Effect of PMN modification on structure and electrical response of xPMN–(1−x)PZT ceramic systems

The structural and electrical properties of xPb(Mg_1/3Nb_2/3)O₃–(1−x)Pb(Zr,Ti)O₃ ternary ceramic system with the composition near to the morphotropic phase boundary (MPB) and of xPb(Mg_1/3Nb_2/3)O₃–(1−x)Pb(Zr_0.47Ti_0.53)O₃ ceramics were investigated as a function of the Pb(Mg_1/3Nb_2/3)O₃ (PMN) content by scanning electron microscopy (SEM), X-ray diffraction (XRD), dielectric and piezoelectric spectroscopy and polarization-electric field measurement technique. Studies were performed on the samples prepared by a columbite precursor method for x=0.125, 0.25 and 0.5. Room temperature SEM investigations revealed common trends in the grain structure with increasing PMN content. XRD analysis demonstrated that with increasing PMN content in xPb(Mg_1/3Nb_2/3)O₃–(1−x)Pb(Zr_0.47Ti_0.53)O₃, the structural change occurred from the tetragonal to the pseudocubic phase at room temperature. Changes in the dielectric and ferroelectric behavior were then related to these structural trends and further correlated with the piezoelectric properties. The results of ferroelectric hysteresis measurements, in conjunction with dielectric spectroscopy, demonstrated an intermediate, relaxor-like behavior between normal and relaxor ferroelectrics in the solid solution system, depending on the PMN content.     

Phase formation and transitions in the lead nickel niobate–lead zirconate titanate system

Despite the many previous studies of the synthesis and characterization of several perovskite ferroelectric materials which have potential applications in electronic and medical diagnostic devices, the synthesis and phase formation of the whole series in the solid solution of (1 ? x)Pb(Ni_1/3Nb_2/3)O₃–xPb(Zr_1/2Ti_1/2)O₃ (PNN–PZT) system has rarely been studied. In this work, the phase formation, morphology, particle size and chemical composition of perovskite powders in the (1 ? x)PNN–xPZT system were investigated. Powders were prepared by a modified mixed-oxide synthesis route for various chemical compositions under different calcination temperatures. It is found that the perovskite phase undergoes a pseudo-cubic to tetragonal transition as composition changes. The degree of spherical shape and agglomeration were observed to increase with increasing PZT content.     

Structural and piezoelectric properties of <001> textured PZT‐PZNN piezoelectric ceramics

Rhombohedral 0.69Pb(Zr_0.47Ti_0.53)‐0.31Pb(Zn_0.6Ni_0.4)NbO₃ (PZT‐PZNN) ceramics were textured using 10.0 vol. % BaTiO₃ (BT) platelets along the <001> direction at 950°C with a high Lotgering factor of 95.3%. BT platelets did not react with the PZT‐PZNN ceramics, and the textured PZT‐PZNN ceramic had a tetragonal structure. The PZT‐PZNN ceramics exhibited a strain of 0.174% with a piezoelectric strain constant (d*₃₃) of 580 pC/N at 3.0 kV/mm. The textured PZT‐PZNN ceramic showed an increased strain of 0.276% and d*₃₃ of 920 pC/N at 3.0 kV/mm, which can be explained by the domain rotation. However, the d₃₃ values of the textured specimens are smaller than those of the untextured specimens because of the small remanent polarization and relative dielectric constant of BT platelets. The textured PZT‐PZNN ceramic synthesized in this work can be used for piezoelectric multilayer actuators because of its large strain and low sintering temperature.     

Stability and single crystal growth of dielectric materials containing lead under hydrothermal conditions

Stability of lead magnesium niobate (PMN; Pb(Mg_1/3Nb_2/3)O₃), lead scandium niobate (PSN; Pb(Sc_0·5Nb_0·5)O₃), a solid solution in the PSN–lead titanate system (PSNT), and lead zirconate titanate (PZT; Pb(Zr_0·53Ti_0·47)O₃) were all examined in a platinum capsule under hydrothermal conditions. The perovskite PMN was formed from the low crystalline pyrochlore PMN at 600°C by the hydrothermal treatment in pure water. However, the perovskite was decomposed to the pyrochlore by further hydrothermal treatment in pure water for a longer time or at higher temperature. In KF solutions, single crystals of PMN, PSN and PSNT with a pyrochlore structure were grown at the top of the capsule by hydrothermal treatments at 600°C with a temperature gradient of 40°C. In the case of PZT, single crystals of the tetragonal PZT were grown, but the content of Zr in the grown crystals decreased in comparison with that of the starting material.     

Nanocrystalline buildup,relaxor behavior,and polarization characteristic in PZT–PNZN quaternary ferroelectrics

The Pb(Zr_0.47Ti_0.53)O₃–Pb[(Ni_0.6Zn_0.4)_1/3Nb_2/3]O₃ (PZT–PNZN) quaternary ferroelectrics presenting the high piezoelectric coefficients are the active element in a range of piezoelectric devices. However, the buildup of nanoceramics with stable perovskite structure is still a big challenge, which prohibits the miniaturization of piezoelectric devices. In this work, the high dense PZT–PNZN nanoceramics with average grain size of 130 nm were prepared by a combination of high‐energy ball milling (HEBM) and spark plasma sintering (SPS). The domain configuration and relaxor behavior in this nanoceramic are reported for the first time. Although the noncubic crystal structure and dielectric anomaly suggest a ferroelectric behavior, only very slim polarization–electric (P–E) hysteresis loops are observed. The suppression of macroscopic ferroelectric polarization mainly originates from the decrease in crystal tetragonality and the enhanced clamping effect on domain wall motion. The piezoelectric properties, d₃₃=65 pC/N and k_p=17%, raise the possibility of PZT–PNZN nanoceramics for application in multilayer piezoelectric devices.     

Effect of pressure on electric generation of PZT(30/70) and PZT(52/48) ceramics near phase transition pressure

Impact experiment of Pb(Zr_0.3Ti_0.7)O₃ and Pb(Zr_0.52Ti_0.48)O₃ ceramics were conducted by empolying shock reverberation techniques within 3-7 GPa and X-ray diffraction patterns of these materials have been measured at pressure up to 32 GPa with a diamond anvil cell and synchrotron radiation. To refine the crystal structure, Rietveld analysis was performed and bulk moduli were calculated using Birch-Murnaghan equation of state. We found a tetragonal phase transforming to a cubic phase in Pb(Zr_0.3Ti_0.7)O₃ and Pb(Zr_0.52Ti_0.48)O₃ ceramics at ∼7.4 GPa and ∼4 GPa respectively. For dynamic pressure experiment, a metal flyer accelerated by a gas gun facility impacts into PZT ceramics to investigate electric energy. As pressure increased, output voltage of Pb(Zr_0.3Ti_0.7)O₃ and Pb(Zr_0.52Ti_0.48)O₃ ceramics slightly increased below ∼7 GPa and ∼4 GPa. But the voltage increased near ∼7 GPa and ∼4 GPa. From the result, we could confirm that the phase transition influenced the considerable effect on the electrical power generation.     

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.     

Piezoelectric Properties of Ink‐Jet–Printed Lead Zirconate Titanate Thick Films Confirmed by Piezoresponse Force Microscopy

An ink consisting of Pb(Zr_0.53Ti_0.47)O₃ (PZT) particles with a median size of 170 nm and a narrow size distribution, in a dispersion of water and glycerol, and with a low viscosity and surface tension, was used for the fabrication of thick films by piezoelectric ink‐jet printing. This study reports the printing conditions, the subsequent thermal treatment of the as‐deposited layers, and the properties of the sintered PZT thick film. The film, sintered at 1100°C, had a locally dense microstructure and consisted of grains that are a few 100 nm across, as revealed by scanning electron microscopy. A local piezoelectric response of 15 pm/V was measured in the ink‐jet–printed PZT thick film by piezoresponse force microscopy.     

Reaction sintering of lead zinc niobate–lead zirconate titanate ceramics

Lead zinc niobate (PZN)–lead zirconate titanate (PZT) ceramics were produced by the reaction-sintering process. The specimens were prepared directly from a mixture of their constituent oxides without any calcination step. When 50% PZN was added to tetragonal Pb(Zr_0.47Ti_0.53)O₃ ceramics, the densities and electrical properties were found to be optimal (ρ = 7.91 g/cm³, K = 1947 at 1 kHz and room temperature, d₃₃ = 530 pC/N, k_p = 0.61). However, the specimen containing more than 50% PZN showed reduced density and decreased electrical properties, due to the formation of pyrochlore phases. The improved densification behavior of the reaction-sintering process was attributed to the enhanced diffusion of lattice defects, which were created by differences in the ionic valence of the B-sites ions of the perovskite structure.     

Higher permittivity of Ni-doped lead zirconate titanate,Pb[(Zr0.52Ti0.48)(1-x) Nix]O3, ceramics

The paper reports highest obtained dielectric constant for Ni-doped Lead Zirconate Titanate [PZT, Pb(Zr_0.52Ti_0.48)O₃] ceramics. The Ni-doped PZT ceramic pellets were prepared via conventional solid-state reaction method with Ni content chosen in the range 0–20?at%. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy were employed to investigate the crystal structure of the prepared ceramics. The X-ray diffraction analysis indicated that the ceramic pellets had crystallized into tetragonal perovskite structure. A minute displacement of XRD peaks was detected in the diffraction spectra of Ni-doped PZT ceramic samples which when examined by size-strain plot (SSP) method revealed presence of homogenous strain that decreased with increase in concentration of Ni. In FTIR the maximum absorption at 597?cm^?1, 608?cm^?1, 611?cm^?1, 605 and 613?cm^?1 for Ni?=?0, 5, 10, 15 and 20?at%, respectively, confirmed the formation of perovskite structure in all the compositions and the slight shift suggests decrease in cell size on doping. The values of dielectric constant (ε′) & tanδ as a function of frequency and temperature were measured for the prepared ceramics and it revealed highest ever reported dielectric constant for Ni - doped PZT with Ni?=?5?at%. The dielectric variation with temperature exhibited a diffused type ferroelectric–paraelectric phase transition for the doped samples. Also, the maximum dielectric constant value (ε′_max) decreased while the phase transition temperature increased with increase in doping concentration of Ni. The estimated activation energy of different compositions was found to increase from 0.057 to 0.068?eV for x?=?0.00 to x?=?0.20 in ferroelectric phase. The piezoelectric, ferroelectric and magnetic properties were also investigated.     

Diffusion Across M/Pb(Zr,Ti)O3 Interfaces (M=Pt3Pb or Pt) Under Different System Conditions

Interfaces between functional ceramics, such as Pb(Zr_0.5Ti_0.5)O₃ or PZT, and metal electrodes, such as Pt, are important for many devices. Maintaining an interface that is free of secondary phases is necessary for the efficient transfer of electrons and device function. However, there are instances where unstable transient phases form at the interface due to atomic diffusion, such as Pt₃Pb. Here, we investigate the migration barriers for the diffusion of Pb across the PZT/Pt and PZT/Pt₃Pb interfaces using density functional theory (DFT) and the climbing image nudge elastic band (c‐NEB) method. Our calculation models take into account the influence of atmospheric conditions on Pb diffusion through the preferential stabilization of defects near the interface as a result of changes to the Pb and O chemical potentials. In addition, the PZT structures that are stable above and below the Curie temperature are considered. The migration barriers are predicted to be strongly dependent on atmospheric conditions and the phase of the PZT, tetragonal or cubic. In particular, an inversion of the Pb diffusion direction at the PZT/Pt interface is predicted to take place as the oxygen partial pressure increases. This prediction is confirmed by experimental in situ X‐ray diffraction measurements of a PZT/Pt interface.     

Dielectric,magnetic and magnetoelectric properties of Ni0.5Zn0.5Fe2O4+Pb(Zr0.48Ti0.52)O3 composite ceramics

Magnetoelectric composite ceramics of spinel ferrite Ni_0.5Zn_0.5Fe₂O₄ (NZFO) with high magnetic permeability and tetragonal perovskite Pb(Zr_0.48Ti_0.52)O₃ (PZT) with high piezoelectric constant were synthesized by common solid state reaction method. XRD and SEM showed that high dense composite ceramics without any foreign phases were obtained. The ceramics showed excellent dielectric and magnetic properties, which were stable in a large frequency range. The dielectric peak became wider with the ferrite content in the permittivity spectrum with temperature. With the increase in the ferrite content, the magnetic Curie temperature shifted to higher temperature and closed to that of the pure ferrite. In addition, the magnetoelectric coefficient enhanced as the increase in the ferrite content. The properties of the composite ceramics could be adjusted by the ferrite content. These research results provided a powerful experimental basis for the sensor and transducer in microelectronic and microwave devices.     

Crystal structure and piezoelectric properties of xPb(Mn1/3Nb2/3)O3–(0.2 − x)Pb(Zn1/3Nb2/3)O3–0.8Pb(Zr0.52Ti0.48)O3 ceramics

Pb(Mn_1/3Nb_2/3)O₃–Pb(Zn_1/3Nb_2/3)O₃–Pb(Zr_0.52Ti_0.48)O₃ (designated as PMnN–PZN–PZT) piezoelectric ceramics were prepared and the effects of PMnN content on the crystal structure and electrical properties were investigated. The results show that the pure perovskite phase forms in these ceramics. The crystal structure changes from tetragonal to rhombohedral and the lattice constant decreases with increase of PMnN content. The morphotropic phase boundary (MPB) of xPMnN–(0.2 ? x)PZN–0.8PZT ceramics occurs where the content of PMnN, x, lies between 0.05 and 0.085 mol. The dielectric constant (?), piezoelectric constant (d₃₃) and Curie temperature (T_c) decrease, while the mechanical quality factor (Q_m) increases with the increase of PMnN content. The ceramic with composition 0.075PMnN–0.125PZN–0.8PZT has the optimal piezoelectric properties, ? is 842, d₃₃ is 215 pC/N, T_c is 320 °C, k_p is 0.57 and Q_m amounts to 1020, which makes it a promising material for high power piezoelectric devices.     

Synthesis and characterization of nanostructured PZT encapsulated PVA–PAA hydrogel

Hydrogel/PZT composite was prepared by encapsulating, Pb(Zr_0.52Ti_0.48)O₃ (PZT) nanoparticles in an electroactive (PVA–PAA) hydrogel. The XRD studies confirmed the presence of pure tetragonal phase in PZT with crystallite size of 13 nm in the composite matrix. PZT nanoparticles were found to be embedded in the micro pores of PVA–PAA hydrogel as indicated by the SEM images. The composite shows three step degradation process in the TG/DTA measurements. Dielectric properties were studied from room temperature to 120 °C within wide frequency range of 100 Hz–600 kHz. At room temperature and intermediate frequency range, the composite shows a high dielectric constant of ~225 to 600 and low dielectric loss of 0.08.     

Effect of Ru and LaNiO3 barrier layers on lead zirconate titanate films grown on nickel-based metal foils by sol–gel process

Lead zirconate titanate [Pb(Zr_0.52, Ti_0.48)O₃ (PZT)] films were grown by sol–gel process on nickel and hastelloy foils. PZT perovskite phase was obtained at 650 °C annealing condition and surface topography showed uniform and dense microstructure. The characterization on dielectric properties indicates that diffusion of foil elements into the PZT and the formation of low capacitance interfacial layer occur during process. In order to reduce the diffusion effect of foil element and/or interfacial layer, barrier layers such as Ru(RuO₂) and LaNiO₃ layers were utilized on foil substrates. The increase of grain size was observed in PZT films grown on barrier layers. Dielectric properties are greatly improved without degrading ultimate dielectric breakdown strength.     

Effect of neodymium substitution on crystalline orientation,microstructure and electric properties of sol-gel derived PZT thin films

Pb(Nd_xZr_0.52Ti_0.48)O₃ (PNZT) (x = 0%, 1%, 2%, 3%, 4%, 5%) thin films were prepared by sol-gel process to investigate the effects of neodymium substitution on crystalline orientation, microstructure and electric properties of lead zirconate titanate (PZT) films. X-ray diffraction (XRD) and scanning electron microscope (SEM) analysis showed that PNZT films with Nd doping concentration below 3% exhibited dense perovskite structure with (100) preferred orientation. The average grain size of PNZT films decreased as the Nd substitution increased. The maximum dielectric constant, remnant polarization and minimum coercive field were obtained in 2% Nd-doped PZT films. Fatigue resistance was also improved significantly with 2% Nd dopant.     

Effect of milling time and pH on the dispersibility of lead zirconate titanate in aqueous media for inkjet printing

Micrometre-sized Pb(Zr_0.53Ti_0.47)O₃ (PZT) powder was dispersed in water, stabilized with the ammonium polyacrylate (PAANH₄) and milled to reduce the particle size. The influence of the pH, the amount of PAANH₄, and the milling time on the zeta potential, the PZT particle size and the particle size distribution was studied. The agglomeration took place regardless the milling time at pH 3. The suspension, containing 5 vol.% of PZT and 5 wt.% of PAANH₄, milled at pH 10 for 240 min, was stable and contained particles with a narrow, log-normal particle size distribution with the median size of 160 nm. The dissociated carboxyl groups from the PAANH₄ interacted with the PZT particles as evidenced by Fourier transform infrared spectroscopy and electrosterically stabilized the particles in water at pH 10. The PZT particle size and the stability of the suspension fitted the requirements for the ink, suitable for ink-jet printing.     

Rapid Microwave Annealing of Amorphous Lead Zirconate Titanate Thin Films Deposited by Sol‐Gel Method on LaNiO3/SiO2/Si Substrates

The heating behavior of LaNiO₃ (LNO) films on SiO₂/Si substrate heated by 2.45 GHz microwave irradiation in the microwave magnetic field was first investigated, and then amorphous Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films were deposited on LNO‐coated SiO₂/Si substrates by a sol‐gel method and crystallized in the microwave magnetic field. The crystalline phases and microstructures as well as the electrical properties of the PZT films were investigated as a function of the elevated temperature generated by microwave irradiation. The perovskite PZT films with a highly (100)‐preferred orientation can be obtained by microwave annealing at 700°C for only 180 s of total processing time, and have good electrical properties. The results demonstrated that conductive metal oxide LNO as a bottom electrode layer is an advantage for the crystallization of PZT thin films by microwave irradiation in the microwave magnetic field.     

Enhancing high power performances of Pb(Mn1/3Nb2/3)O3–Pb(Zr,Ti)O3 ceramics by Bi(Ni1/2Ti1/2)O3 modification

High power piezoelectric ceramics 0.04Bi(Ni_1/2Ti_1/2)O₃-xPb(Mn_1/3Nb_2/3)O₃-(0.96-x)Pb(Zr_yTi_1-y)O₃ (BNT-xPMnN-PZ_yT) with various contents of PMnN from 0 to 12 mol% (keep y = 0.50) and Zr/Ti ratio gradually increasing from 48/52 to 52/48 (keep x = 0.06) were prepared by solid-state method. X-ray diffraction (XRD) results show a single phase of polycrystalline perovskite and indicate that the phase structure transforms from tetragonal phase to rhombohedral with x and y increasing. The optimal comprehensive properties of BNT-xPMnN-PZ_yT ceramic, d₃₃ (355 pC/N), k_p (0.58), ε_r (1512), tanδ (0.40%), T_c (336 °C) and Q_m (2010), are obtained at x = 0.06 and y = 0.50, which are apparently superior to typical or commercial Pb(Zr,Ti)O₃ (PZT) based power ceramics. Within the range from room temperature to 200 °C, the variation of electric-field induced strains is less than 8.3%, indicating its good temperature stability. The maximum vibration velocity of the ceramic at temperature rise of 20 °C is measured to be 0.92 m/s, which is about 2 times higher than that of commercial hard PZT ceramics, suggesting the BNT-xPMnN-PZ_yT ceramic is a competitive and potential candidate for power piezoelectric transduction and actuation applications.     

In situ sol-gel co-synthesis at as low hydrolysis rate and microwave sintering of PZT/Fe2CoO4 magnetoelectric composite ceramics

Pb(Zr_0.53Ti_0.47)O₃/Fe₂CoO₄ (PZT/Fe₂CoO₄) diphase particulate composites were prepared in an 80:20 M ratio by the in situ sol-gel co-synthesis method. Controlling the hydrolysis rate of the metal-organic reagents used in the formation of the sol was essential to obtain a nanostructured system with a highly homogeneous and immiscible two-phase distribution. The compact diphase powders were densified throughout the microwave-assisted sintering methods for controlling grain growth, and to evaluate this new nanostructure and effect on the physical properties of this material. The characterizations revealed that the new in situ sol-gel co-synthesis method was successful in producing highly homogeneous nanopowders without secondary phases. The powders processed at low hydrolysis rates showed the formation of a core-shell particle architecture. After microwave-assisted sintering, the samples showed uniform distribution of the cobalt ferrite phase in the PZT phase, with an average nanograin size of about 300 nm, while the same material sintered conventionally had an average cobalt ferrite grain size of about 6 µm. Innovative PZT/Fe₂CoO₄ nanostructures were obtained with magnetoelectric response.