Adhesion at Al-hydroxide-polymer interfaces: Influence of chemistry and evidence for microscopic self-pinning

We present a combined chemical (auger electron spectroscopy) and microscopic (optical microscopy, scanning electron microscopy and scanning probe microscopy) study of the work of adhesion and delamination mechanisms at interfaces between a glassy polymer (glycol-modified polyethylene terephthalate) and Al covered with different types of surface hydroxides. A clear correlation between the measured work of adhesion and the chemical nature of the Al surface, specifically the hydroxyl coverage and the iso-electric point is found. The magnitude of the work of adhesion points to important contributions from plastic deformation in the glassy polymer for some cases. Delamination is shown to be accompanied by the formation of microscopic shear bands at such interfaces. The non-monotonous stress-strain behaviour of the glassy polymer that gives rise to the shear bands is also shown to lead to peculiar pinning events at the crack front. Evidence indicates that the occurrence of protrusions in the crack front deriving for example from the presence of stress concentrators and crack initiation sites ahead of the front, combined with mode and rate dependence of the local energy release rate along the front may pin the front at positions adjacent to a protrusion. It is believed such microscopic mode-dependent pinning phenomena may be relevant for the adhesion on patterned interfaces.