Surface characterization and adhesion of black-oxide-coated copper substrate: effect of surface hardening processes

The effects of surface-hardening processes on the changes in surface characteristics and adhesion of black copper oxide substrate with epoxy resins are studied. Various techniques, namely SEM, XPS, AFM, XRD, Auger electron spectroscopy, contact angle goniometry, D-SIMS and RBS, were used to identify the changes in surface characteristics. Dense, fibrillar cupric oxide crystals characterized the as-deposited oxide coating with high surface roughness. The surface-hardening process flattened and consolidated the fibrils without changing the compositional and thermodynamic characteristics of the coated surface. The surface-hardening process reduced the total thickness of copper oxide by approximately 50-150 nm. The reduction in oxide thickness was not a predominant factor for the reduced bond strength of the surface-hardened coating. The bond strengths of both the as-deposited and surface-hardened black oxide coatings increased with oxidation time, until saturation at about 120-150 s. For the as-deposited oxide coating, mechanical interlocking, high wettability and resistance to surface contamination are the three major sources for improved adhesion, amongst which the enhanced mechanical interlocking provided by the fibrillar cupric oxide is the most important. Surface hardening reduced the efficiency of mechanical interlocking mechanism. There was close functional dependence between the button-shear strength and surface characteristics, such as surface roughness, coating thickness and surface free energy.