Derivatization Technique to Increase the Spectral Selectivity of Two-Dimensional (2D) Fourier Transform Infrared Focal Plane Array (FT-IR FPA) Imaging: Analysis of Binder Composition in Aged Oil and Tempera Paint.

The interpretation of standard Fourier transform infrared spectra (FT-IR) on oil-based paint samples often suffers from interfering bands of the different compounds, namely, binder, oxidative aging products, carboxylates formed during aging, and several pigments and fillers. The distinction of the aging products such as ketone and carboxylic acid functional groups pose the next problem, as these interfere with the triglyceride esters of the oil. A sample preparation and derivatization technique using gaseous sulfur tetrafluoride (SF4), was thus developed with the aim to discriminate overlapping signals and achieve a signal enhancement on superposed compounds. Of particular interest in this context is the signal elimination of the broad carboxylate bands of the typical reaction products developing during the aging processes in oil-based paints, as well as signal interference originating from several typical pigments in this spectral range. Furthermore, it is possible to distinguish the different carbonyl-containing functional groups upon selective alteration. The derivatization treatment can be applied to both microsamples and polished cross sections. It increases the selectivity of the infrared spectroscopy technique in a fundamental manner and permits the identification and two-dimensional (2D) localization of binder components in aged paint samples at the micrometer scale. The combination of SF4 derivatization with high-resolution 2D FT-IR focal plane array (FPA) imaging delivers considerable advances to the study of micro-morphological processes involving organic compounds.