Miguel Algueró

Synthesis and characterization of lead-free 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 ceramic

Polycrystalline sample of lead-free 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 ceramic has been synthesized by solid state reaction method. Single-phase perovskite structure with rhombohedral symmetry was confirmed by x-ray diffraction. Temperature dependent dielectric permittivity studies demonstrated frequency independent behavior, indicating that the studied sample was not a typical relaxor ferroelectric. A polymorphic phase transition between rhombohedral and tetragonal phase was noticed near room temperature followed by a tetragonal to cubic transition with 97 °C as the temperature of maximum permittivity. The macroscopic values of d33 and d31 were ∼350 pC/N and −141 pm/V, whereas the electromechanical coupling factors kp and kt were 44.5% and 41.6%, respectively. Bulk P-E hysteresis loop was obtained with saturation polarization 11 μC/cm2 and coercive field ∼4 kV/cm. Distinct polarization contrast with a complex mosaic-like domain structure was observed in the out-of-plane mode of piezoresponse force m...

Size effect in morphotropic phase boundary Pb(Mg1∕3Nb2∕3)O3–PbTiO3

Phases, domain configuration, and properties of 0.65Pb(Mg1∕3Nb2∕3)O3–0.35PbTiO3 ceramics with grain sizes of 4 and 0.15μm have been studied. The average phase is monoclinic Pm in coexistence with tetragonal. An evolution from micron-sized lamellar domains towards submicron/nanometer sized crosshatched domains is found with the decrease in size, which results in electrical relaxor type behavior and hindered switching. This is proposed to be associated with the slowing down of the relaxor to ferroelectric transition that causes the long time presence of an intermediate domain configuration. Nevertheless, a high sensitivity piezoelectric submicron-structured material is obtained under tailored poling (d33∼300pCN−1).

Macroscopic ferroelectricity and piezoelectricity in nanostructured BiScO3–PbTiO3 ceramics

We have studied the macroscopic electrical properties of highly dense, nanostructured ceramics of BiScO3–PbTiO3 with high Curie temperature and piezoelectric activity. Materials were processed by spark plasma sintering of nanocrystalline powder obtained by mechanosynthesis. Results indicate that the nanostructured material still presents the ferroelectric transition above 700K. Ferroelectric switching is unambiguously demonstrated. Furthermore, ceramic disks were poled and their radial piezoelectric resonance was excited, which has not been achieved in nanostructured BaTiO3 ceramics.

Very high remnant polarization and phase-change electromechanical response of BiFeO3-PbTiO3 at the multiferroic morphotropic phase boundary

We have investigated the occurrence of phase-change functional responses in the BiFeO3-PbTiO3 perovskite solid solution, analogous to those anticipated by a recent first-principles study of BiFeO3-BiCoO3. Like the former system, BiFeO3-PbTiO3 shows a morphotropic phase boundary (MPB) between multiferroic polymorphs of rhombohedral and tetragonal symmetries. MPB BiFeO3-PbTiO3 is a high temperature ferroelectric with the phase transition around 900 K, and a room temperature square-shape hysteresis loop with remnant polarization as high as 62 μC cm−2. Strain under the electric field was studied, and a phase-change response was found. Analogous magnetoelectric effects are expected from the multiferroic nature of this MPB.

Chemistry-Crystallization-Microstructure Relations of Sol-Gel Derived Lanthanum Modified Lead Titanate Thin Films

Lanthanum modified lead titanate thin films have been obtained by the deposition of sol-gel solutions onto platinized (100) silicon substrates. Crystallization of perovskite films was achieved by thermal treatments at 650°C with slow or rapid heatings. Lead oxide excesses were used in the precursor solutions to counterbalance the lead losses produced during the thermal treatment. Rapid heatings and large excesses of lead produce a preferred orientation of the films. These films have more homogeneous and denser microstructures than slow heated films without lead excess.

Piezoelectric PMN-PT ceramics from mechanochemically activated precursors

Piezoelectric Pb(Mg 1/3 Nb 2/3 )O 3 -PbTiO 3 (PMN-PT) ceramics with 0.2 and 0.35 PT have been prepared from mechanochemically activated powders. Pressureless sintering in air and hot pressing were tested. PbZrO 3 packing was necessary to limit lead oxide losses and to avoid the formation of second phases at the surface when temperatures above 1000 °C were used. Ceramics sintered at 1200 °C presented densities of 90% and a grain size of 4 μm. Hot pressed ceramics hardly showed porosity and had submicron (0.1-0.5 μm) grain size, which make the mechanoactivated powders very suitable for templated grain growth matrices. Electrical and electromechanical characterisation was accomplished. The 0.2 PT composition combined relaxor dielectric behaviour with piezoelectricity after poling. The 0.35 PT ceramics presented a first order ferroelectric-paraelectric transition at 171 °C and a complex transverse piezoelectric coefficient of -(181.8-13.6) pC N -1 at room temperature.

Broadband dielectric spectroscopy of phonons and polar nanoclusters in PbMg 1 / 3 Nb 2 / 3 O 3 − 35 % PbTiO 3 ceramics: Grain size effects

Dielectric response e*(f,T) and polar phonon spectra of coarse grain (grain size ~ 4 mkm) and fine grain (grain size ~ 150 nm) ceramics of PbMg_(1/3)Nb_(2/3)O3-35%PbTiO3 were investigated at temperatures 10 - 900 K. e*(f,T) in coarse-grain ceramics exhibits relaxor behavior at high temperatures and a sharp anomaly at the ferroelectric phase transition. The fine-grain ceramics exhibit mainly relaxor ferroelectric behavior with a smaller dielectric constant. The difference is explained by different relaxational dynamics of polar nanoclusters, which appear to be more stabilized at high temperatures in the fine-grain ceramics by pinning at grain boundaries. Below Tc, the growth of ferroelectric domains is suppressed in fine-grain ceramics as supported also by a second harmonic generation. On the other hand, polar phonon frequencies and their temperature dependences are almost independent of the grain size, but the selection rules for the cubic symmetry are not obeyed and all phonons are split due to a locally broken symmetry by polar nanoregions and chemical disorder. The lowest-frequency polar phonon undergoes partial softening down to ~ 0.1 THz near Tc = 440 K in both ceramics, but the dielectric anomaly is caused predominantly by flipping and breathing of polar nanoclusters. Due to contribution of both the soft phonon mode and dielectric relaxations into the dielectric constant, the ferroelectric phase transition, which corresponds to the percolation threshold of the polar nanoregions into macroscopic domains, can be considered as a special case of crossover between the displacive and order-disorder type.

Rayleigh type behavior of the Young's modulus of unpoled ferroelectric ceramics and its dependence on temperature

The dependence on stress of the low frequency Youngs modulus and mechanical losses of unpoled ferroelectric ceramics has been studied as a function of temperature. The Youngs modulus of unpoled Pb(Zr,Ti)O3 (PZT) showed a Rayleigh type dependence, analogous to the one already described for the longitudinal piezoelectric coefficient. This has been associated to ferroelectric/ferroelastic domain wall movements across, and their pinning/depinning on, randomly distributed defects. The Rayleigh coefficient was found to increase with temperature. The activation energy of the Rayleigh process was obtained, which must be related to the pinning energy. The Youngs modulus of Mn doped 0.65Pb(Mg1/3Nb2/3)O3–0.35PbTiO3 showed no stress dependence.

High-field electromechanical response of Bi0.5Na0.5TiO3?Bi0.5K0.5TiO3 across its morphotropic phase boundary

Lead-free (1 − x)Bi0.5Na0.5TiO3–xBi0.5K0.5TiO3 [(BNKTx); x = 0.18, 0.20, 0.22, 0.24] piezoelectric ceramics were prepared via conventional solid-state reactions. Phase characterization using x-ray diffraction showed coexistence of perovskite rhombohedral and tetragonal polymorphs as anticipated for compositions across the morphotropic phase boundary (MPB). Electrical and electromechanical properties were studied as a function of x. Permittivity and polarization figures were comparable to the best values previously reported. Largest piezoelectric and high field electromechanical responses were obtained for BNKT0.20 samples, considered to have optimum MPB phases. This material exhibited giant field-induced strains of 0.13% and 0.38% under electric fields of 1 and 2.4 kV mm−1 at room temperature by a phase-change mechanism. Figures are comparable to those reported for other BNT-based systems, but under significantly lower driving fields, which is a clear advantage for actuation.

Monoclinic morphotropic phase and grain size-induced polarization rotation in Pb(Mg1∕3Nb2∕3)O3–PbTiO3

A detailed Rietveld analysis of x-ray data, collected at room temperature, was done on ceramics with controlled grain size between 100nm and 4μm for (PbMg1∕3Nb2∕3O3)0.80–(PbTiO3)0.20 (PMN-PT20), i.e., a compound at the border of the so-called morphotropic phase boundary. With size reduction the polarization rotates within the monoclinic plane from MB, i.e., Px=Py>Pz to MA, i.e., Px=Py<Pz, and finally reaches a rhombohedral phase, i.e., Px=Py=Pz, below a critical value of ∼200nm without diminishing the amplitude of the polarization. This study provides an easy way to tailor the direction of polarization of these materials.