We report on the effect of grain size on the ionic conductivity of yttria-stabilized zirconia samples synthesized by ball milling. Complex impedance measurements, as a function of temperature and frequency are performed on 10$\hskip0.3em${}mol\,% yttria-stabilized zirconia nanocrystalline samples with grain sizes ranging from 900 to 17 nm. Bulk ionic conductivity decreases dramatically for grain sizes below 100 nm, although its activation energy is essentially independent of grain size. The results are interpreted in terms of a space-charge layer resulting from segregation of mobile oxygen vacancies to the grain-boundary core. The thickness of this space-charge layer formed at the grain boundaries is on the order of 1 nm for large micron-sized grains but extends up to 7 nm when decreasing the grain size down to 17 nm. This gives rise to oxygen vacancies depletion over a large volume fraction of the grain and consequently to a significant decrease in oxide-ion conductivity.

The presence of organic ligands on the surface of colloidal nanoparticles strongly limits their performance in technological applications where charge carrier transfer/transport plays an important role. We use metal salts, matched with the nanoparticle composition, to eliminate the surface organic ligands without introducing extrinsic impurities in the final nanomaterial. The potential of the simple, general and scalable processes presented here is demonstrated by characterizing the thermoelectric properties of nanostructured Ag₂Te produced by the bottom up assembly of Ag₂Te nanocrystals. A 6-fold increase of the thermoelectric figure of merit of Ag₂Te was obtained when organic ligands were displaced by AgNO₃. The same procedure can enhance the performance of nanocrystals and nanocrystal-based devices in a broad range of applications, from photovoltaics and thermoelectrics to catalysis.

Material Extrusion Additive Manufacturing (MEAM) is a novel technology to produce polymeric, metallic, and ceramic complex components. Filaments composed of a high-volume content of metal powder and a suitable binder system are needed to obtain metallic parts. Thermal and energetic controversies do not affect MEAM technology, although common in other additive manufacturing (AM) techniques. High thermal conductivity and reflectivity of copper to high-energy beams are the most challenging properties. A material extrusion technique to produce high density and quality copper parts is deeply studied in this research. Characterization of the filament, printed parts, brown parts and final sintered parts is provided. The sintering stage is evaluated through density analysis of the sintered copper parts, as well as their dimensional accuracy after part shrinkage inherent to the sintering process. The mechanical behavior of sintered parts is assessed through tensile, hardness and impact toughness tests. In addition, the measured electrical and thermal conductivities are compared to those obtained by other AM technologies. High-density components, with 95% of relative density, were successfully manufactured using MEAM technology. Similar or even superior mechanical, thermal and electrical properties than those achieved by other 3D printing processes such as Electron Beam Melting, Selective Laser Melting and Binder Jetting were obtained.

The blocking of ion transport at interfaces strongly limits the performance of electrochemical nanodevices for energy applications. The barrier is believed to arise from space-charge regions generated by mobile ions by analogy to semiconductor junctions. Here we show that something different is at play by studying ion transport in a bicrystal of yttria (9% mol) stabilized zirconia (YSZ), an emblematic oxide ion conductor. Aberration-corrected scanning transmission electron microscopy (STEM) provides structure and composition at atomic resolution, with the sensitivity to directly reveal the oxygen ion profile. We find that Y segregates to the grain boundary at Zr sites, together with a depletion of oxygen that is confined to a small length scale of around 0.5 nm. Contrary to the main thesis of the space-charge model, there exists no evidence of a long-range O vacancy depletion layer. Combining ion transport measurements across a single grain boundary by nanoscale electrochemical strain microscopy (ESM), broadband dielectric spectroscopy measurements and density functional calculations, we show that grain-boundary-induced electronic states act as acceptors, resulting in a negatively charged core. Besides the possible effect of the modified chemical bonding, this negative charge gives rise to an additional barrier for ion transport at the grain boundary.