The sintering behavior of nanocrystalline ZnO was investigated at only 250 °C. Densification was achieved by the combined effect of uniaxial pressure and the addition of water both in a Field Assisted Sintering Technology/Spark Plasma Sintering apparatus and a warm hand press with a heater holder. The final pure ZnO materials present high densities (> 90 % theoretical density) with nano-grain sizes. By measuring the shrinkage rate as a function of applied stress it was possible to identify the stress exponent related to the densification process. A value larger than one points to non-linear relationship going beyond single solid-state diffusion or liquid phase sintering. Only a low amount of water (1.7 wt.%) was needed since the process is dictated by the adsorption on the surface of the ZnO particles. Part of the adsorbed water dissociates into H + and OH -ions, which diffuse into the ZnO crystal structure, generating grain boundaries/interfaces with high defect chemistry. As characterized by Kelvin Probe Force Microscopy, and supported by impedance spectroscopy, this highly defective grain boundary area presents much higher surface energy than the bulk. This highly defective grain boundary area with high potential reduces the activation energy of the atomic diffusion, leading to sinter the compound at low temperature.

Single crystalline ceria samples with the composition Ce0.9Gd0.1O2-δ were pre-polarized with ±5 V for up to 300 s using a Pt coated AFM tip as working electrode. The direct contact zone had a diameter of < 50 nm. Subsequently, the effect of the polarization on the surface potential of the samples was investigated by mapping the introduced defect gradient and its decay with time using Kelvin probe force microscopy. The generated surface potential gradients were found to have a diameter of up to 1 µm, which is explained by the local ionization of defect associates by the applied high electric field. Measurements were performed at room temperature and 50 °C. The polarization behavior of the Ce0.9Gd0.1O2-δ single crystals was compared to cyclovoltammetry and polarization-relaxation experiments at T ≤ 350°C and in dry air or nitrogen which were performed using a specially suited AFM (Controlled Atmosphere High Temperature Scanning Probe Microscope CAHT-SPM by Semilab).

No abstract