The applications of ESCA to polymer surface analysis include the use of the secondary final-state effects which lead to satellite structure near the core-level photoemission (PE) lines. Specifically, unsaturated and aromatic functionalities in organic compounds and polymers lead to π* ← π shakeup peaks of less than 10 eV lower kinetic energy (higher binding energy). In the surface analysis of polymers, these features can be utilized for qualitative analysis, identification of the presence and structure of aromatic bonding, and quantitative analysis in determining the amount of a particular block or the aromatic containing function in the near-surface region. Carbon Is shakeups are most often used, but the present study includes detailed qualitative and quantitative analysis of shakeup structures from PE lines from each type of atom in hydrocarbon-, siloxane-, and sulfur-containing polymers. These results show the importance of including the shakeup intensity in quantitative peak area calculations and in peak fitting of complex PE envelopes. These studies prove in a variety of systems that the effects of third-row atoms on the final state lead to the presence of shakeup features in atoms with orbitals which do not participate in the aromatic orbital initial state, thus complicating interpretation of structure from the presence of these features. Results from the siloxane and sulfone polymers indicate that previously held assumptions about the nature of the initial-state molecular orbital may overlook the contribution of empty 3d orbitals or increased charge density on the Si or S atom which would spread the pi orbitals to the oxygen in the aromatic siloxane or sulfone systems. Finally, analysis of these features can provide quantitative analysis of polymeric surface structure by monitoring the relative intensity of the feature to the main PE line.

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The structural characteristics of Co/Mo/A1203 hydrodesulfurization catalysts have been investigated with a variety of surface spectroscopic techniques: ESCA, ISS, and photoacoustic spectroscopy (PAS). All catalysts were prepared by sequential impregnation of Mo and Co into -1203 with the Mo concentration held constant at 15% Mo03 by weight as the cobalt concentration was varied from 1 to 9% CoO. In all catalysts interaction between Co and the support was observed which rendered a portion of the Co inert toward H2 reduction and H2S sulfidation. This interaction species (Co-t) is dominant for catalysts of low cobalt loading (i.e., 1% CoO). As the cobalt concentration is increased a new phase is formed characterized by interactions between Co and Mo. This species (Co-M) is produced up to a concentration of 7% CoO. Above this level, Co304 is formed. From ISS it was determined that the Co ions were situated beneath the Mo ions as Co-t and the Co-Mo interaction species. The presence of cobalt was found to have no effect on the reduction or sulfidation of Mo.