Femtosecond laser-induced porosity on poly(ethylene) surfaces—A crystallographic and rheological study

In recent years, femtosecond (fs) laser irradiation of polymer surfaces has been shown to produce novel porous topologies that present a multi-scale roughness. In our study, grazing incidence x-ray diffractometry results showed the appearance of a monoclinic crystalline phase on fs laser machined high density polyethylene (HDPE) which is a deformation of the orthorhombic phase typically observed in pristine HDPE. This was accompanied by a local decrease in crystallinity. These findings confirmed that the induced porosity was a consequence of the rapid quenching of a superheated melt layer undergoing phase explosion. In addition, several poly(ethylene) samples with different average molecular weights were machined under the same conditions. Scanning electron micrography, along with small angle oscillatory shear tests, indicated that the final pore size decreases with increasing average molecular weight or increasing melt viscosity since these parameters act against bubble growth during phase explosion. In addition, through computed tomography, the internal structure of the porous layer was investigated. Through this technique, the average pore size and pore size distribution can be computed by chord length analysis. In conclusion, in this study, the mechanisms behind the formation of femtosecond laser-induced porous structures and the parameters that control their dimensions have been established.