Eng. Cezar GEAMBASU

This work was devoted to the first multi-parametric unitary comparative analysis of a selection of sintered piezoceramic materials synthesised by solid-state reactions, aiming to delineate the most promising biocompatible piezoelectric material, to be further implemented into macro-porous ceramic scaffolds fabricated by 3D printing technologies. The piezoceramics under scrutiny were: KNbO3, LiNbO3, LiTaO3, BaTiO3, Zr-doped BaTiO3, and the (Ba0.85Ca0.15)(Ti0.9Zr0.1)O-3 solid solution (BCTZ). The XRD analysis revealed the high crystallinity of all sintered ceramics, while the best densification was achieved for the BaTiO3-based materials via conventional sintering. Conjunctively, BCTZ yielded the best combination of functional properties-piezoelectric response (in terms of longitudinal piezoelectric constant and planar electromechanical coupling factor) and mechanical and in vitro osteoblast cell compatibility. The selected piezoceramic was further used as a base material for the robocasting fabrication of 3D macro-porous scaffolds (porosity of similar to 50%), which yielded a promising compressive strength of similar to 20 MPa (higher than that of trabecular bone), excellent cell colonization capability, and noteworthy cytocompatibility in osteoblast cell cultures, analogous to the biological control. Thereby, good prospects for the possible development of a new generation of synthetic bone graft substitutes endowed with the piezoelectric effect as a stimulus for the enhancement of osteogenic capacity were settled.

Zr0.8Sn0.2TiO4 powders synthesized by solid state reaction route have been consolidated by conventional and spark plasma sintering methods. Single-phase ceramics with various microstructures and, consequently, different extrinsic absorption were investigated by terahertz time-domain spectroscopy. The results showed that the terahertz spectroscopy can be used for tailoring in the " synthesis - microstructure - properties" cycle.

Zr0.8Sn0.2TiO3 (ZST) powders synthesized by solid-state reaction were subject to processing by spark plasma sintering (SPS). A single-phase ceramic with a high relative density of 95.7% and 99.6% was obtained for sintering temperatures of 1150 degrees C and 1200 degrees C, respectively, and for a dwell time of 3 min. In order to reduce the oxygen vacancies, as-sintered discs were annealed in air at 1000 degrees C. The dielectric loss of the annealed samples, expressed by the Q x f product, measured in the microwave (MW) domain, varied between 35 THz and 50 THz. The intrinsic losses (Q x f ~ 60 THz) were derived by using terahertz time-domain spectroscopy (THz-TDS).

Terahertz time-domain spectroscopy (THz-TDS) was employed for estimation of intrinsic dielectric loss of Zr0.8Sn0.2TiO4 (ZST) ceramics. Single-phase ZST dielectric resonators (DRs) with various synthesis parameters and, consequently, different extrinsic losses, were prepared by conventional ceramic technology. Even though the DRs exhibit a similar microstructure, their quality factor (Q is the inverse of dielectric loss tangent) measured in microwave (MW) domain at 6 GHz varies between 2500 and 8400. On the other hand, it was found that the THz dielectric loss is less sensitive to the sample preparation. The intrinsic losses (Q x f similar to 60 THz) of the ZST ceramics have been derived from THz data.

Solid-state reaction synthesized Zr0.8Sn0.2TiO3 powders have been compacted by spark plasma sintering. In order to reduce the oxygen vacancies, the sintered samples were annealed ex-situ in air. Single-phase ceramics with different amount of oxygen vacancies and, consequently, different extrinsic absorption were investigated by terahertz time-domain spectroscopy. The results showed that the terahertz spectroscopy could be a suitable technique for tailoring the absorption properties of the spark plasma sintered materials.

Low-loss dielectrics with various microstructure and, consequently, different extrinsic losses were investigated by using terahertz time-domain spectroscopy. The losses have been extrapolated and compared with those measured at microwave frequencies. The results showed that extrinsic factors have a considerably contribution in microwave domain. The intrinsic limit of dielectric loss of low absorption polycrystalline materials have been estimated by terahertz spectroscopy.

Zinc silicate ceramics have been prepared by using conventional ceramic technology. Morphological, structural, and dielectric characterizations of the samples were performed using scanning electron microscopy, X-ray diffraction, and terahertz time-domain spectroscopy. The achieved absorption properties of zinc silicates make them very attractive solutions for submillimeter-wave applications.