Piezoelectric K0.5Na0.5NbO3 Ceramics Textured Using Needlelike K0.5Na0.5NbO3 Templates

Improved performance by texturing has become attractive in the field of lead‐free ferroelectrics, but the effect depends heavily on the degree of texture, type of preferred orientation, and whether the material is a rotator or extender ferroelectric. Here, we report on successful texturing of K_0.5Na_0.5NbO₃ (KNN) ceramics by alignment of needlelike KNN templates in a matrix of KNN powder using tape casting. Homotemplated grain growth of the needles was confirmed during sintering, resulting in a high degree of texture parallel to the tape casting direction (TCD) and the aligned needles. The texture significantly improved the piezoelectric response parallel to the tape cast direction, corresponding to the direction of the strongest <001>_pc orientation, while the response normal to the tape cast plane was lower than for a nontextured KNN. In situ X‐ray diffraction during electric field application revealed that non‐180° domain reorientation was enhanced by an order of magnitude in the TCD, compared to the direction normal to the tape cast plane and in the nontextured ceramic. The effect of texture in KNN is discussed with respect to possible rotator ferroelectric properties of KNN.     

Piezoelectric voltage constant and sensitivity enhancements through phase boundary structure control of lead-free (K,Na)NbO3-based ceramics

The piezoelectric voltage constant (g₃₃) is a material parameter critical to piezoelectric voltage-type sensors for detecting vibrations or strains. Here, we report a lead-free (K,Na)NbO₃ (KNN)-based piezoelectric accelerometer with voltage sensitivity enhanced by taking advantage of a high g₃₃. To achieve a high g₃₃, the magnitudes of piezoelectric charge constant d₃₃ and dielectric permittivity ε_r of KNN were best coupled by manipulating the intrinsic polymorphic phase boundaries effectively with the help of Bi-based perovskite oxide additives. For the KNN composition that derives benefit from the combination of ε_r and d₃₃, the value of g₃₃ was found to be 46.9 × 10^?3 V·m/N, which is significantly higher than those (20 – 30 × 10^?3 V·m/N) found in well-known polycrystalline lead-based ceramics including commercial Pb(Zr,Ti)O₃ (PZT). Finally, the accelerometer sensor prototype built using the modified KNN composition demonstrated higher voltage sensitivity (183 mV/g) when measuring vibrations, showing a 29% increase against the PZT-based sensor (142 mV/g).     

Duplex structure in K0.5Na0.5NbO3-SrZrO3 ceramics with temperature-stable dielectric properties

Temperature-stable dielectric properties have been developed in the 0.86 K_0.5Na_0.5NbO₃-0.14SrZrO₃ solid solution system. High dielectric permittivity (ε′ = 2310) with low loss sustained in a broad temperature range (−55–201 °C), which was close to that of the commercial BaTiO₃-based high-temperature capacitors. Transmission electron microscopy with energy dispersive X-ray analysis directly revealed that submicron grains exhibited duplex core-shell structure. The outer shell region was similar to the target composition, whilst a slightly poor content of Sr and Zr presented in the core region. Based on Lichtenecker’s effective dielectric function analysis along with Lorentz fit of the temperature dependence of dielectric permittivity, a plausible mechanism explaining the temperature-stable dielectric response in present work was suggested. These results offer an opportunity to achieve the X8 R specification high-temperature capacitors in K_0.5Na_0.5NbO₃ based materials.     

Enhanced electromechanical properties of CaZrO3-modified (K0.5Na0.5)NbO3-based lead-free ceramics

Pairing of large strain response and high d₃₃ with high T_c in (K_0.5Na_0.5)NbO₃-based materials is of high significance in practical applications for piezoelectric actuators. Here, we report remarkable enhancement in the electromechanical properties for (1-x)(K_0.52Na_0.48) (Nb_0.95Sb_0.05)O₃-xCaZrO₃ (KNNS-xCZ) lead-free ceramics through the construction of a rhombohedral (R)-tetragonal (T) phase boundary. We investigated the correlation between the composition-driven phase boundary and resulting ferroelectric, piezoelectric, and strain properties in KNNS-xCZ ceramics. The KNNS-xCZ ceramics with x=0.02 exhibited a large strain response of 0.23% while keeping a relatively large d₃₃ of 237pC/N, which was mainly ascribed to the coexistence of R and T phases confirmed by the XRD and dielectric results. It was found that pairing of large strain response and high d₃₃ in KNN-based materials was achieved. As a consequence, we believe that this study opens the possibility to achieve high-performance lead-free electromechanical compounds for piezoelectric actuators applications.     

High performance lead-free Na0.5K0.5NbO3 piezoelectric ceramics obtained via oscillatory hot-pressing

Lead-free Na_0.5K_0.5NbO₃ (KNN) piezoelectric ceramics is regarded as a potential candidate for PZT material, while high performance is difficult to be obtained due to its poor sinterability and non-stoichiometric component. In this work, oscillatory pressure-assisted hot pressing (OPAHP) is utilized to fabricate KNN ceramics with high density. The KNN ceramics sintered at 860 °C exhibits superior performance with piezoelectric parameter (d₃₃) of 142 pC/N, electromechanical coupling factors (k_p) of 0.41, and relative permittivity (ε^T₃₃/ε₀) of 472–620. Additionally, hardness and flexural strength are measured as 3.55 GPa and 99.13 MPa, respectively. This work indicates that OPAHP technique is effective for fabricating KNN piezoelectric ceramics with high performance.     

Low-Temperature Sintering of (K0.5Na0.5)NbO3 Piezoelectric Ceramics

(K_0.5Na_0.5)NbO₃ piezoelectric ceramics can be sintered at a temperature as low as 750 °C for 5 h by incorporating Li₂CO₃ + Bi₂O₃ + ZnO as the sintering aid, whereas the conventional sintering temperature is around 1,100 °C. The optimal “soft” piezoelectric properties are obtained for ceramics sintered at 850 °C for 5 h. The dielectric permittivity (ε), piezoelectric coefficient (d ₃₃), electromechanical coupling (k _p) and mechanical quality factors (Q _m) of (K, Na)NbO₃ modified with 5.5 wt% sintering aids are 1,436, 90 pC/N, 0.3 and 10, respectively. These values are similar to the values obtained for (K_0.5Na_0.5)NbO₃ ceramics sintered above 1,100 °C. The underlying mechanism for abrupt change of dielectric permittivity is explained.     

Preparation and characterization of (K0.5Na0.5)NbO3 ceramics

In this paper the preparation and characterization of the ceramic material (K_0.5Na_0.5)NbO₃ (KNN) has been studied. Although conventional processing of KNN is often reported to result in sintered bodies lacking sufficient density, samples produced in this work exhibit theoretical density over 95% and yield superior piezoelectric properties than those obtained by the same method and reported previously. The electromechanical coupling coefficient in the thickness direction, k_t, is found to reach 45%. Apart from k_t, the piezoelectric coefficients in longitudinal and planar directions (d₃₃ of 100pC/N and d₃₁ of 43pC/N), hysteresis loop, pyroelectric coefficient measurements and dielectric properties are presented.     

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%.     

K0.5Na0.5NbO3-LiSbO3-BiFeO3无铅压电陶瓷的烧结特性

采用传统无压固相烧结法制备0.996(0.95K0.5NbO3-0.05LiSbO3)-0.004BiFeO3[0.996(0.95KNN-0.05LS)-0.004BF]无铅压电陶瓷,着重研究烧结保温时间对陶瓷结构、压电性能与介电性能和Curie温度Tc的影响.结果表明:随着烧结保温时间的延长,陶瓷趋于形成更稳定的四...     

Fine structural analysis and phase transition behavior for Li-modified Na0.5K0.5NbO3 lead-free piezoelectric ceramics

The fine crystal structure of Li_x(Na_0.5K_0.5)_1?xNbO₃ ceramics has been studied by means of Nb-K edge extended X-ray absorption fine structure (EXAFS) and X-ray internal strain measurement technique in the vicinity of the compositions showing a polymorphic phase boundary (PPB) between orthorhombic and tetragonal structures. The anisotropic distortion of the NbO₆ octahedral initially occurred when x was increased from 0.050 to 0.053, prior to the completion of the phase transition from orthorhombic to tetragonal symmetry. EXAFS clearly revealed that the bond distance of Nb–O1 with [0 0 1] configuration was increased, and that of Nb–O2 with [1 1 0] configuration was oppositely decreased in the NbO₆ octahedral. In the vicinity of the PPB compositions, the internal strain η_(0 1 1) also increased from 4.5 × 10^?3 to the maximum value of 12.0 × 10^?3 in the narrow x range from 0.040 to 0.055, then decreased to 3.2 × 10^?3 at x = 0.06. On the other hand, the η_(1 0 0) increases from 1.5 × 10^?3 to the maximum value of 2.9 × 10^?3 in the next narrow x range from 0.055 to 0.060. The variation of η_(1 0 0) differed in Li dependence from that of η_(0 1 1), which indicates that a large anisotropic strain remains in the crystal lattice in the PPB compositions.     

Phase-composition dependent domain responses in (K0.5Na0.5)NbO3-based piezoceramics

Lead-free (K_0.5Na_0.5)NbO₃-based (KNN) piezoceramics featuring a polymorphic phase boundary (PPB) between the orthorhombic and tetragonal phases at room temperature are reported to possess high piezoelectric properties but with inferior cycling stability, while the ceramics with a single tetragonal phase show improved cycling stability but with lower piezoelectric coefficients. In this work, electric biasing in-situ transmission electron microscopy (TEM) study is conducted on two KNN-based compositions, which are respectively at and off PPB. Our observations reveal the distinctive domain responses in these two ceramics under cyclic fields. The higher domain wall density in the poled KNN at PPB contributes to the high piezoelectric properties. Upon cycling, however, a new microstructure feature, “domain intersection”, is directly observed in this PPB composition. In comparison, the off-PPB KNN ceramic develops large domains during poling, which experience much less extent of disruption during cycling. Our comparative study provides the basis for understanding the relation between phase composition and piezoelectric performance.     

Synergistic engineering of doping and vacancy in K0.5Na0.5NbO3-based photochromic ceramics to boost luminescent readout ability

Photon-mode ultracapacity storage media made of inorganic photochromic luminescent materials are highly anticipated, and widely explored in the development of new optical data storage (ODS) technologies. Despite some recent breakthroughs, the optical storage capacity of defect-rich photochromics is still limited to low luminescent readout abilities. Herein, oxygen vacancy rich and bismuth doped K_0.5Na_0.5NbO₃:Eu³⁺ ceramics were designed, and synergistically boost the luminescence intensity, photochromic efficiency, and luminescent modulation properties, then effectively improving the luminescence readout abilities. The luminescence modulation ratio reaches up to 97.5% from 68.4% with the increase of oxygen vacancy concentrations due to hetero-valent bismuth doping, accompanied by high photochromic efficiency (35.7% from 21.9%) and excellent reproducibility. These results demonstrate that the synergistic engineering of oxygen vacancy and doping is a promising strategy for obtaining high-performance photochromic materials.     

K0.5Na0.5NbO3-BaCu0.5W0.5O3无铅压电陶瓷的结构与性能

以传统固相法工艺制备(1-x)K0.5Na0.5NbO3-xBaCu0.5W0.5O3[(1-x)KNN-xBCW]无铅压电陶瓷,研究不同BCW掺量(x=0％,0.1％,0.25％,0.5％,1.0％,摩尔分数,下同)对KNN陶瓷的晶体结构和电性能的影响,结果表明:x＜0.5％时,KNN陶瓷的相结构没有改变,仍为正交相...     

Enhanced piezoelectric property in Mn-doped K0.5Na0.5NbO3 ceramics via cold sintering process and KMnO4 solution

Through mixing the KMnO₄ solution with K_0.5Na_0.5NbO₃ (KNN) powders, cold sintering process (CSP) was employed to fabricate high-density Mn-doped KNN green pellets and ceramics. The microstructure, doping effect of Mn and electrical properties of these ceramics were studied in detail. Compared with conventional sintering (CS), the CSP supports the homogeneity of dopants and then promotes grain growth and ceramic densification; thus the Mn-doped KNN ceramics prepared by CSP show the obviously higher density and larger grain size. Besides, the less alkalis volatilization and oxygen vacancies result in more Mn³⁺ but less Mn⁴⁺ in CSP ceramics compared to CS ones, which endows the pinning effect and good poling characteristics in CSP ceramics. All the previous results contribute to the high dielectric constant and remnant polarization in CSP ceramics, which support the enhanced piezoelectric coefficient and are much superior than Mn-doped KNN ceramics prepared by CS. This work reveals that CSP can be a new doping strategy to perform chemical modification of electrical properties in KNN ceramics.     

Microstructural changes in (K0.5Na0.5)NbO3 ceramics sintered in various atmospheres

(K_0.5Na_0.5)NbO₃ is a potential lead-free piezoelectric ceramic, but often suffers from abnormal grain growth. Previous work on BaTiO₃ and SrTiO₃ has shown that abnormal grain growth can be suppressed by controlling the sintering atmosphere. In the present work, (K_0.5Na_0.5)NbO₃ was sintered in atmospheres ranging from O₂ to H₂ and the effect on grain growth behaviour studied. Sintering in reducing atmospheres causes a delay in the onset and a reduction in the amount of abnormal grain growth. The effect of sintering atmosphere on grain growth behaviour can be explained using the 2D nucleation-controlled theory of grain growth. Changes in the grain shape during sintering in reducing atmospheres indicate a reduction in the edge free energy of (K_0.5Na_0.5)NbO₃ caused by an increase in the concentration of oxygen vacancies. This decreases the critical driving force necessary for rapid grain growth and causes a transition from abnormal to pseudo-normal followed by abnormal grain growth.     

Defect structure,ferroelectricity and piezoelectricity in Fe/Mn/Cu-doped K0.5Na0.5NbO3 lead-free piezoelectric ceramics

For perovskite Pb-based ceramics, outstanding hardening piezoelectric properties can be easily induced by acceptor dopings of Fe, Mn or Cu, but in this work, completely different hardening effects are observed in Fe/Mn/Cu-doped K_0.5Na_0.5NbO₃ ceramics. Pure K_0.5Na_0.5NbO₃ exhibits a well-saturated single P-E loop, giving low Q_m of 72. Fe₂O₃-doped ceramic exhibits the combined effects of dominant donor and slight acceptor, giving a slightly slanted single P-E loop and relatively low Q_m of 156. For MnO₂-doped ceramic, moderate hardening properties with a slightly pinched P-E loop and relatively high Q_m of 370 are exhibited. Unlike Fe₂O₃ and MnO₂-doped ceramics, a double P-E loop and superhigh Q_m of 1965 are obtained in CuO-doped ceramic. The defect structure and corresponding microscopic mechanisms in the ceramics have been systematically investigated. Our study shows that defect characteristics should be responsible for distinct hardening properties in Fe, Mn and Cu-doped K_0.5Na_0.5NbO₃ materials.     

High‐Performance (Na0.5K0.5)NbO3 Thin Film Piezoelectric Energy Harvester

The pseudocubic structure of a (Na_0.5K_0.5)NbO₃ (NKN) film grown on a Pt/Ti/SiO₂/Si substrate changed to an orthorhombic structure when the film was transferred onto a polyimide substrate. Piezoelectric constant for the transferred NKN film increased considerably from 74 ± 11 to 120 ± 18 pm/V because the crystal structure of the film had changed from pseudocubic to orthorhombic. A gold interdigitated electrode was deposited onto the transferred NKN film to synthesize a NKN piezoelectric energy harvester. The NKN piezoelectric energy harvester was poled before bending under a 100 kV/cm DC electric field across the electrodes. When a strain of 0.85% and a strain rate of 4.05%/s were applied to the NKN piezoelectric energy harvester, it produced a maximum output voltage of 1.9 V and a current of 38 nA, corresponding to a power density of 2.89 μW/cm³.     

Large electrostrictive effect and dielectric properties of (K0.5Na0.5)NbO3-BaZrO3 ceramics

Electrostrictive materials are sought after in high-precision displacement actuators due to their ultra-low hysteresis electrostrain. Here we report a very promising electrostrictive material by doping barium zirconate into a sodium potassium niobate matrix. Also, the dielectric behaviors and electrostrictive properties of (1-x)K_0.5Na_0.5NbO₃-xBaZrO₃ (x = 0.10, 0.12, 0.14 and 0.16) ceramics are investigated in details. The doping of barium zirconate allows the diffuse phase transition to occur near room temperature. Diffuse dielectric anomalies at high temperatures are observed in poled ceramics, which are closely related to the activation of defects. High electrostrain (～0.1 %) with ultra-low strain hysteresis (< 12 %) are obtained at x = 0.14. Moreover, electrostrain exhibits excellent stability over a wide temperature range from 30 ℃ to 120 ℃.Further, the electrostrictive coefficient of ～0.066 m⁴/C² for the component was determined at high temperatures and high electric fields, demonstrating the excellent potential of the K_0.5Na_0.5NbO₃-BaZrO₃ solid solutions as electrostrictive materials.     

Thermally-induced local structural transformations in Na0.5Bi0.5TiO3-KNbO3 ceramics

The local symmetry of (1-x)Na_0.5Bi_0.5TiO₃-xKNbO₃ (NBT-xKN, x = 0.01?0.07) ceramics was thoroughly examined using high-energy synchrotron x-ray scattering and analysed using the pair distribution function (PDF) method. At room temperature, the structure of NBT-xKN (x = 0.01?0.07) ceramics was best refined using monoclinic C1c1 structures within the local-range (r<22 Å) and rhombohedral R3c within medium-range (22 Å <r <52 Å). Furthermore, the local monoclinic C1c1 structure exists from room temperature to > 420 °C (above the temperature of the maximum dielectric peak, T_m), as confirmed by in-situ temperature-dependent PDF analysis.     

Dielectric,ferroelectric and field-induced strain behavior of K0.5Na0.5NbO3-modified Bi0.5(Na0.78K0.22)0.5TiO3 lead-free ceramics

Lead-free piezoelectric (1 ? x)Bi_0.5(Na_0.78K_0.22)_0.5TiO₃–xK_0.5Na_0.5NbO₃ (BNKT–xKNN, x = 0–0.10) ceramics were synthesized using a conventional, solid-state reaction method. The effect of KNN addition on BNKT ceramics was investigated through X-ray diffraction (XRD), dielectric, ferroelectric and electric field-induced strain characterizations. XRD revealed a pure perovskite phase with tetragonal symmetry in the studied composition range. As the KNN content increased, the depolarization temperature (T_d) as well as maximum dielectric constant (?_m) decreased. The addition of KNN destabilized the ferroelectric order of BNKT ceramics exhibiting a pinched-type hysteresis loop with low remnant polarization (11 μC/cm²) and small piezoelectric constant (27 pC/N) at 3 mol% KNN. As a result, at x = 0.03 a significant enhancement of 0.22% was observed in the electric field-induced strain, which corresponds to a normalized strain (S_max/E_max) of ～434 pm/V. This enhancement is attributed to the coexistence of ferroelectric and non-polar phases at room temperature.