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–FTIR), is a well-established method for polymeric material analysis. However, ATR-FTIR 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-FTIR 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-FTIR reflection devices working in external reflection (ER-FTIR) and diffuse reflection (DRIFT) 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-FTIR and DRIFT spectra are thus expected when the same polymer is analyzed. So far, ER-FTIR and DRIFT spectroscopy have been individually explored for the identification of plastic objects, but comparative studies between the application of two reflectance FTIR modes have not been presented yet. In this work, the use of two portable FTIR spectrometers equipped with ER-FTIR and DRIFT 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-FTIR 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-FTIR and DRIFT in plastic analysis.

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Surface cleaning of plastic materials of historical value can be challenging due to the high risk of inducing detrimental effects and visual alterations. As a result, recent studies have focused on researching new approaches that might reduce the associated hazards and, at the same time, minimize the environmental impact by employing biodegradable and green materials. In this context, the present work investigates the effects and potential suitability of dense carbon dioxide (CO2) as an alternative and green solvent for cleaning plastic materials of historical value. The results of extensive trials with CO2 in different phases (supercritical, liquid, and vapor) and under various conditions (pressure, temperature, exposure, and depressurization time) are reported for new, transparent, thick poly(methyl methacrylate) (PMMA) samples. The impact of CO2 on the weight, the appearance of the samples (dimensions, color, gloss, and surface texture), and modifications to their physicochemical and mechanical properties were monitored via a multi-analytical approach that included optical microscopy, Raman and attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopies, and micro-indentation (Vickers hardness). Results showed that CO2 induced undesirable and irreversible changes in PMMA samples (i.e., formation of fractures and stress-induced cracking, drastic decrease in the surface hardness of the samples), independent of the conditions used (i.e., temperature, pressure, CO2 phase, and exposure time).