Recognition of kinetic transient process in corrosion scales of fuel elements by impedance spectroscopy

The presented study concerns with the corrosion kinetics of two zirconium alloys: Zr-Nb-Sn-Fe and Zr-Nb-Fe. Alloy samples were pre-exposed at 360 °C in a LiOH solution containing 70 mg/l of lithium ions. Ex-situ electrochemical impedance spectroscopy (EIS) performed in 0.5 M potassium sulphate solution at 25 °C was used to study the properties of the oxide and kinetic transient effect. Evaluation of the impedance spectroscopy data was based on application of a simple equivalent circuit. The setup of the equivalent circuit conformed to Jonscher´s universal law of dielectric response. The analysis of the impedance data was aimed at estimation of non-dispersive capacitance of the oxide formed during the pre-exposure. Effective values of dielectric constant were calculated using the non-dispersive capacitance and the oxide thickness values, calculated from weight gains. For the pre-transient samples relatively higher values of dielectric constants were obtained. Typical pre-transient dielectric constants for Zr-Nb-Sn-Fe alloy ranged between 20–21, while slightly lower values were obtained for Zr-Nb-Fe alloy. In both alloys steep and significant decrease in effective dielectric constant (e_ef = 9–13) was found for the transient samples. The decrease correlated very well with the drop in percentage of tetragonal oxide determined by Raman spectroscopy and corresponded to the increase of the weight gains of the transient samples. Literature data indicate values of dielectric constants for tetragonal zirconium oxide between 38–46, while those for monoclinic oxide are usually presented between 12–22. The evidenced changes in dielectric constants are therefore in agreement with the expected decrease of tetragonal phase fraction in the oxide layer during the transient. In the Zr-Nb-Sn-Fe post-transient samples values of dielectric constant increased again to 18–20, therefore almost to the pre-transient level. This increase was not evidenced with Raman spectroscopy data, which show constant low content of the tetragonal fraction. Possible explanation of this disagreement is the location of the newly formed post-transient tetragonal oxide presumably at the metal/oxide interface. Oxide thickness of the post-transi-ent samples is 4–7 m and the oxide/metal interface is beyond access of the laser beam of Raman spectrometer. We can conclude that using ex-situ EIS, the transient was observable in both alloys; the change in the ratio of monoclinic and tetragonal phase can be evaluated based on the difference of effective dielectric constant of the two phases. The Zr-Nb-Sn-Fe alloy showed the onset of the transient after the 105th day of pre-exposure, but the change in the ratio of the monoclinic and tetragonal phases was less significant than in the Zr-Nb-Fe alloy, in which, however, the transient could be observed only after 147 days of pre-exposure. The resulting values of the effective dielectric constant of oxides correlated well with the percentage of tetragonal oxide determined by Raman spectroscopy and with the results of the weight gain method.

Cation–Anionic Interactions of Dyes in Aqueous Solutions: Bromocresol Purple in the Processes of Dissimilar Association

The interaction between single- or double-charged anions of bromocresol purple (BP) and cyanine cations (quinaldine blue, QB, or quinaldine red, QR) at concentrations of dyes 5.0·10−7–4.0·10−5 mol/L has been investigated by vis-spectroscopy. The thermodynamic constants of dissimilar associations (Kas) have been studied. Comparison of the values of lg Kas shows that QB− associates of BP− are more stable (6.61 ± 0.07) than QR associates (4.84 ± 0.06); a similar phenomenon is observed for associates of the BP2− anion. Semi-empirical calculations (PM3 method) are in agreement with the vis-spectroscopy data and indicate that the association of dye into an associate is possible. The standard enthalpies of formation of associates (ΔfHo) and energy diagrams have been determined. The ΔfHo data indicate that the formation of an associate between dye ions is an energetically favourable process. The gain in energy significantly exceeds the systematic error of semi-empirical calculations and increases from 157 kJ/mol (associate ”BP− + QB+”) to 729 kJ/mol (associate “BP2− + QR+”). The most probable structures of dissimilar associates are presented. The study of the dissimilar association develops the concept of intermolecular interactions in solutions.

The Prion Protein Octarepeat Domain Forms Transient β-sheet Structures Upon Residue-Specific Cu(II) and Zn(II) Binding

Misfolding of the cellular prion protein (PrPC) is associated with the development of fatal neurodegenerative diseases called transmissible spongiform encephalopathies (TSEs). Metal ions appear to play a crucial role in the protein misfolding, and metal imbalance may be part of TSE pathologies. PrPC is a combined Cu(II) and Zn(II) metal binding protein, where the main metal binding site is located in the octarepeat (OR) region. Here, we used biophysical methods to characterize Cu(II) and Zn(II) binding to the isolated OR region. Circular dichroism (CD) spectroscopy data suggest that the OR domain binds up to four Cu(II) ions or two Zn(II) ions. Upon metal binding, the OR region seems to adopt a transient antiparallel β-sheet hairpin structure. Fluorescence spectroscopy data indicates that under neutral conditions, the OR region can bind both Cu(II) and Zn(II) ions, whereas under acidic conditions it binds only Cu(II) ions. Molecular dynamics simulations suggest that binding of both metal ions to the OR region results in formation of β-hairpin structures. As formation of β-sheet structures is a first step towards amyloid formation, we propose that high concentrations of either Cu(II) or Zn(II) ions may have a pro-amyloid effect in TSEs.

MEGANE investigations of Phobos and the Small Body Mapping Tool

The MEGANE instrument onboard the MMX mission will acquire gamma-ray and neutron spectroscopy data of Phobos to determine the elemental composition of the martian moon and provide key constraints on its origin. To produce accurate compositional results, the irregular shape of Phobos and its proximity to Mars must be taken into account during the analysis of MEGANE data. The MEGANE team is adapting the Small Body Mapping Tool (SBMT) to handle gamma-ray and neutron spectroscopy investigations, building on the demonstrated record of success of the SBMT being applied to scientific investigations on other spacecraft missions of irregularly shaped bodies. This is the first application of the SBMT to a gamma-ray and neutron spectroscopy dataset, and the native, three-dimensional foundation of the SBMT is well suited to MEGANE’s needs. In addition, the SBMT will enable comparisons between the MEGANE datasets and other datasets of the martian moons, including data from previous spacecraft missions and MMX’s multi-instrument suite.