Enhanced microstructure and electrical properties of Mn-modified Bi0.5(Na0.65K0.35)0.5TiO3 ferroelectric ceramics

Bi_0.5(Na_0.65K_0.35)_0.5TiO₃ (BNKT) and Mn-modified Bi_0.5(Na_0.65K_0.35)_0.5(Mn_xTi_1−x)O₃ (BNKMT-10³x), (x=0.0–0.5%) ferroelectric ceramics were synthesized by solid-state reaction method. Optimization of calcination temperature in Mn-doped ceramics was carried out for the removal of secondary phases observed in XRD analysis. BNKMT ceramics sintered at 1090 °C showed enhanced dielectric, piezoelectric and ferroelectric properties in comparison to pure BNKT. The average grain size was found to increase from 0.35 μm in BNKT to 0.52 μm in Bi_0.5(Na_0.65K_0.35)_0.5(Mn_0.0025Ti_0.9975)O₃ (BNKMT-2.5) ceramics. The dielectric permittivity maximum temperature (T_m) was increased to a maximum of 345 °C with Mn-modification. AC conductivity analysis was performed as a function of temperature and frequency to investigate the conduction behavior and determine activation energies. Significant high value of piezoelectric charge coefficient (d₃₃=176 pC/N) was achieved in BNKMT 2.5 ceramics. Improved temperature stability of ferroelectric behavior was observed in the temperature dependent P–E hysteresis loops as a result of Mn-incorporation. The fatigue free nature along with enhanced dielectric and ferroelectric properties make BNKMT-2.5 ceramic a promising candidate for replacing lead based ceramics in device applications.     

Dielectric,ferroelectric and field-induced strain response of lead-free (Fe,Sb)-modified (Bi0.5Na0.5)0.935Ba0.065TiO3 ceramics

Lead-free piezoelectric ceramics (Bi_0.5Na_0.5)_0.935Ba_0.065Ti_1−x(Fe_0.5Sb_0.5)_xO₃ (BNBT6.5–xFS, x=0.005, 0.010, 0.015, 0.020) were prepared by a conventional solid sintering technique. The effects of B-site doping of (Fe, Sb) on the phase structure, microstructure, dielectric, ferroelectric, and piezoelectric properties of BNBT6.5 ceramics were systematically investigated. Results showed that (Fe, Sb) can completely diffuse in the BNBT6.5 lattice in the all studied components. The addition of (Fe, Sb) destroyed the ferroelectric long-range order, and thus promoted the electric field induced strain response. The maximum electric field-induced strain (S_max=0.37%) with normalized strain (d₃₃*=S_max/E_max=454 pm/V) at an applied electric field of 80 kV/cm was obtained at x=0.015. Temperature dependent measurements of both polarization and strain from room temperature to 120 °C suggested that the origin of the large strain is due to a reversible field-induced ergodic relaxor to ferroelectric phase transformation.     

Low temperature sintering of lead-free Bi0.5(Na0.82K0.18)0.5TiO3 piezoelectric ceramics by co-doping with CuO and Nb2O5

Effect of excess CuO additive on the sintering behavior and piezoelectric properties of Bi_0.5(Na₈₂K_0.18)_0.5TiO₃ ceramics was investigated. The addition of small amount of excess CuO as low as 1 mol% was quite effective to lower the sintering temperature (T_s) of BNKT ceramics down to 975 °C while their piezoelectric properties were degraded by Cu doping. However, the electric field-induced strain was markedly enhanced by further addition of Nb₂O₅ with CuO without elevating T_s. The normalized strain S_max/E_max of 427 pm/V was obtained with a specimen sintered with 0.02 mol CuO and 0.03 mol Nb₂O₅ in excess.     

Lead-free Bi1/2(Na0.82K0.18)1/2TiO3 relaxor ferroelectrics with temperature insensitive electrostrictive coefficient

The electric field-induced strain of Bi_1/2(Na_0.82K_0.18)_1/2TiO₃ (BNKT) ceramics modified with BaZrO₃ (BZ) was investigated as a function of composition and temperature. Unmodified BNKT ceramics revealed a typical ferroelectric butterfly-shaped bipolar S–E loop at room temperature, whose normalized strain (S_max/E_max) showed a significant temperature coefficient of 0.38 pm/V/K. As the BZ content increased in the solid solution up to 5 mol%, the ferroelectric BNKT gradually transformed to a relaxor. Finally, 5 mol% BZ-modified BNKT ceramics showed a typical electrostrictive behavior with a thermally stable electrostrictive coefficient (Q₃₃) of 0.025 m⁴/C², which is comparable to that of Pb(Mg_1/3Nb_2/3)O₃ (PMN) ceramics that have been primarily used as Pb-based electrostrictive materials.     

Effects of thickness on structures and electrical properties of K0.5Na0.5NbO3 thick films derived from polyvinylpyrrolidone-modified chemical solution

Lead-free ferroelectric K_0.5Na_0.5NbO₃ (KNN) films with different thicknesses were prepared by polyvinylpyrrolidone (PVP)-modified chemical solution deposition (CSD) method. The KNN films with thickness up to 4.9 μm were obtained by repeating deposition-heating process. All KNN thick films exhibit single perovskite phase and stronger (1 1 0) peak when annealed at 650 °C. The variation of dielectric constant with thickness indicates that there exists a critical thickness for the dielectric constant in the KNN films which should lie in 1.3–2.5 μm. The similar trend is observed for the ferroelectric and piezoelectric properties of KNN films. Both the remnant polarization P_r and the piezoelectric coefficient d₃₃ of KNN thick films increase with the film thickness and become saturated after the critical thickness.     

Compositional inhomogeneity and segregation in (K0.5Na0.5)NbO3 ceramics

In this report, the effects of the calcination temperature of (K_0.5Na_0.5)NbO₃ (KNN) powder on the sintering and piezoelectric properties of KNN ceramics have been investigated. KNN powders are synthesized via the solid-state approach. Scanning electron microscopy and X-ray diffraction characterizations indicate that the incomplete reaction at 700 °C and 750 °C calcination results in the compositional inhomogeneity of the K-rich and Na-rich phases while the orthorhombic single phase is obtained after calcination at 900 °C. During the sintering, the presence of the liquid K-rich phase due to the lower melting point has a significant impact on the densification, the abnormal grain growth and the deteriorated piezoelectric properties. From the standpoint of piezoelectric properties, the optimal calcination temperature obtained for KNN ceramics calcined at this temperature is determined to be 800 °C, with piezoelectric constant d₃₃=128.3 pC/N, planar electromechanical coupling coefficient k_p=32.2%, mechanical quality factor Q_m=88, and dielectric loss tan δ=2.1%.     

Field-induced large strain in lead-free 0.99[(1−x) Bi0.5(Na0.80K0.20)0.5TiO3–xBiFeO3]–0.01(K0.5Na0.5)NbO3 piezoelectric ceramics

Lead-free 0.99[(1−x) Bi_0.5(Na_0.80K_0.20)_0.5TiO₃–xBiFeO₃]–0.01(K_0.5Na_0.5)NbO₃ (BNKT20–100xBF–1KNN) piezoelectric ceramics were fabricated through conventional techniques. Results showed that changes in BF content of BNKT20–100xBF–1KNN induced transition from the ferroelectric phase to the ergodic relaxor phase. These changes also significantly disrupted long-range ferroelectric order, thereby correspondingly adjusting the ferroelectric-relaxor transition point T_F-R to room temperature. A large strain of 0.39% at the electric-field of 80 kV/cm (corresponding to a large signal d₃₃^* of 488 pm/V) was obtained at x=0.06, which originated from the composition proximity to the ferroelectric-relaxor phase boundary. Moreover, the high-strain material exhibited exceptional fatigue resistance (up to 10⁶ cycles) as a result of the reversible field-induced phase transition. The proposed material exhibits potential for novel ultra-large stroke and nonlinear actuators that require enhanced cycling reliability.     

Textured (K0.5Na0.5)NbO3 ceramics prepared by screen-printing multilayer grain growth technique

The screen-printing multilayer grain growth (MLGG) technique is successfully applied to alkaline niobate lead-free piezoelectric ceramics. Highly textured (K_0.5Na_0.5)NbO₃ (KNN) ceramics with 〈0 0 1〉 orientation (f = 93%) were fabricated by MLGG technique with plate-like NaNbO₃ templates. The influence of sintering temperature on grain orientation and microstructure was studied. The textured KNN ceramics showed very high piezoelectric constant d₃₃ = 133 pC/N, and high electromechanical coupling factor k_p = 0.54. These properties were superior to those of conventional randomly oriented ceramics, and reach the level of those of textured KNN ceramic prepared by tape-casting technique. Compared with other grain orientation techniques, screen-printing is a simple, inexpensive and effective method to fabricate grain oriented lead-free piezoelectric ceramics.     

Polarization and strain behaviors of 0.74BiNaTiO3–0.26SrTiO3/Bi0.5(Na0.8K0.2)0.5TiO3 ceramic composite

We investigated the temperature- and frequency-dependent polarization and strain of two bismuth-based perovskite materials, a matrix material and a seed material, with which we formed a composite whose properties we likewise investigated. The chosen matrix material is 0.74Bi_0.5Na_0.5TiO₃–0.26SrTiO₃ (BNT-ST) which has a transition point of ~65 °C, from the relaxor to the ferroelectric phase (T_R-F). The seed material was Bi_0.5(Na_0.8K_0.2)_0.5TiO₃ (BNKT), which possesses a T_R-F of 120 °C. Different polarization and strain behaviors were observed in the BNT-ST/BNKT composite at different test temperatures. At T=25 °C (<T_R-F of the relaxor BNT-ST), the composite exhibited a hysteretic polarization loop and parabolic strain curves which involve an ergodic relaxor-to-normal ferroelectric phase transition with application of an external electric field and the reverse ferroelectric-to relaxor phase transition with removal of the field. When T=80 and 100 °C (>T_R-F °f the relaxor BNT-ST and <T_R-F of the ferroelectric BNKT), the BNT-ST/BNKT has a slim polarization loop and strain magnitudes that are slightly increased from those of pure BNT-ST. When T=120 °C (~T_R-F of the ferroelectric BNKT), the composite has a very slim polarization loop and strain behavior with values that are almost same as those of pure BNT-ST. In addition, the P-S relation for the BNT-ST/BNKT is identical to that of BNT-ST as the operating frequency increases up to 100 Hz. This may be because the polarization of BNT-ST is lower than that of BNKT. The electric field-induced polarization and strain of the BNT-ST/BNKT composite with respect to the temperature and frequency are related to the thermal stability of the ferroelectric seed and the degree of the phase transition in the relaxor matrix.     

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.     

Phase structure and enhanced piezoelectric properties in (1-x)(K0.48Na0.52)(Nb0.95Sb0.05)O3-x(Bi0.5Na0.42Li0.08)0.9Sr0.1ZrO3 lead-free piezoelectric ceramics

The piezoelectric properties of KNN lead-free piezoelectric ceramics could be greatly enhanced by forming multiphase coexistence. In this work, binary system (1-x)(K_0.48Na_0.52)(Nb_0.95Sb_0.05)O₃-x(Bi_0.5Na_0.42Li_0.08)_0.9Sr_0.1ZrO₃ [(abbreviated as (1-x)KNNS-xBNLSZ] ceramics with rhombohedral-tetragonal (r-T) phase boundary was designed and synthesized using the conventional solid-state sintering method, and effects of BNLSZ contents on their micrograph, phase structure and electrical properties were also investigated. According to phase diagram from the results of temperature-dependent capacitance and dielectric constant, the ceramics exhibit the R-T phase coexistence in the composition range of 3.5%≤x<4.5%, and an enhanced dielectric, ferroelectric, and piezoelectric behavior was obtained at such a phase boundary zone. As a result, the ceramics with x=0.04 exhibit optimum electrical properties of d₃₃~461 pC/N, k_p~46%, tan δ~0.03, P_r~16.9 μC/cm², and E_c ~9 kV/cm, together with a Curie temperature (T_C) of ~228 °C. Such a good comprehensive performance obtained in this present work is due to the R-T phase transition and enhanced ɛ_rP_r. It was believed that this ceramic system would promote the development of KNN-based lead-free ceramics.     

Grain size control of lead-free Li0.06(Na0.5K0.5)0.94NbO3 piezoelectric ceramics by Ba and Ti doping

In this study, Ba- and Ti-doped Li_0.06(Na_0.5K_0.5)_0.94NbO₃ [(1 ? x)Li_0.06(Na_0.5K_0.5)_0.94NbO₃–xBaTiO₃ (x = 0–0.07)] ceramics were prepared by using conventional solid state reaction method, and the microstructure and electric properties of these samples were investigated. The grain size distribution of non-doped Li_0.06(Na_0.5K_0.5)_0.94NbO₃ ceramics was relatively wide. The microstructure was composed of grains ranging 1.1–5.0 μm in size. However, with increasing Ba and Ti content, the grain size distribution became narrow and the average grain size decreased from 2.0 to 0.9 μm in size. In particular, the microstructure of x = 0.07 sample was composed of grains ranging 0.5–2.2 μm in size. As a result, the frequency dispersion of dielectric constant for the (1 ? x)Li_0.06(Na_0.5K_0.5)_0.94NbO₃–xBaTiO₃ (x = 0–0.07) ceramics was reduced and the mechanical quality factor Q_m was enhanced with increasing Ba and Ti content.     

Low-temperature sintering and electrical properties of (K,Na)NbO3 based lead-free ceramics with high Curie temperature

Lead-free ceramics (1 ? x)(K_0.48Na_0.52)NbO₃–(x/5.15)K_2.9Li_1.95Nb_5.15O_15.3 (x = 0.3–0.6, KNN–KLN100x) were prepared by conventional sintering technique at a low temperature of 960 °C. The effects of KLN contents on microstructure, dielectric, and piezoelectric properties were investigated. After the addition of KLN, the sintering performance and Curie temperature of the ceramics were markedly improved. The ceramics with x = 0.3 exhibited very good piezoelectric properties: d₃₃ = 138 pC/N, k_p = 45.03%, T_c = 495 °C, the dielectric constant at room temperature ?_r (RT) = 478 and the maximum dielectric constant ?_r (max) = 5067. These results indicated that the KNN–KLN100x lead-free ceramics sintered at low temperatures are promising for high temperature piezoelectric applications.     

Ferroelectric Bi(Na,K)TiO3-based materials for lead-free piezoelectrics

A lead-free piezoelectric materials of Cu-doped Bi_0.5(Na_0.79K_0.21)TiO₃ (BNKT–xCu) have been synthesized using a conventional ceramic process. The addition of a small amount of CuO increased the d₃₃-value up to 156 pC/N for BNKT–0.6Cu, while the large amout of CuO (>0.6 mol%) decreased it down to 80 pC/N for BNKT–2.0CuO. However, it was found that the mechanical quality factor (Q_m) was not increased until the CuO content was less then 0.6 mol%, but it was significantly increased when CuO exceeded 0.6 mol%, resulting from the development of small defect. The inverse dielectric permittivity followed the Curie–Weiss law above the deviation temperature (T_dev.) at high temperatures for the BNKT–xCu. The thermal hysteresis for BNKT–xCu confirmed that with an increase in the amount of CuO addition, the variation of the temperature in dielectric permittivity maximum (T_m) increased gradually while the depolarization temperature (T_d) decreased during the heating and the cooling cycles.     

Effect of Ba0.85Ca0.15Ti0.90Zr0.10O3 content on the microstructure and electrical properties of Bi0.51(Na0.82K0.18) 0.50TiO3 ceramics

(1?x)Bi_0.51(Na_0.82K_0.18)_0.50TiO₃–xBa_0.85Ca_0.15Ti_0.90Zr_0.10O₃ [(1?x)BNKT–xBCTZ] ceramics were prepared by the conventional solid-state method, and the effect of BCTZ content on their microstructure and electrical properties was investigated. A stable solid solution with a pure perovskite phase is formed between BNKT and BCTZ, and these ceramics have a coexistence of rhombohedral and tetragonal phases in the range of 0 ≤ x < 0.15. Their T_m and T_d values are strongly independent on the BCTZ content. Moreover, the sintering temperature strongly affects the ferroelectric and piezoelectric properties of these ceramics with x = 0.02. These ceramics with x = 0.02 exhibit an optimum electrical behavior of d₃₃ ～ 205, k_p ～ 0.25, P_r ～ 31.8 μC/cm², and E_c ～ 19.1 kV/cm together with a high T_d value of ～91 °C when sintered at 1180 °C and poled at an optimum condition. As a result, the (1?x)BNKT–xBCTZ ceramic is a promising candidate material for lead-free piezoelectric ceramics.     

Large strain and relaxation behavior in CeO2 doped Bi0.487Na0.427K0.06Ba0.026TiO3 piezoceramics

xCeO₂-doped Bi_0.487Na_0.427K_0.06Ba_0.026TiO₃ lead-free piezoelectric ceramics (BNTC1000x, x=0, 0.3, 0.6, 0.8, 1.0, 1.2, 1.4 wt%), were synthesized by the solid-state reaction method. XRD patterns showed that all BNTC1000x ceramics exhibit pure single perovskite phase. At the critical composition BNTC12, a large electric-field-induced strain of 0.39% with normalized strain (S_max/E_max) of 561 pm/V was obtained under an electric field of 65 kV/cm. The ferroelectric phase was fully poled with electric field, and depoled once the applied electric field was removed. During that cycle, the non-180°-domains repeated switching and back-switching and the large strain was induced. The relaxation behavior was involved in BNTC1000x ceramics and induced by oxygen vacancy migration. Besides, this behavior was more predominant in BNTC12 than in BNTC0.     

Electric-field-temperature phase diagram and electromechanical properties in lead-free (Na0.5Bi0.5)TiO3-based incipient piezoelectric ceramics

In this work, the (1-x)(0.8Na_0.5Bi_0.5TiO₃-0.2K_0.5Bi_0.5TiO₃)-xSrTiO₃ (NKBT-xST) incipient piezoelectric ceramics with x = 0–0.07 (0ST-7ST) were prepared by the solid-state reaction method and their structural transformation and electromechanical properties were investigated as a function of ST content. As the ST content increases, the long-range ferroelectric order is disrupted, and the ferroelectric-relaxor phase transition temperature (T_FR) shifts to around room temperature for NKBT-5ST ceramics, accompanied by a relatively high electrostrain of 0.3% at 6 kV/mm. The large strain response associated with the vanished ferroelectric properties around T_FR can be attributed to the reversible relaxor-ferroelectric phase transition. The electric-field-temperature (E-T) phase diagrams were established, and the transition between the two field-induced long-range ferroelectric states were found to take place via a two-step switching process through an intermediate relaxor state. The threshold electric field to trigger the conversion between ferroelectric state and relaxor state depends strongly on the dynamics of polarization relaxation, which is influenced by temperature and composition.     

Influence of the composition-induced structure evolution on the electrocaloric effect in Bi0.5Na0.5TiO3-based solid solution

The present work investigated the influence of the composition induced structure evolution on the electrocaloric effect in lead-free (0.935−x)Bi_0.5Na_0.5TiO₃–0.065BaTiO₃–xSrTiO₃ (BNBST, BNBSTx) ceramics. It was found that broad ∆T peak could be observed for all compositions and the electrocaloric strength α (α=ΔT_max/ΔE) in BNBST0.02 could reach as high as 0.27 K mm/kV. The increase of the SrTiO₃ concentration led to a shift of ∆T_max to a lower temperature, resulting in a large near room-temperature electrocaloric strength α of 0.17 K mm/kV in BNBST0.22.     

Temperature-insensitive dielectric and piezoelectric properties in (1-x)K0.5Na0.5Nb0.997Cu0.0075O3-xSrZrO3 ceramics

Systematic investigation on phase transition, dielectric and piezoelectric properties of (1-x)K_0.5Na_0.5Nb_0.997Cu_0.0075O₃-xSrZrO₃ (x = 0, 0.03, 0.06, 0.09, 0.12, 0.15, abbreviated as KNNC-100xSZ) ceramics was carried out. Due to the coexistence of orthorhombic and tetragonal phase in a wide temperature range, a diffused polymorphic phase transition (PPT) region was achieved in KNNC with x ≥ 0.06. KNNC-12SZ ceramics exhibited high dielectric permittivity (∼1679), low dielectric loss (∼0.02) and small variation (Δe'/ε'_25 °C ≤ 15%) in dielectric permittivity from −78 °C to 237.3 °C. KNNC-6SZ ceramic possessed a high level of unipolar strain (∼0.15%) and maintained a smaller variation of ±12% under the corresponding electric field of 60 kV cm⁻¹ at 10 Hz from 25 °C to 175 °C. d₃₃^*, which was calculated according to the unipolar strain at 60 kV cm⁻¹, was 230 pm V⁻¹ and remained stable below 100 °C. Therefore, our work provided a new promising candidate for temperature-insensitive capacitors and piezoelectric actuators.     

Dielectric and ferroelectric properties of (1 − x)BaTiO3–xBi0.5Na0.5TiO3 ceramics

Lead-free (1 − x)BaTiO₃–xBi_0.5Na_0.5TiO₃ (x = 0.01, 0.02, 0.05, 0.1, 0.2, 0.3) ferroelectric ceramics were fabricated by the conventional ceramic technique. Sintering was made at 1200 °C for 2–4 h in air atmosphere. The crystal structure was investigated by X-ray diffraction. The dielectric and ferroelectric properties were also studied. Room temperature permittivity was found to decrease as Bi_0.5Na_0.5TiO₃ (BNT) content increases. Only the sample with 0.3 mol BNT was found to have relaxor behaviour. The T_c shifted slightly only for BNT addition lower than 0.1 mol. The highest T_c (about 150 °C) was obtained for 0.2 mol BNT addition. The remanent polarization, P_r, decreases whereas the coercive field, E_c, increases monotonously as the BNT content increases.