Contribution of archaeological analogs to the estimation of average corrosion rates and long term corrosion mechanisms of low carbon steel in soil

In the context of the French nuclear waste storage, a multi-barriers disposal is envisaged. Wastes could be put in metallic overpacks disposed in a clay soil. As these overpacks could be made of low carbon steel, it is important to understand the corrosion behaviour of this material in soil during period of several centuries. Indeed, it is necessary to consolidate the empirical data by a phenomenological approach. This includes laboratory experiments and modelling of the phenomenon which have to be validated and completed by the study of archaeological artefacts. This was the aim of this PhD-work. To this purpose, an analytical protocol has been elaborated: about forty archaeological artefacts coming from five dated sites (2. to 16. centuries) have been studied on cross section in order to observe on the same sample all the constituents of the system: metallic substrate/corrosion products/environment. The corrosion products are divided into two zones: the Dense Product Layer (DPL) in contact with the metal, and the Transformed Medium (TM) which are the corrosion products formed around soil minerals (quartz grains). The metallic substrate has been studied by the classical methods of materials science (optical and scanning electron microscope, energy and wavelength dispersive spectroscopies). It has been verified that despite their heterogeneity of structure and composition, they are all hypo-eutectoids steels that can contain phosphorous until 0.5 wt%. The corrosion products have been analysed by local structural analytical methods as micro-diffraction under synchrotron radiation (μXRD) and Raman micro-spectroscopy. These two complementary techniques and also the elemental composition analysis conducted to the characterisation of the corrosion forms. On the majority of the samples coming from four sites, the DPL are constituted by goethite including marbles of magnetite/maghemite. On the artefacts from the fifth site, a particular corrosion form has been identified. This corrosion form, constituted among others by a siderite layer is due to a particular environment: waterlogged soil containing wood. In the whole, analyses conducted in the TM show that it is composed of goethite badly crystallized in comparison with those of the DPL. Moreover, in this zone, the average elemental iron amount decreases progressively from the metal to the soil in which it stabilizes. In order to know the behaviour of the identified phases in soil water, some thermodynamic data have been involved to calculate their solubility in function of pH, potential and various water composition. The first conclusion concerns the influence of the composition and the structure of the material which is not important for the corrosion behaviour. From the results, some hypothesis have been formulated on the long term corrosion mechanisms of hypo-eutectoids steels in the considered environment. The role of the cracks formed in the DPL during the burial was evidenced. Moreover, these corrosion products undertake a dissolution in the soil water and a reprecipitation, explaining the progressive decrease of the iron amount in the TM. Lastly, some average corrosion rates have been measured with the help of the analytical and thermodynamic results: they do not exceed 4 μm/year. (author)