Degradation of glass artifacts: application of modern surface analytical techniques

A detailed understanding of the stability of glasses toward liquid or atmospheric attack is of considerable importance for preserving numerous objects of our cultural heritage. Glasses produced in the ancient periods (Egyptian, Greek, or Roman glasses), as well as modern glass, can be classified as soda-lime-silica glasses. In contrast, potash was used as a flux in medieval Northern Europe for the production of window panes for churches and cathedrals. The particular chemical composition of these potash-lime-silica glasses (low in silica and rich in alkali and alkaline earth components), in combination with increased levels of acidifying gases (such as SO(2), CO(2), NO(x), or O(3)) and airborne particulate matter in today's urban or industrial atmospheres, has resulted in severe degradation of important cultural relics, particularly over the last century. Rapid developments in the fields of microelectronics and computer sciences, however, have contributed to the development of a variety of nondestructive, surface analytical techniques for the scientific investigation and material characterization of these unique and valuable objects. These methods include scanning electron microscopy in combination with energy- or wavelength-dispersive spectrometry (SEM/EDX or SEM/WDX), secondary ion mass spectrometry (SIMS), and atomic force microscopy (AFM). In this Account, we address glass analysis and weathering mechanisms, exploring the possibilities (and limitations) of modern analytical techniques. Corrosion by liquid substances is well investigated in the glass literature. In a tremendous number of case studies, the basic reaction between aqueous solutions and the glass surfaces was identified as an ion-exchange reaction between hydrogen-bearing species of the attacking liquid and the alkali and alkaline earth ions in the glass, causing a depletion of the latter in the outermost surface layers. Although mechanistic analogies to liquid corrosion are obvious, atmospheric attack on glass ("weathering") is much more complex due to the multiphase system (atmosphere, water film, glass surface, and bulk glass) and added complexities (such as relative humidity and atmospheric pollutant concentration). Weathered medieval stained glass objects, as well as artifacts under controlled museum conditions, typically have less transparent or translucent surfaces, often with a thick weathering crust on top, consisting of sulfates of the glass constituents K, Ca, Na, or Mg. In this Account, we try to answer questions about glass analysis and weathering in three main categories. (i) Which chemical reactions are involved in the weathering of glass surfaces? (ii) Which internal factors (such as the glass composition or surface properties) play a dominant role for the weathering process? Can certain environmental or climatic factors be identified as more harmful for glasses than others? Is it possible to set up a quantitative relationship or at least an approximation between the degree of weathering and the factors described above? (iii) What are the consequences for the restoration and conservation strategies of endangered glass objects? How can a severe threat to precious glass objects be avoided, or at least minimized, to preserve these artifacts of our cultural heritage for future generations?