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Étude des mécanismes de déchloruration d'objets archéologiques ferreux d'origine sous-marine

Abstract : The excavation of archaeological iron artefacts are accompanied by degradation if they are not readily stored in an inert atmosphere or treated. In the case of artifacts from underwater excavations, the presence of chlorinated volatile corrosion products on contact with air accelerates the recovery of corrosion phenomena. To limit this degradation and stabilize the object, it is necessary to remove chloride ions trapped in the corrosion pattern. Various dechlorination treatments have been developed by conservation workshops (immersion in alkaline solutions, cathodic polarization, hydrogen plasma, subcritical fluid ...). Despite a genuine efficiency, these treatments need to be optimized (processing time, reliability, reproducibility ...) by a better understanding of dechlorination mechanisms (structural evolution of corrosion pattern during treatment, transport phenomena in the layer, kinetics of extraction of chlorides ...). The objectives of this study are multiple. At first the detailed characterization of the corrosion pattern developed in the marine environment and then when it was abandoned in air was performed using multiscale techniques on an experimental corpus consists of wrought iron ingots from Gallo-Roman ships discoveries off the Saintes-Maries-de-la-Mer (Bouches-du-Rhone, France) submerged for over 2000 years. In particular it was shown that the corrosion pattern of an freshly excavated object is mainly composed of the ferrous hydroxychloride β-Fe2(OH)3Cl, chlorinated phase containing about 20 wt% chlorine. In a second time the evolution of the corrosion pattern was followed during the treatment steps constituting dechlorination: the step of processing, strictly speaking, which consists of the circulation of a NaOH solution aerated or deaerated, step then washing the drying step. The second axis was conducted in two stages. First, the in situ monitoring of the corrosion layer's evolution in the step of processing was carried out under synchrotron radiation by X-ray diffraction coupled to the determination of chloride ions in solution extracts. Then the corrosion pattern was characterized ex situ, elementarily and structurally, from the steps of washing and drying. The whole data allowed us firstly to refine processes structural evolution of the corrosion layer at each stage and also discuss models of chloride extraction proposed in the literature
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Florian Kergourlay. Étude des mécanismes de déchloruration d'objets archéologiques ferreux d'origine sous-marine. Autre. Université Paris-Est, 2012. Français. ⟨NNT : 2012PEST1027⟩. ⟨tel-00721176v2⟩

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