Probing Surface Concentration of Cyclic/Linear Blend Films Using Surface Layer MALDI-TOF Mass Spectrometry.

Surface layer matrix-assisted laser desorption ionization time-of-flight mass spectrometry (SL-MALDI-TOF MS) is a powerful new surface sensitive technique to quantify the surface concentration of multicomponent polymer films with enrichment of one component at the surface. Its capabilities are demonstrated for the novel case of a blend of cyclic polystyrene with linear polystyrene, in which we find the composition of linear chains enriched at the surface after annealing, contrary to the expectation of a self-consistent field theory. The probing depth was confirmed to be monomolecular, which for these short chains is less than 2 nm, even though material at a much greater depth is removed by the analysis.