Papers by Author: Carmen Galassi

Abstract: Bilayer thick films of sacrificial titanium dioxide and Nb-doped lead zirconate titanate (PZTN) have been deposited on bare silicon wafers using electrophoretic deposition (EPD) technique. Deposition of such ceramic particles, dispersed ethanol-based suspensions, on semiconductor substrate has been made possible after preparation of alloyed junctions Al/Si characterized by ohmic behaviour. Sintering of green TiO₂/PZTN films was performed at 900 °C for 1 h. The composition of the films, the thickness and relative density of the deposited materials have been analysed by EDS-SEM analysis. The lead diffusion through the silicon wafer has been reduced.

Abstract: Submicron-structured (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (BNBT6) dense ceramics, from nanometric powder synthesized by sol gel auto-combustion at 500°C and obtained by hot-pressing (800°C-2h) and subsequent recrystallization at moderate temperature (1000-1050°C-1h), have been studied. In-situ measurements at the shear mode of electromechanical resonance of non-standard thickness-poled shear plates as a function of the temperature show higher depolarization temperature than measurements at the radial mode of thin disks. Shear mode related material coefficients are measurable up to 160°C, being k₁₅≈30% and d₁₅≈250 pC.N^-1 at 130°C. Depolarization is a complex phenomena caused by a ferroelectric (FE) macrodomains thermal randomization and a phase transition from the field-induced FE phase to a relaxor phase. The early stage of such a transition involves a non-negligible piezoelectricity arising most probably by the percolative coexistence of ferroelectric macrodomains in the resonator under the given stress field for each resonance mode.

Abstract: Cobalt ferrite (CoFe₂O₄) and magnetite (Fe₃O₄) nanoparticles suspensions in diethylene glycol were tested as candidate systems for the EPD of CoFe₂O₄ and Fe₃O₄. It was found that despite the high stability and high zeta potential of such suspensions and the occurrence of mass transport at the electrode, they are not viable systems for EPD, due to coagulation failure. However, dilution of both suspensions with ethanol caused film coagulation at electric field between 20 and 60 V cm^-1. Combinations of electric field and DEG volume fraction in ethanol/suspension mixtures that allow EPD to take place are detailed, and a description of the outcome of EPD trials is provided. A qualitative discussion of the causes of film consolidation in the presence of ethanol is presented.

Abstract: Anelastic and dielectric relaxation measurements have been carried out on poled and unpoled samples of the ferroelectric perovskite (Na_0.5Bi_0.5)_1−xBa_xTiO₃ (NBT-xBT), with composition in the range between pure NBT and the morphotropic phase boundary, 0 ≤ x ≤ 0.08. The complex elastic compliance spectra contain clear indications of both the rhombohedral/tetragonal and tetragonal/cubic transitions, allowing the determination of the phase diagram, which is difficult to obtain by diffraction techniques due to the very low distortions in both the tetragonal and rhombohedral phases and to the structural disorder in the Na/Bi sublattice. An extensive study is made for concentrations in the region of the morphotropic boundary (x ∼ 0.06) in order to find possible signatures of monoclinic phase, as for the case of PbZr_1-xTi_xO₃ (PZT). The main features in the anelastic curves are compared with those in the dielectric spectra and are tentatively related to different modes of octahedral rotations and polar cation shifts.

Abstract: Anelastic and dielectric spectroscopy measurements are presented, which, together with previous measurements [1], clarify some controversial aspects of the phase diagram of PbZr_1xTi_xO₃ close to the border with the antiferroelectric (AFE) phase, and at the morphotropic phase boundary (MPB). No evidence is found of a border separating monoclinic (M) from rhombohedral (R) phases, supporting recent structural studies according to which the two phases coexist, with the fraction of M prevailing near the MPB. A large frequency independent softening at the MPB indicates a genuine M phase over only finely twinned R phase. A new phase transition is found in both the anelastic and dielectric spectra at x = 0.1, at a temperature T_IT between the Curie temperature T_C and the boundary T_T to the phases with tilted octahedra. Such a diffuse transition is interpreted as onset of disordered tilts, which finally become ordered below T_T. In this manner, the phase diagram of PZT is rationalised with respect to the common tendency of perovskites to undergo tilting when the mismatch between the cation sizes exceeds a threshold.

Abstract: The perovskite (Na_1/2Bi_1/2)TiO₃ (NBT) undergoes a series of structural and polar transitions starting from the high temperature paraelectric phase: tetragonal paraelectric, tetragonal antiferroelectric, rhombohedral antiferroelectric and finally rhombohedral ferroelectric, according to neutron diffraction and dielectric spectroscopy. In solid solution with BaTiO₃ (BT) the ferroelectric phase changes from rhombohedral to tetragonal, at the so-called morphotropic phase boundary, and the phases at higher temperature become ill-defined, also because of the large lattice disorder induced by the coexistence of differently charged cations in the same sublattice. Combined dielectric and anelastic spectroscopy measurements are presented, which clarify some issues related to the phase transitions in NBT-BT. The influence of Ba substitution on the tetragonal antiferroelectric phase is determined for the first time, and the possibility that a monoclinic phase, although with very short coherence length, exists near the morphotropic phase boundary is discussed in view of a large maximum of the elastic compliance.

Abstract: The rheological behaviour of ceramic suspensions affects the quality of the products and the yield of the processes. Therefore, rheology control is needed to obtain materials with enhanced properties and to reduce energy consumption. The importance of rheology control in slip casting, spray-drying, screen-printing, ink-jet printing, glazing, and so on, either for Quality Control (QC) aims or for system formulation, has been acknowledged from many years. As in these control procedures the determination of the rheological behavior is a critical issue, this work is focused on the assessment of viscosity (flow behavior) and its dependency on time (usually, thixotropic behavior). Most of ceramic factories still use simple and cheap instruments to investigate rheological behaviors (or something related to it). However, the information provided by such instruments is not completely satisfactory. Therefore, optimization of the procedures is important to improve reproducibility and precision. Suggestions about simple tests and protocols applicable to viscometers ordinarily available in ceramic factories are given. Protocols consider besides a precise description of the tests, all other factors that can affect the results, such as the thermo-mechanical history of the samples before testing.

Abstract: Ink-jet printing is becoming a leading technology for traditional ceramics, due to its capacity of reproducing highly resolved and customized images on tile surfaces. Nano-sized inks, produced by the polyol synthesis route, proved to fulfil the printing requirements, tailoring their chemico-physical properties (e.g. viscosity, surface tension) on industrial ink-jet devices, so representing a major breakthrough in the quadrichromy process.