Transmission electron microscopy for archaeo-materials research: Nanoparticles in glazes and red/yellow glass and inorganic pigments in painted context

This dissertation addresses the application of Transmission Electron Microscopy (TEM) to historic objects, concentrating on colour-causing nanoparticles in vitreous materials and pigments with the focus on substrates in lake pigments used in thin glaze layers, and on manuscript illustrations.; TEM is well suited for archaeometry: it gives chemical elemental information, imaging and diffraction information and the amount of material needed is minimal. Sample preparation techniques suitable for historic materials are discussed.; Nanoparticles can be incorporated in glass through staining. Yellow coloured glass plates contain Ag particles. Baking temperatures and different Ag-salts determine the density of the nanoparticles. Dense layers cause more saturated colours. Red glass plates can be obtained by staining with Cu-salts. Metallic Cu particles have a diameter of about 24 nm. Comparison with XRF results suggests that often a combination of Cu and Ag was used for warmer colours. Red glass can be "flashed" to the substrate glass. Then, the colour is also caused by metallic Cu particles. The red layer often displays a band structure of stacked red and transparent bands. In the transparent bands, no nanoparticles have been found. In lustre-ware, Ag and metallic Cu occur. Their distribution throughout the material determines the colour of the fragment. In both there is a dense top layer with particles of sizes smaller than 15 nm. If this top layer consists of Ag particles, the resulting colour is golden. In one sample, under this top layer the amount of Cu particles increases. This underlying layer causes the colour to redden. Particles are mainly between 5 and 15 nm in diameter.; Using reconstructions, it has been demonstrated that TEM can detect and identify a stacking of thin layers in parchment decorations. A pink powder sample from Pompeii consists of a basis of allophane type clay. The lake substrates consist of Al, O, S and their amorphous structure does not seem to be noticeably changed by the addition of organic colourants. Hydrocerussite crystals (i.e. the main component of lead white) have been added to some historic glaze layers. Further it was confirmed that sometimes crystalline CaSO4 particles were added to lakes.