Preparation of Pb(Zr,Ti)O<Subscript>3</Subscript>–Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> piezoelectric ceramics by dry–dry method

Ternary perovskite ceramics of Pb[(Zr_0.5Ti_0.5)_0.8−x (Mg_1/3Nb_2/3)_0.2+x]_0.98Nb_0.02O_3.01 (PZTMN, x = −0.075, −0.05, −0.025, 0, 0.025, 0.05, and 0.075 ), are synthesized via dry–dry method. B-site precursors of PZTMN ([(Zr_0.5Ti_0.5)_0.8−x (Mg_1/3Nb_2/3)_0.2+x ]_0.98Nb_0.02O_2.01, ZTMN) can be synthesized via a two-step solid state reaction method. The first calcination temperature is 1,300 °C, and the second is not higher than 1,360 °C. Incorporation of magnesium and niobium ions promotes the formation of the single phase solid solution with ZrTiO₄ structure. Single phase perovskite PZTMN is formed at 780 °C, much lower than that in conventional process. Dense ceramics can be sintered at about 1,260 °C with dielectric and piezoelectric properties comparable to that of wet–dry method and higher than that of conventional method. It seems that B-site precursor method is cost effective in preparation of ternary piezoelectric ceramics.     

Perovskite phase formation in the PbMg1/3Nb2/3 O3-PbZrO3-PbTiO3 system by the columbite route

The reaction mechanism of PbMg_1/3Nb_2/3O₃-PbZrO₃-PbTiO₃ (PMN-PZT) perovskite phase prepared by the columbite route has been studied in the temperature range from 600 to 800 °C. The effects of heating and cooling rate during the calcination of 3PbO +MgNb₂O₆+PZT powder mixtures have also been investigated. Nearly pure perovskite phase, 0.9 PMN-0.1 PZTsolid solution with no pyrochlore phase, as determined by X-ray diffraction, could be prepared at 800 °C for 2 H. From DTA/TGA, dilatometry and XRD data the reaction mechanism of PMN-PZT solid solution formation could be divided into three steps: (i) decomposition of columbite (MgNb₂O₆) by reacting with PbO at 350 to 600 °C (ii) the formation of a B-site-deficient pyrochlore phase Pb₂Nb_1.33Mg_0.17O_5.50 at close to 650 °C, and (iii) the formation of perovskite phase PMN-PZT solid solution from the reaction of Pb₂Nb_1.33Mg_0.17O_5.50 pyrochlore phase with MgO and PZT above 650 °C.     

Stoichiometric Pb(Mg1/3Nb2/3)O3 perovskite ceramics produced by reaction-sintering process

Stoichiometric lead magnesium niobate, Pb(Mg_1/3Nb_2/3)O₃ (PMN), perovskite ceramics produced by reaction-sintering process were investigated. Without calcination, a mixture of PbO, Nb₂O₅, and Mg(NO₃)₂ was pressed and sintered directly. Stoichiometric PMN ceramics of 100% perovskite phase were obtained for 1, 2, and 4 h sintering at 1250 and 1270 °C. PMN ceramics with density 8.09 g/cm³ (99.5% of theoretical density 8.13 g/cm³) and K_max 19,900 under 1 kHz were obtained.     

New preparation method of low-temperature sinterable Pb(Mg1/3Nb2/3)O3 powder and its dielectric properties

A relaxor ferroelectric material, Pb(Mg_1/3Nb_2/3)O₃(PMN) with perovskite phase was prepared by one-step calcination in the present study. The PMN powder with >99% perovskite phase was prepared successfully by adding an aqueous Mg(NO₃)₂ solution rather than MgO to the alcoholic slurry of PbO and Nb₂O₅, followed by calcination at 950°C for 2 h. The DSC and XRD analysis showed that the pathway in the one-step calcination was different from those of the known columbite or solution processes. The PMN powder sintered to 95.6% of the theoretical density at even 900°C for 2 h. Its room temperature dielectric constant showed 13800 at 1 kHz, the loss of dielectric constant of 0.05% and the specific resistivity of 2.4 × 10¹⁰ ·cm.     

Effect of Bi substitution level on dielectric characteristics of Pb[(Mg1/3Nb2/3),Ti]O3 ceramics

Bi(Mg_2/3Nb_1/3)O₃ was systematically substituted (up to 30 mol%) into Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ and resultant changes in the phase formation, crystallographic aspects as well as dielectric properties of the ceramic samples were investigated. Columbite and rutile solid solutions were mostly detected in the B-site precursor compositions, whereas only a monophasic perovskite structure was identified after the addition of PbO and Bi₂O₃. Frequency-dependent dielectric relaxation behavior was observed in all of the compositions investigated. The maximum dielectric constant values decreased substantially with increasing substituent fractions of Bi. By contrast, the dielectric maximum temperatures changed in somewhat complicated ways in that the increase became comparatively insensitive to the PbTiO₃ concentration with increasing levels of Bi substitution.     

Reaction chemistry and subsolidus phase equilibria in lead-based relaxor systems Part II The ternary system PbO-MgO-Nb2O5

Subsolidus compatibility relations in the lead-based relaxor system PbO-MgO-Nb₂O₅ were investigated by the solid-state reaction technique and the various phase assemblages that occur at 825°C in this system established. The existence of two previously reported ternary compounds, i.e. a cubic perovskite Pb₃MgNb₂O₉ [Pb(Mg_1/3Nb_2/3)O₃] and an oxygen- deficient cubic pyrochlore Pb₆MgNb₆O₂₂ [Pb_1.714(Mg_0.286Nb_1.714)O_6.286] was confirmed. A minor amount of PbO enters into the pyrochlore lattice and forms a narrow homogeneity range within the ternary system PbO-MgO-Nb₂O₅ which corresponds to a general formula Pb_{2 – x} (Mg_0.286Nb_1.714)O_{6.571 – x} , where 0 > x > 0.286. At subsolidus temperatures (<825°C), the perovskite Pb(Mg_1/3Nb_2/3)O₃ is compatible with the ternary pyrochlore solid solution and together they form a biphasic area within the system in which the perovskite and the pyrochlore phases coexist with one another. Both PbO and MgO are compatible with the perovskite Pb(Mg_1/3Nb_2/3)O₃ and these phases constitute a compatibility triangle with one another in the ternary system. However, the perovskite Pb(Mg_1/3Nb_2/3)O₃ is not compatible with Nb₂O₅ and these two phases react with one another to yield the pyrochlore Pb₆MgNb₆O₂₂ and MgO. The ternary pyrochlore solid solution is compatible with several binary lead niobates, i.e. Pb₃Nb₂O₈, Pb₅Nb₄O₁₅, Pb₂Nb₂O₇ and Pb₃Nb₄O₁₃ and forms pseudobinary tie-lines with these compounds in the ternary system PbO-MgO-Nb₂O₅. The pyrochlores Pb₃Nb₄O₁₃ [Pb_1.5Nb₂O_6.5] and Pb₆MgNb₆O₂₂ [Pb_1.714(Mg_0.286 Nb_1.714)O_6.286] are isostructural compounds and a series of continuous solid solution is formed between them.     

Processing, sintering characteristics and dielectric properties of barium-substituted Pb(Mg1/3Nb2/3)O3–PbTiO3 solid solution

Solid solutions in the lead-based relaxor system Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ were modified by minor substitutions of Ba in the Pb-site of the perovskite lattice. The modified compositions were calcined at 830 °C for 3 h to yield fine-grained, single-phase perovskite materials. A small amount of excess MgO(0.05 wt %), which mostly served as a sintering aid, was added to the calcined batches and the resulting mixtures were sintered at temperatures between 1150 and 1250 °C for periods ranging from 3 to 5 h. The substitutions of BaO for PbO in the perovskite solid solution lattice caused a progressive lowering of the Curie point with increasing BaO content. On average, the Curie point decreased by about 10 °C for each mole of BaO substituted for PbO. Among the various Ba-substituted solid solutions studied, the one with a nominal composition Pb_0.99Ba_0.01[(Mg_1/3Nb_2/3)_0.9Ti_0.1]O₃ which has a Curie point located near 28 °C, exhibited excellent dielectric properties. On sintering at 1250 °C for 3 h, this composition yielded a density near 96% of the theoretical density. The peak dielectric constant of the composition at 1 KHz was slightly higher than 22000, and the corresponding tan δ value was 1.5% with a specific resistivity of 2.5 × 10¹² Ω cm^-1. This revised version was published online in November 2006 with corrections to the Cover Date.     

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.     

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.     

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.     

Electric-field-induced strain and piezoelectric properties of a high Curie temperature Pb(In1/2Nb1/2)O3-PbTiO3 single crystal

The temperature dependence of dielectric and piezoelectric properties, electric-field-induced strains of 0.66 Pb(In_1/2Nb_1/2)O₃-0.34 PbTiO₃ single crystals, which were grown directly from melt by using the modified Bridgman technique with the allomeric Pb(Mg_2/3Nb_1/3)O₃-PbTiO₃ seed crystals, were determined as a function of crystallographic orientation with respect to the prototypic (cubic) axes. Ultrahigh piezoelectric response (d₃₃∼2000 pC/N, k₃₃∼94%) and strain levels up to 0.8%, comparable to rhombohedral (1−x)Pb(Mg_2/3Nb_1/3)O₃-xPbTiO₃ and (1−x)Pb(Zn_2/3Nb_1/3)O₃-xPbTiO₃ single crystals, were observed for the 〈0 0 1〉-oriented crystals. Strain levels up to 0.47% and piezoelectric constant d₃₃∼1600 pC/N could be achieved being related to an electric-field-induced rhombohedral-orthorhombic phase transition for the 〈1 1 0〉-oriented crystals. In addition, high electromechanical coefficients k₃₃ (∼88%) can be achieved even heating to 110 °C. High T_C (∼200 °C), large electromechanical coefficients k₃₃ (∼94%) and low dielectric loss factor (∼1%), along with large strain make the crystals promising candidates for a wide range of electromechanical transducers.     

Pyrochlore free 0.67PMN–0.33PT ceramics prepared by particle-coating method

In present study, pyrochlore-free 0.67Pb(Mg_1/3Nb_2/3)O₃–0.33PbTiO₃ (0.67PMN–0.33PT) powders and ceramics have been successfully prepared. Using oxides as raw materials, pyrochlore-free 0.67PMN–0.33PT powders were obtained by two-step particle-coating method. The XRD and EDS results confirmed that the Mg–citric acid polymeric complex coatings effectively prevent the direct contact between PbO and Nb₂O₅ and thus avoid the formation of pyrochlore phase. The obtained pyrochlore-free 0.67PMN–0.33PT powders at 800 °C showed uniform and even grain size. The 0.67PMN–0.33PT ceramics sintered at 1150 °C for 2 h exhibited 99% of relative density and a piezoelectric coefficient (d₃₃) of 576pC/N, a remnant polarization (P_r) of 28.4 μC/cm², a planar electromechanical coupling factor (k_p) of 0.55 and a mechanical quality factor (Q_m) of 90.     

Triple-like hysteresis loop and microdomain-macrodomain transformation in the relaxor-based 0.76Pb(Mg1/3Nb2/3)O3-0.24PbTiO3 single crystal

Polarization and depolarization behavior of the relaxor-based 0.76Pb(Mg_1/3Nb_2/3)O₃-0.24PbTiO₃ single crystal has been studied between 25 and 200 °C by means of dielectric measurement with or without dc bias, Polarization-Electric field (P-E) hysteresis loop and discharging current measurements. Triple-like P-E loops were obtained in a temperature range between 80 and 90 °C, disclosing the transformation between microdomain state and metastable macrodomain state. For the poled crystals, the microdomain state with dipoles partially oriented was indicated to exist in the similar temperature range and mediate between the lower temperature macrodomain state with dipoles oriented and the higher temperature microdomain state with dipoles in a random system.     

Reaction chemistry and subsolidus phase equilibria in lead-based relaxor systems: Part I Formation and stability of the perovskite and pyrochlore compounds in the system PbO-MgO-Nb2O5

The reaction chemistry involved in the synthesis of perovskite Pb(Mg_1/3Nb_2/3)O₃ [Pb₃MgNb₂O₉] was studied by the solid state reaction technique using precursor oxides as reactants. At the initial stage of the reaction process, a large fraction of PbO present in the mixtures combined with Nb₂O₅ and a small amount of MgO to form an oxygen-deficient pyrochlore phase with a composition Pb_1.714(Mg_0.286Nb_1.714)O_6.286 [Pb₆MgNb₆O₂₂]. The pyrochlore phase thus formed further reacted with the remaining PbO and MgO to yield the perovskite Pb(Mg_1/3Nb_2/3)O₃. The pyrochlore Pb_1.714(Mg_0.286Nb_1.714)O_6.286 accomodates a small amount of PbO into its lattice and forms a narrow homogeneity range which extends from the composition Pb_1.714(Mg_0.286Nb_1.714)O_6.286 [Pb₆MgNb₆O₂₂] to a composition Pb₂(Mg_0.286Nb_1.714)O_6.571 [Pb₇MgNb₆O₂₃] with a corresponding increase in the lattice constant value from a = 10.586 to 10.601 Å. The pyrochlore phase melts incongruently at a temperature near 1230°C to yield Mg₄Nb₂O₉ and a liquid. Below this temperature, the perovskite Pb(Mg_1/3Nb_2/3)O₃ coexists with the pyrochlore solid solutions. However, the compound Pb(Mg_1/3Nb_2/3)O₃ is not compatible with Nb₂O₅ and these two phases react with one another to form the pyrochlore Pb_1.714(Mg_0.286Nb_1.714)O_6.286 and MgO.     

Reaction sintering and characterization of lead magnesium niobate relaxor ferroelectric ceramics

The formation and densification of Pb(Mg_1/3Nb_2/3)O₃ ceramics prepared by reaction sintering have been investigated. Two kinds of lead sources. PbO and Pb₃O₄ are used as the starting materials for Pb(Mg_1/3Nb_2/3)O₃. During heating processes, the specimens first expand while the pyrochlore phase is formed. At elevated temperatures, the formation and rapid sintering of Pb(Mg_1/3\Nb_2/3)O₃ occur simultaneously. The starting materials of the Pb₃\O₄ system exhibit better reactivity and sinterability than those of the PbO system. With Pb₃\O₄ as the starting material, monophasic Pb(Mg_1/3\Nb_2/3)O₃ ceramics with high sintering density are successfully achieved by reaction sintering at as low as 900 °C. While for the PbO system, pure perovskite phase could not be synthesized because of the existence of residual pyrochlore phase, and the ceramics obtained have low sintering density. The dielectric permittivity of the Pb(Mg_1/3Nb_2/3)O₃ ceramics obtained in the Pb₃O₄ system is higher than that in the PbO system. This is attributed to the formation of pure perovskite phase and high sintering density in the former system.     

Synthesis and microwave dielectric properties of Sr3Zn1−xMgxNb2O9 phases

Oxides of the type, Sr₃Zn_1−xMg_xNb₂O₉ (0≤x≤1) have been obtained by the ceramic method. These oxides crystallize in the hexagonal cell corresponding to ordered triple perovskites. Sintered disks show nearly frequency-independent dielectric constant for all the compositions. Compositions sintered at 1425°C yield dielectric constant of 20-22 at ∼6 GHz, with quality factor ranging from 1300 to 1500. Sr₃Zn_0.5Mg_0.5Nb₂O₉ shows a very low temperature coefficient of resonant frequency (τ_f) of +4 ppm/°C.     

Inverse hysteresis of field induced elastic deformation in the solid solution 90 mol% Pb(Mg1/3Nb2/3)O3-10 mol% PbTiO3

Elastic deformations induced by high electric fields in the solid solution system Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ have been measured using a strain gauge method at temperatures in the relaxation range. Unusual inverse hysteretic curves have been observed in the relation between the deformation and electric field typically in 90 mol% Pb-(Mg_1/3Nb_2/3)O₃-10 mol% PbTiO₃ at temperatures outside the range where they would be of practical use in electrostrictive displacement control.     

Sintering and piezoelectric properties of Pb(Ni1/3Sb2/3)O3-PbZrO3-PbTiO3 ceramics

The sintering and piezoelectric properties of Pb(Ni_1/3Sb_2/3)O₃-PbZrO₃-PbTiO₃ ceramics have been investigated. When the powders contain 48 mol% PbTiO₃ and less than 10 mol% Pb(Ni_1/3Sb_2/3)O₃ followed by calcination at 850°C for 2 h, the calcine only contains the perovskite structure; but if the Pb(Ni_1/3Sb_2/3)O₃ content is between 12 mol% and 14 mol%, both tetragonal and rhombohedral phases are obtained. The composition of the morphotropic phase boundary(MPB) in the Pb(Ni_1/3Sb_2/3)O₃-PbZrO₃-PbTiO₃ system is Pb(Ni_1/3Sb_2/3)O₃ = 12 mol%, PbZrO₃ = 40 mol% and PbTiO₃ = 48 mol%. As the composition at the MPB is sintered at 1260°C and 1280°C for 2 h, respectively, the maximum density (7.8 g/cm³) is obtained. The SEM micrographs indicate that a decrease in porosity with increasing sintering temperature is attained at 1280°C, which is due to a decrease in the number and size of pores. When the sintering temperature is higher than 1280°C, the porosity increases due to PbO evaporation leading to an increase of the number of pore sites and in enlargement of the pore diameter. When the compact composition at MPB is sintered at 1280°C for 2 h, the planar coupling coefficient (K _p) and mechanical quality coefficient (Q _m) tend to approach the maximum (0.488) and minimum values (292.5), respectively.     

Role of La0.5Sr0.5CoO3 template layers on dielectric and electrical properties of pulsed-laser ablated Pb(Nb2/3Mg1/3)O3-PbTiO3 thin films

Relaxor ferroelectric thin films of 0.7Pb(Mg_1/3Nb_2/3)O₃-0.3PbTiO₃ (PMN-PT) deposited on platinized silicon substrates with and without template layers were studied. Perovskite phase (80% by volume) was obtained through proper selection of the processing conditions on bare Pt/Ti/SiO₂/Si substrates. The films were initially grown at 300 °C using pulsed-laser ablation and subsequently annealed in a rapid thermal annealing furnace in the temperature range of 750-850 °C to induce crystallization. Comparison of microstructure of the films annealed at different temperatures showed change in perovskite phase formation and grain size etc. Results from compositional analysis of the films revealed that the films initially possessed high content of lead percentage, which subsequently decreased after annealing at temperature 750-850 °C. Films with highest perovskite content were found to form at 820-840 °C on Pt substrates where the Pb content was near stoichiometric. Further improvement in the formation of perovskite PMN-PT phase was obtained by using buffer layers of La_0.5Sr_0.5CoO₃ (LSCO) on the Pt substrate. This resulted 100% perovskite phase formation in the films deposited at 650 °C. Dielectric studies on the PMN-PT films with LSCO template layers showed high values of relative dielectric constant (3800) with a loss factor (tan δ) of 0.035 at a frequency of 1 kHz at room temperature.