Mario Maglione

Effect of diamagnetic Ca, Sr, Pb, and Ba substitution on the crystal structure and multiferroic properties of the BiFeO3 perovskite

In this work, we studied the effect of heterovalent Ca, Sr, Pb, and Ba substitution on the crystal structure, dielectric, local ferroelectric, and magnetic properties of the BiFeO3 multiferroic perovskite. Ceramic solid solutions with the general formula Bi0.7A0.3FeO3 (A is a doping element) were prepared and characterized by x-ray diffraction, dielectric, piezoresponse force microscopy (PFM), and magnetic measurements. It is shown that the crystal structure of the compounds is described within the space group R3c, permitting the spontaneous polarization, whose existence was confirmed by the PFM data. Magnetic properties of the solid solutions are determined by the ionic radius of the substituting element. Experimental results suggest that the increase in the radius of the A-site ion leads to the effective suppression of the spiral spin structure of BiFeO3, resulting in the appearance of net magnetization.

Revised structural phase diagram of (Ba0.7Ca0.3TiO3)-(BaZr0.2Ti0.8O3)

The temperature-composition phase diagram of barium calcium titanate zirconate (x(Ba0.7Ca0.3TiO3)-(1 − x)(BaZr0.2Ti0.8O3); BCTZ) has been reinvestigated using high-resolution synchrotron x-ray powder diffraction. Contrary to previous reports of an unusual rhombohedral-tetragonal phase transition in this system, we have observed an intermediate orthorhombic phase, isostructural to that present in the parent phase, BaTiO3, and we identify the previously assigned T-R transition as a T-O transition. We also observe the O-R transition coalescing with the previously observed triple point, forming a phase convergence region. The implication of the orthorhombic phase in reconciling the exceptional piezoelectric properties with the surrounding phase diagram is discussed.The temperature-composition phase diagram of barium calcium titanate zirconate (x(Ba{sub 0.7}Ca{sub 0.3}TiO{sub 3})-(1 - x)(BaZr{sub 0.2}Ti{sub 0.8}O{sub 3}); BCTZ) has been reinvestigated using high-resolution synchrotron x-ray powder diffraction. Contrary to previous reports of an unusual rhombohedral-tetragonal phase transition in this system, we have observed an intermediate orthorhombic phase, isostructural to that present in the parent phase, BaTiO{sub 3}, and we identify the previously assigned T-R transition as a T-O transition. We also observe the O-R transition coalescing with the previously observed triple point, forming a phase convergence region. The implication of the orthorhombic phase in reconciling the exceptional piezoelectric properties with the surrounding phase diagram is discussed.

The crossover from a ferroelectric to a relaxor state in lead-free solid solutions

We investigate the gradual crossover from ferroelectric to relaxor behaviour versus substitution in lead-free ceramics. We show that the Vogel?Fulcher law in the relaxor state is the extrapolation of the ferroelectric line. To explain this extrapolation, we suggest that both the host matrix and the impurity induced clusters are triggered by the BaTiO3 soft mode correlation length. The Ti?O bond oscillations are the key mechanism.

Low-losses, highly tunable Ba0.6Sr0.4TiO3/MgO composite

Spark plasma sintering (SPS) is an efficient tool to obtain highly densified ferroelectric-dielectric ceramic composites with clean interfaces and tunable properties. Dielectric MgO and ferroelectric Ba0.6Sr0.4TiO3 (BST) were combined in two-dimensional multilayer and three-dimensional random powders design. Their unmodified BST Curie temperature proves the suppression of interdiffusion while dielectric losses are below 0.5% and the tunability is 40% at room temperature. The composites and pure BST with similar densities (>95%) were obtained, owing reliable comparison of their dielectric properties. Such SPS ceramics can be used as experimental input for simulation and are potential candidates for high frequency applications.

Dielectric relaxation in BaTi0.85(Fe1∕2Nb1∕2)0.15O3 perovskite ceramic

A polycrystalline sample of BaTi0.85(Fe1∕2Nb1∕2)0.15O3 is synthesized by high temperature solid state reaction technique. This sample crystallizes in cubic pervoskite structure at room temperature. The dielectric properties have been investigated at temperature range from 80to450K at various frequencies (100–107Hz). Frequency dielectric dispersion phenomena in a BaTi0.85(Fe1∕2Nb1∕2)0.15O3 ceramic has been analyzed by impedance spectroscopy in the temperature range from 250to450K. The Cole-Cole relaxation equation modified by introducing the conductivity was used to describe the experimental dielectric spectra of a high permittivity. Excellent agreement has been obtained in wide frequency domain (100–107Hz) between the measured and calculated permittivities in the 250–450K temperature range. The dielectric relaxation frequency obeys the Arrhenius behavior with activation energy of 0.181eV. A separation of the grain and grain boundary properties has been achieved using an equivalent circuit model. The diffe...

Single-step synthesis of well-crystallized and pure barium titanate nanoparticles in supercritical fluids

Single-step synthesis of ultra-fine barium titanate powder with a crystallinity as high as 90% and without barium carbonate contamination has been successfully performed under supercritical conditions using a continuous-flow reactor in the temperature range 150–380 °C at 16 MPa. To synthesize this bimetallic oxide, alkoxides, ethanol and water were used. The influence of the synthesis parameters on the BaTiO3 powder characteristics was investigated. The results show that the water to alkoxide precursor ratio, the reactor temperature and the Ba:Ti molar ratio of alkoxide precursor play a major role in the crystallization of pure and well-crystallized BaTiO3 nanoparticles. The continuous mode of operation without post-treatments for powder washing, drying or crystallization increase the industrial interest.

Quasi-ferroelectric state in Ba(Ti1−xZrx)O3 relaxor: dielectric spectroscopy evidence

The dielectric spectroscopy of perovskite Ba(Ti0.675Zr0.325)O3 (BTZ325) relaxor ceramics is performed in a wide frequency range of 10?2?106?Hz. In contrast to other known relaxors, where the dipole dynamics is subject to non-Arrhenius slowing-down and freezing upon cooling so that the cubic ergodic relaxor phase transforms into a cluster dipolar-glass phase or a ferroelectric phase, none of these transformations are observed in BTZ325. In the course of cooling from the ergodic relaxor phase the characteristic time and the spectral width of the main relaxation process first increase rapidly in a Vogel?Fulcher manner, but then become almost temperature independent below the temperature of permittivity maximum, indicating the onset of the state which we call quasi-ferroelectric. The properties and the origin of this state are discussed.

Linking large piezoelectric coefficients to highly flexible polarization of lead free BaTiO3-CaTiO3-BaZrO3 ceramics

We report a large d31 piezoelectric coefficient and corresponding electromechanical coupling factor, Kp, of 0.5Ba(Zr0.2Ti0.8)O3–0.5(Ba0.7Ca0.3)TiO3 (BCTZ50) and 0.68Ba(Zr0.2Ti0.8)O3–0.32(Ba0.7Ca0.3)TiO3 (BCTZ32) lead-free piezoceramics. The piezoelectric coefficient, d31, reaches a high value of 200 pC/N for BCTZ50 at room temperature which is comparable to the one of the soft PZT. This confirms the previously reported d33 for the same material. A useful way to achieve such performances at the expense of a smaller thermal budget is suggested, enabling better control of the ceramics composition and microstructure. Based on pyroelectric and ferroelectric hysteresis loops measurements, we show that such outstanding properties are likely due to the high flexibility of polarization under thermal and electric stresses.

Dielectric and polarization experiments in high loss dielectrics: A word of caution

The recent quest for improved functional materials like high permittivity dielectrics and/or multiferroics has triggered an intense wave of research. Many materials have been checked for their dielectric permittivity or their polarization state. In this report, we call for caution when samples are simultaneously displaying an insulating behavior and a defect-related conductivity. Many oxides containing mixed valent cations or oxygen vacancies fall into this category. In such cases, most of the standard experiments may result in an effective high dielectric permittivity, which may not be related to ferroelectric polarization. Here we list a few examples of possible discrepancies between measured parameters and their expected microscopic origin.

Controlling internal barrier in low loss BaTiO3 supercapacitors

Supercapacitor behavior has been reported in a number of oxides including reduced BaTiO3 ferroelectric ceramics. These so-called giant properties are however not easily controlled. We show here that the continuous coating of individual BaTiO3 grains by a silica shell in combination with spark plasma sintering is a way to process bulk composites having supercapacitor features with low dielectric losses and temperature stability. The silica shell acts both as an oxidation barrier during the processing and as a dielectric barrier in the final composite.