₃ coefficient of 260 pC/N and dielectric constant of 1800), which are very close to the values obtained by conventional method on the same composition. As only a few and recent works have been found in the literatures on such systems, this study highlights the considerable and growing potential of robocasting techniques in the field of piezoelectric ceramics. The obtained d₃₃ coefficient is revealed as the highest value reported for printed BT doped systems.     

Enhancement of dielectric properties and energy storage performance in 3Y-TZP ceramics with BaTiO3 additives

With the fast charge-discharge speed and ultrahigh power density, electrostatic energy storage materials offer great potential in the applications for pulsed power systems. As a very important member of structural ceramics, 3Y-TZP (3 mol% Y₂O₃ doped tetragonal zirconia polycrystals) has shown extraordinary mechanical properties. However, the research on their energy storage performance is still lacking. Herein, a ferroelectric phase, BaTiO₃ (BT), was introduced and demonstrated to improve the dielectric properties and energy storage performance of 3Y-TZP ceramic matrix via the conventional solid-state reaction method. With increasing the BT content from 0 to 15 mol%, the permittivity of the composite ceramics could be effectively increased from 40.2 to 64.1 measured at 1 kHz. Simultaneously, the dielectric loss could be effectively decreased by depressing the response of charged defects, which was further interpreted by the thermally stimulated depolarization current technique. Meanwhile, the breakdown strength showed a typical increase-then-decrease trend with increasing BT content, and reached their maximum values when doped with 7 mol% BT. Together with the enhancement of dielectric properties, the 7 mol% BT-doped 3Y-TZP ceramics exhibited a maximum energy storage density of 0.42 J/cm³, which was approximately 150% larger than that of the pure 3Y-TZP ceramics.     

Microstructure and electrical properties of Er-doped 0.67 Pb(Mg1/3Nb2/3)O3-0.33PbTiO3 ceramics with BaTiO3 templates

In this study, [001]-oriented Er-doped 0.67 Pb(Mg_1/3Nb_2/3)O₃-0.33PbTiO₃ (0.67PMN-0.33 PT) textured ceramics with different BaTiO₃ (BT) template concentrations were explored. The samples were prepared by tape-casting. Er³⁺ was added to modify the electrical properties of the polycrystalline ceramics, and the BT template was used to improve the texture of polycrystalline ceramics. The 0.67PMN-0.33 PT textured ceramics contained coexisting rhombohedral and tetragonal phases. The ceramics became increasingly textured as the sintering temperature increased up to 1250 °C. The piezoelectric coefficient of 0.67PMN-0.33 PT with 5 wt% BT was 634 pC/N, which is 1.2 times than that of randomly oriented 0.67PMN-0.33 PT. The strain of the ceramic with 5 wt% BT increased by 12.5% relative to a random control specimen. Analysis of the electrical properties and microstructure suggested that the enhancement of the piezoelectric coefficient and strain may be caused by the addition of Er³⁺ and the BT template. First, the directional growth of grains along the template affected the change-of-phase distribution of the system and formed a more adaptive phase. Second, Er³⁺ was substitutionally doped on the A-site of the perovskite to form local heterostructures. Finally, the relaxation components of the templates and Er³⁺ changed in the solid solution with the matrix. The solid solution of the BT templates and Er-doped-matrix powder changed the relaxation degree, which affected the interactions at the polar nanoregions and increased the piezoelectric coefficient of the ceramics.     

Microstructure,mechanical behavior and oxidation resistance of disorderly assembled ZrB2-based short fibrous monolithic ceramics

Axially aligned fibrous monolithic ceramics present non-catastrophic fracture behavior via crack deflection and delamination along cell boundaries. However, severe in-plane anisotropy and time-consuming preparation procedures prevent their extensive promotion. The introduction of high content of weak phase components with poor oxidation resistance in weak interface destroys the excellent oxidation resistance of ceramic matrix. In this work, ZrB₂-based short fibrous monolithic (SFM) ceramics with in-plane isotropic mechanical properties and excellent oxidation resistance were easily prepared by hot pressing randomly assembled short ceramic fibers. The microstructure and mechanical behavior of ZrB₂-based SFM ceramics densified at various temperatures were systematically investigated. The mechanical properties of ZrB₂-based SFM ceramics slightly improved with the increase of sintering temperature. ZrB₂-based SFM ceramics exhibited excellent oxidation resistance and remained intact without macroscopic cracks after ablation for 615 s in oxyacetylene flame with maximum temperatures exceeding 2150 °C. The oxidation behavior was analyzed in detail.     

Si3N4-BN-SiCN ceramics with unique hetero-interfaces for enhancing microwave absorption properties

SiCN-based ceramics with broadband and strong microwave absorption properties are desired for the structural and functional integration of ceramic matrix composites. The elemental composition and thermal expansion coefficients of the ceramics matrix crucially affect its microstructure and electromagnetic wave (EMW) absorption properties. BN layer with lower electrical conductivity and higher specific area, exhibits both the impedance matching characteristic and EMW attenuation in the process of multiple reflections, electrical conductivity loss, dipole polarization and interfacial polarization. Therefore, Si₃N₄-BN-SiCN ceramics, which were synthesized using chemical vapor infiltration (CVI) method, construct unique hetero-interface of Si₃N₄-BN, Si₃N₄–SiCN and BN-SiCN. Therefore, the Si₃N₄-BN-SiCN ceramics have outstanding EMW absorption performance and realize an effective absorption bandwidth (EAB) that covers the whole X band and the minimum reflection coefficient (RC) reaches -18.43 dB at a thickness of 3.37 mm.     

Grain size effects and structure origin in high-performance BaTiO3-based piezoceramics with large grains

Grain size shows significant influence on electrical properties of piezoceramics. However, there are few works to investigate the grain size effects in high-performance and large-grain piezoceramics and uncover the structure origin. In this work, large grain size from ~53 to ~92 µm was achieved in a high-performance BaTiO₃ (BT)-based ceramic via tuning sintering conditions. With grain size increasing, the ceramics exhibit same multiphase coexistence state, similar phase transition temperature, upward T_C dielectric peaks and reduced diffuseness degree. Because of the larger and more complex non-180° domains within bigger grains, the improvement in remnant polarization (P_r), coercive field and negative strain were observed in bigger-grain ceramics. The elevated P_r finally leads to the piezoelectric coefficient d₃₃ increasing from 500 to 650 pC/N. However, too large grains may cause the reduced strain due to the high remnant strain in first cycle. Therefore, big grain size is conducive to achieve high piezoelectricity while moderate grain size can facilitate strain response in high-performance ceramics with large grains, which is quite different with pure BT ceramic. This work presents insights into the grain size effects and affords guides to further optimize electrical properties in high-performance piezoceramics with large grains.     

Relaxor ferroelectric behavior of La substituted BPZT ceramics

Barium titanate (BT) based compounds have been of great importance in the fabrication of multilayer ceramic capacitors. Several substitutions are used to tailor its structural, electrical and ferroelectric properties. Substituent like zirconium (Zr) for titanium results in decrease in non-centrosymmetric tetragonal to centrosymmetric cubic phase transition temperature (Curie temperature). Whereas substituent like lead (Pb) for barium results in the increase in the Curie temperature. Here we are reporting effect of lanthanum (La) substitution on the properties of Zr and Pb co-substituted BT. The system Ba_0.80−xLa_xPb_0.20Ti_0.90Zr_0.10O₃ with x = 0 and 0.01 was selected for study of structural and dielectric properties. Samples were prepared using solid state ceramic route. X-ray diffraction studies (XRD) were used to confirm single phase structure. Dielectric properties were studied as a function of frequency and temperature. Composition with x = 0.01 was found to show relaxor behavior.     

Structural,magnetic, vibrational and impedance properties of Pr and Ti codoped BiFeO3 multiferroic ceramics

Single-phase (Bi_1−xPr_x)(Fe_1−xTi_x)O₃ ceramics (x=0.03, 0.06, and 0.10 as BPFT-3, BPFT-6 and BPFT-10, respectively) were synthesized by conventional solid state reaction method. The effect of varying Pr and Ti codoping concentration on the structural, magnetic, dielectric and optical properties of the BPFT ceramics have been investigated. X-ray diffraction indicated pure rhombohedral phase formation for BPFT-3 and BPFT-6 ceramics, however, a structural phase transition from a rhombohedral to an orthorhombic phase has been observed for BPFT-10 ceramic. The maximum remnant magnetization of 0.1824 emu/g has been observed in BPFT-6. With increasing codoping concentration the room temperature dielectric measurements showed enhancement in dielectric properties with reduced dielectric loss. UV–vis diffuse reflectance spectra demonstrated the strong absorption of light in the visible region for a band gap variation 2.31–2.34 eV. Infrared spectroscopy indicated the shifting of Bi/Pr–O and Fe/Ti–O bonds vibrations and change in Fe/Ti–O bond lengths. Decrease in the conductivity on increasing Pr and Ti concentration in BFO is attributed to an enhancement in the barrier properties leading to suppression of lattice conduction path arising due to lattice distortion as confirmed from impedance analysis.     

Mechanical and thermal expansion properties of Dy2TiO5 ceramic neutron absorbers with small grains

Dy₂TiO₅ ceramics with small grain size range of 1.5–3 μm were successfully prepared by microwave sintering method. The phase composition, microstructure, thermal expansion, stability, corrosion resistance and neutron absorption properties of Dy₂TiO₅ ceramics were investigated. The results show that Dy₂TiO₅ ceramics possess high mechanical properties due to the small grain size, with a microhardness of 12.26 GPa. The addition of Mo significantly reduces the thermal expansion phenomenon of the sample. The oxide film formed on the surface of the Dy₂TiO₅ ceramic enhances its excellent corrosion resistance. In addition, the Dy₂TiO₅ ceramic shows excellent neutron absorption with 87.34% neutron absorption and over 94% thermal neutron absorption in 8 cm thick particles.     

Enhancing the dielectric and energy storage properties of lead-free Na0.5Bi0.5TiO3–BaTiO3 ceramics by adding K0.5Na0.5NbO3 ferroelectric

A novel strategy of enhancing the dielectric and energy storage properties of Na_0.5Bi_0.5TiO₃–BaTiO₃ (NBT–BT) ceramics by introducing a K_0.5Na_0.5NbO₃ (KNN) ferroelectric phase is proposed herein, and its underlying mechanism is elucidated. The lead-free KNN ceramic decreases the residual polarisation and increases the electric breakdown strength of the NBT–BT matrix through the simultaneous modification of its A-sites and B-sites. The obtained NBT?BT?x?KNN ceramics have a perovskite structure with unifying grains. A bulk 0.9NBT–BT–0.1KNN ceramic sample with a thickness of 0.2 mm possesses a high energy storage density of 2.81 J/cm³ at an applied electric field of 180 kV/cm. Moreover, it exhibits good insulation properties and undergoes rapid charge and discharge processes. Therefore, the obtained 0.9NBT–BT–0.1KNN ceramic can be potentially used in high-power applications because of its high energy density, good insulation properties, and large discharge rate.     

Dielectric properties and impedance analysis of BaTiO3-based ceramics with core-shell structure

In this paper, a core-shell structure, where the BaTiO₃ (BT) particles were coated with 0.25Bi(Zn_1/2Ti_1/2)O₃-0.75BaTiO₃ [BT@x(0.25BZT-0.75BT)] by sol-gel method, was fabricated and confirmed by transmission electron microscopy (TEM). The impedance data of BT, 0.25BZT-0.75BT and BT@x(0.25BZT-0.75BT) (x=0.5–1.0) ceramics was collected and fitted by different equivalent circuits. The core and shell regions of BT@x(0.25BZT-0.75BT) (x=0.5–1.0) ceramics can be separated in complex impedance plots (fitted by a 4RC equivalent circuit), according to the activation energies of BT and 0.25BZT-0.75BT. The calculated activation energy of the core part in BT@x(0.25BZT-0.75BT) ceramics is relatively stable, being closer to the activation energy (0.86 eV) of BT, while the activation energy of the shell was found to increase from 0.28 eV to 0.53 eV with increasing the shell thickness. The average core/shell ratio (d_gc/d_gs) for BT@0.8(0.25BZT-0.75BT) ceramics was found to be on the order of 7.26, calculated by a modified two-layer dielectric model. In addition, Lichtenecker formula was used to simulate the dielectric constant of BT@0.8(0.25BZT-0.75BT) ceramics at room temperature and the simulated results are in agreement with the measured values.     

Highly enhanced dielectric loss of MgO-doped Ba0.67Sr0.33TiO3 ceramics prepared by a non-contamination DCC-HVCI method

MgO-doped Ba_0.67Sr_0.33TiO₃ (BST) ceramics with uniform microstructure and enhanced dielectric loss were prepared by direct coagulation casting via high valence counter ions (DCC-HVCI) method. MgO was utilized as acceptor dopant as well as coagulating agent to release Mg²⁺ solidifying ceramic suspensions. Effect of sintering temperature and MgO doping content on microstructure and dielectric properties of BST ceramics was investigated. It was found that the loss tangent value (tan δ) decreased remarkably from 0.025 to 0.004 with increasing MgO concentration from 0.5 to 1.5 mol%. The 1.5 mol% MgO-doped BST ceramics processed high density of 99.5% and tan δ of 0.004 which is improved by 150% compared with that of dry-pressed samples. This improvement can be attributed to the ubiquitous distribution of MgO in BST ceramic matrix leading to the enhanced inhibitive effect. This paper provides a novel facial route to prepare high-performance functional ceramics with high reliability and low cost.