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     

Pb(Zn1/3Nb2/3)O3-Ba(Zn1/3Nb2/3)O3铁电陶瓷结构与性能的研究

采用固相反应的方法系统地研究了BZN稳定PZN基陶瓷的相结构与介电性能.随着BZN含量的增加,PZN-BZN陶瓷中钙钛矿相的稳定性增强,居里温度近似呈线性下降,室温介电常数和介质损耗随也显著降低,最小值分别为380和0.002.为获得100%钙钛矿结构的PZN基陶瓷所需BZN的最小用量为8mol%～10mol%,当BZN的mol%超过15mol%时,PZN基陶瓷中钙钛矿相所占的百分比不再受烧结工艺的影响,基本保持100%.1kHz时Pb0.9Ba0.1Zn1/3Nb2/3O3陶瓷的最大介电常数Kmax=8680,tgδ=0.02,相应的居里温度Tm为24℃.     

Dielectric properties of Pb(Zn1/3, Nb2/3)O3 ceramics modified by Ba(Zn1/3, Nb2/3)O3 and BaTiO3

Dielectric properties of lead zinc niobate (PZN) ceramics modified by barium zinc niobate (BZN) and BaTiO₃ (BT) were investigated. By adding the modifier of BT and BZN, the stabilization of perovskite phase of PZN increased, but its Curie temperature decreased linearly with the amount of added modifier. Room temperature dielectric constant of PZN increased by addition of stabilizers up to 12 and 15 mol% of BZN and BT, respectively. The maximum room temperature dielectric constant was observed to be 7800 at 12 mol% of BZN, and 9800 at 15 mol% of BT, respectively.     

Preparation and dielectric properties of Pb(Zn1/3Nb2/3)O3-based ferroelectric ceramics

The sintering behavior of mechanochemically prepared 0.9Pb(Zn_1/3Nb_2/3)O₃-0.1ABO₃ (ABO₃ = BaBiO₃, BaMnO₃, BaTiO₃) powders is studied. PbO and Bi₂O₃ are shown to volatilize at relatively low temperatures owing to partial reduction of these oxides during the mechanochemical synthesis. Dense (97% of theoretical density) ceramics are obtained under mild sintering conditions, and their dielectric properties are studied at different frequencies. The observed variations of their dielectric permittivity and loss tangent with frequency are typical of relaxor ferroelectrics, but the ceramics have a reduced dielectric permittivity, which is attributable to nanostructuring.     

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     

Stabilization of the perovskite phase in Pb(Zn1/3, Nb2/3)O3 ceramics modified by Ba(Zn1/3, Nb2/3)O3 and BaTiO3

Stabilization of the perovskite phase in PZN-BT-BZN ceramics prepared by solid-state sintering was investigated. With the addition of BT and/or BZN, the amounts of perovskite phase in PZN ceramics increased, but the amount of pyrochlore phase decreased. Optimum calcination conditions for this system, to obtain PZN ceramics with the minimum amount of the pyrochlore phase, are a temperature range between 950 and 1000°C and a sintering time of 2–4 h. The perovskite phase of these systems could be 100% stabilized by the addition of more than 7 mol% BT, 8 and 10 mol% BTZN and BZN, respectively. This revised version was published online in November 2006 with corrections to the Cover Date.     

Perovskite formation and dielectric responses in Pb(Zn1/3Nb2/3)O3-modified Pb(Zn1/3Ta2/3)O3-PbTiO3 ceramics

Pb(Zn_1/3Ta_2/3)O₃-PbTiO₃ ceramic compositions were modified by the introduction of Nb to the octahedral lattice sites. Resultant tendencies in the perovskite formation and dielectric properties were examined. System powders were prepared using a B-site precursor method. Developed structures and lattice parameters of the system compositions were investigated by powder X-ray diffractometry, from which the parameter of a hypothetical perovskite Pb(Zn_1/3Ta_2/3)O₃ is proposed. Weak-field low-frequency dielectric responses of the system ceramics were measured.     

液相包裹法制备Pb(Mg1/3Nb2/3)O3-CoFe2O4磁电耦合材料

以无机盐Nb2O5、Mg(NO3)2、Pb(NO3)4、Co(NO3)2、Fe2(NO3)3为原料,柠檬酸和EDTA为络合剂,分别制备了Nb5+、Mg2+、Pb2+、Co2+、Fe3+等离子的络合溶液。采用络合法制备了铌酸镁-铁酸钴先驱体(MgNb2O6-CoFe2O4,简称MN-CFO)。此先驱体在1000℃煅烧1h后,得到纯净的MgNb2O6-CoFe2O4固溶体。采用液相包裹法制备了铌镁酸铅-铁酸钴(Pb(Mg1/3Nb2/3)O3-CoFe2O4)先驱体,在1000℃煅烧1h,Pb(Mg1/3Nb2/3)O3-CoFe2O4先驱体分解为具有铁电相Pb(Mg1/3Nb2/3)O3和铁磁相CoFe2O4的复相组织。研究了10%过量的PbO对煅烧过程中烧绿石相向铁电相的转变作用,并在700℃煅烧5h条件下制备了不含烧绿石相的Pb(Mg1/3Nb2/3)O3-CoFe2O4固溶体。     

Synthesis of Pb(Mg1/3Nb2/3) O3 perovskite by an alkoxide method

Pb(Mg_1/3Nb_2/3)O₃ materials have been synthesized using sol-gel, freeze-drying or spray-pyrolysis techniques. The as-prepared powders were of an amorphous form which could be converted into a crystalline form by calcination. The pyrochlore phase was inevitably formed with an accompanying perovskite phase. As the calcining temperature increased, greater proportions of the desired perovskite phase occurred. The residual pyrochlore phase could be completely transformed into the perovskite phase when the powders were prepared via freeze-drying or by a spray-pyrolysis method. The maximum proportion of the pyrochlore phase was, however, only 92% when the powders were synthesized by a sol-gel route. Thermal gravimetric analysis/differential thermal analysis (TGA/DTA) and infrared transmission spectroscopy (FTIR) indicated that Mg(OEt)₂ and Nb(OEt)₅ formed a double alkoxide but Pb(OAc)₂ formed separate clusters during the hydrolysis of the solution in the sol-gel process. Inhomogeneous mixing meant that the intermediate phase formed was rather difficult to eliminate completely. Homogeneous mixing was preserved when the solution was directly freeze dried or spray pyrolysed. The size of the preferentially formed pyrochlore phase was very fine and further transformation was feasible. Pb(Mg_1/3Nb_2/3)O₃ materials, free of the pyrochlore phase, could therefore be obtained.     

Preparation of Mg-modified Pb[Zn1/3(Ta0.4Nb0.6)2/3]O3 ceramics and dielectric characteristics

Mg (full composition range) and Nb (60 at %) were simultaneously substituted into Pb(Zn_1/3Ta_2/3)O₃, in an attempt to stabilize the perovskite structure. System powders were prepared using a B-site precursor method in order to enhance perovskite formation. The developed structures were examined by X-ray diffraction, from which perovskite phase yields as well as lattice parameters of the pyrochlore and perovskite were determined. Low-frequency dielectric responses of the ceramics were investigated. Phase transition modes (reflected in the dielectric constant spectra) were further analyzed in terms of diffuseness parameters.     

Effect of high pressure on the dielectric properties of relaxor compositions [Pb(Fe1/2Nb1/2)O3]1-x-y-[Pb(Zn1/3Nb2/3)O3]x- [BaTiO3]y

Abstracts are not published in this journal     

Dielectric characteristics of Mg-replaced Pb[(Zn1/3Ta2/3)0.2(Zn1/3Nb2/3)0.6Ti0.2]O3 ceramics

Powders of a Pb[(Zn_1/3Ta_2/3)_0.2(Zn_1/3Nb_2/3)_0.6Ti_0.2]O₃ system with gradual replacement of Zn by Mg were prepared by employing a B-site precursor method and developed structures were studied by X-ray diffractometry. Dielectric properties of the sintered ceramics were characterized under weak-field low-frequency conditions. A high maximum dielectric constant value of 38,000 (@1 kHz) was realized when 3/4 of octahedral Zn was replaced by Mg. Field-dependent polarization responses were also monitored at various temperatures to investigate ferroelectricity. Microstructures of the fractured ceramics were examined using a scanning electron microscope.     

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.     

Investigation into the growth and electromechanical properties of Pb(Mg1/3Nb2/3)O3 thin films

Pulsed laser deposition (PLD) has been used to fabricate relaxor thin films and thin film capacitors based on the Pb(Mg_1/3Nb_2/3)O₃ system. Best capacitor structures show dielectric constants (_r) of 1000 and losses (tan ) 0.02 at 1 kHz at 300 K. Electromechanical investigations show that tensile longitudinal strains of up to 0.2% can be achieved in these films.     

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.     

Preparation of B2O3-P2O5-SiO2 coating films by the sol-gel method

ThexB₂O₃ · (20-x) P₂O₅ · 80SiO₂ (in mol%) glass films withx=0, 10 and 20 have been prepared from metal alkoxides by carrying out the coating in a dry atmosphere. These coating films have shown a larger value of load at scratch and a smaller shrinkage during heat-treatment by replacing P₂O₅ in the films with B₂O₃. It has been found that B₂O₃ more effectively reduces the glass transition temperature of SiO₂ glass than P₂O₅. The concentrations of sodium ions, which migrated from soda-lime-silica glass substrates during the film formation, were higher in phosphosilicate and borophosphosilicate films than in borosilicate and pure silica films. This finding should be ascribed to the gettering effects of phosphorus for sodium ions.