Marta Vallotto

Early stage of weathering of medieval-like potash–lime model glass: evaluation of key factors

PurposeThroughout history, a consequent part of the medieval stained glass windows have been lost, mostly because of deliberate or accidental mechanic destruction during war or revolution, but, in some cases, did not withstand the test of time simply because of their low durability. Indeed, the glasses that remain nowadays are for many in a poor state of conservation and are heavily deteriorated. Under general exposure conditions, stained glass windows undergo different kinds of weathering processes that modify their optical properties, chemistry, and structure: congruent dissolution, leaching, and particle deposition (the combination of those two leading together to the formation of neocrystallisations and eventually crusts). Previous research has studied the weathering forms and the mechanisms from which they are originated, some others identified the main environmental parameters responsible for the deterioration and highlighted that both intrinsic (glass composition) and extrinsic (environmental parameters) factors influence glass degradation. Nevertheless, a clear quantification of the impact of the different deterioration extrinsic factors has not been performed.MethodsBy analysing the results obtained with model glass (durable and nondurable) exposed in the field, this paper proposes a simple mathematical computation evaluating the contribution of the different weathering factors for the early stages of exposure of the stained glasses.ResultsIn the case of non durable glass, water runoff was identified as the main factor inducing the leaching (83.4 ± 2.6% contribution), followed by gas (6.4 ± 1.5%) and particle deposition (6.8 ± 2.2%) and adsorbed water (3.4 ± 0.6%). Moreover, it was shown that the extrinsic stimuli superimposes with the impact of glass composition to the weathering.ConclusionsThose results show that the role played by dry deposition, even if less important than that of the wet deposition, cannot be neglected.

EDS and μ-XRF mapping of amalgam degradation products in ancient mirrors

An amalgam mirror is a mirror type, used from the fifteenth century until the end of the nineteenth century, where the reflective layer is constituted by a tin amalgam layer adhered to a glass sheet. In this work, two amalgam mirrors samples were studied by scanning electron microscopy with an energy dispersive spectrometer and by micro-X-ray fluorescence elemental mapping to go deeply into the understanding of the degradation mechanism of the amalgam layer of ancient mirrors. The investigation has been focused for the first time on the reflective surface of the amalgam layer adherent to the glass sheet to better understand the processes of amalgam corrosion. The two amalgam degradation compounds, romarchite and cassiterite, has been spatially differentiated by scanning electron microscope (SEM) and energy dispersive spectrometer (EDS) maps. SEM images and micro-X-ray fluorescence and EDS maps showed that the amalgam degradation products grow up to form hemispherical stratified calottes. This structure is probably due to a mechanism involves cyclic phases and oxygen radial diffusion from a superficial oxidation nucleus.

SEM-EDS, EPMA and MRS analysis of neo-crystallisations on weathered glasses

When a glass is exposed to the atmosphere the combined action of water and environmental elements leads to the weathering of the glass surface. Both the chemical composition of the glass and the environmental parameters influence the mechanism of glass weathering mainly consisting in the formation of a layer of hydrated leached glass and salt deposits. The study of these phenomena is very important for both industrial and cultural heritage applications. In order to study the weathering mechanism of glasses exposed outdoor the chemical composition of the glass and the chemical and mineralogical nature of the reaction products should be determined. X-ray micro-analytical techniques such as scanning electron microscopy and X-ray microanalysis (SEM-EDS) and electron probe microanalysis (WD-EPMA) are traditionally employed in this type of investigation. Nevertheless particular compounds are hardly detected with this technique (for ex. nitrates) and no direct information can be obtained on the mineralogical features of the reaction products. Moreover, X-ray diffractometry (XRD) cannot be successfully used because of the very low amounts of deposited material. This work reports the results of a combined complementary X-ray fluorescence spectrometry (WD-XRF), SEM-EDS, WD-EPMA and μ-Raman spectroscopy (MRS) investigation on the surfaces of an industrial float glass and a glass reproducing the low-durable glass of ancient stained windows exposed sheltered outdoor for 6 months. The investigation enabled the identification and characterisation of different reaction products (soluble salts) confirming the need of this analytical approach for the study of the glass weathering process.