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.

Cu-Fe alloys (CFAs) are much anticipated for use in electrical contacts, magnetic recorders, and sensors. The low cost of Fe has inspired the investigation of these alloys as possible replacements for high-cost Cu-Nb and Cu-Ag alloys. Here, alloys of Cu and Fe having compositions of Cu100-xFex (x = 10, 30, and 50 wt.%) are prepared by gas atomization and characterized microstructurally and structurally based on composition and powder size with scanning electron microscopy (SEM) and X-ray diffraction (XRD). Grain sizes and Fe-rich particle sizes are measured and relationships among composition, powder size, and grain size are established. Same-sized powders of different compositions yield different microstructures, as do differently sized powders of equal composition. No atomic-level alloying is observed in the CFAs under the experimental conditions.

To alloy high melting point elements such as boron, ruthenium, and iridium with copper, heat treatment was performed using metal oxides of B2O3, RuO2, and IrO2 at the temperature of 1200 oC in vacuum for 30 minutes. The microstructure analysis of the alloyed sample was confirmed using an optical microscope and FE-SEM. Hardness and trace element analyses were performed using Vickers hardness and WD-XRF, respectively. Diffusion profile analysis was performed using D-SIMS. From the microstructure analysis results, crystal grains were found to have formed with sizes of 2.97 mm. For the copper alloys formed using metal oxides of B2O3, RuO2, and IrO2 the sizes of the crystal grains were 1.24, 1.77, and 2.23 mm, respectively, while these sizes were smaller than pure copper. From the Vickers hardness results, the hardness of the Ir-copper alloy was found to have increased by a maximum of 2.2 times compared to pure copper. From the trace element analysis, the copper alloy was fabricated with the expected composition. From the diffusion profile analysis results, it can be seen that 0.059 wt%, 0.030 wt%, and 0.114 wt% of B, Ru, and Ir, respectively, were alloyed in the copper, and it led to change the hardness. Therefore, we verified that alloying of high melting point elements is possible at the low temperature of 1200 oC.