- Research article
- Open Access
Potash-lime-silica glass: protection from weathering
© De Bardi et al. 2015
- Received: 20 January 2015
- Accepted: 19 June 2015
- Published: 13 July 2015
Potash-lime silica glass was used for window panels in Europe north of the Alps in the medieval era. The high potassium and low silica content of this glass influences its chemical stability. When exposed to atmospheric conditions as well as acidic aqueous solutions, this type of glass can become hazy, foggy and/or flake phenomena can occur, which modify the original appearance of the artworks can occur. For proper conservation it is therefore necessary to understand the mechanisms of corrosion allowing for the selection of better conditions and treatments to slow down or avoid degradation. In previous works the applicability and the protective effect of a sol–gel silica coating on potash-lime-silica glass was tested in aqueous acidic solutions. With this work the previous results are integrated, investigating the protective effect against weathering and accelerated ageing. SEM analyses were performed to monitor the surface of the glass after accelerated ageing, in particular to detect the presence of corrosion products; moreover, ToF–SIMS analysis was performed to visualize the ion distribution as a function of depth and the presence of any changes due to the weathering treatment. The analyses showed that the formation of weathering products on the surface was slowed down significantly compared to the areas of the sample that were not coated with sol–gel. Different results were obtained depending on the glass composition.
- Corrosion Product
- Glass Sample
- Bulk Glass
- Elastic Recoil Detection Analysis
- Coated Part
Glass was widely used to embellish churches and cathedrals with colourful window panels but it is often subjected to degradation due to its interaction with the ambient atmosphere, especially in the last few centuries. As a result of several complex processes, the glass may be not transparent anymore, may assume a hazy appearance, and a flaking phenomenon can occur, influencing the appearance of the objects and influencing its cultural and artistic value. Glass produced in Europe north of the Alps between the 11th and 15th centuries shows a different chemical composition from ancient soda-lime-silica glass probably because of the lack of raw materials or changes in trade routes; the typical glass composition of this time has an increased amount of potassium and calcium and a lower amount of silica which results in a lower chemical stability compared to glass from other periods such as soda-lime-silica glass [1–5]. It is therefore necessary to individuate the risk parameters which could influence negatively the conservation of medieval stained glass artworks and to investigate the best conditions for preserving such objects and test new methods of protection [6–8].
As a consequence a superficial leached layer depleted in alkali and alkaline earth ions and enriched in hydrogen is formed. The leaching is selective meaning that some ions are preferentially depleted on the glass surface depending on their charge; on the other hand the silica structure remains almost unaltered. In a secondary reaction condensation may also occur (Eq. 2) and as water is formed which can evaporate under dry conditions, the leached layer undergoes a formation of cracks. Furthermore, in some cases flaking of the formed leached layer can occur and worsen the degradation of an object. Glass corrosion depends on different parameters including the pH and the nature of the solution, the temperature, the time of exposure, as well as the glass’s composition and its morphology.
To avoid or slow down degradation processes occurring on glass windows different strategies were applied in the past: external protective glazing was installed  or protective synthetic layers were largely applied directly on the glass surfaces, such as the epoxy polyester resins and acrylics or vinyl polymers  extensively used by conservators and restorers on the basis of their experience on wall paintings. Some other products experimented with are hybrid polymer materials synthesized by the sol–gel process by several steps, using an organically modified network which can be customized to particular requirements by chemical means [8, 23–27]. All these treatments have shown promise when tested in the laboratory but show some disadvantages in long term stability such as the necessity of frequent monitoring of the temperature and humidity and low stability to UV light which leads to photo-oxidation reactions changing the properties of the organic treatment materials (solubility, colour, mechanical properties etc.).
In this work a sol–gel silica coating was tested as a protective layer for potash-lime-silica glass formulated to a medieval composition. It is particularly suitable for application to cultural heritage due to the following qualities: its compatibility with the substrate (no adhesion problems), it does not require any heat treatments [28–31], it is transparent, easily applicable on the objects with a brush or by dip or spray coating, and it results in a stable inorganic layer, very thin and homogeneous on the glass surface [32, 33]. Its applicability on potash-lime-silica glass was tested in a previous study as well as its resistance to leaching attacks in aqueous acidic solutions . It was demonstrated that the coating allows ion migration from the bulk to the solution but the speed of diffusion is slowed down and no visible signs such as cracks or flaking are noticeable even after long periods of testing. One aim of this work is to test the protective effect of the same coating to corrosive atmospheres by means of an accelerated increase of SO2 content compared to the normal mean values in the atmosphere (5–30 ppb = 1 × 10−9 mol/mol). An overall aim is to continue the tests necessary to make this treatment (still in the development phase) applicable to real cases and therefore improve the stability of potash-lime-silica glass.
Sample preparation and weathering
Two kinds of potash-lime-silica glass were analysed in this work and their compositions are shown in Table 1. Sample slides (1.5 × 1 × 0.5 cm3) were prepared from synthetic glasses made at the Fraunhofer Institute für Silicatforschung in Würzburg (Germany) starting from a glass bar and progressively polished with SiC paper up to ~4 µm (4,000 mesh), details already described in the literature . The glass samples were only partially coated (3/4 of the surface) with a TEOS based sol–gel silica coating using SIOX-5  provided by Siltea S.r.l. (Spin Off of the University of Padua, Italy). The protective layer (~250 nm thick) was applied by dip-coating (drawing rate: 10 cm min−1) and dried at room temperature.
Artificial weathering was performed using an air-mixing unit enabling the control of the content of SO2 and RH. The gas concentrations expressed in this paper are in ppm (1 × 10−6 mol/mol). Samples were kept for 7 days in an environment of 1 ppm SO2 and 80% RH and analysed every 24 h with SEM. In a second experiment, a more aggressive accelerated ageing was performed using 10 ppm SO2 and 80% RH for a total of 4 weeks. In total for the 1 ppm experiment seven glass samples were exposed whereas for the 10 ppm experiment only four glass samples were necessary since clear results were obtained, as discussed below.
Analyses at three different areas of the coated and uncoated parts of the specimen were carried out. Investigation by Scanning Electron Microscopy (SEM) was useful for the acquisition of secondary electron images (SE) and energy dispersive X-ray analysis (EDAX), which gave elemental information about the weathering products formed on the glass surfaces [36, 37]. Time of Flight Secondary Ions Mass Spectrometry (ToF–SIMS) was performed to determine the initial stages and small variations in ion concentration at the near-surface in comparison to the bulk glass. ToF–SIMS has been used in the past mainly for studying glass corroded at high temperatures  as well as at room conditions [39–41]. Beside other techniques commonly applied to monitor H+ diffusion such as NRA (Nuclear Reaction Analysis) and ERDA (Elastic Recoil Detection Analysis), SIMS analysis were performed to study the hydration of glass [40–42] and to date obsidian and natural glass [43, 44].
ToF–SIMS is a powerful tool that allows very precise measurements, as well as a detailed reconstruction of ion distribution, but its application on insulating samples might be difficult because of the charging effect of ion bombardment. Nevertheless newer instruments are equipped with specific tools such as an electron flood gun to minimize this effect and, combined particular measurement conditions, it was possible to carry out the ToF–SIMS analyses of the samples without any conductive coating.
For the SEM measurements a FEI Quanta 200 SEM was available. Samples were not coated and the pressure in the sample chamber was 70 Pa (low vacuum-ESEM). Secondary electron images (SE) were acquired at magnifications between 5 k and 20 k using an accelerating energy of 20 keV.
ToF–SIMS measurements were performed with TOF–SIMS 5 (ION TOF GmbH, Münster, Germany) using a LMIG (Bi1 +, 25 keV) in positive detection with High Current Bunched Mode. Sputtering was performed with a raster size of 300 × 300 μm2 using O2 + (1 keV, ~200 nA). The Field of View used was 100 × 100 μm2 and the sampling was 128 × 128 pixels.
A pause time between sputtering and measurement was set to give time for the sample to dissipate the charge; for further compensation of the charging on the sample surface an electron flood gun (20 V) was applied. Samples were not coated with an electrically conductive material and the analyses were performed immediately after the weathering.
The size of these corrosion products is between 1 and 4 µm, without well-defined shapes and irregular edges. They are mainly localised close to scratches caused by polishing and they appear to be flat and thin, since the underlying pattern remains visible. Furthermore, the results of EDAX analysis performed on an area with weathering products does not differ from the one carried out in an area without such products, because of their low thickness. Contrary to these results, the coated part does not show any weathering phenomena (Figure 1b). The dark spots visible in the image are due to the presence of irregularities on the surface (scratches) which were only partially filled by the coating and therefore still visible in the image.
Chemical composition of glass M1 and M3 expressed in wt% (mol% in brackets)
A previous study using ToF–SIMS demonstrated that network modifiers such as K, Na and partly Ca and Mg can diffuse from the glass into the sol–gel coating material as long as it is in a liquid state and not yet completely polymerized . The SIMS depth profiles of glass M1 show alkali and alkali earth ions in the coating, which can be the reason for the formation of crystals on the surface of the coating. Nevertheless the amount of those ions is much lower compared to the untreated glass surface , which explains the different concentration and size of corrosion products on the coating compared to the uncoated glass. Since glass M3 is more stable than glass M1 due to the lower K content and a higher amount of Si, no effect has been determined on the coated glass surfaces.
Comparing the depth distribution of the alkali (K, Na) and alkali earths ions (Ca, Mg) in the untreated and coated glass sample (Figure 5a) with the depth distribution of the coated glass specimen exposed for 1 week at 10 ppm SO2 and 80% RH (Figure 5b), it can be seen that the ion intensities of K and Na are increased close to the surface (50–100 nm), whereas Ca and Mg show no substantial differences. Additionally, no intensity changes of K, Na as well as Ca and Mg could be detected in the domains deeper than 100 nm in the coating and in the bulk glass. Even after 4 weeks of exposure the intensity did not change in the coating of the glass (Figure 5c). The signals at the interface between coating and bulk glass results in an anomalous signal due to the change of chemical and physical properties between the two layers, as already discussed [34, 48]. Nevertheless, after a short time, the signal reaches a stable value indicating that the bulk has been reached.
The protective effect of a sol–gel silica coating was tested on two kinds of potash-lime-silica glass, one richer in K and Na and the other one richer in silica and Ca and therefore chemically more resistant. In particular the effectiveness of the coating to weathering and accelerated ageing was checked. The coating protects efficiently both types of glasses from the corrosive effect of an atmosphere with 1 ppm SO2 and 80% RH. After increasing the concentration of SO2 up to 10 ppm, no modification could be noticed for the coated part of the most durable glass (M3), even after 4 weeks of ageing. The less resistant glass (M1) showed the formation of small crystals (<1 µm) on the coated surface after the same exposure. SEM investigation has revealed that the crystals do not increase in size but in number with an increase in weathering time. Nevertheless, the protective effect is clearly visible when comparing the coated and the uncoated part of the same glass. ToF–SIMS analysis revealed that the ion distribution in the coating is not modified by a long and aggressive exposure to artificial weathering except in the uppermost domain of approximately 100 nm.
Future experiments will deal with real medieval glass specimens already weathered under natural conditions and showing a weathering crust. These glasses have to be coated with the sol–gel solution and tested, in order to proof the application of this new treatment in practice.
MDB carried out the studies and drafted the manuscript. HH contributed to ToF-SIMS measurements and interpretations, MS to glass stability and RB to sol-gel coating. All authors read and approved the final manuscript.
The authors are very grateful to Siltea S.r.l. (Spin Off of the University of Padua, Italy) for their availability to provide and apply the sol–gel silica coating. They are also very grateful to Ing. E. Eitenberger for SEM-EDX measurements.
Compliance with ethical guidelines
Competing interests The authors declare that they have no competing interests.
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- Gillies KJS, Cox A (1988) Decay of medieval stained glass at York, Canterbury and Carlisle. Part 2. Relationship between the composition of the glass, its durability and the weathering products. Glastech Ber 61:101–107Google Scholar
- Newton R, Davison S (1989) Conservation of glass. Butterworth, LondonGoogle Scholar
- Newton R, Fuchs D (1987) Chemical composition and weathering of some medieval glasses from York Minster. Glass Technol 29:43–48Google Scholar
- Schreiner M (1988) Deterioration of stained medieval glass by atmospheric attack. Glastechn Ber 61:223–230Google Scholar
- Schreiner M (1991) Glass of the past: the degradation and deterioration of Medieval Glass Artifacts. Mikrochim Acta 2:255–264View ArticleGoogle Scholar
- Davison S (2003) Conservation and restoration of glass. Butterworth and Heinemann, New YorkGoogle Scholar
- Hamilton D (2000) Glass conservation, Conservation Research Laboratory, Texas A&M University, College StationGoogle Scholar
- Kasemann R, Schmidt H (1994) Coatings for mechanical and chemical protection based on organic-inorganic sol-gel nanocomposites. New J Chem 18:1117–1123Google Scholar
- Boksay Z, Bouquet G, Dobos S (1967) Diffusion processes in the surface layer of glass. Phy Chem Glasses 8:140–144Google Scholar
- Boksay Z, Bouquet G, Dobos S (1968) The kinetics of the formation of leached layers on glass surfaces. Phy Chem Glasses 9:67–71Google Scholar
- Doremus RH (1970) Weathering and Internal Friction in Glass. J Non-Cryst Solids 3:369–374View ArticleGoogle Scholar
- El-Shamy TM, Douglas RW (1972) Kinetics of the reaction of water with glass. Glass Technol 13:77–80Google Scholar
- Sanders DM, Person WB, Hench LL (1972) New methods for studying glass corrosion kinetics. Appl Spectrosc 26:530–536View ArticleGoogle Scholar
- El-Shamy TM (1973) The chemical durability of K2O-CaO-MgO-SiO2 glasses. Phys Chem Glasses 14:1–5Google Scholar
- Sanders DM, Hench LL (1973) Environmental effects on glass corrosion kinetics. Ceramic Bulletin 52:662–669Google Scholar
- Sanders DM, Hench LL (1973) Mechanism of glass corrosion. J Am Ceram Soc 56:373–377View ArticleGoogle Scholar
- Sanders DM, Person WB, Hench LL (1974) Quantitative analysis of glass structure with the use of infrared reflection spectra. Appl Spectrosc 28:247–255View ArticleGoogle Scholar
- Hench LL (1975) Characterisation of glass corrosion and durability. J Non-Cryst Solids 19:27–39View ArticleGoogle Scholar
- Clark DE, Dilmore MF, Ethridge EC, Hench LL (1976) Acqueous corrosion of soda-silica and soda-lime-silica glass. J Am Ceram Soc 59:62–65View ArticleGoogle Scholar
- Clark DE, Pantano CG, Hench LL (1979) Corrosion of glass. Books for industry, The Glass Industry, New YorkGoogle Scholar
- Douglas RW, El-Shamy TM (1967) Reactions of glasses with aqueous solutions. J Am Ceram Soc 50:1–8View ArticleGoogle Scholar
- Bernardi A, Becherini F, Bassato G, Bellio M (2006) Condensation on ancient stained glass windows and efficiency of protective glazing systems: two French case studies, Sainte-Chapelle (Paris) and Saint-Urbain Basilica (Troyes). J Cult Herit 7:71–78View ArticleGoogle Scholar
- Kron J, Amberg-Schwab S, Schottner G (1994) Functional coatings on glass using ORMOCER®-Systems. J Sol-Gel Sci Techn 2:189–192View ArticleGoogle Scholar
- Haas KH, Wolter H (1999) Synthesis, properties and applications of inorganic–organic copolymers (ORMOCER®s). Curr Opin Solid St M 4:571–580View ArticleGoogle Scholar
- Carmona N, Wittstadta K, Römich H (2009) Consolidation of paint on stained glass windows: comparative study and new approaches. J of Cult Herit 10:403–409View ArticleGoogle Scholar
- De Ferri L, Lottici PP, Lorenzi A, Montenero A, Vezzalini G (2013) Hybrid sol-gel based coatings for the protection of historical windows glass. J Sol-Gel Sci Technol 66:253–263View ArticleGoogle Scholar
- Piqué F, Dusan S (2004) Conservation of the Last Judgment mosaic, St. Vitus Cathedral, Prague. Getty Conservation Institute, Los AngelesGoogle Scholar
- Carmona N, Villegas MA, Navarro JMF (2004) Protective silica thin coatings for historical glasses. Thin Solid Films 458:121–128View ArticleGoogle Scholar
- Armelao L, Bertoncello R, Coronaro S, Glisenti A (1998) Inorganic thin coating deposition to consolidate and protect historical glass surface Part 1 cleaning of the glass substrates. Part 2: synthesis, deposition and characterisation of the protective siliceous film. Sci Tech Cult Herit 7:47–69Google Scholar
- Dal Bianco B, Bertoncello R (2008) Sol-gel silica coatings for the protection of cultural heritage glass. Nucl Instrum Meth B 266:2358–2362View ArticleGoogle Scholar
- Dal Bianco B, Bertoncello R, Bouquillon A, Dran JC, Milanese L, Roehrs S et al (2008) Investigation on sol-gel silica coatings for protection of ancient glass: Interaction with glass surface and protection efficiency. J Non-Cryst Solids 354:2983–2992View ArticleGoogle Scholar
- Brinker CJ, Scherer GW (1990) Sol-gel science: the physics and chemistry of sol-gel processing. Academic Press Inc, San Diego, CAGoogle Scholar
- Bertoncello R, Bortolussi C, Cecchin M, Lattanzi D (2013) Silica thin film synthetized by sol-gel process for the protection of outdoor artistic ceramic in architecture. In: Valmar (Ed.) Science and Technology for the Safeguard of Cultural Heritage in the Mediterranean Basin, AthensGoogle Scholar
- De Bardi M, Hutter H, Schreiner M, Bertoncello R (2014) Sol–gel silica coating for potash–lime–silica stained glass: applicability and protective effect. J Non-Cryst Solids 390:45–50View ArticleGoogle Scholar
- De Bardi M, Wiesinger R, Schreiner M (2013) Leaching studies of potash-lime-silica glass with medieval composition by IRRAS. J Non-Cryst Solids 360:57–63View ArticleGoogle Scholar
- Melcher M, Schreiner M (2006) Leaching studies on naturally weathered potash-lime-silica glasses. J Non-Cryst Solids 352:368–379View ArticleGoogle Scholar
- Melcher M, Wiesinger R, Schreiner M (2010) Degradation of glass artifacts: application of modern surface analytical techniques. Acc Chem Res 43:916–926View ArticleGoogle Scholar
- Lodding A, Odelius H, Clark DE, Werme LO (1985) Element profiling by secondary ion mass spectrometry of surface layers in glass. Mikrochim Acta 11:145–161Google Scholar
- Fearn S, McPhail DS, Oakley V (2004) Room temperature corrosion of museum glass: an investigation using low-energy SIMS. Appl Surf Sci 231–232:510–514View ArticleGoogle Scholar
- Fearn S, McPhail DS, Morris RJH, Dowsett MG (2006) Sodium and hydrogen analysis of room temperature glass corrosion using low energy Cs SIMS. Appl Surf Sci 252:7070–7073View ArticleGoogle Scholar
- Fearn S, McPhail DS, Hagenhoff B, Tallarek E (2006) TOF-SIMS analysis of corroding museum glass. Appl Surf Sci 252:7136–7139View ArticleGoogle Scholar
- Hauri EH, Shaw AM, Wang J, Dixon JE, King PL, Mandeville C (2006) Matrix effects in hydrogen isotope analysis of silicate glasses by SIMS. Chem Geol 235:352–365View ArticleGoogle Scholar
- Liritzis I, Stevenson CM, Novak SW, Abdelrehim I, Perdikatkis V, Bonini M (2007) New prospects in obsidian hydration dating: an integrated approach. In proceedings of the Hellenic Archaeometry Society, British Archaeological Reports (BAR), Athens, pp 9–22Google Scholar
- Rutten FJM, Roe MJ, Henderson J, Briggs D (2006) Surface analysis of ancient glass artefacts with ToF-SIMS: a novel tool for provenancing? Appl Surf Sci 252:7124–7127View ArticleGoogle Scholar
- De Ferri L, Lottici PP, Vezzalini G (2014) Characterization of alteration phases on Potash–Lime–Silica glass. Corros Sci 80:434–441View ArticleGoogle Scholar
- Schreiner M, Woisetschläger G, Schmitz I, Wadsak M (1998) Characterisation of surface layers formed under natural environmental conditions on medieval stained glass and ancient copper alloys using SEM, SIMS and atomic force microscopy. J Anal Atom Spectrom 14:395–403View ArticleGoogle Scholar
- Gillies KJS, Cox A (1988) Decay of medieval stained glass at York, Canterbury and Carlisle. Part 1. Composition of the glass and its weathering products. Glastech Ber 61:75–84Google Scholar
- De Bardi M, Hutter H, Schreiner M (2013) ToF-SIMS analysis for leaching studies of potash-lime-silica glass. Appl Surf Sci 282:195–201View ArticleGoogle Scholar