Composition segregation and grain growth in (K0.5Na0.5)NbO3 piezoceramics prepared by two-step cold sintering process

Cold sintering process (CSP) is a new method to prepare ceramics under quite low temperature. In this work, two-step CSP under different pressures was employed to prepare (K_0.5Na_0.5)NbO₃ (KNN) ceramics. The density of KNN green pellets can be raised by enhancing the pressure of second-step CSP. Energy-dispersive spectroscopy reveals the composition segregation of A-site cations in large grains. The dissolution rate of K⁺ in an aqueous medium is faster than Na⁺, and high pressure can accelerate K⁺ dissolution, resulting in more Na⁺ in some grains. Besides, the diffusion rate of Na⁺ in grains is better than K⁺, which promote the grains growth. Finally, the piezoelectric property is improved even with low ceramic density due to the larger grains, which possess the higher performance composition. This result demonstrates that the pressure and inhomogeneous dissolution of alkali metal ions among CSP play an important role in grain growth and piezoelectric enhancement.     

K0.5Na0.5NbO3 ceramics fabricated by combining cold sintering with annealing in air atmosphere or low pO2 atmosphere

Dense K_0.5Na_0.5NbO₃ lead-free ceramics were successfully fabricated by combining cold sintering process (CSP) with annealing in air atmosphere or low pO₂ atmosphere. Acetic acid was used as transition liquid. By optimizing the liquid content and pressure during CSP, the CSP samples with relative densities 74.2% were obtained with adding 15 wt% acetic acid under 800 MPa. The CSP samples were then annealed in air atmosphere between 1000 and 1100°C. The ceramics annealed at 1050°C exhibit excellent electrical properties with piezoelectric constant d₃₃ = 125 pC/N, dielectric constant ε_r = 509, dielectric loss tan δ = 0.04, and remanent polarization P_r = 38.17 μC/cm². Additionally, the mixture of K_0.5Na_0.5NbO₃ and base metal Ni powders was also cold-sintered and then annealed in the low pO₂ atmospheres in order to detect whether Ni was oxidized or not. The optimized low pO₂ atmospheres to protect the Ni from oxidation are pO₂ = 10⁻¹⁰ atm followed by reoxidizing in pO₂ = 10⁻⁶ atm. The K_0.5Na_0.5NbO₃ fabricated by CSP with annealing in the optimized low pO₂ atmospheres exhibits comparable electrical properties of the ceramics annealed in air atmosphere, providing an optional approach for using base metals as electrodes.     

Simultaneous realization of high transparency and piezoelectricity in low symmetry KNN-based ceramics

Transparent piezoelectric ceramic, as a lead-free multifunctional ceramic, is in dire need of development for future high-tech industries. However, excellent piezoelectricity and high transmittance are usually hard to achieve simultaneously, mainly due to the two mutual restricting factors (phase structure and grain size). In this work, we report that high piezoelectricity and transmittance can be obtained simultaneously in K_0.5Na_0.5NbO₃ ceramics via Sr(Sc_0.5Nb_0.5)O₃ (SSN) modification. The superior piezoelectric performance comes from the retain of orthorhombic phase structure at room temperature (RT); while the high transparency (>70% at 780 nm) can be attributed to the improved relative density and reduced grain size via SSN modification. Remarkably, in the sample with 0.05SSN modification, we realized a comprehensively high transmittance (73% at 780 nm) accompanied by a superior piezoelectric constant (d₃₃ = 101 pC/N), which outperform other reported KNN-based transparent ceramics to our best knowledge. Our results may provide insight for further developing the transparent piezoelectric ceramics by controlling the grain size and phase structure.     

Large recoverable energy storage density and low sintering temperature in potassium‐sodium niobate‐based ceramics for multilayer pulsed power capacitors

Multilayer pulsed power ceramic capacitors require that dielectric ceramics possess not only large recoverable energy storage density (W_rec) but also low sintering temperature (<950°C) for using the inexpensive metals as the electrodes. However, lead‐free bulk ceramics usually show low W_rec (<2 J/cm³) and high sintering temperature (>1150°C), limiting their applications in multilayer pulsed power ceramic capacitors. In this work, large W_rec (~4.02 J/cm³ at 400 kV/cm) and low sintering temperature (940°C) are simultaneously achieved in 0.9(K_0.5Na_0.5)NbO₃–0.1Bi(Mg_2/3Nb_1/3)O₃–1.0 mol% CuO ceramics prepared using transition liquid phase sintering. W_rec of 4.02 J/cm³ is 2‐3 times as large as the reported value of other (Bi_0.5Na_0.5)TiO₃ and BaTiO₃‐based lead‐free bulk ceramics. The results reveal that 0.9(K_0.5Na_0.5)NbO₃–0.1Bi(Mg_2/3Nb_1/3)O₃–1.0 mol% CuO ceramics are promising candidates for fabricating multilayer pulsed power ceramic capacitors.     

BNT-based ferroelectric ceramics: Electrical properties modification by Ta2O5 oxide addition

Due to their superior piezo-responses (strain S > 0.3%), bismuth sodium titanate (BNT)-based relaxor ferroelectrics have received much attention. Compared to other chemical elements, tantalum (Ta) doping provides superior electro-strain for these ferroelectrics, while the effect of Ta₂O₅ as oxide additive has been rarely reported. Herein, lead-free piezoceramics of Bi_0.5(Na_0.72K_0.22Li_0.06)_0.5TiO₃-xTa₂O₅ (BNKLT-xTa₂O₅, x = 0-0.015) are synthesized. We study the effects of Ta₂O₅ addition on the crystal structure, piezoelectric responses, dielectric properties, and ferroelectric properties of BNKLT ceramics. All of the ceramics exhibit a typical perovskite structure, and Ta₂O₅ diffuses into the BNKLT lattice to form a uniform solid solution. The addition of Ta₂O₅ can make the grains more regular and uniform, while excess Ta₂O₅ result in finer grains. The undoped BNKLT ceramics show good ferroelectric and piezoelectric properties (remnant polarization P_r = 22.5 μC/cm² and piezoelectric coefficient d₃₃ = 250 pC/N); however, the addition of Ta₂O₅ leads to an clear degradation in d₃₃ and P_r. Meanwhile, the addition of an appropriate Ta₂O₅ amount leads to an increase in the electro-strain, and the unipolar strain reaches 0.385% under 60 kV/cm for x = 0.003, together with a higher normalized strain (d₃₃^*=S_max/E_max) of 633 pm/V (x = 0.003). The enhanced strain behaviors can be attributed to the coexistence of the ferroelectric and relaxor states, and an excellent electrostriction coefficient Q₃₃ (Q₃₃ = S/P²) value of 0.038 m⁴C⁻² is obtained under 60 kV/cm for x = 0.003.     

Evaluation of pore scattering in transparent ceramics: A simplified model for nanometric spherical pores

It is well known that light scattering by nanometric pores is adverse to realize a high transparency in ceramics; however, a suitable model that gives this phenomenon a quantitative evaluation is still lacking. In this work, a simplified model based on Rayleigh's theory was developed in order to unravel the light scattering by nanometric pores, taking polycrystalline KNNB-xSm ceramics with high transparency (>67% at 780 nm) as example. The validity of this model was further verified by its good agreement with experimental results. Based on detailed simulations, we came to the conclusion that the pore volume fraction p is a more important parameter on the transparency of KNNB-xSm ceramics than pore size d_pore. Our findings in this work might provide inspiring insight to obtain highly transparent KNN-based ceramics and more.     

Composition‐induced phase transitions and enhanced electrical properties in bismuth sodium titanate ceramics

Here, the composition‐induced phase transition and enhanced electrical properties were investigated in terms of lead‐free {[Bi_0.5(Na_0.82?xK_0.18Li_x)_0.5]_1?ySr_y}TiO₃ (BNKLST‐x/y, x=0‐0.175 and y=0‐0.125) ceramics. The rhombohedral and tetragonal phase boundary can be constructed, and then the enhancement of piezoelectric properties (d₃₃~271 pC/N and k_p~0.38) can be observed for x=0.10 and y=0.05, which is superior to most reported results in polycrystalline BNT‐based ceramics. In particular, a fatigue‐free behavior after 10⁶ polarization switching cycles was shown in the BNKLST‐0.10/0.05 ceramics due to the reversible field‐induced phase transition, and a slight decrease in d₃₃ (~4.5%) was also shown. More importantly, the general model of electric field, temperature, and composition‐induced phase transition was employed to explain the enhancement of piezoelectric and fatigue properties. We believe that the composition design of this system can promote the development of bismuth sodium titanate lead‐free ceramics.     

Improved mechanical properties and toughening mechanism of mullite ceramics reinforced by introducing Ti3AlC2 particles

Ti₃AlC₂, as a toughening phase, was introduced into mullite ceramics for the first time by the pressureless sintering process aiming at improving the mechanical properties. Significant enhancement in density and mechanical performance of mullite ceramics was achieved through the introduction of Ti₃AlC₂ particles. The density of as-prepared mullite–Ti₃AlC₂ composites was increased by 23% (from 2.86 g/cm³ to 3.51 g/cm³) with Ti₃AlC₂ increasing from 0 wt% to 20 wt%. The formation of the liquid phase and decomposed particles from Ti₃AlC₂ are supposed to be responsible for the densification of mullite–Ti₃AlC₂ composites. The optimal mechanical properties were obtained in the mullite–Ti₃AlC₂ composites with 15 wt% Ti₃AlC₂. The bending strength, fracture toughness as well as Vickers hardness were reached 214.36 MPa, 4.84 MPa·m^1/2, and 9.21 GPa, which are 40%, 74%, and 113% higher than pure mullite ceramics, respectively. The improved mechanical performance was mainly attributed to the synergetic action of crack deflection, crack branching and bridging, and strengthened grain boundary.     

Enhanced piezoelectric properties and electrocaloric effect in novel lead‐free (Bi0.5K0.5)TiO3‐La(Mg0.5Ti0.5)O3 ceramics

The crystal structure, electromechanical properties, and electrocaloric effect (ECE) in novel lead‐free (Bi_0.5K_0.5)TiO₃‐La(Mg_0.5Ti_0.5)O₃ ceramics were investigated. A morphotropic phase boundary (MPB) between the tetragonal and pseudocubic phase was found at x = 0.01‐0.02. In addition, the relaxor properties were enhanced with increasing the La(Mg_0.5Ti_0.5)O₃ content. In situ high‐temperature X‐ray diffraction patterns and Raman spectra were characterized to elucidate the phase transition behavior. The enhanced ECE (ΔT = 1.19 K) and piezoelectric coefficient (d₃₃ = 103 pC/N) were obtained for x = 0.01 at room temperature. Meanwhile, the temperature stability of the ECE was considered to be related to the high depolarization temperature and relaxor characteristics of the Bi_0.5K_0.5TiO₃‐based ceramics. The above results suggest that the piezoelectric and ECE properties can be simultaneously enhanced by establishing an MPB. These results also demonstrate the great potential of the studied systems for solid‐state cooling applications and piezoelectric‐based devices.     

Abnormal grain growth in (K,Na)NbO3-based lead-free piezoceramic powders

Abnormal grain growth (AGG) is frequently observed in sintered (K, Na)NbO₃ (KNN)-based piezoceramics. However, in the present study, abnormal grain growth was unexpectedly discovered in calcined KNN-based powders. To explain the phenomenon, three well-established models that account for the AGG in sintered ceramics were discussed, including (a) liquid-phase-assisted grain growth, (b) two-dimensional nucleation grain growth, and (c) complexion coexistence. However, the AGG in calcined powders was concluded to be none of them, but a consequence of the A-site compositional inhomogeneity in the K₂CO₃-Na₂CO₃-Nb₂O₅ ternary system. Since repeated calcination and ball milling have low efficiency on solving AGG and the accompanied compositional inhomogeneity, abnormal grains were found to coexist with normal grains at a very high calcination temperature, that is, 1000°C. The compositional inhomogeneity is believed to be remaining even after sintering and consequently deteriorate the comprehensive performances, which might be a determinant for the unstable reproduction of KNN-based piezoceramics.     

Improved ultraviolet -visible optically transmittance and luminescent properties in Yb,Lu: Sr5(PO4)3F transparent ceramics via Lu3+ co-doping

The asymmetric hexagonal Sr₅(PO₄)₃F (S-FAP) crystal material is considered to be the most suitable solid state laser gain medium for small laser diode pumping in the future due to its large absorption, emission interface, and long fluorescence lifetime. However, the mediocre optical transmittance of S-FAP transparent ceramics and the degradation of luminescence properties due to the doping of Yb activated ions seriously hinder its application prospects. In view of this, a series of 0.02Yb, xLu: S-FAP (x = 0–0.02) transparent ceramics with excellent optical properties were synthesized by hot pressing sintering. The powder SEM results show that Lu doping has no obvious effect on the morphology, grain size, and dispersion of powder. The linear transmissivity curves show that the ultraviolet (200 nm) and visible (500 nm) transmissivity increase by 54 % and 17 %, respectively, with Lu doping compared with the undoped ceramic samples. The surface SEM of ceramics revealed that Lu³⁺ promoted the increase of ceramic grain size significantly. The emission spectrum and fluorescence decay curves at room temperature also show that the emission intensity and fluorescence lifetime of ceramic samples increase significantly with Lu co-doping.     

Modulation of electrostriction and strain response in bismuth sodium titanate‐based ceramics

The electrostriction and strain response of lead‐free Bi_0.5Na_0.5TiO₃–BaTiO₃ piezoceramics with La and Nb [(Bi_0.47Na_0.47Ba_0.06)_1?xLa_xTi_1?yNb_yO₃] were modified by optimizing the depolarization temperature. The influences of La and Nb on their phase structure and electrical properties were systematically investigated. All the ceramics exhibited a pseudocubic phase, which is independent of the addition of La and Nb. The strain values increased gradually with the addition of La, and a high strain of ~0.5% (80 kV/cm) was attained without any remnant strain when the compositions had a value of x = 0.015. Instead, the piezoelectric constant d₃₃ dropped down ~20 pC/N due to the shift of the T_d (or T_f?r) to room temperature. Interestingly, by establishing the relationship between T_d and strain values, it should be feasible to optimize the strain property of Bi_0.5Na_0.5TiO₃ (BNT)‐based ceramics by regulating T_d to ambient temperature. In addition, a very high electrostriction coefficient Q₃₃ of ~0.0758 m⁴ C^?2 can be found under high temperatures of 125 and 150°C. We believe that the strain and electrostriction behavior of BNT‐based ceramics can be well modified by the modulation of depolarization temperature.     

Microstructural,ferroelectric, and photoluminescent properties of (100)‐oriented Sm3+‐doped Na0.5Bi0.5TiO3 thin films

(100)_C‐oriented Na_0.5Bi_0.5‐xSm_xTiO₃ (NBST) lead‐free ferroelectric thin films were prepared on Pt/Ti/SiO₂/Si substrates by chemical solution deposition method, and their microstructural, dielectric, ferroelectric, and photoluminescent properties were studied. X‐ray diffraction and scanning electron microscopy analysis indicated that both the grain size and (100)_C orientation degree of NBST thin films were decreased by doping Sm³⁺ ions. Raman spectra showed that structural symmetry of NBST thin films decreased at low Sm³⁺ doping concentration and then increased at high doping concentration of Sm³⁺ ions. An appropriate amount of Sm³⁺ dopants was confirmed to enhance dielectric and ferroelectric properties of the NBST thin films. Among all the compositions, the Na_0.5Bi_0.492Sm_0.008TiO₃ thin film exhibited the largest remnant polarization (2P_r) of 27.3 μC/cm² and high dielectric constant of 1068, as well as a low dielectric loss of 0.04. Temperature‐ and frequency‐dependent dielectric characteristics illustrated the relaxor ferroelectric behavior of Na_0.5Bi_0.492Sm_0.008TiO₃ thin film. Meanwhile, the Na_0.5Bi_0.492Sm_0.008TiO₃ thin film also showed optimal orange‐red emission at 600 nm, which is originating from the ⁴G_5/2 → ⁴H_7/2 transition of Sm³⁺ ions.     

Improved ferroelectric,piezoelectric, and dielectric properties in pure KNN translucent ceramics by optimizing the normal sintering method

In this study, it is reported that various properties can be selectively derived in a pure (K_0.5Na_0.5)NbO₃, KNN ceramics through optimizing the sintering temperature by the conventional sintering method. High piezoelectric, ferroelectric, and dielectric properties such as d₃₃ = 127 pC/N, P_r = 31 μC/cm², and ε_r = 767 are obtained at the sintering temperature of 1100 °C. On the contrary, the specimen sintered at 1130 °C does not show high piezoelectric and ferroelectric properties, but it is translucent with a transmittance of 22% and 57% at the wavelength of 800 and 1600 nm respectively and shows a very high dielectric constant ε_r of 881. The origin of the high piezoelectric constant owes to large remanent polarization and dielectric constant, and dense microstructure with uniform distribution of large grains with the conjunction of relatively large crystal anisotropy. On the other hand, dense microstructure with almost no porosity, highly compacted grain boundaries, uniform distribution of grains, and relatively low crystalline anisotropy are responsible for the translucency and large dielectric constant of the ceramic specimens. This study demonstrates that the lead-free KNN ceramic has the potential to show multiple noteworthy properties such as piezoelectric, ferroelectric, dielectric, and transparent properties. This work provides a pure KNN ceramic simultaneously with high piezoelectric and transparent characteristics prepared only by using the conventional sintering method at a moderate sintering temperature for the first time in the literature.     

Effect of holmium substitution on structural and electrical properties of barium zirconate titanate ferroelectric ceramics

The holmium substituted Ba_1−3x/2Ho_xZr_0.025Ti_0.975O₃ (x=0.01, 0.02, 0.025, 0.05) compositions were synthesized by the solid state reaction technique. The synthesized specimens were characterized for their structural and electrical properties using X-ray diffractometer, scanning electron microscopy, impedance analyzer and loop tracer. Phase analysis shows the formation of secondary phase Ho₂Ti₂O₇ for Ho≥2.5 mol% substitution. The microstructural investigation shows that the holmium substitution significantly reduces the grain size. The substitution of holmium increases the Curie temperature for x≤0.02 whereas Curie temperature decreases for x≥0.025. The maximum dielectric constant at transition temperature is observed for x=0.02. The solubility limit is 2 mol% and for x≥0.025 some of the holmium atoms enter B-sites and forms the secondary phase. An increase is observed in the coercive field of the specimens with the increasing holmium content.     

固相微波法制备Pd/La0.5Pb0.5MnO3催化剂及其催化性能

以MnCO3P、PbCO3和La2O3为原料,利用固相微波法制备La0.5Pb0.5MnO3钙钛矿型复合氧化物载体,并用XRD、SEM以及WJL激光粒度仪进行表征.通过沉淀法得到负栽型钯催化剂,以氧化羰基化合成碳酸二苯酯为评价对象,考察不同载体制备工艺对催化性能的影响.实验结果表明,载体最佳制备条件是微波烧结功率450...     

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.     

Piezoelectric and ferroelectric properties of (Bi,Na)TiO3–(Bi,Li)TiO3–(Bi,K)TiO3 ceramics for accelerometer application

The piezoelectric and ferroelectric properties of 0.76(Bi_0.5Na_0.5)TiO₃–0.04(Bi_0.5Li_0.5)TiO₃–0.2(Bi_0.5K_0.5)TiO₃ (abbreviated as 0.76BNT–0.04BLT–0.2BKT) ceramics were investigated to clarify the optimal sintering temperature, and the vibration characteristics were examined for a compression‐mode accelerometer assembly in which 0.76BNT–0.04BLT–0.2BKT ceramics sintered at the optimized temperature served as the piezoelectric elements. The increase in the grain size of the 0.76BNT–0.04BLT–0.2BKT ceramics with the sintering temperature provides a beneficial contribution to the piezoelectric coefficient; however, it detrimentally contributes to the depolarization temperature. The charge sensitivity of the prototype accelerometers was evaluated with changes in the seismic mass and the layer number of the piezoceramics. The deviation between the theoretical and measured values of charge sensitivity was less than 10%.     

High Qm values and humidity effect on the electrical properties of (K,Na)NbO3 lead‐free piezoceramics doped with B2O3–CuO mixed oxides

To greatly enhance the mechanical quality factor (Q_m) of piezoceramic materials, B₂O₃–CuO mixed oxides were added to a K_0.48Na_0.52NbO₃‐based lead‐free piezoceramic (abbreviated as BC‐KNN). The results suggest that the B₂O₃–CuO additives effectively improved the sinterability and Q_m value of the piezoceramic. An optimal Q_m value as high as 2128 was obtained, which is 35 times higher than that of pure KNN ceramic. Interestingly, we found that the Q_m value was sensitive to humidity of the surrounding environment. As the relative humidity (RH) increased from 25% RH to 78% RH, the Q_m value of the BC‐KNN ceramics decreased from 2128 to 267. We found that the dependence of the Q_m value on humidity was closely related to the instability of the relative dielectric constant (?_r). Our results show that a dense microstructure is critical for maintaining a stable high Q_m performance in a humid environment.     

Correlation between the grain size and phase structure,electrical properties in BiScO3-PbTiO3-based piezoelectric ceramics

As one of the most promising candidates of high-temperature piezoelectric sensors, BiScO₃-PbTiO₃ (BS-PT)-based ceramics are commonly modified by end-member substitution to modify the phase structures and electrical properties. In this work, BS-PT-based piezoelectric ceramics with various grain sizes (1.4-3.7 μm) of the composition 0.98(0.36BiScO₃-0.64PbTiO₃)-0.02Bi(Sn_1/3Nb_2/3)O₃ were prepared by conventional solid-state reaction method at different sintering temperatures from 1100℃ to 1180℃. X-Ray diffraction results show that the tetragonal phase content increases from 68.9% to 85.7% with the increasing sintering temperature. Transmission electron microscope characterizations reveal that micromorphology and domain morphology are sensitive to grain size. In addition, the dielectric and ferroelectric properties are almost independent on the sintering temperature, whereas an optimal piezoelectric constant d₃₃ of 450 pC/N is achieved when the sintering temperature is 1120℃, which can be due to the suitable coexistence of the rhombohedral and tetrahedral phase, as well as the coexistence of nanodomains and subsize strip-like domain. All of the results not only open a new window to improve d₃₃ of piezoelectric ceramics but also help to further understand microstructure-property relationships in piezoelectric ceramics.