Studying Chemisorption at Metal–Polymer Interfaces by Complementary Use of Attenuated Total Reflection–Fourier Transform Infrared Spectroscopy (ATR-FTIR) in the Kretschmann Geometry and Visible–Infrared Sum-Frequency Generation Spectroscopy (SFG)

Abstract The molecular configuration and chemistry at the zinc/zinc oxide–polyester interface were studied by using two complementary spectroscopic techniques: attenuated total reflection–Fourier transform infrared spectroscopy (ATR-FTIR) and sum-frequency generation (SFG) spectroscopy. It was shown that ATR-FTIR should be considered as a (3D) interphase-sensitive technique with probing depths of 250–400 nm in the headgroup region (2000–1200 cm–1). On the other hand, SFG is known to be a (2D) interface-sensitive technique. The ATR-FTIR measurements showed that carboxylate groups are formed within the near-interface region of the polyester phase. SFG measurements showed that the carboxylic acid groups are stable at the polymer–zinc/zinc oxide interface. In addition, in situ ATR-FTIR and SFG measurements have been conducted when exposing the polyester–zinc/zinc oxide system to D2O. The exposure to D2O is observed to lead to an additional conversion of ester and carboxylic acid groups to carboxylate groups. The comparison of the SFG and ATR-FTIR measurements shows that this conversion occurs much slower at the polyester–zinc/zinc oxide interface than in the bulk of the polyester. Finally, the strengths and limitations as well as the complementarity of both techniques are discussed.