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Heritage (Patrimonio Ingls). As, las soluciones han involucrado micro-ambientes ajustados a las necesidades de grupos de objetos. Un tema recurrente ha sido el rol de los gases contaminantes en el deterioro de los objetos, en particular el de los gases sulfurosos y los cidos orgnicos. Este trabajo presenta una visin general de estas investigaciones en el contexto ms amplio de las prcticas de conservacin preventiva en el British Museum (Museo Britnico). TTULOPesquisa e prtica em conservao preventiva no British Museum (Museu Britnico). RESUMODesde o incio da dcada de 1970 os cientistas de conservao do British Museum (Museu Britnico) tm seguido um programa de pesquisa que ficou conhecido como conservao preventiva. Esta pesquisa baseada no objeto foi quase sempre iniciada pela investigao sobre as causas de deteriorao, a fim de compreender o tratamento e as necessidades ambientais necessrios para a estabilizao. A maioria das galerias e reas de armazenagem de objetos no esto equipadas com sistemas de controle de ar; tais sistemas nem sempre so viveis em edifcios, os quais por si s tm tamanha importncia que so classificados como grau um na listagem do English Heritage (Patrimmio Ingls). Por conseguinte, as solues envolvendo microambientes so desenhadas medida das necessidades de grupos de objetos. Um tema constante tem sido o papel dos gases poluentes, em particular dos gases sulfricos e cidos orgncios, na deteriorao. Este artigo apresenta uma viso geral destas investigaes no contexto mais amplo da prtica da conservao preventiva no British Museum (Museu Britnico).
1 INTRODUCTION
The importance of the interaction of environment and collections was recognized long before the then Keeper of the British Museum Research Laboratory published The Conservation of Antiquities and Works of Art (Plenderleith 1956). This book contains a section on The Influence of Environment based on research on the deterioration of objects in the collection carried out by the Museum scientists between 1922 and 1950. By today's standards the information is rudimentary, but it did give useful guidance on collections care. In parallel to the work at the British Museum, research into the effects of the environment on oil paintings and on Japanese art was being carried out in other institutions. This work informed two important publications, The Museum Environment (Thomson 1978) and Characteristics of Japanese Art that Condition Its Care (Toishi and Washizuka 1987), both of which have contributed to the framework of what has become known as preventive conservation. In the early 1970s, under the leadership of A. E. A. Werner, British Museum conservation scientists began a concerted program of research into the effects of the environment on the collection. This research was driven by the development of new galleries and the need to establish whether or not control of temperature and/or relative humidity was needed to safeguard the objects, to justify its inclusion in the projects. There were several reasons not to attempt largescale climate control. First of all, being designated grade one listed by English Heritage means that the British Museum building is of such historical importance that it should be maintained in its original form. Putting in air conditioning for galleries without affecting the structure is very
costly, aside from the expense of installation, running, maintenance, and replacement of the systems. Secondly, the trend was away from single-object galleries, such as the run of upper floor galleries displaying Greek pottery, to thematic mixed-object galleries where no one environment would be suitable for all of the objects. Finally, much of the collection is stable in the ambient conditions in the Museum and air conditioning was simply not needed. Hence, simple approaches and targeted control were favored for the display and storage of those objects which were found likely to deteriorate in normal ambient conditions. The research focused on single objects or groups of objects which were deteriorating, to identify the cause and a method of prevention. The role of relative humidity soon became apparent. Determining an appropriate relative humidity and suitable method of control was part of the prevention strategy. Gases given off by the materials used in storage and display, and sometimes given off by the objects themselves, were found to cause corrosion of metal objects and to form mixed salts on the surface of some porous stone and ceramic objects. In this paper an overview of the research between 1970 and 2005 on temperature, relative humidity, and pollutant gases is put in the context of the development of preventive conservation practice in the British Museum.
provided, control of relative humidity is now the primary method of preventing bronze disease.
only dehumidifying to maintain a low relative humidity and only humidifying to maintain a higher relative humidity. There has been respectively no counter humidification or dehumidification, and no temperature control other than winter heating. This has meant that for the dehumidified cases the winter low internal relative humidity has been accepted and for humidified cases the summer high relative humidity has been accepted. The relative humidity inside the controlled showcases has drifted accordingly, although the well-sealed showcases in use since 1988 buffer effectively against the peaks and troughs in relative humidity. The fact that no observable damage has occurred to any of the copper alloy or ivory objects in a controlled relative humidity has justified this approach. There have been instances of glass apparently starting to weep in the dehumidified case. Research into this problem is ongoing with the focus on occasional very low relative humidity compared to the target of of 3842% RH, and high levels of indoor pollutant gases in the dehumidified case.
had indicated that fading occurred during the exhibition period between 1987 and 1997, when the light levels on the body were up to 400 lux. In 1997 Lindow Man was moved to the Late Bronze Age and Celtic Europe Gallery where it is displayed under a maximum light level of 50 lux. Since then the color change has slowed dramatically.
that the sculptures should be stored and displayed at a controlled temperature and relative humidity of 1820C, 30-40% RH with filtration to remove sulfur dioxide. Under these conditions in storage and on exhibition in the Asahi Shimbun Gallery of Amaravati sculptures, the sculptures have been stable. (Bradley 2003a).
a reliable supply of disposable silicone stoppers which fitted the quickfit tubes used for the accelerated corrosion test. The coupons were inserted into slits in the stoppers and the rest of the test set up was as before. For a six-month evaluation period the 3-in1 test and the normal test were run on every material which came in for testing. Currently the 3-in-1 test method is used for the routine testing of materials for use in storage or display of the collection. More complex methods for evaluating materials have been suggested and one has been published (Reedy et al. 1998). This method requires equipment, expertise, and time that are not available in most museum science laboratories. The Oddy test and 3-in-1 test are pass/fail tests which can be carried out by a scientist or conservator who is trained in the test procedure and has a good understanding of laboratory practice. These tests provide a simple way of ensuring that the risk to objects from indoor pollutant gases given off by materials used in storage and display is minimized.
and Carpenter 1987). Researchers at the University of East Anglia showed that formaldehyde could be oxidized to formic acid at ambient temperature. However the experimental levels of oxidant were high compared to what normally would be expected in the air (Raychaudhuri and Brimblecombe 2000). Another mechanism suggested is that of the high-temperature Cannizaro reaction (Schmidt 1992), but this seems unlikely to occur at ambient temperature. The wood industry changed formulations and lowor zero-formaldehyde MDF emerged. These products still gave off copious acetic and formic acid and failed the accelerated corrosion test. For more than thirty years in which the accelerated corrosion test has been in use, most of the woods and wood products tested have corroded the lead test coupon. Even ancient wood can corrode lead. An eighthcentury BC lead figurine (188012-16-46) formed from tiny lead and ivory squares had a wood core which was found to be the source of the regular corrosion of the lead (Duncan 1986a). In the British Museum the corrosion product identified most frequently on lead objects by X-ray diffraction (XRD) is hydrocerrusite, PbCO3. Pb(OH)2. The corrosion of lead to basic lead carbonate has been described as a two-stage process via an intermediate, lead acetate, which reacts with water and carbon dioxide in the air to form basic lead carbonate. In the last few years, more findings have been made of acetateand formatecontaining corrosion products on lead and other metals, and of mixed salts on porous stone, ceramics, and glass. These occur where composite wood products or untested paints are in use. Recent improvements in analysis by ion chromatography (IC) in the Museum have identified the presence of carbonates in salt mixtures which would previously have been identified only as formate and/or acetate. Measurement of the acetic and formic acid levels using the diffusion tube method described by Gibson et al. (1997a) have shown acetic acid to always be present at a higher concentration than formic acid. The prevalence of formatecontaining corrosion and salts suggests that either formic acid is more reactive than acetic acid at some object surfaces, or oxidation of formaldehyde to formic acid is occurring.
drying. It is likely that the moisture promoted a reaction between acetic acid from the wood and the soluble salts in the stone forming the mixed salt. The soluble salt profiles through the thickness of this stela and one which had not been treated with water and did not have salt efflorescence present were compared. In addition to the expected chloride and nitrate, acetate and formate ions were present in amounts of 0.010.06% w/w throughout both stele (Bradley and Thickett 1999). This shows that gases given off by the oak storage boxes had been adsorbed not only on the surface of the porous limestone but throughout its structure. A white efflorescence had formed on the surface of marble relief (MLA OA 10562) following leakage from a water pipe. This was identified as a calcium acetate formate hydrate (Thickett 1995), a mixed salt which had previously been identified on shells (Tennent and Baird 1985). The relief was mounted in a glass-fronted wood box that was a source of acetic and formic acid. Acetates and formates have been found on the surface of glass and enamels. Many gases readily adsorb onto the surface of glass, and it is highly likely that acetic and formic acids were taken up during long periods of storage in wood cupboards or display in wood showcases. Like many objects around the world, those in the British Museum have traditionally been stored in wood cupboards, resulting in long-term exposure to emissions of acids and aldehydes, which have been adsorbed onto the surface or even throughout the structure of many of the objects. This appears to be a substantial problem, but there are not that many instances of corrosion or salts on objects containing acetate or formate. On investigation, incidents of formation of corrosion or salts containing acetates and formates have involved the presence of water, applied during conservation, leaking onto the object, or in high relative humidity. From the analysis of acetic and formic acid levels in showcases and store cupboards, an empirical relationship between high humidity and temperature and the rate of outgassing from materials has emerged (Bradley 2003b). In the non-air-conditioned galleries of the Museum there is a seasonal variation in levels of acetic and formic acid and aldehydes, with winter levels considerably lower than summer levels. Since wood is still in use in showcases, albeit wrapped in a barrier film to reduce out-gassing (Thickett 1998), acids and aldehydes are present. However an examination of at-risk objects on display showed that they were not being affected by the gases and lead coupons in showcases did not corrode (Bradley and Thickett 1999). Even very high levels of acetic acid in cupboards used for the storage of Egyptian copper alloy objects did not corrode lead coupons. The relative humidity was at or below 45%. In general, the presence of moisture is needed for mixed corrosion products or mixed salts to form on objects; when conditions are favorable, formation is rapid. Further work is needed to establish if these types of reactions can be eliminated by keeping objects at a low relative humidity.
used in the storage or display of collections since they can be easily identified during the accelerated corrosion test. However even though only materials which do not tarnish silver are used in the Museum, reduced sulfur gases are present in the external air at concentrations of parts per trillion and are present in the unfiltered air in the Museum. Very low concentrations of these gases can cause silver to tarnish. In the British Museum research into these gases has focused on the tarnishing of silver since this has such an impact on conservation effort and time, with many objects requiring regular cleaning. Silver used to be lacquered to reduce the rate of tarnishing, but removing lacquer was difficult and residues have recently been shown to promote tarnishing (Thickett and Hockey 2003). Another approach was to use silver cleaners which included tarnish inhibitors, usually mercaptan based (Wilthew 1981, 1987).
Table .
Laboratory Evaluation of Tarnish Inhibitors. Results of XPS Analysis of Silver Coupons Expressed as Atomic Weight Percent. sulfide (Pope et al. 1968). Laboratory air was selected as the most readily available source of low level concentrations of reduced sulfur gases and had the advantage of providing a natural mix of hydrogen sulfide and carbonyl sulfide for the experiments. A small aquarium pump was used to pump air through a series of 2L capacity containers. Two holes were drilled into the screw tops of the containers, one for the inlet tubing and one for the air outlet. The containers were connected by rigid Teflon tubing and polythene T-connectors. The arrangement ensured that the pathway to each of the containers was exactly the same length, volume and had the same number of joins and that each container received an equal air flow. Eleven materials were evaluated in this experiment but only the results on the two most effective ICI catalysts, now named Puraspec 5040 and 2040, and on Charcoal Cloth are reported here (Table 1). The materials were placed in individual containers with the cloth cut to cover the base and the Puraspec pellets added to form a monolayer. Analar silver coupons were cleaned by abrasion and degreased in high purity acetone before being pierced and weighed. One coupon was then suspended from the screw top of each container, all at the same height. Controls were set up with a silver coupon suspended in a container alone and one suspended in the area of the apparatus in the laboratory. The experiment was started in July 1994 and completed in April 1995. When the experiment was stopped the control in the laboratory was a dark yellow brown color and that in the container was distinctly yellowed. The silver coupons exposed with the Charcoal Cloth and Puraspec 5040 and 2040 showed no visible change, but at 60x magnification, black spots could be seen.
Table .
Carbonyl sulfide and hydrogen sulfide gas concentrations measured between 31 January and 28 February 2001 errors into account, this location had the highest hydrogen sulfide and carbonyl sulfide levels. These coupons were analyzed by XPS and Static Secondary Ion Mass Spectrometry (SSIMS). The SSIMS analysis was carried out using a Millbrook Chemical Microscope in large area (2.25 mm2), static mode for both negative and positive ions. The primary beam is provided by a raster scanned gallium liquid metal ion gun with low energy optics for secondary ion extraction into a 300 Da quadropole mass spectrometer. Although both methods are surface analysis techniques the information they provided is different. In XPS the elements present are separated according to their binding energy (eV) and hence sulfur as sulfide and as sulfate are discriminated. The analysis is quantified as atomic concentration percent. SSIMS is a non-quantitative technique and the output is a mass spectrum detecting fragments as well as ions. Sodium, chlorine, oxygen, zinc, sulfur as sulfide and as sulfate, silicon, and carbon were detected on the surface of the silver coupons.
SSIMS equipment and storage in aluminum containers prior to exposure and analysis. Hence carbon species in the atmosphere were indicated as the primary source of this contamination (Hallett et al. 2003). Carbonyl sulfide was shown to be the predominant reduced sulfur gas in the air and not hydrogen sulfide; hence, the strategy of basing a tarnish prevention system on a material designed to remove hydrogen sulfide was flawed.
Gallery trial of passive deployment of Puraspec 5040. XPS analysis of silver coupons expressed as ratios of element to silver into a rectangular case with silver objects and no Puraspec. Silver coupons were also deployed in two control locations, the gallery, and a showcase containing glass objects alone which would not have been a sink for reduced sulfur gases. The coupons in the control locations tarnished after 42 days. All of the coupons were then analyzed by XPS. The results are presented in Table 3 as ratio atomic percent. There was more sulfur present on the silver coupon exposed in the showcase containing glass objects than that containing silver objects and no Puraspec. Hence the trial showed that silver objects are likely to tarnish at a slower rate in showcases containing other silver objects. This is presumably because the silver objects act as a sink for reduced sulfur and other gases. The Puraspec 5040 in passive mode did not reduce the rate of tarnishing. The results of this experiment were later found to have been affected by the high air exchange rate of the complex L-shaped showcase, more than 8 air changes per day. A trial of a positive pressure system was undertaken replacing Puraspec 5040 with Puraspec 2030 which was suggested by ICI Katalco. This product is also formed from zinc oxide and contains aluminum oxide which oxidizes carbonyl sulfide to hydrogen
sulfide which is in turn absorbed by the zinc oxide, and a copper compound which acts as an indicator, turning from green to black when it takes up sulfides. A simple filter bed was prepared in a tubular container using Puraspec 2030 and activated carbon cloth. It was decided to incorporate the cloth since it absorbs a broad range of pollutant gases and pumping air into a case could lead to a build up of pollutants at the surface of the objects. The filter bed was connected through the base of a showcase displaying only silver by plastic tubing and a small pump. Silver coupons were deployed to monitor the rate of tarnish formation and these were visually tarnished after 60 days. Again they were analyzed by XPS which showed that the pump had been effective at reducing sulfide formation (Table 4). On the basis of this research, current thought is to use positive pressure systems in all showcases where silver objects are displayed.
5 CONCLUSIONS
Greater understanding of the interaction of the museum environment with the collection has been achieved through research by the scientists in the British Museum. Increase in knowledge has been incremental, with improvements in scientific technology providing the capability to extend the work into levels of detail unimaginable in 1970. So that actual object needs are met in a cost-effective way, Museum scientists conducted object-based research designed to inform the preventive conservation strategy (Bradley 1996), rather than advocating wholesale implementation of conditions taken from the literature. Full air-conditioning of the building is not appropriate given the historical significance of the building itself, the range of materials and their levels of deterioration; and the mixed object displays which
Table .
Gallery trial of pump system to deploy of Puraspec 2030. XPS analysis of silver coupons expressed as ratios of element to silver are used to interpret the collection in themed galleries. However, when large numbers of objects are identified as needing environmental control, a global gallery or storage area approach is justified. The research has been utilized both in the British Museum and in the wider museum community informing showcase and storage unit design. It has prompted manufacturers to move away from wood to metal storage units, and glass and metal showcases, and to develop in-case conditioning systems which are superior to those based on humidifiers and dehumidifiers which we used for 25 years. Design of new galleries and storage facilities incorporates conservation requirements such as air cooling and filtration which are justified by the research. Most importantly, in new galleries and new storage areas, the objects are displayed and stored in safe conditions that are a vast improvement over those which existed in 1970 when this research was begun.
ACKNOWLEDGEMENTS
I would like to thank all the members of the Conservation Science team who have worked over the years to develop our understanding of deterioration and the Museum environment. In particular Lorna Lee (ne Green) and David Thickett have made a substantial contribution to this research. I would like to acknowledge the help of the conservators, curators, museum assistants, designers, particularly Geoff Pickup and buildings staff who point out incidents of objects changing, help with measurements in galleries and stores, and implement solutions. I would also like to thank Sheridan Bowman for reading the manuscript and suggesting improvements.
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AUTHOR INFORMATION
SUSAN BRADLEY, Head of Conservation Science and Analytical Chemistry in The British Museum Department of Conservation, Documentation and Science, has a degree
in chemistry from the University of London. In 1972 she joined the Museum to work on conservation problems, researching conservation methods for waterlogged wood and leather, the deterioration and conservation of stone, metals, ceramics, and glass, the storage of collections, and the museum environment. In 1988 she became Head of Conservation Research Group, leading a small team of scientists on object-centred research. Currently her main interests are the deterioration of glass and enamel and the museum environment. Address: Department of Conservation, Documentation and Science, The British Museum, Great Russell St., London WC1B 3DG, UK