Enhanced electrical properties of the polymorphic phase boundary on the tetragonal side in K0.48Na0.52NbO3-based lead-free piezoelectric ceramics

Herein, (0.95?x)K_0.48Na_0.52NbO₃-0.05SrTiO₃-xCaZrO₃ piezoelectric ceramics were prepared using a conventional solid sintering process, and their microstructures, phase structures, and ferroelectric, dielectric, and strain properties were studied. The crystal structure of the ceramics changed from the coexistence of an orthogonal–tetragonal phase on the orthogonal side at x = 0 to that on the tetragonal side at x = 0.02 by improving the orthogonal–tetragonal transition temperature (～20 °C) with increasing CaZrO₃ (abbreviated as CZ) doping. A high electric field–induced strain of 0.33% with a Curie temperature of T_c = 256 °C was obtained at x = 0.02 and was approximately two times that observed at x = 0. The dielectric constant and maximum polarization were the highest at x = 0.02 in this (0.95?x)K_0.48Na_0.52NbO₃-0.05SrTiO₃-xCaZrO₃ system. These materials would be promising lead-free ceramics in the future.     

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%.     

Large strain and low hysteresis in (0.64-x) Bi0.5Na0.5TiO3- 0.36Sr0.7Bi0.2TiO3- x(K0.5La0.5)(Ti0.9Zr0.1)O3 piezoceramics

In this work, (0.64-x)Bi_0.5Na_0.5TiO₃- 0.36Sr_0.7Bi_0.2TiO₃- x(K_0.5La_0.5)(Ti_0.9Zr_0.1)O₃ lead-free piezoceramics were designed and fabricated by a conventional solid-phase sintering process. It is found that large strains (0.33 %), low hysteresis coefficients (32 %), and large dynamic d₃₃* (367 p.m./V) were obtained at x = 0.01. The large strain originates from the reversible transition of the relaxor to the long-range ferroelectric order in the electric field. When the ferroelectric and relaxor phases coexist in a proper ratio, they can provide a favorable condition for the easier movement of the domains and improve the strain properties. In addition, after 10⁵ cycles, the bipolar strain loop of x = 0.01 content changed slightly, demonstrating excellent fatigue resistance. This work provides a new way to design piezoelectric ceramics with large strain and low hysteresis.     

Improved solid-state conversion and piezoelectric properties of 90Na1/2Bi1/2TiO3-5BaTiO3-5K1/2Na1/2NbO3 single crystals

Na_1/2Bi_1/2TiO₃-BaTiO₃-K_1/2Na_1/2NbO₃ (NBT-BT-KNN) is a promising candidate system for actuator applications in lead-free piezoelectric materials because of its large electric-field-induced strain. We were able to fabricate 96.9% dense 90NBT-5BT-5KNN (mol%) single crystals by the solid-state single crystal growth technique using sintered pellets and SrTiO₃ seed crystals. The fabricated single crystals with a 〈001〉 direction exhibited high piezoelectric performance with a large strain of 0.67% and a high converse piezoelectric constant (S_max/E_max) of about 1670 pm/V at 4 kV/mm. These values are much higher than those previously reported for ceramics, 0.45% and 560 pm/V at 8 kV/mm, and for single crystals, 0.57% and 950 pm/V at 6 kV/mm, of the NBT-BT-KNN system. The measured piezoelectric properties are even comparable with those of lead-containing piezoelectric single crystals, which demonstrates high applicability of the fabricated NBT-5BT-5KNN single crystals for actuators.     

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.     

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.     

Effects of sintering aid and atmosphere powder on the growth of (K0.5Na0.5)NbO3 single crystals fabricated by solid-state crystal growth method

(K_0.5Na_0.5)NbO₃ (KNN) + x (= 1, 0.5, 0.05, and 0) wt%Co₃O₄ single crystals were fabricated by a solid-state crystal growth method with a KTaO₃ seed crystal and a KNN atmosphere powder, and the effects of the sintering aid content x and the addition of Co₃O₄ to the atmosphere powder on the growth of the single crystals were investigated. The formation of pores in the single crystals was suppressed by a decrease of x, which, however, decreased the crystal growth length. On the other hand, dense and large KNN single crystals could be fabricated by sintering with a KNN + 5 wt%Co₃O₄ atmosphere at x = 0. The dielectric, ferroelectric, and piezoelectric properties of the KNN single crystals were comparable to those of reported (K,Na)NbO₃ single crystals. These results would be useful for fabricating dense and large single crystals by the solid-state crystal growth method.     

Thickness-dependent switching behavior of 0.8(Bi0.5Na0.5)TiO3-0.2SrTiO3 lead-free piezoelectric thin films

0.8(Bi_0.5,Na_0.5)TiO₃-0.2SrTiO₃ (BNT-0.2ST) thin films, with thicknesses ranging from 90 to 364 nm, were fabricated on platinized silicon substrates by sol-gel method. These films were investigated by switching spectroscopy piezoresponse force microscope (SS-PFM) as a function of frequency at room temperature, revealing the enhanced ferroelectric response in ∼ 210 nm film at all frequencies (0.1 Hz - 1.5 Hz). This enhancement was ascribed to the largest thermally-activated stress at such thicknesses generated during film fabrications. As the temperature of the investigated films increases from room temperature to 200 ^oC, the piezoelectric parameters were obtained from SS-PFM, such as switching polarization (R_s), coercive bias (V₀), work of switching (A_s), maximum strain (S_max), and negative strain (S_neg), indicating an occurrence of phase transition from ferroelectrics to relaxors. This work revealed that thickness plays a crucial role for ferroelectric response and temperature-dependent phase transition in BNT-0.2ST films, since it affects the stress state and switching behavior.     

Phase structure and enhanced piezoelectric properties in (1-x)(K0.48Na0.52)(Nb0.95Sb0.05)O3-x(Bi0.5Na0.42Li0.08)0.9Sr0.1ZrO3 lead-free piezoelectric ceramics

The piezoelectric properties of KNN lead-free piezoelectric ceramics could be greatly enhanced by forming multiphase coexistence. In this work, binary system (1-x)(K_0.48Na_0.52)(Nb_0.95Sb_0.05)O₃-x(Bi_0.5Na_0.42Li_0.08)_0.9Sr_0.1ZrO₃ [(abbreviated as (1-x)KNNS-xBNLSZ] ceramics with rhombohedral-tetragonal (r-T) phase boundary was designed and synthesized using the conventional solid-state sintering method, and effects of BNLSZ contents on their micrograph, phase structure and electrical properties were also investigated. According to phase diagram from the results of temperature-dependent capacitance and dielectric constant, the ceramics exhibit the R-T phase coexistence in the composition range of 3.5%≤x<4.5%, and an enhanced dielectric, ferroelectric, and piezoelectric behavior was obtained at such a phase boundary zone. As a result, the ceramics with x=0.04 exhibit optimum electrical properties of d₃₃~461 pC/N, k_p~46%, tan δ~0.03, P_r~16.9 μC/cm², and E_c ~9 kV/cm, together with a Curie temperature (T_C) of ~228 °C. Such a good comprehensive performance obtained in this present work is due to the R-T phase transition and enhanced ɛ_rP_r. It was believed that this ceramic system would promote the development of KNN-based lead-free ceramics.     

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.     

Electrical properties and relaxor phase evolution of Nb-Modified Bi0.5Na0.5TiO3-Bi0.5K0.5TiO3-SrTiO3 lead-free ceramics

In this work, the crystalline phase, domain structure, and electrical properties of [Bi_0.5(Na_0.84K_0.16)_0.5]_0.96Sr_0.04Ti_1-xNb_xO₃ (x = 0.010–0.030) ceramics are investigated. Increasing the Nb content induces the phase transition from coexistent rhombohedral and tetragonal phases to a single pseudo-cubic phase, and the lamellar ferroelectric domains evolve into polar nanoregions. Decreased ferroelectric-to-relaxor transition temperature and enhanced frequency dispersion are found in the temperature-dependent dielectric constant and loss, implying a transition from the non-ergodic to ergodic relaxor state. The Nb substitution significantly degrades the long-range ferroelectric order with sharply decreased piezoelectric coefficients from ? 140 to ? 1 pC/N. However, a large strain of 0.32% at 5 kV/mm (normalized strain of 640 pm/V) is obtained around the critical composition of x = 0.0225. The composition of x = 0.030 shows good temperature insensitivity of the strain response, characterized by 308 pm/V with less than 15% reduction from 25 °C to 125 °C.     

Enhanced piezoelectric property and promoted depolarization temperature in Fe doped Bi1/2(Na0.8K0.2)1/2TiO3 lead-free ceramics

Piezoelectric sensors and energy harvesters require piezoelectric materials with large piezoelectric responses and good thermal stability. However, a commonly accepted concept is that the promotion of depolarization temperature of Bi_1/2Na_1/2TiO₃-based lead-free ceramics is usually companied by deterioration of piezoelectric properties. In the present study, the effects of acceptor-Fe doping on piezoelectric property and thermal depolarization behavior of Bi_1/2(Na_0.8K_0.2)_1/2TiO₃ ceramics are investigated. Fe doping at an appropriate level (≤ 3.0%) improves piezoelectric property and thermal stability simultaneously, due to the stabilization of long-range ferroelectric order. Piezoelectric constant d₃₃ increases from 125 pC/N to 148 pC/N with Fe amount of 3.0%, and then decreases. The depolarization temperature T_d is promoted continuously with Fe addition, from 76 °C for the undoped sample to 118 °C for the sample with Fe amount of 5.0%. It is proposed that the piezoelectric property and thermal stability can be simultaneously improved by stabilizing the long-range ferroelectric order in Bi_1/2Na_1/2TiO₃-based systems with obvious relaxor character. This work provides a new insight into the improvement of Bi_1/2Na_1/2TiO₃-based lead-free piezoelectric ceramics.     

Dielectric and piezoelectric properties of lead-free (K0.44Na0.46)NbO3-0.5%MnO2 single crystals grown by the TSSG method

Lead-free (K_0.44Na_0.46)NbO₃-0.5%MnO₂ (KNN-0.5%MnO₂) single crystals with dimensions of Ф30×10 mm were successfully grown by a top seeded solution growth technique (TSSG). The X-ray diffraction pattern has shown that the as-grown crystals have an orthorhombic perovskite structure. The orthorhombic-tetragonal (T_O-T) and tetragonal-cubic phase transition temperature (the Curie temperature T_C) of the single crystal were found at 184 °C and 412 °C, respectively. The KNN-0.5%MnO₂ single crystals exhibited high piezoelectric constants d₃₃ and dielectric permittivity ε_r, being 261 pC/N and 275. Well saturated P-E hysteresis loop with remnant polarization P_r=22.06 µC/cm² and coercive field E_c=17.93 kV/cm was obtained at a maximum electric field of 3 kV/mm. A high strain (0.24%) and electromechanical coupling coefficient K_t (65.9%) were obtained along the (001) orientation. These excellent results indicated that the KNN-0.5%MnO₂ single crystals could be used as high quality lead-free material.     

铜掺杂对(Na0.5K0.5)NbO3无铅压电陶瓷性能的影响

采用传统固相反应法对(Na0.5K0.5)NbO3压电陶瓷进行铜掺杂改性研究。使用SEM、XRD并结合常规压电陶瓷性能测试手段对该体系的显微结构、压电性能等进行表征。研究结果表明:CuO的掺入使材料出现“硬化”现象,即材料的压电系数d33、平面机电耦合系数Kp和介电损耗tanδ下降了,机械品质因子Qm大大提高;CuO掺入量在1%mol时各项性能最佳。另外,从SEM图片中可以看出:(Na0.5K0.5)NbO3压电陶瓷材料的平均晶粒尺寸随着CuO掺入量的增加明显变大。这表明CuO有烧结助熔作用,能降低烧成温度。     

Optical dispersion and bandgap of pure and Mn-doped 0.92Na0.5Bi0.5TiO3-0.08K0.5Bi0.5TiO3 lead-free single crystals

Optical properties of lead-free ferroelectric pure and Mn-doped 0.92Na_0.5Bi_0.5TiO₃-0.08K_0.5Bi_0.5TiO₃ (NBT-8KBT) single crystals have been investigated systematically. Refractive index and extinction coefficient were measured and the critical parameters are obtained by modified Sellmeier dispersion equations and single-oscillator dispersion relation. The decline of refractive index for Mn:NBT-8KBT could be related to the lattice distortion of the Mn ions doping. High transmittance (>70%) over the transparent region (>400 nm) was found in the pure NBT-8KBT, higher than that of Mn:NBT-8KBT, which could be caused by the increase of domain wall density. An about 100 nm red-shift of absorption edge was observed in the Mn:NBT-8KBT single crystal, which is located in the visible region. Optical bandgap energies calculated through Tauc equation and a large bandgap difference of 2.96 and 2.62 eV occurs in the NBT-8KBT and Mn:NBT-8KBT, respectively, which illustrates the modulation of the band structures by Mn doping.     

Study of relaxor behavior in a lead-free (Na0.5Bi0.5)TiO3-SrTiO3-BaTiO3 ternary solid solution system

In this work, single phase lead-free (0.8-x)(Na_0.5Bi_0.5)TiO₃−0.2SrTiO₃-xBaTiO₃ (NBT-ST-BT) ceramics were prepared by conventional solid state reaction method. The effect of BT on the structure and on the dielectric and ferroelectric properties of NBT-ST-BT were investigated. A structural transformation from pseudo-cubic to tetragonal along with possible phase coexistence was witnessed as the BT content was increased. A diffuse phase transition with considerable frequency dispersion in the dielectric response and slim P-E loops evidenced strong relaxor behavior for the ternary system at higher compositions of BT. An analysis of the frequency dependent T_m according to V-F and Power law indicated substantial interaction between the polar nano-regions and relatively broad distribution of freezing temperatures. The study of the dielectric constant at much higher and lower temperatures than T_m in the range of Burn's temperature (T_B) to freezing temperature (T_f) to provide useful information about the growth rate of polar nano-regions and their interactions for a better understanding of the relaxor behavior exhibited by the present ternary system.     

Electric-field-temperature phase diagram and electromechanical properties in lead-free (Na0.5Bi0.5)TiO3-based incipient piezoelectric ceramics

In this work, the (1-x)(0.8Na_0.5Bi_0.5TiO₃-0.2K_0.5Bi_0.5TiO₃)-xSrTiO₃ (NKBT-xST) incipient piezoelectric ceramics with x = 0–0.07 (0ST-7ST) were prepared by the solid-state reaction method and their structural transformation and electromechanical properties were investigated as a function of ST content. As the ST content increases, the long-range ferroelectric order is disrupted, and the ferroelectric-relaxor phase transition temperature (T_FR) shifts to around room temperature for NKBT-5ST ceramics, accompanied by a relatively high electrostrain of 0.3% at 6 kV/mm. The large strain response associated with the vanished ferroelectric properties around T_FR can be attributed to the reversible relaxor-ferroelectric phase transition. The electric-field-temperature (E-T) phase diagrams were established, and the transition between the two field-induced long-range ferroelectric states were found to take place via a two-step switching process through an intermediate relaxor state. The threshold electric field to trigger the conversion between ferroelectric state and relaxor state depends strongly on the dynamics of polarization relaxation, which is influenced by temperature and composition.     

(1-x)Na0.5 Bi0.5 TiO3-xNaNbO3系无铅压电陶瓷的机电性能

采用传统陶瓷的制备方法,制备了(1-x)Na0.5Bi0.5TiO3-xNaNbO3(r=0～0．08)压电陶瓷。X射线衍射分析表明：所研究的组成均能够形成纯钙钛矿(ABOx)型固溶体。不同频率下陶瓷材料的介电常数-温度曲线显示该体系材料具有典型的弛豫铁电体特征,且随着x的增加,其弛豫性特征愈明显。室温下陶瓷材料的饱和电滞回线表明：所研究组成均为铁电体．材料的剩余极化强度P1在x=0．02时具有最大值。检测了不同组成陶瓷的雎电性能,发现材料的压电常数d33和平面机电耦合系数Kp随着x值的增加先增加后降低,在x=0．02时．陶瓷的d33=88pC／N,Kp=0．1792,为所研究组成中的最大值．材料的介电常数εI3/ε0和介电损耗tanδ则随x值的增加而增加。     

A位元素非化学计量Bi0.5(Na,K)0.5TiO3-BiFeO3压电陶瓷

采用传统陶瓷制备方法,制备了A位元素非化学计量无铅压电陶瓷0.79(Bi0.5Na0.5)tTiO3–0.18(Bi0.5K0.5)tTiO3–0.03BitFeO3(t=0.95～1.05)。研究了A位元素非化学计量对该体系陶瓷微观结构、压电性能的影响,同时通过测量不同外加应力下压电应变常数(d33),研究了影响d33和径向机电耦合系数(kp)的不同机理。结果表明:A位元素缺乏较多时,析出第二相。kp随A位元素过量与不足的增加而减少,d33随A位元素过量的增加基本不变,随A位元素不足的增加而减少。采用极化相位角(θmax)衡量陶瓷极化程度,发现kp随θmax增加而增加,d33随θmax增加变化不明显。d33在低于临界应力时基本不变,当应力高于临界应力后,随应力增加而下降。压电陶瓷中的应力场对畴壁运动与弹性偶极子的作用是影响d33的作用机理之一。     

Dielectric properties and relaxor behavior of 0.935(Na0.5Bi0.5)TiO3-0.065BaTiO3 lead free piezoelectric ceramic

Dielectric properties of 0.935(Na_0.5Bi_0.5)TiO₃-0.065BaTiO₃ lead free piezoelectric ceramic are studied. The study shows a diffuse phase transition (DPT) characterized by a frequency dispersion of permittivity which is related to cation disorder at A-site. Additionally to this dispersion, this solid solution exhibits relaxor behavior. The mechanism of relaxor behavior was discussed according to Debye, Vogel–Fulcher (V–F) and Power law models and the suitable model was predicted by means of goodness of parameter.