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.     

Enhanced microwave absorption and electromagnetic shielding property of (1-x)K0.5Na0.5NbO3 ~ xAl2O3 nano-ceramics

(1-x) K_0.5Na_0.5NbO₃ ~ xAl₂O₃ (x = 0, 0.2, 0.4, 0.6) ceramics were prepared via a traditional solid-state reaction method. The phase structure, micro-morphology, dielectric properties and electromagnetic properties of ceramic samples were studied and analyzed. Results indicate that all the samples are similar to K_0.5Na_0.5NbO₃ (KNN) in perovskite structure. With the increase of Al₂O₃ content, the X-ray diffraction peaks move to a large angle region, suggesting the substitution of niobium ions by aluminium ions and the distortion of the KNN lattice with a new phase arising. With the increase of Al₂O₃ content the grain size reduces and the dielectric constant decrease, yielding to the decrease of the electromagnetic shielding performance of ceramic. When the x is 0.4, the minimum value of reflectivity of sample is −28 dB at the frequency of 11.6 GHz. It can be concluded that both the grain size and Al₂O₃ content can obviously affect the electromagnetic properties of ceramics, which can be easily turned through a multi-layer SiO₂ heterojunction structure.     

Piezoelectric enhancements in K0.5Na0.5NbO3-based ceramics via structural evolutions

The current work aims to compare the effect of systematic A-site and B-site substitutions on the piezoelectricity of Ka_0.5Na_0.5NbO₃ (KNN)-based perovskite ceramics. The A-site elements was replaced by Li⁺ while Nb5⁺ was substituted by Sb⁵⁺ to form (K_0.4675Na_0.4675Li_0.065)NbO₃ (KNLN) and (K_0.4675Na_0.4675Li_0.065)(Nb_0.96Sb_0.04)O₃ (KNLNS) respectively. The ceramics were prepared using solid-state sintering method. The density of the ceramics steadily improved with the substitutions while the crystal structure evolved from monoclinic (in KNN) to the coexistence of monoclinic and tetragonal (in KNLN) and finally tetragonal in KNLNS. Distinct variations on size and morphology were recorded. Although density, crystal structure and morphology have minor effect on the E_c, they imposed considerable influences on P_r, d₃₃ and k_p. Despite relatively lower density, KNLN exhibited the highest P_r, d₃₃ and k_p at 9.80 μC/cm²,185 pC/N and 0.43 respectively signifying the positive enhancement brought by the co-existence of monoclinic and tetragonal crystal structures. More importantly, this work systematically proved that the co-existence of both structures signified the morphotropic phase boundary (MPB) composition as the primary factor for the enhancement of KNN piezoelectric properties.     

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.     

Improved transmittance and ferroelectric properties realized in KNN ceramics via SAN modification

Transparent, Sr(Al_0.5Nb_0.5)O₃‐modified K_0.5Na_0.5NbO₃ (KNN) ceramics were successfully fabricated by a solid‐state pressureless sintering method in this work. The obtained microstructure, transmittance, and electrical properties were characterized in detail. Our results indicated that the modification by Sr(Al_0.5Nb_0.5)O₃ significantly limited the grain growth behavior of KNN, resulting in dense ceramics with submicron grain size (<0.5 μm) and small pore size. Consequently, the ceramic with the 0.96K_0.5Na_0.5NbO₃‐0.04Sr(Al_0.5Nb_0.5)O₃ composition showed superior transmittance and electrical properties: T = 55% in the visible region (0.78 μm), d₃₃ = 105 pC/N, ε_r = 1021, and P_r = 15.1 μC/cm², which were significantly higher than those of pure KNN. Our findings implied that the addition of Sr(Al_0.5Nb_0.5)O₃ could be a good strategy to obtain superior transmittance and electrical properties in KNN and may shed light on other ferroelectric systems.     

The structure and electrical properties of Ca0.6(Li0.5Bi0.5-xPrx)0.4Bi2Nb2O9 high-temperature piezoelectric ceramics

Ca_0.6(Li_0.5Bi_0.5-xPr_x)_0.4Bi₂Nb₂O₉ ceramics were prepared via a solid-state reaction method. The effect of the Pr content on the structural and electrical properties was systematically investigated. X-ray diffraction (XRD) combined with Rietveld refinement and X-ray photoelectron spectroscopy (XPS) demonstrated that a moderate amount of Pr³⁺ can be incorporated into the NbO₆ octahedra, while excess Pr³⁺ ions probably enter into the (Bi₂O₂)²⁺ layers, thus resulting in an increase in the tetragonality of the crystal structure. The introduction of Pr suppressed the generation of oxygen vacancies and improved the preferential grain growth along the c-axis, which might be responsible for enhancing the resistivity (ρ ~ 10⁶ Ω cm at 600°C). The replacement of Pr³⁺ for A-site Bi³⁺ enhanced the piezoelectric property, and the piezoelectric constant d₃₃ increased from 13.8 pC/N to 16.3 pC/N. The high depolarization temperature (up to 900°C) implied that CBN-LBP100x ceramics are promising candidates for ultrahigh-temperature application.     

Enhancing the dielectric and energy storage properties of lead-free Na0.5Bi0.5TiO3–BaTiO3 ceramics by adding K0.5Na0.5NbO3 ferroelectric

A novel strategy of enhancing the dielectric and energy storage properties of Na_0.5Bi_0.5TiO₃–BaTiO₃ (NBT–BT) ceramics by introducing a K_0.5Na_0.5NbO₃ (KNN) ferroelectric phase is proposed herein, and its underlying mechanism is elucidated. The lead-free KNN ceramic decreases the residual polarisation and increases the electric breakdown strength of the NBT–BT matrix through the simultaneous modification of its A-sites and B-sites. The obtained NBT?BT?x?KNN ceramics have a perovskite structure with unifying grains. A bulk 0.9NBT–BT–0.1KNN ceramic sample with a thickness of 0.2 mm possesses a high energy storage density of 2.81 J/cm³ at an applied electric field of 180 kV/cm. Moreover, it exhibits good insulation properties and undergoes rapid charge and discharge processes. Therefore, the obtained 0.9NBT–BT–0.1KNN ceramic can be potentially used in high-power applications because of its high energy density, good insulation properties, and large discharge rate.     

Microstructure and electrical conductivity of A-site fully stoichiometric Na0.5+xBi0.5−xTiO3−δ with different Na/Bi ratios

The effect of nominal Na/Bi ratio on the microstructure and electrical conductivity of A-site fully stoichiometric sodium bismuth titanates, Na_0.5+xBi_0.5?xTiO_3?δ, was investigated in this study. Bulk samples with x?=?0, 0.01, 0.03, 0.05, 0.07, and 0.1 were prepared by conventional solid state reaction method. The as-calcined powders primarily exhibited the perovskite structure, which was identified by X-ray diffraction. Electron microscopic investigation of the sintered samples, however, revealed the presence of secondary phases, the amounts of which were found to increase with increasing Na/Bi ratio. Further elemental analysis by energy dispersive spectroscopy indicated that the secondary phases were mainly composed of sodium titanates with different Na/Ti ratios. The grain bulk and grain boundary conductivities of Na_0.5+xBi_0.5?xTiO_3?δ, measured by two-probe AC electrochemical impedance spectroscopy, significantly increased with increasing Na/Bi ratio when x?≤?0.03, but remained almost constant at higher x. The synergetic effect of oxygen vacancy creation, grain size reduction, and secondary phase formation on the variation in the conductivity upon increasing the nominal Na/Bi ratio in Na_0.5+xBi_0.5?xTiO_3?δ was discussed.     

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%.     

Effect of closed pores on dielectric properties of 0.8Na0.5Bi0.5TiO3-0.2K0.5Bi0.5TiO3 porous ceramics

Porous 0.8Na_0.5Bi_0.5TiO₃-0.2K_0.5Bi_0.5TiO₃ ceramics are fabricated via the pore-forming agent method with polymethyl methacrylate (PMMA) and stearic acid (SA) as pore forming agents, and microstructure observations demonstrate that the porosity, pore shape, and pore sizes can be controlled by the synthesis technology. The dielectric properties of porous ceramics are found not only correlated to the pore-matrix composite model, but also have a significant grain-size effect. Based on the Zener Theory, pining forces exerted by pores on the grain boundary are calculated, to explain the shape effect of pores on grain boundary migration. A phase-field simulation is carried out to investigate pore shape effect on the grain size regulation in porous polycrystalline, and simulation results are in good agreements with experiential results as well as theoretical calculations. Thus, a modified equation is proposed to predict the effective permittivity of the porous piezoelectric ceramics by considering effects of porosity, pore shape and grain size.     

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.     

Effect of A-Site Ionic Radius on the Structure and Microwave Dielectric Characteristics of Sr1+xSm1−xAl1−xTixO4 Ceramics

SrSmAlO₄ microwave dielectric ceramics were modified by Sr/Ti cosubstitution for Sm/Al. The effects of radius difference of A-site ions on the microwave dielectric characteristics were investigated together with the structure. Sr_1+xSm_1−xAl_1−xTi_xO₄ (x=0, 0.05, 0.10, and 0.15) ceramics were prepared by a solid-state reaction approach. X-ray diffraction studies revealed a single-phase K₂NiF₄-type solid solution with corresponding peaks shifting to lower 2θ as x increased. Minor inhomogeneous grain morphology for x=0.05 and a trace amount of second phases for x=0.10, 0.15 were detected by backscattered-electron microscopy and energy-dispersive X-ray analysis. With increasing Sr/Ti cosubstitution, the dielectric constant ɛ_r increased from 18.4 to 20.4, and the temperature coefficient of resonant frequency τ_f was adjusted from −1.8 to 7.4 ppm/°C almost linearly. However, the Q×f value decreased from 74,500 GHz at x=0–53,000 GHz at x=0.15. The internal stresses caused by the decreased tolerance factor and the large ionic radii difference between Sr²⁺ and Sm³⁺ should be the predominant reasons for such a decrease in the Q×f value. The high-resolution transmission electron microscopic results revealed an increase in the lattice distortion with increasing Sr/Ti cosubstitution, and subsequently supported the above conclusion upon the increased internal stresses.     

Composition,microstructure and electrical properties of K0.5Na0.5NbO3 ceramics fabricated by cold sintering assisted sintering

In this paper, cold sintering was served as a forming method to assist the conventional sintering, which is so-called cold sintering assisted sintering (CSAS) method. Lead-free K_0.5Na_0.5NbO₃ piezoelectric ceramics were prepared by the CSAS method, and the effects of the different procedures on the sintering behaviors and electrical properties of KNN ceramics were studied. Compared with conventional sintering (CS), cold sintering process can induce potassium-rich phase on the KNN particle surface, and remarkably increase both the green and sintering density of KNN ceramics. Meanwhile, the potassium-rich phase would transform to K₄Nb₆O₁₇ second phase on the grain surface, and subsequently suppress the volatilization of potassium element. The sinterability and electrical properties were greatly improved, and KNN piezoelectric ceramics with high performance can be manufactured in a wide sintering temperature range (1055 °C–1145 °C), which proves that CSAS has the potential to be an excellent sintering technique for producing KNN based ceramics.     

Room-temperature ferromagnetism in (K0.5Na0.5)NbO3-xBaNi0.5Nb0.5O3-δ ferroelectric ceramics with narrow bandgap

In this paper, a simple, reproducible and cost-effective solid-state reaction sintering process is developed to fabricate (K_0.5Na_0.5)NbO₃-xBaNi_0.5Nb_0.5O_3-δ (KNN-xBNN) ceramics with a narrow bandgap and room-temperature ferromagnetism. Here, we report a systematic investigation of the influence of the BaNi_0.5Nb_0.5O_3-δ (BNN) concentration on the properties of KNN-xBNN ceramics. All ceramics form orthorhombic perovskite structures with a space group Amm2 and a weak peak at the wavelength of 550 cm^?1 that is characteristic of the pillow shoulder of the orthorhombic phase. KNN-xBNN ceramics with x between 0.02 and 0.08 have a narrow bandgap of about 2.5 eV—much smaller than the 3.5 eV of its parent (K_0.5Na_0.5)NbO₃ (KNN) ceramic—which is attributed to Ni²⁺-oxygen vacancy combinations (Ni²⁺-V_O) raising the valence electron energy level of the KNN ceramic. Furthermore, doping BNN into KNN ceramics can significantly convert the magnetism from diamagnetism to ferromagnetism and the component of x = 0.08 achieves both maximum saturation magnetisation intensity (14 memu/g) and minimum coercive magnetic field (80 Oe). Our findings provide a systematic insight into the bandgap tunability and ferromagnetism induction at room temperature in lead-free perovskite KNN-xBNN ceramics, as well as demonstrate their potential applications in perovskite solar cells and multiferroic devices.     

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.     

Enhancement in electrical and magnetic properties of (Li0.5Ga0.5)2+ and (Li0.5Er0.5)2+-Modified BiFeO3-BaTiO3 ceramics

Effects of (Li_0.5Ga_0.5)²⁺ and (Li_0.5Er_0.5)²⁺ doping on the phase structure, electrical, and magnetic properties of 0.75BiFeO₃-0.25BaTiO₃ (BFO-BT) ceramics were investigated and analyzed. X-ray diffraction measurements suggested a rhombohedral distorted perovskite structure and no structural transformation with the increasing doping content. Rietveld refinement results revealed that (Li_0.5Ga_0.5)²⁺ ions were more susceptible to replace the B-sites and (Li_0.5Er_0.5)²⁺ ions tended to substitute the A-sites. A significant improvement in the dielectric loss, ferroelectricity, and magnetization was observed for both (Li_0.5Ga_0.5)²⁺ and (Li_0.5Er_0.5)²⁺-modified BFO–BT ceramics without the addition of MnO₂ compared to undoped ceramic samples. Remnant magnetization (M_r) of 0.35 emu/g was reached for LG6. The enhanced magnetic properties were related to the suppressed cycloidal spin structure, the presences of the local lattice disorder and the magnetic impurities induced by the (Li_0.5Ga_0.5)²⁺ and (Li_0.5Er_0.5)²⁺ substitution.     

Green and red upconversion luminescence of Er-doped K0.5Na0.5NbO3 ceramics

Er³⁺ doped K_0.5Na_0.5NbO₃ (KNN) lead-free piezoelectric ceramics were synthesized by the solid-state reaction method. The upconversion emission properties of Er³⁺ doped KNN ceramics were investigated as a function of Er³⁺ concentration and incident pumping power intensity. Bright green (~555 nm) and red (670 nm) upconversion emission bands were obtained under 980 nm excitation at room temperature, which are attributed to (²H_11/2, ⁴S_3/2)→⁴I_15/2 and ⁴F_9/2→⁴I_15/2 transitions, respectively. The upconversion emission intensity can be adjusted by changing Er³⁺ concentration, and the mechanism of upconversion processes involve not only a two-photon absorption but also a three-photon absorption. In addition to the admirable intrinsic piezoelectric properties of KNN, this kind of material may have potential application as a multifunctional device by integrating its upconversion and piezoelectric property.     

Chemical stability of KNbO3, NaNbO3, and K0.5Na0.5NbO3 in aqueous medium

In recent years, potassium sodium niobate (K_0.5Na_0.5NbO₃, KNN) has become popular and promising among perovskite lead‐free piezoceramic systems. In this study, the chemical stability of KNN powders in aqueous medium was investigated as a function of pH, time, and powder surface area. To better understand the dissolution behavior of the complex KNN stoichiometry, subconstituents such as potassium niobate (KNbO₃, KN) and sodium niobate (NaNbO₃, NN) were investigated separately first. Results showed that all of the cations in the structure underwent dissolution in different values. Indicating that KNN undergoes incongruent dissolution in aqueous medium, the dissolution of A site cations was higher at lower pH while the dissolution of B site cations increased at higher initial pH. The order of released cation concentrations (C_A1 = K > C_{A2 = Na} > C_B = Nb) fits with inverse relationship of cation field strength (FS) order, B = Nb⁵⁺_FS > A₂ = Na⁺_FS>A₁ = K⁺_FS, at pH 4, 7 and 10 for NN, KN, and KNN. Calculated diffuse layer thickness from the ICP data confirmed to outer amorphous layer in TEM image. Also, the ratio of normalized cation concentration versus surface area of powders showed that incongruent dissolution kinetic was driven by the diffusion step.     

Ferroelectric K0.5Na0.5NbO3 catalysts for dye wastewater degradation

K_0.5Na_0.5NbO₃ (KNN) particles were prepared by a solid–state method. X–ray diffraction, scanning electron microscopy, UV–visible spectrophotometry, and electrochemical impedance spectroscopy were used to study the structure, morphology, and properties of the samples. The obtained KNN is a ferroelectric material with orthorhombic perovskite structure at room temperature. The KNN particles can be used as piezo/photo–bicatalysts for degrading organic pollutants by utilizing vibrational and solar energy; the catalytic activity of the particles can be significantly improved owing to their polarization under an applied electric field. Poled KNN particles show a bicatalytic degradation ratio of rhodamine B (RhB) dye reaching 92% after 60 min. The results indicate that the KNN particles can be applied as attractive ferroelectric catalysts for organic pollutant degradation.     

In situ synthesis of Ba0.5Sr0.5TiO3–Mg3B2O6 composites and their dielectric response

Ba_0.5Sr_0.5TiO₃–Mg₃B₂O₆ (BST–MB) composites have been prepared in situ by a citrate gel process, and their structure and effective dielectric response have been investigated. The precursor with pH≥7 is suitable for in situ formation of the diphase structure consisting of BST and MB. Accordingly, MB particles homogeneously disperse in BST particles, accompanied by the formation of boron-rich grain boundary resulting from liquid phases sintering of B₂O₃. Related with the existence of boron-rich grain boundary and the incorporation of Mg²⁺ into BST lattice, permittivity decreases rapidly with increasing volume fraction of MB from 0.0 to 0.2 and then decreases slowly with further increasing, which coincides with theoretical prediction of the layered model.