Thermodynamic aspects of ion intercalation in KhFek[Fe(CN)(6)](l)center dot mH(2)O compounds: Application to the Everit's salt/Prussian Blue transition

The K+ reversible processes for ion exchange in KhFek[Fe(CN)(6)](l)center dot mH(2)O host compounds (Prussian Blue) were thermodynamically analyzed. A thermodynamic approach was established and developed based on the consideration of a lattice-gas model where the electronic contribution to the chemical potential is neglected and the ion-host interaction is not considered. The occupation fraction of the intercalation process was calculated from the kinetic parameters obtained through ac-electrogravimetry in a previous paper. In this way, the mass potential transfer function introduces a new way to evaluate the thermodynamic aspect of intercalation. Finally, based on the thermodynamic approach, the energy used to put each K+ ion into the host material was calculated. The values were shown to be in good agreement with the values obtained through transient techniques, for example, cyclic voltammetry. As a result, this agreement between theory and experimental data validates the thermodynamic approach considered here, and for the first time, the thermodynamic aspects of insertion were considered for mixed valence materials.

Structural and Electronic Properties of Lithiated SnO2. A Periodic DFT Study

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

PLA and Organoclays Nanocomposites: Degradation Process and Evaluation of ecotoxicity Using Allium cepa as Test Organism

In this study, nanocomposites of PLA and organoclays Cloisite 20A and Cloisite 30B were prepared by the melt intercalation method and the obtained samples were characterized by transmission electron microscopy (TEM). Since composting is an important proposal to the final disposal of biopolymers, the influence of clays on the hydrolytic degradation process of PLA was evaluated by visual analysis and monitoring of molecular weight after periods of 15 and 30 days of degradation in compost. After degradation of the materials in composting environment, the evaluation of cytotoxic, genotoxic and mutagenic effects of compost aqueous extract was carried out using a bioassay with Allium cepa as test organism. The TEM micrographs permitted the observation of different levels of dispersion, including exfoliated regions. In the evaluation of hydrolytic degradation it was noted that the presence of organoclays can decrease the rate of degradation possibly due to the barrier effect of clay layers and/or the higher degree of crystallinity in the nanocomposite samples. Nevertheless, even in the case of nanocomposites, the molecular weight reduction was significant, indicating that the composting process is favorable to the chain scission of PLA in studied materials. In the analysis performed by the bioassay using A. cepa as test organism, it was found that after degradation of the PLA and its nanocomposites the aqueous extract of compost samples induced a decreasing in the mitotic index and an increasing in the induction of chromosomal abnormalities. These results were statistically significant in relation to the negative control (distilled water). By comparing the results obtained for the nanocomposites in relative to pure polymer, there were no statistically significant differences. The types of the observed chromosomal aberrations indicated a possible genotoxic effect of the materials, which may be related to an aneugenic action of PLA degradation products. © 2013 Springer Science+Business Media New York.