High-frequency ultrasonic transducer based on lead-free BSZT piezoceramics

This paper describes the fabrication and evaluation of a high-frequency (40 MHz) transducer based on lead-free piezoceramics for ultrasonic imaging. The transducer with an aperture size of 0.9 mm has been fabricated using barium strontium zirconate titanate ((Ba_0.95Sr_0.05)(Zr_0.05Ti_0.95)O₃, abbreviated as BSZT) ceramics. The lead-free BSZT has a piezoelectric d₃₃ coefficient of 300 pC/N and an electromechanical coupling factor k_t of 0.45. High-frequency ultrasound transducers were fabricated and a bandwidth of 76.4% has been achieved with an insertion loss of −26 dB. Applications in high resolution biological and medical imaging could be possible with this lead-free material.     

0.90(Bi1/2Na1/2)TiO3–0.05(Bi1/2K1/2)TiO3– 0.05BaTiO3 transducer for ultrasonic wirebonding applications

Lead-free piezoelectric ceramic 0.90(Bi_1/2Na_1/2)TiO₃–0.05(Bi_1/2K_1/2)TiO₃–0.05BaTiO₃ (BNKBT-5) rings (OD=12.7 mm, ID=5.1 mm and 2.3-mm thick) were fabricated and characterized. Four ceramic rings were used as the driving element in an ultrasonic wirebonding transducer and the performance of the transducer was characterized. The lead-free transducer was found to have comparable voltage rise and fall times as a lead-based PZT transducer and has a relatively large vibration amplitude, thus showing that BNKBT-5 has the potential to be used in fabricating lead-free ultrasonic wirebonding transducers. PACS 77.22.Ej; 77.84.-s; 85.50.-n     

Study of compressive type accelerometer based on lead-free BNKBT piezoceramics

Lead-free piezoelectric 0.90(Bi_1/2Na_1/2)TiO₃-0.05(Bi_1/2K_1/2)TiO₃-0.05BaTiO₃ ceramics(abbreviated as BNKBT-5) rings were fabricated using a conventional mixed oxide method. The ceramics have a piezoelectric constant d₃₃=168 pC/N, electromechanical coupling factors k_p=0.313 and k_t=0.487. The BNKBT lead-free ceramic rings were used as the transduction elements in a compressive type accelerometer and its performance compared with a lead zirconate titanate (PZT) APC 840 ceramic accelerometer with similar structure. The lead-free accelerometer shows good performance and has a broader frequency response compared to the lead-based PZT accelerometer. PACS 77.22.Ej; 77.84.-s; 85.50.-n     

Microstructure and piezoelectric properties of Bi0.5(Na0.82K0.18)0.5TiO3−NaSbO3 ceramics

Lead-free piezoelectric ceramics (1−x)Bi_0.5(Na_0.82K_0.18)_0.5TiO₃−xNaSbO₃ have been prepared by a conventional ceramics technique, and their microstructure and electrical properties have been investigated. The addition of NaSbO₃ has no remarkable effect on the crystal structure within the studied doping content; however, an obvious change in microstructure took place. With increase in NaSbO₃ content, the temperature from a ferroelectric to antiferroelectric phase transition increases, and the temperature for a transition from antiferroelectric phases to paraelectric phases changes insignificantly. Simultaneously, the temperature range between the rhombohedral phase transition point and the Curie temperature point becomes smaller. The piezoelectric properties significantly increase with increase in NaSbO₃ content and the piezoelectric constant and electromechanical coupling factor attain maximum values of d₃₃=160 pC/N and k_p=0.333 at x=0.01. The results indicate that (1−x)Bi_0.5(Na_0.82K_0.18)_0.5TiO₃−xNaSbO₃ ceramic is a promising lead-free piezoelectric candidate material.     

Growth of high performance piezoelectric crystal Pb(Zn1/3Nb2/3)O3-PbTiO3 using PbO flux

Novel piezoelectric crystal (1 − x)Pb(Zn_1/3Nb_2/3)O₃-xPbTiO₃ (PZNT) has attracted much attention due to its high piezoelectric properties and potential applications in medical ultrasonic devices, sonar transducers, solid state actuators. However, the applications of PZNT crystals are limited by the lack of a simple and reproducible growth technique. In this work, large size PZNT crystals were grown by the vertical Bridgman method using 50 mol% PbO as a flux. The growth conditions were optimized as mole ratio of raw materials and flux = 1:1, soaking temperature 1150-1200 °C, soaking time 10 h, the lowering rate of the crucible 0.5 mm/h and the temperature gradient near solid-liquid interface about 50 °C/mm. The maximum size of as-grown PZNT crystal was about 60 mm in length. The crystal was oriented and its piezoelectric constant d₃₃ and coupling coefficient k₃₃ were measured over 2000 pC/N and 0.92, respectively.     

Lead-free transducer for non-destructive evaluation

Lead-free piezoelectric ceramics with the formula 0.90(Bi_0.5Na_0.5)TiO₃ - 0.05(Bi_0.5K_0.5)TiO₃ - 0.015(Bi_0.5Li_0.5)TiO₃-0.05BaTiO₃ (abbreviated as BNKLBT-1.5) were prepared by a conventional mixed-oxide method. A disc of this material was fabricated and used to construct an ultrasonic transducer suitable for use in non-destructive evaluation (NDE). Using a laser vibrometer, it was observed that both BNKLBT and PZT exhibited a surface displacement pattern indicative of coupling of the radial mode vibration with the thickness mode vibration. This is consistent with the measurements of electrical impedance vs frequency which showed that for both discs a strong radial mode with many harmonics was clearly observed and many (usually undesired) modes existed near the thickness mode resonance frequency. The discs were mounted in stainless steel housings with appropriate electrical connections to form transducers. Tungsten/epoxy backing was incorporated to provide a very short ring-down time, a characteristic required for many NDE applications. The characteristics of the BNKLBT transducer were quite similar to that of a PZT transducer of similar structure, showing that this lead-free material has the potential to replace PZT in transducers for NDE applications. PACS 43.20.Tb; 43.20.Ye; 43.35.Zc; 43.35.Yb; 43.38.Ar; 43.35.Fx     

Properties of non-stoichiometric 0.935(K0.5+xNa0.5+x)NbO3-0.065LiSbO3 lead-free piezoelectric ceramics

0.935(K_0.5+xNa_0.5+x)NbO₃-0.065LiSbO₃ lead-free piezoelectric ceramics were prepared by normal sintering, and their piezoelectric and dielectric properties were investigated by varying the compensating amount x of alkaline elements (Na and K) addition. It was found that the crystal structure changed from tetragonal to orthorhombic with increasing x from −0.010 to 0.010. An MPB was tailored by optimizing the alkaline elements contents. Enhanced electrical and electromechanical responses of d₃₃=253 pC/N, k_p=0.47, k_t=0.45 and tanδ=0.027 were obtained in the ceramics with x=0.005. These excellent piezoelectric and electromechanical properties indicate that this system may be an attractive lead-free material for a wide range of electro-mechanical transducer applications.     

Phase transition,dielectric and piezoelectric properties of NaNbO3–Bi0.5Li0.5TiO3 lead-free ceramics

Lead-free ceramics (1?x)NaNbO₃–xBi_0.5Li_0.5TiO₃ have been fabricated by an ordinary sintering technique, and their electric properties and temperature characteristics have been studied. All the ceramics possess a perovskite structure with orthorhombic symmetry, indicating that (Bi_0.5Li_0.5)TiO₃ diffuses into NaNbO₃ lattices to form a new solid solution. A low (Bi_0.5Li_0.5)TiO₃ doping level transforms the NaNbO₃ ceramics from antiferroelectric to ferroelectric. The ceramics with x ≤ 0.075 are normal ferroelectric, and the ferroelectric-paraelectric phase become diffusives with the doping level of Bi_0.5Li_0.5TiO₃ increasing. As x increases, the Curie temperature of the ceramics decreases linearly, while the relative permittivity ε_r increases. 0.925NaNbO₃–0.075(Bi_0.5Li_0.5)TiO₃ ceramic exhibits the relatively large piezoelectric constant (d₃₃ = 58 pC/N), high Curie temperature (T_C = 228 °C) and good temperature stability, suggesting that the ceramics are one of new possible candidates for lead-free piezoelectric materials.     

Theoretical investigation of the intrinsic piezoelectric properties for tetragonal BaTiO3 epitaxial films

The orientation dependences of the converse longitudinal piezoelectric constant d_33,f, and the in-plane converse piezoelectric constant e_31,f, are calculated for tetragonal barium titanate epitaxial films. The calculations demonstrate that both e_31,f and d_33,f have their maximum values along an axis close to the (1 1 1) direction of the pseudo-cubic system, which are similar to the orientation dependence results for a tetragonal BaTiO₃ single crystal. The calculated piezoelectric constants for a (1 1 1) oriented BaTiO₃ epitaxial film (e_31,f = −23 C/m², d_33,f = 124 pm/V) suggest that it is a good candidate material for lead-free MEMS applications.     

Phase transition behavior and piezoelectric properties of low-Li and high-Sb modified KNN based piezoceramics

(Na_0.5K_0.5)_0.975Li_0.025Nb_0.82−xSb_xTa_0.18O₃ lead-free piezoceramics were prepared by the conventional solid-state sintering method. All samples possess a pure perovskite phase, and no secondary phase could be certified. The crystal structure changes from tetragonal to pseudo-cubic with increasing amount of Sb. The ferroelectric Curie temperature (T_c) shifts to lower temperature while the tetragonal to orthorhombic phase transition temperature (T_o-t) shows no obvious change with increasing Sb⁵⁺. Enhanced piezoelectric and electromechanical properties are obtained with x=0.06: d₃₃=352 pC/N, k_p=47% and k_t=38%, showing that they could be promising candidates as lead-free piezoelectric materials.     

铌酸钾钠基无铅压电陶瓷纵振换能器*

高性能环境友好型无铅压电陶瓷及其应用是当前压电材料研究的热点之一,为了探究其在水声换能器领域的应用潜力,该文对铌酸钾钠基无铅压电陶瓷和锆钛酸铅压电陶瓷纵振式换能器进行了对比研究。依据仿真结果优化结构尺寸,制作了两种换能器样机并测试了其在空气中和水中的电声性能。测试结果表明,铌酸钾钠基无铅压电陶瓷换能器的谐振频率为35kHz,最大发送电压响应为 151dB,声源级可达 190dB,在 26kHz~67kHz 的频率范围内发送电压响应的起伏不超过±4.5dB,谐振频率处-3dB 的指向性开角约为 76°。该无铅压电陶瓷换能器具有和锆钛酸铅压电陶瓷换能器相当的发射性能,有望推动无铅压电材料在水声换能器领域的应用进程。     

Na0.5K0.5NbO3-BiFeO3 lead-free piezoelectric ceramics

Lead-free (Na_0.5K_0.5)NbO₃-based piezoelectric ceramics were successfully fabricated by substituting with a small amount of BiFeO₃ (BF). Difficulty in sintering of pure NKN ceramics can be eased by adding a few molar percent of BF, and the crystalline structure is also changed, leading to a morphotropic phase boundary (MPB) between ferroelectric orthorhombic and rhombohedral phases. The MPB exists near the 1-2 mol% BF-substituted NKN compositions, exhibiting enhanced ferroelectric, piezoelectric, and electromechanical properties of P_r=23.3 μC/cm², d₃₃=185 pC/N, and k_p=46%, compared to an ordinarily sintered pure NKN ceramics. The MPB composition has a Curie temperature of ∼370 °C, comparable to that of some commercial PZT materials.     

Effects of K4CuNb8O23 on phase structure and electrical properties of K0.5Na0.5NbO3–LiSbO3 lead-free piezoceramics

Dense K₄CuNb₈O₂₃ (KCN) modified 0.948K_0.5Na_0.5NbO₃–0.052LiSbO₃ (KNNLS) ceramics were prepared by conventional solid state reaction method. The effect of addition of K₄CuNb₈O₂₃ liquid phase sintering aid on the phase structure and electrical properties of ceramics was studied. Results showed that K₄CuNb₈O₂₃ induced a perovskite structure transition from coexistence of orthorhombic and tetragonal phases to orthorhombic symmetry. The addition of K₄CuNb₈O₂₃ promoted the sintering of KNNLS ceramics. In particular, the K₄CuNb₈O₂₃ addition to the KNNLS greatly improved the mechanical quality factor Q_m value. The ceramics with x=0.8 sintered at 1090 °C possess the optimum properties (Q_m=192, d₃₃=135 pC/N, tan δ=0.024 and k_p=0.357). These results indicate that the ceramic is a promising candidate for lead-free high-power piezoelectric devices, such as piezoelectric actuators, transformers and filter materials.     

Electrical and electromechanical properties of lead-potassium-yttrium-niobate ceramics—piezoelectric applications

Tungsten bronze (TB)-type oxide ceramic Pb_0.74K_0.13Y_0.13Nb₂O₆ (PKYN) has been synthesized by the standard solid state reaction method. Single phase formation, orthorhombic crystal structure was confirmed by X-ray diffraction (XRD). The substitution of Y³⁺ in Pb_0.74K_0.52Nb₂O₆ (PKN) decreased the unit cell volume and T_C=260 °C. PKYN exhibited the remnant polarization, P_r=8.5 μC/cm², and coercive field, E_c=28.71 kV/cm. Electrical spectroscopy studies were carried out over the temperature (35-595 °C) and frequency (45 Hz-5 MHz) ranges, and the charge carrier phenomenon, grain-grain boundary contribution and non-Debye-type relaxation were analyzed. The relaxation species are immobile charges in low temperature and oxygen vacancies at higher temperature. The theoretical values computed using the relations, ε′=ε_∞+sin(n(T)π/2)(a(T)/ε₀)(ω^n(T)−1); σ(ω)=σ_dc+Aωⁿ are fitted with the experimental one. The n and A parameters suggested that the charge carrier's couple with the soft mode and become mobile at T_C. The activation enthalpy, H_m=0.38 eV, has been estimated from the hopping frequency relation ω_p=ω_e exp(−H_m/k_BT). The piezoelectric constants K_t=35.4%, d₃₃=69×10⁻¹² C/N, d₃₁=−32×10⁻³ mV/N, S₁₁^E=17.8 pm²/N, etc., achieved in PKYN indicate the material is interesting for transducer applications. The activation energies from different formalisms confirmed the ionic-type conduction.     

Piezoelectric properties of [Li0.03(K0.48Na0.52)0.97](Nb0.97Sb0.03)O3-(Ba0.85Ca0.15)(Ti0.90Zr0.10)O3 lead-free piezoelectric ceramics

[Li_0.03(K_0.48Na_0.52)_0.97](Nb_0.97Sb_0.03)O₃-(Ba_0.85Ca_0.15)(Ti_0.90Zr_0.10)O₃ [(1−x)LKNNS-xBCTZ] lead-free piezoelectric ceramics were prepared by the conventional solid state method, and effects of BCTZ content on the piezoelectric properties of LKNNS ceramics were mainly investigated. A stable solid solution has been formed between LKNNS and BCTZ, and a morphotropic phase boundary of (1−x)LKNNS-xBCTZ ceramics is identified in the range of 0 < x ≤ 0.02. The Curie temperature of (1−x)LKNNS-xBCTZ ceramics decreases with increasing BCTZ content. A higher ?_r value and a lower tan δ value are demonstrated for the (1−x)LKNNS-xBCTZ ceramic with x = 0.02. The (1−x)LKNNS-xBCTZ ceramic with x = 0.02 has an enhanced electrical behavior of d₃₃ ∼ 237 pC/N, k_p ∼ 48.6%, ?_r ∼ 1451, tan δ ∼ 0.037, and T_c ∼ 335 °C. As a result, (1−x)LKNNS-xBCTZ ceramics are promising candidate materials for the field of lead-free piezoelectric materials.     

Dielectric properties of Cu0.5Tl0.5Ba2Ca3Cu4O12−δ bulk superconductor

The dielectric properties of Cu_0.5Tl_0.5Ba₂Ca₃Cu₄O_12−δ superconductor samples were studied at 79 and 290 K by means of capacitance (C) and conductance (G) measurements with the test frequency (f) in the range of 10 kHz to 10 MHz. A negative capacitance (NC) phenomenon has been observed, which is most likely arising due to higher Fermi level of ceramic superconductor samples than metal electrodes. Also the NC may be due to the space charge located at the multiple insulator–superconductor interfaces (grain boundaries) in the materials. The negative dielectric constant (ε′) and loss factor (tan δ) show strong dispersion at low frequencies. The lower thermal agitation at 79 K may enhance the polarizability and hence the dielectric constants (ε′ and ε″).     

Preparation and properties of nanocrystalline BNT-BTx piezoelectric ceramics by sol-gel and spark plasma sintering

(Bi_0.5Na_0.5)TiO₃ was doped in situ with 5, 8, and 11 mol% BaTiO₃ (BNT-BT_x; x = 0.05, 0.08 and 0.11) using a sol-gel technique. The resulting powders from gel precursors showed microstructures consisting of nano-sized grains and crystalline perovskite structure. Spark plasma sintering (SPS) technique was used to prepare high densified (98–99%ρ_theor) BNT-BT_x ceramics from these nanopowders. The results confirm the spark plasma sintering method applied to nano-scale powders, obtained by sol-gel, as a viable route in producing nanostructured ceramics. The evolution of the structure and electrical properties of the ceramics with BaTiO₃ concentration (x) was investigated. The permittivity of BNT-BT_0.08 ceramic is higher (ε_r = 2090, at 100 kHz) than that for x = 0.05 (ε_r = 1350) and x = 0.11 (ε_r = 1800). BNT-BT_0.08 ceramic shows maximum values for the frequency constants (N_p, N_t), piezoelectric charge coefficient (d₃₁) and piezoelectric voltage coefficient (g₃₁), and minimum values for the electromechanical coupling factor (k_p) and piezoelectric charge coefficient (d₃₃). The electrical properties of these ceramics are influenced by grains size, oxygen deficiency and non-uniform internal stresses due to these oxygen deficiencies. BNT-BT_x ceramics sintered by SPS seem to be good ceramic resonators with high mechanical quality factor (Q_m).     

Enhanced piezoelectric properties near the morphotropic phase boundary in lead-free (1-x)(Bi0.5K0.5)TiO3-xBi(Ni0.5Ti0.5)O3 ceramics

Lead-free piezoelectric ceramics of the composition (1-x)(Bi_0.5K_0.50)TiO₃-xBi(Ni_0.50Ti_0.50)O₃ or (1-x)BKT-xBNiT (when x = 0–0.20 mol fraction) were prepared by a conventional mixed-oxide method and sintered at 1050 °C for 4 h. The effects of BNiT content on the phase equilibria, and the dielectric, ferroelectric and piezoelectric properties were systematically investigated. High density sintered specimens (5.71–6.12 g/cm³) were obtained for all compositions. X-ray diffraction patterns showed that all BKT-BNiT samples exhibited a single perovskite phase which confirms that BNiT and BKT formed a solid solution up to x = 0.20. A morphotropic phase boundary (MPB) separating a BKT-rich tetragonal phase and a BNiT pseudo-cubic phase was identified over the compositional range 0.05 < x < 0.10, where enhanced electrical properties were observed. The optimum dielectric properties (ε_r = 1710, tanδ = 0.036), ferroelectric properties (P_r = 16.6 μC/cm², E_c = 22.5 kV/cm and R_sq = 0.86) and piezoelectric properties (d₃₃ = 288 pC/N, S_max = 0.22% and d^*₃₃ = 313 pm/V) were observed with a relatively high T_m ∼ 304 °C within this MPB region. Overall, these results indicate that the BKT-BNiT ceramic system is a promising lead-free piezoelectric candidate for further development for actuator applications.     

Influence of Ba addition on the dielectric and optic properties of (1 – x) Na0.5Bi0.5TiO3–xBaTiO3 (x = 0, 0.025, 0.0325 and 0.05) single crystals

High-quality, large-size lead-free (1 – x)Na_0.5Bi_0.5TiO₃–xBaTiO₃ ((1 – x)NBT–xBT) single crystals (x = 0, 0.025, 0.0325 and 0.05) were grown using the Czochralski method. Dielectric and transmitted light intensity properties were measured for these crystals. The broad anomalies exhibited in the temperature dependence of the transmitted light corresponded to structural and dielectric anomalies and were related to the temperature dependence of polar regions and the appearance of a long-range ferroelectric state. We explain our results based on local electromechanical fields, by inhomogeneity of the ion distribution and the mismatch in ion size. We suggested that the NBT–BT system can be a promising lead-free piezoelectric material for ultrasonic delay-line applications, broadband transducers and sensors.     

Phase formation and electrical properties of BNLT–BZT lead-free piezoelectric ceramic system

Phase formation study in lead-free piezoelectric ceramics based on lanthanum doped bismuth sodium titanate (Bi_0.4871Na_0.4871La_0.0172TiO₃:BNLT) and zirconium doped barium titanate (BaZr_0.05Ti_0.95O₃:BZT), has been carried out in the system of (1−x)BNLT–xBZT where x = 0.0–1.0, by two-step mixed oxide method. It was observed that the addition of BZT in the BNLT ceramics developed the dielectric and piezoelectric properties of the ceramics with the optimum piezoelectric constant (d₃₃) and dielectric constant (ε_r) at room temperature of about 138 pC/N and 1651, respectively, from the 0.2 BNLT to 0.8 BZT ceramic sample. The Curie temperature (T_C) of this ceramic was found at 295 °C which is 195 °C higher than that of pure BZT ceramics, promising the use of this ceramic in a higher range of temperature.