High Electric‐Induced Strain and Temperature‐Dependent Piezoelectric Properties of 0.75BF–0.25BZT Lead‐Free Ceramics

0.75BiFeO₃–0.25Ba(Zr_xTi_1?x) + 0.6 wt% MnO₂ (0.75BF–0.25BZT) ceramics with Mn addition were prepared by the solid‐state reaction method. The high‐field strain and high‐temperature piezoelectric properties of 0.75BF–0.25BZT ceramics were studied. Introduction of Zr in the solid solutions decreased the Curie temperature slightly, and improved the dielectric and piezoelectric properties obviously. The piezoelectric properties of 0.75BZT–0.25BT ceramics reached the maximum at Zr content of 10 mol%. The Curie temperature T_c, dielectric constant ε and loss tanδ (1 kHz), piezoelectric constant d₃₃, and planner electromechanical coupling factor k_p of 0.75BF–0.25BZT ceramics with 10 mol% Zr were 456°C, 650, 5%, 138 pC/N, and 0.30, respectively. The high‐field bipolar and unipolar strain under an electric field of 100 kV/cm reached up to 0.55% and 0.265%, respectively, which were comparable to those of BiScO₃–PbTiO₃ and “soft” PZT‐based ceramics. The typical “butterfly”‐shaped bipolar strain and frequency‐dependent peak‐to‐peak strain indicated that the large high‐field‐induced strain may be due to non‐180° domain switching. Rayleigh analysis reflected that the improved piezoelectric properties resulted from the enhanced extrinsic contribution by Zr doping. The unipolar strain of 0.75BF‐0.25BZT ceramics with 10 mol% Zr was almost linear from RT to 200°C. These results indicated that 0.75BF–0.25BZT ceramics were promising candidates for high‐temperature and lead‐free piezoelectric actuators.     

Nanodomain Engineered (K,Na)NbO3 Lead‐Free Piezoceramics: Enhanced Thermal and Cycling Reliabilities

The growing environmental concerns have been pushing the development of viable green alternatives for lead‐based piezoceramics to be one of the priorities in functional ceramic materials. A polymorphic phase transition has been utilized to enhance piezoelectric properties of lead‐free (K, Na)NbO₃‐based materials, accepting the drawbacks of high temperature and cycling instabilities. Here, we present that CaZrO₃‐modified (K, Na)NbO₃ piezoceramics not only possess excellent performance at ambient conditions benefiting from nanodomain engineering, but also exhibit superior stability against temperature fluctuation and electrical fatigue cycling. It was found that the piezoelectric coefficient d₃₃ is temperature independent under 4 kV/mm, which can be attributed to enhanced thermal stability of electric field engineered domain configuration; whereas the electric field induced strain exhibits excellent fatigue resistance up to 10⁷ sesquipolar cycles. These findings render the current material an unprecedented opportunity for actuator applications demanding improved thermal and cycling reliabilities.     

Influence of composition on the unipolar electric fatigue of Ba(Zr0.2Ti0.8)O3‐(Ba0.7Ca0.3)TiO3 lead‐free piezoceramics

The lead‐free (1?x)Ba(Zr_0.2Ti_0.8)O₃‐x(Ba_0.7Ca_0.3)TiO₃ system is considered as promising candidate for the replacement of lead‐based piezoceramics in actuation applications, during which electric fatigue is a major concern. This issue was addressed in this work, where the unipolar fatigue resistance of three (1?x)Ba(Zr_0.2Ti_0.8)O₃‐x(Ba_0.7Ca_0.3)TiO₃ compositions with different crystallographic structures (rhombohedral, orthorhombic, and tetragonal) was evaluated. Strain asymmetry and development of an internal bias field were observed in all compositions. The decrease in the remanent polarization and the large signal piezoelectric coefficient after 10⁷ unipolar cycles was found to lie between 6%‐12% and 2%‐13%, respectively. The most pronounced fatigue was observed for the orthorhombic composition, which has the largest extrinsic contribution to strain. On the other hand, the best fatigue resistance was observed for the tetragonal composition, which has a predominantly intrinsic strain response. The correlation of fatigue resistance with strain mechanism was corroborated with determination of the Rayleigh parameters and changes in the domain morphology after cycling as confirmed by piezoresponse force microscopy.     

Enhanced and stable strain memory in Mn‐doped Pb(Mn1/3Sb2/3)O3–Pb(Zr,Ti)O3 ceramics realized by sesquipolar loading

The negative electric field, field cycling and frequency dependence of strain memory effect in poled and aged Mn‐doped Pb(Mn_1/3Sb_2/3)O₃–Pb(Zr,Ti)O₃ (PMS–PZT) piezoceramics under sesquipolar loading were investigated. The strain memory effect of Mn‐doped PMS–PZT is especially sensitive to the applied negative electric field. Maximum strain memory of 0.32% is achieved when the negative electric field is around negative coercive field of ~2.1 kV/mm, which can be ascribed to the partially depoled state with randomized domains. And this strain memory shows very good cycling stability, varying less than 5% up to 10⁴ cycles, while almost 40% degradation is found under bipolar signal. In addition, due to the stabilized defect dipoles, the strain memory exhibits stable characteristic over a broad frequency range from 0.01 Hz to 20 Hz. The results may shed new insights into designing the novel strain memory actuators where stable strain state could be realized after the removal of electric field.     

The Composition and Temperature‐Dependent Structure Evolution and Large Strain Response in (1−x)(Bi0.5Na0.5)TiO3−xBa(Al0.5Ta0.5)O3 Ceramics

The (1?x) (Bi_0.5Na_0.5)TiO₃?xBa(Al_0.5Ta_0.5)O₃((1?x)BNT‐xBAT) lead‐free piezoceramics was fabricated using a conventional solid‐state reaction method. The temperature and composition‐dependent strain behavior, dielectric, ferroelectric (FE), piezoelectric, and pyroelectric properties have been systematically investigated to develop lead‐free piezoelectric materials with large strain response for actuator application. As the BAT content increased, the FE order is disrupted resulting in a degradation of the remanent polarization, coercive field, and the depolarization temperature (T_d). A large strain of 0.36% with normalized strain d₃₃* = 448pm/V was obtained for the optimum composition x = 0.045 at room temperature. The bipolar and unipolar strains for the compositions x = 0.035 and x = 0.04 reach almost identical maximum values when the temperature is in the vicinity of their respective depolarization temperature (T_d). The Raman‐spectra analysis, macroscopic properties, thermal depolarization results, and temperature‐dependent relationships of both polarization and strain demonstrated that the origin of the large strain response for this investigated system is attributed to a field‐induced relaxor to FE phase transformation.     

A series of 0‐3 composites of lead zirconate titanate and ferroelectric nylon77: Preparation and electrical properties

A series of 0‐3 composites of lead zirconate titanate (PZT) and nylon77 was prepared with PZT volume fractions between 0.1 and 0.6 using the combined method of solvent casting and hot pressing. Depending upon the volume fraction of PZT, the relative permittivities of the composites were found to be in the range of 200–2000 when measured at the highest practically possible temperature of 200°C. As PZT volume fraction increases, both the relative permittivity and the piezoelectric constant d₃₃ increase. The best combination of electrical properties and flexibility was obtained in 0.5 PZT volume fraction composites. At this composition, the remanent polarization P_r of composites was up to 1000 mC/m² at the applied electric field of 40 MV/m and it increased with an increase in temperature. The highest piezoelectric strain coefficient d₃₃ was obtained at 17 pC/N in 0.6 PZT volume fraction composites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

High Bipolar Fatigue Resistance of BCTZ Lead‐Free Piezoelectric Ceramics

(Ba, Ca)(Ti, Zr)O₃ ceramics have been considered as a potential lead‐free alternative to commonly used lead‐based piezoelectric ceramics due to their high piezoelectric performance at room temperature. In this study, the bipolar fatigue behavior of this material is investigated at room temperature. Two compositions were cycled with a bipolar electric field signal at 10 Hz with a maximum of three times the coercive field for up to approximately 10⁷ cycles. Both investigated compositions exhibited high bipolar fatigue resistance compared to other ceramics reported in the literatures. The high fatigue resistance originates from the lack of mechanical damage and a weak domain wall pinning effect due to their location in the phase transition region. It was also found that pore morphology affected bipolar fatigue behavior.     

Electrical Properties and Relaxor Phase Evolution of Li‐Modified BNT‐BKT‐BT Lead‐Free Ceramics

By conventional ceramics sintering technique, the lead‐free 0.85Bi_0.5Na_0.5(1?x)Li_0.5xTiO₃‐0.11Bi_0.5K_0.5TiO₃‐0.04BaTiO₃ (x =0–0.15) piezoelectric ceramics were obtained and the effects of Li dopant on the piezoelectric, dielectric, and ferroelectric properties were studied. With increasing Li addition, the temperature‐dependent permittivity exhibited the normal ferroelectric‐to‐ergodic relaxor (FE‐to‐ER) transition temperature (T_FE‐ER, abbreviated as T_F‐R) decreasing down to room temperature. The increasing Li content also enhanced the diffuseness of the FE‐to‐ER transition behavior. For composition with x = 0.15, a large unipolar strain of 0.37% ( = S_max/E_max = 570 pm/V) was achieved under 6.5 kV/mm applied electric field at room temperature. Both unipolar and bipolar strain curves related to the temperature closely, and when the temperature reached the T_F‐R, the normalized strain achieved a maximum value (e.g., for x = 0.10, = 755 pm/V) owing to the electric‐field‐induced ER‐to‐FE state transition.     

Temperature‐insensitive piezoelectricity in lead‐free NaNbO3‐based ceramics

In this work, we report a lead‐free piezoelectric ceramic of (0.9‐x)NaNbO₃‐0.1BaTiO₃‐xBaZrO₃, and the effects of BaZrO₃ on the phase structure, microstructure, electrical properties and temperature stability are investigated. A morphotropic phase boundary‐like region consisting of rhombohedral (R) and tetragonal (T) phases is constructed in the compositions with x = 0.035‐0.04. More importantly, in situ temperature independence of the piezoelectric effect {piezoelectric constant (d₃₃) and strain} can be achieved below the Curie temperature (T_c). Intriguingly, the electric field‐induced strain is still observed at T ≥ T_c due to the combined actions of the electrostrictive effect and the electric field‐induced phase transition. We believe that NaNbO₃‐based ceramics of this type have potential for applications in actuators and sensors.     

Electric‐Field‐Driven Phase Transition Process in (K,Na, Li)(Nb,Ta, Sb)O3 Lead‐Free Piezoceramics

The electric‐field‐driven phase transition in (K, Na, Li)(Nb, Ta, Sb)O₃ lead‐free piezoelectric ceramics was investigated by X‐ray diffraction, Raman spectra, and the temperature dependences of permittivity spectra. After poling under different electric fields, phase of the ceramics transformed gradually from orthorhombic–tetragonal coexisting phase to orthorhombic phase, indicating that the crystal structure of ceramics was strongly sensitive to electric field as an external stimulus. A secondary phase K₃Li₂Nb₅O₁₅ induced by electric field was detected in the ceramics with Li content of 7 mol%, which was close to the solubility limit of lithium. This field‐induced secondary phase resulted from the movement of Li ions and the structural deformation induced by electric field. Moreover, piezoelectric constant d₃₃ increased with the increasing poling field strength and the enhancement can be attributed to the field‐triggered domain switching. This study implied that in addition to temperature and composition, which has been reported in previous researches, electric field might be an effective way for inducing phase transition in lead‐free piezoelectric ceramics and improving the electrical performances simultaneously.     

Photoluminescence and Temperature Dependent Electrical Properties of Er‐Doped 0.94Bi0.5Na0.5TiO3‐0.06BaTiO3 Ceramics

Er‐doped 0.94Bi_0.5Na_0.5TiO₃‐0.06BaTiO₃ (BNT‐6BT: xEr, x is the molar ratio of Er³⁺ doping) lead‐free piezoceramics with x = 0–0.02 were prepared and their multifunctional properties have been comprehensively investigated. Our results show that Er‐doping has significant effects on morphology of grain, photoluminescence, dielectric, and ferroelectric properties of the ceramics. At room temperature, the green (550 nm) and red (670 nm) emissions are enhanced by Er‐doping, reaching the strongest emission intensity when x = 0.0075. The complex and composition‐dependent effects of electric poling on photoluminescence also have been measured. As for electrical properties, on the one hand, Er‐doping tends to flatten the dielectric constant‐temperature (ε_r‐T) curves, leading to temperature‐insensitive dielectric constant in a wide temperature range (50°C–300°C). On the other hand, Er‐doping significantly decreases the ferroelectric‐relaxor transition temperature (T_F–R) and depolarization temperature (T_d), with the T_F–R decreasing from 76°C to 42°C for x = 0–0.02. As a result, significant composition‐dependent electrical features were found in ferroelectric and piezoelectric properties at room temperature. In general, piezoelectric and ferroelectric properties tend to become weaker, as confirmed by the composition‐dependent piezoelectric coefficient (d₃₃), planar coupling factor (k_p), and the shape of polarization‐electric field (P–E), current‐electric field (J–E), bipolar/unipolar strain‐electric field (S–E) curves. Furthermore, to understand the relationship between the T_F–R/T_d and the electrical properties, the composition of x = 0.0075 has been intensively studied. Our results indicate that the BNT‐6BT: xEr with appropriate Er‐doping may be a promising multifunctional material with integrated photoluminescence and electrical properties for practical applications.     

Small Reduction of the Piezoelectric d33 Response in Potassium Sodium Niobate Thick Films

We have investigated the electromechanical response of potassium sodium niobate (K_0.5Na_0.5NbO₃ or KNN) thick films. The high‐field strain hysteresis loops and weak‐field converse piezoelectric d₃₃ coefficient of the films were measured and compared with those of KNN bulk ceramics under the same electric field conditions. The converse d₃₃ values of the thick films and bulk ceramics were equal to 82.5 and 138 pm/V, respectively, at 0.4 kV/mm. The fundamental difference between the piezoelectric response of the KNN films and the ceramics was studied in terms of the effective (“clamped”) piezoelectric d₃₃ coefficient. The reduction in the piezoelectric d₃₃ coefficient of the KNN films, resulting from the clamping by the substrate, was compared to lead‐based ferroelectric thick films, including Pb(Zr,Ti)O₃ (PZT) and (1 ? x)Pb(Mg_1/3Nb_2/3)O₃?xPbTiO₃ (PMN‐PT). We propose a possible explanation, based on the particular elastic properties of KNN, for the small relative difference observed between the “clamped” and “unclamped” (“bulk”) d₃₃ of KNN, in comparison with lead‐based systems.     

Temperature‐ and E‐field‐dependent domain configuration and electrical properties in (K,Na, Li)(Nb,Ta, Sb)O3 single crystal

E‐field‐ and temperature‐dependent domain evolution of lead‐free tetragonal (K, Na, Li)(Nb, Sb, Ta)O₃ (KNLNTS) single crystals as well as its corresponding electrical properties have been investigated. When E field is applied along [011]_C direction, (2T) engineered domain structure is formed. Spontaneous polarizations switch under a critical electric field (around 4‐5 kV/cm), resulting in significant changes in domain structure and great improvement in piezoelectric properties. Furthermore, it is found that piezoelectric constant d₃₁ and electromechanical coupling factor k₃₁ of [011]_C poled KNLNTS single crystal decrease with temperature. The extrinsic and intrinsic piezoelectric responses are discussed from the viewpoint of domain structure and lattice distortion, respectively. Our results show that the nanodomain structure relaxes and the lattice distortion declines with temperature, resulting in reduction of extrinsic and intrinsic piezoelectric responses, respectively. Therefore, the piezoelectric instability is ascribed to the decrease of both extrinsic and intrinsic contributions. This work provides a better understanding of domain engineering technique, and the useful information on the improvement of both piezoelectricity and temperature stability of the lead‐free piezoelectric materials.     

Effect of heat treatment on the electrical properties of lead zirconate titanate/poly (vinylidene fluoride) composites

Ceramic/polymer composites are attracting increasing interest in materials research and practical applications due to the combination of excellent electric properties of piezoelectric ceramics and good flexibility of polymer matrices. In this case, the crystallization of the polymer has a significant effect on the electric properties of ceramic/polymer composites. Based on different heat treatment methods, the crystallization of poly(vinylidene fluoride) (PVDF) in composites of lead zirconate titanate (PZT) and PVDF can be controlled effectively. PZT/PVDF composites with various PVDF crystallizations exhibit distinctive dielectric and piezoelectric properties. When the crystallization of PVDF is 21%, the PZT/PVDF composites show a high dielectric constant (ε) of 165 and a low dielectric loss (tan δ) of 0.03 at 10³ Hz, and when the crystallization of PVDF reaches 34%, the piezoelectric coefficient (d₃₃) of PZT/PVDF composites can be up to ca 100 pC N^?1. By controlling the crystallization of PVDF, PZT/PVDF composites with excellent dielectric and piezoelectric properties were obtained, which can be employed as promising candidates in high‐efficiency capacitors and as novel piezoelectric materials. Copyright © 2010 Society of Chemical Industry     

Performance improvement of piezoelectric‐rubber by particle formation of linear aggregates

We investigate the piezoelectric response of piezoelectric‐rubber consisting of lead zirconate titanate (PZT) particles and silicon rubber prepared by holding it at 100°C for 60 min. Two types of piezoelectric‐rubber were used; one was mixed with PZT particles forming linear aggregates, and the other was mixed with PZT particles forming a random dispersion. The piezoelectric‐rubber whose PZT particles were aligned normal to the rubber surface had much higher piezoelectric effect than the type of piezoelectric‐rubber whose PZT particles were randomly dispersed. The reason for this is that force applied on the former is directly transmitted to PZT particles and the electric charges generated from PZT particles had higher mobility because of the aligned PZT particles, which were connected with each other. As a result, the formation of linear aggregates of PZT particles in rubber was effective in enhancing piezoelectric properties of piezoelectric‐rubber. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39862.     

Secondary phase softening effect in PZT-based ceramics by introducing the random electric fields

In this work, the random electric fields are constructed in the hard PZT ceramics by adding the ZnO particles as a secondary phase to tune the piezoelectric properties and losses. It is found that the internal bias electric field existing in the hard PZT ceramics has been tuned successfully by the random electric fields and its value reduces with the increased ZnO content. As a consequence, the piezoelectric constant d₃₃ reaches up to 483 pC/N in the PZT/0.75 wt%ZnO composite, which is much higher than that of the hard PZT matrix. In the meantime, the electromechanical quality factor Q_m, dielectric loss tan δ, and Curie temperature T_C for this composite are about 1109, 0.55%, and 279°C, respectively. The promoted d₃₃ is attributed to the small domain size and reduced internal bias electric field, whereas the low losses (large Q_m and low tan δ) can be put down to the still existing nonzero internal bias electric field.     

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.     

The Relationship Between Phase Structure and Electrical Properties in (1 − x)(Bi0.5Na0.5TiO3–Ba0.5K0.5TiO3–BaTiO3)‐ xK0.5Na0.5NbO3 Quaternary Lead‐Free Piezoelectric Ceramics

(1 ? x)(0.85Bi_0.5Na_0.5TiO₃–0.11Ba_0.5K_0.5TiO₃–0.04BaTiO₃)‐ xK_0.5Na_0.5NbO₃ lead‐free piezoelectric ceramics with x = 0.00, 0.02, 0.03, 0.04, 0.05, and 0.10 were prepared by a conventional solid state method. A coexistence of rhombohedral (R) and tetragonal (T) phases was found in the system, which tended to evolve into pseudocubic symmetry when x increases. The x = 0.04 sample exhibited improved electrical properties: the dielectric constant ε_r = 1900 with the low loss tangents 0.06, the S_max/E_max of ~400 and ~460 pm/V under unipolar and bipolar electric field, respectively. Meanwhile, piezoelectric constant d₃₃ still maintained ~160 pC/N. These could be owed to the formation of polar nanoregions for relaxor phase.     

Control of ferroelectric and linear piezoelectric response of PZT films through texture

The high and low field ferroelectric response of freestanding PbZr_0.52Ti_0.48O₃ (PZT) films, with texture varying from 100% (001) to 100% (111) was investigated via 500 nm thick PZT unimorphs deposited on the same substrate. It is shown that the ferroelectric and piezoelectric properties depend strongly on texture, and the effective transverse strain and stress coefficients vary linearly with %(001) and %(111) texture factors. PZT films with 100% (001) orientation displayed 150%, 140%, and 80% larger linear piezoelectric strain coefficient, saturated strain coefficient, and saturated stress coefficient, respectively, compared to films with 100% (111) orientation. As a result, pure (001) textured PZT films with 20% higher dielectric constant have 50% higher figure of merit in sensing than films with pure (111) texture. The piezoelectric and ferroelectric properties of all but one combinations of (001) and (111) texture were shown for the first time to be bounded by the values for 100% (001) and 100% (111) texture. A notable exception was PZT films comprised of 73% (001) and 27% (111) texture which showed stable piezoelectric coefficients at all electric fields, with major technological implication to low power microdevices. Finally, the coercive field was shown to decrease with (001) texture factor and excess‐Pb in the PZT and the PbTiO₃ seed layer.     

Demonstration of Copper Co‐Fired (Na,K)NbO3 Multilayer Structures for Piezoelectric Applications

A Li and Ta modified (Na, K)NbO₃ piezoelectric ceramic has been successfully co‐fired with inner copper electrodes in a reduced atmosphere. Highly dense NKN ceramics (95% relative density, 4.64 g/cm³) were obtained by sintering the samples in a low oxygen partial pressure (low pO₂) atmosphere at 1050°C. The poly(propylene carbonate) binder system was used to permit a clean burnout at low temperature in N₂ atmosphere, and also prevent the electrode copper particles from undergoing any oxidation. No interdiffusion of copper, chemical reactions, and/or carbon residues were observed in the grains, grain boundaries, or at the electrode–ceramic interface of the co‐fired samples from a detailed transmission electron microscopy (TEM) analysis. Dielectric and piezoelectric properties were characterized from those co‐fired prototyped samples. The samples displayed high relative dielectric permittivity above 800, with low dielectric loss about 3.6%. A normalized strain coefficient (max. strain/max. electric field) of = 220 pm/V was obtained under unipolar converse electromechanical measurement at 20 kV/cm. This paper presents the feasibility of co‐firing a Cu inner electrode with NKN ceramics toward multilayer lead‐free piezoelectric applications, providing an engineering route to narrow the performance differences between soft lead‐based piezoelectrics and lead‐free materials.