Effects of lanthanum modification on dielectric properties of Pb(Zr-0.90,Ti-0.10)O-3 ceramics: enhanced antiferroelectric stability

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

Mechanochemical synthesis of ceramic powders with perovskite structure

The mechanical activation is one of the most effective method for obtaining highly disperse system due to mechanical action stress fields form in solids during milling procedure. This effect results in changes of free energy, leading to release of heat, formation of a new surface, formation of different crystal lattice defects and initiation of solid-state chemical reaction. The accumulated deformation energy determines irreversible changes of crystal structure and consequently microstructure resulting in the change of their properties. Mechanochemical processing route has been developed recently for the production of intermetallic and alloy compounds. The intrinsic advantage of this process is that the solid-state reaction is activated due to mechanical energy instead of the temperature. It was shown that the chemical reactivity of starting materials could be improved significantly after mechanochemical activation and, subsequently, the calcination temperature was reduced. Besides, it was apparent that the mechanochemical treatment could enhance the reactivity of constituent oxides; however, the sintering process could not be avoided to develop the desired ceramics. A novel mechanochemical technique for synthesis of fine-grained perovskite structured powders has shown that it is possible to form perovskite at room temperature. The effect of milling on the formation of perovskite structure of barium titanate (BT), lead titanate (PT), PZT, PZN, magnesium niobate (PMN) and LM ceramic materials was analyzed. The dielectric properties of sintered ceramics are comparable with those prepared by other methods in the literature. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Niobium doped Bi4Ti3O12 ceramics obtained by the polymeric precursor method

Pure and niobium doped bismuth titanate ceramics (Bi4Ti3-xNbxO12 (BTN)), with x ranging from 0 to 0.4 were prepared by the polymeric precursor method. X-ray diffraction showed no secondary phases. Increasing niobium content leads to more resistive ceramics. The shape and size of the grains are strongly influenced by the niobiurn added to the system. The dielectric constant is not influenced by the niobium addition while hysteresis loops are significantly narrowed. (c) 2006 Elsevier B.V All rights reserved.

Influence of microwave energy on structural and piezoelectric response of Bi 4Ti 3O 12 ceramics

Bismuth titanate ceramics (Bi 4Ti 3O 12) with 10 wt% in excess of bismuth (BIT10) were prepared by the polymeric precursor method and sinterized in microwave (MW) and conventional furnaces (CF). The effect of microwave energy on structural and electrical behavior of BIT10 ceramics was investigated by means of X-ray diffraction (XRD), Scanning electron microscopy (SEM) and electrical measurements. The results of the BIT10 ceramics processed in the microwave furnace (MW) showed a high structural organization compared to conventional treatment (CF). Size of grains and dieletrical properties are influenced by annealing conditions while coercitive field is not dependent on it. The maximum dielectric permittivity (12000) was obtained for the sample sintered in the microwave furnace. Piezoelectric force microscopy images reveals that in-plane response may not change its sign upon polarization switching, while the out-of-plane response does with the influence of microwave energy. Copyright © 2010 American Scientific Publishers All rights reserved.

Size-induced diffuse behavior in Pb0.89La0.11Zr0.40Ti0.60O3 nanocrystalline ferroelectric ceramics

The Pb1-xLaxZryTi1-yO3 system is a perovskite ABO(3) structured material which presents ferroelectric properties and has been used as capacitors, actuators, transducers and electro-optic devices. In this paper, we describe the synthesis and the characterization of Pb0.89La0.11Zr0.40Ti0.60O3 (PLZT11) nanostructured material. The precursor polymeric method and the spark plasma sintering technique were respectively used to prepare ceramic samples. In order to compare the effect of grain size, microcrystalline PLZT11 ceramic samples were also prepared. PLZT11 samples were characterized by X-ray diffraction technique which results show a reduction on the degree of tetragonality as the average grain size decreases. Moreover, the grain size decrease to a nanometer range induces a diffuse behavior on the dielectric permittivity curves as a function of the temperature and a reduction on the dielectric permittivity magnitude. Furthermore, the large number of grain boundaries due to the nanometer size gives rise to a dielectric anomaly. (C) 2012 Elsevier Masson SAS. All rights reserved.

Short-range structure of Pb(1-x)Ba(x)Zr(0.65)Ti(0.35)O(3) ceramic compounds probed by XAS and Raman scattering techniques

Ti K-edge x-ray absorption near-edge spectroscopy (XANES) and Raman scattering were used to study the solid solution effects on the structural and vibrational properties of Pb(1-x)Ba(x)Zr(0.65)Ti(0.35)O(3) with 0.0 < x < 0.40. Compared with x-ray diffraction techniques, which indicates that the average crystal symmetry changes with the substitution of Pb by Ba ions or with temperature variations for samples with x=0.00, 0.10, and 0.20, local structural probes such as XANES and Raman scattering results demonstrate that at local level, the symmetry changes are much less prominent. Theoretical XANES spectra calculation corroborate with the interpretation of the XANES experimental data.

A high order model for piezoelectric rods: an asymptotic approach

Preprint submitted to International Journal of Solids and Structures. ISSN 0020-7683

Hybrid Multiferroic Nanostructure with Magnetic−Dielectric Coupling

The development of methods to economically synthesize single wire structured multiferroic systems with room temperature spin−charge coupling is expected to be important for building next-generation multifunctional devices with ultralow power consumption. We demonstrate the fabrication of a single nanowire multiferroic system, a new geometry, exhibiting room temperature magnetodielectric coupling. A coaxial nanotube/nanowire heterostructure of barium titanate (BaTiO3, BTO) and cobalt (Co) has been synthesized using a template-assisted method. Room temperature ferromagnetism and ferroelectricity were exhibited by this coaxial system, indicating the coexistence of more than one ferroic interaction in this composite system

Lead free heterogeneous multilayers with giant magneto electric coupling for microelectronics/microelectromechanical systems applications

Lead free magneto electrics with a strong sub resonant (broad frequency range) magneto electric coupling coefficient (MECC) is the goal of the day which can revolutionise the microelectronics and microelectromechanical systems (MEMS) industry. We report giant resonant MECC in lead free nanograined Barium Titanate–CoFe (Alloy)-Barium Titanate [BTO-CoFe-BTO] sandwiched thin films. The resonant MECC values obtained here are the highest values recorded in thin films/ multilayers. Sub-resonant MECC values are quite comparable to the highest MECC reported in 2-2 layered structures. MECC got enhanced by two orders at a low frequency resonance. The results show the potential of these thin films for transducer, magnetic field assisted energy harvesters, switching devices, and storage applications. Some possible device integration techniques are also discussed

Photoluminescent behavior of SrZrO(3)/SrTiO(3) multilayer thin films

A detailed investigation was made into the origin of photoluminescence in an alternate multilayer system of SrZrO(3) (SZO) and SrTiO(3) (STO) thin films. XRD and room-temperature PL studies revealed a high consistency with respect to improved crystallization at elevated temperatures. The photoluminescence behaviour of SZO/STO multilayered system consists in the superposition of independent photoluminescence emissions of both STO and SZO films. Based on the present results and on previous experimental and theoretical data, we propose that the origin of the photoluminescence emission results from structural disorder generated by the presence of distortions in the ideal constituent clusters of these materials. (c) 2009 Elsevier B.V. All rights reserved.

Phase-transition studies of Ba(0.90)Ca(0.10)(Ti(1-x)Zr(x))O(3) ferroelectric ceramic compounds

Perovskite-structured Ba(0.90)Ca(0.10)(Ti(1-x)Zr(x))O(3) ceramics were prepared in this work and subsequently studied in terms of composition-dependent dielectric and high-resolution long-range order structural properties from 30 to 450 K. The dielectric response of these materials was measured at several frequencies in the range from 1 kHz to 1 MHz. Combining both techniques, including Rietveld refinement of the X-ray diffraction data, allowed observing that, when increasing Zr(4+) content, the materials change from conventional to diffuse and relaxor ferroelectric compounds, the transition occurring spontaneously at the x = 0.18 composition. Interestingly, this spontaneous transition turned out to be prevented for a further increase of Zr(4+). On the basis of all the dielectric and structural results processed, a phase diagram of this system is presented. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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.

Electrophoretic deposition of Ba0.77Ca0.23TiO3 nanopowders

Ba0.77Ca0.23TiO3 (BCT23) nanometric powders, synthesized by the modified Pechini method, were used as precursor to produce thick films (50-130 mu m) employing the electrophoretic deposition (EPD) technique. The BCT23 powder presented a single crystalline phase with an average particle size and a crystallite size of similar to 60 nm and similar to 20 nm, respectively, when calcined at 800 degrees C/2h. BCT23 thick films were deposited on platinum substrates starting from different suspensions prepared by dispersion of the powder into: isopropyl alcohol (IPA) or a mixture of acetylacetone (Acac) and ethanol (EtOH) (1:1, volumetric ratio). A milling process was used to deagglomerate the powders in order to increase the suspension stability and improving the deposition. Dense and crack free thick films with uniform microstructure were obtained after sintering at 1300 degrees C/2 h from Acac+EtOH solution. (C) 2007 Elsevier B.V. All rights reserved.

Electrical properties of screen printed BaTiO3 thick films

The deposition of thick film pastes by screen-printing is a relatively simple and convenient method to produce thicker layers with thickness up to 100 mum. In the present work, the barium titanate thick films were prepared from mechanically activated powders based on BaC03 and TiO2. After mixing, the powders were calcined at low temperature by slow heating and cooling rates. The thick films were deposited on to Al2O3 substrates through hybrid technology. The obtained films were fired at 850 degreesC together with electrode material (silver/palladium). The electrical properties of thick films: dielectric permittivity, dielectric losses, Curie temperature, hysteresis loop were reported. The obtained BT thick films can be applied in as multilayer capacitors or in gas sensor application. (C) 2003 Elsevier Ltd. All rights reserved.

Composites PVDF-TrFE/BT used as bioactive membranes for enhancing bone regeneration

In this paper a piezoelectric composite membranes were developed for charge generator to promoter bone regeneration on defects sites. Is known that the osteogenesis process is induced by interactions between biological mechanisms and electrical phenomena. The membranes were prepared by mixing Barium Titanate (BT) powders and PVDF-TrFE (PVDF:TrFE = 60:40 mol%) on dimethylformamide medium. This precursor solution was dried and crystallized at 100degreesC for 12 hours. Composites membranes were obtained by following methods: solvent casting (SC), spincoating (SP), solvent extraction by water addition (WS) and hot pressing (HP).The microstructural analysis performed by SEM showed connectivity type 3-0 and 3-1 with high homogeneity for samples of ceramic volume fraction major than 0.50. Powder agglomerates within the polymer matrix was evidenced were observed for composites with the BT volume fraction major than 40%. The composite of ceramic fraction of 0.55 presented the best values of remanent polarization (similar to33 muC/cm(2)), but the flexibility of these composites with the larger ceramic fraction was significantly affected.For in vivo evaluation PVDF-TrFE/BT 90/10 membranes with 3cm larger were longitudinally implanted under tibiae of male rabbit. After 21 days the animals were sacrificed. By histological analyses were observed neo formed bone with a high mitotic activity. In the interface bone-membrane was evidenced a pronounced callus formation. These results encourage further applications of these membranes in bone-repair process.