Etude par spectroscopies d'impédance électrochimique globale et locale d'une monocouche hybride organique-inorganique respectueuse de l'environnement pour la protection contre la corrosion de l'alliage d'aluminium 2024

L'utilisation de revêtements sol-gel pour la protection contre la corrosion des métaux est une alternative aux traitements à base de chromates, proscrits du fait de leur forte toxicité. Ces travaux de thèse ont porté sur la caractérisation de revêtements sol-gel hybrides organique-inorganique contenant des pigments inhibiteurs de corrosion non toxiques, pour la protection contre la corrosion de l'alliage d'aluminium 2024. Tout d'abord, la caractérisation par spectroscopie d'impédance électrochimique de différents revêtements relativement poreux a permis d'analyser l'influence de l'épaisseur, de la température de séchage, de l'hydrolyse de la partie silane et du ratio silane/amine sur les performances du revêtement, en particulier des propriétés barrière. Puis, l'ajout d'un époxy dans la formulation a permis d'augmenter de façon significative les propriétés barrière du film. Les diagrammes d'impédance présentent une dispersion en fréquence, exprimée en termes de « constant phase element (CPE) », en haute et basse fréquence. En haute fréquence, ce comportement a été analysé à l'aide d'un modèle qui permet d'obtenir des profils de résistivité dans l'épaisseur du revêtement et au cours du temps d'immersion. Ce modèle est appliqué pour la première fois à l'étude de revêtements. Différents pigments inhibiteurs de corrosion ont ensuite été incorporés dans des revêtements de porosité différente. L'action des inhibiteurs est exacerbée lorsqu'ils sont incorporés dans un revêtement poreux. Néanmoins, lorsqu'ils sont incorporés dans un film dense, les performances vis-à-vis de la résistance à la corrosion sont élevées. ABSTRACT : The use of sol-gel coatings for the protection against the corrosion of metals is an alternative to chrome-based treatments, banned for the industry for their high toxicity. This work is based on the characterisation of hybrid organic-inorganic coatings, filled with non-toxic corrosion inhibitors, for the protection against the corrosion of aluminium alloy 2024. First, the characterisation by electrochemical impedance spectroscopy of different, relatively porous coatings, allowed the investigation of the influence of thickness, drying temperature, silane hydrolysis, and the silane/amine ratio on the coating performances, in particular the barrier properties. Then, the addition of an epoxy compound in the formulation allowed a significant increase in the film barrier properties. The impedance diagrams show a frequency dispersion, expressed in terms of a constant phase element (CPE), both in the high and low frequency range. In the high frequency range, this behaviour was analyzed using a model that allows obtaining resistivity profiles in the thickness of the coating and with immersion time. This model is applied for the first time to study coatings. Different corrosion inhibitors were then incorporated in coatings of different porosity. The action of the inhibitors was heightened when they are incorporated in a porous coating. Nevertheless, in a dense coating, the performances towards corrosion are high

Étude par spectroscopies d'impédance électrochimique globale et locale d'une monocouche hybride organique-inorganique respectueuse de l'environnement pour la protection contre la corrosion de l'alliage d'aluminium 2024

L'utilisation de revêtements sol-gel pour la protection contre la corrosion des métaux est une alternative aux traitements à base de chromates, proscrits du fait de leur forte toxicité. Ces travaux de thèse ont porté sur la caractérisation de revêtements sol-gel hybrides organique-inorganique contenant des pigments inhibiteurs de corrosion non toxiques, pour la protection contre la corrosion de l'alliage d'aluminium 2024. Tout d'abord, la caractérisation par spectroscopie d'impédance électrochimique de différents revêtements relativement poreux a permis d'analyser l'influence de l'épaisseur, de la température de séchage, de l'hydrolyse de la partie silane et du ratio silane/amine sur les performances du revêtement, en particulier des propriétés barrière. Puis, l'ajout d'un époxy dans la formulation a permis d'augmenter de façon significative les propriétés barrière du film. Les diagrammes d'impédance présentent une dispersion en fréquence, exprimée en termes de constant phase element (CPE) , en haute et basse fréquence. En haute fréquence, ce comportement a été analysé à l'aide d'un modèle qui permet d'obtenir des profils de résistivité dans l'épaisseur du revêtement et au cours du temps d'immersion. Ce modèle est appliqué pour la première fois à l'étude de revêtements. Différents pigments inhibiteurs de corrosion ont ensuite été incorporés dans des revêtements de porosité différente. L'action des inhibiteurs est exacerbée lorsqu'ils sont incorporés dans un revêtement poreux. Néanmoins, lorsqu'ils sont incorporés dans un film dense, les performances vis-à-vis de la résistance à la corrosion sont élevées.The use of sol-gel coatings for the protection against the corrosion of metals is an alternative to chrome-based treatments, banned for the industry for their high toxicity. This work is based on the characterisation of hybrid organic-inorganic coatings, filled with non-toxic corrosion inhibitors, for the protection against the corrosion of aluminium alloy 2024. First, the characterisation by electrochemical impedance spectroscopy of different, relatively porous coatings, allowed the investigation of the influence of thickness, drying temperature, silane hydrolysis, and the silane/amine ratio on the coating performances, in particular the barrier properties. Then, the addition of an epoxy compound in the formulation allowed a significant increase in the film barrier properties. The impedance diagrams show a frequency dispersion, expressed in terms of a constant phase element (CPE), both in the high and low frequency range. In the high frequency range, this behaviour was analyzed using a model that allows obtaining resistivity profiles in the thickness of the coating and with immersion time. This model is applied for the first time to study coatings. Different corrosion inhibitors were then incorporated in coatings of different porosity. The action of the inhibitors was heightened when they are incorporated in a porous coating. Nevertheless, in a dense coating, the performances towards corrosion are high.TOULOUSE-INP (315552154) / SudocSudocFranceF

Adherence measurements and corrosion resistance in primer/hot-dip galvanized steel systems

This paper focuses on the adherence during ageing of a primer (made of polyester resins crosslinked with melamine) applied onto hot-dip galvanized (HDG) steel for coil coating application and its influence on corrosion protection. A chromium-free surface treatment, composed of fluorotitanic acid, phosphoric acid, manganese phosphate, and vinylphenol was applied on the HDG steel to obtain high corrosion resistance and high adherence of a polyester and melamine primer. The influence of the manganese phosphate on the corrosion and adherence was investigated. To measure the adherence between the metal and the primer, a three-point flexure test was set up. The adherence was then linked with corrosion resistance during ageing, using electrochemical impedance spectroscopy

Global and local electrochemical impedance spectroscopy study of an environmentally friendly hybrid organic-inorganic mono layer for the protection against the corrosion of aluminium alloy 2024

L'utilisation de revêtements sol-gel pour la protection contre la corrosion des métaux est une alternative aux traitements à base de chromates, proscrits du fait de leur forte toxicité. Ces travaux de thèse ont porté sur la caractérisation de revêtements sol-gel hybrides organique-inorganique contenant des pigments inhibiteurs de corrosion non toxiques, pour la protection contre la corrosion de l'alliage d'aluminium 2024. Tout d'abord, la caractérisation par spectroscopie d'impédance électrochimique de différents revêtements relativement poreux a permis d'analyser l'influence de l'épaisseur, de la température de séchage, de l'hydrolyse de la partie silane et du ratio silane/amine sur les performances du revêtement, en particulier des propriétés barrière. Puis, l'ajout d'un époxy dans la formulation a permis d'augmenter de façon significative les propriétés barrière du film. Les diagrammes d'impédance présentent une dispersion en fréquence, exprimée en termes de « constant phase element (CPE) », en haute et basse fréquence. En haute fréquence, ce comportement a été analysé à l'aide d'un modèle qui permet d'obtenir des profils de résistivité dans l'épaisseur du revêtement et au cours du temps d'immersion. Ce modèle est appliqué pour la première fois à l'étude de revêtements. Différents pigments inhibiteurs de corrosion ont ensuite été incorporés dans des revêtements de porosité différente. L'action des inhibiteurs est exacerbée lorsqu'ils sont incorporés dans un revêtement poreux. Néanmoins, lorsqu'ils sont incorporés dans un film dense, les performances vis-à-vis de la résistance à la corrosion sont élevées.The use of sol-gel coatings for the protection against the corrosion of metals is an alternative to chrome-based treatments, banned for the industry for their high toxicity. This work is based on the characterisation of hybrid organic-inorganic coatings, filled with non-toxic corrosion inhibitors, for the protection against the corrosion of aluminium alloy 2024. First, the characterisation by electrochemical impedance spectroscopy of different, relatively porous coatings, allowed the investigation of the influence of thickness, drying temperature, silane hydrolysis, and the silane/amine ratio on the coating performances, in particular the barrier properties. Then, the addition of an epoxy compound in the formulation allowed a significant increase in the film barrier properties. The impedance diagrams show a frequency dispersion, expressed in terms of a constant phase element (CPE), both in the high and low frequency range. In the high frequency range, this behaviour was analyzed using a model that allows obtaining resistivity profiles in the thickness of the coating and with immersion time. This model is applied for the first time to study coatings. Different corrosion inhibitors were then incorporated in coatings of different porosity. The action of the inhibitors was heightened when they are incorporated in a porous coating. Nevertheless, in a dense coating, the performances towards corrosion are high

Constant-phase-element behavior caused by inhomogeneous water uptake in anti-corrosion coatings

International audienceThe impedance of a substrate/coating/electrolyte system was calculated with the assumptions: (i) the coating uptakes electrolyte to an extent that progressively decreases from the coating/electrolyte interface to the substrate/coating interface where it becomes negligible; (ii) the volume fraction of the electrolyte varies along the coating thickness according to a power-law; (iii) the resistivity and permittivity profiles of the electrolyte-penetrated coating can be calculated through an effective medium theory (EMT) formula corresponding to a parallel combination of the two media (electrolyte and coating material); and (iv) some pores extend from the coating/electrolyte interface to the substrate/coating interface, providing a low resistance path. The impedance plots thus calculated exhibited a constant phase element (CPE) behavior in a large frequency range. Some experimental results obtained with 2024 aluminum alloy/hybrid sol-gel coating samples immersed in a NaCl solution were analyzed with reference to the above described model. The extension of the recently developed power-law CPE model to anti-corrosion coatings is shown to yield insight into the distribution of resistivity and associated water uptake. Evaluation of mixing rules for conductivities and permittivities of the two media (coating and electrolyte) showed that the linear combination provided results that were consistent with the observed impedance response; whereas, distributions resulting from a series combination of the two media, an EMT formula proposed in the literature, and the Maxwell approximation were incompatible with the observed CPE impedance response

Nativeness and Intelligibility of Japanese accented English Consonants by French Listeners

International audienceThe presence of a Foreign Accent (FA) in the communicative process may interfere with the correct transmission of a message. This interference can arise from various traits, such as rhythm, intonation and speech rate. This can affect perception by both L1 and L2 listeners. Therefore, in this study we focused on the segments of Japanese FA in English as perceived by French listeners. Seven consonants ([l, ɹ, t h , k h , θ, f, v]) were extracted from the beginning of CVC English words. Using sound manipulation techniques, they were transformed into their most expected Japanese realisation ([ɾ, ɾ, t, k, s, ɸ, b] respectively) to generate a new set of words in which only the first segment was accented. The French cohort showed clear differences in perceived intelligibility of rhotic consonants and the [f/ɸ] contrast compared with previously analysed groups of Japanese and American listeners

Bias Dependence of the Electrical Spin Injection into GaAs from Co − Fe − B / MgO Injectors with Different MgO Growth Processes

International audienc

General and abdominal adiposity and hypertension in eight world regions: a pooled analysis of 837 population-based studies with 7·5 million participants

International audienceSummaryBackground Adiposity can be measured using BMI (which is based on weight and height) as well as indices of abdominal adiposity. We examined the association between BMI and waist-to-height ratio (WHtR) within and across populations of different world regions and quantified how well these two metrics discriminate between people with and without hypertension.MethodsWe used data from studies carried out from 1990 to 2023 on BMI, WHtR and hypertension in people aged 20–64 years in representative samples of the general population in eight world regions. We graphically compared the regional distributions of BMI and WHtR, and calculated Pearson’s correlation coefficients between BMI and WHtR within each region. We used mixed-effects linear regression to estimate the extent to which WHtR varies across regions at the same BMI. We graphically examined the prevalence of hypertension and the distribution of people who have hypertension both in relation to BMI and WHtR, and we assessed how closely BMI and WHtR discriminate between participants with and without hypertension using C-statistic and net reclassification improvement (NRI).FindingsThe correlation between BMI and WHtR ranged from 0·76 to 0·89 within different regions. After adjusting for age and BMI, mean WHtR was highest in south Asia for both sexes, followed by Latin America and the Caribbean and the region of central Asia, Middle East and north Africa. Mean WHtR was lowest in central and eastern Europe for both sexes, in the high-income western region for women, and in Oceania for men. Conversely, to achieve an equivalent WHtR, the BMI of the population of south Asia would need to be, on average, 2·79 kg/m² (95% CI 2·31–3·28) lower for women and 1·28 kg/m² (1·02–1·54) lower for men than in the high-income western region. In every region, hypertension prevalence increased with both BMI and WHtR. Models with either of these two adiposity metrics had virtually identical C-statistics and NRIs for every region and sex, with C-statistics ranging from 0·72 to 0·81 and NRIs ranging from 0·34 to 0·57 in different region and sex combinations. When both BMI and WHtR were used, performance improved only slightly compared with using either adiposity measure alone.InterpretationBMI can distinguish young and middle-aged adults with higher versus lower amounts of abdominal adiposity with moderate-to-high accuracy, and both BMI and WHtR distinguish people with or without hypertension. However, at the same BMI level, people in south Asia, Latin America and the Caribbean, and the region of central Asia, Middle East and north Africa, have higher WHtR than in the other regions