Vinyl emulsions started to be used by artists in paintings at least since the early 1960s, being now present in several artworks worldwide. However, different vinyl formulations can result in distinct behaviours over time, and if some artworks are currently showing a good condition, others already show damages due to the use of compositions more susceptible to degradation. For this reason, it is fundamental to identify the main components in the vinyl acetate-based (VAc-based) emulsion. This work focuses on the molecular study of VAc-based emulsions by infrared and Raman spectroscopies. It aims at deepening the knowledge on the variability of the composite formulation and on the identification of characteristic bands and spectral profiles (identified as spectral markers) for both polymer and additives. To this end, a broad set of vinyl emulsions was gathered, including reference materials, historical commercial brands in use by Portuguese artists, and commercial brands collected from industrial companies. The entire set includes vinyl homopolymers produced for the purpose of the study and known formulations of vinyl homopolymers and copolymers, with and without plasticisers, according to technical data sheets and previous studies. Furthermore, unknown formulations have been included to validate the usefulness of the identified spectral markers. This set has been studied in the form of solid films deposited in glass slides by infrared spectroscopy in attenuated total reflection mode (ATR-FTIR) and micro-Raman spectroscopy (µ-Raman), both conducted in situ. As conclusions, the combined use of ATR-FTIR and µ-Raman proved to be very useful as different spectral markers were detected by each technique, confirming their complementarity. Besides the clear identification of vinyl acetate-based emulsions by both techniques, it was also possible to suggest spectral markers for the copolymerisation of vinyl acetate with vinyl versatate by µ-Raman, the stabilisation of the emulsion with poly(vinyl alcohol) by ATR-FTIR, and the addition of phthalates or benzoates plasticisers by both ATR-FTIR and µ-Raman.

Plastics have been increasingly used to create modern and contemporary art and design, and nowadays, museum collections hold numerous objects completely or partially made of plastics. However, the preservation of these materials is still a challenging task in heritage conservation, especially because some plastics show signs of degradation shortly after their production. In addition, different degradation mechanisms can often take place depending on the plastic composition and appropriate environmental and packaging conditions should be adopted. Therefore, methods for in situ and rapid characterization of plastic artifacts’ composition are greatly needed to outline proper conservation strategies. Infrared (IR) spectroscopy, such as attenuated total reflection Fourier transform infrared spectroscopy (ATR FT-IR), is a well-established method for polymeric material analysis. However, ATR FT-IR requires an intimate contact with the object, which makes its application less appropriate for the in situ investigation of fragile or brittle degraded plastic objects. Mid-FT-IR reflectance spectroscopy may represent a valid alternative as it allows in situ measurements with minimum or even no contact, and IR data can be acquired rapidly. On the other hand, spectral interpretation of reflectance spectra is usually difficult as IR bands may appear distorted with significant changes in band maximum, shape, and relative intensity, depending on the optical properties and surface texture of the material analyzed. Presently, mid-FT-IR reflection devices working in external reflection (ER FT-IR) and diffuse reflection infrared Fourier transform spectroscopy (DRIFTS) modes have been used in cultural heritage research studies. As the collected vibrational information depends on the optical layout of the measuring system, differences between ER FT-IR and DRIFT spectra are thus expected when the same polymer is analyzed. So far, ER FT-IR and DRIFT spectroscopy have been individually explored for the identification of plastic objects, but comparative studies between the application of two reflectance FT-IR modes have not been presented yet. In this work, the use of two portable FT-IR spectrometers equipped with ER FT-IR and DRIFTS modes were compared for plastics identification purposes for the first time. Both references of polymeric materials and historical plastic objects (from a Portuguese private collection) were studied and the differences between ER FT-IR and DRIFT spectra were discussed. The spectra features were examined considering the two different optical geometries and analytes’ properties. This new insight can support a better understanding of both vibrational information acquired and practical aspects in the application of the ER FT-IR and DRIFTS in plastic analysis.