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A series of low-density polyethylene (LDPE) surfaces, chemically modified using a number of oxidative techniques employed for adhesion enhancement (pretreatments), have been studied by time-of-flight (ToF) SIMS and XPS. The methods consisted of corona discharge, flame, electrochemical, chromic acid, acid dichromate and acid permanganate treatment. All except flame treatment were performed under mild and fairly severe conditions to yield a range of surface chemistries. The XPS analysis, using high energy resolution and a refined approach to C 1s curve-fitting, provided some new insights into the quantitative assessment of the type and concentration of functional groups. Both positive and negative ion ToF-SIMS spectra were obtained at high mass resolution. The oxygen-containing fragments were identified by accurate mass analysis and subjected to a detailed comparison with the XPS results. No convincing relative intensity correlations could be identified that would allow particular secondary ion fragments to be associated strongly with particular functional groups (in this multi-functional surface situation). Inorganic residues resulting from wet chemical treatments were also investigated and here the two techniques were found to be more complementary.

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