The major concern in the deep geological disposal of spent nuclear fuels include sulfide-induced corrosion and stress corrosion cracking of copper canisters. Sulfur diffusion into copper canisters may induce copper embrittlement by causing Cu2S particle formation along grain boundaries; these sulfide particles can act as crack initiation sites and eventually cause embrittlement. To prevent the formation of Cu2S along grain boundaries and sulfur-induced copper embrittlement, copper alloys are designed in this study. Alloying elements that can act as chemical anchors to suppress sulfur diffusion and the formation of Cu2S along grain boundaries are investigated based on the understanding of the microscopic mechanism of sulfur diffusion and Cu2S precipitation along grain boundaries. Copper alloy ingots are experimentally manufactured to validate the alloying elements. Microstructural analysis using scanning electron microscopy with energy dispersive spectroscopy demonstrates that Cu2S particles are not formed at grain boundaries but randomly distributed within grains in all the vacuum arc-melted Cu alloys (Cu-Si, Cu-Ag, and Cu-Zr). Further studies will be conducted to evaluate the mechanical and corrosion properties of the developed Cu alloys.

Copper is used for deep geological disposal canisters of spent nuclear fuels, because of excellent corrosion resistance in an oxygen-free environment. However, sulfide formation during the long-term exposure under deep geological disposal condition can be harmful for the integrity of copper canisters. Sulfur around the canisters can diffuse along grain boundaries of copper, causing grain boundary embrittlement by the formation of copper sulfides at the grain boundaries. The development of copper alloys preventing the formation of copper sulfides along grain boundaries is essential for the longterm safety of copper canisters. In this research, the mechanisms of copper sulfide formation at the grain boundary are identified, and possible alloying elements to prevent the copper sulfide formation are searched through the first principle calculations of solute atom-vacancy binding energy and the molecular dynamics calculation of grain boundary segregation energy. The comparison with the experimental literature results on the mitigation of copper embrittlement confirmed that the theoretically identified mechanisms of copper sulfide formation and the selected alloy elements are valid. Thereafter, binary copper alloys were prepared by using a vacuum arc melting furnace. Sulfur was added during casting of the copper alloys to induce the sulfide formation. The cast alloys were cold-rolled into a plate after homogenization heat treatment. The microstructure and mechanical property of each alloy were investigated after recrystallization in a vacuum tube heat treatment furnace. The copper alloys developed in this study are expected to contribute in increasing the long-term safety of deep geological disposal copper canisters by reducing the embrittlement caused by the sulfide formation.