Crystal structure and orthorhombic–tetragonal phase transition of nanoscale (Li0.06Na0.47K0.47)NbO3

Lead-free nano (Li_0.06Na_0.47K_0.47)NbO₃ powders, with pure perovskite structure and various grain sizes between about 30 and 60 nm, have been successfully synthesized by a novel sol–gel method, in which Nb₂O₅ was used as the Nb source. The refining XRD and Raman spectra were used in combination with TEM to investigate the evolution of lattice structure and phase transformation behavior as a function of grain size. The results demonstrated that the growth process of grains has been divided into two stages, and the distortion of unit cell apparently decreases with decreasing grain size. At around 35 nm, the phase structure of (Li_0.06Na_0.47K_0.47)NbO₃ changed from orthorhombic to tetragonal. This phenomenon is related to a grain size-induced structural phase transition. For the well accepted wisdom that niobates get super piezoelectric properties in orthorhombic–tetragonal transition region, our results suggested a critical size for the application of (Li_0.06Na_0.47K_0.47)NbO₃ in nano piezoelectric devices.     

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.     

Temperature stability and phase transition of Li0.02(KxNa1−x)0.98NbO3 ceramics

Li_0.02(K_xNa_1?x)_0.98NbO₃(x = 0.35–0.55) ceramics were prepared using the conventional solid state sintering method. The thermal behaviors of Li-modified (K_xNa_1?x)NbO₃ ceramics were investigated from ?30 to 150 °C, and the effect of Na/K ratio in (K_xNa_1?x)NbO₃ ceramics on thermal behavior and electrical properties was also studied. In the case of Li_0.02(K_xNa_1?x)_0.98NbO₃ ceramics with 0.5 wt.% ZnO, the transition temperature was sharply decreased because of a phase transition as the composition range of x was 0.425–0.475. From the results of the temperature dependence of piezoelectric properties, it is assumed that the Na-rich phase is less stable than the K-rich phase for temperature change.     

Li2O excess (Na0.51K0.47Li0.02)(Nb0.8Ta0.2)O3 lead free piezoelectric ceramics

1 mol% Li₂O excess (Na_0.51K_0.47Li_0.02)(Nb_0.8Ta_0.2)O₃ ceramics were prepared by the conventional mixed oxide method and sintered from 950 to 1200 °C. Also, Li₂O was employed as a sintering aid for high densification and low temperature sintering process. X-ray diffraction results of 1 mol% Li₂O excess (Na_0.51K_0.47Li_0.02)(Nb_0.8Ta_0.2)O₃ lead free piezoelectric ceramics indicated that the specimens were well crystallized and have tetragonal structure. The specimens which sintered at 1050 °C showed the highest piezoelectric properties compared with others. The measured piezoelectric constant and electromechanical coupling coefficient were 231 pC/N and 38.9%, respectively. Curie temperature of (Na_0.51K_0.47Li_0.02)(Nb_0.8Ta_0.2)O₃ ceramics was 344.32, 344.4 and 344.5 °C at 1, 10 and 100 kHz, respectively.     

Preparation and characterization of lead-free (K0.47Na0.51Li0.02)(Nb0.8Ta0.2)O3 piezoceramic/epoxy composites with 0–3 connectivity

Lead-free (K_0.47Na_0.51Li_0.02)(Nb_0.8Ta_0.2)O₃ (KNLNT) piezoceramic/epoxy composites with 0–3 connectivity were prepared using cold-pressing. The dielectric and piezoelectric properties of the composites were examined as a function of mean particle size (D) within the range of 27–174 μm at a fixed ceramic content of 85 vol%. The dielectric constant increased with D by the combined effects of increased connectivity and decreased surface-to-volume ratio of ceramics. When D = 125 μm, the piezoelectric constant showed a highest value of 44 pC/N that is much greater than those of previous reports on lead-free piezoelectric 0–3 ceramic/polymer composites.     

Effect of high energy milling process on microstructure and piezoelectric/dielectric properties of K0.475Na0.475Li0.05NbO3 solid solution

K_0.475Na_0.475Li_0.05NbO₃ (abbreviated as NKLN) ceramic of near the morphotropic phase boundary (MPB) composition was synthesized by two different processes. The first one is the high energy milling [sometimes abbreviated as HEM hereafter] process, which involves mixing the starting materials and milling the calcined powder using a high energy nano-mill, in order to obtain nano-sized particles. The second one is a conventional mixed oxide method. The HEM process of the starting materials lowered the calcination temperature to the extent of 200 °C as compared with conventionally fabricated NKLN. The particle size of the powder, exposed to the HEM process, reduced to 40 nm, whereas the conventionally ball-milled powder had a larger size of 420 nm after the mixing process. Furthermore, the HEM process improved the reaction activity and homogeneity of the materials used throughout the process, accompanying the enhancement of the sintering density, grain uniformity, and the decrease of grain size. In order to investigate the effects of the HEM process on the electric properties of NKLN ceramics, the dielectric and piezoelectric properties of sintered specimens fabricated by two different processes were evaluated. It was found that the properties of the nano-sized NKLN ceramic near the MPB composition were increased by the modified method, showing the maximum values of d₃₃=179 pC/N, k_p=34% and K₃₃^T=440 compared with 132 pC/N, 29%, and 400, respectively in the conventional process. Further evidence for the grain size effect was investigated by the polarization–electric field curve at room temperature. The remnant polarization for the nano-sized NKLN specimen had a higher value of 24.3 μC/cm² compared with that of 13.7 μC/cm² for conventional NKLN, whereas the coercive field had a similar value. The modified mixing and milling method was considered to be a new and promising process for lead-free piezoelectric ceramics owing to their excellent piezoelectric/dielectric properties.     

An enhanced mechanical quality factor and a low dielectric loss in lithium sodium niobate lead-free ceramics

(Li_0.12Na_0.88)(Nb_0.96?xSb_0.04Ta_x)O₃ (LNNST) ceramics were fabricated by the normal sintering. These LNNST ceramics endure a phase transition from an orthorhombic phase, a coexistence of orthorhombic and tetragonal phases, to a tetragonal phase with increasing Ta content. Dense microstructure has been developed for all ceramics. The T_c decreases and the ?_r increases with increasing Ta content, together with a very low dielectric loss of less than 1.3%. A high Q_m value of ～1230 is demonstrated for the ceramic with x = 0.06. Enhanced piezoelectric properties are also demonstrated for the ceramic with x = 0.03 because of a coexistence of two phases. Therefore, this ceramic is a promising candidate for the transducer and transformer applications.     

Phase transition behavior and temperature-stable piezoelectric properties of new quaternary (K,Na)NbO3 based ceramics

(K, Na)NbO₃-based lead free materials have been found to exhibit good piezoelectric properties due to the orthorhombic–tetragonal polymorphic phase transition (PPT) temperature compositionally shifted downward to near room temperature. However, this transition correspondingly results in a strong temperature dependence of the dielectric and piezoelectric properties. In this work, new quaternary (1?x) (K_0.4425Na_0.52Li_0.0375)(Nb_0.8925Sb_0.07Ta_0.0375)O₃ (KNLNST)–xSrTiO₃ (ST) lead-free piezoelectric ceramics were fabricated by a conventional ceramic technique and their structure and piezoelectric properties were also studied. The results of X-ray diffraction reveal that SrTiO₃ diffuses into the KNLNST lattices to form a new solid solution with a perovskite structure. After the addition of SrTiO₃, tetragonal–orthorhombic phase transition shifts to lower temperatures. The good piezoelectric properties of 0.995 KNLNST–0.005 ST material were found to be d₃₃～295 pC/N, k_p～42%, and ε_r～1902, with greatly improved temperature stability over the temperature range of 0–100 °C, demonstrating practical potential for actuator and ultrasonic transducer applications.     

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.     

Cytotoxicity and degradation behavior of potassium sodium niobate piezoelectric ceramics

In the present study, two lead-free piezoelectric ceramics, potassium sodium niobate (K_0.5Na_0.5NbO₃, KNN) and lithium-doped potassium sodium niobate (Li_0.06K_0.47Na_0.47NbO₃, LKNN), were prepared by a solid-state reaction process. The cytotoxicity evaluation indicated that the cytotoxicity of KNN is low. However, a strength decrease was noted after soaking in saline solution for 7 days. The addition of 6 mol% Li into the KNN improves its density; the strength and piezoelectric coefficient are enhanced consequently. Nevertheless, the cytotoxicity of LKNN is slightly higher than that of KNN. The higher cytotoxicity is related to the release of Li ions. The release of Li ion also induces the degradation of piezoelectric performance.     

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.     

Domain configuration and piezoelectric properties of (K0.50Na0.50)1−xLix(Nb0.80Ta0.20)O3 ceramics

Domain structure plays an important role in determining piezoelectric properties of ferroelectric materials. However, limited studies have been carried out on the domains of (K,Na)NbO₃-based lead free ceramics. The domain configuration, domain reversal behavior and piezoelectric properties of (K_0.50Na_0.50)_1−xLi_x(Nb_0.80Ta_0.20)O₃ (KNN-Li_x) ceramics with x = 0.02, 0.035 and 0.05, were studied in this research. It was observed that ceramics with different phases show distinctly different domain configurations and domain reversal behaviors. When compared to other two compositions, x = 0.035 with coexistent orthorhombic-tetragonal phases at room temperature was found to possess curved domain stripes and larger average domain width, leading to optimal piezoelectric properties with d₃₃* = 260 pm/V and k_p = 48%. Based on the microstructures, polarization hysteresis loops and unipolar strain curves under high electric field, it was concluded that the larger domain size and easier domain switching are due to the coexistence of orthorhombic and tetragonal phases, account for the improved properties in KNNT-Li_0.035 ceramics.     

Influence of calcination temperature on the piezoelectric properties of Ag2O doped 0.94(K0.5Na0.5)NbO3–0.06LiNbO3 ceramics

The effects of calcination temperature on the bulk density, piezoelectric, and ferroelectric properties were investigated for the Ag₂O doped 0.94(K_0.5Na_0.5)NbO₃–0.06LiNbO₃ ceramics. The calcination temperatures were varied from 750 to 950 °C by 50 °C differences. An tetragonal XRD pattern, consistent with single-phase 0.94(K_0.5Na_0.5)NbO₃–0.06LiNbO₃ was obtained after calcination at 850 °C for 2 h. And the experimental results showed that Ag₂O doped 0.94(K_0.5Na_0.5)NbO₃–0.06LiNbO₃ ceramics calcined at 850 °C had a remnant polarization P_r=24.5 μC/cm², bulk density=4.32 g/cm³, piezoelectric constant d₃₃=282 pC/N and electromechanical coefficient k_p=37.8%.     

Phase transition behavior and electrical properties of (1 − x)Bi0.5Na0.5TiO3–x(Na0.53K0.44Li0.04)(Nb0.88Sb0.08Ta0.04)O3 lead-free ceramics

(1 ? x)Bi_0.5Na_0.5TiO₃–x(Na_0.53K_0.44Li_0.04)(Nb_0.88Sb_0.08Ta_0.04)O₃ (BNT–xNKLNST) with x = 0–0.10 lead-free piezoelectric ceramics were prepared by a solid state method, and the structure and electrical properties were investigated in this study. It is found that a morphotropic phase boundary (MPB) of rhombohedral (R) and tetragonal (T) phase exists in the range of 0.03 ≤ x ≤ 0.05 and the structure changes to paraelectric phase when x > 0.07. The samples with x = 0.05 exhibit improved electrical properties owing to the formation of MPB, which are as follows: piezoelectric constant d₃₃ = 120 pC/N, remnant polarization P_r = 39.4 μC/cm² and coercive field E_c = 3.6 kV/mm. These results indicate that the enhanced piezoelectric properties for BNT can be achieved by forming the coexistence of R and T phase.     

Optical and electrical properties of pressureless sintered transparent (K0.37Na0.63)NbO3-based ceramics

Lead-free (1−x)(K_0.37Na_0.63)NbO₃-xCa(Sc_0.5Nb_0.5)O₃ (x=0.050, 0.070, 0.090, 0.095 and 0.100) transparent ferroelectric ceramics have been fabricated by pressureless sintering procedure. Transmittance of 0.91(K_0.37Na_0.63)NbO₃-0.09Ca(Sc_0.5Nb_0.5)O₃ ceramics sintered in sealed alumina crucible was 15% higher than those sintered unsealed in air. By increasing the content of Ca(Sc_0.5Nb_0.5)O₃, the phase structure of (K_0.37Na_0.63)NbO₃ ceramics transformed from orthorhombic to tetragonal symmetry first and then to pseudo cubic symmetry. The 0.91(K_0.37Na_0.63)NbO₃-0.09Ca(Sc_0.5Nb_0.5)O₃ ceramics exhibited high density (98%), high transmittance (60%) in the near-IR region and relatively good electrical properties (ε_r=1914, tanδ=0.037, T_c=147 °C, P_r=6.88 μC/cm², E_c=8.49 kV/cm). Meanwhile, the introduction of Ca(Sc_0.5Nb_0.5)O₃ induced a composition fluctuation in the (K_0.37Na_0.63)NbO₃ lattice and made the ceramics more relaxor-like, which would lead to a further reduction of light scattering. These results demonstrated that 0.91(K_0.37Na_0.63)NbO₃-0.09Ca(Sc_0.5Nb_0.5)O₃ could be promising lead-free transparent ferroelectric ceramics.     

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.     

Enhanced piezoelectric properties of (Na0.53K0.47)(Nb1−xTax)O3 ceramics by Ta substitution

The effects of Ta substitution for B-site Nb in (Na_0.53K_0.47)(Nb_1?xTa_x)O₃ (NKNT) ceramics were investigated in the range of x = 0–0.6. It was found that polymorphic phase transitions (PPT) were significantly influenced by Ta substitution. Transitions among orthorhombic, tetragonal, and cubic phases in sequence with temperature, T_O-T and T_C, respectively, decreased linearly with x. At x = 0.45, T_O-T was reduced to room temperature from 182 °C at x = 0, and subsequently piezoelectric coefficient (d₃₃) at room temperature was enhanced up to 284 pC/N from 120 pC/N at x = 0 due to the coexistence of ferroelectric orthorhombic and tetragonal NKNT phases. With x further increasing beyond x = 0.45, d₃₃ decreased due to there being no orthorhombic but only a tetragonal NKNT phase at room temperature with T_O-T below room temperature.     

Effects of CaTiO3 addition on microstructures and electrical properties of Na0.52K0.48NbO3 lead-free piezoelectric ceramics

In this article, various amounts of CaTiO₃ (CT) were added into (Na_0.52K_0.48)NbO₃ (NKN) ceramics using conventional oxide-mixing method for improving NKN's properties. The experimental results show that the (1?x)(Na_0.52K_0.48)NbO₃–xCaTiO₃ (x=0～0.07) solid solution system can be successfully synthesized. Addition of CaTiO₃ not only effectively prevents materials from deliquescence, but also improves the density and the electrical properties of the ceramics. The dielectric constant–temperature (ε_r?T) curves exhibit that the temperatures of the Curie point (T_c) and the phase transition from tetragonal to orthorhombic (T_O?T) are decreasing monotonously as the amount of CT addition is increased. A morphotropic phase boundary (MPB) can be found in the (1?x)NKN?xCT solid solution system as the doping amount of x=0.03, and the 0.97NKN–0.03CT ceramics, with a high bulk density, 98% theoretical density, and an appropriate grain size of about 1～2 μm, present a superior domain switching ability and the optimum properties: d₃₃=117 pC/N, k_p=0.39, P_r=21 μC/cm², and T_c=333 °C.     

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.     

Lead-free BaTiO3-Bi0.5Na0.5TiO3-Na0.73Bi0.09NbO3 relaxor ferroelectric ceramics for high energy storage

A series of (1-x)(0.65BaTiO₃-0.35Bi_0.5Na_0.5TiO₃)-xNa_0.73Bi_0.09NbO₃ ((1-x)BBNT-xNBN) (x = 0–0.14) ceramics were designed and fabricated using the conventional solid-state sintering method. The microstructure, dielectric property, relaxor behavior and energy storage property were systematically investigated. X-ray diffraction results reveal a pure perovskite structure and dielectric measurements exhibit a relaxor behavior for the (1-x)BBNT-xNBN ceramics. The slim polarization electric field (P-E) loops were observed in the samples with x ≥ 0.02 and the addition of Na_0.73Bi_0.09NbO₃ (NBN) could decrease the remnant polarization (P_r) of the (1-x)BBNT-xNBN ceramics obviously. The sample with x = 0.08 exhibits the highest energy storage density of 1.70 J/cm³ and the energy storage efficiency of 82% at 172 kV/cm owing to its submicron grain size and high relative density. These results show that the (1-x)BBNT-xNBN ceramics may be promising lead-free materials for high energy storage density capacitors.