In order to contribute to the improvement of restoration and conservation sciences of metallic artefacts belonging to Cultural Heritage, a wide research has been started on the study of artificial (artistic) and natural (corrosion or alteration) patinas of copper-based alloys. Micro-Raman spectroscopy (mRS) coupled with scanning electron microscopy (SEM) equipped with energy Dispersive X-Ray Spectroscopy (EDXS) were applied for the characterization of a number of patinas made on metallic substrate reproducing the typical copper-based alloys used for statuary. A non alloyed copper sheet has been also used to simulate the architectural cover typically used after a specific cold spray coating. To reach these goals, a number of patinas were experimentally produced in our laboratory using the torch technique and reactive solutions based on water as a solvent containing, respectively, copper nitrate, iron nitrate and potassium sulfide (‘liver of sulfur’). The only exception is a sample reproducing the architectural cover of a recent building nearly completely covered with copper sheets coated with copper salts. All the produced patinas were aged in a salt spray chamber and then studied with mRS, SEM and EDXS in order to understand their evolution between the two known terms and therefore the reactions involved in all patinas. mRS allowedus todetect asmain constituents of the ‘artistic’ patinas, before and after ageing: copper oxides (Cuprite and Tenorite), copper nitrates (Rouaite and Gerhardtite), copper chlorides (Botallackite, Atacamite and Paratacamite), a copper sulfate (Posnjakite), iron oxides (Magnetite and Hematite) and an iron hydroxide (Limonite)

Metallic interconnects represent the main component of a solid oxide fuel cell (SOFC) stack in terms of weight and volume. They are typically made of ferritic stainless steel (FSS) coated on the air side. At the stack operating conditions, the interconnect is exposed to a dual atmosphere: air at the cathode side; fuel (a hydrogen-rich mixture) at the anode side. The stacks considered in this study were field operated in reformed natural gas for 5000, 9000 and 20,000 h respectively. The analyzed interconnects are made from CROFER22APU and coated on the air side with Co-Mn base spinel. One interconnect has been studied for each stack by sampling and preparing cross section the inlet and outlet positions. The samples were characterized by SEM-EDXS in order to investigate the evolution of the interconnect at the air side. The interaction between the metal substrate and the coating is investigated highlighting the formation of chromia based thermal grown oxide (at the FSS/coating interface) and the solid-state diffusion of Cr and Fe from the metal into the coating. The microstructural features evolving as a function of time are also quantified.

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Analyses performed on a stack operated for more than 4000h at 750°C at high fuel utilization (80%) revealed significant differences in aging behaviour of stack components when comparing fuel inlet and fuel outlet areas. Two samples were cut from the fuel inlet and outlet manifolds of the operated SOFC stack. The glass-ceramic sealing material and the interconnect alloy were exposed to a dual atmosphere (external air and internal fuel stream). The fuel composition was dry H 2 /N 2 (60:40 vol. %) at the inlet and H 2 O/H 2 /N 2 (48:12:40 vol. %) at the outlet. The stack was operated in co-flow configuration, with a large excess of air. It was found that the interfaces between the seal and the alloy were significantly affected by the difference in fuel composition. The sealant exposed to the outgoing air was significantly polluted by chromium generated in the stack and transported by the air stream. These investigations therefore reveal that the long-term evolution of the sealing and of the metallic support depends on the local conditions in the stack, as well as on additional interactions with other degradation phenomena.