Vincenzo Buscaglia

Influence of foreign ions on the crystal structure of BaTiO3

Abstract The influence of dopants (Cr, Co, Fe, Ni, Y, Er, Tb, Gd, Pr and La) on the crystal structure of barium titanate was studied at room temperature and at 250°C using X-ray diffraction. Fine BaTiO3 powders (Ba/Ti=1.02, size ≈30 nm) have been doped with 1 at% of the foreign element and annealed for 14 and 62 h at two different temperatures: 950 and 1350°C. The room temperature structure of doped BaTiO3 was in any case tetragonal with c/a ratio lower than in the undoped perovskite, but dependent on dopant nature and particle size. For powders calcined at 1350°C, the particle size was in the range 1–5 μm and the decrease in tetragonality was mainly determined by dopant incorporation. Powders treated at 950°C had particles more than one order of magnitude finer (0.1–0.2 μm) and a systematic lowering of the c/a ratio in comparison to the samples annealed at higher temperature was observed. Comparison of the experimental variations of the unit cell edge of cubic BaTiO3 (250°C) with the results of atomistic computer simulations gives indication on the preferential incorporation site of the dopant. In particular, La3+ and Pr3+ prefer to substitute at the Ba site, whereas Tb3+ and Gd3+ give partial substitution at the Ti site. For Er3+ and Y3+ preferential substitution at the Ti site is predicted. For transition metal ions, substitution at the Ti site with oxygen vacancy compensation is confirmed, although their behaviour is less accurately reproduced.

Ferroelectric properties of dense nanocrystalline BaTiO3 ceramics

Dense BaTiO3 ceramics with 50?nm average grain size obtained by spark plasma sintering were investigated. The dielectric data show a broad ferro?para phase transition with a maximum permittivity of at 390?K and 1?kHz. The local ferroelectric switching behaviour was investigated by piezoresponse force microscopy. Typical piezoelectric hysteresis loops were recorded at different positions of the sample. The present results provide experimental evidence for polarization switching at the local scale, indicating that the critical grain size for the disappearance of ferroelectric behaviour in dense, bulk BaTiO3 nanocrystalline ceramics is below 50?nm.

Functional properties of BaTiO3–Ni0.5Zn0.5Fe2O4 magnetoelectric ceramics prepared from powders with core-shell structure

In the present work, diphasic ceramic composites with core-shell nanostructures formed by Ni0.50Zn0.50Fe2O4 core and BaTiO3 shell were investigated. Their properties were compared with those of composites prepared by coprecipitation. The core-shell structure was confirmed by microstructural powder analysis. Homogeneous microstructures with a good phase mixing and percolated dielectric phase by the magnetic one were obtained from coprecipitated powders. Less homogeneous microstructures resulted in ceramics produced from the powder prepared by core-shell method, with isolated small ferrite grains besides large ferrite aggregates embedded into the BaTiO3 matrix. Both the ferroelectric and magnetic phases preserve their basic properties in bulk composite form. However, important differences in the dielectric relaxation and conduction mechanisms were found as result of the microstructural difference. Extrinsic contributions play important roles in modifying the electric properties in both ceramics, causing spa...

Barium perovskites as humidity sensing materials

The response to humidity of porous ceramics with composition BaMO3, with M=Ti, Zr, Hf or Sn, was studied. Samples were obtained by cold isostatic pressing and sintering of fine powders prepared by wet chemical synthesis. Sensitivity and response time have been obtained by electrical impedance measurements realised in different conditions of relative humidity (R.H.) at 25 � C. An increase of both capacitance and conductivity with humidity was observed in all samples with open porosity. Sensitivity increased with R.H. and decreased with frequency, indicating a major contribution from the surface of crystals exposed to water vapour, particularly in BaTiO3 where 4000% change in permittivity was registered over the range 20–80% R.H. Time response was in the typical range of capacitive humidity sensors, with fast (10–100 s) equilibration time for intermediate values of R.H. # 2001 Elsevier Science Ltd. All rights reserved.

Grain size effect on the nonlinear dielectric properties of barium titanate ceramics

The nonlinear dielectric properties of dense BaTiO3 ceramics with grain size of 1 μm–90 nm were investigated. In the finest ceramics, the permittivity reduces below 1000 and a remarkable nonhysteretic linear dc-tunability [e(E)] is obtained at high field, above 40 kV/cm. The observed behavior was explained by considering the nanostructured ceramic as a composite formed by ferroelectric grains, whose nonlinearity is reducing, and by low-permittivity nonferroelectric grain boundaries, whose volume fraction increases when decreasing the grain size. Reducing the grain size in ferroelectric dense materials is an alternative route to accomplish the application requirements: nonhysteretic tunability and permittivity below 1000.

Reaction sintering of aluminium titanate: I—Effect of MgO addition

Abstract The effect of 2 wt% MgO addition on the reactive sintering of Al 2 TiO 5 was studied starting from commercially available alumina and rutile powders. The formation of titanate, the successive sintering process and the corresponding microstructure evolution have been investigated using differential dilatometry, X-ray powder diffraction and scanning electron microscopy. For pure Al 2 TiO 5 the reaction occurs initially by a nucleation and rapid growth process and, afterwards, by the slow conversion of unreacted oxide particles by solid-state diffusion. The addition of MgO changes the mechanism of titanate formation, probably by making easy the nucleation of the new phase through the intermediate formation of MgAl 2 O 4 , followed by the growth of a Mgrich solid solution. The main result is a strong reduction of the average grain size and remarkable increase of the density of the final material.

Intrinsic/extrinsic interplay contributions to the functional properties of ferroelectric-magnetic composites

Recent literature data about the preparation and the functional properties of two-phase ceramic composites comprising of a ferroelectric perovskite and a magnetic ferrite are presented and critically compared, together with new results found in BaTiO3–(Ni,Zn)Fe2O4 composites. The phase assemblage and the spontaneous strain of the ferroelectric perovskite, the microstructural aspects and the phase percolation problem, the functional properties (resistivity, magnetic, dielectric, ferroelectric and magnetoelectric coupling) and the use of effective field models for predicting the permittivity and permeability of these composites are discussed in detail.

Second-harmonic generation of single BaTiO3 nanoparticles down to 22 nm diameter.

We investigate the second-harmonic generation (SHG) signal from single BaTiO3 nanoparticles of diameters varying from 70 nm down to 22 nm with a far-field optical microscope coupled to an infrared femtosecond laser. An atomic force microscope is first used to localize the individual particles and to accurately determine their sizes. Power and polarization-dependent measurements on the individual nanoparticles reveal a diameter range between 30 and 20 nm, where deviations from bulk nonlinear optical properties occur. For 22 nm diameter particles, the tetragonal crystal structure is not applicable anymore and competing effects due to the surface to volume ratio or crystallographic modifications are taking place. The demonstration of SHG from such small nanoparticles opens up the possibilities of using them as bright coherent biomarkers. Moreover, our work shows that measuring the SHG of individual nanoparticles reveals critical material properties, opening up new possibilities to investigate ferroelectricity at the nanoscale.

Reactive growth of niobium silicides in bulk diffusion couples

Abstract The diffusion-controlled growth of niobium silicides (NbSi 2 and Nb 5 Si 3 ) was studied in Nb/Si and Nb/NbSi 2 bulk diffusion couples annealed at 1200–1350 °C for 2–24 h. Both compounds were found to grow as parallel layers, according to the parabolic rate law. The concept of the integrated diffusion coefficient is used to describe the growth kinetics of the two silicides. The corresponding activation energy is 263 kJ/mol for Nb 5 Si 3 and 304 kJ/mol for NbSi 2 . The activation energy (in eV) scales as 0.98 T m (K)/1000 for Nb 5 Si 3 and as 1.4 T m (K)/1000 for NbSi 2 in agreement with the general behavior observed for many transition metal silicides. The position of the Kirkendall plane inside the Nb 5 Si 3 layer developed in Nb/NbSi 2 couples indicates that, in the present temperature range, the diffusion of Si in Nb 5 Si 3 is considerably faster than that of Nb.

Average and local atomic-scale structure in BaZrxTi1?xO3 (x = 0.10, 0.20, 0.40) ceramics by high-energy x-ray diffraction and Raman spectroscopy

High-resolution x-ray diffraction (XRD), Raman spectroscopy and total scattering XRD coupled to atomic pair distribution function (PDF) analysis studies of the atomic-scale structure of archetypal BaZrxTi(1-x)O3 (x = 0.10, 0.20, 0.40) ceramics are presented over a wide temperature range (100-450 K). For x = 0.1 and 0.2 the results reveal, well above the Curie temperature, the presence of Ti-rich polar clusters which are precursors of a long-range ferroelectric order observed below TC. Polar nanoregions (PNRs) and relaxor behaviour are observed over the whole temperature range for x = 0.4. Irrespective of ceramic composition, the polar clusters are due to locally correlated off-centre displacement of Zr/Ti cations compatible with local rhombohedral symmetry. Formation of Zr-rich clusters is indicated by Raman spectroscopy for all compositions. Considering the isovalent substitution of Ti with Zr in BaZrxTi1-xO3, the mechanism of formation and growth of the PNRs is not due to charge ordering and random fields, but rather to a reduction of the local strain promoted by the large difference in ion size between Zr(4+) and Ti(4+). As a result, non-polar or weakly polar Zr-rich clusters and polar Ti-rich clusters are randomly distributed in a paraelectric lattice and the long-range ferroelectric order is disrupted with increasing Zr concentration.