We report on a heterogeneity study, down to the atomic scale, on a representative multiple-element-modified ceramic based on potassium sodium niobate (KNN): 0.95(Na_0.49K_0.49Li_0.02)(Nb_0.8Ta_0.2)O₃–0.05CaZrO₃ with 2 wt % MnO₂. We show that different routes for incorporating the MnO₂ (either before or after the calcination step) affect the phase composition and finally the functionality of the material. According to X-ray diffraction and scanning electron microscopy analyses, the ceramics consist of orthorhombic and tetragonal perovskite phases together with a small amount of Mn-rich secondary phase. The addition of MnO₂ after the calcination results in better piezoelectric properties, corresponding to a ratio between the orthorhombic and tetragonal perovskite phases that is closer to unity. We also show, using microscopy techniques combined with analytical tools, that Zr-rich, Ta-rich and Mn-rich segregations are present on the nano and atomic levels. With this multi-scale analysis approach, we demonstrate that the functional properties are sensitive to minor modifications in the synthesis route, and consequently to different material properties on all scales. We believe that detecting and learning how to control these modifications will be a step forward in overcoming the irreproducibility problems with KNN-based materials.

Hydraulic calcium silicate-based cements (HCSCs) have become a superior bioceramic alternative to epoxy-based root canal sealers in endodontics. A new generation of purified HCSCs formulations has emerged to address the several drawbacks of original Portland-based mineral trioxide aggregate (MTA). This study was designed to assess the physio-chemical properties of a ProRoot MTA and compare it with newly formulated RS+, a synthetic HCSC, by advanced characterisation techniques that allow for in situ analyses. Visco-elastic behaviour was monitored with rheometry, while phase transformation kinetics were followed by X-ray diffraction (XRD), attenuated total reflectance Fourier transform infrared (ATR-FTIR), and Raman spectroscopies. Scanning electron microscopy with energy-dispersive spectroscopy, SEM-EDS, and laser-diffraction analyses was performed to evaluate the compositional and morphological characteristics of both cements. While the kinetics of surface hydration of both powders, when mixed with water, were comparable, an order of magnitude finer particle size distribution of RS+ coupled with the modified biocompatible formulation proved pivotal in its ability to exert predictable viscous flow during working time, and it was more than two times faster in viscoelastic-to-elastic transition, reflecting improved handling and setting behaviour. Finally, RS+ could be completely transformed into hydration products, i.e., calcium silicate hydrate and calcium hydroxide, within 48 h, while hydration products were not yet detected by XRD in ProRoot MTA and were obviously bound to particulate surface in a thin film. Because of the favourable rheological and faster setting kinetics, synthetic, finer-grained HCSCs, such as RS+, represent a viable option as an alternative to conventional MTA-based HCSCs for endodontic treatments.