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The electrochemical oxidation processes that occur during a voltammetric assay in wine samples lead to the formation of species that obstructs the surface and reduce their active area. This effect is critical for screen printed carbon electrodes (SPCE) and leads to abnormal low values of the total polyphenols content of wines, ca. 72 % lower than those obtained with glassy carbon electrodes. This effect was examined using 10 red and Port wine samples. Mechanical polishing and electrochemical‐based treatments for the removal of this fouling layer were tested. The best results were obtained by electrochemical activation in at a constant potential of 1.2 V during 100 s Na2CO3 saturated solution, and by polishing. The success of some of these treatments brings an added value to SPCE, as it opens the possibility of their reuse in the wine analysis. This outcome is particularly relevant for quality control where a huge number of analysis is performed and the reduction of cost may dictates the choice of the analytical method.  相似文献   
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This work focuses on interstitial solid solutions of hydrogen in the face-centred cubic (fcc) host lattice of palladium and nickel, using a first-principles based approach. Cluster Variation Method (CVM) and Monte Carlo simulation algorithms were especially designed, allowing a coupled use of both techniques, to study hydrogen–vacancy interactions inside an fcc metallic host lattice. First-principles calculations provided the H–Vac interaction energies by structure inversion method. The phase diagrams and thermodynamic properties were computed using only theoretical inputs. The mechanisms leading to the formation of the miscibility gaps observed for both Pd–H and Ni–H systems and the hydrogen ordering on palladium interstitial lattice were reproduced without any empirical term.  相似文献   
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Titanium oxynitride layers were formed by surface laser treatment of Ti plates in air using a Nd:YAG laser source of short pulse duration about 5 ns. The cumulated laser fluence was varied in the 100-1200 J cm−2 range and its influence on the composition and the structure of the formed layers was studied by different characterization techniques providing physico-chemical and structural information. It was shown that the laser treatment induces the insertion of light elements as O, N and C in the formed layer with the amount increasing with the laser fluence. The in-depth composition of the layers and the co-existence of different phases were also studied.The way in which the laser parameters such as fluence affect the insertion of nitrogen and oxygen was discussed in connection with the effects of the plasma plume formed above the target.  相似文献   
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A specific flow rules and the corresponding constitutive elasto-viscoplastic model combined with new experimental strategy are introduced in order to represent a spheroidal graphite cast-iron behaviour on a wide range of strain, strain rate and temperature. A “full model” is first proposed to correctly reproduce the alloy behaviour even for very small strain levels. A “light model” with a bit poorer experimental agreement but a simpler formulation is also proposed. These macroscopic models, whose equations are based on physical phenomena observed at the dislocation scale, are able to cope with the various load conditions tested – progressive straining and cyclic hardening tests – and to correctly describe anisothermal evolution. The accuracy of these two models and the experimental databases to which they are linked is estimated on different types of experimental tests and compared with the accuracy of more standard Chaboche-type constitutive models. Each test leads to the superiority of the “full model”, particularly for slow strain rates regimes. After developing a material user subroutine, FEM simulations are performed on Abaqus for a car engine exhaust manifold and confirm the good results obtained from the experimental basis. We obtain more accurate results than those given by more traditional laws. A very good correlation is observed between the simulations and the engine bench tests.  相似文献   
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