Microstructure and electrical properties of Er-doped 0.67 Pb(Mg1/3Nb2/3)O3-0.33PbTiO3 ceramics with BaTiO3 templates

In this study, [001]-oriented Er-doped 0.67 Pb(Mg_1/3Nb_2/3)O₃-0.33PbTiO₃ (0.67PMN-0.33 PT) textured ceramics with different BaTiO₃ (BT) template concentrations were explored. The samples were prepared by tape-casting. Er³⁺ was added to modify the electrical properties of the polycrystalline ceramics, and the BT template was used to improve the texture of polycrystalline ceramics. The 0.67PMN-0.33 PT textured ceramics contained coexisting rhombohedral and tetragonal phases. The ceramics became increasingly textured as the sintering temperature increased up to 1250 °C. The piezoelectric coefficient of 0.67PMN-0.33 PT with 5 wt% BT was 634 pC/N, which is 1.2 times than that of randomly oriented 0.67PMN-0.33 PT. The strain of the ceramic with 5 wt% BT increased by 12.5% relative to a random control specimen. Analysis of the electrical properties and microstructure suggested that the enhancement of the piezoelectric coefficient and strain may be caused by the addition of Er³⁺ and the BT template. First, the directional growth of grains along the template affected the change-of-phase distribution of the system and formed a more adaptive phase. Second, Er³⁺ was substitutionally doped on the A-site of the perovskite to form local heterostructures. Finally, the relaxation components of the templates and Er³⁺ changed in the solid solution with the matrix. The solid solution of the BT templates and Er-doped-matrix powder changed the relaxation degree, which affected the interactions at the polar nanoregions and increased the piezoelectric coefficient of the ceramics.     

Structural and piezoelectric properties of <001> textured PZT‐PZNN piezoelectric ceramics

Rhombohedral 0.69Pb(Zr_0.47Ti_0.53)‐0.31Pb(Zn_0.6Ni_0.4)NbO₃ (PZT‐PZNN) ceramics were textured using 10.0 vol. % BaTiO₃ (BT) platelets along the <001> direction at 950°C with a high Lotgering factor of 95.3%. BT platelets did not react with the PZT‐PZNN ceramics, and the textured PZT‐PZNN ceramic had a tetragonal structure. The PZT‐PZNN ceramics exhibited a strain of 0.174% with a piezoelectric strain constant (d*₃₃) of 580 pC/N at 3.0 kV/mm. The textured PZT‐PZNN ceramic showed an increased strain of 0.276% and d*₃₃ of 920 pC/N at 3.0 kV/mm, which can be explained by the domain rotation. However, the d₃₃ values of the textured specimens are smaller than those of the untextured specimens because of the small remanent polarization and relative dielectric constant of BT platelets. The textured PZT‐PZNN ceramic synthesized in this work can be used for piezoelectric multilayer actuators because of its large strain and low sintering temperature.     

Achieving both high electromechanical properties and temperature stability in textured PMN-PT ceramics

Textured piezoelectric ceramics, such as textured Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (PMN-PT) ceramics, have attracted considerable attention from both academia and industry, as they possess crystal-like piezoelectric properties, high composition homogeneity, and low manufacturing cost. However, the main difficulty with the textured piezoelectric ceramics is the presence of BaTiO₃ (BT) templates, which greatly reduces their piezoelectricity and phase transition temperature. Thus, it is highly recommended to fabricate textured piezoelectric ceramics using as few templates as possible. Here, we successfully fabricated high-quality <001>-textured PMN-28PT ceramics (texturing degree of 99%) by using an extremely small amount of BT templates (1 vol.%) with the help of CuO/B₂O₃ sintering aids. The textured PMN-28PT ceramic exhibits 80% piezoelectric coefficient (d₃₃ ∼ 1200 pC/N), 96% electromechanical coefficient (k₃₃ ∼ 88%) and the same temperature stability (T_rt ∼ 100, T_c ∼ 150°C) when compared to its single crystal counterpart. In addition, by using an alternating current electric field poling (AC-poling), the piezoelectric coefficient d₃₃ and dielectric permittivity ε₃₃ of the textured PMN-28PT ceramics were further enhanced around 5–8%. It is believed that the advantages of high electromechanical properties, low cost, and easy mass production of textured PMN-28PT ceramic will make it a promising candidate for advanced electromechanical devices.     

Simultaneously enhanced piezoelectric response and piezoelectric voltage coefficient in textured KNN‐based ceramics

<001> ‐textured 0.99(K_0.49Na_0.49Li_0.02)(Nb_0.97‐xSb_0.03Ta_x)O₃‐0.01CaZrO₃ [abbreviated as 0.99KNLN_0.97‐xST_x‐0.01CZ, x = 0.03, 0.07, 0.10, 0.15, 0.20, 0.25] ceramics were prepared by templated grain growth (TGG) method and a two‐step sintering process. Giant longitudinal piezoelectric coefficient d₃₃ (391 pC/N) and piezoelectric strain coefficient d₃₃* (630 pm/V under an AC E‐field of 20 kV/cm) can be obtained in the textured ceramics with x = 0.25. All textured ceramics display superior k_p (>54%) and g₃₃ (>23 × 10^?3 Vm/N) which are in an order of magnitude with PZT ceramics. The maximum value of k_p (~63.3%) obtained in textured ceramics with x = 0.15 is higher than that of famous textured LF4 ceramics. Excellent comprehensive properties suggest that <001> ‐textured 0.99KNLN_0.97‐xST_x‐0.01CZ ceramics are promising candidates in the field of lead‐free piezoelectric materials.     

Textured CaBi4Ti4O15 ceramics with large piezoelectricity,excellent thermal stability and high resistivity

The bismuth layer-structured ferroelectrics (BLSF) are promising high-temperature piezoelectric materials, in which large piezoelectricity, good thermal stability and high electrical resistivity are desired. Here highly textured CaBi₄Ti₄O₁₅ BLSF ceramics with orientation factor of 82% have been fabricated by spark plasma sintering technique. The piezoelectric coefficient d₃₃ is significantly enhanced by 250%, from 7.2 pC/N for the texture-less sample to 25.3 pC/N for the textured one, accompanied by a high Curie temperature T_C= 788 °C. The variation of d₃₃ is below 5% in the temperature range of 25–500 °C, showing excellent thermal stability. The textured sample exhibits high electrical resistivity ρ = 2.1 × 10¹¹ Ω·cm, an order of magnitude larger than that of the texture-less sample. At the temperature as high as 500 °C, the textured sample still maintains excellent electrical properties of d₃₃ = 24.2 pC/N, tanδ = 9.9% and ρ = 2.7 × 10⁶ Ω·cm, suggesting that the textured CaBi₄Ti₄O₁₅ ceramics could be a potential candidate for high-temperature piezoelectric sensor or detector applications.     

Fabrication and electrical properties of textured (Na,K)0.5Bi0.5TiO3 ceramics by reactive-templated grain growth

Textured (Na_0.85K_0.15)_0.5Bi_0.5TiO₃ (NKBT) ceramics with a relative density of >94% were fabricated by reactive-templated grain growth. Plated-like Bi₄Ti₃O₁₂ template particles synthesized by the NaCl–KCl molten salt process were aligned by tape casting in a mixture of original oxide powders. The effect of sintering temperature on the grain orientation and electrical properties of textured NKBT ceramics were investigated. The results show that the textured ceramics have a microstructure with plated-like grains aligning in the direction parallel to the casting plane. The degree of grain orientation increased at increasing sintering temperature. The textured ceramics show anisotropic electrical properties in the directions parallel and perpendicular to the casting plane. The dielectric constant parallel to {h 0 0} plane is three times higher than that of the perpendicular direction in textured NKBT ceramics. The optimized sintering temperature is 1150 °C where the maximum dielectric constant is 2041, the remnant polarization is 68.7 μC/cm², the electromechanical coupling factor (k₃₁) and the piezoelectric constant (d₃₃) amount to 0.31 and 134 pC/N, respectively.     

Enhanced Field‐Induced Strain in the Textured Lead‐Free Ceramic

Reactive template grain growth method was applied to prepare <001> grain oriented 0.94(Na_0.52K_0.48)NbO₃–0.06LiNbO₃ ceramics using plate‐like NaNbO₃ particles as template. A two‐step sintering procedure was put forward to obtain textured ceramics with electromechanical coupling factor k_p = 64%, piezoelectric constant d₃₃ = 220 pC/N, and in practical application the value of available (converse piezoelectric constant) is about 516 pm/V, which are much higher than these of random form with same composition. Based on the analysis for the behavior of piezoelectricity against the measuring frequency and the intensity of external field, a possible mechanism considering the interaction between defect dipoles induced by the doping of Cu²⁺ and spontaneous polarization dipoles was proposed to elucidate the field‐induced giant strain in textured ceramics. This study does not only provide an insight to the origin and coupling effect of two kinds of dipole but also renders a general approach of defect engineering to take advantage of point defect in ceramics realizing certain function enhancement.     

Achieving large piezoelectric response and ultrahigh electrostriction in [001] textured BiScO3-PbTiO3 high-temperature piezoelectric ceramics

[001] textured 0.40BiScO₃-0.60PbTiO₃-0.125 mol%Nb⁵⁺ (BS-60PT-0.125Nb) high-temperature piezoelectric ceramics were synthesized using templated grain growth process. A high texture degree F₀₀₁ of 99% was obtained using 2 vol% BaTiO₃ (BT) templates. The piezoelectric charge constant d₃₃ and the unipolar strain under 40 kV cm⁻¹ at room temperature for the textured ceramics are 646 pC N⁻¹ and 0.36%, respectively, which is over two times as those for untextured ceramics (∼243 pC N⁻¹ and 0.17%). The electrostriction Q₃₃ value of the textured sample remarkably increased from 0.034 m⁴ C⁻² to 0.068 m⁴ C⁻² under 30 kV cm⁻¹, showing a twice higher than untextured. Compared with random ceramics, the improvement piezoelectric response of the textured ceramics is primarily attributed to the increase of the dielectric constant ε_r and electrostriction coefficient Q₃₃ along [001] orientation, which is originating from the anisotropy of piezoelectricity. The BS-60PT-0.125Nb textured ceramics have large piezoelectric response and ultrahigh electrostriction with high temperature stability (high depolarization temperature T_d of ∼360°C and high Curie temperature T_c of 421°C), showing great potential for the piezoelectric applications at high temperatures.     

Pb(Mg1/3Nb2/3)O3–PbTiO3 Textured Ceramics with High Piezoelectric Response by a Novel Templated Grain Growth Approach

Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ is used as a model system of perovskite solid solutions with very high piezoelectric response at tailored morphotropic phase boundaries to demonstrate the processing of textured ceramics by ceramic‐only technology. A novel homogeneous templated grain growth approach that uses conventional ceramic procedures and a single‐source nanocrystalline powder for the matrix and also for obtaining the templates is described. Two batches of (100) faceted cube‐shaped microcrystals with average sizes of 27 and 10 μm were successfully used as templates, and aligned by tape casting for the processing of <001>‐textured Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ piezoelectric ceramics. Materials with effective piezoelectric coefficients up to 1000 pC/N and ferroelectric properties approaching those of single crystals are obtained.     

Dielectric,Ferroelectric, and Piezoelectric Properties of BiFeO3–BaTiO3 Ceramics

Perovskite solid solution ceramics of (1 ? x)BiFeO₃–xBaTiO₃ (1 ? x)BF–xBT, 0.2 ≤ x ≤ 0.45) with high electrical resistivity were prepared by solid‐state reaction method. Actual ferroelectric hysteresis loops and temperature dependence of dielectric constant of the ceramics were obtained. Ceramics of 0.7BF–0.3BT with small rhombohedral distortion show highest remnant polarization (P_r = 26.0 μC/cm²) and piezoelectric coefficient (d₃₃ = 134 pC/N). Compositions with pseudo‐cubic symmetry (intermediate phases) show relaxor‐like dielectric anomaly. The values of P_r and d₃₃ decrease with increasing BT content, from 24.8 μC/cm² and 104 pC/N for 0.65BF–0.35BT to 8.2 μC/cm² and 5 pC/N for 0.55BF–0.45BT.     

Buffered template strategy for improving texture quality and piezoelectric properties of heterogeneous templated grain growth (K,Na)NbO3-based ceramics through interface engineering

Notwithstanding the advances in improving piezoelectric properties through templated grain growth, insights into the mechanical stress and microstructure of such materials are necessary. This is because the properties can be significantly varied depending on these parameters. Constructing heterostructure templates (²D–⁰D), in which the 0D nanoparticles have compositions similar to that of matrix powders, has significant potential in improving the above aspects. Here, BaTiO₃ (BT) templates and elements-doped (K,Na)NbO₃ (KNN) matrix powders were selected. Heterostructure BT (h-BT) templates were prepared by nucleation and growth of dopant-free KNN nanoparticles on bare BT. h-BT enabled a reduction in the mechanical stress at the interfaces within textured ceramics (h-BT-KNN), leading to larger grain growth and a higher texturing degree than those of textured ceramics (BT-KNN) fabricated using bare BT. The h-BT-KNN exhibited the enhanced piezoelectric constant (d₃₃) by ～170% and ～600% compared to those of the BT-KNN and nontextured ceramics, respectively.     

Effect of washing of barium titanate powders synthesized by hydrothermal method on their sinterability and piezoelectric properties

BaTiO₃ (BT) powders were synthesized by the hydrothermal method for fabricating lead-free barium titanate piezoelectric ceramics. The obtained powders were washed by distilled water and 0.01N acetic acid solutions separately, and utilized to obtain piezoelectric ceramics by traditional sintering. BT ceramics with the highest piezoelectric properties (d₃₃ value is over 190 pC/N) was obtained from the BT powder synthesized at 250 °C and washed by acetic acid solution. The influence of washing method and sintering temperature on the piezoelectric properties of BT ceramics were studied. The reasons were investigated by comparing the properties of BT powders and their compacts sintered at different temperature.     

Piezoelectric properties of [001]-textured high-power PMnN-PZT piezoceramics sintered at a low temperature

The 1.0 mol% CuO-added 0.14Pb(Mn1/3Nb2/3)O₃-0.86Pb(Zr_0.55Ti_0.45)O₃ (CPMnN-PZT) piezoceramics were synthesized at low temperatures (≤ 950 °C) by the columbite method to remove the pyrochlore phase. It exhibited a high Q_m of 3016 and a high T_C of 309 °C. However, it showed small d₃₃ and k_p values of 143 pC/N and 0.43, respectively. The CPMnN-PZT piezoceramic was textured along the [001] direction using BaTiO₃ (BT) templates to enhance its soft piezoelectric properties. The [001]-textured CPMnN-PZT + y vol% BT piezoceramics (1.0 ≤ y ≤ 5.0) were densified at a low temperature of 950 °C with a high Lotgering factor (≥ 92%). The textured sample (y = 1.0) showed a high Q_m of 1400 with increased d₃₃ and k_p values of 278 pC/N and 0.58, respectively, and its piezoelectricity showed excellent temperature stability up to 225 °C. Therefore, the textured CPMnN-PZT sample can be used for developing high-power piezoelectric devices.     

3D printing orientation controlled PMN-PT piezoelectric ceramics

Piezoelectric textured ceramics have drawn increasing research and industry interests by balancing the production cost and material performances. A new approach to realize the texture in piezoelectric ceramics is developed based on 3D printing stereolithography (SL) technique and successfully applied in the preparation of < 001 > -textured 0.71(Sm_0.01Pb_0.985)(Mg_1/3Nb_2/3)O₃-0.29(Sm_0.01Pb_0.985)TiO₃ (1 %Sm-PMN-29PT) ceramics in this work. As a critical process in texture ceramic fabrication, the alignment of BaTiO₃ templates along the horizontal direction is achieved by the shear force produced from the relative motion between the resin container and the blade during SL. The textured ceramics with obvious grain orientation features are successfully obtained. The enhanced piezoelectric properties of d₃₃ ≈ 652 pC N^?1 and d₃₃* ≈ 800 pm V^?1 are achieved in the 3D printed textured ceramic, which are about 60 % and 40 %, respectively, higher than their non-textured counterparts. Moreover, the textured sample shows a significant improvement on thermal stability of d₃₃*_T, which varies by less than ± 6 % from RT to 110 °C. Furthermore, the introduction of 3D printing into the synthesis of textured piezoelectric ceramics shows great advantages over the traditional tape-casting method. This work is expected to provide a promising way for the future design of textured piezoelectric functional materials.     

Enhancement of piezoelectric properties of BF–BT ceramics by using ZrO2 powder bed during the sintering process

ZrO₂ powders of various particle sizes (0.15, 0.7, 500 µm) were used to simulate loose powder bed sintering to prepare BF–BT piezoelectric ceramics. The phase structure, dielectric properties, ferroelectric properties, and piezoelectric properties were compared with the samples sintered by the conventional powder bed method (i.e., powder of the same composition as the sample). Results showed that the use of loose ZrO₂ powder bed could improve the heat conduction rate and the sintering quality of bulk BF–BT piezoelectric ceramics. The XPS results showed that the samples sintered with 500 µm ZrO₂ powder beds had the lowest concentration of Fe²⁺, exhibited the largest piezoelectric coefficients (d₃₃ = 201 pC/N). In contrast, the sample sintered with a conventional powder bed under the same sintering conditions had a piezoelectric coefficient d₃₃ of 156 pC/N.     

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.     

Low‐temperature sintering and enhanced piezoelectric properties of random and textured PIN–PMN–PT ceramics with Li2CO3

Low‐temperature sintered random and textured 36PIN–30PMN–34PT piezoelectric ceramics were successfully synthesized at a temperature as low as 950°C using Li₂CO₃ as sintering aids. The effects of Li₂CO₃ addition on microstructure, dielectric, ferroelectric, and piezoelectric properties in 36PIN–30PMN–34PT ternary system were systematically investigated. The results showed that the grain size of the specimens increased with the addition of sintering aids. The optimum properties for the random samples were obtained at 0.5 wt% Li₂CO₃ addition, with piezoelectric constant d₃₃ of 450 pC/N, planar electromechanical coupling coefficient k_p of 49%, peak permittivity ε_max of 25 612, remanent polarization P_r of 36.3 μC/cm². Moreover, the low‐temperature‐sintered textured samples at 0.5 wt% Li₂CO₃ addition exhibited a higher piezoelectric constant d₃₃ of 560 pC/N. These results indicated that the low‐temperature‐sintered 36PIN–30PMN–34PT piezoelectric ceramics were very promising candidates for the multilayer piezoelectric applications.     

Large electric field induced strain of Bi(Mg1/2Ti1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 ceramics textured by Template Grain Growth

<001> oriented xBi(Mg_1/2Ti_1/2)O₃-(0.7-x)Pb(Mg_1/3Nb_2/3)O₃-0.3PbTiO₃ (BMT-PMN-PT) textured ceramics are successfully fabricated by the template grain growth method using BaTiO₃ platelets as template. BMT-PMN-PT textured ceramics with different BMT contents are studied in terms of crystal structure, microstructures, dielectric and ferroelectric properties, and electric field induced strain. The as-fabricated BMT-PMN-PT textured ceramics were found to have a strong orientation along <001> direction. The frequency dispersion of dielectric constant of BMT-PMN-PT textured ceramics increases gradually and its relaxability becomes stronger with increasing BMT content. A large electric-field induced strain (0.42 % at 4 kV/mm) is obtained in 0.25BMT-0.45PMN-0.3PT textured ceramics with Lotgering factor 0.94, which is about 83 % enhancement than that of the randomly oriented ceramics (0.23 % at 4 kV/mm). The strain of 0.25BMT-0.45PMN-0.3PT textured ceramics have a relatively high thermal stability, with a slight decrease from 0.42 % to 0.28 % in the temperature range of 20−100 °C. Our research suggests that 0.25BMT-0.45PMN-0.3PT textured ceramics have a greatly potential for actuator devices applications owing to its advantages of large electric field induced strain response.     

Enhanced piezoelectric properties and temperature-insensitive strain behavior of <001>-textured KNN-based ceramics

In this study, <001>-textured 0.99(K_0.5Na_0.5)_0.95Li_0.05Nb_0.93Sb_0.07O₃−0.01CaZrO₃ [abbreviated as 0.99KNLNS-0.01CZ] lead-free ceramics were prepared by templated grain growth (TGG) using plate-like NaNbO₃ templates and sintered by a two-step sintering process with different soaking time. All textured samples with high Lotgering factor (f >85%) presented orthorhombic and tetragonal coexisting phase, and the proportion of orthorhombic phase was varied with prolonged soaking time. A large piezoelectric constant d₃₃ (~ 310 pC/N) was obtained in the textured samples with a 12 h soaking time, which was almost twice larger compared to the randomly oriented one. Furthermore, the field-induced piezoelectric strain coefficient d₃₃^*(~ 440 pm/V) of the textured ceramics with 6 h soaking time was larger than the value of randomly oriented one (~ 298 pm/V) at room-temperature. Enhanced piezoelectric response and good temperature stability prove that <001>-textured 0.99KNLNS-0.01CZ ceramics are promising candidates in the field of lead-free piezoelectric materials.     

Correlation between grain size and electrical properties of high-temperature lead-free 0.70BiFeO3-0.30BaTiO3 ceramics

0.70BiFeO₃-0.30BaTiO₃ (0.70BF-0.30BT) ceramics have been widely concerned because of their potential applications for high-temperature piezoelectric devices. In this work, a series of dense 0.70BF-0.30BT ceramics with average grain size variation from 0.55 to 6.0 μm were prepared. XRD results indicate that 0.70BF-0.30BT ceramics show the coexistence of rhombohedral and pseudo-cubic phases and the volume fraction of the rhombohedral phase increase with the grain size. The dielectric, ferroelectric and piezoelectric properties increase with the grain size initially from 0.55 to 5.0 μm and then decrease slightly. Values of d₃₃, P_r, and ε_r, of 0.70BF-0.30BT ceramics with the grain size of 5.0 μm are 185 pC/N, 21.2 μC/cm², and 638, respectively, about five times higher than those ceramics with fine-grain of 0.55 μm. Of particular importance is that 0.70BF-0.30BT ceramics with large grain sizes possess better piezoelectric thermal stability due to the much stabler poled domain state with the rising temperature. The detailed structural studies indicate that the enhanced electric properties are owing to the significantly improved domain motion and the increased lattice distortion. This clarifying the relationship between electrical properties and grain size offers a novel way of improving the performances of piezoceramics.