RESUMO
The microscopic and macroscopic dynamics of calcium alkali nitrate melts are studied in their supercooled regime by means of shear rheology and nuclear magnetic resonance (NMR). The structural relaxation is probed using shear rheology to access the viscoelastic flow as well as using physical aging experiments. By exploiting the strongly quadrupole-perturbed 87Rb nucleus, the local dynamics is probed on the milliseconds to nanoseconds range using various NMR methods involving central-transition stimulated-echo techniques, line shape analyses, spin relaxations, and second-order dynamic shift effects. The time scales monitored via the local Rb probe are in harmony with the electrical conductivity relaxation times. The low-temperature NMR line shapes agree excellently with those predicted by the Czjzek model. The temperature dependent second-order dynamic frequency shift is described using the imaginary part of the spectral density. It is demonstrated how the latter quantity can be generalized to include effects of correlation time distributions.
RESUMO
There is great technological interest in elucidating the effect of particle size on the luminescence efficiency of doped rare earth oxides. This study demonstrates unambiguously that there is a size effect and that it is not dependent on the calcination temperature. The Y2O3:Eu and Gd2O3:Eu particles used in this study were synthesized using wet chemistry to produce particles ranging in size between 7 nm and 326 nm and a commercially available phosphor. These particles were characterized using three excitation methods: UV light at 250 nm wavelength, electron beam at 10 kV, and X-rays generated at 100 kV. Regardless of the excitation source, it was found that with increasing particle diameter there is an increase in emitted light. Furthermore, dense particles emit more light than porous particles. These results can be explained by considering the larger surface area to volume ratio of the smallest particles and increased internal surface area of the pores found in the large particles. For the small particles, the additional surface area hosts adsorbates that lead to non-radiative recombination, and in the porous particles, the pore walls can quench fluorescence. This trend is valid across calcination temperatures and is evident when comparing particles from the same calcination temperature.
RESUMO
Size effects, including the occurrence of superparaelectric phases associated with small scale, are a significant research topic for ferroelectrics. Relevant phenomena have been explored in detail, e.g. for homogeneous, thin ferroelectric films, but the related effects associated with nanoparticles are usually only inferred from their structural properties. In contrast, this paper describes all the steps and concepts necessary for the direct characterization and quantitative assessment of the ferroelectric properties of as-synthesized and as-received nanoparticles. The method adopted uses electrical polarization measurements on polymer matrix composites containing ferroelectric nanoparticles. It is applied to ten different BaTiO3 particle types covering a size range from 10 nm to 0.8 µm. The influence of variations of particle characteristics such as tetragonality and dielectric constant is considered based on measurements of these properties. For composites containing different particle types a clearly differing polarization behaviour is found. For decreasing particle size, increasing electric field is required to achieve a given level of polarization. The size dependence of a measure related to the coercive field revealed by this work is qualitatively in line with the state of the knowledge for ferroelectrics having small dimensions. For the first time, such results and size effects are described based on data from experiments on collections of actual nanoparticles.
