Reaction Mechanisms in the Formation of Lead Zirconate Titanate Solid Solutions under Hydrothermal Conditions

Reaction mechanisms in the formation of PZT solid solution were studied under hydrothermal conditions (Pb/(Zr+Ti) = 1.0 to 1.9, Zr/Ti = 0/10 to 10/0, 1 M to 5 M KOH, 100° to 220°C, 2 h). A yellow tabular crystallite with tetragonal symmetry and Pb/Ti ∼ 2 was formed at 100° to 130°C. A PZT crystallite was formed just above 150°C. The crystallite was a mixture of Ti-rich PZT and Zr-rich PZT phases. When the temperature and KOH concentration were increased, the composition of the PZT product tended to be homogeneous. The PZT in the morphotropic phase boundary zone was formed at Zr/Ti = 5/5, 5M KOH, 220°C, 2 h. Neither PbTiO₃ nor PbZrO₃ was detected as a separate phase under the above hydrothermal conditions.     

Phase Homogeneity and Segregation in PZT Powders Prepared by Thermal Decomposition of Metal–EDTA Complexes Derived from Nitrate and Chloride Solutions

Fine, homogeneous lead zirconate titanate (PZT) powders have been prepared by the thermal decompostion of metalorganic complexes derived from nitrate solutions using ethylenediaminetetraacetic acid (EDTA) as a complexing agent. It has been shown that nitrate ions accelerate the decomposition of the precursor and the crystallization of the PZT phase initiates at temperatures as low as 250°C. No intermediate phases, other than PbO, were found. The coexistence region of the rhombohedral and tetragonal phases in the sintered ceramic was found to be a little over 1 at.%. The chloride-EDTA precursor did not form the desired PZT phase, even after calcination at 1000°C. The segregation and loss of lead was observed for this material, due to the formation and evaporation of PbCl₂. DTA/TGA, SEM, and XRD were employed to characterize the powders. The use of TEM with nanoprobe energy dispersive X-ray analysis (EDX), allowed the identification of the phase segregation in the chloride-EDTA derived powder. A possible reaction mechanism for this phase segregation is suggested.     

Preparation of Pb(Zr,Ti)03 Through the Use of Cupferron

An organic chelation reagent, cupferron, was used to coprecipitate Ti⁴⁺ andZr⁴⁺. After the materials were fired, they were mixed with PbO powder and fired again at high temperatures to obtain Pb(Zr,Ti)0₃ (PZT). It was confirmed that this method is useful for the preparation of homogeneous PZT having no compositional fluctuations. No coexistence range of the tetragonal and rhombohedral phases was observed in the PZT compositions near the morphotropic phase boundary.     

Compositional Change and Compositional Fluctuation in Pb(Zr,Ti)O3 Containing Excess PbO

Compositional changes which take place during sintering of Pb(Zr,Ti)O₃ (PZT) containing excess PbO were studied. The excess PbO forms a liquid phase during the sintering process. The solubility of the TiO₂ component of PZT in liquid PbO is higher than that of ZrO₂ component. Thus, if an excess PbO exists, the composition of PZT phase shifts towards the Ti-lean side. A change in the lattice constants due to this compositional change was actually observed. Coexistence of tetragonal and rhombohedral phases, due to a compositional fluctuation caused by excess PbO, was observed near the morphotropic phase boundary. When PZT containing excess PbO was sintered at 1100°C, a compositional fluctuation occurred early in the process and then decreased with sintering time. These phenomena have agreed with a result of computer simulation of dissolution of TiO₂ component in PZT phase into liquid PbO phase.     

Mechanism of Phase Formation in Pb(ZrxTi1–x)O3 Synthesized by a Partial Oxalate Method

The phase formation mechanism, as well as the morpho-tropic phase boundary, of lead zirconate titanate (PZT) processed by a partial oxalate method was investigated by simultaneous thermal analysis (TG-DTA) and by qualitative and quantitative X-ray diffraction (XRD). The results show that the Zr_xTi_1–xO₂ (ZT) phase reacts with PbO forming the PZT phase without intermediate phases. XRD analysis showed the coexistence of rhombohedral and tetragonal phases for 0.47 ≤ x ≤ 0.55 with the phase boundary composition for x = 0.51. For low calcination temperatures, preferential formation of the PZT rhombohedral phase was observed. A model for phase formation of PZT by the partial oxalate method is proposed based on the existence of two interfaces of reaction (PbO-PZT and PZT-ZT) and diffusion of cations.     

Thermal Behaviors and Phase Evolution of Lead Zirconate Titanate Prepared by Sol–Gel Processing: The Role of the Pyrolysis Time before Calcination

Lead zirconate titanate (PZT) (53/47) powders were fabricated by the alkoxide-based sol–gel process, and the different drying times (1 and 12 h) at the pyrolysis temperature (300°C) of lead acetate were studied. The different pyrolysis time before calcination affects the onset and the violently dominant decomposition temperatures of lead acetate. According to the estimated activation energy results, the 1 h pyrolysis time showed that the transformation of the pyrochlore to perovskite phase is nucleation-controlled (424.5 kJ/mol), but the 12 h pyrolysis time is growth-controlled (125 kJ/mol). It was also found that the relative PZT perovskite contents were controlled by the carbonaceous material contents within the dried gels and the release rate of hydrocarbon during the pyrolysis process. With the proper pyrolysis-treated PZT powders, the dense, phase-coexisted PZT bulks could be produced at a low sintering temperature of 950° and 1000°C. The phase transformation of the PZT ceramics changed from the rhombohedral phase (900°C) to rhombohedral and tetragonal phase coexistence (950° and 1000°C), then finally to the monolithic tetragonal phase (1050° and 1100°C). A phase diagram is plotted based on the different sintering conditions. The dielectric properties were dependent on the relative densities of the PZT bulks, and the PZT bulks sintered at 1000°C for 6 h had superior dielectric constant (1080) and lowest dielectric loss (0.7%).     

Homogeneity and Properties of Lead Zirconate Titanate Prepared by a Combination of Thermal Spray Decomposition Method with Solid-Phase Reaction

A solution containing titanium and zirconium ions was spray decomposed. The product thus obtained was mixed with PbO powder and fired at high temperatures to obtain Pb(Zr,Ti)O₃ (PZT). A phase of PZT began to form at a very low temperature (450°C). This formation reaction was complete at about 650°C. Reactivity of the spray-decomposed product with lead titanate powder was high. For PZT prepared by this process with a firing condition of 1100°C for 1 h, the compositional fluctuation was estimated from the width of the X-ray diffraction peaks. Fluctuations were about 3 at.%. This value agreed with that estimated from the range of the tetragonal-rhombohedral coexistence region near the morphotropic phase boundary. The peak of the dielectric constant near the Curie temperature was sharp and very high (ε∼12000).     

Phase formation,electrical properties and morphotropic phase boundary of 0.95Pb(ZrxTi1−x)O3–0.05Pb(Mn1/3Nb2/3)O3 ceramics

Ferroelectric ceramics in specific composition of 0.95Pb(Zr_xTi_1?x)O₃–0.05Pb(Mn_1/3Nb_2/3)O₃ or PZT–PMnN (with x=0.46, 0.48, 0.50, 0.52, and 0.54) have been investigated in order to identify the morphotropic phase boundary (MPB) composition. The effects of Zr/Ti ratio on phase formation, dielectric and ferroelectric properties of the specimens have also been investigated and discussed. X-ray diffraction patterns indicate that the MPB of the tetragonal and rhombohedral phase lies in x=0.52. The crystal structure of PZT–PMnN appeared to change gradually from tetragonal to rhombohedral phase with increasing Zr content. The dielectric and ferroelectric properties measurements also show a maximum value (ε_r, tan δ and P_r) at Zr/Ti=52/48, while the transition temperature decreases with increasing Zr content.     

Characterisation of ceria–zirconia solid solutions after hydrothermal ageing

Ce_1−xZr_xO₂ (x=0–0.84) solid solutions prepared by co-precipitation were characterised after calcination at 700 or 900°C, and after hydrothermal ageing at 1000 or 1200°C. The solid solutions were formed at 700°C, and crystallise as cubic or tetragonal phases depending on their compositions. Despite the rather high surface areas obtained after calcination at 700°C, the sintering is important at 900°C, and tremendous after hydrothermal ageing at 1000°C. For all compositions between 16 and 83 mol% ceria, complete de-mixing of the solid solutions into two phases was observed after ageing at 1200°C: one Zr-rich, tetragonal phase, and one Ce-rich, cubic phase. XPS and ISS measurements show that the phase separation takes place with surface enrichment in Zr, the Zr-rich phase being formed at the periphery of the particles, whereas the core is composed of the Ce-rich phase.     

Synthesis of the Orthorhombic Phase of 2Y˙ZrO2

A mixture of tetragonal and monoclinic 2Y˙ZrO₂ (2 mol% Y₂O₃–ZrO₂) powder was treated from 400° to 800°C and from 4 to 7 GPa for 30 min. The products were identified by powder XRD, Raman spectroscopy, and TEM. Results indicated that an orthorhombic phase was synthesized at T=400° to 600°C and P>4 GPa. The lattice parameters were obtained as a=0.505, b=0.525, and c=0.509 nm; the density was 6.17 Mg/m³. The orthorhombic phase always coexisted with the tetragonal phase in the products. The amounts of the tetragonal phase before and after treatment remained largely unchanged, whereas the amount of new orthorhombic phase was nearly the same as the decreased amount of the monoclinic phase. It was assumed, therefore, that only the monoclinic phase transformed into the orthorhombic phase.     

Study of PbZr0.53Ti0.47O3 solid solution formation by interaction of perovskite phases

The formation of Pb(Zr_0.53Ti_0.47)O₃ solid solution around the MPH was studied by mutual interaction of perovskite PZT phases (rhombohedral and tetragonal) and by interaction of PZT phases with PbTiO₃ or PbZrO₃ at sintering temperature. Starting perovskite phases were prepared by the mechanical homogenization of oxidic precursors and calcination of mixtures at 1000 °C. The final Pb(Zr_0.53Ti_0.47)O₃ ceramic systems prepared from perovskite mixtures were monophasic (tetragonal symmetry) in comparison with the biphasic ceramics prepared from calcinate with the same stoichiometry. The magnitude of deviation from equilibrium chemical composition or fluctuation from final stoichiometry in PZT phase in starting powder perovskite mixtures was not crucial for the formation of monophase Pb(Zr_0.53Ti_0.47)O₃ ceramic system prepared using such a method.     

Temperature dependence of field‐responsive mechanisms in lead zirconate titanate

An electric field loading stage was designed for use in a laboratory diffractometer that enables in situ investigations of the temperature dependence in the field response mechanisms of ferroelectric materials. The stage was demonstrated by measuring PbZr_1?xTi_xO₃ (PZT) based materials—a commercially available PZT and a 1% Nb‐doped PbZr_0.56Ti_0.44O₃ (PZT 56/44)—over a temperature range of 25°C to 250°C. The degree of non‐180° domain alignment (η₀₀₂) of the PZT as a function of temperature was quantified. η₀₀₂ of the commercially available PZT increases exponentially with temperature, and was analyzed as a thermally activated process as described by the Arrhenius law. The activation energy for thermally activated domain wall depinning process in PZT was found to be 0.47 eV. Additionally, a field‐induced rhombohedral to tetragonal phase transition was observed 5°C below the rhombohedral‐tetragonal transition in PZT 56/44 ceramic. The field‐induced tetragonal phase fraction was increased 41.8% after electrical cycling. A large amount of domain switching (η₀₀₂=0.45 at 1.75 kV/mm) was observed in the induced tetragonal phase.     

Thermodynamic Analysis of the FR(LT)-FR(HT) Phase Transition in the Pb(Zr,Ti)O3 System under a Hydrostatic Pressure

Effects of hydrostatic pressure on the ferroelectric phase transition between the two rhombohedral phases in the Zr-rich Pb(Zr,Ti)O₃ (PZT) system have been investigated using the Landau-Devonshire phenomenological theory. For this purpose, the rotostrictive coefficients related to the coupling between the oxygen octahedron and the stress were evaluated first. It was shown that the transition temperature between the two rhombohedral phases F_R(LT) and F_R(HT) decreased with increasing tensile hydrostatic pressure. Contrary to this, an opposite trend was predicted under the condition of compressive hydrostatic pressure.     

Formation of Lead Zirconate Titanate Powders by Spray Pyrolysis

Twin-fluid atomization spray pyrolysis (SP) has been investigated for the production of lead zirconate titanate (PZT) powders, using aqueous solutions of lead acetate and zirconium and titanium alkoxide precursor reagents. The particle size distribution of the PZT powder showed a d ₅₀ value of 0.3 μm, but with a small fraction of relatively large particles, several micrometers in size. Most particles were spherical but many of the largest particles, in the size range ca. 1–5 μm, were irregular. It was demonstrated that the morphology of the final PZT powder was controlled by decomposition processes occurring during the initial drying stages, at ≤200°C. A pyrochlore or fluorite-type intermediate crystalline phase was present in the final powders, but when the maximum reactor temperature was raised, and/or when the levels of excess lead in the starting solutions were increased, the proportion of the desired perovskite phase increased. However, at the highest process temperatures studied, ∼900°C, small crystallites of another phase formed on the surface of the PZT particles; these were probably lead oxide carbonate particles. Overall, a starting solution composition containing around 5 mol% excess Pb, and a maximum reactor temperature of 800°C, were selected as offering the most suitable conditions for producing PZT (52/48) powder, with minimal secondary phases(s). Preliminary densification studies showed that the powders could be sintered at 1150°–1200°C to give pellets of 95%–96% theoretical density.     

Piezoelectric Resonances, Linear Coefficients and Losses of Morphotropic Phase Boundary Pb(Mg1/3Nb2/3)O3–PbTiO3 Ceramics

A method based on the use of four piezoelectric resonances for three sample geometries that allows obtaining the full set of linear electric, mechanical, and electromechanical coefficients, and all related losses of a piezoelectric ceramic has been applied to Mn-doped 0.655Pb(Mg_1/3Nb_2/3)O₃–0.345PbTiO₃ at the morphotropic phase boundary (MPB PMN–PT). Length-poled MPB PMN–PT ceramic plates presented piezoelectric shear double resonances associated with a thickness gradient of tetragonal and rhombohedral (or monoclinic) phases that originated during poling. The versatility of the method still allowed addressing these double resonances and obtaining all the linear coefficients and losses of the well-poled material. These are given for MPB PMN–PT and compared with those of a Navy type II Pb(Zr,Ti)O₃ (PZT) ceramic. MPB PMN–PT presents piezoelectric coefficients as high as soft PZT but significantly lower losses, and so less overheating and hysteresis under high driving fields. Its thermal stability has been studied up to 100°C, and the temperature dependence of a number of linear coefficients and of the thickness and planar coupling factors and frequency constants of disks has been obtained. The latter thickness parameters hardly changed with temperature, while planar ones showed a relative variation of 10%.     

Low-Temperature Synthesis of Fully Crystallized Spherical BaTiO3 Particles by the Gel–Sol Method

The synthesis of spherical BaTiO₃ particles was attempted by a new technique, the "gel–sol method," at 45°C. The (Ba–Ti) gel used as a starting material was prepared by aging mixtures of titanyl acylate with a barium acetate aqueous solution ([glacial acetic acid (AcOH)]/[titanium isopropoxide (TIP)] = 4, [barium acetate]/[TIP] = 1) at 45°C for 48 h. Potassium hydroxide (KOH) was used as a catalyst for the formation of BaTiO₃. Powder X-ray diffractometry (XRD) results and Fourier-transform infrared (FT-IR) measurements for the (Ba–Ti) gel showed that the gel was amorphous, but the spatial arrangement of barium and titanium in the (Ba–Ti) gel is similar to that in crystalline BaTiO₃ particles. Fully crystallized spherical BaTiO₃ powder with a particle size of 40–250 nm formed at the very low reaction temperature of 45°C. Scanning electron microscopy images showed that the final particles formed via aggregation of the fine particles that seem to be the primary particles of bulk (Ba–Ti) gel. From the XRD, FT-IR, and Raman spectroscopy analysis, it was found that the crystal structure of the as-prepared particles continuously transformed from cubic to tetragonal as the calcination temperature increased, and high crystalline tetragonal BaTiO₃ phase was obtained at 1000°C after 1 h of heat treatment.     

Lead Zirconate Titanate Thin Films by Aerosol Plasma Deposition: Microstructure Analysis

Lead zirconate titanate (Pb(Zr,Ti)O₃, PZT) thin films were grown on silicon 〈100〉 substrate by aerosol plasma deposition (APD) using solid-state-reacted powder containing donor oxide Nb₂O₅ when keeping the substrate at room temperature and 200°C. Crystalline phases of the deposited films have been analyzed via X-ray diffractometry (XRD), and microstructure via scanning and transmission electron microscopy (SEM and TEM). Cross-sectional TEM revealed that the microstructure comprised several layers including the deposited PZT film and the platinum-electrode-and-titanium-buffered layers on SiO₂–Si substrate. The Pt-electrode layer contained (111)_Pt twinned columnar grains with a slight misorientation and forming low-angle grain boundaries among them. The PZT layer contained randomly oriented grains embedded in an amorphous matrix. Some of the PZT grains, oriented with the zone axis Z = [[Twomacr]11]_PZT parallel to Z = [111]_Pt, were grown epitaxially on the Pt layer by sharing the (111)_PZT plane with the (111)_Pt twinned columnar Pt crystals. However, the existence of such an orientation relationship was confined to several nanosize grains at and near the PZT-Pt interface, and no gross film texture has been developed. An amorphous grain boundary phase, generated by pressure-induced amorphisation (PIA) in the solid state, was identified by high-resolution imaging. Its presence is taken to account for the densification of the PZT thin films via a sintering mechanism involving an amorphous phase on deposition at 25° and 200°C.     

Characterization of Bi0.5Na0.5TiO3-PbTiO3M Dielectric Materials

Bi_0.5Na_0.5TiO₃ (BNT) modified with Pb showed an increased and broadened dielectric constant and limited grain growth. Pb also lowered the first transition temperature. The phases of BNT were confirmed to be ferroelectric at room temperature which transformed to antiferroelectric above 220°C. When BNT was doped with 10% Pb, the first transition decreased to 140°C and abruptly disappeared in the composition with 17% Pb. The crystal structure of 17%-Pb-doped BNT at room temperature is tetragonal, which differs from the rhombohedral structure at lower Pb contents. Thus, the phase boundary between rhombohedral and tetragonal ferroelectric phase was determined to be between 15% to 17% Pb in this study.     

PLZT Phases Near Lead Zirconate: 1. Determination by X-Ray Diffraction

The room temperature phase diagram of PLZT, (Pb,La)(Zr,Ti)O₃, or L / Z / T for L <12 and T <10 was constructed using X-ray diffraction patterns of sintered and crushed PLZT material. The orthorhombic antiferroelectric phase, a tetragonal phase, the rhombohedral (hexagonal) ferroelectric phases, and the mixed La-rich zone were identified. Increasing substitution of La for Pb in the structure of orthorhombic PLZT leads to a change toward the cubic structure with less anisotropy in a direction corresponding to the cubic 200 direction. At La above ∼8 to 11 mol%, La₂Zr₂O₇ appears in the mixed zone. With increasing substitution of Ti for Zr, there is no change toward a cubic structure as the anisotropy is nearly unchanged. However, at a Ti substitution above ∼6 mol%, a rhombohedral and a tetragonal structure appear.     

Li2CO3掺杂对0.2PMN-0.8PZT陶瓷的影响

利用铌铁矿预产物合成法,研究不同温度烧结下Li2CO3掺杂对0.2 PMN-0.8PZT压电陶瓷(简称PLC)的相结构和电性能的影响。X射线衍射(XRD)和扫描电镜(SEM)的分析结果表明,掺杂LiCO3的0.2PMN-0.8PZT压电陶瓷经不同温度煅烧后,所有陶瓷样品的相组成均为纯钙钛矿相,并随着烧结温度的升高,PLC的相结构有由四方相向菱方相转变的趋势。通过0.2PMN-0.8PZT压电陶瓷掺杂LiCO3煅烧后的微观形貌、介电常数、压电性能、铁电性能的分析,发现经1200℃烧结的样品的介电和压电性能最佳:介电常数(εr)为38512,室温压电常数(d33)为300 pC/N,剩余极化强度(Pr)为31.3 C/cm2,矫顽电场(Ec)为7.5 kV/cm。