Morphotropic phase boundary and electrical properties of 1-x[Bi 0.5Na0.5]TiO3 -xBa[Zr0.25Ti 0.75]O3 lead-free piezoelectric ceramics

Lead-free solid solutions (1-x)Bi0.5Na0.5TiO 3 (BNT)-xBaZr0.25Ti0.75O3 (BZT) (x=0, 0.01, 0.03, 0.05, and 0.07) were prepared by the solid state reaction method. X-ray diffraction (XRD) and Rietveld refinement analyses of 1-x(BNT)-x(BZT) solid solution ceramic were employed to study the structure of these systems. A morphotropic phase boundary (MPB) between rhombohedral and cubic structures occured at the composition x=0.05. Raman spectroscopy exhibited a splitting of the (TO3) mode at x=0.05 and confirmed the presence of MPB region. Scanning electron microcopy (SEM) images showed a change in the grain shape with the increase of BZT into the BNT matrix lattice. The temperature dependent dielectric study showed a gradual increase in dielectric constant up to x=0.05 and then decrease with further increase in BZT content. Maximum coercive field, remanent polarization and high piezoelectric constant were observed at x=0.05. Both the structural and electrical properties show that the solid solution has an MPB around x=0.05. © 2012 Elsevier Ltd and Techna Group S.r.l.

Lead-free BaBi4Ti4O15 ceramics: Effect of synthesis methods on phase formation and electrical properties

The processing of ferroelectric BaBi4Ti4O15 (BBT) ceramics from powders prepared by conventional solid state reaction (SSR) and mechanochemical activation (MA) has been investigated. It was shown that MA synthesis reduces the synthesis temperature of BBT powders, leading to smaller particles with reduced anisotropy and consequently to smaller grain size of ceramics. Dielectric properties were investigated in a wide range of temperatures (20-800 degrees C) and frequencies (1.21 kHz to 1 MHz). The relative dielectric permittivity at Curie temperature was higher for solid state obtained ceramics than for the mechanically treated ones. The conductivity of sintered samples was studied, suggesting decreasing of conductivity of BBT-MA in comparison with BBT-SS ceramics. The influence of the grain and the grain boundaries contribution to the dielectric behavior in both ceramics was analyzed through impedance spectroscopy. A well-defined ferroelectric hysteresis loop was obtained for both samples. (C) 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Structure and optical properties of [Ba(1-x)Y(2x/3)](Zr(0.25)Ti(0.75))O(3) powders

[Ba(1-x)Y(2x/3)](Zr(0.25)Ti(0.75))O(3) powders with different yttrium concentrations (x = 0, 0.025 and 0.05) were prepared by solid state reaction. These powders were analyzed by X-ray diffraction (XRD). Fourier transform Raman scattering (FT-RS), Fourier transform infrared (FT-IR) and X-ray absorption near-edge (XANES) spectroscopies. The optical properties were investigated by means of ultraviolet-visible (UV-vis) absorption spectroscopy and photoluminescence (PL) measurements. Even with the addition of yttrium, the XRD patterns revealed that all powders crystallize in a perovskite-type cubic structure. FT-RS and FT-IR spectra indicated that the presence of [YO(6)] clusters is able to change the interaction forces between the O-Ti-O and O-Zr-O bonds. XANES spectra were used to obtain information on the off-center Ti displacements or distortion effects on the [TiO(6)] clusters. The different optical band gap values estimated from UV-vis spectra suggested the existence of intermediary energy levels (shallow or deep holes) within the band gap. The PL measurements carried out with a 350 nm wavelength at room temperature showed that all powders present typical broad band emissions in the blue region. (C) 2010 Elsevier Masson SAS. All rights reserved.

The electrical admittance of a homogeneous polarized fully electroded circular disc, loss-less and mechanically free : analysis, including Rayleigh correction, data for routine determination of elastic modulus and Piezoelectric coupling, and discussion of limitation of correction, anisotrophy parameters involved, and deductions concerning dimensional standarization /

"ONR Contract No. Nonr-1055(00)."

Piezoelectric properties of Bi4Ti3O12 thin films annealed in different atmospheres

Bismuth titanate (Bi4Ti3O12-BIT) films were evaluated for use as lead-free piezoelectric thin-films in micro-electromechanical systems. The films were grown by the polymeric precursor method on Pt/Ti/SiO2/Si (1 0 0) (Pt) bottom electrodes at 700 degrees C for 2 h in static air and oxygen atmospheres. The domain structure was investigated by piezoresponse force microscopy (PFM). Annealing in static air leads to better ferroelectric properties, higher remanent polarization, lower drive voltages and higher piezoelectric coefficient. on the other hand, oxygen atmosphere favors the imprint phenomenon and reduces the piezoelectric coefficient dramatically. Impedance data, represented by means of Nyquist diagrams, show a dramatic increase in the resistivity for the films annealed in static air atmopshere. (c) 2006 Elsevier Ltd. All rights reserved.

Preparation of pyrochlore-free PMN by an alternative chemical method

This work reports the synthesis of the MgNb(2)O(6) and the ferroelectric lead magnesium niobate Pb(Mg(1/3)Nb(2/3))O(3) (PMN) using fine precursor powders obtained from a chemical Oxide Precursor Method (OPM). To obtain pyrochlore-free PMN ceramics, the synthesis of the precursor MgNb(2)O(6) powders was studied for 2-25 mol% excess of MgO and 10 mol% excess of PbO. Structural and microstructural properties of the sintered ceramics obtained by the cited method and by the classical columbite method were studied and compared. Results lead to good quality, pyrochlore-free PMN ceramic prepared by OPM, presenting greater grain size if compared with ceramic prepared by columbite method.

Effect of oxidizing atmosphere on ferroelectric and piezoelectric response of CaBi2Nb2O9 thin films

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Ferroelectric and piezoelectric properties of bismuth titanate thin films grown on different bottom electrodes by soft chemical solution and microwave annealing

Bismuth titanate (Bi4Ti3O12, BIT) films were evaluated for use as lead-free piezoelectric thin films in micro-electromechanical systems. The films were grown by the polymeric precursor method on LaNiO3/SiO2/Si (1 0 0) (LNO), RuO2/SiO2/Si (1 0 0) (RuO2) and Pt/Ti/SiO2/Si (1 0 0) (Pt) bottom electrodes in a microwave furnace at 700 degrees C for 10 min. The domain structure was investigated by piezoresponse force microscopy (PFM). Although the converse piezoelectric coefficient, d(33), regardless of bottom electrode is around (similar to 40 pm/V), those over RuO2 and LNO exhibit better ferroelectric properties, higher remanent polarization (15 and 10 mu C/cm(2)), lower drive voltages (2.6 and 1.3 V) and are fatigue-free. The experimental results demonstrated that the combination of the polymeric precursor method assisted with a microwave furnace is a promising technique to obtain films with good qualities for applications in ferroelectric and piezoelectric devices. (c) 2006 Elsevier Ltd. All rights reserved.

Active control in flexible plates with piezoelectric actuators using linear matrix inequalities

The study of algorithms for active vibrations control in flexible structures became an area of enormous interest, mainly due to the countless demands of an optimal performance of mechanical systems as aircraft, aerospace and automotive structures. Smart structures, formed by a structure base, coupled with piezoelectric actuators and sensor are capable to guarantee the conditions demanded through the application of several types of controllers. The actuator/sensor materials are composed by piezoelectric ceramic (PZT - Lead Zirconate Titanate), commonly used as distributed actuators, and piezoelectric plastic films (PVDF-PolyVinyliDeno Floride), highly indicated for distributed sensors. The design process of such system encompasses three main phases: structural design; optimal placement of sensor/actuator (PVDF and PZT); and controller design. Consequently, for optimal design purposes, the structure, the sensor/actuator placement and the controller have to be considered simultaneously. This article addresses the optimal placement of actuators and sensors for design of controller for vibration attenuation in a flexible plate. Techniques involving linear matrix inequalities (LMI) to solve the Riccati's equation are used. The controller's gain is calculated using the linear quadratic regulator (LQR). The major advantage of LMI design is to enable specifications such as stability degree requirements, decay rate, input force limitation in the actuators and output peak bounder. It is also possible to assume that the model parameters involve uncertainties. LMI is a very useful tool for problems with constraints, where the parameters vary in a range of values. Once formulated in terms of LMI a problem can be solved efficiently by convex optimization algorithms.

Multilaminati piezoelettrici a gradiente funzionale

Aim of this thesis was the production of porosity-graded piezoelectric ceramics for ultrasonic applications by tape casting and screen printing. The study and optimization of each single step of the tape casting process allowed to produce flat and crack-free multilayers of Pb0.988(Zr0.52Ti0.48)0.976Nb0.024O3 (PZTN) of uniform and graded porosity. The multilayers of thickness ranging between 400 and 800 µm were produced stacking optimized green layers with different amount of pore former. The functionally graded materials showed porosity ranging between 10 and 30% with piezoelectric properties suitable for the specific ultrasonic applications. Screen printing inks of PZTN for deposition onto four different substrates were studied and optimized. Thick films with thickness ranging between 4 and 20 µm were produced tailoring the screen printing parameters and number of depositions.

Cross-talk response analysis on a piezoelectric

The study of the cross-talk and its effects in the performance of a matrix array of piezoelectric elements is an important issue. This corresponds to the study of the cross mode of vibration of each one of the piezoelectric elements that form the ultrasonic array. The aim is to detect and measure the cross-talk that is generated for the cross mode of vibration. In order to accomplish this task, an array of 2x3 elements was designed and developed. This was constructed using 8 MHz piezoelectric ceramics. A number of configurations have been experimented, considering the excitation of an increasing number of elements, in order to detect and measure the propagation of wave interference. Initial results show the way cross-talk interferes the beam generated by the array, this causing attenuation of the main beam and other negative effects.

PHB/PZT composite

Flexible standing films of piezoelectric composite made of lead zirconate titanate (PZT) ceramic powder and Poly(3-hydroxybutyrate) (PHB) in powder form were obtained by mixing both polymers mechanically and pressed at 180°C. The piezoelectric coefficient d33 were investigated as function of PZT content, poling temperature and electric field. The highest value for d 33 coefficient was around 6pC/N for 50 vol% of PZT content in the composite. As PHB is a biodegradable polymer the composite has potential application as sensor minimizing the environmental problems.

New Improved Version of J 1 ...J 4 Interferometry Method and its Application to Nanometric Vibration Measurements

Piezoelectric ceramics, such as PZT, can generate subnanometric displacements, bu t in order to generate multi- micrometric displacements, they should be either driven by high electric voltages (hundreds of volts ), or operate at a mechanical resonant frequency (in narrow band), or have large dimensions (tens of centimeters). A piezoelectric flextensional actuator (PFA) is a device with small dimensions that can be driven by reduced voltages and can operate in the nano- and micro scales. Interferometric techniques are very adequate for the characterization of these devices, because there is no mechanical contact in the measurement process, and it has high sensitivity, bandwidth and dynamic range. A low cost open-loop homodyne Michelson interferometer is utilized in this work to experimentally detect the nanovi brations of PFAs, based on the spectral analysis of the interfero metric signal. By employing the well known J 1 ...J 4 phase demodulation method, a new and improved version is proposed, which presents the following characteristics: is direct, self-consistent, is immune to fading, and does not present phase ambiguity problems. The proposed method has resolution that is similar to the modified J 1 ...J 4 method (0.18 rad); however, differently from the former, its dynamic range is 20% larger, does not demand Bessel functions algebraic sign correction algorithms and there are no singularities when the static phase shift between the interferometer arms is equal to an integer multiple of  /2 rad. Electronic noise and random phase drifts due to ambient perturbations are taken into account in the analysis of the method. The PFA nanopositioner characterization was based on the analysis of linearity betw een the applied voltage and the resulting displacement, on the displacement frequency response and determination of main resonance frequencies.

Development of the Oxide Ion Conductor Na0.5Bi0.5TiO3 (NBT) for Solid Oxide Cells

Na0.5Bi0.5TiO3 (NBT) is a well-known lead-free piezoelectric material with potential to replace lead zirconate titanate (PZT),1 however high leakage conductivity for the material has been widely reported.2 Through a combination of Impedance Spectroscopy (IS), O2- ion transference (EMF) number experiments and O18 tracer diffusion measurements, combined with Time-of-flight Secondary Ion Mass Spectrometry (TOFSIMS), it was identified that this leakage conductivity was due to oxygen ion conductivity. The volatilization of bismuth during synthesis, causing oxygen vacancies, is believed to be responsible for the leakage conductivity.3 The oxide-ion conductivity, when doped with magnesium, exceeds that of yttria-stabilized zirconia (YSZ) at ~500 °C,3 making it a potential electrolyte material for Intermediate Temperature Solid Oxide Cells (ITSOCs). Figure 1 shows the comparison of bulk oxide ion conductivity between 2 at.% Mg-doped NBT and other known oxide ion conductors.

As part of the UK wide £5.7m 4CU project, research has concentrated on trying to develop NBT for use in Intermediate Temperature Solid Oxide Cells (ITSOCS). With the aim of achieving mixed ionic and electronic conduction, transition metals were chemically doped on to the Ti-site. A range of experimental techniques was used to characterize the materials aimed at investigating both conductivity and material structure (Scanning Electron Microscopy (SEM), IS, X-ray Photoelectron Spectroscopy (XPS) and X-ray Absorption Spectroscopy (XAS)). The potential for NBT as an ITSOC material, as well as the challenges of developing the material, will be discussed.

(1) Takenaka T. et al. Jpn. J. Appl. Phys 1999, 30, 2236.

(2) Hiruma Y. et al. J. Appl. Phys 2009, 105, 084112.

(3) Li. M. et al. Nature Materials 2013, 13, 31.