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.     

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.     

Cold sintering of the ceramic potassium sodium niobate, (K0.5Na0.5)NbO3, and influences on piezoelectric properties

Cold Sintering was applied to densify a Potassium-Sodium Niobate solid solution composition, 0.5KNbO₃-0.5NaNbO₃ (KNN); the process uses a transient chemical sintering aid, moderate pressure (400 MPa), and temperatures between 230–300 °C to obtain ceramics of ～92 to 96 % theoretical density. Typically, sintering temperatures between ～1000?1050 °C are required to density KNN using conventional methods. In this paper, the densification was investigated during heating, particularly the shrinkage in the first 60 min of the cold sintering process. The low-field dielectric and electrical properties of the resulting ceramics were found to be comparable to conventionally sintered KNN. Electric fields up to 80 kV/cm could be applied, however the ceramics showed pinched hysteresis loops, even after poling over a wide range of temperatures and electric fields. A Rayleigh analysis was used to investigate domain dynamics and high reversible permittivity. The irreversible behavior was an order of magnitude lower than in conventionally sintered KNN, likely associated with defect pinning of ferroelectric domains. A Transmission Electron Microscopy (TEM) study revealed a high density of line defects in most grains; dislocations in the grains limit poling and domain wall movement, thus suppressing both the piezoelectric properties and the hysteresis. Furthermore, TEM observations indicated crystalline grain boundaries that were faceted with terrace kink ledges. These observations point to the importance of the initial powder optimization and grain boundary diffusion when using cold sintering to prepare ceramics that are intended to show bulk cooperative properties such as ferroelectricity. The impact of limited high temperature homogenization of bulk diffusional processes is discussed.     

The unusual case of plastic deformation and high dislocation densities with the cold sintering of the piezoelectric ceramic K0.5Na0.5NbO3

K_0.5Na_0.5NbO₃ (KNN) can be readily densified using the cold sintering process, but despite observing high relative permittivity, the ferroelectric hysteresis is strongly suppressed along with a major suppression in the all-important piezoelectric properties. In this study, KNN is fabricated using a NaOH+KOH transient flux under a uniaxial pressure of 400 MPa and heating to 300 °C for 2 h to drive densification to 93% theoretical. It is only after a secondary heat treatment that we observe improvements of the ferroelectric hysteresis and piezoelectric properties. From a detailed structural-property-processing study using analytical transmission electron microscopy (TEM), X-ray line broadening and high field dielectric characterization methodologies we conclude that there is an unusual in-situ plastic deformation process that takes place in addition to the densification under the cold sintering process. High densities of dislocations within grains were observed that lead to multiple pinning sites that impact both the intrinsic and extrinsic contributions to the high field dielectric and piezoelectric properties. Annealing significantly reduced the dislocation density in the highly defective crystallites, observed directly from the TEM and from the sharpening of the X-ray diffraction peaks, resulting in piezoelectric and ferroelectric properties that approached those of conventionally sintered KNN.     

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.     

Preparation of Na0.5Bi0.5TiO3 ceramics by hydrothermal-assisted cold sintering

A recently proposed novel technique, termed “cold sintering process” (CSP), can provide dense ceramic solids at remarkably low temperatures around 180?°C. In a recent work, we successfully obtained dense Na_0.5Bi_0.5TiO₃ ceramics by this method. Bismuth titanate sodium nanoparticles were prepared as the raw material powder by the hydrothermal synthesis route. A hydrothermal precursor solution was used as the transient solvent for cold sintering. Under the combined action of pressure and temperature, the Na_0.5Bi_0.5TiO₃ green body was densified by dissolution-precipitation, and a preliminary densified ceramic sheet was obtained. The amorphous phase in the ceramic sheet was then transformed into a crystalline phase by annealing. Finally, densified Na_0.5Bi_0.5TiO₃ ceramic sheets were obtained, with density of up to 99%, relative permittivity of 681, and dielectric loss of 0.08 at 10?kHz and room temperature. The piezoelectric coefficient d₃₃ of the sample was 52.5?pC/N. The properties of the prepared ceramics were comparable to those of the conventional sintered ceramics.     

Microstructures,piezoelectric properties and energy harvesting performance of undoped (K0.5Na0.5)NbO3 lead-free ceramics fabricated via two-step sintering

Piezoelectric energy harvesters have become increasingly popular in the field of green energy because of the ability to convert low-frequency environmental vibrations into usable electricity. To fabricate high-performance energy harvesters, the key requirements are piezoelectric ceramics with a small grain size, of near-full density, the intended stoichiometric ratio and a high transduction coefficient. In this work, the effects of two-step sintering on the sinterability, microstructure, piezoelectric properties and energy harvesting performance of (K_0.5Na_0.5)NbO₃ were systematically investigated. Compared with conventional single-step sintering, two-step sintering samples were of higher density, increasing from 91 % to 95 % of theoretical, reduced mean grain size, down from 17 μm to 7.5 μm, and decreased evaporation of the alkali metals. This translated into an improved piezoelectric performance (d₃₃ ∼122 pC/N, k_p ∼36 % and Q_m ∼76), a higher transduction coefficient and energy conversion efficiency as well as a higher open-circuit voltage and power density. This demonstrates the potential of two-step sintering as a high through-put sintering technique for moderate-performance, pure KNN ceramics.     

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.     

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%.     

Highly dense 0.3CaCeNbWO8-0.7LaMnO3 composite ceramics fabricated by cold sintering process

The cold sintering process (CSP) has been used for fabricating functional ceramics at a low sintering temperature. In this study, highly dense 0.3CaCeNbWO₈-0.7LaMnO₃ composite ceramics have been successfully fabricated by CSP. The phase structure, microstructure, and electrical properties of composite ceramics have been investigated. The composite ceramic is mainly composed of a tetragonal CaCeNbWO₈ phase with scheelite structure and an orthorhombic LaMnO₃ phase with perovskite structure. The relative density of composite ceramic is 94.5%, and is higher than that of single phase ceramic. The resistivity of composite ceramic exhibits negative temperature coefficient characteristics, with an aging coefficient less than 2%. Such a sintering methodology is of great significance, since it provides a feasible idea for preparing composite ceramics.     

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.     

High piezoelectric performance and domain configurations of (K0.45Na0.55)0.98Li0.02Nb0.76Ta0.18Sb0.06O3 lead-free ceramics prepared by two-step sintering

Research for high-performance lead-free piezoelectric materials has become an urgent issue from the environmental concern. Very limited attempts on two-step sintering had been made so far. In this study, (K_0.45Na_0.55)_0.98Li_0.02Nb_0.76Ta_0.18Sb_0.06O₃ ceramics were prepared by both conventional sintering and two-step sintering. Piezoelectric properties, microstructure and domain structure were found to change significantly with sintering methods and sintering conditions. Two-step sintering was performed in the way that temperature is first quickly raised to 1180 °C, kept for 1 min, then immediately cooled down to 1120 °C and maintained for a desired time length. The effects of dwelling time on piezoelectric performance and microstructure as well as domain structure were investigated. High piezoelectric properties of d₃₃ = 455 pC/N, k_p = 0.54 and k₃₃ = 0.67 were obtained in a ceramic prepared under the dwelling time of 20 h. This ceramic also possesses a very good piezoelectric thermal-ageing stability over −50 °C–150 °C. Further investigation reveals that this ceramic has a quite uniform grain-size distribution with the average grain size of about 12 μm in microstructure and shows domain patterns of simple parallel stripes with a hierarchical nanodomain structure appearing inside some of broad stripes. The observed excellent piezoelectric performance is considered to associate closely with the unique domain structure.     

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.     

Effects of Bi0.5Na0.5HfO3 addition on the phase structure and piezoelectric properties of (K,Na)NbO3‐based ceramics

Lead‐free perovskite (1‐x)(K_0.48Na_0.48Li_0.04)Nb_0.95Sb_0.05O₃‐x(Bi_0.5Na_0.5)HfO₃ piezoelectric ceramics were prepared by a traditional ceramic fabrication method. An investigation was conducted to assess the effects of (Bi_0.5Na_0.5)HfO₃ content on the crystal structure, microstructure, phase‐transition temperatures, and piezoelectric properties of the ceramics. The X‐ray diffraction results, combined with the temperature dependence of dielectric properties, revealed that the ceramics experienced a structural transition from an orthorhombic phase to a tetragonal phase with the addition of (Bi_0.5Na_0.5)HfO₃, and a coexistence of orthorhombic and tetragonal phases was identified in the composition range of 0.005≤x≤0.015. An obviously improved piezoelectric activity was obtained for the ceramics with compositions near the orthorhombic‐tetragonal phase boundary, among which the composition x=0.005 exhibited the maximum values of piezoelectric constant d₃₃, and planar and thickness electromechanical coupling coefficients (k_p and k_t) of 246 pC/N, 0.435, and 0.554, respectively. Furthermore, the Curie temperature of the ceramics was found decreasing with the increase in (Bi_0.5Na_0.5)HfO₃ content, but still maintaining above 300°C for the phase boundary compositions. These results indicate that the ceramics are promising lead‐free candidate materials for piezoelectric applications.     

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.     

Low-temperature synthesis of K0.5Na0.5NbO3 ceramics in a wide temperature window via cold-sintering assisted sintering method and enhanced electrical properties

High temperatures (≥ 1100 °C) and narrow temperature window (～ 20 °C) for sintering dense K_0.5Na_0.5NbO₃ ceramics always deteriorate their electrical properties. Here, via cold-sintering assisted sintering method, dense K_0.5Na_0.5NbO₃ ceramics were obtained in a wide temperature span between 800 °C and 1000 °C. An aqueous solution of NaOH and KOH mixture was used as transient liquid. Effects of liquid content (LC), molar concentration (MC) of liquid, cold-sintering temperature (T_CS), and post-annealing temperature (T_AN) on densification and electrical properties of the ceramics were investigated in detail. The ceramics prepared using LC = 10 wt%, MC = 10 mol/L, T_CS = 350 °C, and T_AN = 900 °C exhibit excellent electrical properties with d₃₃ = 123 pC/N, ε_r = 609, tanδ = 0.021, P_r = 28.0 μC/cm², P_m = 39.2 μC/cm², and E_c = 20.3 kV/cm. Compared to the ceramics with same or similar compositions via conventional solid-state sintering, the present K_0.5Na_0.5NbO₃ ceramics exhibit excellent electrical properties. The study endows the cold-sintering assisted sintering the successful method to prepare K_0.5Na_0.5NbO₃ ceramics at low temperatures and in a wide temperature window.     

Electrocaloric effect and pyroelectric performance in (K,Na)NbO3-based lead-free ceramics

The issue of how to achieve an electrocaloric effect (ECE) and pyroelectric effect in a material simultaneously remains to be a challenge for developing practical solid-state cooling devices and RF-detectors. Here, we structure a polymorphic phase transition (PPT) region by doping modification in KNN-based ceramics, which are developed to achieve the ECE. The direct measured ECE and pyroelectric properties are investigated in lead-free (1-x)K_0.5Na_0.5NbO₃-xBi_0.5Na_0.5ZrO₃ (KNN-xBNZ) ceramics. The adiabatic temperature change (∆T) of 0.22 K at 100°C, 0.14 K at 70°C and 0.16 K at 30°C can be obtained under an electric field of 35 kV cm^–1 for x = 0.03, 0.04 and 0.05, respectively. In addition, the temperature dependence of pyroelectric coefficient (p) is established for all compositions via the Byer-Roundy method. A large p of 454.46 × 10^–4 C m^–2 K^–1 is detected at Curie temperature (T_C) in the ceramics with x = 0.03. Achieving electrocaloric effect and pyroelectric performance simultaneously may shed light and provide a feasible design scheme for developing practically useful electrocaloric and pyroelectric materials.     

Rapid preparation of Bi0.5Na0.5TiO3 ceramics by reactive flash sintering of Bi2O3-NaCO3-TiO2 mixed powders

Lead-free Bi_0.5Na_0.5TiO₃ piezoelectric ceramics were successfully prepared by reactive flash sintering of Bi₂O₃-NaCO₃-TiO₂ mixed powders, where phase transformation and densification occurred simultaneously. The influence of electric field strength, current density and holding time at constant current state on the phase transformation and densification were investigated. The current density had a significant influence on the extent of phase transformation and densification. The holding time had no influence on the phase transformation, but had an important effect on crystallinity of sample. The sintered bulks exhibited the maximum polarization P_m of 16.8 μC/cm², remanent polarization P_r of 9.6 μC/cm², coercive field E_c of 29 kV/cmm, maximum electric-field-induced strain of 0.053 %, and piezoelectric coefficient d₃₃ of 85 pC/N. The reactive flash sintering can prepare the dense and single-phase ceramics from multiphase precursor powders in one step of flash, providing a new way for rapid production of ceramic materials.     

Preparation and properties of LiF transparent ceramics by cold sintering process

The development of optoelectronic devices depends on the development of optoelectronic materials such as transparent ceramics. LiF transparent ceramics are photoelectronic ceramics with excellent photoelectric properties. Still, the traditional preparation of LiF transparent ceramics generally needs a high temperature or high-pressure environment, and the cost is high. This paper adopts a cold sintering process to prepare high-density LiF transparent ceramics at low temperatures to reduce the preparation conditions. The effects of different cold sintering temperatures on microstructure, density, hardness, visible and near-infrared transmittance, and electrical properties of transparent ceramics were studied. The results show that using LiOH solution as the solvent, the relative density of LiF ceramics can reach up to 99.64% under the sintering condition of 375 °C/470 MPa, and the Vickers hardness is 1.34 GPa. Vickers hardness is 1.34 GPa. The transmittance in the visible and near-infrared regions is 60.45% and 85.31%, respectively. The dielectric constant and dielectric loss of 13 GHz are 4.36 and 1.11 × 10⁻³, respectively.