New synthesis route for lead zirconate titanate powder

Phase pure lead zirconate titanate (PZT) powder was produced via a new aqueous coprecipitation method. A suite of characterization techniques, including FTIR, Raman, X-ray diffraction, SEM as well as nitrogen sorption were employed to investigate the structural evolution of the synthesized and calcined powder. The dried precipitate formed in aqueous phase yielded approximately 80 wt% final product after calcination. The PZT perovskite structure was obtained after calcination at 550 °C for 3 h. Milling of the calcined powder reduced the mean particle size from approximately 10 µm to 2 µm. With increasing calcination temperature from 550 °C to 700 °C, both surface area and pore volume decreased while pore size increased from 3.4 nm to 9.8 nm. The bulk density of pelletized samples increased from 4.83 to 7.57 g/cm³ with increasing sintering temperature from 800 °C to 1200 °C. Powder processing using this aqueous route is simple and reproducible leading to a method that is readily scalable for industrial applications.     

Effects of dispersant concentration and pH on properties of lead zirconate titanate aqueous suspension

Lead zirconate titanate (PZT) aqueous suspensions were prepared at 60 wt.% solids loading using a commercial ammonium polyacrylate (APA) dispersant. Effects of the dispersant concentration on rheological behavior, dispersion and stability of PZT aqueous suspensions were investigated by means of zeta potential, viscosity and sedimentation height measurements. The results showed that, under suitable conditions, APA dispersant promoted particle dispersion and stabilization in PZT aqueous suspensions. For 60 wt.% solids loading suspensions, the dispersant concentration yielding the lowest viscosity was 0.5 wt.% based on PZT powder dried weight basis. Effects of pH on particle dispersion in the suspensions prepared with APA were studied by laser light scattering technique and scanning electron microscopy. The results showed an improvement in particle dispersion for the alkaline condition, which led to relatively low viscosity and highly stable suspension. Possible particle stabilization mechanisms at various pHs were discussed based on dissociation of the dispersant in water, polymer conformation and adsorption behavior of the dispersant on the particle surface.     

Model for the cold sintering of lead zirconate titanate ceramic composites

A model was developed to describe the cold sintering process (CSP) of lead zirconate titanate (PZT) using moistened lead nitrate as a sintering aid. The densities of PZT powder with different volume fractions of lead nitrate were evaluated after cold sintering at 300°C and 500 MPa for 3 hours. The densities were categorized into three zones. In zone I, the relative density following cold sintering increases from 66% to 80%, as the lead nitrate contents rise from 0 to 14 vol%. In this case, the lead nitrate acts to fill some of the pore volume between PZT grains. Zone II serves as a transition region, where there is both pore filling and dilution of the PZT grains associated with lead nitrate contents from 14 to 34 vol%. In zone III, the relative density drops due to dilution at lead nitrate contents exceeding 34 vol%. To slow the process down so that the kinetics could be studied more readily, samples were cold sintered at room-temperature and 500 MPa. It was found that during the first few seconds of compaction, 85PZT/15Pb(NO₃)₂ rapidly densified from 51% to 61% relative density due to particle re-arrangement. For longer times at pressure, the CSP improved the packing relative to PZT compacted without the lead nitrate, yielding a higher relative density. The late stages of the PZT/Pb(NO₃)₂ CSP could be well described using a viscous sintering model for pressures from 50 MPa to 1000 MPa and temperatures from 25°C to 300°C.     

Domain switching characteristics of lead zirconate titanate piezoelectric ceramics on a nanoscopic scale

Domain switching characteristics of lead zirconate titanate ceramics with and without poling under compressive loading are investigated using electron backscatter diffraction. For loading in the poling direction, the switching strain is stronger than that for loading perpendicular to the poling direction. There is strong domain switching when the domain (c-axis of the tetragonal structure) is orientated close to the loading direction. A large number of domains are switched between 85.4° and 90.0°, with many crossing the loading axis. Each grain consists of domains with three different patterns; i.e., with c-axis orientated in three directions in each grain. The patterns remain unchanged even with domain switching and strong deformation. However, the ratios among the patterns depend on compressive stress. Under stress, one or two specific domain modes are switched to about 90°, although others are not switched as much. These domain switching characteristics are related to the poling and loading directions. 90° domain switching model is proposed on the basis of twin deformation model. Due to the aspect ratio of c/a = 1.014 (tetragonal structure), the angle of the switching is less than 90° (89.2°). This angle is corresponding to the switching angle obtained by an electron backscatter diffraction analysis (Ave. 88.9°).     

Development of crystallographic texture in chemical solution deposited lead zirconate titanate seed layers

Direct seeding of {001} textured lead zirconate titanate (PZT) on platinized silicon substrates was achieved by chemical solution deposition. The processing space for {001} PZT texturing was explored, under fixed PZT pyrolysis and crystallization conditions, by varying the lead content in solution, dopant species, and PZT layer thicknesses for deposition on platinized Si substrates with different platinum grain sizes. Strong {001} texture was achieved on fine‐grained (25 nm) platinum deposited at room temperature and dense, large‐grained platinum (80 nm) deposited at elevated temperature. Increases in lead content of solutions (from lead excesses of 10 at.% to 16 at.%) reduced surface pyrochlore coverage, with no substantial influence on orientation or grain size. Seed layer texturing was found to be insensitive to doping (Mn and Nb) on room temperature platinum, although niobium doping increased pyrochlore coverage. Conversely, on platinum deposited at high temperature, manganese doping reduced the perovskite nucleation, producing a rosette microstructure. Undoped seed layers from 30 to 70 nm thick were found to be strongly {001} textured while thicker layers were {111} textured and thinner layers were poorly crystallized.     

Effect of lead content on the performance of niobium‐doped {100} textured lead zirconate titanate films

Niobium‐doped, {100} textured, gradient‐free, lead zirconate titanate (PZT) films were fabricated from solutions with different lead contents. Film lead content was controlled through changes in the average solution lead excess from 14.7% to 17 at.%. The low field dielectric response as well as the polarization‐electric field hysteresis loops were not a strong function of lead content. However, films with lower lead contents in the precursor tended to withstand higher poling fields than films prepared from more lead‐rich precursors. Although no residual PbO was observed at the grain boundaries, films prepared from more lead‐rich solutions had higher levels of grain‐boundary porosity, lower breakdown strengths, and lower threshold electric fields at which cracking was observed.     

Rheological properties of nanosized barium titanate prepared by HGRP for aqueous tape casting

The conditions for the preparation of stable nanosized barium titanate suspensions with high solids content for the production of aqueous tape casting are identified. The rheological behavior of colloidal barium titanate suspension with Ammonium polyacrylate (NH₄-PAA) as a dispersant to aid the powder dispersion has been investigated. Nanosized barium titanate powder was synthesized by a continuous high-gravity reactive preparation (HGRP) technique, and then annealed at 900 °C for 2 h. Measuring the zeta potential, the particle size distributions and ball-milling time, assessed the optimum conditions of the suspension with low viscosity and stability. An isoelectric point (IEP) at pH = 2.8 was found. Particle size distribution tests identified an optimum pH value about 10 and an optimum dispersant addition about 1.2 wt.% (based on the dry powder weight). As the ball-milling time was longer than 8 h, the amount NH₄-PAA adsorbed on the barium titanate reached to saturation. The maximum solid content attained during this work was 45 vol.% at pH of 10, with dispersant addition 1.2 wt.%. High green density value (up to ∼55.4% of the theoretical density) in BaTiO₃ sheet was achieved with a solid content 40 vol.%. After sintering at 1200 °C for 2 h a final density of 95% is reached.     

锆钛酸锶的烧结及其介电性能表征

以四氯化钛、氧氯化锆、硝酸锶和氢氧化钠为原料,采用共沉淀法在25℃反应90℃陈化2h制备了锆钛酸锶(SrTixZr1-xO3)粉体,用X射线衍射(XRD)表征了锆钛酸锶粉体的物相.用透射电子显微镜表征了锆钛酸锶粉体的粒径.并采用干压成型法压制素坯进行烧结;确定了烧结制度为:升温速率3℃/min,1 400℃保温4h.对烧结后的陶瓷坯体进行介电性能表征,在1 kHz下SrTio.7 Zr0 3 O3陶瓷坯体的相对介电常数为135.6,介电损耗tanδ为24.4×10-3;SrTi0 5 Zro.5 O3陶瓷坯体的相对介电常数为122.3,介电损耗tanδ为137.38×10-3.     

Comparison of different sintering aids in cold sinter-assisted densification of lead zirconate titanate

Ceramics such as lead zirconate titanate (PZT) tend to dissolve incongruently, and thus pose a challenge in the cold sintering process. Moist lead nitrate has previously been shown to enable a cold sinter-assisted densification of PZT by a viscous phase sintering mechanism. In this paper, lead acetate trihydrate is demonstrated to lower the required temperature of the cold sintering step to 200°C. This densification process was described as a two-step process: cold sintering of PZT with lead acetate trihydrate and post-annealing the as-cold sintered PZT ceramics. Unlike in the case of lead nitrate, PZT densification with lead acetate trihydrate occurs by a liquid phase assisted sintering mechanism, leading to an as-cold sintered relative density of 84% at 200°C. After performing a post-anneal step at 900°C, >97% relative densities were achieved in samples that were cold sintered with lead acetate trihydrate. This step not only densified PZT but also refined the grain boundaries. In the post-annealed samples, the room-temperature relative permittivity at 100 Hz was ~1600, slightly higher than that reported in samples that used lead nitrate as a sintering aid; the loss tangent was about 3.8%. For measurements at 10 Hz, the remanent polarization in both cases was ~28 µC/cm². Both Rayleigh analysis and aging studies showed that a higher irreversible contribution to the permittivity exists in samples that used lead nitrate as a cold sintering aid.     

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.     

Influence of PbO content on the dielectric failure of Nb-doped {100}-oriented lead zirconate titanate films

A series of niobium-doped, {100} textured, “gradient free,” lead zirconate titanate (PNZT) films with different PbO contents were fabricated by the chemical solution deposition method. The films’ PbO content was controlled by changing the average PbO content in the solution from 114.7 to 117 at.%. During the dielectric breakdown process of 1.5 μm thick PNZT films with Pt top and bottom electrodes, two phenomena were observed: cracking and thermal breakdown of the piezoelectric film. At 150°C, with an applied 400 kV/cm electric field, the crack density of PNZT films induced by electromechanical failure increased from 0.060/μm to 0.090/μm as the solution's PbO content increased from 114.7% to 117%. In addition, the films showed higher crack densities and more frequent thermal breakdown events when the electric field was oriented downward (from top to bottom electrode) compared with an upward oriented electric field (from bottom to top electrode). The films with higher PbO content had a lower breakdown strength. Also, all films showed lower breakdown strength when measured in the field down direction. The Schottky barrier height (SBH) decreased from 0.82 ± 0.06 to 0.68 ± 0.04 eV in the field up direction measurement as the PbO content increased. The SBH value did not show significant change in the field down direction measurement. This suggests that the asymmetry in the film/electrode interfaces is a function of the PbO content in the original solution.     

Discharge characteristics of pre-polarized doped lead zirconate titanate under impact at room and high temperature

Piezoelectric materials have more and more applications in modern smart fuzes due to their multiple uses such as energy storage and sensing. The electrical output characteristics of piezoelectric ceramics under high temperature and high overload environments are critical to the reliability of the device. In this paper, the mechanical and electrical response of pre-polarized doped lead zirconate titanate (PZT-5H) under impact at room temperature to 250°C, that is, above the Curie temperature, was investigated through a split-Hopkinson pressure bar experiment with an additional electrical output measurement system. The depolarization effect caused by temperature and the mechanical load was analyzed. A thermoviscoelastic constitutive model considering temperature and the strain rate was built based on the experimental data. The model can successfully predict the mechanical and electrical response of PZT-5H under impact at different temperatures. The discharge characteristics of PZT-5H under impact in the cooling stage after high-temperature depolarization were also investigated, and the apparent flexoelectric coefficient of the PZT after complete depolarization was calculated. The research results show that the dynamic piezoelectric coefficient of PZT-5H has a nonlinear relationship with temperature. During the high-temperature cooling process, PZT has a shock-induced polarization under the impact, and the output voltage is less than the polarized piezoelectric ceramic but higher than the flexural polarization at the same temperature. After complete depolarization, the apparent flexoelectric coefficient of PZT-5H is 127 μC/m.     

Dielectric and ferroelectric properties of lanthanum‐modified lead zirconate stannate titanate (42/40/18) ceramics

The effect of lanthanum (La) content on the phase transformation of Pb_1?3x/2La_x(Zr_0.42Sn_0.40Ti_0.18)O₃ (PLZST 100x/42/40/18, 0 ≤ x ≤ 0.06) ceramics was investigated by the dielectric and ferroelectric properties. The base composition PLZST 0/42/40/18 located in the ferroelectric (FE) rhombohedral phase region. As x increased, the compositions showed successively FE and antiferroelectric (AFE) state at room temperature, and their peak temperatures (T_max) decreased gradually in line as T_max = 162.21‐1507x. Evidence was presented that there were two dielectric anomalies in PLZST 2/42/40/18, which were corresponding to the FE‐AFE and AFE‐paraelectric (PE) phase transformations, respectively. With increasing the dc bias fields, the two phases merged into one. PLZST 3/42/40/18 showed AFE characteristics with the first loop outside of the second loop and there was only one dielectric inflection. The critical lanthanum content occurred at x = 0.03 from the dielectric temperature spectra and hysteresis loops. Furthermore increase in La above 0.03, these compositions showed typical antiferroelectric behaviors with double hysteresis loops. The stored energy properties of the three compositions (PLZST 4/42/40/18, 5/42/40/18 and 6/42/40/18) displayed different temperature dependencies from room temperature to 140°C (over their respective T_max). Comparing the above results with previous investigations on PLZSTs, some questions were discussed.     

Influence of co-dopants average valence on microstructural and electromechanical properties of lead titanate ceramics

Effects of Ni, Nb and Mn co-doping on microstructural, dielectric and electromechanical properties of lead titanate (PT) dense ceramics, obtained as a result of decreasing lattice anisotropy with increasing amount of co-dopants, were investigated.Different values of the average valence (AV) of Ni–Nb co-dopants were obtained by mutual valence compensation between these acceptor–donor ions of various relative concentrations.Significantly higher amounts of Mn²⁺ (resulted by reduction of Mn⁴⁺ in presence of donor co-dopants) were found in materials with Ni–Nb AV > 4+. These materials show higher coupling factors, correlated with higher mechanical quality factors, compared to the rest of materials. Hard-like piezoelectric behavior was manifested in materials with Ni–Nb AV < 4+, whereas ceramics with Ni–Nb AV > 4+, and without manganese, turned out to have a soft-like behavior.Electromechanical properties of PT ceramics are discussed in terms of average valence of Ni–Nb co-dopants and multivalence state of manganese.     

Revisiting the structural stability and electromechanical properties in lead zinc niobate-lead titanate-barium titanate (PZN-PT-BT) ternary system

Lead zinc niobate-lead titanate (PZN-PT) system is of particular interest for scientific researches and commercial applications due to the unique relaxation feature and superior electromechanical responses. However, it is difficult to prepare polycrystalline ceramics near the morphotropic phase boundary due to the stability of a competing lead niobate pyrochlore phase. BaTiO₃ (BT) was reported to be an effective perovskite phase stabilizer at a cost of reduction in Curie temperature and piezoelectric properties. Herein, the amount of BT in PZN-PT-BT system and the sintering conditions were optimized to simultaneously stabilize the perovskite phase and maintain high dielectric and piezoelectric response. An optimum piezoelectric coefficient d₃₃ ∼ 870 pC/N along with a T_m ∼ 133 °C and an electromechanical coupling coefficient k₃₃ ∼ 0.61 was obtained in the PZN-8PT-6BT ceramics sintered at 1100 °C. The low sintering temperature, wide processing window, and improved dielectric and piezoelectric properties make PZN-PT-BT ceramics potential candidates for piezoelectric devices.     

Effect of particle size on the optical properties of lead zirconate titanate nanopowders

Nanopowder samples of lead zirconate titanate (Pb_1.1Zr_0.52Ti_0.48O₃ or PZT) were prepared by the sol‐gel method with controlled pH values. The samples were characterized using FTIR spectroscopy, XRD, FE‐SEM, and TEM techniques. Most of the peaks in the XRD pattern were related to the coexistence of tetragonal‐rhombohedral phases and confirmed the formation of PZT with a perovskite structure. Also, the crystallite size of PZT nanopowders was in a range of 17‐28 nm. FTIR spectroscopy revealed a longitudinal optical (LO) and transverse optical (TO) phonon modes corresponding to the stretching vibration of Ti‐O and Zr‐O bonds. The influence of pH values on the LO and TO phonon modes, LO‐TO splitting, refractive index n(ω), extinction coefficient k(ω), and the real ?₁(ω) and imaginary ?₂(ω) parts of dielectric function was discussed. These properties were investigated in the mid‐infrared region (450‐750 cm^?1). The energy loss function Im[?1/(?)] of PZT nanopowders was obtained by Kramers‐Kronig dispersion relations. The TO phonon frequency decreases with increasing crystallite size of the PZT samples. This effect does not happen at pH 8 to pH 9. As the crystallite size increased from 17.26 nm (at pH 5) to 27.25 nm (at pH 7), the LO‐TO splitting increased as well. This result showed that the optimum pH for absorption of IR radiation and optical application was at pH 7.     

Effect of pore size and porosity on piezoelectric and acoustic properties of Pb(Zr0.53Ti0.47)O3 ceramics

We studied the effect of porosity and pore morphology on the functional properties of Pb(Zr_0.53Ti_0.47)O₃ (PZT) ceramics for application in high frequency ultrasound transducers. By sintering a powder mixture of PZT and polymethylmetacrylate spherical particles (1.5 and 10?μm) at 1080°C, we prepared ceramics with ～30% porosity with interconnected micrometer sized pores and with predominantly ～8?μm spherical pores. The acoustic impedance was ～15?MRa for both samples, which was lower than for the dense PZT. The attenuation coefficient α (at 2.25?MHz) was higher for ceramics with ～8?μm pores (0.96?dB?mm^??1?MHz^??1), in comparison to the ceramic with smaller pores (0.56?dB?mm^??1?MHz^??1). The high α value enables the miniaturisation of the transducer, which is crucial for medical imaging probes. The dielectric and piezoelectric coefficients, polarisation, and strain response decreased with increased porosity and decreased pore/grain size. We suggest a possible role of pore/grain size on the switching behaviour.     

Electrosynthesis of lactic acid on copper and lead cathodes in aqueous media

The present study concerns the electrochemical reduction of pyruvic acid in different aqueous media on lead and copper electrodes. Some parameters such as electrode material, nature of the electrolyte, reduction potential and concentration of the organic substrate were systematically studied. The cathodic behavior of pyruvic acid was studied by cyclic voltammetry and suitable conditions were found in order to optimize the conversion of pyruvic acid during prolonged electrolyses. The results obtained showed that the pH of the solution (pH 10), the electrode material (Pb) and potential of electrode (−2.0 V (MSE)) allowed to enhance the selectivity of lactic acid which reached 90% with a conversion yield of 92%.     

Recycling of steelmaking electric arc furnace dust into aqueous cyan ceramic ink for inkjet printing process and its printability

Recycling of electric arc furnace dust (EAFD) has great potential for industrial applications, due to its useful metal contents, including zinc. In this study, aqueous cyan ceramic ink for ink-jet printing applications was synthesized using EAFD. More specifically, cyan ceramic pigments were synthesized using an empirical composition of Zn(EAFD)_XCo_1-XAl₂O₄, in which expensive cobalt oxide is replaced by Zn-enriched EAFD. Zn(EAFD)_0.25Co_0.75Al₂O₄, which has a vivid cyan color, was selected as the optimum composition of cyan ceramic pigments for synthesizing aqueous cyan ceramic ink for ink-jet printing applications. To prevent nozzle clogging during ink-jet printing, the cyan ceramic pigments were micronized. The micronized pigments were mixed with distilled water and dispersant to fabricate aqueous cyan ceramic ink. To determine the optimized jettability and printability of this ink, its rheological properties, including viscosity and surface tension, were adjusted and analyzed. It was concluded that the jettability and printability of aqueous cyan ceramic ink produced via ink-jet printing could be enhanced by appropriately adjusting its viscosity.     

Effect of Nb and K doping on the crack propagation behaviour of lead zirconate titanate ceramics

In the present study, we investigated the effect of doping on the crack propagation behaviour of lead zirconate titanate ceramics (PZT), particularly crack growth resistance and slow crack growth. Three PZT grades were processed: an undoped PZT, a soft PZT doped with niobium, PNZT, and a hard PZT doped with potassium, PKZT. The composition was chosen close to that of the morphotropic phase boundary (MPB), known to give excellent electromechanical properties. The soft material showed an important crack growth resistance and its slow crack growth curve V–K_I (crack velocity versus stress intensity factor, K_I) is shifted toward higher values of K_I. The results are discussed in terms of toughening due to ferroelastic domain switching under mechanical loading.