Escolar Documentos
Profissional Documentos
Cultura Documentos
Occasional Paper
Number 111
British Museum
Occasional Papers
Publishers
The British Museum
Great Russell Street
London WC1B 3DG
Production Editor
Josephine Turquet
Distributors
British Museum Press
46 Bloomsbury Street
London WC1B 3QQ
Selection of Materials for the Storage or Display
of Museum Objects
D.Thickett and L.R. Lee
Occasional Paper No. 111, first published 1996,
new and completely revised edition 2004
ISBN 0 86159 117 8
ISSNISSN 0142 4815
The Trustees of the British Museum 2004
Front cover: Silver tigress from the Hoxne hoard, Romano-British,
probably intended as one of a pair of handles for a large silver
amphora or vase. Buried in the 5th century AD, excavated in 1992
and conserved at the British Museum.
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II
Introduction
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9
Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9
Selection of tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9
Tests for potential to emit harmful volatiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .12
Accelerated corrosion tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .12
The Oddy test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .13
3 IN 1' accelerated corrosion test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .15
The azide test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .16
The Beilstein test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .18
The iodide-iodate test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .18
The Purpald test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .19
The chromotropic acid test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .20
Tests for materials to be used in direct contact with artefacts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .21
Aqueous extract pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .21
Surface pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .22
The phloroglucinol test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .22
The aluminon test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .23
Suppliers of chemicals and apparatus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .24
3 Practical Methods of Display and Storage
25
4 References
29
III
Plate 5
Plate 6
Detail of a scroll by Matabei showing tarnishing of silver (JA 1946 02-09 032, Jap Ptg Add 194 . . . . . . . . . . . . . . . . . . . . . . . . . . . .4
Necklace from Somalia with beads made of silver alloy and cullulose nitrate (Ethno 1933 11-14 82) . . . . . . . . . . . . . . . . . . . . .7
Detail of corrosion on silver alloy beads due to degradation of cellulose nitrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7
Reference photographs for the Oddy test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .14
a) silver coupons
b) copper copons
c) lead coupons
Reference photographs for the azide test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .17
a) posative test
b) slight positive test
c) negative test
Reference photograph for the aluminon (alum) and phloroglucinol (lignin) tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .23
Figures
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Tables
Table 1
Table 2
IV
Introduction
1.
Effects of pollutants
Air is composed mainly of nitrogen and oxygen, but also
contains a complex mixture of many different gases present
at much lower concentrations, for example ozone, sulphur
dioxide and oxides of nitrogen. These low background
concentrations can cause slow deterioration of objects;
outdoor stone sculpture will form a sulphate crust and
bronze statues become covered with a patina of corrosion
products, particularly in an industrial or maritime area.
However, these outdoor pollutants are generally
present at much lower levels inside a building (Graedel and
McGill 1986), and the indoor environment often possesses
its own characteristic range of pollutants. For example it
may contain higher levels of organic acids, particularly
formic (methanoic acid) and acetic acid. This is because they
are emitted by materials such as timber and timbercomposites. The problems arise when such materials are
used in confined spaces, where any emissions become
trapped and their concentration increases.
If enclosed with inappropriate materials, metal artefacts
can corrode, inorganic objects can suffer adverse reactions
such as the formation of mixed salts and organic materials
can become brittle. In this section, effects of various
pollutant gases on each of these types of object will be
explored in turn. At this point it is worth mentioning the
deleterious effects of particulate matter; this absorbs
moisture and pollutant gases, and therefore a layer of dust
on an object can exacerbate any of the following effects. The
importance of clean storage and display areas cannot be
over-emphasised.
If silver is placed on open display, it will become dull and
eventually acquire a tarnished appearance. This is due to
3
Sources of pollutants
Table 1 summarises the major sources and effects of common
indoor pollutants.
In a museum situation a wide range of materials are used
to construct and dress showcases, and in fitting out a store.
Wood is one such material as it is versatile, comparatively
inexpensive and easily worked. It also has the advantage of
buffering changes in relative humidity (RH), an effect which
may be beneficial to certain types of artefact. However all
wood emits varying levels of organic acids and
formaldehyde. As wood is a natural, non-homogeneous
material, it is difficult to be specific about properties
regarding outgassing of certain species or products, and lists
of results from previous tests are of minimal use. General
statements can however be made, for example oak and
sweet chestnut emit higher levels of organic acids than
beech or spruce (Arni et al. 1965, Blackshaw and Daniels
1978). Variations in emissions from the same species can be
influenced by several factors including time of felling,
whether the wood is heart or sapwood and treatment after
felling; kiln drying has been found to produce higher levels
of free organic acids in a sample of wood than air drying.
The moisture content of wood and timber products also
affects their corrosive nature. Certain woods have been
5
Main source
wool
fabrics, eg felt
rubber
adhesives
timber
timber composites
paints
adhesives,
varnishes
sealants
moth and rot proofing
formaldehyde CH2O
Affects
adhesives
timber
timber composites
urea and phenol formaldehyde high levels can attack most metals and
all
organic artefacts under suitable conditions
MDF*, plywood,
blockboard, chipboard
fabrics, paints
chlorides
plastics
fire retardants
PVC, PVDC
inorganic salts
plastics
cellulose nitrate
Key
* medium density fibreboard
poly vinyl chloride
poly vinylidene chloride
Plate 2 Necklace from Somalia, with beads made of silver alloy and cellulose
nitrate (Ethno 1933 11-14 82)
2.
Test Methods
Introduction
Sampling
Selection of tests
The flowcharts, Figures 1 and 2, provide a swift method to
decide which tests need to be applied to a storage and
display material proposed for use with specific groups of
artefacts.
Two accelerated corrosion tests are included, the
method as standardised and published in 1995 and a
modification of that method designed to streamline the test
production and reduce the amount of time required to set up
the test. An alternative formaldehyde test has also been
added to this edition, using less toxic materials than the
chromotropic acid test.
10
12
Test method
The following recommended method should be followed
exactly. Care should be taken to ensure all equipment is
clean and that it does not become contaminated during
preparation of the test. This can lead to erroneous results.
The cleaning procedure previously used for the glassware at
the British Museum involves cleaning in chromic acid,
washing with hot detergent solution, rinsing with distilled
water, drying and passing through a Bunsen flame. The
chromic acid used is extremely toxic and may cause cancer,
see safety notes at the end of this section.
1. AnalaR (99.5% pure or better) metal foils, 0.1mm thick,
should be used: copper to assess the effects of the test
material on copper-based artefacts, silver for silver-based
artefacts and lead for lead-based artefacts. If artefacts
are made of high lead bronze which can contain discrete
particles of lead, then both copper and lead tests should
be carried out. It is recommended that metal foils of the
desired thickness are purchased, as processing of a
thicker foil may introduce impurities and inconsistencies
in the coupons, leading to irreproducible results.
2. A 10 x 15mm coupon is cut from the metal foil. Both faces
of the coupon are lightly abraded using a glass bristle
brush. Care should be taken to keep the coupons as flat
as possible, as physical distortion can lead to problems at
the assessment stage. A separate glass bristle brush
should be reserved for each metal to avoid
contamination.
3. A small hole is pierced in each coupon, close to one edge.
It has been found that this can be done effectively by
using the guide pin on a pair of dissecting tweezers.
4. Nylon monofilament (maximum diameter 0.053mm) is
threaded through the hole in the coupon and tied in
place.
5. The coupon is degreased in a glass dish of acetone for a
few minutes with slight agitation. Using tweezers, the
coupon is removed and allowed to dry between tissue
paper. The coupon is subsequently handled using only
tweezers and while wearing gloves.
6. Approximately 2g of the test material are added to a
50ml glass boiling tube with a ground glass seal, which is
a convenient reaction vessel. Bulky materials should be
cut into pieces approximately 10 x 10 x 5mm. When it is
impossible to fit 2g of certain materials in the tube eg
expanded foams, as much test material as is reasonably
practical should be used, ie without causing contact with
the metal coupon.
7. A 0.5ml test tube is filled with distilled water, stoppered
with a small plug of cotton wool and added to the boiling
tube.
8. The nylon monofilament holding the cleaned coupon is
trapped in the ground glass joint of the boiling tube. A
collar of heat shrink tubing (type NMW360),
9.
10.
11.
12.
13.
13
U
Plate 4a Reference photograph for
silver coupons
Control: should show no change
P: no change compared with
control. No discolouration of the
coupon.
T: slight discolouration only, often
seen along lower edge and sides.
Alternatively a few localised small
spots of tarnish.
U: clearly visible tarnish.
14
16
Test method
1. 3g of sodium azide are dissolved in 100ml of Convol
0.05M iodine solution (supplied in solution form) and
3ml of industrial methylated spirits (IMS) are added.
The reagent should be stored in a brown glass bottle and
has a shelf life of 3 months.
2. A few fibres are separated from the test material with
tweezers and placed on a clean microscope slide.
3. A clean cover-slip is placed over the fibres which are
viewed under magnification of at least x20.
4. One drop of azide solution is placed on the microscope
slide, away from the fibres and covered with a clean
cover-slip. This is a control.
5. One drop of the azide solution is placed at the edge of
the cover slip with the fibres. It will be drawn under the
cover-slip and onto the fibres by capillary action.
Plate 5a Positive azide test unsuitable for use (U) with silver or copper.
Immediate and vigorous bubbling with nitrogen evolved from most of the
sample
Plate 5b Slight positive azide test suitable for temporary use (T, up to 6
months only) with silver and copper.A few bubbles gradually form
Plate 5c Negative azide test suitable for permanent use (P) with silver and
copper. No or very few bubbles
17
Test method
1. A copper wire is cleaned by dipping in dilute nitric acid.
2. The wire is held in the hot region of Bunsen burner
flame until red heat is attained.
3. A small sample of test fabric is held with tweezers and
introduced into the Bunsen flame so that the products of
combustion pass over the copper wire.
4. If a green colour is noted in the flame, the test material
contains chlorine and is unsuitable for use with copper,
silver or iron-based artefacts.
18
+
5I + IO3 + 6H 3H2O + 3I2
Test method
1. The following solutions are prepared using distilled water:
(a) potassium iodide, KI, 2%, weight to volume (w/v), shelf
life six weeks in a brown glass bottle
(b) potassium iodate, KIO3, 4% (w/v), shelf life eight weeks
(c) soluble starch, 0.1% (w/v), shelf life four weeks
2. Two drops of each of the solutions (a) (c) are placed into
the reaction dish, shown in Figure 5.
3. 2g of the sample under test is added to the reaction flask,
a 50ml Quickfit conical flask with a ground glass neck.
4. The stoppered flask is placed in an oven at 60C.
5. The solution in the flask is examined after 30 minutes. If
the solution shows any sign of blue, the sample is a
source of volatile acids, and should not used with
materials known to be susceptible to deterioration in the
presence of such volatiles, for example lead.
19
Test method
1. A solution of Purpald (7.5% w/v) is prepared in 0.1M
sodium hydroxide. The solution should be stored in a
tightly sealed, all glass container (plastics often emit
formaldehyde), and used within 7 days.
2. Approximately 0.2ml (10 drops) from a Pasteur pipette of
the Purpald solution is placed into the reaction dish,
shown in Figure 6.
3. 2g of the sample under test is added to the reaction flask,
a 50ml Quickfit conical flask with a ground glass neck.
4. The stoppered flask is placed in an oven at 60C.
5. The solution in the flask is examined after 5 minutes. If
the solution shows any sign of blue, the sample under
test is a source of aldehydes and is therefore not suitable
for use with materials known to be susceptible to
deterioration by aldehydes, such as lead.
Test method
1. A solution of chromotropic acid (1% w/v) is prepared in
concentrated sulphuric acid (97%). The solution should
be stored below 4C, and used within 2 days.
2. Approximately 0.2ml (10 drops) from a Pasteur pipette of
the chromotropic acid solution is placed into the reaction
dish, shown in Figure 6.
3. 2g of the sample under test is added to the reaction flask,
a 50ml Quickfit conical flask with a ground glass neck.
4. The stoppered flask is placed in an oven at 60C.
5. The solution in the flask is examined after 30 minutes. If
the solution shows any blue, the sample under test is a
source of aldehydes and is therefore not suitable for use
with materials known to be susceptible to deterioration
by aldehydes, such as lead.
20
very acidic
weakly acidic
neutral
alkaline
Test method
Hydrogen ion
concentration (M)
0.1
0.001
0.0000001
0.00000000000001
hydrochloric acid
acetic acid
water
ammonia
21
Test method
1. Distilled water is boiled for at least ten minutes to
remove dissolved gases, covered and allowed to cool to
room temperature. Water to 18.2M quality can be used
without boiling.
2. A glass plate is cleaned with distilled water and dried.
3. The pH meter is calibrated using drops of buffers (pH7
and pH4) on a glass plate, according to manufacturers
instructions.
4. The sample is placed on a glass plate. A drop of boiled
out distilled water is placed on the sample surface and
left to stand for 1 minute. The surface electrode is placed
onto the wetted surface, and the reading is allowed to
settle. This step should be repeated at least 5 times on
different areas of the sample, and the average pH
calculated. All readings used to calculate the average
should be within 0.2 pH units of each other. If the pH is
alkaline the reading may take up to 30 minutes to settle.
5. The pH of a material intended for direct contact with
organic artefacts should lie in the range 5.5 to 8.5.
Test method
1. 1g of phloroglucinol is dissolved in 50ml of 1M
hydrochloric acid.
2. A drop of the reagent solution is placed on the paper
being tested, which rests on a clean glass plate. If lignin
is present, the solution spot will turn a deep purplish red,
otherwise the solution will remain colourless, as shown
in Plate 6.
3. The solution degrades with time and should be replaced
when it becomes yellow.
NB: this test requires a discriminating eye and it is recommended
that controls are run using papers known to contain lignin, eg
newsprint, and conversely with papers known to be free of lignin.
Test method
1. 1g of aluminon is dissolved in 1 litre of distilled water.
This produces a pale pink solution.
23
Azide test
24
Beilstein test
Nitric acid
VWR (as above)
Iodide-iodate test
Potassium iodide, potassium iodate, soluble starch, Quickfit
conical flasks (50ml, size 24/29 joint)
VWR (as above)
Modified stoppers (made to order)
Radleys
Laboratory Equipment and Scientific Glassblowing
Shire Hill
Saffron Walden
Essex
CB11 3AZ
Tel: 01799 513320
Purpald test
Purpald
Aldrich Chemical Company Ltd
The Old Brickyard
New Road
Gillingham
Dorset
SP8 4JL
Tel: 0800 717117
Sodium Hydroxide
VWR (as above)
pH measurement
pH meters and buffers
VWR (as above)
3.
27
References
Arni, P.C., Cochrane, G.C. and Gray, J.D., 1965, The emission of
corrosive vapours by wood II. The analysis of the vapours
emitted by certain freshly felled hardwoods and softwoods by
gas chromatography and spectrometry, Journal of Applied
Chemistry, 15, 463-8
Barrow, W.J., 1969, Permanence/Durability of the Book VI. Spot
Testing for Unstable Book and Record Papers, The Dietz Press Inc,
Richmond, 9-18
Blackshaw, S.M., 1982, The testing of display materials, Occasional
Paper No. 1, The Care of Ethnographic Materials, ed: D.L. Jones,
The Area Museums Service for South Eastern England, 40-5
Blackshaw, S.M. and Daniels V.D., 1978, Selecting safe materials in
the display and storage of antiquities, ICOM Committee for
Conservation, 5th Triennial Meeting, Zagreb, 78/23/2-9
Blackshaw, S.M. and Daniels, V.D., 1979, The testing of materials for
use in the storage and display in museums, The Conservator, 3,
16-19
Blackshaw, S.M., King, J. and Hughes, M., 1974, The testing and
identification of new materials for conservation and display,
British Museum Research Laboratory Report 1974/Con 2,
unpublished
Bogarty, H., Campbell, K.S., and Appel, W.C., 1952, The oxidation of
cellulose by ozone in small concentrations, Textile Research
Journal, 22, 81
Bradley, S.M., 1989, Hydrogen sulphide scavengers for the
prevention of silver tarnishing, in Environmental Monitoring and
Control, SSCR, Dundee, 65-7
Brauns, F.E., 1952, The Chemistry of Lignin, Academic Press, New
York, 24-38
Brimblecombe, P., 1990, The composition of museum atmospheres,
Atmospheric Environment, 24B, (1), 1-8
Brimblecombe, P., Shooter, D. and Kaur, A., 1992, Wool and reduced
sulphur gases in museum air, Studies in Conservation, 37, 53-60
Brysson, R.J., Trask, B.J., Upham, J.B. and Booras, S.G., 1967, The
effects of air pollution on exposed cotton fabrics, Journal of Air
Pollution Control Association, 17, 294 8
BS4971, 2002, Repair and allied processes for the conservation of
documents, British Standards Institution, London
Byne, L., 1899, The corrosion of shells in cabinets, Journal of
Conchology, 9, 172-178, 253-4
Daniels, V.D. and Meeks, N., 1992, An investigation into foxing
phenomena with particular attention to the inorganic
components, Biodeterioration of Cultural Property 2, 2nd
International Conference, Yokohama, Japan, 292-305
Daniels, V.D. and Meeks, N., 1995, Foxing caused by copper alloy
inclusions in paper, Symposium 88- Conservation of Historic and
Artistic Works on Paper, Ottawa, eds: H.D. Burgess J. Krill, CCI,
Canada, 229-33
Daniels, V.D. and Thickett, D., 1992, The reversion of blackened lead
white on paper, The Institute of Paper Conservation, Manchester
1992, ed: S. Fairbrass, 109-15
Daniels, V.D. and Ward, S., 1982, A rapid test for the detection of
substances which will tarnish silver, Studies in Conservation, 27,
58-60
Doree, C., 1947, The Methods of Cellulose Chemistry, Chapman and
Hall, London, 339
Dupoint, A.L. and Tetrault, J., 2000, Cellulose degradation in an
acetic acid environment, Studies in Conservation, 45, 201-210
Fenn, J., 1995, Secret sabotage: reassessing museum plastics in
display and storage, preprints Resins Ancient and Modern, eds:
M. Wright and J. Townsend, SSCR, Aberdeen, 38-41
Gibson, L.T., Cooksey, B.G., Littlejohn, D. and Tennent, N.H., 1997,
Characterisation of an unusual crystalline efflorescence on an
Egyptian limestone relief, Analytica Chimica Acta, 337, 151-164
Gilroy, D. and Mayne, J.E.O., 1965, The inhibition of the corrosion of
30