Complete set of material properties of single domain 0.24Pb(In(1∕2)Nb(1∕2))O(3)-0.49Pb(Mg(1∕3)Nb(2∕3))O(3)-0.27PbTiO(3) single crystal and the orientation effects

Multidomain relaxor-based single crystals have intrigued the enthusiasm of many researchers due to their superior electromechanical properties. In order to understand the physical origin of multidomain properties, one must know the complete set of material coefficients in single domain state. Previous published single domain data were all measured under bias because single domain state is unstable. Here, we report a set of single domain data without bias for rhombohedral 0.24Pb(In(1∕2)Nb(1∕2))O(3)-0.49Pb(Mg(1∕3)Nb(2∕3))O(3)-0.27PbTiO(3) single crystal. Comparing rotated coefficients from single domain data with measured multidomain material coefficients, we concluded that the orientation effects account for more than 90% of the observed multidomain properties.     

Dielectric and elastic properties of 0.70Pb(Mg1/3Nb2/3)O3–0.30PbTiO3 single crystal and their electric-field dependence

The dielectric and elastic properties of [001]_c-oriented 0.7Pb(Mg_1/3Nb_2/3)O₃–0.3PbTiO₃ (PMN–0.3PT) crystal were investigated as a function of poling field at 300 and 360 K, respectively. At 300 K, the dielectric constant and elastic compliance of rhombohedral PMN–0.3PT crystal change drastically at a critical field corresponding to an electric-induced ferroelectric phase transition. At 360 K, the PMN–0.3PT crystal is tetragonal, its dielectric constant and elastic compliance change drastically at two critical fields, which indicates an intermediate phase. Furthermore, much small dielectric loss factors and mechanical loss factors are observed in mono-domain state, which indicates that losses mainly come from domain wall contributions.     

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.     

Field-induced effect in the <111>-oriented 0.70Pb(Mg1/3Nb2/3)O3–0.30PbTiO3 single crystals

Temperature-dependent dielectric constant, X-ray diffraction(XRD), thermally stimulated discharging current (TSDC) and polarization hysteresis loops for <111>-oriented 0.70Pb(Mg_1/3Nb_2/3)O₃–0.30PbTiO₃ crystals after poling under different fields were measured. Comparing with unpoled sample during heating, except that there is a transition from the state of normal ferroelectric rhombohedral (macro-domain) to the state of relaxor ferroelectric rhombohedral (micro-domain) for the poled samples, it was found that no other phase transition was induced by poling fields. XRD showed that after poling the piezoelectric elongation of the unit cell occurred along the polar direction. It was suggested that an extra peak in the T–ε curve of poled sample around 105 °C is not only caused by a macro–micro domain transition but also caused by the depolarization process of 180° and 71° domain switching simultaneously.     

Electromechanical properties of fine-grain, 0.7 Pb(Mg(1/3)Nb(2/3))O3-0.3PbTiO3 ceramics

A fine grain, relaxor-based piezoelectric ceramic 0.7 Pb(Mg(1/3)Nb(2/3))O3-0.3PbTiO3 (PMN-30% PT) has been investigated, which was fabricated using the columbite precursor method. The complete set of electromechanical properties of the piezoceramic at room temperature is determined using a combination of ultrasonic and resonance techniques. This fine-grain ceramic (grain size < or = 2.5 microm) exhibits ultra-high dielectric permittivity (epsilon33(T)/epsilon0 approximately 7000) and a high coupling coefficient k(33) (= 0.78). Ultrasonic spectroscopy was used to measure the dispersion of the phase velocity and attenuation for the longitudinal wave propagating in the poling direction. Lower attenuation and smaller velocity dispersion were observed compared to modified Pb(Zr(x)Ti(1-x)O3 (PZT-5H) ceramics. The measurement results show that this fine-grain PMN-30% PT ceramic is a very good material for making ultrasonic array transducers.     

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.     

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.     

Microstructural and compositional study of a bulk Pb(Mg1/3Nb2/3)O3–PbTiO3 single crystal grown from a BaTiO3 seed

The microstructure, composition and homogeneity of a Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PMNT) single crystal were studied using a combination of electron-microprobe techniques: scanning electron microscopy, orientation analysis and quantitative X-ray microanalysis. A PMNT single crystal was grown from a polycrystalline PMNT matrix using a BaTiO₃ single crystal as a seed. The PMNT crystal retained the same crystallographic orientation as the seed with no interdiffusion at the interface. The average chemical composition, determined with optimized quantitative wavelength-dispersive X-ray microanalysis, was Pb(Mg_1/3Nb_2/3)_1−XTi_XO₃ where x = 0.33. A statistical evaluation of the data using the analysis of variance showed that the achieved experimental uncertainty was below ± 1% relative. The compositional homogeneity of the crystal was verified on the micrometer-scale; however on the macro-scale slight fluctuations of the Mg, Nb and Ti concentrations were observed across the crystal. The measured variations from the average composition were ± 2.3% relative for Ti, ± 1.3% for Nb and ± 1.4% for Mg. In contrast, the Pb concentration was found to be uniform on both the micro- and macro-scale, showing a variation below ± 0.5% relative.     

67Pb(Mg1/3Nb2/3)O3-33PbTiO3单晶的微结构与铁电畴

用偏光显微镜(PLM)和透射电镜(TEM)观察了67Pb(Mg1/3Nb2/3)O3-33PbTiO3单晶的畴结构.在PLM下,光学质量不同的晶体具有不同的畴结构,透明晶体具有毫米尺度的大畴,透明性差的晶体的带状孪生畴宽约为0.1mm;在TEM下,雾状晶体中存在着复杂的微米尺度的孪生畴,而均匀晶体中存在着不规则的微米尺度的180°畴.原位EDS分析表明,在孪生晶体中存在Nb-Ti-Mg-Pb-O非晶相.透明晶体的介电和压电常数显著地高于雾状晶体.讨论了化学不均性对畴结构的影响.     

A 3.7 MHz phased array probe using 0.91Pb(Zn(1/3)Nb(2/3))O(3)-0.09PbTiO(3 )

A novel 128-channel phased array probe for echocardiography with a center frequency of 3.7 MHz using 0.91Pb(Zn(1/3)Nb(2/3))O(3)-0.09PbTiO(3 ) (PZN-9%PT) single crystal has been fabricated to realize greater sensitivity and broader bandwidth properties. The echo amplitude of the PZN-9%PT single-crystal probe is about 5 dB higher than that of the conventional lead airconate titanate (PZT) ceramic probe, and the fractional bandwidth is about 25 percentage points broader. The quality of B mode images obtained by the PZN-9%PT probe satisfies the performance of the two types of conventional PZT ceramic probes that have center frequencies of 2.5 and 3.75 MHz. At the reference frequency of 3 MHz, the Doppler sensitivity of the PZN-9%PT probe is about 5 dB higher than that of the 3.75 MHz PZT probe; the blood flow of a pulmonary vein in a hard-to-image patient is much more clearly imaged than in the case of using the PZT probe. These superior images are attributable to the use of sufficiently large PZN-9%PT single crystals obtained by the self-flux method.     

Anisotropy in domain engineered 0.92Pb(Zn1/3 Nb2/3)O3-0.08PbTiO3 single crystal and analysis of its property fluctuations

The orientation dependence of slowness and electromechanical coupling coefficients of 0.92Pb(Zn/sub 1/3/Nb/sub 2/3/)O/sub 3/-0.08PbTiO/sub 3/ (PZN-8%PT) domain engineered single crystal was analyzed based on the measured complete set of elastic, piezoelectric, and dielectric constants. There exist one quasi-longitudinal, one quasi-shear, and one pure shear wave in each of the [100]-[010], [010]-[001], and [001]-[110] planes. The slowness of the quasi-shear wave exhibits strong anisotropy in all three planes, and the coupling coefficient k/sub 33/ and k/sub 31/ reach their maximum in [001] and [110] directions of cubic axis, respectively. Because the composition of the PMN-8%PT system is very close to the morphotropic phase boundary, the extraordinary large piezoelectric coefficients d/sub 31/ and d/sub 33/, and high coupling coefficient k/sub 33/ are very sensitive to compositional variation. We have performed error analysis and proposed an improved characterization scheme to derive a complete data set with best consistency.     

Top-cooling-solution-growth and characterization of piezoelectric 0.955Pb(Zn1/3Nb2/3)O3-0.045PbTiO3 [PZNT] single crystals

A technique of top-cooling-solution-growth (TCSG) has been developed to grow the piezo-/ferroelectric perovskite single crystals of 0.955Pb(Zn_1/3Nb_2/3)O₃-0.045PbTiO₃ [PZNT95.5/4.5]. The flux composition and concentration, and the thermal parameters have been optimized, leading to the growth of high quality PZNT crystals with a size up to 20 × 15 × 10 mm³. The perovskite crystals are found to form upon slow cooling down to 1020°C, while the undesirable pyrochlore crystals of Pb_1.5Nb₂O_6.5-type start growing upon further cooling from 1020°C to 950°C. By controlling the growth pathway, the formation of the pyrochlore phase can be avoided. The dielectric properties of the grown PZNT95.5/4.5 crystals have been measured as a function of temperature at various frequencies. Upon heating, the phase transition for the rhombohedral R3m to the tetragonal P4mm phase takes place at 132°C, while the tetragonal to cubic phase transition occurs at 160°C. The TCSG developed in this work provides an alternative technique to grow PZNT piezocrystals of medium size at low cost for transducer applications.     

Composites of 0.9Pb(Mg1/3Nb2/3)O3-0.1PbTiO3 prepared by a sol-gel method: effect of atmosphere powders

Dielectric and electrical properties of relaxor ferroelectric 0.9PMN-0.1PT ceramics prepared by a sol-gel method were investigated as a function of PbZrO₃ atmosphere powders. The proper amount of atmosphere powders led to better properties of dielectric constant, polarization, and strain by preventing PbO volatilization from ceramics. Excessive amount of atmosphere powder, however, resulted in aging characteristics such as decreases in dielectric constant and loss exhibiting saddle-shaped dielectric constant and loss vs. temperature curves. A propeller-shaped P-E hysteresis curve indicating aging characteristics was also observed when an excessive amount of atmosphere powder was used during sintering. The aging of ceramics caused by absorption of PbO into the ceramics resulted in decreased polarization and strain. These aging characteristics associated with defects by excessive PbO absorption could not be reversed even though the aged ceramics underwent a heat-treatment above the dielectric maximum temperature.     

67 Pb(Mg1/3Nb2/3)O3-33PbTiO3单晶90铁电畴光学研究

采用偏光显微镜观察了67Pb(Mg1/3Nb2/3)O3-33PbTiO3固溶体铁电单晶在室温时90铁电畴结构.铁电畴结构与晶体质量有关,在正交偏光显微镜下光学透明晶体中存在着尺寸为23mm的均匀大畴,不同极化方向的大畴重叠形成雾状区,使晶体表现出光学质量宏观不均匀.在光学质量差的雾状晶体中则存在着0.1mm宽的110型带状孪生畴,使晶体形成表面浮凸,带状畴内还存在着90°亚畴.并对这些畴的形成作了讨论