Structural characterisation of corrosion products on archaeological iron. An integrated analytical approach to establish corrosion forms

International audienceThe description and identification of corrosion products formed on archaeological iron artefacts needs various approaches at different observation scales. For this study, samples of five different sites were prepared using two techniques. The first one consists in cutting cross sections perpendicular to corrosion layers. This allows local observations and analysis of the corrosion layer stratigraphy at different levels. The second one consists in performing manual grinding or abrading of the corrosion layers starting from the current surface of the excavated artefact to the metal core. It allows the description of the successive layers and is well adapted for the analysis on a larger scale. In addition to these two observation scales, the identification of the iron oxides formed needs the coupling of several complementary techniques. Elementary compositions were determined by SEM-EDX and Electron Micro-Probe Analysis (EMPA). Structural identification was performed by X-ray micro Diffraction under synchrotron radiation (µXRD) and micro Raman spectroscopy. These analyses were performed on the same samples both with X-ray diffraction and Raman spectroscopy in order to ensure a reliable characterisation. In some cases there are some ambiguities or overlapping between signatures of different phases by micro X-rays diffraction (as maghemite/magnetite) or Raman spectroscopy (as goethite/magnetite) which can be raised by the association of the two methods. The final aim is to set up an analytical methodology that will be the best for the study of ancient iron corrosion products. It is the first step of the study of long term mechanisms of iron in soil

In situ monitoring of corrosion processes by coupled micro-XRF/micro-XRD mapping to understand the degradation mechanisms of reinforcing bars in hydraulic binders from historic monuments

International audienceHistoric monuments have been partly built since antiquity with iron or steel reinforcements sealed in mortars or hydraulic binders. But the presence of chloride in the environment can weaken the structures due to the corrosion of these metallic parts, leading to the cracking of the binder. In this context, in order to better understand the first steps of these corrosion mechanisms a chemical cell was designed to operate in situ analyses of the phases precipitated when a chlorinated solution is introduced in the vicinity of the bar. The chemical and structural characterization (micro-XRF and micro-XRD respectively) was performed under synchrotron radiation at the SOLEIL-DiffAbs beamline. Moreover, complementary SEM-EDS analyses were carried out before and after the in situ cell experiment in order to determine the final localisation of the corrosion products inside the crack network. The results show that iron can spread up to 1 mm away from the metallic bar inside the pores of the binder after 44 h of corrosion. Moreover, in accordance with laboratory experiments conducted in solution in the presence of Fe2+ and Cl- ions the reaction pathways conduct to the successive formation of an intermediate Fe(ii)-Fe(iii) chlorinated green rust which transforms into ferric oxyhydroxides such as akaganeite or goethite depending on the local concentration of iron

Laser cleaning of Cu-based artefacts: laser/corrosion products interaction

This study aims to develop a low invasive and selective laser cleaning procedure for the removal of reactive corrosion products on Cu-based artefacts without damage the substrate. In a preliminary step, laser cleaning was performed on two typologies of artificially corroded copper reference samples. The effect of the variation of laser parameters as pulse duration and output power, was thus evaluated on an oxide layer, simulating a protective patina, and a hydroxychloride layer, simulating a reactive corrosion products layer to be removed. The optimized cleaning procedure was validated on an archaeological artefact, a bronze coin. Morphological, microchemical and microstructural characterizations were performed by means of optical microscopy, confocal microscopy, field emission scanning electron microscopy, X-Ray diffraction and Raman spectroscopy, before and after laser cleaning. The experimental findings show that laser cleaning, in optimized conditions, can reduce the thickness of the hydroxychloride layers slightly affecting the oxide layers. The difference in the interaction with laser radiation of these two layers seems to be mainly related to the difference in grain size and porosity. Notwithstanding these encouraging results, in order to define the real feasibility of the laser cleaning procedure, a further validation on real artefacts is mandatory due to the variation in thickness and composition of the corrosion products formed during long-lasting uncontrolled degradation processes.</p

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

The James Webb Space Telescope Mission

Twenty-six years ago a small committee report, building on earlier studies, expounded a compelling and poetic vision for the future of astronomy, calling for an infrared-optimized space telescope with an aperture of at least $4m$. With the support of their governments in the US, Europe, and Canada, 20,000 people realized that vision as the $6.5m$ James Webb Space Telescope. A generation of astronomers will celebrate their accomplishments for the life of the mission, potentially as long as 20 years, and beyond. This report and the scientific discoveries that follow are extended thank-you notes to the 20,000 team members. The telescope is working perfectly, with much better image quality than expected. In this and accompanying papers, we give a brief history, describe the observatory, outline its objectives and current observing program, and discuss the inventions and people who made it possible. We cite detailed reports on the design and the measured performance on orbit.Comment: Accepted by PASP for the special issue on The James Webb Space Telescope Overview, 29 pages, 4 figure

Du nucléaire à la conservation du patrimoine - Compréhension des mécanismes de corrosion des alliages ferreux sur le long terme grâce à la caractérisation multi-échelles

The corrosion of metals such as steel presents a high variability depending on the environments of alteration (aqueous aerated and deaerated atmosphere, binders and concrete ...) and durations considered. As part of my research, in order to understand these mechanisms over long periods the study of archaeological artefacts corroded over tens to hundreds of years has been chosen. This research was crucial in many application areas, ranging from the preservation of objects of cultural heritage and studies for the storage and disposal of radioactive waste in deep geological environment. In this area the archaeological artefacts constitute unparalleled analogues for the study of corrosion of steel elements embedded in the multi-barrier to separate the radionuclides from the biosphere. Characterization of corrosion systems was conducted through a methodology based on the coupling of multiscale techniques for materials characterization (SEM-EDS, Raman microspectroscopy, microXRD, XAS synchrotron radiation ...) providing information on the location, morphology, composition and structure of the crystalline phases present in a layer of corrosion products. Moreover, studies of the reaction processes and of the chemical or electrochemical reactivity of the systems by recorrosion experiments of archaeological objects in labeled medium (D2O, O18) or under external stimuli (chemical, electrochemical) have highlighted phenomena controlling the corrosion process at the micrometric scale. Perspectives of my research are the study of further constraints of the corrosion processes such as the presence of bacteria in the environment, the study of processes at the nanoscale (TEM, STXM) but also the methodological development of new analytical approaches based on a combination of morphological imaging methods (FEG-SEM), composition (EDS), structure (μXRD under synchrotron radiation) or hyperspectral (Raman microspectroscopy) to determine the synergy of the nano and microscale phenomena at the scale of an object. Taken together, these studies should lead to develop further protocols for diagnosis, treatment and conservation of cultural objects and reinforce the mechanistic models developed for the design of ferrous elements included in the storage facilities of radioactive waste.Les phénomènes de corrosion des métaux tels que les aciers présentent une grande variabilité en fonction des milieux d'altération (aqueux aéré et désaéré, atmosphère, liants et béton...) et des durées prises en compte. Dans le cadre de mes activités de recherche, afin d'appréhender ces mécanismes sur le très long terme il a été choisi d'étudier des objets archéologiques corrodés sur plusieurs dizaines à centaines d'années. Cet axe de recherche est en effet crucial dans plusieurs domaines d'applications, allant de la conservation des objets du patrimoine culturel aux études menées pour l'entreposage et le stockage des déchets radioactifs en milieu géologique profond. Dans ce domaine les objets archéologiques constituent des analogues sans équivalents pour la corrosion des éléments en acier constitutifs de la multibarrière destinée à séparer les radioéléments de la biosphère. La caractérisation des systèmes de corrosion a été menée grâce à une méthodologie d'étude basée dans un premier temps sur le couplage de techniques de caractérisation des matériaux multi-échelles (MEB-EDS, , microspectroscopie Raman, microXRD, XAS sous rayonnement synchrotron...) donnant des informations sur la localisation, la morphologie, la composition et la structure des phases cristallines présentes dans une couche de produits de corrosion. Par ailleurs les études des processus réactionnels et de la réactivité chimique ou électrochimique des systèmes à l'aide de remise en corrosion de ces objets archéologiques en milieu marqué (D2O, O18) ou sous sollicitations externes (chimique, électrochimique) ont mis en évidence des phénomènes à l'échelle micrométrique contrôlant les processus de corrosion d'objets archéologiques. Les perspectives de mes recherches sont d'une part l'étude de nouvelles perturbations des processus de corrosion telles que la présence de bactéries dans le milieu, l'étude des processus à l'échelle nanométrique (MET, STXM) mais également sur le plan méthodologique, le développement de nouvelles approches analytiques basées sur la combinaison de méthodes d'imagerie de morphologie (MEB-FEG), de composition (EDS), de structure (µXRD sous rayonnement synchrotron) ou hyperspectrale (microspectroscopie Raman) afin de déterminer la synergie des phénomènes nano et microscopiques à l'échelle d'un objet. L'ensemble de ces études devra conduire à d'une part développer les protocoles de diagnostic, de conservation et de traitement des objets culturels ferreux et d'autre part conforter les modèles mécanistiques mis en place pour le dimensionnement des éléments ferreux inclus dans les dispositifs de stockage des déchets radioactifs

Corrosion of Archaeological and Historical Artefacts

International audienceThis special issue of Material and Corrosion derives from research within Working Party 21 " Corrosion of archaeological and historical artefacts " of the European Federation of Corrosion. It specifically reports on the analysis, corrosion, conservation and management of heritage metals deriving from ancient through to modern contexts. The annual meeting of Working Party members at EUROCORR is an occasion for reporting research and generating ideas and collaborations between working groups across broad international contexts. It offers opportunity to identify common ground between researchers and to focus direction of research activities. Additionally the group aims to publish proceeds of such meetings and has delivered two EFC Green Books and this special issue continues that tradition. Preserving the tangible cultural heritage faces challenges from many directions that include climate change, under-funding and a basic need for more directed research that translates into planning and management outputs. While the advances in innovative high technological tools within physics and chemistry offer strong platforms for micro-investigation of corrosion products and processes that can be used to develop successful treatments, challenges exist for funding projects that will deliver this type of heritage focused data. While more dedicated funding is necessary to develop such research, the emergence of groups dedicated to delivering sector relevant data, often on a collaborative basis, has led to the growth of conservation science as a discipline to underpin the work of conservation practitioners. The discipline was recently defined (ICCROM " Conservation Science " forum, Rome 2013) as the application of science and technology to the conservation of cultural heritage. A primary goal is developing better understanding of the structure and decay of ancient materials and linking this to the development of treatment guidelines in conservation practice. Conservation science encompasses professionals from workshops, museum and research laboratories working on the improvement of analytical tools and restoration protocols. The annual meeting of Working Party 21 at EUROCORR involves delivery of current research by workers in conservation science from public and private institutes. This issue of Materials and Corrosion contains papers derived from selected oral contributions at the 2014 EUROCORR session that took place in Pisa. The reader will gain an overview of current research across a range of areas in which working party members are active, specifically: dating of metallic materials by the application of electrochemical methods; understanding long-term corrosion mechanisms; the impact of environment on corrosion rates and longevity of heritage metals; developing treatment methods and assessing their outcomes; and the delivery of management protocols and production of sector wide guidelines on their application. This range of papers touches on the scope of conservation science in relation to its delivery to the heritage sector and the synergy between science and evidence based practice. These working party meetings serve to identify the links that will develop such synergy and to generate the ideas and collaborations that will make it possible

Preservation of metallic artefacts: understanding the long term degradation processes thanks to multi-scale characterisation

International audiencePreservation of metallic artefacts: understanding the long term degradation processes thanks to multi-scale characterisation Metallic artefacts undergo corrosion over long periods. This conducts to a loss of readability or shape of the artefacts prejudicial for the preservation of metallic cultural heritage. Stabilisation and protection treatments are conducted to preserve them from destruction. They are based on immersion or coating protocols who can lack of efficiency. That is why the development of scientific studies to understand the physico-chemical processes involved is necessary. This presentation will explained how the NIMBE/LAPA has developed a specific approach to achieve this aim. It will be shown how this scientific researches are conducted in close collaboration with curators. Case studies of artefacts coming from the archaeological terrestrial site of Glinet (16 th c, Normandy, France) and the marine site of Les Saintes Maries de la mer (1 st BC, Bouches du Rhône, France) will be presented