SUPERFACT: A Model Fuel for Studying the Evolution of the Microstructure of Spent Nuclear Fuel during Storage/Disposal.

The transmutation of minor actinides (in particular, Np and Am), which are among the main contributors to spent fuel α-radiotoxicity, was studied in the SUPERFACT irradiation. Several types of transmutation UO2-based fuels were produced, differing by their minor actinide content (241Am, 237Np, Pu), and irradiated in the Phénix fast reactor. Due to the high content in rather short-lived alpha-decaying actinides, both the archive, but also the irradiated fuels, cumulated an alpha dose during a laboratory time scale, which is comparable to that of standard LWR fuels during centuries/millenaries of storage. Transmission Electron Microscopy was performed to assess the evolution of the microstructure of the SUPERFACT archive and irradiated fuel. This was compared to conventional irradiated spent fuel (i.e., after years of storage) and to other 238Pu-doped UO2 for which the equivalent storage time would span over centuries. It could be shown that the microstructure of these fluorites does not degrade significantly from low to very high alpha-damage doses, and that helium bubbles precipitate.

Effect of Temperature, Precursor Type and Dripping Time on the Crystallite Size of Nano ZnO Obtained by One-Pot Synthesis: 2k Full Factorial Design Analysis.

The aim of this work was to determine the effect of temperature, precursor and dripping time on the crystallite size of ZnO nanoparticles synthesized by controlled precipitation according a 2k full factorial design. ZnCl2, Zn(NO3)2 and NaOH were used as precursors. After synthesis, the nano crystalline powder was characterized by XRD (Cu Kα), UV-Vis, and HR-TEM. The nano ZnO particles presented a crystallite size between 210 and 260 Å (HR-TEM and XRD). The results show that the crystallite size depends on the type of precursor and temperature of synthesis, but not on the dripping time.

Potentiodynamic study of Al-Mg alloy with superhydrophobic coating in photobiologically active/not active natural seawater.

Superhydrophobic coating technology is regarded as an attractive possibility for the protection of materials in a sea environment. DC techniques are a useful tool to characterize metals' behavior in seawater in the presence/absence of coatings and/or corrosion inhibitors. In this work, investigations concerning Al-5%Mg alloy with and without a sprayed superhydrophobic coating were carried out with potentiodynamic scans in photobiologically active and not active seawater (3 weeks of immersion). In not photobiologically active seawater, the presence of the superhydrophobic coating did not prevent pitting corrosion. With time, the coating underwent local exfoliations, but intact areas still preserved superhydrophobicity. In photobiologically active seawater, on samples without the superhydrophobic coating (controls) pitting was inhibited, probably due to the adsorption of organic compounds produced by the photobiological activity. After 3 weeks of immersion, the surface of the coating became hydrophilic due to diatom coverage. As suggested by intermediate observations, the surface below the diatom layer is suspected of having lost its superhydrophobicity due to early stages of biofouling processes (organic molecule adsorption and diatom attachment/gliding). Polarization curves also revealed that the metal below the coating underwent corrosion inhibiting phenomena as observed in controls, likely due to the permeation of organic molecules through the coating. Hence, the initial biofouling stages (days) occurring in photobiologically active seawater can both accelerate the loss of superhydrophobicity of coatings and promote corrosion inhibition on the underlying metal. Finally, time durability of superhydrophobic surfaces in real seawater still remains the main challenge for applications, where the early stages of immersion are demonstrated to be of crucial importance.

Growth and characterization of SiGeSn quantum well photodiodes.

We report on the fabrication and electro-optical characterization of SiGeSn multi-quantum well PIN diodes. Two types of PIN diodes, in which two and four quantum wells with well and barrier thicknesses of 10 nm each are sandwiched between B- and Sb-doped Ge-regions, were fabricated as single-mesa devices, using a low-temperature fabrication process. We discuss measurements of the diode characteristics, optical responsivity and room-temperature electroluminescence and compare with theoretical predictions from band structure calculations.

Superhydrophobic surfaces for applications in seawater.

OBJECTIVE: Technological fields in which seawater is implied are numerorus, working in seawater (shipping, oil industry, marine aquaculture,..), and exploiting seawater in plants (cooling heat-exchange, desalination, power plants,..). All suffer from detrimental effects induced by biofouling mainly enhancing material failures and limiting energetic efficiencies. Among the remediation solutions, technologies coniugating economical, green and efficiency criteria should represent the direction. With the aim to meet these criteria, superhydrophobic (SH) technology attracted many researches for the protection of materials operating in contact with seawater. METHOD: In this work, the literature focusing on such technology for the protection of surfaces in contact with seawater has been reviewed, mainly focusing on boat and ship hull protection. RESULTS: Despite the growing interest around SH technology in seawater for fouling control and friction drag reduction of hulls, to date literature shows that superhydrophobicity in seawater is still limited if compared with a time window compatible with technological needs (set on years). An evaluation of the causes of early superhydrophobicity loss under operative conditions clearly indicates that, to the best of present knowledge, a SH surface cannot preserve this feature by itself alone (especially in real seawater). Hence, we have considered to highlight the behaviour of SH surfaces in seawater in relation to early stages of biocolonization (conditioning film and pioneering bioslime formation). Considering the annual costs sustained for the biofouling impact control, advantages coming from SH surfaces, in terms of foul control and friction drag reduction, would allow economical savings allowing to cover both the appliance of longevity keeping strategies of the SH surfaces and investments in green technologies of SH coating life cycle (production, storing). In addition a brief outlook is provided on technological fields exploiting seawater in pipelines (power and desalination plants), where the SH surface finishing finds potentially interesting application for fouling and corrosion prevention applications.

Surfactant induced complex formation and their effects on the interfacial properties of seawater.

The effect of a cationic surfactant, hexadecyltrimethylammonium bromide (CTAB), on the interfacial properties of seawater has been studied by dynamic and equilibrium surface tension and by dilational rheology essays. Important modifications of the surface tension and dilational rheology response have been observed already at the very low CTAB concentrations, where the effects due to the high ionic strength are negligible. The comparison with the effects of CTAB in different seawater models, or in natural seawater fractions, points out the establishment of strong interactions between the surfactant molecules and the lipophilic fraction of organic material dispersed/dissolved in seawater, affecting the interfacial activity of the molecules. Considering the biochemical richness of seawater, these results can be explained assuming interaction mechanisms and adsorption schemes similar to those speculated for protein and other macromolecules in the presence of surfactants, which in fact show similar features. Thus already at the low concentrations the surfactant molecules form highly surface-active complexes with part of the organic fraction of seawater. At the larger surfactant concentrations these complexes compete for adsorption with an excess of free CTAB molecules which, according to the thermodynamic conditions, are most favoured to occupy the liquid interface. The results of this study underline the important role of the sea organic content in enhancing the surface-activity of surfactants, which is relevant for a deeper understand of the direct and indirect effects of these types of pollutants on the physico-chemical environment in the sea coastal areas and develop mitigation strategies.

Applying cathodically polarised substrata to the restoration of a high value coral.

Larval settlement of the high value red coral, Corallium rubrum, was studied on three different CaCO(3) substrata, viz. lithogenic (marble), electro-accreted calcium carbonate in the presence and in the absence of cathodic polarisation. The last two substrata consisted of stainless steel plates galvanically coupled with Zn anodes. The electrochemical characterization of the settlement device was studied in order to investigate correlations between cathodic parameters (polarisation potential, current density, calcareous deposit composition) and larval settlement. The results obtained in the natural habitat (at 35 m depth) showed that settlement was five times lower on the electro-accreted aragonite in the presence of low cathodic current densities (i≤1 µA cm(-2)) compared to both marble tiles and electro-accreted aragonite in the absence of polarisation. These last two substrata showed similar settlement values. The implications of these findings on restoration strategies for C. rubrum are discussed.

Evidence of enzymatic catalysis of oxygen reduction on stainless steels under marine biofilm.

Cathodic current trends on stainless steel samples with different surface percentages covered by biofilm and potentiostatically polarized in natural seawater were studied under oxygen concentration changes, temperature increases, and additions of enzymic inhibitors to the solution. The results showed that on each surface fraction covered by biofilm the oxygen reduction kinetics resembled a reaction catalyzed by an immobilised enzyme with high oxygen affinity (apparent Michaelis-Menten dissociation constant close to K(O(2))(M)  ≈ 10 µM) and low activation energy (W ≈ 20 KJ mole(-1)). The proposed enzyme rapidly degraded when the temperature was increased above the ambient (half-life time of ∼1 day at 25°C, and of a few minutes at 50°C). Furthermore, when reversible enzymic inhibitors (eg sodium azide and cyanide) were added, the cathodic current induced by biofilm growth was inhibited.

Self-organized Ce(1-x)Gd(x)O(2-y) nanowire networks with very fast coarsening driven by attractive elastic interactions.

Assembling arrays of ordered nanowires is a key objective for many of their potential applications. However, a lack of understanding and control of the nanowires' growth mechanisms limits their thorough development. In this work, an appealing new path towards self-organized epitaxial nanowire networks produced by high-throughput solution methods is reported. Two requisites are identified to generate the nanowires: a thermodynamic driving force for an unrestricted elongated equilibrium island shape, and a very fast effective coarsening rate. These requirements are met in anisotropically strained Ce(1-x)Gd(x)O(2-y) nanowires with the (011) orientation grown on the (001) surface of LaAlO(3) substrates. Nanowires with aspect ratios above ≈100 oriented along two mutually orthogonal axes are obtained leading to labyrinthine networks. A very fast effective nanowire growth rate (≈60 nm min(-1)) for ex-situ thermally annealed nanostructures derives from simultaneous kinetic processes occurring in a branched network. Ostwald ripening and anisotropic dynamic coalescence, both promoted by strain-driven attractive nanowire interaction, and rapid recrystallization, enabled by fast atomic diffusion associated with a high concentration of oxygen vacancies, contribute to such an effective growth rate. This bottom-up approach to self-organized nanowire growth has a wide potential for many materials and functionalities.

Electrochemical activity and bacterial diversity of natural marine biofilm in laboratory closed-systems.

Even if a widely shared mechanism actually does not exist, it is now generally accepted that, in aerobic conditions, marine electrochemically active biofilms (MEABs) induce faster oxygen reduction on stainless steel immersed in seawater. This phenomenon has been widely studied, but nearly all the experiments found in literature have been conducted in open-systems (i.e. experimental environments where seawater is constantly renewed). In this work we tried to obtain, in open circuit and potentiostatic conditions, MEABs in different laboratory closed-systems without water renewal (mesocosms), in order to verify the relationship between electrochemical activity and biofilm composition. The diversity of the microbial populations of biofilms obtained by our new kind of approach was examined by the DGGE technique (denaturing gradient gel electrophoresis). MEABs were obtained in all the mesocosms from 2000 to 2 L, showing in some cases electrochemical performances comparable to those of open-systems, and a very high genetic variability. Our DGGE results underline the difficulty in finding a correlation between electrochemical activity and composition of microbial populations.