ToF‐SIMS depth profiling of a complex polymeric coating employing a C60 sputter source

A complex poly(vinylidene difluoride) (PVdF)/poly(methyl methacrylate) (PMMA)‐based coil coating formulation has been investigated using time‐of‐flight SIMS (ToF‐SIMS). Employing a Bi₃⁺ analysis source and a Buckminsterfullerene (C₆₀) sputter source, depth profiles were obtained through the polymeric materials in the outer few nanometres of the PVdF topcoat. These investigations demonstrate that the PVdF coating's air/coating interface is composed principally of the flow agent included in the formulation. Elemental depth profiles obtained in the negative ion mode demonstrate variations in the carbon, oxygen and fluorine concentrations within the coating with respect to depth. All three elemental depth profiles suggest that the PVdF coating bulk possesses a constant material composition. The oxygen depth profile reveals the presence of a very thin oxygen‐rich sub‐surface layer in the PVdF coating, observed within the first second of the sputter/etch profile. Retrospectively, extracted mass spectra (from the elemental depth profile raw data set) of the PVdF coating sub‐surface and bulk layers indicates this oxygen‐rich sub‐surface layer results from segregation of the acrylic co‐polymers in the formulation towards the PVdF coating air/coating interface. Molecular depth profiles obtained in both the positive and negative secondary ion modes provide supporting evidence to that of the elemental depth profiles. The molecular depth profiles confirm the presence of a sub‐surface layer rich in the acrylic co‐polymers indicating segregation of the co‐polymers towards the PVdF topcoats air‐coating surface. The molecular depth profiles also confirm that the PVdF component of the topcoat is distributed throughout the coating but is present at a lower concentration at the air‐coating interface and in the sub‐surface regions of the coating, than in the coating bulk. Copyright © 2007 John Wiley & Sons, Ltd.