Time-of-flight secondary ion mass spectrometry of poly(alkyl acrylates) : comparison with poly(alkyl methacrylates)

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) has been used to examine a series of poly(alkyl acrylate) (PAA) homopolymers containing a variety of ester groups. Reproducible spectra for the PAAs are obtained up to 3500 Da. The spectra are composed of clusters arranged in a series of repeating patterns. These clusters are silver cationized neutral fragments of the main polymer chain. Free radical fragmentation mechanisms are proposed for PAAs under ion beam bombardment. The effect of the nature of the ester group on the fragmentation patterns of PAAs is discussed. The PAA spectra are also compared with spectra obtained from a previous TOF-SIMS study of poly(alkyl methacrylates).