Recent advances in ion and electron spectroscopy of polymer surfaces

The structure of microdomains and bonding at multicomponent polymer material interfaces has been studied using a variety of surface sensitive spectroscopic techniques. In our laboratory, low energy ion scattering spectroscopy (ISS) and static secondary ion mass spectrometry (SIMS) serve to complement results from angular dependent X-ray photoelectron spectroscopy (XPS or ESCA), Fourier transform infrared (FTIR) with attenuated total reflectance (ATR) sampling and SEM techniques to provide a quantitative picture of the relationships between structure, bonding, morphology and microdomain formation in near surface regions of polymeric systems. The added surface sensitivity of ISS can yield quantitative information at a sampling depth of 3-5 Å, which, with ESCA and FTIR analysis yields a "non-destructive" depth profile of domain formation in copolymer and blend systems. These studies will be illustrated with results from siloxane and siloxane/polycarbonate copolymer systems, where a complete picture of surface domain formation and morphology as a function of composition and polymer crystallinity has been developed. ISS can also yield information regarding the orientation of surface functional groups which ESCA and FTIR do not have either sensitivity and/or sufficient detection limits to analyze. These studies will be illustrated by the analysis of plasma hydrolysis/oxidation of stereoregular poly(methyl-methacrylate). The effects of functional group orientation on reactivity will be explored using results from ISS, ESCA and FTIR for stereoregular (isotatic, syndiotactic) and random (atactic) PMMA. Electron energy loss spectroscopy at high resolution (HREELS) has recently been extended to the examination of polymer and organic surfaces. Vibrational information from this experiment can yield very precise results about surface functional groups (1-20 Å) but at much lower resolution than is typical from IR and Raman techniques. However, the promise of evaluating surface functionality in the presence of a vibrational active bulk makes HREELS investigations of polycrystalline, polymeric and organic systems extremely exciting. Recent results from Langmuir-Blodgett prepared monomeric and polymeric mono and multilayer systems will be contrasted with other recent reports of HREELS applications to this important field of emerging materials science.