The chemistry behind the first Portuguese postage stamps (1853–1894). A non-destructive analytical and chemometric analysis of pigments, fillers and binders

The analysis of 28 specimens of some of the first Portuguese postage stamps, dated from 1853 to 1894, was undertaken with non-destructive techniques: X-Ray fluorescence (XRF), Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR) and Ultraviolet–Visible Reflectance Spectroscopy (UV–Vis). Ink, paper and cancellation of the postage stamps were analysed, and the pigments, binders and fillers identified. Prussian blue was found present in all blue and also in green and brown specimens. Chrome and zinc yellow, lead sulphate and mars red were also found in other of the investigated postage stamps. Binders consist mostly of protein glue. Fillers such as calcite and kaolinite were found dominant. The presence of the latter served as an indicator for distinguishing between genuine and forged samples. UV–Vis spectra also proved useful for the same purpose. All the above information was processed and organized using chemometric techniques. These include mainly Hierarchical Cluster Analysis (HCA), for clustering stamps of similar composition, and Principal Component Analysis (PCA) for mapping the samples and identifying the more relevant variables. The latter are, in the paper, content of calcium, potassium, sulphur and silicon and, in the dye pigment area, of iron, zinc and lead content. The study introduces an approach in which, by combination of non-destructive multi analytical techniques with chemometric analysis, extensive information on different aspects of the composition of the studied postage stamps is provided, including that of paper and dyes.