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Multiscale Study of Interactions Between Corrosion Products Layer Formed on Heritage Cu Objects and Organic Protection Treatments

Maëva L'héronde 1, 2, 3 Muriel Bouttemy 3 Florence Mercier-Bion 1, 2, 4, * Delphine Neff 1, 4 Emilande Apchain 1, 4 Arnaud Etcheberry 3 Philippe Dillmann 1, 4
* Corresponding author
1 LAPA - UMR 3685 - Laboratoire Archéomatériaux et Prévision de l'Altération
NIMBE UMR 3685 - Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M)
4 IRAMAT - LMC - IRAMAT - Laboratoire Métallurgies et Cultures
IRAMAT - Institut de Recherches sur les Archéomatériaux
Abstract : In the framework of the protection of copper objects exposed to atmospheric corrosion, different solutions are envisaged, among them carboxylate treatments (HC$_{10}$). In this study, an analytical approach based on complementary techniques from micrometer to nanometer scale ($\mu$RS, SEM-EDS, SAM) is used to describe the properties of the corrosion products layer (CPL) and determine the penetration depth of the HC$_{10}$ protection treatment inside the CPL of copper samples issued from the roof of the Saint Martin church in Metz. The CPL consists in a thick brochantite layer (20 to 50 $\mu$m), mainly composed of Cu$_4$ SO$_4$ (OH)$_6$ , on top of a thinner (1 to 5 $\mu$m thick) cuprite layer, Cu$_2$O, acting as a natural corrosion barrier on the metal. Application of the organic treatment is implemented by immersing the corroded samples in HC$_{10}$ solution, consistent with future requirements for large scale applications. Even for short-term duration (one minute), the HC$_{10}$ treatment penetrates to the cuprite/brochantite interface, but Cu(C$_{10}$)$_2$ precipitate is only detected locally, whereas for a longer immersion of thirty minutes, it is present in higher proportions in the whole brochantite layer, filling the pores, up to the cuprite/brochantite interface. Cu(C$_{10}$)$_2$ acts as a second inner barrier and prevents liquid infiltration.
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Maëva L'héronde, Muriel Bouttemy, Florence Mercier-Bion, Delphine Neff, Emilande Apchain, et al.. Multiscale Study of Interactions Between Corrosion Products Layer Formed on Heritage Cu Objects and Organic Protection Treatments. American Heritage, American Heritage, 2019, 2 (3), pp.2640-2651. ⟨10.3390/heritage2030162⟩. ⟨cea-02293434⟩

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