The Oddy Test Possibilities and limits

Prof. Univ.-Doz. Dipl.-Ing. Dr. Gerhard Banik, former head of the

"Restaurierung und Konservierung von Graphik-, Archiv- und Bibliotheksgut" at
the State Fine Art Academy, Stuttgart, comments after three years of in-depth
examination on the implementation of the ODDY Test.
The Oddy Test was first proposed in 1973 by Antony Werner and in 1975, the
conservation scientist Andrew Oddy, then at the British Museum, Scientific
Department, developed the test to evaluate the suitability of materials for use
in storage and display cases. The evaluation and identification of potential
damaging storage materials is accomplished by monitoring the tarnish of the
metal indicators (Oddy 1975). The procedure is basically a corrosion test at
100% relative humidity, where three indicator metals (silver, copper and lead)
when in contact with contaminants emit gas pollutants (VOCs). The evaluation
factor of the indicator metals out-gassing at 100% RH and 60C is reached
after a treatment period of 28 days.
A study by Lee and Thickett released in 1979 describes the test method, but
the authors strictly recommend to observe the research methodology: The
following recommended method should be followed exactly. Accordingly two
grams of the sample material in crushed form is placed at the bottom of a
clean glass vessel, for example an Erlenmayer test tube or any glass reaction
vessel, the purified indicator metal is suspended from a nylon thread over the
sample material and then for the relative humidity adjustment a glass vessel
filled with distilled water is placed into the analysis container, which is then
hermetically sealed with either a suitable plastic or glass seal. The heat
treatment is then carried out over the prescribed test duration of 28 days in a
drying oven at constant 60C. An improved and simplified procedure can be
found in the recent publication by Robinet and Thickett (2003), which is
mediated in the HTW Berlin (see literature appendix) in ODDY Test training
workshops.
In order to be able to compare test results, the authors have suggested the
necessity of strict adherence of the research methodology, considering that
approximately twenty different types of testing methods are carried out mainly in museum laboratories or by restorers - and their results are really not
comparable.
The Oddy test as a corrosion test with indicator metals is fraught with a great
number of uncertainties, which are due mainly to the following facts:

1) The corrosion of test metals at 100% RH is definitely different in comparison

to corrosion that takes place under normal humidity conditions. (50% rF)
2) The corrosion of test metals in direct contact with tested material is not the
same compared to the corrosion that takes place if in direct contact with the
outgassing emittants. (VOCs)
3) The corrosion of the test material decisively depends on the method how
the surface of the metals has been treated and prepared. This applies both to
the precision grinding of the metal surface as well as its subsequent
purification. For the comparability of the results and the interpretation of a
corrosive change of even one of the test metals, it is of utmost importance that
the grinding and purification the indicator metals is carried out with absolute
precision. In this context please refer to the evidences of Lee and Thickett, and
of other publications. (Zang et al. 1994, Robinet und Thickett 2003)
4) The corrosion of the three test metals copper, silver and lead in most cases
lead to the following outgassing substances: sulfide (silver), acetic acid
(copper) and acetic acid from lead, whereby the mechanisms of the respective
corrosion process due to the mixture and mingling of outgassing pollutants is
visually unassessed.
5) Additional intensive colour changes on the surfaces of copper and lead are
due to oxidization.
6) The comparison of the changes that have taken place on the metal surfaces
can be categorized into three levels: no corrosion slight corrosion severe
corrosion and are subject to the visual impressions of the person testing and
can therefore not be assessed or considered as reproducible for a clearly
interpretable scientific result.
7) The sample selection, handling and storage of the material to be examined
in either workshops or laboratories can have a significant influence on the test
result, especially the latter plays an important role because of the absorption
of contaminants present in the atmosphere during storage.
One of the main issues of the ODDY Test is that there is some subjectivity to
the interpretation of the results, since it is primarily a visual determination.
Accordingly, it is not a sufficiently precise analytical tool to interpret the causes
of the corrosion phenomena or of the discolouration of the indicator metals.
Despite the wide implementation of this testing method in the museum sector
it is still of great controversial discussion. (Grzywacz, 2006). The test is
basically only suitable to prove that under certain experimental conditions, test
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materials can emit harmful gases and are thus not suitable, but are not
meaningful to derive risks for other materials that have also been in contact
with the test material for long periods of time. A direct transfer of data is
subject only to the tested material and here again is basically only applicable
for silver (blackening effect due to the formation of silver sulfide in the
presence of sulphide and sulphuric pollutants) and in the case of lead
(formation of white deposits due to alkaline lead carbonate or lead acetate
released by acetic acid). For more information about corrosion of lead in the
presence of acetic acid, please refer to Tetreault (1998).
Recent studies from the years 2003 and 2010, which are listed in the literature
appendix, allude more accurate testing methods, for example the optimized
ODDY Test (Robinet and Thickett, 2003) and a modified experimental set-up
with precise analysis (Strli 2011). The Strli Test is especially suitable with
precise statements with respect to the danger degree for cellulose-based
materials, however, this test demands a considerably higher analytical effort.
In the studies of Strli one finds evidence of the examination of paper an board
materials and cellulosic materials used for manufacturing ageing resistant
products, however further verification is necessary. It is well-known that
gaseous pollutants have an influence on the ageing resistance of paper,
however the degree of risk depends upon the composition of paper and the
respective pollutant compounds. One can formulate that gaseous acids have a
relatively significant effect, but also aldehydes after oxidization to acidic
compounds also cause the degradation of paper. Acetic acid is emitted during
the ageing process of paper with lignin content, but its presence, according to
current research (Di Pietro und Ligterink, 2012) has no or hardly any effect on
the stability of paper. Besides the formation of acetic acid also formic acid and
other compounds occur, but it is difficult to estimate their influence (Volland et
al., in print). Above all, it should definitely be noted that historical documents
stored in such containers also emit these kind of pollutants.
It is remarkable that the standard for wrapping materials (ISO 16245:201104) has not considered materials emitting gaseous pollutants and their
accumulation in packaging's and storage containers. From a collector's pointof-view it advisable to consider modifying these standards, because one can
estimate that not only the boxing and mounting material can emit acetic acid
to a certain extent but also the collectables stored within the containers could
emit these gases. It is difficult to estimate the extent of damage caused due to
the concentration of acetic acid, but it is probably insignificant, otherwise it
would obviously be seen on many collection items, especially with acidsensitive colourings.
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Likewise, from the museum point-of-view one should consider, whether the
current standard in force for wrapping materials of collections (ISO
11799:2003) is still up to the mark, and whether the limitations for acidic acid
concentration <4ppb and for formaldehyde <4ppb are still appropriate, even
though recent developed research results indicate that the damage of acetic
acid on cellulose is very marginal.
Literature appendix:
E DIN ISO 16245: 2011-04: Information und Dokumentation Schachteln
Archivmappen und andere Umhllungen aus zellulosehaltigem Material fr die
Lagerung von Schrift- und Druckgut aus Papier und Pergament. Deutsches
Institut fr Normung, Berlin: Beuth.
DIN ISO 11799: 2005-06:Information und Dokumentation Anforderungen an
die Aufbewahrung von Archiv- und Bibliotheksgut. Deutsches Institut fr
Normung, Berlin: Beuth.
DI Pietro, G., F. Ligterink, F.: The limited impact of acetic acid in libraries and
archives. In:Indoor Air Quality 2012, 10th International Conference Indoor Air
Quality in Heritage and Historic Environments Standards and Guidelines,
Book of Abstracts, London: UCL Centre for Sustainable Heritage, 2012, 19
Green,L.R., Thickett, D.: TESTING MATERIALS FOR USE IN THE STORAGE AND
DISPLAY OF ANTIQUITIES-A REVISED METHODOLOGY. Studies in
Conservation 40 (1995): 145-152.
Grzywacz C.,:Monitoring for gaseous pollutants in museum environments. Los
Angeles: TheGetty Conservation Institute, 2006.
Hochschule fr Technik und Wirtschaft Berlin: Eine Weiterbildung zum
Indikatortest nach Oddy. http://weiterbildung.htwBerlin.de/SysBilder/File/HTW_Weiterbildung_Oddy_2013.pdf
Lee, L.R., Thicket, D .:Selection of materials for the storage or display of
museum objects. London: Britisch Museum Occasional Paper 111.
Oddy, A.: The corrosion of metals on display. Conservation in Archaeology and
the Applied Arts,(N. S.Brommelle und P.Smith Hrsg.), London: IIC (1975):
235-237
Potthast
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Robinet, L., Thickett, D.: A new methodology for accelerated corrosion testing.
Studies in Conservation 48 (2003): 263-268
Strli, M., Kralj Cigi, I., Moir;A.,de Bruin; G., Kolar, J., Cassar, M.: The
effect of volatile organic compounds and hypoxia on paper degradation.
Polymer Degradation and Stability 96 (2011): 608-615
Jean Tetreault, J., Jane Sirois, J., Stamatopoulou, E.: STUDIES OF LEAD
CORROSION IN ACETIC ACID. Studies in Conservation 43 (1998): 17-32
Volland, G., Hansen, D., Knjasev, V., Meyer ,F.: The Schinkels Legacy
Project at the Kupferstichkabinett / Schinkelmuseum Berlin. Subproject: Air
Quality in Warehouse Storage Cabinets Cause and Effect. Restaurator 34,
No.3, in Druck.
Zhang, J., Thickett, D., und Green L.: Two tests for the detection of volatile
organic acids and formaldehyde. Journal of the American Institute for
Conservation 33 (1994): 47-53