The interaction of pigments and binding media may result in the production of metal soaps on the surface of paintings which modifies their visible appearance and state of conservation. To characterise more fully the metal soaps found on paintings, several historically accurate oil and egg yolk tempera paint reconstructions made with different pigments and naturally aged for 10 years were submitted to attenuated total reflectance Fourier transform infrared (ATR FTIR) microspectroscopic analyses. Standard metal palmitates were synthesised and their ATR spectra recorded in order to help the identification of metal soaps. Among the different lead-based pigments, red lead and litharge seemed to produce a larger amount of carboxylates compared with lead white, Naples yellow and lead tin yellow paints. Oil and egg tempera litharge and red lead paints appeared to be degraded into lead carbonate, a phenomenon which has been observed for the first time. The formation of metal soaps was confirmed on both oil and egg tempera paints based on zinc, manganese and copper and in particular on azurite paints. ATR mapping analyses showed how the areas where copper carboxylates were present coincided with those in which azurite was converted into malachite. Furthermore, the key role played by manganese in the production of metals soaps on burnt and raw sienna and burnt and raw umber paints has been observed for the first time. The formation of copper, lead, manganese, cadmium and zinc metal soaps was also identified on egg tempera paint reconstructions even though, in this case, the overlapping of the spectral region of the amide II band with that of metal carboxylates made their identification difficult.

Few research studies from the early seventies reported the use of far infrared (FIR) spectroscopy and its analytical potential. Especially in the field of cultural heritage, particular attention has not been given to this technique because of its destructive character; however, this can be overcome by employing Raman microscopy. Provided that enough quantity of the sample is available, FIR spectroscopy may represent a useful analytical method in the case of inorganic compounds that are not active in the mid infrared region and, because of the fluorescent effect produced by the organic media, not detectable even by Raman spectroscopy. In this article, the application of FIR spectroscopy has been applied for the characterisation of several inorganic pigments. A preparation method based on the use of polyethylene has been developed that allows analyses with moderate quantity of sample (0.5-1.5 mg). The data obtained have been compared with Raman results with the aim to build a common database. Some applications on real case studies are presented and discussed.

In the field of FTIR spectroscopy, the far infrared (FIR) spectral region has been so far less investigated than the mid-infrared (MIR), even though it presents great advantages in the characterization of those inorganic compounds, which are inactive in the MIR, such as some art pigments, corrosion products, etc. Furthermore, FIR spectroscopy is complementary to Raman spectroscopy if the fluorescence effects caused by the latter analytical technique are considered. In this paper, ATR in the FIR region is proposed as an alternative method to transmission for the analyses of pigments. This methodology was selected in order to reduce the sample amount needed for analysis, which is a must when examining cultural heritage materials. A selection of pigments have been analyzed in both ATR and transmission mode, and the resulting spectra were compared with each other. To better perform this comparison, an evaluation of the possible effect induced by the thermal treatment needed for the preparation of the polyethylene pellets on the transmission spectra of the samples has been carried out. Therefore, pigments have been analyzed in ATR mode before and after heating them at the same temperature employed for the polyethylene pellet preparation. The results showed that while the heating treatment causes only small changes in the intensity of some bands, the ATR spectra were characterized by differences in both intensity and band shifts towards lower frequencies if compared with those recorded in transmission mode. All pigments' transmission and ATR spectra are presented and discussed, and the ATR method was validated on a real case study.

Architectural paint analysis is an important technique for establishing the palette of historical paint colours, and reconstructing how a room or a facade might have looked at an earlier time. In its simplest form, it has often been achieved by using paint scrapes, which involves revealing a stepped sequence of layers of paint using a blade or solvents. Cross-sections are used as an alternative to, or in combination with, scrapes. Mounted cross-sections can be examined by optical microscopy. Accumulated layers of paint, wallpaper or other applied decorative finishes can be defined from their textures and colours. Knowledge of the identity of the components in paint layers can be used to reconstruct a certain paint and also to date the paint layers. It is demonstrated that micro-Raman spectroscopy combined with optical microscopy and low-vacuum scanning electron microscopy-energy-dispersive spectrometry are versatile tools for the characterization of pigments and fillers in cross-sections from architectural decorations. The paper gives an example of the examination of an interior decoration from a historical building.

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