Effect of the pH of the electrolyte on the formation and on the corrosion properties of ceria based coating on carbon steel

International audienceThe effects of the modification of the pH in 0.1M cerium nitrate solutions in the elaboration and corrosion resistance of ceria based coatings on carbon steel are investigated. Increasing the concentration of acetic acid impedes an efficient electrodeposition. At low concentrations, acetic acid seems to prevent the precipitation of Ce(OH)3 and the formation of even films of cerium oxides is favoured. The increase of pH through the addition of NaOH to the cerium nitrate solutions with 0.008M of acetic acid is shown to provide superior corrosion resistance for exposures in air and immersed in 0.5M NaCl for 30 days

Characterisation of iron (II) sulfides in wet archaeological woods: the wreck of Mandirac (IV th century, antique ports of Narbonne, France)

International audienceThe wreck of Mandirac (Narbonne, France, IV century) was excavated in 2013 and 2014 from waterlogged soil. A magnetic prospection campaign performed in 2014 revealed that the wood was abnormally magnetic. A plank extracted from the hull, containing an iron nail, was analysed using Environmental Scanning Electron Microscopy, micro-Raman spectroscopy, X-Ray diffraction and magnetic characterization methods in order to identify the mineral composition inside the wood and of the nail. Results revealed an accumulation of greigite and pyrite in the wood around the nail, where the pH was measured below 3. The nail was completely corroded into pyrite and siderite, with no metal left. Marcasite was also identified far from the nail, where the pH was measured around 5. Greigite was the only phase responsible of the magnetic signal emitted from the wood and proved to be present in varying amounts throughout the entire wreck. The iron sulfides were probably formed via anaerobic sulphidogenic bacteria influenced corrosion processes, which occurred on the nails. These results are very different from those obtained from more recent shipwrecks (XIX century). So the nature of these iron sulfides in wet archaeological woods is discussed

Assemblages bois-fer et biocorrosion : étude des sulfures de fer formés en conditions anoxiques dans des bois d'épaves

International audienceLes conséquences de la corrosion des renforts de fer dans les assemblages de bois peuvent compromettre la durabilité d'une structure. Si le bois est gorgé d'eau, les conditions à la surface du métal deviennent anoxiques. La présence de fer et l'activité microbiologique favorisée par la présence de matière organique font des systèmes composites bois-fer des milieux propices à l'apparition de sulfures de fer. Or ces derniers se transforment soit en milieux anaérobies sulfurés, soit lorsque l'oxygène diffuse dans le bois, soit lors d'une remise à l'air de la structure, avec pour conséquence de contribuer à la dégradation du bois. Afin de mieux comprendre les mécanismes impliqués, nous étudions des bois d'épaves archéologiques. Cet article sera illustré par des exemples d'époques récentes (18 è s. 19 è s.) et antiques et par une approche analytique multi-techniques originale. La mackinawite, la greigite et la pyrite ont été identifiées et il semble que la nature des sulfures de fer présents soit liée à l'âge du vestige conformément aux schémas proposés dans la littérature d'évolution de ces composés. La greigite est intéressante à considérer. Seule phase détectée quel que soit l’âge, elle peut s’avérer un bon marqueur de la biocorrosion du fer dans les assemblages bois-fer

Application of ToF-SIMS for sulfur isotopic fractionation in sulfide phases of iron corrosion layers: determination of bacterial impact on the formation of these phases

International audienceTo a better understanding of the iron corrosion mechanisms, it is crucial to elucidate the role of bacteria. Thus, in order to have a diagnosis of the action of bacteria in the iron corrosion, the objective of this study is to determine by ToF-SIMS the isotopic sulfur fractionation δ 34 S in iron sulfides of (sub)micrometric size located in the corrosion product layers of the ferrous objects corroded in anoxic soils and marine environment. These iron sulfides may have two origins: an abiotic origin resulting in the dissolution/reprecipitation of sulfides from the surrounding medium (for example from pyrite in a soil) or a biotic origin by the action of the sulfate-reducing bacteria that reduce sulfate ions into sulfides leading to the formation of iron sulfides with ferrous ions issued from the aqueous dissolution of metal iron. A difference in the isotopic sulfur fractionation δ 34 S in the sulfur phases according to the abiotic or biotic origin of these phases is reported in the literature. Thus in this study, the isotopic sulfur fractionation δ 34 S in the iron sulfides formed in the corrosion product layers of iron was determined to identify the formation origin of these phases and the role of bacteria in the iron corrosion. After characterization of the distribution of the different iron sulfides within the layers (optical microscopy, SEM-EDS, μRaman spectroscopy), the local isotopic fractionation of sulfur is measured by the imaging and spectroscopy ToF-SIMS technique. Some important results have been obtained. First of all, the reproducibility and the accuracy of the method were established by the choice and the validation of a hydrothermal pyrite sample calibrated relatively to the international sulfur isotopic standard Canon Diablo Troilite. Secondly, it was observed that there was no or little variation in the isotopic sulfur fractionation δ 34 S with the degree of oxidation of sulfur. Finally, a noticeable difference in the isotopic sulfur fractionation δ 34 S between iron sulfides formed in laboratory under abiotic or biotic conditions was evidenced: δ 34 S is close to 0 in abiotic conditions whereas in biotic conditions it is shifted from 0 with values up to up to some tens per mil. These first results being promising, the study is actually in progress to determine the formation origin (abiotic/biotic) of the Fe-S present in the corrosion product layers of natural systems of iron corrosion, from soils, subaquatic and marine environments

Etude des processus de dégradation des manuscrits anciens écrits à l'encre ferrogallique (analyse d'échantillons originaux et d'éprouvettes de laboratoire)

LA ROCHELLE-BU (173002101) / SudocSudocFranceF

Vitriol manufacture in the middle Ages: variety and homogeneity of possible products

International audienc

Contribution of magnetic measurement methods to the analysis of iron sulfides in archaeological waterlogged wood‑iron assemblies

International audienc