The conservation of cultural heritage for sustainable development

Preventive conservation strategy for glass collections. Identification of glass objects susceptible to crizzling
Jerzy KUNICKI-GOLDFINGER

Summary
Protection of glass collections in museums includes many different issues. The chemical instability of glass constitutes one of the most difficult problems. A scheme of preventive conservation strategy for collections is presented, with special emphasis on the identification of glass susceptible to crizzling. The strategy allows us to identify such glass before symptoms of irreversible deterioration appear. As a consequence, it is possible to undertake certain preventive conservatory activities. The strategy has already been applied and is presented hereunder regarding Central European 18th century tableware. However, a further long-term collaboration of many museums and scientific institutions is required in order to conduct an interdisciplinary project and cover other technological groups of glass.

very high, the glass in these cases might show a very high durability (MÜLLER, 1995). So-called ‘sick glass’ constitutes a slightly different phenomenon (see for example: BRILL, 1975; NEWTON, 1989; OAKLEY, 1992; 18th ICG, 1998; 19th ICG, 2001). A reason for this is nothing other than the chemical nature of such unstable glass. It is caused by the application of incorrect production technology: over-purification of some raw materials and/or wrong batch formulation. A deficiency of stabilisers and an excess of alkali is believed to be the main cause of this phenomenon. Such glass is simply susceptible to an attack by the moisture that exists in our surroundings. Sodium and potassium ions leach from the glass to form alkali hydroxide solutions. These solutions pick up carbon dioxide from the atmosphere. The resulting carbonates either crystallise and cause delaminating and flaking, or appear as droplets or slippery film depending on the environmental conditions. The phenomenon is irreversible and eventually leads to the total decay of the glass. Curators and conservators are nearly helpless when facing this problem (see for example: PAGE, 1998). Poor durability manifests itself in a number of ways: a loss of translucency (a cloudy appearance), colour alteration, weeping (tearing, sweating), efflorescence (salt deposition), crizzling, flaking, and so on. Crizzling is one of the most distinctive symptoms of the decay of such unstable glass. The cycles of hydration and dehydration that occur during environmental fluctua-

Introduction
In the discussion of protection of glass collections in museums, many issues must be taken into consideration. Maintaining proper indoor climate conditions is one of the most important factors that might influence the preservation of glass objects. Relative humidity (RH), temperature, lighting, air pollutants, biodegradation and many other factors should be considered. On the other hand, generalisations about glass collections should not be made basing on single objects. Depending on the glass technology applied and the state of preservation of the glass, different storage conditions are often required. The same sometimes also concerns the conservation and restoration procedures. During our surveys of glass collections, we have encountered many kinds of symptoms of glass deterioration, leading us to take note of many different deterioration processes that occur on glass surfaces. In the case of vessel glass, one of the most frequently occurring symptoms are fingerprints (Figure 1), which are irremovable in many cases, and which result from handling the object without gloves. Missing areas, as well as fractures, often arise as a result of a mechanical impact. The same concerns scratches, which follow a mechanical abrasion of the surface. If they are very fine, these scratches are often wrongly identified as crizzling. As for the chemical corrosion of vessel glass, in most cases we can find an external silica-rich protective film. If the pH of the contact medium is not

Figure 1. ‘Fingerprint’, one of the deterioration symptoms that follow the handling of vessels without gloves (National Museum in Warsaw, photo by P. Ligier).

301

Workshop 4
tions lead to the formation of surface cracks. The surface simply swells and shrinks by turns. There are several forms distinguished in the literature. ‘Incipient crizzling’ concerns the case when the outer glass surface is hydrated and has become equilibrated with the surrounding environment over a long time (BRILL, 1972). During the process of partial dehydration, very fine cracks appear (Figure 2). When subjected to dry conditions, such glass may develop heavy crizzling within a very short time. The expression ‘crizzling’ is used when the network of cracks is well visible with a naked eye (Figure 3). The cracks may grow and penetrate the whole body of glass. Such decay leads sometimes to the delaminating and flaking of small pieces of glass (Figure 4). The flakes often fall away, leaving holes. The nature of this phenomenon is quite different from the well-known in-depth corrosion, like pitting, which frequently occurs on burial (archaeological)

Figure 4. Crizzling might be associated with delamination, salt depositions, flaking and holes followed by the loss of the flakes (National Museum in Warsaw, photo by P. Ligier).

glass and window glass (NEWTON, 1989). The deterioration process of unstable glass affects almost the entire glass surface, since it is mainly influenced by the nature of glass, not by the aggressive external agents. The progress of the phenomenon discussed depends neither on the origin, nor on the age of the glass. It may affect both clear and coloured glass, translucent and opaque glass, as well as glazed and enamelled surfaces. But what is really note-worthy is that most of the affected glass objects are very rare specimens. The only remedy is to keep such objects in a stabilised and controlled environment. The main factor to be considered is the stability of relative humidity (RH) and temperature. The safe RH range depends on the chemical type of glass (such as sodium glass, potassium glass, etc.), as well as on the stage of glass deterioration (first of all: on the stage of glass hydration). But due to the different deliquescence points of sodium and potassium carbonates and hydroxides, it is very difficult to determine the RH at which the ‘sick’ glass would really be stable (ERHARD, 1994). We can really only slow down the process nowadays. Very seldom can we stop it. Therefore, it would be highly beneficial to identify unstable glass objects before the decay symptoms occur.

Figure 2. ‘Incipient crizzling’, very fine cracks through the hydrated outer glass layer, frequently visible only under magnification (National Museum in Warsaw, photo by P. Ligier).

Identification of glass susceptible to crizzling – 18th century Central European example
After long-term studies consisting of conservation surveys and physicochemical examinations carried out in glass collections, it might be stated that in certain cases it is possible to distinguish a set of objects potentially susceptible to crizzling. It includes, for example,

Figure 3. ‘Crizzling’, a network of cracks that appears during the dehydration process (National Museum in Warsaw, photo by P. Ligier).

302

The conservation of cultural heritage for sustainable development

18th century Central European colourless vessels (KUNICKI-GOLDFINGER, 2002, 2003a, and 2003b). Over 1,000 objects from many Polish museums, originating from German lands, Silesia, Bohemia, the PolishLithuanian Commonwealth and Russia, have been subjected to conservation surveys as well as chemical analysis. The energy dispersive x-ray fluorescence analysis (EDXRF) has been applied for the latter (KUNICKI-GOLDFINGER, 2000). Three main technological groups have been distinguished: crystal, white (chalk) and ordinary glass. All of them belong to the Si-Ca-K type. Both written documentary sources and the results of chemical analysis confirm the classification. Only among the groups of crystal glass and white glass a distinctive subgroup of glass, melted with lead as one of the raw materials, was discovered. A surprising observation was that all of the crizzled glass was melted, without any exception, according to the leaded crystal formulation (Figure 5). It might therefore be assumed that all glass melted according to that formulation might be susceptible to crizzling when subjected to inappropriate environmental conditions. Obviously, when considering other technological types of glass from other periods and/or areas, further studies are still required. The results obtained for the 18th century Central European glass objects allow us to suggest a preventive conservation strategy for glass collections that would be aimed mainly at the identification of glass susceptible to crizzling.

nological, stylistical and historical analysis. It seems that such an interdisciplinary approach to the surveys of historical glass is the only way to find new and better solutions for the protection thereof.

Conservation surveys and treatments
The glass objects with obvious symptoms of decay should be treated separately, depending on their technology and on the state of their preservation. One should not treat all ‘sick’ glass equally. There is a tendency to forget that a relative humidity that is acceptable for one object may be disastrous for another.

Technological recognition
Technological knowledge might be the key to forecasting the durability of historical glass. But such interpretation should be supported by both the results of chemical analysis and written documentary sources. It requires multidisciplinary projects and the application of both the screening examination and quantitative analysis of selected objects. It allows us to estimate the potential threat of the deterioration progress in reference to single items without any need of the precise, complex analysis of samples taken from them.

Separation of glass objects susceptible to crizzling
It is necessary to separate from a general glass collection selected glass objects that might appear sound, but are potentially unstable. Only technological recognition might allow us to differentiate such glass objects. They should be treated with special attention, with respect to the surrounding environment as well as conservation surveys and treatments.

Preventive conservation strategy for glass collections
The suggested strategy consists in comprehensive studies of glass collections encompassing the state of preservation of the objects, as well as chemical, techThree main technological groups of colourless glass melted in the 18th century in central Europe Crystal Ordinary

Conclusions
The strategy presented above might allow us to slow down the progress of the phenomenon and sometimes to preserve glass objects without any visible symptoms of decay for a long time. It might allow the undertaking of certain protective activities, such as providing the glass objects susceptible to crizzling with safe climate conditions and ensuring their special care by conservators before the visible symptoms of deterioration appear. However, the further long-term collaboration of many museums and scientific institutions is still required in order to conduct the interdisciplinary project which would cover other technological groups of glass than those examined already.

White

Glass melted with lead as one of the raw materials Crizzled glass

Figure 5. Among the 18th century Central European tableware, all the crizzled items had been melted according to the leaded crystal formulation.

303

Workshop 4
Acknowledgements
My special acknowledgements are due to the Boards of the following museums: the National Museums in Cracow, Poznań, Warsaw and Wrocław, the Royal Castle and Historical Museum in Warsaw, the District Museum in Tarnów, the Museum Palace in Wilanów (all of which are located in Poland). The project was partially supported by a grant from the Polish Ministry of Culture during the second half of the year 2000.
Research: a Pan-European Challenge (5th EC Conference, Cracow, 16–18 May 2002). Conference Report (2003b, this volume). MÜLLER W., TORGE M. and ADAM K., ‘Primary stabilization factor of the corrosion of historical glass: the gel layer’, Glastechnische Berichte – Glass Science and Technology, 68, 9, 285–292, 1995. NEWTON R. and DAVISON S., Conservation of Glass, Butterworths, London, 1989. OAKLEY V., ‘The deterioration of vessel glass’, in Glass and Enamel Conservation, UKIC Occasional Papers No. 11, UKIC, London, 18–22, 1992. PAGE J.A., ‘Crizzling: a curatorial point of view’, in Proceedings of the 18th International Congress on Glass, San Francisco 1998, The American Ceramic Society, Westerville, 1998 [CD-ROM]. 18th ICG, – ‘Crizzling and Related Problems in Glass’ I and II, sessions’ papers, in Proceedings of the 18th International Congress on Glass, San Francisco 1998, The American Ceramic Society, Westerville, 1998 [CD-ROM]. 19th ICG, – ‘Crizzling’, session papers, in Proceedings of the 19th International Congress on Glass, Edinborough, 2001 [CD-ROM].

References
BRILL R.H., ‘Incipient crizzling in some early glass’, Bulletin of the American Group – IIC, 12, 2, 46–47, 1972. BRILL R.H., ‘Crizzling – a problem in glass conservation’, in Conservation in Archaeology and the Applied Arts (Congress of the International Institute for Conservation, Stockholm, 2–6 June 1975), ed. N.S. BROMMELLE and P. SMITH, IIC, London, 121-134, 1975. ERHARDT D. and MECKLENBURG M., ‘Relative humidity re-examined’, in Preventive Conservation. Practice, Theory and Research. Preprints of the Contributions to the Ottawa Congress of the International Institute for Conservation, Ottawa, 12-16 September 1994, ed. A. ROY and P. SMITH, IIC, London, 32–38, 1994. KUNICKI-GOLDFINGER J., KIERZEK J., KASPRZAK A. and MAŁOŻEWSKA-BUĆKO B., ‘A study of eighteenth century glass vessels from Central Europe by x-ray fluorescence analysis’, X-Ray Spectrometry, 29, 310–316, 2000. KUNICKI-GOLDFINGER J., KIERZEK J., MAŁOŻEWSKABUĆKO B. and KASPRZAK A., ‘Some observations on crizzled glass (preliminary results of a survey of 18th century Central European tableware)’, Glass Technology, U3C, 364–368, 2002. KUNICKI-GOLDFINGER J., KIERZEK J., KASPRZAK A. and MAŁOŻEWSKA-BUĆKO B., ‘Analyses of 18th century Central European colourless glass vessels’, in Annales du 15e Congrès de l’Association Internationale pour l’Histoire du Verre (New York – Corning 2001), AIHV, Nottingham, 224–229, 2003a. KUNICKI-GOLDFINGER J., KIERZEK J., KASPRZAK A., MAŁOŻEWSKA-BUĆKO B. and DZIERŻANOWSKI P., ‘A provenance study of Baroque glass’, in Cultural Heritage

Jerzy Kunicki-Goldfinger Institute of Nuclear Chemistry and Technology ul. Dorodna 16, 03-195 Warszawa, Poland e-mail: jkunicki@ichtj.waw.pl Graduated in conservation of art from Nicholas Copernicus University in Toruń, Poland, taught conservation and received his doctorate in conservation at the same university in 1998. Since 1984, an art conservator in private practice (architectural details, stone sculpture, ceramics, glass and related materials). In 1999 he joined the Institute of Nuclear Chemistry and Technology in Warsaw where he has been head of research on historic glass. Main current research interest is non-destructive examinations, glass corrosion processes, dating and provenance studies of glass, protection of glass collections.

304