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。     

Role of Mn in controlling the dielectric loss and ageing effect in Pb(Zn1/3Nb2/3)O3–Pb(Fe2/3W1/3)O3–Pb(Fe1/2Nb1/2)O3

Compositions in the Pb(Zn1/3Nb2/3)O3–Pb(Fe2/3W1/3)O3–Pb(Fe1/2Nb1/2)O3 (PZN–PFW–PFN) system show a high dielectric constant, insulation resistance and bend strength. In addition they can be sintered at very low temperatures. Hence they find technological applications as multilayer capacitors with low cost Ag-based internal electrodes. The dielectric loss in these ceramics was controlled by doping with Mn in the form of Mn-acetate, MnO2, and Pb(Mn1/3Nb2/3)O3. The subtle differences in the dielectric properties of PZN–PFW–PFN, when Mn is taken in these forms are reported in this paper. A possible way of controlling the ageing effect is highlighted. © 1998 Chapman & Hall     

Complete set of material properties of [011](c) poled 0.24Pb(In(1/2)Nb(1/2))O(3)-0.46Pb(Mg(1/3)Nb(2/3))O(3)-0.30PbTiO(3) single crystal

A complete set of elastic, piezoelectric, and dielectric constants of [011](c) poled multidomain 0.24Pb(In(1/2)Nb(1/2))O(3)-0.46Pb(Mg(1/3)Nb(2/3))O(3)-0.30PbTiO(3) ternary single crystal has been determined using resonance and ultrasonic methods and the temperature dependence of the dielectric permittivity has been measured at 3 different frequencies. The experimental results revealed that this [011](c) poled ternary single crystal has very large transverse piezoelectric coefficient d(32) = -1693 pC/N, transverse dielectric constant ε(11)/ε(0) ~ 7400 and a high electromechanical coupling factor k(32) ~ 90%. In addition, its coercive field is 2 times of that of the corresponding binary 0.7Pb(Mg(1/3)Nb(2/3))O(3)-0.30PbTiO(3) single system with much better temperature stability. Therefore, the crystal is an excellent candidate for transverse mode electromechanical devices.     

Preparation of Pb(Mg1/3Nb2/3)O3–Pb(Zn1/3Nb2/3)O3 ceramics by the B-site precursor method and dielectric characteristics

Powders in the Pb(Mg1/3Nb2/3)O3–Pb(Zn1/3Nb2/3)O3 system, with a high perovskite yield, were prepared by a B-site precursor method. PbO was added to pre-reacted B-site components of Mg1-xZnxNb2O6 solid solution, which was further calcined to form a perovskite structure. Perovskite phase contents and lattice parameters were obtained from X-ray analyses. Weak-field low-frequency dielectric constants and losses of sintered pellets were measured as functions of composition, temperature and frequency. Dielectric relaxation behaviours were investigated in terms of diffuseness coefficients. Microstructures were observed to correlate with other characteristics. © 1998 Chapman & Hall     

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.     

Study on the structures of N-containing melilite Y2Si3O3N4 and Nd2Si2.5Al0.5O3.5N3.5

Rietveld refinements have been used to determine the structure of Y2Si3O3N4 from X-ray data and Nd2Si2.5Al0.5O3.5N3.5 from neutron powder diffraction data. The refinements show that in the melilite phase Y2Si3O3N4 and melilite solid solution Nd2Si2.5Al0.5O3.5N3.5 the distributions of cations and anions are almost identical. They are analogous to the akermanite (Ca2MgSi2O7) structure, with Si/Si,Al atoms at the origin and centre of the unit cell and with four N/N,O atoms forming the SiN4/(Si,Al)(N3.5O0.5) tetrahedra which share corners with SiO2N2/(Si,Al)O2.25N1.75 tetrahedra to form a continuous sheet structure. Each Y3+ or Nd3+ ion is surrounded by eight N/O atoms forming the coordination polyhedron in Y2Si3O3N4 and Nd2Si2.5Al0.5O3.5N3.5 respectively. The arrangement of Al, Si atoms in the tetrahedra in Nd2Si2.5Al0.5O3.5N3.5 structure is also discussed. This revised version was published online in November 2006 with corrections to the Cover Date.     

Structural investigations on Pb(ZrxT1?x)O3 solid solutions using the X-ray Rietveld method

Solid solutions in the series Pb(Zr _x Ti_1-x )O₃ which belong to ABO₃ type compounds were studied using the X-ray Rietveld technique from the tetragonal PbTiO₃ end to Pb(Zr_0.53 Ti_0.47)O₃ which is near the morphotropic phase boundary. A systematic structure analysis carried out for this series revealed that tetragonal and rhombohedral phases coexist even when Zr/Ti ratio is 40/60. Quantitative phase analysis using Rietveld method has been carried out for compositions falling in the two phase region. Substantial decrease in distortions of the BO₆ octahedra has been observed for the compositions near the morphotropic phase boundary.     

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.     

Harmonic analysis of the polarization response in Pb(Mg(1/3 )Nb(2/3))O(3)-based ceramics-A study in aging

The polarization response of a ferroelectric ceramic displays nonlinear behavior at high applied fields due to saturation effects. Weak-field dielectric aging imposes additional nonlinearity on the hysteresis loops of these materials. Harmonic analysis using a discrete Fourier transform (DFT) permitted an observation of the change in the polarization frequency spectrum as Pb(Mg(1/3)Nb(2/3))O (3)-based relaxor ceramics aged. It also facilitated the calculation of ac current, power, and "internal bias field". The results show that particular harmonics in the polarization signal are sensitive indications of aging behavior. The average power dissipated at weak ac fields was found to decrease with aging time; and the power dissipated at strong fields tended to increase.     

Effect of strain on ferroelectric and magnetic behavior in Pb(Zr0.52Ti0.48)O3-based magnetoelectric heterostructures

In this paper, the "sandwich" structured magnetoelectric composite films of Pb(Zr0.52Ti0.48)O3/ NiFe2O4/Pb(Zr0.52Ti0.48)O3 and Pb(Zr0.52Ti0.48)O3/CoFe2O4/Pb(Zr0.52Ti0.48)O3 are epitaxially grown on SrRuO3/SrTiO3 substrates by pulsed-laser deposition. The crystalline quality and microstructures of these heterostructures are investigated by X-ray diffraction technique. The effects of strain on the ferroelectric, magnetic and magnetoelectric coupling properties of these thin films are systematically studied. The results show that the strain effect induced by lattice mismatch between the ferroelectric/ferromagnetic layers plays an important role in the ferroelectric and magnetic properties of these composite films. Compared to the strained Pb(Zr0.52Ti0.48)O3/ CoFe2O4/Pb(Zr0.52Ti0.48)O3 heterostructure, improved ferroelectric properties with an out-of-plane polarization (2P(r)) of 34.2 microC/cm2 and electric coercivity field of 158 kV/cm are obtained in the strain-free Pb(Zr0.52Ti0.48)O3/NiFe2O4/Pb(Zr0.52Ti0.48)O3 heterostructure. The ME measurement results not only show that the strain induced by lattice mismatch has great influence on the ME behavior, but also provide an understanding of the multilayers with full control over the interface structure at the atomic-scale.     

Neutron and X-ray powder diffraction studies of the oxynitrides SrW(O,N)3, Ba3W2(O,N)8 and Ba3Mo2(O,N)8

Oxynitrides of composition SrW(O,N)₃, Ba₃W₂(O,N)₈ and Ba₃Mo₂(O,N)₈ have been prepared by the ammonolysis of stoichiometric mixtures of oxides and carbonates. Combined Rietveld refinements of powder neutron and powder X-ray diffraction data have allowed the structure of each to be determined. SrW(O,N)₃ was found to have a cubic Perovskite structure whereas Ba₃W₂(O,N)₈ and Ba₃Mo₂(O,N)₈ have a layered hexagonal structure. In the hexagonal structures the oxygen and nitrogen atoms are distributed almost randomly over two sites in the unit cell producing 4-fold co-ordination to tungsten and molybdenum, a distorted octahedral co-ordination to one barium site and a 10-fold co-ordination to the other.     

Temperature dependence of oriented growth of Pb[Yb(1/2)Nb(1/2)]O(3)-PbTiO(3) thin films deposited on LNO/Si substrates

(1-x)Pb[Yb(1/2)Nb(1/2)]O(3)-xPbTiO(3) (PYbN-PT, x=0.5)(001) oriented thin films were deposited onto LaNiO3 (LNO)/Si(001) substrates by sol-gel processing. The crystallographic texture of the films was controlled by the annealing temperature and heating rate. Highly (001) oriented LNO thin films were prepared by a simple metal organic decomposition technique, and the samples were annealed at 700 °C and 750 °C using a rapid thermal annealing process and furnace, respectively. X-ray diffraction analysis revealed that the films of PYbN-PT were highly (001) oriented along LNO/Si substrates. The degree of PYbN-PT orientation is dependent on the heating rate and annealing temperature. Annealing heating rate of 10 °C/s and high annealing temperature near 750 °C produce the greatest degree of (001) orientation, which gives rise to improved dielectric properties.     

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。     

Thickness dependence of structural and ferroelectric properties of sol-gel Pb(Zr0.56Ti0.44)0.90(Mg1/3Nb2/3)0.10O3 films

Sol-gel Pb(Zr_0.56Ti_0.44)_0.90(Mg_1/3Nb_2/3)_0.10O₃ (PZT-PMN) films were prepared onto the Ti/Pt/Ti bottom electrode by multilayer spin coating. The film thickness ranged from 0.22 to 0.88 μm. The Pt top electrodes were deposited on the PZT-PMN films by DC sputtering. The structural and ferroelectric properties of PZT-PMN films were investigated as a function of film thickness by X-ray diffraction (XRD), scanning electron microscopy (SEM), cross-sectional transmission electron microscopy (XTEM), and by measuring the relative permittivity. The film retains the tetragonal perovskite structure with the [111] and [100] preferred orientations perpendicular to the film surface independent of film thickness. The [100] texture increases with increasing film thickness although the [111] texture is always predominant. The film consists of columnar grains. The average grain size is nearly independent of film thickness. The surface layer containing fine grains about 30 nm in diameter is induced on the top of the film. As the film thickness exceeds 0.44 μm, the number of the fine grains decreases remarkably. The crystalline interface layer about 10 nm thick is formed between the film and the bottom electrode. This interface layer is composed of Pt, Pb, Zr, Ti and O, while it is rich in Ti and deficient in Pb and O as compared with the inside of the film. The measured relative permittivity of the film increases with increasing film thickness, following the low permittivity interface model. On the basis of this model, the relative permittivity is estimated to be 3200 for the intrinsic PZT-PMN film, 750 for the surface layer and 50 for the interface layer.     

Determination of nonlinear electromechanical energy conversion and the field-dependent elastic modulus of Pb(Mg(1/3)Nb(2/3 ))O(3)-based electrostrictors

Energy conversion efficiency is a critical parameter for all electromechanical materials. Although excellent techniques are available for linear materials, nonlinearities complicate the determination of conversion efficiency in electrostrictive Pb(Mg(1/3)Nb(2/3 ))O(3) (PMN). The field dependence of the elastic modulus presents additional problems. A technique combining pulse-echo ultrasound has been developed to approximate the change in the Young's modulus with applied field. A 30% decrease was observed at 1 MV/m (from ~100 to ~70 GPa). The boundary condition for these measurements was a constant electric field as opposed to constant dielectric displacement. In combination with the results from harmonic analysis, the modulus data may be used to determine the electromechanical conversion efficiency. This has been accomplished using an energy balance criterion for a PMN-based composition (with and without dc bias). The resulting longitudinal coupling values are >0.5 for practical electric fields (<1 MV/m peak).     

高性能铌镁酸铅-钛酸铅定向压电陶瓷的研究

用定向凝固技术制备了择优方向为[112]的0．70Pb(Mg1／3Nb2／3)O3—0．30PbTiO3高性能定向压电陶瓷．该陶瓷[112]方向的取向度约为35％，准静态压电常数d33约为1500～1600pC／N，耦合系数κt～0．51，κ33～0．82，22kV／cm时的场致应变约为0．23％。     

Intermediate Temperature Sintering of La-Modified Pb(Zn1/3Nb2/3)O3-PbZrO3-PbTiO3 Piezoelectric Ceramics

In order to realize the co-firing with Ag/Pd electrodes in multilayer devices, Pb(Zn1/3Nb2/3)1-,-yZrxTiyO3(0.25＜x＜0.35, 0.25＜y＜0.35) piezoelectric ceramics (hereafter designated PZN-PZT)modified by La2O3 has been prepared by conventional technique with sintering temperature from 1100℃ to 1140℃. X-ray diffraction patterns demonstrated that pure perovskite phase was obtained. Secondary electron image (SEI) showed that crystalline grains in ceramics were well grown. d33 of manufactured sample was as high as 560×10-12C/N. kp was about 0.61 and tgδabout 30×10-3. The existence of liquid phase examined by electron diffraction in PZN-PZT sample is beneficial to sintering of the ceramic.     

Synthesis and neutron structural studies of (Pb/Cu)-1201 superconductor

A 1201-phase superconductor (Pb_0.5Cu_0.5)SrLaCuO_5± exhibiting a zero-resistance (R=0) state at 21 K has been synthesized. Neutron Rietveld refinement of the structure shows substantial oxygen disorder in the (Pb/Cu)-O(3) monolayer and excess occupancy of oxygen at the O(3) sites. The superconducting behavior of (Pb_0.5Cd_0.5)SrLaCuO_5± , prepared under identical conditions, yields a value ofT _c (R=0) equal to 24 K. The presence of extra oxygen appears to be responsible for trapping of holes within the rock-salt (Pb/Cu)-O(3).     

The (SmZr)Co$_3$Phase in Sm(CoFeCuZr)$_rm z$Magnets

Detailed microstructural characterization of magnets and homogenized as-cast alloys, which included X-ray diffraction Rietveld analysis, has indicated that the so-called platelet or lamellae phase is (SmZr)₁(CoFeCu)₃ with the PuNi₃ structure and lattice parameters a~0.5 nm and c~2.4 nm. The structural and magnetic properties of the (SmZr)Co₃ phase were investigated. The microstructure shows two phases differing in their Zr/Sm ratio. Magnetization curves for the samples (Sm_0.33Zr _0.67)Co₃, (Sm_0.33Zr_0.67)Co _2.97Fe_0.03, and (Sm_0.67Zr_0.33)Co₃ are consistent with the two-phase microstructure observed. Room temperature coercivity values of these samples are low (ap1 kOe.)     

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.