The Influence of Water Concentration on High-Temperature Reactive Evaporation and Condensation of Cr in 800°C Air

Abstract

Deleterious reactive evaporation of chromium from stainless steels commonly used in solid oxide electrochemical systems is well-documented; however, interactions between Cr vapor species and surrounding interfaces during complex and dynamic system exposures is poorly understood. Understanding the interactions between Cr vapor species and downstream components during operation is critical for improving system performance and safeguarding environmental, health and safety, as many condensed Cr compounds contain toxic and carcinogenic hexavalent chromium Cr(VI). Furthermore, the interactions between volatilized Cr species and surrounding interfaces are dependent upon dynamic chemical environments. The objective of this study is to systematically investigate and report on condensation pathways of Cr vapors within representative system environments with variable water concentrations. To accomplish this objective, an experimental platform was designed to generate Cr vapor species from the reactive evaporation of chromia (Cr2O3) powder with high-temperature (>1100 K) air/H2O mixtures, and expose downstream ceramic insulation materials (e.g., aluminosilicate fibers) at reduced temperatures (<600 K). Insulation material chemical compositions investigated include pure silica (SiO2) and alumina (Al2O3) to combinations thereof with and without inclusions of alkaline earth metals (e.g., Ca, Mg, Sr). Materials are studied as a function of exposure conditions using complementary materials characterization tools such as SEM-EDX, XPS, and diphenyl carbazide reactions to assess Cr(VI) concentrations. Reactive evaporation of Cr from chromia occurs in the presence of oxygen and/or water vapor to form various Cr-containing vapor species. Thermodynamic data reveals an equilibrium partial pressure increase of several orders of magnitude at elevated (>500 K) temperatures for all Cr vapor species. In the presence of water vapor, the partial pressure of Cr oxyhydroxide (CrO2(OH)2(g)) is greater by many several orders of magnitude and becomes the dominant species up to ~1500 K. The research objective is to explore effects of water vapor in air on Cr condensation and speciation on different ceramic insulation materials. The experimental setup thus far has exposed aluminosilicate fibers to volatilized Cr species from Cr oxide powder at 1100 K for 150 hours under varying water vapor conditions: 0 vol%(dry), 3 vol%, and 10 vol% H2O. Preliminary results show an increase in Cr(VI) formation on fibers exposed to volatile Cr species as water vapor content increases. See Figure 1 for an overview of the experimental concept, Cr(VI) test kit, and preliminary results for dependency on water vapor. Analyses of these results will be presented and discussed in context of potential implications for SOFC/SOEC systems. Figure 1