Translated abstract:
Gold-ruby glass is a red coloured glass, in which colour is caused by colloidal, metallic gold particles. After melting at a temperature of 1400°C and following rapid cooling to ambient temperature the glass remains colourless. Only upon annealing for minutes or hours between about 500-700°C does the red colour strike as a result of the nucleation and growth of small metallic gold particles. In this theses, the chemical states of gold and the physical mechanisms of the growing process of the particles under the influence of additional ingredients like tin, lead, antimony and selenium before, during and after the colouring process are investigated by using the Mößbauer spectroscopy on 197Au, 119Sn and 121Sb, optical spectroscopy and x-ray-diffraction. Gold in an unnealed, colourless state of the glasses consists of monovalent forming linear bonds to two neighbouring oxygen atoms. The Lamb-Mößbauer factor of these gold oxide bondings is observed as 0.095 at 4.2K. As expected during the annealing there is a strong increase of metallic gold in the gold-ruby glasses with simultanious decrease of the monovalent gold. The gold in it's oxide state transforms to gold particles with a diameter of 3 nm to 60 nm. Due to their interaction with light in the visible spectrum, caused by plasmon and band structure extinction, the gold particles absorb the green and a part of the blue spektrum as well. The size of the gold particles is quite definable within the optical spectra and certain sizes are also discernable within the Mößbauer spectra. One component of the Mößbauer spectra is assigned to the surface layer of the gold particles. By comparing this surface component with the amount of the bulk metallic core, one can calculate the size of the gold particles. The development and the kind of colour is strongly influenced by the additional presence of items like tin, lead, antimony and selenium. Tin acts as a crystillization center, giving rise to the existance of a gold tin alloy, for example. Hence, tin leads to a higher velocity of colouring and to the creation of smaller gold particles, when present. Antimonyoxide, as well as leadoxide, are available as oxidation partners during the melting proces. Around the melting temperature both generate a sufficient high oxygen overpressure so that the gold easily can be transferred to the oxide state. While leadoxide, at temperatures for annealing, still creates an overpressure of oxide and therefore prevents the reduction of gold and respectively the growing of particles, antimonyoxide works as reduction partner during the annealing und provides a good colouring of the glass. In the Mößbauer spectra of the colourless glass one also can find parts of bulk metallic gold. Investigations with x-ray diffraction show that these are gold particles with a diameter of 100 nm to 300 nm and therefore have no additional colouring effect within the visible spectrum. The process of colouring and respectivly growing of particles during annealing is reversable. After melting of the already coloured glasses and cooling down to ambient temperature one can find, that they are colourless again. The Mößbauer spectra on gold of the remelt glasses are similar to those which have been measured on the initial colourless glasses.