The positive and negative ion spectra from homologous series of alkyl methacrylate, hydroxyalkyl methacrylate and alkyl acrylate polymers; poly(methacry1ic acid) and poly(methacry1ic anhydride) are reported. A systematic interpretation of the spectra can be accomplished on the basis of fragmentation pathways consistent with the known effects of other ionizing radiations. The negative ion spectra, previously little studied, are a powerful probe of structure for this class of polymer.

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A series of fluorine-containing segmented poly(ether urethanes) and poly(ether urethane ureas), previously characterized by angular dependent x-ray photoelectron spectroscopy (XPS) have been re-examined using static secondary ion mass spectrometry (SIMS). Comparison of the data from the two techniques has shown that the intensity of secondary ion signals which characterize the hard and soft segments can be used quantitatively for direct analyis of the molecular cymposition at the surface. Moreover, the SIMS sampling depth for the conditions used has been shown to be -10 A, significantly less than the XPS sampling depth under normal conditions, and similar to the XPS sampling depth at high glancing take-off angle (with respect to the surface normal).

Poly(ethy1ene terephthalate) (PET) and polystyrene (PS) have been studied using static secondary ion mass spectrometry (SSIMS). A triple quadrupole analyser has been employed to investigate secondary ion fragmentation and formation mechanisms. Daughter spectra and neutral loss spectra were obtained and fragmentation patterns were deduced. Comparison of the fragmentation data obtained in the gas-phase collisionally activated dissociation (CAD) experiments with the SSIMS data suggested that ion formation probabilities during CAD were similar to ion formation probabilities at the solid surface during low-flux sputtering. It was concluded that lowenergy gas-phase CAD processes model effectively the processes which lead to fragmentation of the polymer during low-flux sputtering.