SECM study of a chromium-free anticorrosion adhesion primer for aluminum 2024

International audienceHexavalent chromium, largely used for anticorrosion surface treatments of aluminum in aeronautics, will soon be completely banned due to its high toxicity (REACH regulation). Looking for an innovative solution, regarding both anticorrosion and adhesion properties, a chromium free replacement treatment directly inspired by the diazonium chemistry has been developed by the CEA (LICSEN). The evolution of the surface electrochemical properties was followed before and after grafting by means of scanning electrochemical microscopy (SECM). These studies showed that the native aluminum oxide layer is etched during the organic grafting step, which is performed in sulfuric acid. SECM also evidenced that the polymeric grafted film is porous enough to allow the reconstruction of this native aluminum oxide layer after the treatment. On the strength of these results, we decided to extend the thickness of the aluminum oxide layer by an anodization treatment, in the idea that Al$_2$O$_3$ could be formed through the organic layer without altering it. In that purpose, SECM was used to characterize the films and allow the determination of the best parameters for the organic coating (concentration, immersion time, diazonium function, rinsing, cleaning, additives…) and for the anodization process (duration, applied tension…). Thus, bi-functional coatings were obtained, giving very satisfying results both in terms of corrosion protection and adhesion with painting. This simple and low cost process has been patented . It validates standardized tests and could be swiftly industrializable

Equidistribution of Heegner Points and Ternary Quadratic Forms

We prove new equidistribution results for Galois orbits of Heegner points with respect to reduction maps at inert primes. The arguments are based on two different techniques: primitive representations of integers by quadratic forms and distribution relations for Heegner points. Our results generalize one of the equidistribution theorems established by Cornut and Vatsal in the sense that we allow both the fundamental discriminant and the conductor to grow. Moreover, for fixed fundamental discriminant and variable conductor, we deduce an effective surjectivity theorem for the reduction map from Heegner points to supersingular points at a fixed inert prime. Our results are applicable to the setting considered by Kolyvagin in the construction of the Heegner points Euler system

Potassium limitation of forest productivity – Part 2: CASTANEA-MAESPA-K shows a reduction in photosynthesis rather than a stoichiometric limitation of tissue formation

Potassium (K) availability constrains forest productivity. Brazilian eucalypt plantations are a good example of the K limitation of wood production. Here, we built upon a previously described model (CASTANEA-MAESPA-K) and used it to understand whether the simulated decline in C source under K deficiency was sufficient to explain the K limitation of wood productivity in Brazilian eucalypt plantations. We developed allocation schemes for both C and K and included these in CASTANEA-MAESPA-K. Neither direct limitations of the C-sink activity nor direct modifications of the C allocation by K availability were included in the model. Simulation results show that the model was successful in replicating the observed patterns of wood productivity limitation by K deficiency. Simulations also show that the response of net primary productivity (NPP) is not linear with increasing K fertilisation. Simulated stem carbon use and water use efficiencies decreased with decreasing levels of K availability. Simulating a direct stoichiometric limitation of NPP or wood growth was not necessary to reproduce the observed decline of productivity under K limitation, suggesting that K stoichiometric plasticity could be different to that of N and P. Confirming previous results from the literature, the model simulated an intense recirculation of K in the trees, suggesting that retranslocation processes were essential for tree functioning. Optimal K fertilisation levels calculated by the model were similar to nutritional recommendations currently applied in Brazilian eucalypt plantations, paving the way for validation of the model at a larger scale and of this approach for developing decision-making tools to improve fertilisation practices.</p

Potassium limitation of forest productivity – Part 1: A mechanistic model simulating the effects of potassium availability on canopy carbon and water fluxes in tropical eucalypt stands

The extent of the potassium (K) limitation of forest productivity is probably more widespread than previously thought, and K limitation could influence the response of forests to future global changes. To understand the effects of K limitation on forest primary production, we have developed the first ecophysiological model simulating the K cycle and its interactions with the carbon (C) and water cycles. We focused on the limitation of the gross primary productivity (GPP) by K availability in tropical eucalypt plantations in Brazil. We used results from stand-scale fertilisation experiments as well as C flux measurements in two tropical eucalypt plantations to parameterise the model. The model was parameterised for fertilised conditions and then used to test for the effects of contrasting additions of K fertiliser. Simulations showed that K deficiency limits GPP by more than 50 % during a 6-year rotation, a value in agreement with estimations in K-limited eucalypt stands. Simulations showed a decrease of modelled canopy transpiration of around 50 % and a decrease in modelled water-use efficiency WUEGPP of 10 %. Through a sensitivity analysis, we used the model to identify the most critical processes to consider when studying K limitation of GPP. The inputs of K to the stands, such as the atmospheric deposition and weathering fluxes, and the regulation of the cycle of K within the ecosystem were critical for the response of the system to K deficiency. Litter leaching processes were of lower importance, since residence time of K in litter was low. The new forest K-cycle model developed in the present study includes multiple K processes interacting with the carbon and water cycles, and strong feedbacks on GPP were outlined. This is a first step in identifying the source or sink limitation of forest growth by K.</p

Interplay between Heavy Fermions and Crystal Field Excitation in Kondo Lattices. Low-Temperature Thermodynamics and Inelastic Neutron Scattering Spectra of CeNiSn

The microscopic theory of interaction between the heavy fermions and the crystal field excitations in Kondo lattices is presented. It is shown that the heavy-fermion spectrum scaled by the Kondo temperature $T_K$ can be modified by the crystal field excitations with the energy $\Delta_{CF}$ provided the inequality $\Delta_{CF}<T_K$ is realized. On the base of general description of excitation spectrum the detailed qualitative and quantitative explanation of anisotropic inelastic neutron scattering spectra and low-temperature specific heat of orthorhombic CeNiSn is given. The theory resolves the apparent contradiction between the metallic conductivity and the gap-wise behavior of thermodynamic properties and spin response of CeNiSn at low temperatures.Comment: 24 pages (LaTeX), 12 Postscript figures, submitted to Phys.Rev.

Magnetocrystalline Anisotropy in a Single Crystal of CeNiGe2

We report measurements on single crystals of orthorhombic CeNiGe2, which is found to exhibit highly anisotropic magnetic and transport properties. The magnetization ratio M(H//b)/M(H^b) at 2 K is observed to be about 18 at 4 T and the electrical resistivity ratio r//b/r^b is about 70 at room temperature. It is confirmed that CeNiGe2 undergoes two-step antiferromagnetic transition at 4 and 3 K, as reported for polycrystalline samples. The application of magnetic field along the b axis (the easy magnetization axis) stabilizes a ferromagnetic correlation between the Ce ions and enhances the hopping of carriers. This results in large negative magnetoresistance along the b axis.Comment: 24 pages, including 9 figure

Quantitative localized proton-promoted dissolution kinetics of calcite using scanning electrochemical microscopy (SECM)

Scanning electrochemical microscopy (SECM) has been used to determine quantitatively the kinetics of proton-promoted dissolution of the calcite (101̅4) cleavage surface (from natural “Iceland Spar”) at the microscopic scale. By working under conditions where the probe size is much less than the characteristic dislocation spacing (as revealed from etching), it has been possible to measure kinetics mainly in regions of the surface which are free from dislocations, for the first time. To clearly reveal the locations of measurements, studies focused on cleaved “mirror” surfaces, where one of the two faces produced by cleavage was etched freely to reveal defects intersecting the surface, while the other (mirror) face was etched locally (and quantitatively) using SECM to generate high proton fluxes with a 25 μm diameter Pt disk ultramicroelectrode (UME) positioned at a defined (known) distance from a crystal surface. The etch pits formed at various etch times were measured using white light interferometry to ascertain pit dimensions. To determine quantitative dissolution kinetics, a moving boundary finite element model was formulated in which experimental time-dependent pit expansion data formed the input for simulations, from which solution and interfacial concentrations of key chemical species, and interfacial fluxes, could then be determined and visualized. This novel analysis allowed the rate constant for proton attack on calcite, and the order of the reaction with respect to the interfacial proton concentration, to be determined unambiguously. The process was found to be first order in terms of interfacial proton concentration with a rate constant k = 6.3 (± 1.3) × 10–4 m s–1. Significantly, this value is similar to previous macroscopic rate measurements of calcite dissolution which averaged over large areas and many dislocation sites, and where such sites provided a continuous source of steps for dissolution. Since the local measurements reported herein are mainly made in regions without dislocations, this study demonstrates that dislocations and steps that arise from such sites are not needed for fast proton-promoted calcite dissolution. Other sites, such as point defects, which are naturally abundant in calcite, are likely to be key reaction sites

Kondo engineering : from single Kondo impurity to the Kondo lattice

In the first step, experiments on a single cerium or ytterbium Kondo impurity reveal the importance of the Kondo temperature by comparison to other type of couplings like the hyperfine interaction, the crystal field and the intersite coupling. The extension to a lattice is discussed. Emphasis is given on the fact that the occupation number $n_f$ of the trivalent configuration may be the implicit key variable even for the Kondo lattice. Three $(P, H, T)$ phase diagrams are discussed: CeRu$_2$Si$_2$, CeRhIn$_5$ and SmS

Specific heat of Ce_{0.8}La_{0.2}Al_{3} in magnetic fields: a test of the anisotropic Kondo picture

The specific heat C of Ce_{0.8}La_{0.2}Al_{3} has been measured as a function of temperature T in magnetic fields up to 14 T. A large peak in C at 2.3 K has recently been ascribed to an anisotropic Kondo effect in this compound. A 14-T field depresses the temperature of the peak by only 0.2 K, but strongly reduces its height. The corresponding peak in C/T shifts from 2.1 K at zero field to 1.7 K at 14 T. The extrapolated specific heat coefficient C/T(T->0) increases with field over the range studied. We show that these trends are inconsistent with the anisotropic Kondo model.Comment: 4 pages, 5 figures, ReVTeX + eps

Electrochemical Nanoprobes for Single-Cell Analysis

The measurement of key molecules in individual cells with minimal disruption to the biological milieu is the next frontier in single-cell analyses. Nanoscale devices are ideal analytical tools because of their small size and their potential for high spatial and temporal resolution recordings. Here, we report the fabrication of disk-shaped carbon nanoelectrodes whose radius can be precisely tuned within the range 5–200 nm. The functionalization of the nanoelectrode with platinum allowed the monitoring of oxygen consumption outside and inside a brain slice. Furthermore, we show that nanoelectrodes of this type can be used to impale individual cells to perform electrochemical measurements within the cell with minimal disruption to cell function. These nanoelectrodes can be fabricated combined with scanning ion conductance microscopy probes, which should allow high resolution electrochemical mapping of species on or in living cells