Reactive vaporization of oxides in solid oxide fuel cell systems :

Abstract

Metals such as chromium, aluminum and silicon are of extreme technological and industrial importance due to the corrosion resistance they offer in oxidizing environments at high temperature. Much of this robustness is based on the formation of a thin, well-adhered metal-oxide (MO) layer on the surface of the metal. In particularly corrosive environments or at high-enough temperatures and or pressures, the MO will chemically react with constituents in the surrounding gas, removing atoms from the solid. For many systems, material loss and subsequent mechanical failure is the foremost concern. However, in solid oxide fuel cell (SOFC) systems, the presence of gaseous metal species leads to severe degradation in electrochemical performance well before mechanical limits are reached. Reactive vaporization from ferritic stainless steels, chromia, aluminosilicates and a candidate electrode material (Sr 2VMoO 6), was investigated using the transpiration method. Two novel collection methods were employed: condensation of vapors on wafer collectors analyzed with Rutherford backscattering spectrometry (RBS); and, condensation of vapors on quartz wool analyzed via inductively coupled plasma mass spectroscopy (ICP-MS). Identification and quantification of vapor species provided assessment of material performance in SOFC environments. Experiments demonstrated that Cr vapor species from ferritic stainless steels used for SOFC interconnect applications could be reduced by as much as one order of magnitude through the application of barrier coatings. Base alloys were compared and exhibited a variety of Cr vaporization rates despite being similar in composition, thus illustrating the importance of minor elemental constituents in the alloy. Measurements identified Si as the primary volatile element in aluminosilicate materials when Si concentrations in the bulk material were as low as one percent. Aluminosilicate materials demonstrated a burn out phase during the first hundred hours at 800°C in humid oxidizing environments, where large amounts of Si and other elements were vaporizing. Mass transport rate versus flow rate experiments on pure Cr 2O 3 indicated that sample surface area influences the measured Cr vapor pressure. This finding helps explain the range of values reported in literature for the equilibrium rate constant of the most common Cr vaporization reaction in SOFC environments.