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

All solution-processed organic photocathodes with increased efficiency and stability via the tuning of the hole-extracting layer †

International audiencePhotoelectrodes based on solution-processed organic semiconductors are emerging as low-cost alternatives to crystalline semiconductors and platinum. In this work, the performance and stability of P3HT:PCBM\MoS 3-based photocathodes are considerably improved by changing the hole-extracting layer (HEL). Oxides such as reduced graphene oxide, nickel oxide or molybdenum oxide are deposited via solution processes. With MoO x , a photocurrent density of 2 mA cm À2 during 1 h is obtained with the processing temperature lower than 150 C – thus compatible with flexible substrates. Furthermore, we show that the performances are directly correlated with the work function of the HEL material, and the comparison with solid-state solar cells shows that efficient HELs are not the same for the two types of devices

New insights in the electronic transport in reduced graphene oxide using Scanning Electrochemical Microscopy

International audienceGraphene and graphene analogues such as GO or reduced-GO (r-GO) are attracting increasing attention from the scientific community. These materials have outstanding properties, so that many potential applications in the fields of electronics, sensors, catalysis and energy storage are being considered. GO combines several advantages such as availability in large quantity, low cost and easy processability. However, contrary to graphene, GO is electronically insulating and has to be reduced into a conductive material, r-GO. In a recent work we introduced a new localized functionalization method of GO deposited on a silicon oxide surface based on its reduction at the local scale thanks to scanning electrochemical microscopy (SECM): the reducer is generated at the microelectrode, that is moved close to the substrate. The recovery of electronic conductivity upon reduction enables the selective electrochemical functionalization of patterns. In the present work, we introduce a new method to evaluate at a local scale the conductivity of r-GO layers with SECM. In addition we show how images of individual and interconnected flakes directly reveal the signature of the contact resistance between flakes in a non-contact and substrate-independent way. Quantitative evaluation of the parameters is achieved with the support of numerical simulations to interpret the experimental results. Overall, these works illustrates the high potential and versatility of SECM to investigate and functionalize 2D materials

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

Thermodynamic and Transport Properties of CeMg2Cu9 under Pressure

We report the transport and thermodynamic properties under hydrostatic pressure in the antiferromagnetic Kondo compound CeMg2Cu9 with a two-dimensional arrangement of Ce atoms. Magnetic specific heat Cmag(T) shows a Schottky-type anomaly around 30 K originating from the crystal electric field (CEF) splitting of the 4f state with the first excited level at \Delta_{1}/kB = 58 K and the second excited level at \Delta_{2}/kB = 136 K from the ground state. Electric resistivity shows a two-peaks structure due to the Kondo effect on each CEF level around T_{1}^{max} = 3 K and T_{2}^{max} = 40 K. These peaks merge around 1.9 GPa with compression. With increasing pressure, Neel temperature TN initially increases and then change to decrease. TN finally disappears at the quantum critical point Pc = 2.4 GPa.Comment: 10 pages, 6 figure

Leaf-associated fungal diversity in acidified streams: insights from combining traditional and molecular approaches

We combined microscopic and molecular methods to investigate fungal assemblages on alder leaf litter exposed in the benthic and hyporheic zones of five streams across a gradient of increasing acidification for 4 weeks. The results showed that acidification and elevated Al concentrations strongly depressed sporulating aquatic hyphomycetes diversity in both zones of streams, while fungal diversity assessed by denaturing gradient gel electrophoresis (DGGE) appeared unaffected. Clone library analyses revealed that fungal communities on leaves were dominated by members of Ascomycetes and to a lesser extent by Basidiomycetes and Chytridiomycetes. An important contribution of terrestrial fungi was observed in both zones of the most acidified stream and in the hyporheic zone of the reference circumneutral stream. The highest leaf breakdown rate was observed in the circumneutral stream and occurred in the presence of both the highest diversity of sporulating aquatic hyphomycetes and the highest contribution to clone libraries of sequences affiliated with aquatic hypho- mycetes. Both methods underline the major role played by aquatic hyphomycetes in leaf decom- position process. Our findings also bring out new highlights on the identity of leaf-associated fungal communities and their responses to anthropogenic alteration of running water ecosystems

Local surface modification via confined electrochemical deposition with FluidFM †

International audienceWe show how the association of AFM with microfluidics, namely FluidFM, is a valuable approach for the versatile electrochemical creation of patterns having diverse shapes and topologies. Localization of the electrochemical reactions was obtained by confining the electroactive species in the microchannel and dispensing them at a precise position through the aperture of FluidFM probes. The force feedback enabled a gentle approach onto the electrode as well as a gentle contact during both the lithography procedure as well as in situ topographical AFM imaging just before or after deposition. As model systems, we demonstrate electroplating of copper and electrografting of organic moieties by reduction of aryldiazonium salts

High-throughput mapping of protein occupancy identifies functional elements without the restriction of a candidate factor approach

There are a variety of in vivo and in vitro methods to determine the genome-wide specificity of a particular trans-acting factor. However there is an inherent limitation to these candidate approaches. Most biological studies focus on the regulation of particular genes, which are bound by numerous unknown trans-acting factors. Therefore, most biological inquiries would be better addressed by a method that maps all trans-acting factors that bind particular regions rather than identifying all regions bound by a particular trans-acting factor. Here, we present a high-throughput binding assay that returns thousands of unbiased measurements of complex formation on nucleic acid. We applied this method to identify transcriptional complexes that form on DNA regions upstream of genes involved in pluripotency in embryonic stem cells (ES cells) before and after differentiation. The raw binding scores, motif analysis and expression data are used to computationally reconstruct remodeling events returning the identity of the transcription factor(s) most likely to comprise the complex. The most significant remodeling event during ES cell differentiation occurred upstream of the REST gene, a transcriptional repressor that blocks neurogenesis. We also demonstrate how this method can be used to discover RNA elements and discuss applications of screening polymorphisms for allelic differences in binding

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

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