The positive SIMS spectrum of poly(methyl methacrylate) (PMMA) has been obtained with a mass resolution in excess of 8000 and all the components assigned up to m/z 200 based on accurate mass measurements. Aspects of the interpretation of the spectrum, previously based on quadrupole SIMS data from a number of acrylic polymers, need to be revised significantly. In particular, the spectrum is dominated by oxygen‐containing fragments derived from oligomeric units rather than hydrocarbon fragments derived from the polymer backbone. To aid further the understanding of the fragmentation of acrylic polymers, a less‐detailed study of poly(methyl acrylate) has also been carried out. Copyright © 2000 John Wiley & Sons, Ltd.

A series of seven chlorine-containing polymers with widely ranging structures have been studied by time-of-flight secondary ion mass spectrometry (ToF-SIMS) at high mass resolution. The prototypical positive ion spectrum of poly(vinyl chloride) has been analysed in detail to identify unambiguously all the components at each nominal mass up to m/z 130. For other polymers based on variously Cl-substituted aliphatic hydrocarbons, the same Cl-containing ions are observed but their relative intensities are different and characteristic. The relative intensities of common fragments containing one or two chlorine atoms in both positive ion spectra (RCl 2 + /RCl + / and negative ion spectra (Cl 2 − /Cl − / have been compared quantitatively with the bulk atomic chlorine concentration. These two ratios also show a remarkable correlation across the polymer series. An ion formation mechanism is proposed to explain the observed correlations.

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