Very harsh environments exist in the iodine sulfur process for hydrogen production. Structural materials for sulfuric acid vaporizers and concentrators are exposed to high-temperature corrosive environments. Immersion tests were carried out to evaluate the corrosion resistance of ceramics and to evaluate corrosion-resistant metals exposed to environments of aqueous sulfuric acids at temperatures of 320, 380, and 460 degrees C, and pressure of 2 MPa. The aqueous sulfuric acid concentrations for the temperatures were 75, 85, and 95 wt%, respectively. Ceramic specimens of silicon carbides (SiC), silicon-impregnated silicon carbides (Si-SiC), and silicon nitrides (Si3N4) showed excellent corrosion resistance from weight loss measurements after exposure to 75, 85, and 95 wt% sulfuric acid. High-silicon irons with silicon content of 20 wt% showed a fair measure of corrosion resistance. However, evidence of crack formation was detected via microscopy. Silicon enriched steels severely suffered from uniform corrosion with a corrosion rate in 95 wt% sulfuric acid of approximately 1 g m(-1) h(-1). Among the tested materials, the ceramics SiC, Si SiC, and Si3N4 were found to be suitable candidates for structural materials in direct contact with the considered environments. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.