Dense coatings on metallic interconnectors are necessary to suppress chromium poisoning of SOFC cathodes. Atmospherically plasma sprayed (APS) Mn1.0Co1.9Fe0.1O4 (MCF) protective layers demonstrated reduced chromium related degradation in laboratory and stack tests. Previous analyses revealed strong microstructural changes comparing the coating's as-sprayed and operated condition. This work concentrates on the layerdensification and crack-healing observed by annealing APS-MCF in air, which simulates the cathode operation conditions. The effect is described by a volume expansion induced by a phase transformation. Reducing conditions during the spray process lead to a deposition of the MCF in a metastable rock salt configuration. Annealing in air activates diffusion processes for a phase transformation to the low temperature stable spinel phase (T < 1050 °C). This transformation is connected to an oxygen incorporation which occurs at regions facing high oxygen partial pressures, as there are the sample surface, cracks and pore surfaces. Calculations reveal a volume expansion induced by the oxygen uptake which seals the cracks and densifies the coating. The process decelerates when the cracks are closed, as the gas route is blocked and further oxidation continues over solid state diffusion. The self-healing abilities of metastable APS coatings could be interesting for other applications.

No abstract

No abstract

As part of two different stack tests with four-plane short stacks and their intensive post-test characterization, two varying diffusionrelated degradation mechanisms were investigated. The first was a short-term test (~1250h) with two different chromium evaporation protection layers on the air-side metallic interconnect and frame and the second was a long-term endurance test (~ 35,000h). For the first stack, two planes were coated with a manganese oxide layer applied by wet powder spraying (WPS), while the other two planes were coated with a manganese-cobalt-iron spinel layer by atmospheric plasma spraying (APS). The voltage loss in the planes with a WPS-coated interconnect was markedly higher than in those coated by means of APS. Finally, it was shown that the microstructure of the layers plays a key role in minimizing Cr evaporation. In this stack, gas-phase diffusion prevails over degradation. In the long-term stack, severe degradation due to solid-state manganese diffusion was observed. This paper draws an interaction hypothesis.

Applying atmospherically plasma-sprayed (APS) Mn 1.0 Co 1.9 Fe 0.1 O 4 (MCF) protective coatings on interconnector steels minimized the chromium-related degradation within solid oxide fuel cell stack-tests successfully. Post-test characterization of the coatings disclosed a severe microstructural and phase evolution. A self-healing of micro-cracks, the formation and agglomeration of small pores, the occurrence of a dense spinel layer at the surface and a strong elemental de-mixing were reported in ex situ experiments. In the present publication, we prove for the first time these mechanisms by tracking the microstructure in situ at a single APS coating using synchrotron X-ray nanotomography at the European Synchrotron Radiation Facility. Therefore, a 100-lm-long cylindrical sample with a diameter of 123 lm was cut from an APS-MCF free-standing layer and measured within a high-temperature furnace. All microstructural changes mentioned above could be verified. Porosity measurements reveal a decrease in the porosity from 9 to 3% during the annealing, which is in good accordance with the literature. Additionally, a partial detachment of an approximately 5-lm-thick layer at the sample surface is observed. The layer is dense and does not exhibit any cracks which are penetrating the layer. This kind of shell is assumed to be gastight and thus protecting the bulk from further oxidation.