Structure,dielectric, and ferroelectric properties of (1-x)Bi0.5Na0.5TiO3 – X K0.5Na0.5NbO3 (0 ≤ x ≤ 0.1) solid solution

The correlation of the phase structure, dielectric, and ferroelectric properties of lead-free (1-x)(Na_0.5Bi_0.5)TiO₃–xK_0.5Na_0.5NbO₃ (NBTKNx) (0 = x ≤ 0.1) polycrystalline ceramics, fabricated via a solid state reaction technique, were investigated. The Rietveld refinement allowed identifying the crystallographic transformation from a rhombohedral to a coexisting rhombohedral-tetragonal or tetragonal long range-ordered ferroelectric (FE) phase. The dielectric investigations showed an increase of the dielectric diffuseness (1.53 = γ ≤ 1.73) and a clear shift of the depolarization temperature (T_d) to a lower temperature while increasing substitution. More importantly, the lattice disorder also generated a plateau-like dielectric anomaly, leading to a thermally stable ϵ_r ∼2859 ± 20% (120–500 °C) and ∼3112 ± 10% (120–420 °C) for x = 0.075 and 0.1 samples, respectively. At room temperature (RT), Raman spectroscopy investigations revealed a downshift of the frequencies as a function of the composition with an inhomogeneous broadening of the Raman lines. On heating, Raman spectra showed changes in the region where the dielectric transitions are observed. Moreover, the composition dependence of the current peaks in the I-E loops confirmed the occurrence of a phase transition from a non-ergodic polar phase to an ergodic weakly polar after the applying of an electric field of 60 kV/cm⁻¹.     

Orthorhombic‐pseudocubic phase transition and piezoelectric properties of (Na0.5K0.5)(Nb1−xSbx)‐SrZrO3 ceramics

0.96(Na_0.5K_0.5)(Nb_1?xSb_x)‐0.04SrZrO₃ ceramics with 0.0≤x≤0.06 were well sintered at 1060°C for 6 hours without a secondary phase. Orthorhombic‐tetragonal transition temperature (T_O‐T) and Curie temperature (T_C) decreased with the addition of Sb₂O₅. The decrease in T_C was considerable compared to that in T_O‐T, and thus the tetragonal phase zone disappeared when x exceeded 0.03. Therefore, a broad peak for orthorhombic‐pseudocubic transition as opposed to that for orthorhombic‐tetragonal transition appeared at 115°C‐78.2°C for specimens with 0.04≤x≤0.06. An orthorhombic structure was observed for specimens with x≤0.03. However, the polymorphic phase boundary structure containing orthorhombic and pseudocubic structures was formed for the specimens 0.04≤x≤0.06. Furthermore, a specimen with x=0.055 exhibited a large piezoelectric strain constant of 325 pC/N, indicating that the coexistence of orthorhombic and pseudocubic structures could improve the piezoelectric properties of (Na_0.5K_0.5)NbO₃‐based lead‐free piezoelectric ceramics.     

Thermally Stable BaTiO3‐Bi(Mg2/3Nb1/3)O3 Solid Solution with High Relative Permittivity in a Broad Temperature Usage Range

A combined X‐ray diffraction (XRD), Raman spectra, X‐ray photoelectron spectroscopy, Scanning electron microscopy, and dielectric characterization of (1–x)BaTiO₃?xBi(Mg_2/3Nb_1/3)O₃ ceramic system were investigated for compositions of 0 ≤ x ≤ 0.2. Single‐phase perovskite‐type XRD patterns were observed for all compositions. A systematically structural change from tetragonal to pseudocubic symmetry occurred at 0.04 < x < 0.06, which agrees well with the analysis of Raman spectra. Dielectric measurements indicated that the crossover from a classic ferroelectric to relaxor ferroelectric occurred at x ≥ 0.04. Compared with other compositions, the temperature independence of relative permittivity at T > T_m significantly ameliorated at x = 0.1: near‐stable temperature coefficient of higher relative permittivity (~6800 ± 15%) and the corresponding loss tanδ ≤ 0.09 over a more broader temperature range of 25°C–240°C (1 kHz), which indicates that this ceramic is a promising dielectric material for elevated temperature dielectrics.     

CaTiO3 induced ferroelectric phase coexistence and low temperature dielectric relaxation in BaTiO3–BaZrO3 ceramics

The series of 0.86BaTiO₃–(0.14?x)BaZrO₃–xCaTiO₃ (abbreviated as BT–BZ–xCT) ceramics with 0.03 ≤ x ≤ 0.11 were studied to obtain high piezoelectric properties. Rietveld refinement analysis indicated that the BT–BZ–CT compositions follow a gradual rhombohedral (R) → orthorhombic (O) + R → O + tetragonal (T) → T phase transformation with increasing x. Clear evidence of the series of ferroelectric phase transitions was also found in the dielectric results. The R‐O and O‐T transition temperature shifted close to ambient temperature, while the Curie temperature slightly increased with increasing x. In addition to the dielectric loss peaks associated with the structural phase transitions, a broad low‐temperature dielectric loss peak was detected in the R phase at T = 90‐150 K. This dielectric relaxation was attributed to the domain wall freezing and fits well to the Vogel‐Fulcher model with activation energy E_a ≈ 60‐300 meV and freezing temperature T_VF ≈ 75‐140 K. High piezoelectric strain coefficient (d₃₃*) of about 1030 pm/V at 10 kV was achieved at x = 0.07, and a high Curie temperature (T_C) was maintained at about 375 K.     

Dielectric Properties and Impedance Analysis of K0.5Na0.5NbO3–Ba2NaNb5O15 Ceramics with Good Dielectric Temperature Stability

(1?x)(K_0.5Na_0.5)NbO₃–xBa₂NaNb₅O₁₅ [(1?x)KNN–xBNN, 0 ≤ x ≤0.1] ceramics were prepared by solid‐state reaction method. X‐ray diffraction analysis of the ceramics revealed that the crystal structure changed from orthorhombic to rhombohedral with increasing BNN content. Dielectric measurement showed that the ceramics exhibited good dielectric temperature stability over a wide temperature range. Basic mechanisms of the conduction and relaxation processes have been investigated using impedance spectroscopy analyses. It was concluded that the conduction and relaxation processes were thermally activated and oxygen vacancies were the possible ionic charge carriers at higher temperatures.     

Large Electromechanical Strain in Lead‐Free Binary System K0.5Bi0.5TiO3‐Bi(Mg0.5Ti0.5)O3

Solid solution formation in the lead‐free binary system (1?x)K_0.5Bi_0.5TiO₃?xBi(Mg_0.5Ti_0.5)O₃ has been studied for compositions x ≤ 0.12. X‐ray powder diffraction shows single‐phase perovskite for x < 0.1, and a mixed phase region between tetragonal and pseudocubic phases for compositions 0.04 ≤ x ≤ 0.06. Large electromechanical strains of ~0.3% at fields of 50 kV/cm are recorded in the mixed phase region, with d₃₃* (S_max/E_max) values of ~600 pm/V. The materials sustain polarization at low electric fields with remnant polarization ~18 μC/cm² and coercive field ~20 kV/cm for x = 0.06. Relative permittivity‐temperature plots display relaxor characteristics, with peak temperature ~340°C.     

Structure and Dielectric Properties of BaTiO3–BiYO3 Perovskite Solid Solutions

(1?x)BaTiO₃–xBiYO₃ [(1?x)BT–xBY] polycrystalline ceramics were prepared by solid‐state reaction method. The ceramics are in tetragonal phase when x ≤ 0.04, transform to pseudocubic at x ≥ 0.06, showing a classic ferroelectric to relaxor transition at x = 0.06, where the phase transition temperature was found to shift to higher temperature with increasing frequency. The dielectric permittivity peaks were analyzed by the modified Curie–Weiss law. Both parameters ΔT_diffuse and ΔT_relaxor were found to increase with increasing BY content, demonstrating a stronger relaxor characteristic.     

Composition‐ and Temperature‐Dependent Large Strain in (1−x)(0.8Bi0.5Na0.5TiO3–0.2Bi0.5K0.5TiO3)– xNaNbO3 Ceramics

Ternary solid solutions of (1 ? x)(0.8Bi_0.5Na_0.5TiO₃–0.2Bi_0.5K_0.5TiO₃)– xNaNbO₃ (BNKT–xNN) lead‐free piezoceramics were fabricated using a conventional solid‐state reaction method. Pure BNKT composition exhibited an electric‐field‐induced irreversible structural transition from pseudocubic to ferroelectric rhombohedral phase at room temperature. Accompanied with the ferroelectric‐to‐relaxor temperature T_F‐R shifted down below room temperature as the substitution of NN, a compositionally induced nonergodic‐to‐ergodic relaxor transition was presented, which featured the pinched‐shape polarization and sprout‐shape strain hysteresis loops. A strain value of ~0.445% (under a driving field of 55 kV/cm) with large normalized strain of ~810 pm/V was obtained for the composition of BNKT–0.04NN, and the large strain was attributed to the reversible electric‐field‐induced transition between ergodic relaxor and ferroelectric phase.     

Crystal structure,dielectric properties,and optical bandgap control in KNbO3–BiMnO3 ceramics

(1 − x)KNbO₃–xBiMnO₃ (0 ≤ x ≤ 0.25) ceramics were prepared by the solid-state reaction method. An X-ray diffraction analysis combined with Raman spectroscopy showed the co-solubility of Bi and Mn in the orthorhombic structure to be less than 5% BiMnO₃. Orthorhombic and pseudocubic symmetries coexist in the 0.05 ≤ x ≤ 0.15 region, coinciding with a bimodal grain size distribution. This coexistence of crystal symmetries is further corroborated by several anomalies in the dielectric behavior, which can be ascribed to structural phase transitions. For x ≥ 0.20, only one dielectric anomaly is detected around 100°C, which is commensurate with in situ Raman spectroscopy analysis. This work also shows that Bi/Mn co-doping can be employed to tailor the bandgap of KNbO_3, which narrows continuously with increasing x, resulting in ∼1-eV narrowing for single-phase x = 0.25. This may offer the possibility to employ this ferroic material in photoresponsive technologies.     

Piezoelectric properties of (Na0.5K0.5)(Nb1‐xSbx)O3‐SrTiO3 ceramics with tetragonal‐pseudocubic PPB structure

CuO‐added 0.96(Na_0.5K_0.5)(Nb_1‐xSb_x)O₃‐0.04SrTiO₃ ceramics sintered at the low temperature of 960°C for 10 hours showed dense microstructures and high relative densities. The specimens with 0.0 ≤  x ≤ 0.04 had orthorhombic‐tetragonal polymorphic phase boundary (PPB) structure. Tetragonal‐pseudocubic PPB structure was observed in specimens with 0.05 ≤  x ≤ 0.07, while the specimen with x = 0.08 has a pseudocubic structure. The structural variation in the specimens is explained by the decreases in the orthorhombic‐tetragonal transition temperature and Curie temperature with the addition of Sb⁵⁺ ions. The specimens with 0.05 ≤  x ≤ 0.07, which have tetragonal‐pseudocubic PPB structure, had large electric field‐induced strains of 0.14%‐0.016%. Moreover, these specimens also showed increased d₃₃ values between 280 pC/N and 358 pC/N. In particular, the specimen with x = 0.055 showed particularly enhanced piezoelectric properties: d₃₃ of 358 pC/N, k_p of 0.45, and the electric field‐induced strain of 0.16% at 4.5 kV/mm.     

The influence of phase transition on electrocaloric effect in lead‐free (Ba0.9Ca0.1)(Ti1−xZrx)O3 ceramics

In this paper, the influence of phase evolution on polarization change and electrocaloric response in lead‐free (Ba_0.9Ca_0.1)(Ti_1?xZr_x)O₃ ceramics (BCTZ) was systematically investigated. With increasing Zr/Ti ratio, the phase structure and phase transition behavior were greatly changed, resulting in various temperature and electric field dependence of electrocaloric responses. For x=0.05, a peak electrocaloric temperature change 1.64 K (at 130°C) and corresponding entropy change 1.78 J·kg^?1·K^?1 were obtained for 0‐7 kV·mm^?1 electric field. Negative electrocaloric temperature change in ?0.1 K was obtained below Curie temperature (T_c), which may be induced by the orthorhombic‐tetragonal ferroelectric phase transition. With the increase in x, the peak value of the electrocaloric response decreased but much better temperature stability was observed. Simultaneously the negative electrocaloric response gradually disappeared with the disappearance of the low temperature ferroelectric‐ferroelectric phase transition. For x=0.2, electrocaloric response showed good temperature stability ranging from room temperature to 130°C, attributing to the relaxor ferroelectric feature.     

Ferroelectric and magnetic properties in (1−x)BiFeO3–x(0.5CaTiO3–0.5SmFeO3) ceramics

Multiferroic ceramics were prepared and characterized in (1?x)BiFeO₃–x(0.5CaTiO₃–0.5SmFeO₃) system by a standard solid‐state reaction process. The structure evolution was investigated by X‐ray diffraction and Raman spectrum analyses. The refinement results confirmed the different phase assemblages with varying amounts of polar rhombohedral R3c and nonpolar orthorhombic Pbnm as a function of the substitution content. In the compositions range of 0.2≤x≤0.5, polar R3c and nonpolar Pbnm coexisted, which was referred to polar‐to‐nonpolar morphotropic phase boundary (MPB). According to the dielectric and DSC analysis results, the ceramics with x≤0.2 changed to diffused ferroelectric, and the ferroelectric properties were enhanced significantly. Two dielectric relaxations were detected in the temperature range of 200‐300 K and 500‐700 K, respectively. The high‐temperature dielectric relaxation was attributed to the grain‐boundary effects. While the low temperature dielectric relaxation obtained in the samples with x=0.3‐0.5 was related to the charge transfer between Fe²⁺ and Fe³⁺. The magnetic hysteresis loops measured at different temperature indicated the enhanced magnetic properties in the present ceramics, which could be attributed to the suppressed cycloidal spin magnetic structure by Ti ions. In addition, the rare‐earth Sm spin moments might also affect the magnetic properties at relatively lower temperature.     

Growth and electrical properties of Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3 lead-free single crystals by the TSSG method

A series of NBT-KBT lead-free crystals with dimensions of Φ 35×10 mm were successfully grown by the TSSG method. The as-grown crystals possess rhombohedral perovskite structure at room temperature. The curves ε(T) for all crystals show two abnormal dielectric peaks. The depolarization temperatures T_d derived from the first peak of curves tan δ(T) vary with the KBT content, which are 130, 150, 140, and 115 °C respectively, for (100−x)NBT−xKBT (x=5, 8, 12, 15) crystals, being well consistent with the T_d obtained from the temperature dependence of k_t. A notable thermal hysteresis, ΔT≈35 °C, for ferroelectric-antiferroelectric phase transition was also disclosed for 92NBT-8KBT crystal. The investigation of orientation dependence for electrical properties disclosed the dielectric parameters show weak anisotropy. The piezoelectric constants (d₃₃) are 147, 175, 205, 238 pC/N and the values of k_t are 38%, 52%, 52%, 54%, respectively for (100−x)NBT−xKBT (x=5, 8, 12, 15) crystals.     

Hexavalent (Me - W/Mo)-modified (Ba,Ca)TiO3-Bi(Mg,Me)O3 perovskites for high-temperature dielectrics

We report on the synthesis of complex lead-free perovskite-type (1−x)(Ba_0.8Ca_0.2)TiO₃–xBi(Mg_0.75W_0.25)O₃ (BCT-xBMW) and (1−x)(Ba_0.8Ca_0.2)TiO₃-xBi(Mg_0.75Mo_0.25)O₃ (BCT-xBMM) solid solutions via conventional solid-state reaction route. The sintering temperature was adjusted as a function of composition x to obtain dense samples (relative densities over 95%) at the same time minimizing bismuth evaporation. X-ray diffraction analysis shows the formation of single-phase perovskites for 0 ≤ x ≤ 0.10 in the BCT-xBMW series and increasing concentrations of impurity phases for x ≥ 0.15 and for x ≥ 0.05 in BCT-xBMM. A transition from a tetragonal to pseudo-cubic perovskite structure is observed in BCT-xBMW and BCT-xBMM at x = 0.05. The dielectric response has been characterized between −60°C and 300°C for BCT-xBMW, and between 30°C and 300°C for BCT-xBMM using impedance spectroscopy, showing a transition from ferroelectric to relaxor-like behavior at x ≥ 0.05. Additional polarization and Raman spectroscopy measurements reveal the occurrence of highly disordered systems. Analysis of the Raman spectra indicates structural phase changes and lattice modifications caused by chemical substitution. For the composition 0.8Ba_0.8Ca_0.2TiO₃-0.2Bi(Mg_0.75W_0.25)O₃, a temperature-stable permittivity of about 600 (±15% between −60°C and 300°C) and small losses of tanδ < 0.02 for T ≤ 230°C at 1 kHz are observed_, making it a suitable dielectric material for high-temperature capacitors.     

Influence of BaSnO3 additive on the energy storage properties of Na0.5Bi0.5TiO3-based relaxor ferroelectrics

(1-x)NBT-xBSN (0.1?≤?x?≤?0.35) ceramics were prepared by solid state methods and their energy storage properties and high-temperature capacitor applications were systematically investigated. All samples showed a perovskite structure and the structure transformed to lower symmetry orthorhombic phase (x?≥?0.1) from rhombohedral phase (x?<?0.1) to with the addition of BSN. The more addition content of BSN significantly decreases phase transition temperature T_m of NBT ceramics. The x?=?0.25 sample exhibits a stable relative permittivity of 1605?±?15% in a broad temperature range of 38?°C to 319?°C. With increasing BSN concentration, the slope of the P-E loops and the energy loss gradually decreases. When x?=?0.25, a high breakdown strength of 190?kV/cm and the maximum discharge energy density of 1.91?J/cm³ were obtained, of which the energy efficiency was as high as 86.4%. Thus, it was believed that our work could provide a significant guidance for designing the new system for energy storage.     

Thermally‐induced phase transformations in Na0.5Bi0.5TiO3–KNbO3 ceramics

The structures and functional properties of Na_0.5Bi_0.5TiO₃–xKNbO₃ (NBT‐xKN) solid solutions, with x in the range from 0.01 to 0.09, were investigated using a combination of high‐resolution synchrotron X‐ray powder diffraction (SXPD) and ferroelectric property measurements. For low KN contents, an irreversible transformation from cubic to rhombohedral phases was observed after the application of a high electric field, indicating that the polar nanoregions (PNRs) in the unpoled state can be transformed into metastable long‐range ordered ferroelectric domains in the poled state. In contrast, the near‐cubic phase of the unpoled ceramics was found to be remarkably stable and was retained on cooling to a temperature of ?175°C. Upon heating, the field‐induced metastable ferroelectric rhombohedral phase transformed back to the nanopolar cubic state at the structural transformation temperature, T_ST, which was determined as approximately 225°C and 125°C for KN contents of 3% and 5% respectively. For the field‐induced rhombohedral phase in the poled specimens, the pseudo‐cubic lattice parameter, a_p, exhibited an anomalous reduction while the inter‐axial angle increased towards a value of 90° on heating, resulting in an overall increase in volume. The observed structural changes were correlated with the results of temperature‐dependent dielectric, ferroelectric and depolarization measurements, enabling the construction of a phase diagram to define the stable regions of the different ferroelectric phases as a function of composition and temperature.     

Impedance spectroscopy,B-site cation ordering and structure–property relations of (1 − x) La[Al0.9(Mg0.5Ti0.5)0.1]O3–x CaTiO3 ceramics for 5G dielectric waveguide filters

Dense (1 ? x) La[Al_0.9(Mg_0.5Ti_0.5)_0.1]O₃–x CaTiO₃ ceramics were synthesized via solid-state reaction. The crystal structure and microwave dielectric properties of the ceramics were systematically investigated. Rietveld refinement revealed that when x ≤ 0.2, the ceramics had a rhombohedral structure with an R-3c space group. When x ≥ 0.5, the ceramics had an orthorhombic structure with a Pbnm space group. Selected area electron diffraction and Raman spectroscopy analyses proved that the microwave dielectric ceramics had a B-site order, which accounted for the great improvement in microwave dielectric properties. The content of oxygen vacancies was identified through X-ray photoelectron spectroscopy, and the change rule of Q × f was closely related to oxygen vacancy content. The perturbation of A-site cations had an important influence on dielectric constant. Specifically, with the increase in Ti⁴⁺ content, the perturbation effect of the A-site cations was enhanced and dielectric constant increased. When x = 0.65, the temperature coefficient of resonant frequency of the (1 ? x) La[Al_0.9(Mg_0.5Ti_0.5)_0.1]O₃–x CaTiO₃ microwave dielectric ceramics was near zero. The optimal microwave dielectric properties of 0.35LaAl_0.9(Mg_0.5Ti_0.5)_0.1O₃–0.65CaTiO₃ were ε_r = 44.6, Q × f = 32,057 GHz, and τ_f = +2 ppm/°C.     

New Lead‐Free (1 − x)(K0.5Na0.5)NbO3–x(Bi0.5Na0.5)ZrO3 Ceramics with High Piezoelectricity

For enhancing the piezoelectric properties of ceramics (Bi_0.5Na_0.5)ZrO₃ (BNZ) was used to partially substitute (K_0.5Na_0.5)NbO₃ (KNN). The addition of BNZ changes the symmetry of KNN ceramics from orthorhombic to tetragonal, and finally to rhombohedral phase. A new phase boundary with both rhombohedral–orthorhombic and orthorhombic–tetragonal phase transitions near room temperature is identified for KNN–0.050BNZ ceramics, where optimum electrical properties were obtained: d₃₃ = 360 pC/N, k_p = 32.1%, ε_r = 1429, tanδ = 3.5%, and T_C = 329°C. The results indicated a new method for designing high‐performance lead‐free piezoelectric materials.     

Temperature‐insensitive piezoelectricity in lead‐free NaNbO3‐based ceramics

In this work, we report a lead‐free piezoelectric ceramic of (0.9‐x)NaNbO₃‐0.1BaTiO₃‐xBaZrO₃, and the effects of BaZrO₃ on the phase structure, microstructure, electrical properties and temperature stability are investigated. A morphotropic phase boundary‐like region consisting of rhombohedral (R) and tetragonal (T) phases is constructed in the compositions with x = 0.035‐0.04. More importantly, in situ temperature independence of the piezoelectric effect {piezoelectric constant (d₃₃) and strain} can be achieved below the Curie temperature (T_c). Intriguingly, the electric field‐induced strain is still observed at T ≥ T_c due to the combined actions of the electrostrictive effect and the electric field‐induced phase transition. We believe that NaNbO₃‐based ceramics of this type have potential for applications in actuators and sensors.     

Synthesis,structure, and dielectric properties of a new binary antiferroelectric solid solution: (1−x)Pb(Mg1/2W1/2)O3–xPbHfO3

Dielectric ceramics are one of the most important electrical insulators because of their excellent electrical stability and nonconducting properties. In this work, new complex perovskite solid solutions, (1−x)Pb(Mg_1/2W_1/2)O₃–xPbHfO₃ [(1−x) PMW–xPHf] (0.00 ≤ x ≤ 0.04), were successfully synthesized in the form of ceramics by the solid-state reaction method and sintering process. The X-ray diffraction results indicate that a single perovskite phase with antiferroelectric (AFE) orthorhombic Pmcn symmetry is formed for x < 0.04 which corresponds to the PMW-type solid solution (SS-PMW). For the composition x = 0.04, however, a small amount (about 1%) of ferroelectric orthorhombic C2mm phase that arises from the PHf-type solid solution (SS-PHf) was found to coexist with the Pmcn phase (99%). The dielectric measurements show that the AFE-paraelectric phase transition temperature T_C of the (1−x)PMW–xPHf ceramics increases from 38.2°C (x = 0) to 40.1°C (x = 0.03) with the increasing PHf content, indicating a slightly enhanced AFE ordering degree. The studied materials show a relatively low dielectric constant (~10²), a low dielectric loss (~10⁻²), a high breakdown field strength (~140 kV/cm), and a linear electric field dependence of polarization at room temperature, which make them a new candidate for potential applications as ceramic insulators.