Frequency dispersion of longitudinal ultrasonic velocity and attenuation in [001]c-poled 0.24Pb(In₁/₂Nb₁/₂O₃- 0.45Pb(Mg₁/₃Nb₂/₃)O₃-0.31PbTiO₃ single crystal

The frequency dispersion of ultrasonic velocity and attenuation in [001](c)-poled 0.24Pb(in(1/2)Nb(1/2))O(3)-0.45Pb(Mg(1/3)Nb(2/3))o(3)-0.31PbTio(3) (PIN-0.45PMN-0.31PT) ternary single crystal were measured by ultrasonic spectroscopy from 25 to 100 MHz for the longitudinal wave. It was found that the velocity has a linear relationship with the frequency f, but the attenuation has a quadratic relation with f. The attenuation and frequency dispersion of the ternary system are lower than that of the (1-x)Pb(Mg(1/3)Nb(2/3))O(3)-xPbTiO(3) (PMN-PT) binary system and the coercive field also increased by a factor of 2.5, hence, the ternary single system is superior to the corresponding binary single-crystal system for high-frequency and high-power transducer applications.     

掺杂对0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3陶瓷结构和电学性能的影响

用传统的固相反应法、通过铌铁矿预合成路线制备了1mol%ZnO、MnO2和CuO掺杂的0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3(0.7PMN-0.3PT)陶瓷。XRD分析表明掺杂的0.7PMN-0.3PT陶瓷都呈现纯三方钙钛矿结构。烧成的陶瓷具有较高的致密度,其中CuO掺杂的0.7PMN-0.3PT陶瓷达到理论密度的93.79%。掺杂的0.7PMN-0.3PT陶瓷都呈现宽化、弥散的介电响应峰,然而介电常数的频率色散现象明显减弱。CuO掺杂的0.7PMN-0.3PT陶瓷呈现优良的综合电学性能:介电常数最大值εm达到21000左右,剩余极化强度Pr达到27.49μC/cm2,压电应变常量d33达到548pC/N。     

Piezoelectric ceramics with high dielectric constants for ultrasonic medical transducers

Complex system ceramics Pb(Sc(1/2)Nb(1/2))O3-Pb(Mg(1/3)Nb(2/3))O3-Pb(Ni(1/2)Nb(1/2))O3-(Pb0.965,Sr0.035) (Zr,Ti)O3 (PSN-PMN-PNN-PSZT abbreviated PSMNZT) have been synthesized by the conventional technique, and dielectric and piezoelectric properties of the ceramics have been investigated for ultrasonic medical transducers. High capacitances of the transducers are desired in order to match the electrical impedance between the transducers and the coaxial cable in array probes. Although piezoelectric ceramics that have high dielectric constants (epsilon33t/epsilon0 > 5000, k'33 < 70%) are produced in many foundries, the dielectric constants are insufficient. However, we have reported that low molecular mass B-site ions in the lead-perovskite structures are important in realizing better dielectric and piezoelectric properties. We focused on the complex system ceramics PSMNZT that consists of light B-site elements. The maximum dielectric constant, epsilon33T/epsilon0 = 7, 200, was confirmed in the ceramics, where k'33 = 69%, d33 = 940 pC/N, and T(c) = 135 degrees C were obtained. Moreover, pulse-echo characteristics were simulated using the Mason model. The PSMNZT ceramic probe showed echo amplitude about 5.5 dB higher than that of the conventional PZT ceramic probe (PZT-5H type). In this paper, the electrical properties of the PSMNZT ceramics and the simulation results for pulse-echo characteristics of the phased-array probes are introduced.     

Single crystal PMN-0.33PT/epoxy 1-3 composites for ultrasonic transducer applications

Lead magnesium niobate-lead titanate 0.67Pb (Mg/sub 1/3/Nb/sub 2/3/)O/sub 3/-0.33PbTiO/sub 3/ (PMN-0.33PT, abbreviated as PMN-PT) single crystals were used to fabricate PMN-PT/epoxy 1-3 composites with different volume fractions of PMN-PT ranging from 0.4 to 0.8. The electromechanical properties of the 1-3 composites were determined by the resonance technique. Theoretical modeling of the 1-3 composites matched quite well with the measured material properties. It was demonstrated that the thickness electromechanical coupling coefficients of the composites could reach as high as 0.8. A 2.4 MHz plane ultrasonic transducer was fabricated using a PMN-PT/epoxy 1-3 composite with 0.37 volume fraction of PMN-PT. It shows a -6 dB bandwidth of /spl sim/61% and an insertion loss of -14 dB.     

半化学法制备0.80Pb(Mg1/3Nb2/3)O3-0.20PbTiO3陶瓷的反应机理

采用半化学法制备了纯钙钛矿相的0．80Pb（Mg1/3Nb2/3）O3－0．20PbTiO3（简称为0．80PMN－0．20PT）陶瓷。反应前驱体是以硝酸镁的饱和溶液代替传统氧化物混合法中的氧化镁，与PbO、Nb2O5和TiO2混合球磨得到的。该前驱体的TG－DTG－DSC和XRD分析表明，半化学法的反应机理不同于传统氧化物混合法和二次合成法的反应机理。在煅烧过程中，硝酸镁与氧化铅反应生成铅的活化中间体Pb6O5（NO3）2，由此活化的PbO或Pb3O4可与Nb2O5生成不稳定的、缺B位的焦绿石相Pb3Nb2O8，再与MgO反应生成钙钛矿相PMN－PT。     

Relaxor behavior in Ba(Zn1/3Nb2/3)O3-PbTiO3 new solid solution

Relaxor behavior has been found in a new solid solution between complex perovskite Ba(Zn(1/3)Nb(2/3))O(3) (BZN) and ferroelectric PbTiO(3) (PT), prepared by solid state reactions. A strong dispersion of the maximum of dielectric permittivity (epsilon(')) appears around the temperature of T(m), which shifts toward higher temperatures with increasing frequency. The variation of T(m) with frequency follows the Vogel-Fulcher relationship. The variation of 1/epsilon(') with temperature above Tm deviates from the Curie-Weiss law, but satisfies a Lorentz-type function. The relaxor behavior becomes weaker upon increasing PT-content.     

High-performance PMN-PT thick films

This article describes some of our work on ?.??Pb(Mg?/?Nb(?/?)O?-?.??PbTiO? (0.65PMN-0.35PT) thick films printed on alumina substrates. These thick films, with the nominal composition ?.??Pb(Mg?/?Nb(?/?)O?-?.??PbTiO?, were produced by screen-printing and firing a paste prepared from an organic vehicle and pre-reacted fine particles of avery chemically homogeneous powder. To improve the adhesion of the 0.65PMN-0.35PT to the platinized alumina substrate,a Pb(Zr?.??Ti?.??)O? layer was deposited between the electrode and the substrate. The samples were then sintered at 950 °C for 2 h with various amounts of packing powder on the alumina (Al?O?) substrates. The sintering procedure was optimized to obtain dense 0.65PMN-0.35PT films. The films were then characterized using scanning electron microscopy as well as measurements of the dielectric and piezoelectric constants.The electrostrictive behavior of the 0.65PMN-0.35PT thick films was investigated using an atomic force microscope(AFM). Finally, substrate-free, large-displacement bending type actuators were prepared and characterized, and the normalized displacement (i.e., the displacement per unit length) of the actuators was determined to be 55 μm/cm at 3.6 kV/cm.     

掺杂对PMN-10PT铁电陶瓷介电性能的影响

铌镁酸铅与钛酸铅组成比为9:1(PMN-10PT)的固溶体陶瓷是典型的弛豫铁电体,其介电行为与偶极玻璃的介电行为极为相似.本文使用常用的Swartz两步法,研究了基体掺杂不同物质对PMN-10PT铁电陶瓷的介电性能的影响.经研究发现,当掺入Li₂O时,材料的峰值介电常数为28640,大于纯PMN-10PT,而频率色散和弥散相变的程度都变小.当掺杂CaO和Yb₂O₃时,材料的峰值介电常数下降,分别为19300和18850,它们的频率色散和弥散相变的程度都变大了.同时通过拉曼光谱研究了PMN-10PT陶瓷的B位离子有序度的变化.     

Forty-channel phased array ultrasonic probe using 0.91Pb(Zn(1/3 )Nb(2/3))O(3)-0.09PbTiO(3) single crystal

A 0.91Pb(Zn(1/3)Nb(2/3))O(3)-0.09PbTiO (3) (PZN-PT) single crystal with high electromechanical coupling factor (k(33))>90% has been used to fabricate a 40-channel phased array ultrasonic probe with greater sensitivity and broader bandwidth than conventional probes. This probe has a center frequency of 3.5 MHz and an aperture of about 6.0x7.5 mm. The standard probe fabrication process was modified for PZN-PT. The dispersion of echo signals was within +/-20% of the mean value. After recovery poling, the echo amplitude of the PZN-PT single-crystal probe is 8 and 5 dB higher than that of one- and two-matching-layer PZT probes, respectively. Moreover, the fractional bandwidth of the single-matching-layer PZN-PT probe is broader than that of the two-matching-layer PZT probes. The PZN-PT single crystals provide great improvements in the sensitivity and bandwidth of phased array probes.     

A 20 MHz single-element ultrasonic probe using 0.91Pb(Zn(1/3 )Nb(2/3))O(3)-0.09PbTiO(3) single crystal

A 20 MHz single-element ultrasonic probe using 0.91Pb(Zn(1/3 )Nb(2/3))O(3)-0.09PbTiO(3) (PZN-PT 91/9) single crystal has been fabricated. The single crystal of PZN-PT 91/9 orientated to the (001) plane has longitudinal coupling factor of k(33)>90%, which is much larger than the k(33)=70 to 80% of conventional Pb(Zr(1-x),Ti(x))O(3) (PZT) based ceramics. A single crystal of PZN-PT 91/9 without inclusion or crack has been grown with dimensions of about 25x15x5 mm by the self-flux method. Because mechanical strength in the fabrication of disk transducers orientated to the (001) plane was sufficiently strong, under the same conditions as are applied to conventional PZT ceramics, a piston single-element probe with a diameter of 2.0 mm and a frequency of 20 MHz was successfully fabricated. The bandwidth of the PZN-PT 91/9 probe was 13-26 MHz, which was 4 MHz broader than that of the conventional PZT probe.     

The influence of defects on ferroelectric and pyroelectric properties of Pb(Mg1/3Nb2/3)O3-0.28PbTiO3 single crystals

Relaxor-based ferroelectric single crystals 0.72Pb(Mg_1/3Nb_2/3)O₃-0.28PbTiO₃ (PMN-0.28PT) were grown by a modified Bridgman technique. The direct current (dc) conductivity was investigated and corresponding conduction mechanisms were discussed. V^″Pb−VO defects are dominant from 245 °C to 650 °C. The ferroelectric properties of [1 1 1]-oriented PMN-0.28PT were systematically investigated, with the coercive field (E_c) of 5.2 kV cm⁻¹ and remnant polarization (P_r) of 37.8 μC cm⁻² at room temperature. Moreover, the dielectric and pyroelectric performances of PMN-0.28PT were measured and the integrated pyroelectric performances greatly enhanced after annealing in oxygen at 500 °C for 20 h. This is due to the decrease of oxygen vacancies in the single crystals when being annealed in the oxygen-rich atmosphere. These make [1 1 1]-oriented PMN-0.28PT crystals a promising candidate for infrared detectors and thermal imagers used at room temperature.     

Temperature and pressure dependence of dielectric properties of ceramic Pb(Fe(1/2)Ta(1/2))O(3)

Dielectric properties such as the real epsilon" and imaginary epsilon" parts of the complex permittivity and the spontaneous polarization P(N) of ceramic Pb(Fe(1/2)Ta(1/2))O(3) with the diffuse phase transition (DPT) were measured under pressures up to 6 kbar. The value of epsilon" shows a broad maximum at a temperature T(m) (mean Curie temperature). As the pressure increases, T(m) of the maximum epsilon" (epsilon"(max)) and the value of epsilon"(max) decrease, and the shape of the maximum in epsilon" around T(m) becomes broader. The pressure coefficient of T(m) is about -3.4 K/kbar. The small heat effect associated with the DPT was observed around T(m). The temperature and pressure dependence of epsilon" and P(s ) is explained in terms of a phenomenological theory using statistical treatments based on a Gaussian distribution of the local Curie temperature. The value of the standard deviation sigma describing the intensity of the DPT is 25 K and increases with increasing pressure.     

Electromechanical coupling properties of [001], [011] and [111] poled Pb(Mg1/3Nb2/3)O3-0.32PbTiO3 single crystals

The electric field induced “butterfly” curves and polarization loops, and the stress induced strain and polarization responses of [001], [011] and [111] oriented Pb(Mg_1/3Nb_2/3)O₃-0.32PbTiO₃ (PMN-0.32 PT) relaxor ferroelectric single crystals have been systematically investigated by experiment study. The focus is on the effect of constant compressive bias stress on the electromechanical coupling behavior along three crystallographic directions of PMN-0.32 PT single crystals. Dependence of the coercive field, remnant polarization, dielectric constant, and piezoelectric coefficient on the bias stress has been quantified for PMN-0.32 PT single crystals oriented in three different directions. Obtained results show that the large piezoelectric responses under zero compressive stress in [001] and [011] orientation are dominated by intrinsic crystal lattice while the engineered domain structure has a relatively minor effect. It is found that observed responses under stress cycle for [001] oriented crystals are due to polarization rotation and phase transformations. However, those for [011] and [111] oriented crystals are due to domain switching. The “butterfly” curves and polarization loops driven by electric field under different bias compression are described by two non-180° domain switching.     

Structural characterization of 0.5PbMg1/3Nb2/3O3-0.5BaxPb(1−x)TiO3 powders

The present work reports the effects caused by barium on phase formation, morphology and sintering of lead magnesium niobate-lead titanate (PMN-50PT). Ab initio study of 0.5Pb(Mg_1/3Nb_2/3)O₃-0.5(Ba_xPb_(1−x)TiO₃) ceramic powders, with x = 0, 0.20, and 0.40 was proposed, considering that the partial substitution of lead by barium can reestablish the equilibrium of monoclinic-tetragonal phases in the system. It was verified that even for 40 mol% of barium, it was possible to obtain pyrochlore-free PMN-PT powders. The increase of the lattice parameters of PMN-PT doped-powders confirmed dopant incorporation into the perovskite phase. The presence of barium improved the reactivity of the powders, with an average particle size of 120 nm for 40 mol% of barium against 167 nm for the pure sample. Although high barium content (40 mol%) was deleterious for a dense ceramic, contents up to 20 mol% allowed 95% density when sintered at 1100 °C for 4 h.     

Elastic, piezoelectric, and dielectric properties of 0.955Pb(Zn(1/3)Nb(2/3))O(3)-0.45PbTiO(3 ) single crystal with designed multidomains

The elastic, piezoelectric, and dielectric properties of a 0.955Pb(Zn(1/3)Nb(2/3))O(3)-0.045PbTiO(3 ) (PZN-4.5%PT) multi-domain single crystal, poled along [001] of the original cubic direction, have been determined experimentally using combined resonance and ultrasonic methods. At room temperature, the PZN-4.5%PT single crystal has rhombohedral symmetry. After being poled along [001], four degenerate states still remain. Statistically, such a domain-engineered crystal may be treated as having an average tetragonal symmetry, and its material constants were determined based on 4 mm symmetry. It was confirmed that the electromechanical coupling coefficient k(33) for the domain-engineered samples is >90%, and the piezoelectric constant d(33) is >2000 pC/N. A soft shear mode with a velocity of 700 m/s was found in the [110] direction. From the measured experimental data, the orientational dependence of phase velocities and electromechanical coupling coefficients was calculated. The results showed that the transverse and longitudinal coupling coefficients, k(31) and k(33), reach their maximum along [110] and [001], respectively.     

高活性锆钛酸铅压电陶瓷粉体的合成及其烧结性能研究

以Pb3O4、ZrO2和TiO2为原料,采用冲击波加载技术合成锆钛酸铅Pb(Zr0.95Ti0.05)O3粉体,并对粉体活性和烧结特性进行XRD和SEM表征,研究结果表明,利用冲击波的高温高压作用可以合成单一钙钛矿相锆钛酸铅粉体,合成粉体产生了细化并存在一定程度的晶格畸变,有利于增强粉体活性,促进了低温活化烧结,也显著地改善了陶瓷的烧结性能,在常压下1200℃烧结150min得到了密度达到7.83g/cm3的锆钛酸铅95/5陶瓷体,比传统固相法制备的粉体烧结温度降低了100℃左右,且得到的陶瓷体晶粒形状、大小均匀。     

Structure and electrical properties of (111)-oriented Pb(Mg1/3Nb2/3)O3-PbZrO3-PbTiO3 thin film for ultra-high-frequency transducer applications

Ternary lead magnesium niobate-lead zirconate titanate system 0.4Pb(Mg(1/3)Nb(2/3))O(3)-0.25PbZrO(3)-0.35PbTiO(3) (40PMN-25PZ-35PT) thin film with a thickness of 1.5 μm was grown on Pt(111)/Ti/SiO(2)/Si substrate via chemical solution deposition. X-ray diffraction and transmission electron microscopy results suggested the film obtained was highly (111)-oriented. The remanent polarization and coercive electric field of the film were found to be 25.5 μC/cm(2) and 51 kV/cm, respectively. In addition, at 1 kHz, the dielectric constant was measured to be 1960 and the dielectric loss 0.036. The film was observed to undergo a diffuse ferroelectric-to-paraelectric phase transition at around 209°C. The leakage current appeared to depend on the voltage polarity. If the Au electrode was biased positively, the leakage current was dominated by the Schottky emission mechanism. When the Pt electrode was biased positively, the conduction current curve showed an ohmic behavior at a low electric field and space-charge-limited current characteristics at a high electric field.     

Electrical properties of Pb(Mg1/3Nb2/3)O3-PbTiO3 ceramics modified with WO3

Ferroelectrics 0.67Pb (Mg_1/3Nb_2/3)O₃-0.33PbTiO₃ (PMN-PT) + x mol% WO₃ (x=0.1, 0.5, 1, 2) were prepared by columbite precursor method. Electrical properties of WO₃-modified ferroelectrics were investigated. X-ray diffraction (XRD) was used to identify crystal structure, and pyrochlore phase were observed in 0.67Pb (Mg_1/3Nb_2/3)O₃-0.33PbTiO₃+2 mol% WO₃. Dielectric peak temperature decreased with WO₃ doping, indicating that W⁶⁺ incorporated into PMN-PT lattice. Lattice constant, pyrochlore phase and grain size contribute to the variation of K_max. Both piezoelectric constant (d₃₃) and electromechanical coupling factors (k_p) were enhanced by doping 0.1 mol% WO₃, which results from the introduction of “soft” characteristics into PMN-PT, while further WO₃ addition was detrimental. We consider that the two factors, introduction of “soft” characteristics and the formation of pyrochlore phase, appear to act together to cause the variation of piezoelectric properties of 0.67PMN-0.33PT ceramics doping with WO₃.     

The improvement of dynamic characteristics of ultrasonic therapeutic transducers using fine-grain PZT-based piezoceramics

Optimizing the dynamic resonant characteristics of ultrasonic therapeutic transducers depends most importantly on fine-grain piezoceramics with good resonant properties. In this paper, we prepare and compare modified Pb/sub 0.99/Sr/sub 0.01/[0.03(Mn/sub 1/3/Nb/sub 2/3/)-0.97(Zr/sub 0.51/Ti/sub 0.49/)]O/sub 3/ piezoceramics with 0.1 wt% CaCO/sub 3/ and 0.8 wt% PbO additives (PMZT3) synthesized by B-oxides precursor (BO) and conventional ceramic mixed-oxide methods (MO). Our experimental results show that the BO-type piezoceramics have better grain microstructure and better material properties [e.g., d/sub 33/= 340 pc/N, k/sub t/= 0.52, Q/sub m/= 1250, temperature coefficient of change rate of resonant frequency (TCF) = 0.01%/°C, and temperature coefficient of change rate of clamped capacitance (TCC) = 0.18%/°C]. We construct 1-MHz transducers using our BO and MO types of piezoceramics and examine their dynamic resonant characteristics as the transducers are driven by a power driver with open-loop control. Results show that the transducers with the BO-type piezoceramics have better dynamic characteristics, such as time stability (e.g., aging rate of resonant frequency at thickness mode = 0.26%/decade cycle, and aging rate of clamped capacitance = 0.55%/decade cycle) and temperature stability as BO-type piezoceramics. Furthermore, we observe that the clamped capacitance variation has more influence on the transducer dynamic characteristics than the resonant frequency variation, and we verify the observation from the partial derivative ratio of the transfer function derived by a simulated ultrasonic equivalent circuit system. It is concluded that the BO-type piezoceramics are better candidates than the MO-type samples for obtaining optimum dynamic resonant characteristics in ultrasonic therapeutic transducers.     

Pb(Mn1/3Sb2/3)0.05Zr0.47Ti0.48O3压电陶瓷的温度稳定性研究

探讨了硬性添加物MnO2、软性添加物Nb2O5和两性添加物Cr2O3对锑锰锆钛酸铅Pb(Mn1/3Sb2/3)0.05Zr0.47Ti0.48O3(简称PMSZT5)压电陶瓷的相组成及温度稳定性的影响.研究结果发现:各掺杂组成在900℃的煅烧温度下,都可以得到钙钛矿结构.随着各掺杂离子的增大,四方相含量减少,准同型相界向三方相移动.综合考虑离子掺杂对PMSZT5压电陶瓷的机电性能及温度稳定性的研究结果表明:锰过量较其它铌和铬掺杂的温度稳定性更好,机电性能最佳的PMSZT5+0.1wt%MnO2的组成,ε33T/ε0=1560,d33=350pC/N,Kp=0.63,25~80℃的fr、K31和d31平均温度系数分别为72×10-6/℃、0.027%/℃和0.100%/℃.