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Grisaille is a glass-based paint made by mixing metal oxides (iron or copper) with ground lead-silica glass. The different materials used in the grisailles production (coloring agents, base glasses, or vehicles) can significantly impact their long-term stability along with the firing conditions. The main objective of this study was to achieve a better understanding of how raw materials influence the production and stability of these paints. To achieve this goal, 27 grisailles were produced, changing the raw materials, proportions, and firing conditions. The produced grisailles were characterized by X-ray fluorescence and diffraction, colorimetry, roughness measurement, and contact angle analysis. Adhesion and cleaning tests were also made. The use of different coloring agents has a significant impact on the final appearance and on the chemical and mechanical stability of the grisailles, but the latest is more affected by both firing temperature and the proportion between pigments and base glasses. [ABSTRACT FROM AUTHOR]

Stained glass restoration generally involves filling glass losses to maintain the coherence of the window and the new glasses used to fill the losses can be painted to chromatically reintegrate the stained glass panel. One of the most common painting materials on stained glass is grisaille, a paint made by mixing metal oxides with a ground lead glass. Grisailles usually have black and brown hues and are used for the creation of outlines as shadows in window glasses. Although several commercial companies sell many types of products to paint on glass, few of them present the necessary compatibility with the original materials that conservation materials must have. Debitus is one of the most renowned companies, and its grisailles are frequently used for chromatic reintegration in stained glass window restoration. Thus, the main objective of this study was to assess the long-term stability and durability of commercial Debitus grisailles. Two alteration tests were carried out, with samples placed in high humidity chambers and submerged in distilled water. The samples and degradation products were characterized by optical microscopy, µ-Raman spectroscopy, and colourimetry. In the immersion, the pH of the water was measured during the experiment, and the leached elements were analyzed at the end by inductively coupled plasma atomic emission spectroscopy. The results showed an alteration of the colour and the formation of degradation products, identified as sulphates. The solution pH was increased by the aqueous extraction of alkaline and alkaline-earth ions from the support glass of the samples. Despite these changes, it was possible to conclude that these commercial grisailles presented good durability and stability for use in conservation treatments. [ABSTRACT FROM AUTHOR]

Abstract: This paper reports the analyses of infrared thermography images of two stained‐glass windows with the objective of the in situ characterization of this type of artworks. The analyses were carried out by active thermography. The observations revealed that glasses absorbed the long‐wave IR radiation emitted by the halogen lamps and their apparent surface temperature progressively increased. After switching the spotlight off, they experienced a progressive decrease in temperature. Silver stained glasses presented the same thermographic behavior than uncolored glasses because silver nanoparticles were too small or the yellow layer was too thin to produce a different response than the base glass with the IR radiation. The apparent surface temperature of enamels and grisailles depended on their thickness and color. Lead cames maintained an almost constant surface apparent temperature, except those painted that behave in a similar way than enamels. Metallic tin‐lead welds experienced the most important variation in the surface apparent temperature in reflection mode due to the energy reflected by the surface of the weld. Glass defects such as big bubbles were also observed. [ABSTRACT FROM AUTHOR]

• Literature from 1984 to 2020 regarding grisaille is reviewed. • The spatio-temporal study reflects changes in grisailles composition. • The iron oxide is the main colouring agent identified throughout the centuries. • In Germany, Italy and Czech Republic the copper oxide is in higher proportion. • The main substrate glasses identified are sodium-rich and potassium-rich glasses. This work presents the first review on the characterisation of grisaille stained-glass paint, in order to follow the evolution of the production materials and methods throughout time and provenance. From the literature review, 38 scientific studies regarding the grisaille paint were found, dated between 1984 and 2020. In these works, various samples from the 13th to the 20th centuries belonging to 11 different European countries were characterised. In general, iron oxide was the main colouring agent identified throughout the centuries and countries, except in the Central and South-Central European countries where copper oxide was preferably used. Different metal oxides, such as cobalt, chromium and manganese were also identified in modern samples (19th and 20th centuries), used together with iron oxides. The base glasses generally presented a lower ratio PbO:SiO 2 (~0.5 to 1) than the expected from the historical recipes, and the addition of borax is suggested for grisailles from the 17th century onwards. The proportion between the base glass and colouring agents showed ratios between 1 and 1.5, related to well-balanced grisailles. The present overview, critical analysis and comparison of published studies regarding this glass-based paint allow to draw a spatio-temporal map of the grisaille composition evolution, which reflects the changes in composition regarding the country of provenance and century. [ABSTRACT FROM AUTHOR]