Engineering the surface orientation of face-centered cubic (fcc) metals to the close-packed {111} plane can significantly enhance their oxidation resistance. However, owing to the synergetic effect of surface energy density ($\dot{\gamma }$) and strain energy density ($\omega$), such close-packed surface orientation can currently only be achieved by atomic-level thin film epitaxy or monocrystallization of polycrystalline metals. In this study, we characterized the microstructures of pure copper (Cu) foil and two types of graphene-coated Cu (Gr/Cu) foils and observed a 12~14 nm thick reconstructed surface layer with the {111} orientation in the high-temperature deposited Gr/{001} Cu surface. Combining the statistical results with thermodynamic analysis, we proposed a surface melting-solidification mechanism for the reconstruction of the Cu surface from {001} orientation to {111} orientation. This process is dominated by Gr/Cu interfacial energy and is particularly promoted by high-temperature surface melting. We also validated such a mechanism by examining Cu surfaces coated by h-BN (hexagonal boron nitride) and amorphous carbon. Our findings suggest a possible strategy to enhance the surface properties of fcc metals via engineering surface crystallography.

Graphene (Gr) has shown great potential in the field of oxidation protection for metals. However, numerous studies have shown that Gr will suffer structural degradation on metal surface during high-temperature oxidation, which significantly limited the effectiveness of their oxidation protection. Therefore, understanding the degradation mechanism of Gr is of great interest to enhance their structural stability. Here, the effect of copper (Cu) surface roughness on the high-temperature structural stability of single-layer graphene (SLG) was examined using Cu covered with SLG as a model material. SLG/Cu with different roughness values was obtained via high-temperature annealing of the model material. After high-temperature oxidation at 500 °C, Raman spectra analysis showed that the defect density of the oxidized SLG increased from 41% to 81% when the surface roughness varied from 37 nm to 81 nm. Combined with density functional theory calculations, it was found that the lower formation energy of the C-O bond on rough Cu surfaces (0.19 eV) promoted the formation of defects in SLG. This study may provide guidance for improving the effectiveness of SLG for the oxidation protection of metallic materials.