Mössbauer and infrared spectroscopic studies of novel mixed valence states in cobaltous ferrocyanides and ferricyanides

Novel mixed valence states have been obtained by the treatment of cobaltous ferrocyanides (Co⁺²Fe^II) and ferricyanides (Co⁺²Fe^III) in an ozone flow. The CN stretching bands occur at 2085 cm^–1 for Co⁺²Fe^II and at 2160 cm^–1 for Co⁺²Fe^III. After the ozonization process of Co⁺²Fe^II, an intense band approximately at 2125 cm^–1 is detected. This intermediate band must correspond to a mixed valence state of the type: Fe^II–CN–Co²⁺–NC–Fe^III Mössbauer spectra recorded in situ during the ozonization of Co⁺²Fe^II show the presence of two components: a doublet with isomer shift and quadrupole splitting values close to the cobalti ferricyanide and a very broad line for the mixed valence state. From the Mössbauer and infrared spectra of the aged samples of the Co⁺²Fe^II after ozonization, a relaxation process to the initial state of the samples is observed but the mixed valence state is stable.     

Corrosion behavior in artificial seawater of thermal-sprayed WC-CoCr coatings on mild steel by electrochemical impedance spectroscopy

The corrosion behavior in artificial seawater of different as-sprayed ceramic-metallic (cermet) coatings applied on low-alloy steel was studied. Five conditions, associated to modifications of the composition of the powder or deposition parameters were evaluated. The degradation mechanisms were studied during extended immersion tests using conventional electrochemical measurement and electrochemical impedance spectroscopy. The extended immersion tests reveal that these as-thermal-sprayed coatings present a cathodic behavior compared with steel. During the first hours of immersion, the electrolyte infiltrates the defects of the coatings, which then result to the local degradation of the substrate accelerated by the galvanic coupling with the cermet coating. Optical observations and Raman analyses reveal the formation of calcium carbonates like aragonite on the cermet surface, very close to the appearance of local anodic sites. The cross-sectioned views reveal the infiltration of the corrosive solution, and the depth penetration of the degradation of steel substrate probably due to the acidification of the anodic sites.     

Holographic moiré in real time

The body of knowledge necessary to observe holographic-moiré patterns in real time is introduced. The basic factors influencing fringe visibility in holographic moiré are analyzed and expressions to evaluate fringe visibility for any given displacement and deformation are given. The application of the introduced theory in the case of real-time observation is discussed. It is shown that the maximum benefits of this technique are achieved by combining it with closed-circuit TV. Several examples of application are given.