Gerhard Eggert and Britta Schmutzler (Eds.

)

Archaeological Iron Conservation Colloquium 2010

Extended Abstracts

Archaeological Iron Conservation Colloquium 2010

State Academy of Art and Design Stuttgart 24th to 26th June 2010

INTRODUCTION: THE MAKING OF A CONFERENCE GERHARD EGGERT1, BRITTA SCHMUTZLER1
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State Academy of Art and Design, Am Weißenhof 1, D-53489 Stuttgart, Germany gerhard.eggert@abk-stuttgart.de; b.schmutzler@abk-stuttgart.de

There's a problem Guess, when this was written: “As is generally known, excavated iron objects decay – depending on their state of deterioration- sooner or later even in the driest exhibition or storage rooms despite all precautions.”? No, although we are today all aware of the problem, that's not a current description from an archaeologist. It was written by the Berlin museum chemist Eduard Krause in 1882, he already supposed the action of chloride and found ferrous chloride in 'weeping iron' (Fig. 1).

Fig. 1: ’Weeping iron’: Who may dry its tears? Photo: I. Wiesner, SABK

But the problem to stabilize iron finds is still with us, washing with water as Krause recommended does not help very much. The alkaline sulphite treatment described by North and Pearson was a big step forward for individual finds without organic remains. For dealing with the tons of iron excavated every year many conservation labs found it too complicated. While working on a book on iron conservation (Scott and Eggert 2009) it became apparent that there might be ways to simplify the treatment (no heating, diluted solutions, alternatives to sulphite to keep the oxygen out). That was start of a research project, generously funded by the Deutsche Bundesstiftung Umwelt (DBU) who also supports this colloquium to share its results with the international conservation community. The idea to compare variations was straight forward: It's not the amount of chloride extracted into the solution, but the chloride left behind in the object which needs to be measured (Eggert and Schmutzler 2009). Fortunately, the Romans left so many nails in the soil of Baden-Württemberg that the Landesamt für Denkmalpflege (LAD Baden-Württemberg), cooperation partner for the research project and co-organiser of this conference, was able to provide us with enough samples. Experimentally, measuring chloride in iron turned out much more complicated than expected from the literature...

We are not alone There was not much innovation or systematic research on remedial conservation of iron finds since North and Pearson (1975). The largest problem in archaeological conservation seemed to be neglected somewhat. But as soon as we started with our project we heard about many other initiatives. Cardiff took up earlier work on extraction rates (Watkinson 1996) and anaerobic desalination. As you can see from the conference programme, London became a hot spot for research on corrosion (British Museum, English Heritage) and treatment (Museum of London). In France, the group of Dillmann and Neff applied their highly advanced microanalytical tools in the ODéFA project to the effects of conservation treatments. In the US, the use of subcritical solutions seems to open a totally new route to desalination. In Germany, the Kulturstiftung des Bundes and the Kulturstiftung der Länder started the KUR-programme for conservation of mobile heritage objects. One of the projects funded deals with mass treatment of iron (Archäologische Staatssammlung Bayern). Another one (Landesmuseum für Vorgeschichte Sachsen-Anhalt in Halle in cooperation with our Academy) tests the use of tetraalkyl ammonium hydroxides for desalination. They also report their results here and support our conference. And there’s so much more… Let's have a conference Our idea: If there are so many research and conservation projects going on, the best thing would be to get all groups together for a conference. Following a series of one day conservation colloquia at the Academy (2005 Metals, 2006 Ceramics, 2007 Bronze, 2008 Glass) with international participation we developed an international Call for Papers. Spreading the news was easy: The ICOM-CC WG Metals (see this booklet for their next Metals 2010 conference in Charleston, South Carolina, Oct. 11-15, 2010) has a specialist group ‘Archaeological Iron after Excavation’ (AIAE). They joined forces and distributed our call worldwide. The response was outstanding (simply see the programme!): Some of our own contributions had to be withdrawn or could only make it as posters to give enough space for our guests. And as soon as we distributed details for registration among German archaeological conservators our seats were outsold within few days. That’s why we are confident that our colloquium meets the interests of the conservation community. We do hope that the mutual exchange in lectures and discussions at the colloquium will inspire future research and will lead to viable solutions for the preservation of our entire excavated ferrous heritage. In 1882 and today, we know the challenge: ‘Rust never sleeps!’ Neither can we.

Acknowledgement We are grateful to all our sponsors for their support in organizing the conference: - Staatliche Akademie der Bildenden Künste, Stuttgart - Landesamt für Denkmalpflege Baden-Württemberg, Esslingen - Deutsche Bundesstiftung Umwelt, Osnabrück - Landesamt für Denkmalpflege und Archäologie Sachsen-Anhalt / Landesmuseum für Vorgeschichte, Halle - AIAE, sub-WG of ICOM-CC WG ’Metals’
References Eggert, G., and Schmutzler , B. (2009), ’Lässt sich die Konservierung von Eisenfunden auf Standard bringen?’, in U. Peltz and O. Zorn (eds) kulturGUTerhalten: Standards in der Restaurierungswissenschaft und Denkmalpflege, Mainz: v. Zabern, 91-95. North, N.A., and Pearson, C. (1975), `Alkaline sulfite reduction treatment of marine iron´ in Icom committee for conservation, 4th Triennial Meeting, Venice, 13-18 October 1975. Preprints, Paris: International Council of Museums, 75/13/ 3/ 1-14. Scott, D.A., and Eggert, G. (2009) Iron and Steel in Art: Corrosion, Colorants, Conservation. London: Archetype Publications. Watkinson, D. (1996) ‘Chloride extraction from archaeological iron: comparative treatment efficiencies’, in A. Roy and P. Smith (eds) Archaeological Conservation and its Consequences: Preprints of the Contributions to the Copenhagen Congress, 26–30 August 1996. London: International Institute for Conservation, 208–12.

Extended Abstracts

Session 1: Iron Conservation Science

PLASMA-REDUCTION, ITS POTENTIAL AND LIMITS IN THE CONSERVATION OF METALS KATHARINA SCHMIDT-OTT1 Swiss National Museum, Collection Centre, Lindenmoostr.1, CH-8910 Affoltern am Albis, katharina.schmidt-ott@snm.admin.ch Introduction Since their initial application to metal artefacts in 1979, gas plasmas have been the subject of research in conservation. The application of the plasma method in the conservation of different metals is investigated to determine its potential and limits. Clarification of the effect of high frequency excited plasmas on iron, silver and lead objects is covered in the paper. Method and Materials In a first step the treatment parameters are improved. Pure hydrogen and previously established hydrogen-argon mixtures are investigated with optical emission spectroscopy. It is assumed that by optimising the gas excitation the plasma operation is also optimised. It is shown that pure hydrogen plasma treatments with relatively low gas flow increase the radical concentration as compared to hydrogen-argon plasmas consisting of ten parts hydrogen to one part argon. These results lead to new standard parameters for archaeological iron objects. The new hydrogen plasmas being at least as efficient as those previously applied but with reduced object temperatures (about 90 °C) during treatment.
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Fig. 1: Iron objects during plasma treatment. The bright light surrounding the object indicates the presence of atomic hydrogen.

Optimal settings are then assumed to be also valid for the treatment of metal artefacts. A group of 20 Roman nails is divided into small groups and differently treated. The effects of hydrogen-argon plasma, pure hydrogen plasma and heat treatment in vaccum are compared. Metallographic samples from each of the nails are taken both before and after drying and/or plasma treatment and observed under a scanning electron microscope. It is shown that only the plasma treatment leads to the desired separation between the original surface layer of the object and outer corrosion layers. Mechanical removal of outer corrosion layers can thereby be more easily and precisely carried out. A separation of layers due to dehydration can be ruled out. The facilitation of mechanical cleaning after plasma reduction is furthermore shown in a double-blind study.

Fig. 2: SEM of a polished sample of a Roman nail after plasma treatment. The arrow indicates the separation between outer corrosion layers and original surface which facilitates the mechanical cleaning of the objects.

The effect of plasma treatment on the iron corrosion products haematite, magnetite, goethite and akaganeite is measured by micro-Raman spectroscopy. Measurements on the powdered samples are carried out before and after the plasma treatment. The reduction of particular corrosion products in surface layers can be confirmed. The penetration of the plasma into different corrosion layers is investigated on archaeological artefacts. Corrosion products from stratigrafically cleaned areas as well as metallographic samples are investigated by means of Raman spectroscopy both before and after plasma treatment. Chemical reduction during treatment was confirmed to be active only at the surface layer, the more deeply situated corrosion layers having not been penetrated.

For the first time, samples are treated with pure argon plasma in order to detect a facilitation of treatment for subsequent mechanical cleaning. A separation of layers is also observed. This separation can be related to the high-frequency field and the displacement current in the sample layers. As plasma treatment carried out with comparatively low temperatures does not lead to a removal of chlorides contained in iron objects, the method is combined with desalination in alkaline sulphite. This combination results in a very good long-term stability of archaeological artefacts. Pure hydrogen plasmas are also applied to corroded historical silver artefacts. The effect of plasma reduction is shown by means of scanning electron microscopy and X-ray fluorescence analyses on a silver sheet with artificially produced silver corrosion layers. Silver corrosion is removed without any damage to the surface of the artefacts. It can be concluded that plasma reduction is a suitable method even for daguerreotypes. The efficient removal of tarnish layers is further demonstrated on selected historical artefacts. A combination of plasma reduction and subsequent burnishing retards new corrosion from forming. As for the treatment of heavily corroded lead artefacts, the effect of hydrogen and hydrogenargon plasmas is investigated. Two samples of the same object are compared. A reduction of the corrosion layers and changes to surface topography can be shown by means of scanning electron microscopy and X-ray fluorescence analyses. Penetration into deeper layers is minimal and comparable to the penetration of iron and silver. Discussion and Results The optical spectroscopy of hydrogen plasmas at smaller operation pressure showed that not only lower treatment temperatures can be reached, but also an increase of radical density is present as compared to the hydrogen-argon treatment. The influence of the plasma treatment on frequently occurring iron corrosion products could be made apparent in surface layers. Investigations of surface regions of archaeological iron samples also showed that a reduction, for example of hematite to magnetite, did take place. Examination of the stratigraphical samples showed that the effect of hydrogen plasma in the deeper lying layers, namely the loosening between layers, is not related to a chemical reduction but to the high frequency field. On silver objects hydrogen plasma leads to the reduction of corrosion and therefore the removal of tarnish layers without any damage to the artefacts. For more details please see reference below. References
Schmidt-Ott, K. (2009): Erhaltung von Kulturgütern. Das Plasma in der Metallkonservierung – Möglichkeiten und Grenzen. Collectio archæologica, Band 7. Zürich: Chronos Verlag.

THE CHLORIDE LEFT BEHIND: (DIS)SOLVING AN ANALYTICAL PROBLEM BRITTA SCHMUTZLER1, GERHARD EGGERT1 State Academy of Art and Design, Am Weißenhof 1, D-70191 Stuttgart, Germany b.schmutzler@abk-stuttgart.de; gerhard.eggert@abk-stuttgart.de Introduction In the research project “Rettung vor dem Rost” systematic research was done to identify the most efficient desalination method for archaeological iron finds from the soil which performances well under the restrictions of mass conservation: saving time and money (funded by DBU, Deutsche Bundesstiftung Umwelt, Osnabrück/ Germany; see the contribution “Simplifying Sulphite Solutions – The DBU-Project `Rettung vor dem Rost´”). During experimental work it became clear that the analytical procedures for the analysis of desalination solutions as well as residual chloride content of desalinated objects are not standardised in any way. In addition, for the applying conservators of alkaline sulphite desalination method a simple test is needed for controlling the chloride content of desalination solutions. Qualitative respectively Semi-Quantitative Chloride Determination For quick and easy chloride analysis of desalination solutions a well-known qualitative chloride test is recommended: the silver nitrate test (Greiff and Bach 2000). But in case of sulphite containing solutions like alkaline sulphite it is important to work in strong acidic conditions, e.g. adjusted with nitric acid. If not, also white silver sulphite precipitates (in neutral and slightly acidic conditions) which is mistaken for silver chloride. For semiquantitative estimation, reference solutions with known chloride content can be used. Commercial quantitative tests are not recommended, since they are in most cases still complex in application, need special sample preparation and are in the end not precise enough for quantitative data (e.g. mercurimetric test basing on two colour reactions as used by Schmidt-Ott and Oswald 2006). Quantitative Chloride Determination In the research project, photometric analysis is used for quantitative chloride measurement of desalination solutions and desalinated objects as suggested by Wunderlich (Wunderlich 2000). The chemical reaction for chloride determination used is the quantitatively reaction of Hg(SCN)2 with chloride to HgCl2, and the freed thiocyanate ions (SCN-) react with Fe3+ to Fe(SCN)3 which is of measurably orange-red colour (Florence and Farrar 1971). In both cases, preparation of sample solution is necessary.
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Determination of chloride-content of desalination solutions For sample preparation, a solution containing 5 mol/l nitric acid and 10 % hydrogen peroxide (oxidation of sulphite) is added in ratio 1:1 to the sample (Beaudoin and Bertholon 1994), and allowed to stand at room temperature for 24 hours in closed bottles. The validity of measurement was checked with alkaline sulphite solutions containing a known amount of chloride, which were heated for 3 weeks at 55 °C and pre-treated as described. The error associated with this pre-treatment lies in a range up to 10 %, which is acceptable considering the many excessive interfering ions in the analytes. Validation of Digestion Strategy and Residual Chloride Analysis In conservation literature, the focus was on the analysis of desalination solutions so far, but only little attention was paid on the analysis of the residual chloride in desalinated objects. However, Ellis et al. report total chloride loss in the form of volatile hydrogen chloride, caused by excessive acid when solving akaganéite powder in sulphuric acid (H2SO4, 20 % w/w; Ellis et al. 1976). This problem was not considered in conservation science, but has direct impact on our research – what, if the sample preparation biases the desalination efficiency results by expelling chloride? Therefore, firstly the own analytical procedure was to be validated, and secondly, checking of published digestion strategies was necessary. For validation measurements, iron powder was digested in sulphuric acid (20 %) with added sodium chloride solution. After dissolution, Fe2+ ions were oxidized to Fe3+ ions by hydrogen peroxide (30 %), and excessive H2O2 was expelled by boiling for 30 minutes. Subsequently, the sample was prepared as given by the protocol for photometric analysis (Florence and Farrar 1971), and directly measured. Three validation measurements gave a mean of 1.10 mg/l chloride (standard deviation of ± 0.042) in contrast to the given reference value of 1.0 mg/l chloride. This difference of about 0.1 mg/l can be expressed as error of 10 %, which is again acceptable for the given reasons. The protocol of Drews et al. (2004) was reproduced with sulphuric acid to check potential chloride loss by digestion applying the mentioned standard, protocol, and analytical method. Measurements show that hot digestion for 48 hours without any covering as suggested by Drews et al. causes loss of chloride from the iron powder–sodium chloride mixture (Drews et al. 2004; for detailed problems concerning other digestion strategies and chloride analysis see Schmutzler and Eggert 2010). Residual Chloride Content Analysis For evaluation of the desalination experiments, the desalinated specimens (Roman nails) were individually cut into small pieces. This allows digestion of two representative, small batches of the objects for acceleration of the solubilization process, avoiding loss and saving sulphuric acid. The mean of chloride content is determined in ‰. In general, working with archaeological objects makes accurate analysis difficult and significant differences between desalination strategies are hard to work out. The data quality of all

experiments is expressed in standard deviation and variation coefficient, which expresses in turn the standard deviation as a percentage of the mean. All in all the variation coefficient of around 400 residual chloride measurements is in average around 16 %. Taking into consideration that small amounts of chloride ions among excessive interfering ions are to be measured, this is definitely a satisfying value. Conclusion This outline shows how important every step in analytical procedure is. It is also to be kept in mind that long hot and open digestion causes loss of chloride and, therefore, manipulates the desalination efficiency data. Acknowledgements We would like to thank Dr. J. Peters (H.C. Starck/ Goslar), Dr. J. Opitz (Institute of Organic Chemistry/ University of Stuttgart) and Dr. M. Völker (fem/ Schwäbisch Gmünd) for helpful discussions and analyses. We are grateful to Landesamt für Denkmalpflege Baden-Württemberg/ Esslingen and Deutsche Bundesstiftung Umwelt DBU/ Osnabrück for their support. References
Beaudoin, A., and Bertholon, R. (1994), `Le Dosage des ions chlorure dans le sulfite alcalin´, Les Cahiers Techniques de l´ARAAFU 1 : 39-48. Drews, M., de Viviés, P., González, N., and Mardikian, P. (2004), `A study of the analysis and removal of chloride in iron samples from the Hunley´, in Metal 2004, Proceedings of the Int. Conference on Metals Conservation, Canberra, Australia, 4-8 October 2004, Canberra: National Museum of Australia, 247-260. Ellis, J., Giovanoli, R., and Stumm, W. (1976), `Ion exchange properties of β-FeOOH´, Chimia 30(3): 194-197. Florence, T.M., and Farrar, Y. (1971), `Spectrophotometric determination of chloride at the parts-perbillion level by the mercury (II) thiocyanate method´, Analytica Chimica Acta, 54: 373-377. Greiff, S. and Bach, D. (2000), `Eisenkorrosion und Natriumsulfitentsalzung: Theorie und Praxis´, Arbeitsblätter für Restauratoren, Gruppe 1: 319-339. Schmidt-Ott, K., and Oswald, N. (2006), `Neues zur Eisenentsalzung mit alkalischem Sulfit´, Beiträge zur Erhaltung von Kunst- und Kulturgut 2: 126-134. Schmutzler, B., and Eggert, G. (2010), `Chloride calamities: assessment of residual chloride analysis and comparison of iron desalination methods´, manuscript submitted for the ICOM-CC Metal Conference 2010, Charleston, South Carolina Wunderlich, C., (2000)´Archäosideroprophylakt - Entsalzung von Eisenfunden mit Hydroxylamin´, Jahresschrift für mitteldeutsche Vorgeschichte 83: 305-316.

FORMATION AND TRANSFORMATION OF AKAGANEITE DAVID THICKETT1, MARIANNE ODLYHA2
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English Heritage, Collections Conservation Team, Rangers House, Chesterfield Walk, London, SE108QX, david.thickett@english-heritage.org.uk 2 Birkbeck College, London, m.odlhya@bbk.ac.uk Formation of Akaganeite The formation of akaganeite and its physical damage has been ascribed as the major mechanism for the deterioration of archaeological iron artefacts. Several RH thresholds were determined experimentally and presented at the first meeting of the Archaeological Iron Sub Working Group. Below 16% RH no akaganeite formation was observed. Below 30% the formation was very slow. Neither of these thresholds appeared to have a strong temperature dependence. At RHs above 55%, and decreasing with increasing temperature, iron dissolution becomes the major mechanism. These thresholds are critical to preventive conservation practice to stop the deterioration of archaeological iron in storage or limit its deterioration on display (where low RHs are extremely expensive to achieve). Watkinson showed that iron and iron (II) chloride mixtures with artificially produced akaganeite have a lower threshold of 11% (Watkinson 2002). This is extremely important for storage. The initial experiments reported at the last meeting had generated a series of akaganeites formed at different RHs; from 30 to 90% in 10% intervals. These were mixed with iron and iron (II) chloride powders to form 1:1:1 mixtures which were then exposed to RHs between 10 and 20% at 1% intervals. The powder mixtures from the lower RH experiments still contained some residual iron and iron (II) chloride. This was quantified by thermomagnetometry and the amounts modified accordingly (Thickett and Odlyha 2003). The RHs were generated above glycerol solutions. After twelve months exposure the powders were analysed with FTIR as KBr disks to quantify the amount of akaganeite (Thickett 2004). Whilst the threshold RH was lowered to 15% with the presence of the akaganeites formed at 80 and 90% RH, no effect was observed with the akaganeites formed at lower RHs. Watkinson’s work used akaganeite precipitated from acidified iron (III) chloride solution. His conclusions are valid for the system being studied, i.e. a ship where the akaganeite will have formed at ambient outdoor RHs which are often in excess of 80%. However most archaeological iron artefacts are stored in dry silica gel from excavation so are unlikely to have experienced RHs above 50% even with very dilatory reconditioning of the silica gel. Hence the 16% threshold (in the presence of copper ions) is appropriate for archaeological iron. Several volatile organic compounds are reported to accelerate the corrosion of iron or carbon steel. In a museum storage or display environment the carbonyl compounds; ethanoic and methanoic acid and methanal are those most commonly encountered (Rance 1956, Grzywacz

1994). Since ethanoic acid is the most damaging and most common, its effects on the akaganeite formation reaction were investigated. A range of ethanoic acid concentrations were used to mimic situations frequently encountered; zero 750 1500 3000 6000 good storage, Stewart boxes (not in wooden cupboards)* good quality showcase, wood products used for base-board and back-board only and Moistop wrapped or Selabond coated to reduce emissions showcases with some wood products with no emmision barriers or with Dacrylate 103 coatings showcases and cupboards made of wood or wood products poor quality cardboard boxes, paper envelopes,

* Larkin et al reported Stewart boxes failing an accelerated corrosion test with lead, the author has undertaken over twenty such tests on Stewart boxes purchased over the past fifteen years without one failing any accelerated corrosion test. Ethanoic acid atmospheres were generated above the appropriate ethanoic acid solutions (Merck Analar). These were added to saturated magnesium chloride, magnesium nitrate and sodium chloride solutions to give RHs of 33.1-33.6, 52-56 and 75.2-75.7%, following the method developed by Tetrault (Tetrault 1999). Brockerhof et al had reported significant non linearity in acetic acid concentrations generated above acetic acid and salt mixtures, in contradiction of Tetrault's findings. The ethanoic acid and salt where also prepared in 250ml jars and the airborne acid concentration determined for four consecutive 14 day periods with duplicate diffusion tubes (Gibson et al 1996). This confirmed that the concentrations were within the 7% instrumental error of the diffusion tube analyses for the two month period. No systematic decrease in ethanoic acid concentration was detected (t-test at 99% confidence interval) over the test period. The use of an impermeable barrier on the reaction vessel top negated the need to change the solutions monthly. The differences between Tetraut's and Brockerhoff's results are most likely due to different reaction vessels used, particularly in the permeabilities of the lid materials and sealing of the lids. The ethanoic acid solution concentration was checked by analysing the solution when the tests were complete with ion chromatography (Dionex DX200 with ICE column and 18mM borax eluent), confirming very little loss of ethanoic acid during the tests. The amount of akaganeite formed was expressed as a percentage of that formed with no ethanoic acid present. Results are shown below.

percentage of akaganeite formed compared to clean environment

350 300 250 200 150 100 0 1000 2000 3000 4000 5000 6000 7000 ethanoic acid concentration (µg/m3) 33% 54% 75% 75% total

All the tests, with the exception of the 75% RH tests at 3000 and 6000ug/m3, produced more akaganeite. Geothite was obvious in the infra-red spectrum at 3000ug/m3 and 75% and was the major product at 6000ug. Close examination of the spectrum also revealed some geothite at 1500 ug/m3. To take this into account, samples were taken from the 75-76% tests and analysed with TGA to quantify the amounts of akaganeite and geothite present. These results are shown as 75-76% total above. The formation of goethite at 75% RH and higher acid concentration is possibly due to the decreased pH during Fe(II)Cl oxidation (Misawa 1974). An alternative explanation could be initial formation of akaganeite, which is then dissolved by the lower pH solution and re-precipitates as geothite. Archaeological iron can be an extremely complex system with many ions and species present. The experiments have used iron and iron (II) chloride mixtures as model systems. To validate the results, a survey was undertaken of the 600 or so archaeological iron artefacts on display throughout English Heritage’s sites. English Heritage has over 50 sites displaying archaeological iron and the RH in the rooms is highly variable from site to site. Additionally the showcases used have been built over a ninety year period and are of highly variable quality. Some can keep RHs below 30%, whilst many can only achieve below 55% with silica gel and some have no silica gel facilities and experience RHs up to 80%. The survey was carried out using a criteria anchored methodology (Sully et al 1999). Results are shown below.

No ethanoic acid
100% 90% p r e ta eo o je ts ec n g f b c 80% 70% 60% 50% 40% 30% 20% 10% 0% 20-30 30-40 40-50 50-60 60-70 70-80 RH ra nge 97 heavy medium slight none 105 31 15 4 2 2 32 23 10 3 1 1 1 1 1 5 1

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Ethanoic acid
100% 90% p r e ta eo o je ts ec n g f b c 80% 70% 60% 50% 40% 30% 20% 10% 0% 20-30 30-40 40-50 50-60 60-70 70-80 RH ra nge heavy medium slight none 26 31 43 24 4 10 25 12 9 10 31 22 7 4 3 14 7 3

As can be seen, the 30% and 55% thresholds appear to hold with real objects. Conversion of Akaganeite The conversion of akaganeite to other iron minerals will almost certainly release chloride back into the object as no other iron mineral contains the same concentration of chloride. Examination of akaganeite crystals formed, in two situations, revealed very thin yellow layers on the surface of the crystals. These layers were identified with Germanium ATR FTIR as Geothite and the lower chloride concentration of the layer compared to the akaganeite confirmed with SEM-EDX. The conversions had occurred at RHs between 21 and 54% (poor quality showcases with silica gel changed every six months) and in storage in an unconditioned store experiencing RHs between 43 and 61% in the cardboard storage boxes. Both situations had significant concentrations of ethanoic acid. In the cases this originated from their particleboard construction and in the store from the cardboard boxes. Stahl has written that there is no release of chloride from akagaleite below 200°C (Stahl 2003). Such isothermal heating experiments are known to underestimate the rates of transformation for solid state reactions. Misura et al have shown that in aqueous media akaganeite relatively rapidly transforms into goethite and it is possible that the high hygroscopicity of the adsorbed chloride on the akaganeite surfaces could provide enough water for this reaction to occur. Stahl’s work was carried out under nitrogen with a nominal RH of 0%.

A method has recently been developed to model the kinetics of solid state reactions and predict the reaction rates under different ambient thermal profiles. Thermogravimetric analyses were undertaken of both synthetic akaganeite and a relatively pure akaganeite sample removed from a anglo-saxon coffin clamp. The synthetic sample was prepared from arial oxidation of ferrous chloride (Aldrych Analar 99.98%) at 60ºC for sixteen hours (Cornell 2003). The samples were coarsely ground between glass slides, and analysed with a Perkin Elmer TGA7 under 40ml/min of nitrogen at 1,2,5,10, 15 and 20°C/min heating rate. The reaction rate was fitted allowing both the pre-exponetial factor and activation energy to vary. The modelling indicated that slow conversion to hematite was likely over a number of years. Samples of Akaganeite taken from objects over the past twenty five years and analysed mainly with XRD were reanalysed with Raman. Although XRD is relatively insensitve to Hematite in Akaganeite each sample was examined under microscopy and the appearance recorded. Visual examination revealed red spots on many of the earlier samples and Raman verified that these were Hematite. References
Brokerhof, A.W., M. van Bommel, (1996) Deterioration of Calcareous Materials by Acetic Acid Vapour: A Model Study." ICOM Committee for Conservation 2, 769-775. Cornell, R.M., U. Schwertmann, (2003) The Iron Oxides 2nd Edition, Wiley VCH, New York. Grzywacz, C.M., N.H. Tennent, (1994) Pollution monitoring in storage and display cabinets, Preventive Conservation Practice, Theory and Research, A. Roy, P.Smith eds, IIC, 164-170 Larkin, N., N. Blades, (2000) Investigation of volatile organic compounds associated with polyethylene and polypropylene containers used for conservation storage. The Conservator 24, 42-51. Misawa, T., K. Hashimoto, (1974) The mechanism of formation of iron oxide and oxyhydroxides in aqueous solutions at room temperature, Corrosion Science 14, 131-149. Rance, V., H.G.Cole, (1958) Corrosion of metals from organic acids: a survey, HMSO, London, 17. Roduit, B. (2000) Computational aspects of kinetic analysis: Part E: The ICTAC Kinetics Project – numerical techniques and kinetics of solid state processes, Thermochimica Acta 355(1-2), 171-180. Roduit, B. (2002) Prediction of the progress of solid-state reactions under different temperature modes, Thermochimica Acta 388(1-2), 377-387. Tetreault, J., J. Sirois, (1998) Studies of lead corrosion in acetic acid environments, Studies in Conservation. 43, 17-32. Thickett, D. (2005) The use of Infra-red and Raman Spectroscopies for Iron Corrosion Products, Postprints of Sixth Infra-Red Users Group, Florence, Il PratoElsevier, Padua, 86-93. Thickett, D., M. Odlyha, (2005) Application of thermomagnetry to corrosion studies of archaeological iron, Journal of Thermal Analysis and Calorimetry, 80 (3), 567-571. Watkinson, D., M. Lewis, (2004) SS Great Britain iron hull: modelling corrosion to define storage relative humidity. Proceedings of the international conference on metals conservation, Metals 04, 88102

‘UNUSUAL’ CORROSION PRODUCTS OF IRON QUANYU WANG1
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Department of Conservation and Scientific Research, The British Museum, Great Russell Street, London WC1B 3DG, UK qwang@thebritishmuseum.ac.uk

Introduction Post excavation corrosion of archaeological iron has been widely studied and most of the research has been focused on akaganeite and iron oxyhydroxides. A wide range of the corrosion products of iron has recently been summarised by Scott and Eggert (2009). It is the author’s intention here to report on some of the corrosion products which had previously not been widely reported. The formation of these “unusual” corrosion products is discussed and questions are addressed. Jarosite A green/yellowish powdery corrosion product was observed on some archaeological iron objects in storage at the museum as well as on freshly excavated iron objects. The Raman spectrum of the corrosion products (Figure 1) indicated that it is probably a member of the jarosite group, i.e. MFe3(SO4)2(OH)6 compounds, where M = K, NH4, Na, etc. It was identified as ammoniojarosite, NH4Fe3(SO4)2(OH)6 by a combination of X-ray fluorescence spectroscopy (XRF) and X-ray diffraction (XRD).

Fig. 1: Raman spectrum of the green/yellowish powdery corrosion product of iron identified as ammoniojarosite

A light yellow powdery material was found on iron knives from the Sutton Hoo 2000 excavation. It was identified as potassium jarosite, KFe3(SO4)2(OH)6, by elemental analysis using scanning electron microscopy equipped with energy dispersive X-ray spectrometer

(SEM-EDX) and by XRD. It needs to be noted that the Raman spectra of different materials from the jarosite group have little difference to distinguish between them and the XRD data for these two members of the group are also very similar, therefore, elemental analysis is important in the identification of these materials. How did these sulphates form, from burial or post excavation? These sulphates could have been formed during burial, because they were found on freshly excavated iron. This does not exclude the possibility of post-excavation corrosion, because the sulphates were sometimes present underneath flakes and in cracks. Sulphur arises from decaying organic matter in burials, from industrial pollutants or from display materials, and the oxidation of sulphides can take place in air to form sulphates. Ammonia and potassium can come from burials and/or agricultural fertilisers. These members of the jarosite group are considered to be stable because of their widespread occurrence in nature (Smith and Lampert 1973). Iron oxyhydroxides resulted from desalination treatment Desalination treatment of archaeological iron for the removal of chloride is one of the approaches taken in the preservation of the objects. A bright yellow corrosion product, which often has a ‘cotton ball’ morphology, was observed on some of the iron objects treated in desalination solutions of either sodium hydroxide or alkaline sulphite (Wang 2007a). It was identified as goethite, α-FeOOH, by Raman spectroscopy. A yellow/brown corrosion product was also found to have formed on archaeological iron nails during rinsing in deionised water following desalination in alkaline sulphite solutions. This corrosion product, which has a loose powdery structure, was identified as lepidocrocite, γ-FeOOH, by Raman spectroscopy. How were these corrosion products formed? The formation of goethite and lepidocrocite, instead of akaganéite, could be the result of atmospheric oxidation promoted by residual OHfrom incomplete washing after desalination treatment and may be due to a low chloride ion concentration. Research carried out by Refait and Genin (1997) suggests that only akaganéite can form at high Cl- ion levels ([Cl-]/[OH-] ≥ 8) and only goethite forms at low Cl- ion levels ([Cl-]/[OH-] ≤ 6). Can these corrosion products cause any further deterioration of the objects? Goethite and lepidocrocite are chemically stable as corrosion products. However, they have been found to grow perpendicular to the surface on some objects which can cause cracking and flaking on the surface. Further studies are needed to investigate in what conditions or at which stages these materials form and how to avoid their formation in the desalination process. Elongated akaganeite It has been found from experiments with iron coupons that the corrosion morphology seems to be affected by relative humidity (RH) levels. Elongated akaganeite was likely to have formed at RH levels between 50 and 60% as the result of atmospheric oxidation, and weeping was more likely to occurr at higher RH levels (Wang 2007b). It is the elongated akaganéite

cryastals that often caused the flaking of archeological iron (Fig. 2 & 3). The RH of 54% was achieved by a saturated Mg(NO3)2.6H2O solution. Comparison of iron coupons exposed, respectively, to the nitrate and glycerol solution which was used to achieve the same RH level showed that the nitrate seemed to accelerate the formation and growth of the elongated akaganeite crystals. This raises the following questions: are other pollutants such as SO2, NO2 harmful to iron objects? Is the formation of elongated cerytalline akaganeite, which is often observed on archaeological iron, promoted by the presence of nitrate in the enviroment? The effect of RH levels and pollutants including nitrogen oxides and nitrate on the corrosion morphology needs further research.

Fig. 2 Elongated akaganeite crystals formed on an iron coupon at 54%RH

Fig. 3 Flaking of an Anglo-Saxon iron axe caused by the formation of elongated akaganeite

References
Refait, P., and Genin, J.-M.R. (1997) ‘The mechanism of oxidation of ferrous hydroxychloride βFe2(OH)3Cl in aqueous solution: The formation of akaganéite vs. goethite’, Corrosion Science 39 (3): 539–553. Scott, D.A., and Eggert, G. (2009) Iron and Steel in Art: Corrosion, Colorants, Conservation. London: Archetype Publications. Smith, W.L., and Lampert, J.E. (1973) ‘Crystal data for ammoniojarosite, NH4Fe3(SO4)2(OH)6’, Journal of Applied Crystallography 6: 490–491. Wang, Q. (2007a) ‘An investigation of deterioration of archaeological iron’, Studies in Conservation 52 (2): 125-134. Wang, Q. (2007b) ‘Effects of relative humidity on the corrosion of iron: an experimental view’, British Museum Technical Research Bulletin 1: 65-73.

METASTABLE IRON SULPHIDES AS CORROSION PRODUCTS OF ARCHAEOLOGICAL IRON OBJECTS CELINE REMAZEILLES1, DELPHINE NEFF2, ELODIE GUILMINOT3, SOLENN REGUER4, PHILIPPE DILLMANN2, PHILIPPE REFAIT1. Laboratoire d’Etude des Matériaux en Milieux Agressifs, Université de La Rochelle, Avenue Michel Crépeau, F-17042 La Rochelle cedex 01, France. celine.remazeilles@univ-lr.fr, philippe.refait@univ-lr.fr 2 LAPA/SIS2M UMR3299 CEA/CNRS et IRAMAT UMR5060 CNRS, CEA Saclay, F91191 Gif sur Yvette cedex, France delphine.neff@cea.fr, philippe.dillmann@cea.fr 3 EPCC Arc’Antique, 26 Rue de la Haute Forêt, F-44300 NANTES, France elodie.guilminot@arcantique.org 4 Synchrotron SOLEIL, L'Orme des Merisiers, BP 48, F-91192 Gif-sur-Yvette cedex, France solenn.reguer@synchrotron-soleil.fr Introduction Archaeological iron objects buried in anoxic conditions can be exposed to microbiologically influenced corrosion (MIC). In some cases, this form of corrosion can be extremely severe. The most common process is associated with the development of sulphate reducing bacteria (SRB) colonies on the metal surface, and requires anoxic conditions. The metabolic activity of such micro-organisms involves the reduction of sulphates, naturally present in the environment, into sulphides. Sulphides react with Fe2+ ions, which leads to the iron(II) sulphide mackinawite (FeS) in the rust layer. Such corrosion processes are often localised and lead to the formation of broad pits in the metal. However, the works dealing with MIC were mainly focused on modern steels. In the case of archaeological ferrous materials, the influence of microorganisms can be suspected similarly when iron sulphides are detected in the rust layer. Sometimes restorers testify of a specific odour of “sulphur”, namely hydrogen sulphide (H2S), while MIC was never mentioned as a possible danger for conservation of archaeological objects. This report is in contradiction with current studies on MIC, assuming a rapid decay of iron objects when microorganisms influence the corrosion mechanisms. As exposed in this presentation, iron(II) sulphides like mackinawite and greigite (Fe3S4) and even SRB have been detected in rust layers of archaeological iron artefacts although these ones presented no alteration patterns (broad pits) characteristic of MIC. Iron(II) sulphides are unstable once exposed to atmosphere. The consequences of their transformation after excavation have never been clearly demonstrated. So this presentation is focused on the identification, localisation and evolution of iron(II) sulphides in rust layers of archaeological iron artefacts. After a short state of art, analysis performed on artefacts
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extracted from different anoxic media (bottom of the sea and soil) is presented. For some of them, namely Roman ingots, dechlorination treatments have been applied (cathodic polarisation and immersion in a NaOH solution) after which remaining iron/sulphur containing compounds were detected. Evolution of iron sulphides in excavated artefacts Previous studies devoted to the analysis of iron sulphides in archaeological iron artefacts are scarce. Among all naturally occurring iron/sulphur containing compounds (table 1), only mackinawite, greigite and framboidal pyrite (FeS2) were mentioned. For instance, these were identified in rust layers of artefacts extracted from a waterlogged soil (Fiskerton, UK) (Fell/Ward 1998; Fell/Williams 2004). General oxidation processes of iron sulphides are widely studied and several mechanisms deduced from works realised on laboratory systems and synthetic products are proposed in literature. Parameters like the oxic/anoxic nature of the environment, sulphur supply via hydrogen sulphide production, temperature, humidity, pH, etc. seem to determine one pathway or another, leading from mackinawite either to the formation of pyrite or to the decomposition into sulphur and iron(III) oxyhydroxides. A recent work focused on the analysis of synthetic mackinawite by Raman spectroscopy demonstrated that this phase can present three physico-chemical states (nanocrystalline, well crystallised and Fe(III)containing mackinawite), each of them being differentiated by a characteristic spectrum (Bourdoiseau 2008). Table 1 : Iron/sulphur containing compounds
Mineral Mackinawite Troilite Pyrrhotite Greigite Smythite Pyrite Marcasite Sulphur Formula FeS FeS Fe1-xS Fe3S4 Fe9S11 FeS2 FeS2 -S8 Oxidation state Fe(+II), S(-II) Fe(+II), S(-II) Fe(+II), S(-II) Fe(+II,+III), S(-II) Fe(+II,+III), S(-II) (?) Fe(+II), S2(-II) Fe(+II), S2(-II) S(0)

In our study, corrosion layers of 16th century old nails coming from a terrestrial site (Glinet, France) and of Roman ingots excavated from a wreck off Les Saintes Marie de la Mer (France) were analysed by combining several methods: scanning electron microscopy (SEM) coupled with X-ray microanalysis and Raman micro-spectroscopy. In each sample, mackinawite was detected, and its three physico-chemical forms could be observed. The corrosion layers were mainly composed of iron(II) compounds such as siderite (FeCO3), chukanovite (Fe2(OH)2CO3) and -Fe2(OH)3Cl, confirming the anoxic conditions of both burial environments. Such conditions are favourable for SRB development. As far as the

microbiological activity of the soil of Glinet is concerned, SRB were actually detected in the rust layers of nails. However as for the nails or the ingots, the sulphur rich zones were located in the external part of the rust layers, meaning that the microbiologically influenced phenomenon do not imply the metallic substrate but rather the corrosion products. This result is not consistent with the classic MIC mechanisms currently admitted. In consequence it is not obvious that the mechanisms proposed for explaining MIC processes of modern materials can be transposed to the archaeological samples that we studied. This point will be discussed in the presentation. Greigite was also identified but its presence is rather explained by the oxidation of initially present mackinawite during -Raman experiments, which were performed without protection against oxygen. In the frame of the French research program ODeFA, which was mainly dedicated to the understanding of dechlorination mechanisms of corrosion layers during treatments, some Roman ingots were treated. Cathodic polarisation in a KOH bath and immersion in a 2% NaOH bath were applied. The analysis of ingots at the end of treatments revealed the presence of remaining iron/sulphur containing compounds. Orthorhombic elemental sulphur ( -S8) was identified in large amount in the rust layer of the ingot treated by cathodic polarisation, while Fe(III)-containing mackinawite was found in the rust layer of the ingot treated in the NaOH solution. In the first case, the presence of elemental sulphur can be explained as the result of the oxidation of mackinawite that led simultaneously to goethite. In the second case, the presence of Fe(III)-containing mackinawite in the middle of a layer mainly composed of goethite is more difficult to explain. Consequences for conservation In most cases the superficial concretion including exogenous compounds is removed during the treatments. Iron sulphides being located rather in the external part of the rust layer, a large amount is certainly removed during this stage. However, the example of the ingot treated in a NaOH solution has shown that when they are located deeper inside the rust layer, they remain. In this case, they can transform at any moment. In wet organic archaeological materials, consequences of iron sulphides oxidation are very dangerous (embrittlement and cracking). For ferrous materials, the impact for conservation is not clearly evaluated yet. References
Bourdoiseau, J.A. et al. (2008), Corrosion Science, 50, 3247-3255. Fell, V. and M. Ward (1998) Proceedings of the Interim Meeting of the ICOM-CC Metal WG, Draguignan, 111-115. Fell, V. and J. Williams (2004) Proceedings of the Interim Meeting of the ICOM-CC Metal WG, Canberra, 17-24.

Gerhard Eggert and Britta Schmutzler (Eds.)

Archaeological Iron Conservation Colloquium 2010

Extended Abstracts

Archaeological Iron Conservation Colloquium 2010

State Academy of Art and Design Stuttgart 24th to 26th June 2010

Extended Abstracts

Session 2: Iron Conservation Projects around the World

ABOUT CORROSION AND CONSERVATION PROBLEMS OF IRON ARTEFACTS COMING FROM ORADEA FORTRESS OLIMPIA MURESAN1 “Tara Crisurilor” Museum, Dacia Boulevard no1-3, Oradea, Romania olimpia_muresan2010@yahoo.com Introduction The today Oradea fortress was built during the XVI-XVII centuries. Ruins of buildings (the XIII-XVII centuries), artefacts and fragments (discovered during archaeological diggings 1991-2001, 2005-2007, 2009) are a great challenge for studyand conservation nowadays (Rusu et al. 2002; Muresan 2009). A special attention will be paid to the corroded iron artefacts. General considerations about archaeological iron corrosion “Rust” is associated with iron corrosion which in the language of chemistry is called oxidation. During the burial period the iron undergoes ionization as a consequence of the electrochemical phenomena: the anodic process consisting of iron oxidation is balanced by the depolarization process at the cathodic areas. The depolarization depends on the parameters of the environment. It is generally known (Selwyn 2004) that the main phases of rust are oxides and oxyhydroxides such as: maghemite (γ-Fe2O3) magnetite (Fe3O4), goethite, α-FeOOH), and lepidocrocite γ-FeO(OH). In addition to the above mentioned corrosion products, other specific ones may be identified due to the particular soil/environmental composition/parameters (soil pH, soluble salts, aeration, soil constituents, and synergic effects). Iron artefacts from Oradea fortress The soil of the fortress may be considered near-anoxic and carbonated, because of a stone pavement from the 18th century that was found at a deeper depth than 20 cm and the other ruins of ancient buildings present there, too. Therefore, carbonates (Saheb 2007) were expected to be present. But things are not so simple: by means of ATR-IR [analysis realized at National Researching Institute for Conservation and Restoration, Bucharest with Bruker Experimental IR-ATR (Diamond, Helios XPM, 5000-400cm-1, 4cm-1 resolution)], organic components (aromatic structures and probably oil), kaolinite, quartz, carbonates, and hydrated water were detected too. The heterogeneity of the soil caused a lot of problems in attributing the peaks and discriminating the components (for the iron corrosion components, too). Now, speaking about the iron artefacts coming from Oradea fortress, each digging brought up hundreds of objects or fragments, with different degrees of mineralization and deformation,
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even without possibility of being identified. Their conservation requires solving a lot of problems. Great battle, few weapons! A strategy may be a useful tool. It is important to acknowledge: which are the problems to be solved; which are the ideal requirements to conserve the discovered artefacts and the realistic ways/possibilities to do that. The problems to be resolved are the following: a lot of metallic artefacts were discovered during each excavation; the iron ones were corroded and mineralized (most of the artefacts looked fragile); the artefacts must be stabilized and conserved; no supporting expenses for the research of the artefacts. To divide the iron artefacts, from the beginnings (by examination tools), in categories based on their emergency degree and degrees of mineralization seems time gaining. Some of badly corroded iron artefacts from Oradea fortress didn’t lost the original shape. It is the case of a fragment of medieval steel armour that was cremated. Details of the morphology of the corrosion products were observed by optical microscope (magnification 50x, 100x). Spectral analysis was performed by ATR-IR on iron compound. Standard spectra were used. Goethite, lepidocrocite, iron oxide, calcite, were detected by both methods. But the research must to be continued (complementary and non-destructive tools are necessary (Neff et al. 2004). Height surface sensitive techniques as IRRAS (infrared reflection absorption spectroscopy, QCM (quartz crystal microbalance) and TM-AFM (tapping-mode atomic force microscopy) were used (Kleber et al. 2007) for studying initial atmospheric corrosion of iron, copper and silver. Now, topography data are linked to the chemical information on the same sample area. The Interdisciplinary and Experimental Research Institute from Cluj-Napoca is equipped with a WITec instrument, an Alpha 300A with Confocal Raman Alpha 300R, that offers the possibility to acquire non-destructive chemical information with a resolution down to the optical diffraction limits (200nm). All this sounds great! It makes the tool an ideal one! But there is a trap here! The surface of the artefact is a rough one and this equipment needs a smooth surface at a nanoscale level. For the moment, the tests made on an iron artefact sample, archaeological glass, polished bone have no significance. Then it is necessary to bring the sample parameters compatible to the equipment! Final considerations The conservation of great quantities of excavated iron artefacts needs particular management strategy. The examination methods are used on every artefact. Complex analysis is done to representative or particular artefacts. Samples of soil, corrosion products, and fragments of artefacts may be collected for further analysis. When new scientific tools are to be tested for studying the artefacts a first stage must be a detailed preliminary analysis. The analysis techniques at nanoscale (molecular!) level may be used for a better conservation of artefacts. To “see” a molecular structure is a scientific success or an intrusion!?!

Acknowledgments The author offers her thanks to the contributions to this paper by Balta Zizi (IR-ATR spectra) and Dr. Astilean Simion (AFM preliminary test). References
Derrick, M.R., Stulik, D., Landuy, J.M., (1999) Infrared Spectroscopy in Conservation Science, Getty Conservation Institute. Kleber, C., Hilfrich, W., Schreiner, M., (2007) “Surface sensitive analytical methods (TM-AFM, IRRAS, QCM) for the in-situ investigation of the metal-atmosphere interface during the early stage of atmospheric corrosion” in Degrigny, Ch., van Langh, R., Joosten, I., Ankersmit, B., Eds. Metal 07:Prerint of the Interm meeting of the ICOM-CC Metal WG Amsterdam, 17-12 sept,.Amsterdam, (2), 42-46. Muresan O., (2009) CETATEA ORADEA REDIVIVUS (I).Artefacte metalice intre descoperire si valorificare, Editura Arca. Neff.D., Reguer, S., Bellot-Gurlet,L., Dillmann,Ph.,Bertholon, R., (2004) Structural characterization of corrosion products on archaeological iron. An integrated analytical approach to establish corrosion forms, in Journal of Raman Spectroscopy, 35, 739-745. Rusu, A.A., and Co., (2002) Cetatea Oradea. Monografie Arheologica (Zona Palatului Episcopal), Editura Muzeul Tarii Crisurilor Oradea. Saheb, M., Neff, D., Dillmann, Ph., Matthiesen, H., (2007) “Long term corrosion behaviour of low car, bon steel in anoxic soils”, in Degrigny, Ch., van Langh, R., Joosten, I., Ankersmit, B., (eds) Metal 07 Preprint of te Interm meeting of the ICOM-CC Metal WG Amsterdam,17-21 sept, Amsterdam, (2), 69-75. Selwyn, L., (2004) “Overview of archaeological iron: the corrosion problem, key factors affecting treatment, and gaps in current knowledge” in Ashton, J. and Hallam (eds) Metal 2004 : Proceedings of interim meeting of the ICOM-CC Metal WG, National Museum of Australia Canberra, 294-306.

THE „CUCAGNA CONSERVATION PROJECT“ - CONSERVATION OF ARCHAEOLOGICAL FINDS AND CONSERVATION RESEARCH IN FRIAUL TOBIAS FRIEDRICH1
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Eythstraße 63, 51103 Köln (Cologne), Germany, tobias.friedrich@mfak.de

Introduction Subject of the archaeological research project in which my conservation project takes place forms/constitutes the systematical exploration of the remains of the medieval castle Cucagna in North-Italy. Since 2001, every summer for a period of four weeks excavations are taking place at Cucagna. The excavation licence is held by Prof. Dr. Sebatian Brather of the Albert-Ludwigs-University Freiburg while Holger Grönwald M.A. leads the excavation. The excavations accompany the reconstruction and restauration of the architectural remains of the castle and are organised by the Istituto per la Ricostruzione del Castello di Chucco-Zucco (IRCCZ) and conducted during an international seminary (Seminario Estivo Internationale di Architettura Medioevale). The seminary is led by Dott. Arch. Roberto Raccanello and Dott. Arch. Katharina von Stietencron. Initiated in 2007 and carried out since 2008, the excavations and reconstruction are supplemented by the section „conservation of finds“. This has only been possible by permission and support of the Soprintendenza Archeologica e per i beni Ambientali, Architettonici, Artistici e Storici del Friuli Venezia-Giulia. First and foremost the scope is to conserve the finds. However given the limited period of time during the annual excavation, the proceeding is forced to be phased. Thus, the primary aims of the project are first, to determine the status quo of conservation of all finds which have been excavated since 2001; second, to provide fast intervention of restoration for important and particulary endangered artefacts and third, to create an infrastructure for a longterm-treatment for conservation, storage and future display. Considering an amount of 1576 finds out of 240 associations and 3400 single finds out of 343 associations only in 2008 and 2009, the task seems to be enormous, even if only about 5-7% of the listed finds belong to the group of finds with indication of urgent intervention. Moreover, there is the point of educating students of conservation sciences and restoration as supplement to the academical curriculum. In order to contribute to the already existing academical discourse and future research into archaeometric analysis of iron and glass finds, this conservation research project will additionally focus on understanding the complex processes of corrosion of these materials. The analysis are beeing held comparative, since iron and glass are in need of very different

conditions of their ideal in-situ conservation. Ideally, advantage can be taken of the possibility of taking soil samples of the surrounding earth of particular finds during excavations. Building history of the castle Cucagna The archaeological field research on the area of Cucagna is an example for the historical research on the evolution of the settlement and ruling system in medieval Friuli, which was influenced by the interplay of the Holy Roman Empire and central Italy. While in the 10th century locally interwoven structures of villages with manors and fortifications dominated, self-sustaining palaces gained importance in the following century. Therefore, Cucagna is an example since it was founded in 1027 by the Swabian house of Auersberg, which has been proved by historical documents and archaeological evidence. Cucagna mainly served to defend the march Verona/Friuli for the German kings and emperors of the Salier and Staufer, namely Konrad II., Henry III. and Friedrich II. Together with several other castles, it also served for controlling the trading routes out of Friuli towards the east. During the 13th century the subsidiary castle Zucco was added to the fortification system of Cucagna. Other buildings, belonging to the defence and supply system of Cucagna, demonstrate its dominant local patronate. These buildings are the broad outer bailey, the fort of Rodingerio, situated on a higher leveled ridge, the motte at Borgo Scubla, a tower at Stremiz di Faedis and some mills in the valley of the nearby river Grivò. The oldest part of Cucagna is the donjon with a height of 22 m and its enclosing wall. In the following century the castle was extended by at least two phases of construction. These phases include two palaces (Palazzo 2a, 2b), a chapel and a cistern inside the inner walls, a defence-like tower palace outside the walls (Palazzo 3) and another palace (Palazzo 4) as well as a peel inside the outer bailey. In the middle of the 14th century Cucagna reached its largest circumference, taking effect of a fortified locality. After the war between the Savorgnan and the Republic of Venice and the “liberation” or occupation of Friuli by Venice in 1420, the castle lost its importance. Nevertheless the extension of the castle continued, i.e. by the demolition of the already destroyed outer bailey including Palazzo 4 and the construction of a wall between Cucagna and Zucco. Following its final destruction during the war between Venice and Austria, the castle was abandoned in 1522. Archaeometric analysis Due to the special crest site of the castle there are very different types of soil which not only were formed as a result of erosion, but also by the influence of the castles population with all its traces including several destructions. Amongst the listed buildings, Palazzo 4 is of particular interest for the planned analysis because the main part of the soil samples are taken from there. As mentioned before, the outer

bailey was deconstructed in the late 14th century when the castle was still in vital use. The area was then only partly site of later utilization. Thus, the state of soil mostly remained untouched from further human interaction already before the abandonment of the castle in the early stages of the 16th century. Consequently, the preconditions for such a proposition are pretty ideal. For an adequate outcome of information it is planned to conduct non destructive measurings of the find’s alloy or matrix and the associated corrosion products as well as the surrounding soil. For their effect to the corrosion of both materials, the chemical compostion of the soil and the local climate are considered to be the parameters with most influence. It will be elaborated to what extend characteristic compositions of the find’s materials effect the corrosion process. In order to comprehend the mutual reaction between the material of the artefacts and the surrounding soil, the results of the measurings of the elementary composition of the selected finds, their corrosion products and the corresponding soil sample will be compared to each other. Furthermore, a climate profile will be compiled, showing the development of the special regional climate at the south-eastern mountainside of the Julian Alpes during the past 600 years. It could provide a basis for estimating the potential of conservation of the soil in comparison to the possibilities of long term storage under realistic atmospheric conditions. In fact the theoretical conditions at open air are far better than below the surface, because corrosion processes mainly base on relative humidity and pH value as well as the rate of ventilation. Nevertheless, the soil climate could be characterized by major constancy than any of the atmospheric conditions mentioned above. The particular horizontal stratigraphy of the phases of constrcution limits the datings of finds available of analysis: the sampling can only be taken at closed assiciations, i.e. all finds combined with the early phases of constrcution from 11th to 13th century, which already have been carried out in the years before 2008, can’t be taken into account. During last year’s excavations at the area of the outer bailey, only finds from the 14th century were recovered. Circumstances of excavation allowed the taking of 56 soil samples from which 13 can be linked with glass finds and 38 with iron finds. Depending on the respective feature, every sample is linked with one or more disposable find. In order to reach significant results in regard to the scope of research, every disposable find has to be measured twice to characterize its alloy/matrix and the corrosion product. For the characterizition of the chemical composition of glass and metal alloys and their corrosion products, EDX (energy dispersive X-ray spectroscopy) and NAA (neutron activation analysis) respectively, are considered to be most suitable. Alternatively XRF (X-ray fluorescence spectroscopy) could be used for analysis of the iron alloy which admittedly is a destructive method, since the corroded surface has to be partly grinded down before measuring.

Corrosion products would be measured additionally with XRD to characterize the relevant mineral phases. To complete the analysis of the finds, they have to be defined according to their phenomenology such as colour, transparency, homogenity of the matrix, number of inclusions and bubbles as well as the state of conservation. The analysis of the soil samples is more complex. It should take into account organo-chemical and petrographical aspects. Other parameters like density and content of oxygen would be definable only in-situ. After sampling these data cannot be acquired anymore. Because of the expected costs of such an attempt, these parameters have to be disregarded. Furthermore a selection of samples has to be considered, which however cannot be decided before the end of the estimated end of the sampling phase of the project in 2011. In order to gain preliminary expertise of the usability of the measuring method and the actual significance of the results, several test cycles of analysis should be run.

IRON FROM LONDON’S WATERLOGGED SITES: ASSESSING THE OUTCOMES OF TREATMENT AND PASSIVE STORAGE ROSE JOHNSON and HELEN GANIARIS1, LIZ BARHAM and LIZ GOODMAN2
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Museum of London, London Wall, London EC2Y 5HN, UK, rjohnson@museumoflondon.org.uk, hganiaris@museumoflondon.org.uk 2 Museum of London Archaeology, London Wall, London EC2Y 5HN, UK, ebarham@museumoflondon.org.uk, lgoodman@museumoflondon.org.uk In the 1980s, a number of conservation treatments were used on ‘waterfront’ iron at the Museum of London and elsewhere. Surveys of condition suggested that the iron objects that had been treated remained in good condition compared to objects that had not been treated. However, since 1990, active conservation treatments for iron have been largely discontinued in the UK. At the Museum of London this is largely due to changes to funding and project priorities, a minimally interventive approach to treatment and environmental issues regarding use and disposal of treatment solutions. However, the effect on ironwork of this approach has not been studied. The original aim of this work was to establish whether untreated iron from waterlogged contexts from the 1980s and 1990s in good desiccated storage had deteriorated since excavation compared to treated iron. By assessing several different sites using a standard statistical method, it is hoped that some conclusions can be made. However as this work progresses, the limitations of assessments of working archives have become apparent. This paper will also discuss these limitations. The material and assessment method The quality of iron objects from London’s excavations with waterlogged conditions can be exceptional. Corrosion layers tend to be thin, conforming to the surface, and features such as plating, pattern welding, maker’s marks, copper alloy, silver and tin inlays survive well. In contrast, iron from aerobic contexts normally has voluminous corrosion that obscures and sometimes destroys surfaces and features.

Fig. 1 Saxon blade with brass and copper alloy inlay, typical of the excellent condition of some iron from London ‘waterfront’ sites

The assessment currently has two parts: • • A reassessment of the condition of a group of ‘waterfront’ iron objects treated in the 1980s and assessed at regular intervals until 2000. Examination of ‘waterfront’ iron objects from sites that have had no active treatment, relying on passive storage in boxes with silica gel.

Assessments will use the Criterion Anchored Rating Scale (CARS) method to create statistically valid data. CARS was applied by Suenson-Taylor and Sully (1996) to archaeological leather and then adapted by Heywood in 2000 for the assessment of iron. CARS is based on the idea of interval data, that is measurement on a scale of equal intervals, eg length or weight, rather than ordinal data, which is a physical measurement that can be put into ranked order or counted. Work in progress: assessment of untreated iron At the time of writing of this abstract, the assessment of an untreated group from a 1990s excavation has been completed using CARS. This group of iron was chosen as it was thought to have received consistent desiccated storage in good archival packaging throughout its excavated life, with the intention of comparing it with treated material. The 741 objects from this one site ranged from pins to knives to styli and a large number of unidentified fragments or parts of objects. Nearly all the objects are packed in perforated clear polythene bags with Tyvek labels. The bags are stacked upright in a polythene box with a sealable lid and a bag of silica gel. The boxes are stored in a dehumidified store designated for metals. It was found that 684 objects, that is, 92% of those examined had the highest possible CARS score. CARS does provide for some corrosion in its top score (up to 15% of the object affected by corrosion is acceptable within this score). As a result, it was decided additionally to get an indication of the proportion of these that have no corrosion at all. 134 objects were surveyed; 109 out of the 134 (over 81%) still had no active corrosion. This demonstrates that most of the objects are in very good condition. This has been achieved, despite long periods when it was found that the desiccated environment had not been maintained over the 15 years since these objects were excavated. It had been assumed that we would be assessing a group of iron that had been in well-maintained silica gel storage for a valid comparison to treated material. However, when this material was retrieved it was found that a low RH (below 12%) could only be assumed for approximately half the time it had been in storage. This was due to periods of examination by finds specialists, illustrators and photographers, and a lack of staff resources to routinely maintain the gel. For the rest of the time it will have been stored in an environment of 30-40% RH and within that, short periods of several months potentially at higher levels when removed from store and not kept in silica gel.

Work in progress: assessment of treated iron At the time of writing the group of treated material from the 1980s is about to be assessed. It will have been over 25 years since this material was treated; the condition of this iron has been tracked with regular assessments (Keene 1994; Heywood 2000). Observations to date With the pressures on budgets in both commercial archaeology and museums, it is essential to establish the effectiveness of treatment and storage regimes. For excavation archives in use (eg for assessments, illustration, research), and with limited staff resources, the reality is that it can be difficult to maintain the desiccated conditions recommended to slow down or halt corrosion. As a result, we do not have a group of untreated iron that can show the effectiveness of consistent desiccated storage. Nevertheless, the material examined to date has survived well despite no treatment and long periods out of desiccation. We cannot claim the sites chosen to be statistically representative of all the excavated ‘waterfront’ iron in our stores, nor are we likely through this assessment to be able to isolate factors in the causes of good preservation for our ‘waterfront’ iron such as burial environment, treatment and length of time in desiccation. Reducing variables is difficult with ‘real’ material. However it does provide a starting point which we would welcome further researchers’ assistance to better define. Stored material can provide an invaluable resource for reviews of treatments and storage methods if limitations are factored in. This body of work is a result of a ‘call to action’ at a recent conference on iron (ICON Archaeology Group, Archaeological Iron: Reflection and Outlook, London, September 2009). Our assessments on ‘real’ material are intended to complement the experimental work in progress at Cardiff University, English Heritage and the British Museum. These studies are looking at optimum conditions for storage of iron, and the effectiveness of treatment in a wider body of UK material. It is hoped that the combination of experimental work and assessments of excavation archives will lead to significant and useful conclusions. References
Heywood, C. (2000) Ferrous metal treatments undertaken by the Museum of London: observations and a statistical evaluation, unpublished thesis, Durham University. Keene, S. (1994) ‘Real-time survival rates for treatments of archaeological iron’, in D. Scott, J. Podany and B. Considine (eds) Ancient and Historic Metals: Conservation and Scientific Research, Getty Conservation Institute, 249-264. Sully, D. and Suenson-Taylor, K. (1996) ‘A condition survey of glycerol treated freeze-dried leather in long-term storage’, in A. Roy and P. Smith (eds) Archaeological Conservation and its Consequences: Preprints of the Contributions to the Copenhagen Congress, 26–30 August 1996. London: International Institute for Conservation, 177-181.

THE KUR-PROJECT “LARGE QUANTITY FINDS IN ARCHAEOLOGICAL COLLECTIONS” CRISTINA MAZZOLA1, PETER ALBERT1
1 Archäologische

Staatssammlung München, Lerchenfeldstr. 2, D-80538 München, Germany

Cristina.Mazzola@extern.lrz-muenchen.de; Peter.Albert@extern.lrz-muenchen.de

The KUR-project – an introduction Large quantities of finds – especially those consisting of archaeological iron and waterlogged wood– are always difficult to handle. To tackle this challenge many different methods of dealing with these finds have been developed. The project wants to examine and compare these treatments with regard to practicability, costs and efficiency. The three year project is funded by the Kulturstiftung des Bundes (German Federal Cultural Foundation) and Kulturstiftung der Länder (Cultural Foundation of the Federal States). Executing institutions are the Archäologische Staatssammlung München (Bavarian State Archaeological Collection, ASM) and the Römisch Germanisches Zentralmuseum (Roman Germanic Central Museum, RGZM) in Mainz. It stands under the direction of Prof. Dr. Rupert Gebhard (ASM) and Prof. Dr. Markus Egg (RGZM). The materials are divided between the institutions – Waldemar Muskalla and Markus Wittköpper work with wood at the RGZM whereas the authors (ASM) focus on iron. General procedure The treatments used so far include packing the finds in different kinds of foils, in some cases adding for example oxygen absorbers or desalination in solutions like alkaline sulphite (see references). The methods are roughly classified into two categories: Storage and desalination. The former has two focuses – the methods for initial treatment on site need to be quick and simple, those for long term storage can involve bigger equipment since this is usually executed in lab environment. The sample objects are taken from two sites: An early medieval burial ground in Steinheim near Dillingen, Bavaria, excavated in 1987. The second site is a settlement located at the Leisenhartfeld in Manching, Bavaria, dug in the first half of 2009.

Fig. 1: Powder sample in the beginning and turned into akaganeite. Photo: C. Mazzola, ASM

An appropriate medium for testing the efficiency of the storage methods is a mixture of iron powder and iron chloride tetrahydrate (Guggenheimer 2006). Under normal climate conditions (ca. 25 °C, 40 % rH , 21 % O2) this will turn into akaganeite after a few days (fig. 1).

Storage
Different, preferably transparent foils (PE in several thicknesses, vacuum bags (PE/PA), ESCAL, aluminium barrier film), Different add-ons (oxygen absorber, silicagel, soil) Storage in a nitrogen filled casesystem

Desalination
Alkaline sulphite- or pure sodium hydroxide-treatment in different variations (vacuum, normal, different temperatures, etc.) Heating in a dry environment (up to 200 °C) Gas reduction Subcritical treatment (in Clemson, USA) Washing in distillied water in overpressure

Table 1: Overview of tested methods

All samples are regularly weighed and photographed, objects x-rayed. For the oxygen monitoring a non-invasive oxygen meter is available. The progress of desalination baths is controlled by titration. For the identification of the different iron minerals xray diffraction (XRD) and Moessbauer spectroscopy are used. An overview of the tested methods is listed in table 1. Most tests were done under laboratory conditions. Some of the objects however have been packed on site in Manching by the excavation staff to see how the handling of foils and equipment fits in the routine.

First observations Looking at the storage options it was of little surprise that the PE-bags usually used on excavations offer only little protection against oxygen. The ESCAL foil holds tight as long as it is not strained extensively. Household vacuum bags seem to be an acceptable alternative – at least for a few months. The conversion into akaganeite – indicated by weight and volume increase and colour change – seems to start already at oxygen levels as low as 1 %. It showed that with both powder and object samples the oxygen level drops after a while independently from the presence of an absorber. Probably the oxygen is used up in the oxidation process. The tests on site were a mixed success. It was criticised, that the packing methods used were time consuming and that a ‘packing person’ would need to be budgeted from the start. A time and material saving alternative would be not to bag every single find in high quality foil.

Instead the finds of the day could be packed in a few bigger bags in the evening. Package on site however is generally advisable and should be considered when planning further excavations. For desalination the suggested bath changing rhythm (3 or more baths à 3-4 weeks; SchmidtOtt & Otto 2006) seems to be confirmed by the titration results. It appeared that the objects from the sodium hydroxide baths were a bit less brittle after the treatment than the alkaline sulphite objects. Two objects have been sent to Clemson, USA for subcritical treatment. A moisture chamber test and analyses in Clemson and Munich point to a good desalination success. The main difference to finds which have been treated in alkaline sulphite solutions is a thin deep red layer of powdery hematite on the surface. However there was no distinction in the subsequent exposing of the Fig. 2: Desalinated objects – in alkaline sulphite solution (above) and subcritical ‘original surface’.
treatment (below) Photo: C. Mazzola, ASM

Future prospects Much remains to be done – more desalination variations, e.g. with the in the ASM available gas reduction machine. Improvement of the packing methods to make them quicker and a broader research in the foil sector are planned to find cheaper alternatives to ESCAL-foil. At present the systematic study of storage in nitrogen filled case-system has started. References
Guggenheimer, S. (2006) Investigation into the potential of low-oxygen and dry/cold storage for freshly excavated iron artifacts (Thesis). School of the University of Applied Sciences Western Switzerland, La Chaux-de-Fonds, (unpublished). Mathias, C., Ramsdale, K. and Nixon, D. (2004) ‘Saving archaeological iron using the Revolutionary Preservation System’, in J. Ashton & D. Hallam (eds): METAL 04, Proceedings of the International Conference in Metals Conservation, Canberra, Australia, October 2004. Canberra: National Museum of Australia, 28 – 42. Schmidt-Ott, K., Otto, N. (2006) ‚Neues zur Eisenentsalzung mit alkalischem Sulfit‘, VdR Beiträge zur Erhaltung von Kunst- und Kulturgut 2, 126 – 134. Selwyn, L. (2004) ‘Overview of archaeological iron: The corrosion problem, key factors affecting treatment and gaps in current knowledge’, in J. Ashton & D. Hallam (eds): METAL 04,etc. (see Mathias et al.), 294 – 306.

METALLURGICAL PROPERTIES OF STEEL USED IN A TRADITIONAL JAPANESE MATCHLOCK GUN MANAKO TANAKA1 and MASAHIRO KITADA1 Graduate School of Conservation for Cultural Property, Tokyo University of the Arts, 12-8 Ueno-Koen, Taito-ku, Tokyo 110-8714, Japan s1308950@fa.geidai.ac.jp ; kitada.masahiro@palette.plala.or.jp Introduction The microstructures, nonmetallic inclusions and mechanical properties of a steel barrel of a traditional Japanese matchlock gun fabricated in the middle of the Edo period (17th-18th century) have been investigated. Guns were introduced into Japan in the 16th century by Europeans. It is said that steel made from domestic iron sand and/or imported steel was used as the raw material of the barrel. However, the details have not been clarified yet because of the limited number of investigations. It is considered that the barrel of a Japanese matchlock gun was made mainly by hot forging, although the detailed fabrication technique of the barrel is not clear as it was carried out in secret. The purpose of this work is to obtain materialsscience data of the raw materials of the Japanese matchlock gun and to investigate the fabrication technique of the steel barrel. Experimental methods The barrel used for analysis is shown in Fig.1. It is considered to have been made after 1624 from the shape of the sight. Specimens are cut from the center of the barrel. The carbon concentration is determined by chemical analysis. The metallurgical microstructure and nonmetallic inclusions of the barrel are observed using an optical microscope, a scanning electron microscope (SEM) and a transmission electron microscope (TEM). To observe the metallurgical structure, specimens were etched with 5% nital after being buffed with cerium oxide. The small-area concentration of a nonmetallic inclusion is obtained by electron dispersive X-ray analysis (EDS). The mechanical properties are evaluated by tension and hardness tests. To check the impact of fabrication (forging), a test piece is annealed (700oC x 1h) in inert atmosphere.
1

Fig. 1: Japanese matchlock gun fabricated in the Edo period. (Property of one of the authors: M.Kitada.)

Results and discussion 1. Microstructures The center of the barrel is made of mild steel containing 0.01-0.1 mass% carbon. Crosssectional optical micrographs of specimens No.1 and No.2 are shown in Fig.2. Although specimens No.1 and No.2 both consist of α-Fe, the grain size is variable. The grain diameters of specimens No.1 and No.2 are 30-200µm and 200-1200µm, respectively. The metallurgical microstructures of a cross section parallel to the barrel and a surface show the same characteristic. The following two causes are considered to be responsible for the grain diameter variation: Firstly, the characteristics of the raw material (steel sheet) of the barrel itself and, secondly, the effects of the forging process, such as annealing temperature and annealing time. A typical transmission electron micrograph of α-Fe is shown in Fig.3. Since many dislocations are observed in the crystals and pinned by Fe3C particles, the steel was slightly forged at room temperature after hot forging.

500nm Fig. 2: Cross-sectional optical micrographs of steel barrel: (a) specimen No.1 and (b) specimen No.2. Arrow indicates Neumann band. Fig. 3: Transmission electron micrograph of α-Fe. Dislocations are pinned by Fe3C particles.

2. Nonmetallic inclusions Two typical microstructures of the nonmetallic inclusions are shown in Fig.4. Fe, Si, Al, Ca, K, Mg, P, Na and Ti are detected from nonmetallic inclusions of the barrel. Most Japanese iron sands contain Ti as ilmenite (FeTiO3), but Japanese iron ore and imported steel do not contain Ti. Since Ti is detected, it is concluded that iron sand was used to make the steel. The distributions of nonmetallic inclusions in the cross sections normal to the barrel and parallel to the barrel and surface are shown in Fig.5. From the distributions of nonmetallic inclusions in two typical Japanese barrels (Fig.6), it is concluded that the barrel was fabricated by the joining of two long edges of a steel sheet, which is called Udonbari (in Japanese: seamed steel pipe).

Fig. 4: SEM images of two typical microstructures of the nonmetallic inclusions, (a) FeO + Fayalite + glass matrix and (b) glass single phase.

Fig. 5: Distributions of on-metallic inclusions in (a) cross section normal to the barrel, (b) cross section parallel to the barrel and (c) surface. Arrow indicates assumed weld area of steel barrel.

Fig. 6: Schematic illustrations of distribution of nonmetallic inclusions (arrows: dotted lines) in the steel barrel of a Japanese matchlock gun: (a) Udonbari and (b) Kazuramaki.

3. Mechanical properties The maximum Vickers hardness and tensile strength are 132Hv and 366Mpa, respectively. The values are slightly higher than those of the standard data of annealed mild steel; therefore, there is a possibility of work hardening by cold forging. Optical micrographs of the specimens before and after annealing are shown in Fig.7 and Fig.8. Crystal growth was observed after annealing. The maximum Vickers hardness and tensile strength are decreased by annealing at 118HV and 325MP, respectively. As the grain size and Vickers hardness of the surface change more markedly than those of the cross section, it is concluded that the steel was forged at room temperature after hot forging.

Fig. 7: Cross-sectional optical micrographs of steel barrel: (a) before annealing and (b) after annealing

Fig. 8: Optical micrographs of surface of steel barrel: (a) before annealing and (b) after annealing.

Conclusions The microstructures, nonmetallic inclusions and mechanical properties of the barrel of a Japanese matchlock gun were investigated. The center of the barrel is made from a mild steel that contains 0.01-0.1 mass% carbon. Since Ti is detected, it is determined that the iron sand was used as the raw material of the barrel. The barrel was fabricated by the hot-forge welding of a long steel sheet. The barrel was forged at room temperature after hot forging. References
Kimura, S. (1854) Houjutsu kunmo vol.3. Kyoto: Tenshinrou; translated from Van Overstraten, J.P.C. (1850) HANDLEIDING TOT DE KENNIS DER ARTILLERIE. Holland: Militaire Akademie. Kitada, M. (2007) ‘Fine Structures of a Japanese Sword Fabricated in the Late Muromachi Era (16th Century)’, Bulletin of the Faculty of Fine Arts Tokyo National University of Fine Arts and Music 45: 5-56. Kitada, M. (2007) JFE 21st Century Foundation Study Report:71-80. Kitada, M. (2009) ‘Microstructures and Mechanical Properties of Japanese Ancient Sword (Straight Sword) Excavated from Old Mound’, Bulletin of the Faculty of Fine Arts Tokyo National University of Fine Arts and Music 46: 5-32. Tanaka, M. and M.Kitada (2009) ‘Microstructure of Japanese Matchlock Gun Fabricated in the Edo Period’, Journal of the Japan Institute of Metals 73: 778-785. Tokoro, S. (1964) Hinawaju. Tokyo: Yuzankaku.

IRON AND THE MICROSCOPE DAVID A. SCOTT1
1

Professor, Department of Art History, UCLA, Los Angeles, California, USA, 90049 dascott@ucla.edu

Ferrous materials have a long history in the crucial stages of development of metallurgical microscopy. The realization that Anglo-Saxon sword blades from Scandinavian excavations in the 19th century, were fabricated from pattern-welded iron of different kinds, spurred investigation and fascination with iron’s past and the achievements of the blacksmith. At the same time, scientists were making significant advances in trying to prepare iron artefacts to examine microstructure, and explain the kind of products being produced, as well as understanding the microstructural reasons for the different behaviour of cast iron, steel and wrought iron. Observations on the structure of iron began in the 17th century, but the development of metallurgical microscopy began with the work of Henry Clifton Sorby in the 19th century, which has been reviewed in detail by Smith (1988). In the Old World, iron was never molten in antiquity, except in small amounts, and was joined by welding or forging of pieces of iron together. As a result, the microstructure of iron is variable, due to weld lines, different carbon contents, and slag inclusions, and these differences are very informative concerning the processes of fabrication which have been employed to produce different artefacts (Smith 1981, Craddock 2005). Carbon content, methods of heat-treatment, extent of corrosion and patination can all be investigated with the microscope, which is part of the reason why conservation measures seek to preserve as much of the original object as possible for future scientific work. The improvement in conservation methods means that we can examine the microstructure of finds from excavations without the fear that they have been altered by treatment as they once might have been. Numerous conservation measures used to conserve iron in the past have failed to maintain the microstructural integrity of the material we were supposed to have preserved. Such techniques as heating iron artefacts to dull red heat, the older plasma reduction processes which used high temperatures, from 300-450 oC, hydrogen reduction and even electrolytic reduction not only stripped away all of the corrosion products in the case of the latter but altered the microstructure of the ferrous material being conserved in the case of the former. Our concern for metallurgical veracity is a major influence on conservation strategies. This veracity can be determined by microscopical examination, by x-ray radiography and by new non-destructive methods such as time-of-flight neutron diffraction analysis, used on a Song Dynasty Chinese iron coin (Huang et al 2010) to determine phase composition. The different phases of the ironcarbon system are very sensitive to fabrication techniques and compositional variations in carbon content.

In this short review of structure, we will examine some typical microstructures of ancient iron artefacts: wrought iron, low-carbon steel, high carbon-steel, welded structures, quenched martensite, tempered martensite, grey cast iron and white cast iron. The iron-carbon phase diagram is an essential backdrop for ferrous metallurgy which will be briefly examined, and which helps to define the phases of ferrite, austenite, ledeburite, pearlite, cementite and graphite. Even low contents of carbon, 0.4% , create remarkable changes in the properties of iron artefacts. Phosphoric iron was also an important product and occasionally nitrogen created nitrides, hardening the iron produced. Phosphoric iron creates possible contrasts with low-carbon steel used in pattern welding. Even in the bloomery process, small amounts of high carbon products, such as grey or white cast iron could be made, although the usual challenge was to retain or get enough carbon into the iron to create steel (Craddock 1995). The Chinese and Indian task was to remove enough carbon from cast iron products to produce steel. The co-fusion of wrought iron and cast iron was one way in which this could be done, used for one of the Indian crucible steel processes (Bronson 1986), or cast iron could be decarburized. The Chinese production of cast iron two thousand years before the Old World could make it in any quantity, resulted in a unique metallurgical development of grey cast iron, white cast iron and mottled or spheroidal graphite cast iron whose ferrous microstructures are often the most difficult to decipher in the corroded state. Diagrams which plot the changes of phases depending on the speed with which steels are quenched, known as time-temperature-transformation diagrams, are useful in determining the presence of the phases, bainite, troostite, martensite and other carbides (Rollason 1973). An example of a Japanese sword blade which shows martensite, troostite and the transition to fine pearlite and a lower carbon steel core will be discussed (Scott 1991). Hardening steels by quenching and tempering gave rise to products which were far superior to the copper alloys of the Bronze Age. Some of these products will be reviewed here, employing the metallurgical microscope and polished and etched sections of some of the iron artefacts examined in the laboratory. References
Bronson, B. (1986) The making and selling of wootz, a crucible steel of India. Archeomaterials 1, 1351. Craddock, Paul T. (1995) Early Mining and Metal Production.Edinburgh University Press: Edinburgh. Huang Wei, Winfried Kockelmann, Evelyn Gordfrey, David A Scott, Wu Xiaohong (2010) Nondestructive Phase Analysis of Song Dynasty Iron Coins by TOF Neutron Diffraction. Acta Scientiarum Naturalium Universitatis Pekinensis, Vol. 46, No. 2, 245-250. Rollason, E. C. (1973) Metallurgy for Engineers. Edward Arnold: London. Scott, David A. (1991) Metallography and Microstructure of Ancient and Historic Metals. J. Paul Getty Press: Malibu. Smith, Cyril Stanley (1981) A search for structure: selected essays on science, art and history. MIT Press: Cambridge, Massachusetts. Smith, Cyril Stanley (1988) A History of Metallography. MIT Press: Cambridge, Massachusetts.

Gerhard Eggert and Britta Schmutzler (Eds.)

Archaeological Iron Conservation Colloquium 2010

Extended Abstracts

Archaeological Iron Conservation Colloquium 2010

State Academy of Art and Design Stuttgart 24th to 26th June 2010

Extended Abstracts

Session 3: Alkaline Chloride Extraction

EFFICIENCY OF CHLORIDE EXTRACTION WITH ORGANIC AMMONIUM BASES: THE KUR-PROJECT “CONSERVATION AND PROFESSIONAL STORAGE OF IRON ARTIFACTS” CHRISTIAN-HEINRICH WUNDERLICH1, CHARLOTTE KUHN2, VERA DRÖBER3, GERHARD EGGERT2, THOMAS SCHLEID4
1

State Museum for Prehistory Sachsen-Anhalt, Richard-Wagner-Str. 9, D-06114 Halle (Saale), chwunderlich@lda.mk.sachsen-anhalt.de 2 State Academy of Art and Design, Am Weißenhof 1, D-70191 Stuttgart charlotte@charlotte-kuhn.de; gerhard.eggert@abk-stuttgart.de 3 Regierungspräsidium Stuttgart, Referat 84/ Archäologische Denkmalpflege, Berliner Strasse 12, 73728 Esslingen a. N., vera.droeber@rps.bwl.de 4 Institute for Inorganic Chemistry, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, schleid@iac.uni-stuttgart.de Introduction The Project “Conservation and Professional Storage of Iron Artifacts” has been launched by the Landesamt für Denkmalpflege Sachsen-Anhalt, Landesmuseum für Vorgeschichte Halle to ensure the long term conservation of our meaningful collection of archaeological iron artifacts. As part of the “KUR-Project” it is supported by the german Kulturstiftung des Bundes and Kulturstiftung der Länder. The project work includes the practical conservation of our collection of iron artifacts, dating between the 10th century BC and the 16th century AD. Most of the about 3500 finds were excavated 50-150 years ago. The collection has been stored at uncontrolled conditions until now and many finds – restored or untreated - corroded after their excavation. A wide range of corrosion phenomena, typical for post excavation corrosion, can be observed. Our challenge now is the conservation of a large amount of iron objects, a well known problem to many archaeological collections throughout Europe. The centre of the project´s research activities, which are conducted in cooperation with the State Academy of Art and Design Stuttgart and the University of Stuttgart, is the evaluation of a new desalination method, to enable an effective improvement of the corrosion stability of the iron finds by extracting chloride ions within the corrosion layers, which catalyse ongoing corrosion processes after excavation.

Desalination of iron artifacts with organic quaternary ammonium hydroxides Although it is well known, that chloride extraction methods considerably improve the corrosion stability of treated archaeological iron artifacts (e. g. Keene and Orton 1985), particularly long treatment times require further ameliorations of established methods. A desalination treatment in solutions based on organic solvents can be expected to be faster and more effective than aqueous methods, due to the lower surface tension of such solutions, resulting in better wetting abilities. Besides, no further corrosion of the artifacts has to be expected during treatment in waterless solutions (Watkinson 1982). To shift the currently accepted desalination processes in alkaline, aqueous media to water free solutions, a hydroxide is needed, which shows a sufficient solubility in organic solvents, and also forms a sufficiently soluble chloride salt. Research activities Within the project solutions of tetra-methyl ammonium hydroxide (TMAH) in methanol and/or water are tested as an alternative to the common alkali hydroxide based desalination procedures (e. g. Watkinson 1982, Al Zahrani 1999). Desalination experiments are conducted using roman nails as test objects. Different concentrations of TMAH in water, methanol, and mixtures of both are compared to the commonly used alkaline sulphite solution. Residual chloride in the test objects, as well as chloride washed into solution, is determined. The behaviour of objects in the tested solutions is monitored weekly by visual surveys, to observe possible ongoing corrosion processes or the partial dismantling of corrosion layers during the process. Additionally, the insoluble, chloride containing corrosion product akaganéite, β-FeO(OH), has been synthesised and is treated in corresponding desalination solutions. Original and residual chloride content of the solid is also determined and possible phase transformations are surveyed using X-ray diffraction. First results First desalination experiments on synthetic akaganéite indeed show, that chloride extraction is basically possible in methanolic, as well as aqueous tetra-alkyl ammonium hydroxide solutions. Perspective Further experiments on akaganéite and archaeological artifacts will be carried out, to allow quantitative comparison of the efficiency of solutions of varying concentrations and solvent contents.

Acknowledgements We are grateful to the Chemisches Labor für Umweltanalytik Halle (CLU GmbH) for the assistance with the chloride analyses. We also thank Nicole Ebinger-Rist from the Landesamt für Denkmalpflege Esslingen for providing test objects. References
Al Zahrani, A. (1999) Chloride ion removal from archaeological iron and β -FeOOH, PhD dissertation, University of Wales, Cardiff. Keene, S. and Orton, C. (1985) Stability of treated archaeological iron: an assessment, Studies in Conservation 30: 136-142. Watkinson, D. (1982) An assessment of the lithium hydroxide treatments for archaeological ironwork, in R. W. Clarke and S. M. Blackshaw (eds) Conservation of iron, Maritime Monographs and reports of the National Maritime Museum 53: 208-213.

THE USE OF SUBCRITICAL ALKALINE SOLUTIONS FOR THE STABILIZATION OF ARCHAEOLOGICAL IRON ARTIFACTS PAUL MARDIKIAN1, NESTOR GONZALEZ1, MICHAEL J. DREWS1, LIISA NASANEN1
1

Clemson University Conservation Center Warren Lasch Laboratory, School of Materials Science and Engineering, 1250 Supply Street Bldg. 255, North Charleston, SC 29405, USA pmardik@clemson.edu, nestorg@clemson.edu, dmichae@clemson.edu, lnasane@clemson.edu New technology for the stabilization of archaeological iron using subcritical fluids has been tested over the last six years at the Clemson Conservation Center. This technique originated from the extensive research carried out in the industrial world with sub and supercritical fluids for waste oxidation, radioactive waste reduction and other chemical reactions and synthesis. Water heated under the appropriate pressure above its atmospheric boiling temperature of 100oC and under its critical temperature (Tc) of 374oC and pressure (Pc) of 221 bar is referred to as subcritical water. Above this temperature and pressure water becomes supercritical; that is, it exhibits properties between those of a liquid and a gas. For practical reasons, it was decided to remain within the subcritical region for the purposes of treating archaeological iron, and define a working temperature as low as possible to avoid alteration of the metallographic structure of the iron. In order to define the optimal operating temperature, experiments were conducted within the temperature range of 130 to 230oC with a pH between 11.6 and 13.1. These temperatures and pH range were selected while taking into account the practical considerations of treating very large artifacts and the likely effectiveness of the treatment. Based on these results, it was decided to undertake treatment of the iron at 180oC at a pH of 13.1, using 0.5% w/w sodium hydroxide (NaOH). The reasoning behind using an alkaline liquid at subcritical conditions, for the treatment of chloride-ridden iron artifacts was that the treatment time would be significantly reduced due to the following reasons: • • The increase in temperature of the solution would result in a significant increase in the chloride diffusion constants. The decrease in the viscosity and density of the treatment solution would improve the diffusion of hydroxide ions into the corrosion layers and promote a more effective chloride exchange.

The decrease in the surface tension of the solution would improve its wettability and capacity to penetrate the interstices of the corrosion layers.

A typical treatment using this technique involves the following steps: once the object is placed inside the pressure vessel, the chamber is filled with a solution of sodium hydroxide and air is purged from the system. Pressure is maintained at approximately 50 bar and the solution is gradually heated until it reaches 180oC. The flow of the solution during treatment is adjusted according to the size of the chamber. The eluent solution is regularly sampled in order to determine the chloride concentration at any given time of the treatment, as well as to calculate the total concentration of chlorides. To date, over 150 experiments have been conducted at the Clemson Conservation Center using wrought and cast iron archaeological samples from marine and terrestrial sites as well as synthetic iron oxides. Most of the initial trials were conducted on a relatively small scale using 40 and 600 ml pressure vessels (Fig.1). The small size of these vessels has restricted the size of the samples and artifacts that can be treated using this technique. So far, hundreds of samples and relatively small artifacts have been successfully treated. These include rivets, nuts and bolts, tools and nails. Recently, a 40-liter reactor was designed and built to enable the treatment of larger artifacts such as ballast blocks from the H.L. Hunley submarine (1864), and other large and more complex artifacts and samples from both marine and terrestrial sites (Fig.2).

Figure 1. Research engineer Nestor Gonzalez operating the first generation subcritical reactor at the Warren Lasch Conservation Laboratory.

Figure 2. Research engineer Nestor Gonzalez and conservator Liisa Nasanen operating the second generation 40-L subcritical reactor.

The chloride release rates using the subcritical technique were found to be significantly higher and treatment times much shorter than those observed using electrolytic treatment. None of the treatments using this technique have exceeded 10 days, compared to over 6 months of treatment using traditional methods on some of the cast iron specimens. During the first years of experimentation with this technique, chemical digestion of the specimen was used to determine the total amount of chloride remaining in the metal after treatment. The residual chloride levels in the treated samples were also found to be at least as low as chloride levels in those treated by electrolysis. In addition, no damage was observed to the graphitized layer on the cast iron samples, and the long-term stability for all of the subcritical treated specimens appears to be very good. Moreover, recent work has shown that the chlorinated oxyhydroxide phase akaganéite (β-FeOOH), thought to be responsible for the long-term instability of iron, was completely transformed into more stable corrosion products such as goethite, magnetite and hematite. These results are particularly encouraging for the stabilization of terrestrial artifacts where akaganéite is often found. In these experiments undertaken at the Clemson Conservation Center, the subcritical technique effectively removed very high levels of entrapped chloride ions from terrestrial and marine iron objects in very short periods of time. While it is true that continuing research and development of the subcritical technique will require considerable investment, the potential is great for reducing the long-term costs associated with lengthy conservation treatments and expensive environmentally controlled post-excavation storage options. The capacity for this treatment to significantly assist the conservation community with the mass-treatment and long-term stabilization of archaeological iron may result in considerable savings both in terms of treatment time and cost of treatment.

References
de Vivies, P., Cook, D., Drews, M.J., Gonzalez, N.G., Mardikian, P., Memet, J.B., (2007) ‘Transformation of akaganéite in archaeological iron artefacts using subcritical treatment’, Proceedings of the International Conference on Metals Conservation, Amsterdam, Netherlands, 17-21 Sept 2007, eds. C. Degrigny, R. Van Langh, I. Joosten, B. Ankersmit, Amsterdam, 17-21. Drews, M. J., de Viviés, P., González, N. G., Mardikian, P., (2004) ‘A study of the analysis and removal of chloride in samples from the Hunley’, Metal 2004, Proceedings of the International Conference on Metals Conservation Canberra, Australia, 4-8 October 2004, ed. J. Ashton and D. Hallam, National Museum of Australia, Camberra, 247-260. Gonzalez, N.G., Cook, D., deVivies, P., Drews, M.J., Mardikian, P., (2007) ‘The effects of cathodic polarization, soaking in alkaline solutions and subcritical water on cast iron corrosion products’, Metal 2007, Proceedings of the ICOM-CC Metal WG Conference, Amsterdam, Netherlands, 17-21 Sept 2007, eds. C. Degrigny, R. Van Langh, I. Joosten, B. Ankersmit, Amsterdam, 32-37. Mardikian, P., Gonzalez, N. G., Drews, M. J., deVivies, P., (2009) ‘New perspectives regarding the stabilization of terrestrial and marine archaeological iron’, Iron, Steel & Steamship. Proceedings of the 2nd Australian Seminar held in Perth, Melbourne and Sydney, 2006, ed. M. McCarthy, Australian National Centre of Excellence for Maritime Archaeology, Fremantle, 113-118.

SOME NEW ADVANCES IN ALKALINE SULPHITE TREATMENT OF ARCHAEOLOGICAL IRON SVETLANA BURSHNEVA1, NATALIA SMIRNOVA2 State Hermitage Museum, Dvortsovaya Naberezhnaya, 34, 190000, St-Petersburg, Russia burshneva@yandex.ru 2 Grabar Art Conservation Center, Vologda brunch office, Zasodimskogo st. 14a, 160000, Vologda, Russia natasha-s@bk.ru Introduction We assume that condition of most archaeological iron finds can be correlated to one of the oxidation stages that we describe in our table “Degree of ironwork oxidation”. This table is based on the analogous one that was proposed by J.M. Cronyn (Cronyn 1990: 183). For marine ironwork, we propose a similar one for archaeological iron. Our table includes some data of oxide films and corrosion crusts formation at each oxidation stage, and also a short description of permissible conservation treatments. According to our table from a conservation point of view the most problematic are iron objects of the IIIrd and IVth oxidation stages. At these stages the artifacts have already undergone a considerable mineralization and their original surface has been hidden by corrosion products. But these objects still have a sound metal core that continues to corrode and provoke flaking of the mineral crust. Finally the objects lose their shape and cannot be considered as historical artifact any more. We examined a number of mineral crusts of different archaeological iron objects with a scanning microscope. We found that the inner structure of mineral crusts of buried archaeological iron is uneven and non-regulated, cracked and capillary. Chloridecontaining compounds are concentrated at goethite dominating iron oxyhydrates zones, and at metal – mineral crust interface. Presence of chloride has not been detected within magnetite zones. It is evidence of good protective properties of magnetite, but unfortunately it does not produce a smooth layer. Problem formulation The alkaline sulphite method for archaeological iron was proposed by N.A. North and C. Pearson (1975) for desalination of marine iron. They reported that the final product of the treatment is mixed iron oxide Fe3O4, magnetite. However N.A. North and C. Pearson did not describe thermodynamics of the process. Later M. Gilberg and N.J. Seeley (1981: 50-56) revealed that the magnetite formation is more complicated process than it was described by previous authors. In 1989 in the Institut de Recherches et de Restoration Archeologiques et Paleometallurgiques in France 107 Iron age axes were treated with the alkaline sulphite
1

method. After two years 27 of them showed new corrosion– pustules and craters have appeared (Beaudoin et al. 1997: 170-177). We decided to analyze once again the sequence of the chemical transformations that take place during the alkaline sulphite treatment of archaeological iron. We calculated chemical processes that take place during immersion of iron objects to alkaline sulphite solution (stage 1) and during washing out after immersion in distilled water (stage 2). Experimental Stage 1. When the alkaline sulphite solution reaches pores of the mineral crust it reacts with oxygen and takes it up. As a result the solution penetrates deeper into the pores: 2SO32- + O2 = 2SO42(1) At the same time Fe3+cations get reduced to Fe2+ cations: 2Fe3+ + SO32- + 6OH- = SO42- + 2Fe(OH)2 + H2O

(2)

According to thermodynamic calculations if in the solution both Fe3+ and Fe2+ are present, there is a high possibility for magnetite formation: 2Fe(OH)2+ + SO32- + Fe(OH)+ + 5OH- = Fe3O4 + SO42+ + 5H2O (3) This conclusion has been proved with experimental data. The pH of the solution falls from 10.4 to 8.8 but does not reach a critical value lower 7. Stage 2. During the washing out procedure of the object after alkaline sulphite treatment concentration of iron (III) hydroxide ions increases, the reaction as follow can take place: (4) 4Fe(OH)2 + O2 + (2n-4)H2O → 2(Fe2O3·nH2O) The presence of soluble Fe3+ and Fe2+ ions again is favorable for magnetite formation. Fe(OH)2 + Fe2O3·nH2O → Fe3O4 + (n+1) H2O

(5)

According to experimental data: - the total number of chlorides that were extracted during alkaline sulphite treatment is 10.52 times higher than those extracted during intensive washing in distilled water. - the mechanism of chloride ions extraction from the object happens due to diffusion and concentrations smoothening according to osmosis law. During washing out procedure the pH of the solution decreases. Washing out of the working solution (together with chloride anions) works only for not deep strata of the mineral crust, because the hydrolysis products (Fe(OH)3) block pores of the mineral crust when pH is lower than ~ 7. It means that some chloride anions are stuck within the object. This fact, together with long-term treatment itself, gives some disadvantages for this method.

To increase extraction of chloride ions and to shorten treatment time of objects we applied an ultrasonic field to the bath. During our experiment first we used samples to select a suitable regime, and then applied it to archaeological objects. Treatment time for objects in ultrasonic bath worked out 1-5 minutes every day during three days, depending object’s size. Washing out the working solution till pH= 7 took only 5 minutes. Conclusions Ultrasonic waves intensify the reduction ability of the solution: the concentration of iron (II) cations increases, and consequently the output of magnetite from chemical reactions also increases. Moreover, in the ultrasonic field liquid degasification and colloids dispersion take place: altogether they favorably affect the penetration ability of the solution and washing water. The treated objects were tested with a scanning microscope. Chloride anions in the mineral crust and at the metal – mineral crust interface were not detected. However using ultrasonic bath in alkaline sulphite treatment has some disadvantages: wrong calculations of immersion time and cavitation energy can provoke the mineral crust to ruin. Objects that have fragile and badly adhered mineral crust also cannot be treated in the alkaline sulphite solution. To protect completeness of objects we propose to use gauze bandages that support fragile areas of mineral crusts. We fix these bandages with Paraloid B-72 glue. The testing shows that polymer films created with Paraloid B-72 do not affect seriously the penetration ability of the alkaline solution, and danger of mineral crust ruining is negligible. Thus we can conclude that nowadays the alkaline sulphite treatment completed with ultrasonic treatment is the most effective method for archaeological iron objects stabilization. For the first time this method has been successfully used in Russia for about ten years for archaeological iron finds from the Russian North and some regions of Siberia, both just after archeological dig and after long-term storage. A condition check of these objects did not detect corrosion renewal. References
Beaudoin A., M-C. Clerice, J. Francoise, J-P. Labbe, M-A. Loeper-Attia and L. Robbiola (1997) “Corrosion d’objets archeologiques en fer après dechloruration par la metode au sulphite alcalin. Caracterisation physico-chimique et retraitement electrochimique”, Metal 95: 170-177 Cronyn J.M. (1990) The elements of archaeological conservation. London and NY. Gilberg M., N.J. Seeley (1981) “The identity of compounds containing chloride ions in marine iron corrosion products: a critical review”, Studies in Conservation 26: 50-56. North N.A., Pearson С. (1975) “Alkaline Sulfite Reduction Treatment of Marine Iron” ICOM-СС, 4th Triennial Meeting. Venice, 13/3: 1-14.

DEGREE OF IRONWORK OXIDATION
Corrosion environment Corrosion layer formation Oxidation stage Corrosion products appearance Oxidation process Oxidation products Degree of conservation treatment

Film formation

Atmospheric

I

Formation of the primary oxide film that works as a protective layer. Very thin and Black thin layer of FeO possibly through The artifacts do not require any transparent in the beginning, it gets thicker with the time and turns black or dark Fe2O3 (hematite) turns to Fe3O4 cleaning. Conservation coating is (magnetite). desirable. Artificial oxidation of the brown. surface can be considered as conservation treatment. Reaction of iron with oxygen and water produces rust on the surface upon oxide film. Film of rust is uneven and has different shades of yellow and light brown. At the same time pitting corrosion, which damages oxide film and irritates metal surface, occurs. Iron hydroxide (II) Fe(OH)2 oxidizes to iron hydroxide (III) Fe(OH)3, which later turns to one of hydrated iron oxides (III) goethite (α-FeOOH) or lepidocrocite (γFeOOH) All conservation cleaning methods are permissible: mechanical, chemical, electrochemical and electrolythic. Conservation coating after cleaning is required.

II

III

IV

Crust formation

Underground

Original surface of an artifact is marked by the primary oxide film that was formed at the stage I of oxidation. Under this primary film the process of mineralization takes place towards the center of the artifact. This primary corrosion crust is dark brown; its thickness is about 1-2 mm (visible to the naked eye). On the primary crust another corrosion crust is formed – so-called secondary crust. This secondary crust is porous, fragile and mixed with organic remains and soil particles. Its color mainly depends on the type of soil in which the artifact was buried. But shades of brown and light brown are predominant. The primary oxide film marks the boundary between primary and secondary crusts. Enlargement of the primary crust provokes the artifact to extend. The crust itself becomes porous and cracked. The secondary crust also enlarges and hides the original shape of the object. The loss of the primary corrosion crust at this stage means the loss of the artifact itself, because the remains of metal core do not indicate the original shape.

Primary crust Chemical cleaning permissible but not goethite (α-FeOOH) possibly through desirable, especially in case of inlay or hematite Fe2O3 slowly turns to magnetite other surface decoration, mechanical Fe3O4. cleaning is required. Stabilizing or desalinating treatment is necessary. Secondary crust Conservation coating after cleaning is goethite (α-FeOOH) + secondary corrosion required. products, soil particles, etc. Chemical cleaning can provoke the Primary crust hematite Fe2O3 slowly turns to magnetite loss of the original surface of an Fe3O4. artifact together with corrosion crust. Stabilizing treatment is necessary, but Secondary crust only special nondestructive methods goethite (α-FeOOH) + secondary corrosion can be applied. After stabilizing products, soil particles, etc. treatment deep polymer impregnation is required. The artifact needs only cleaning and Artifact magnetite Fe3O4. recovering of its original shape. After cleaning deep polymer impregnation Secondary crust is necessary because the artifact goethite (α-FeOOH) + secondary corrosion destruction danger is very high. products, soil particles, etc.

V

The artifact is totally mineralized and highly extended. The primary corrosion crust (i.e. the object itself) is porous and cracked; the cracks are filled with secondary corrosion products. The secondary corrosion crust totally hides the shape of object. Instead of metal core – a void filled with friable secondary products of iron corrosion. The object is stable from corrosion point of view. But the danger of its destruction during storage is very high.

INDEX Primary oxide film, original surface Sound metal Void instead sound metal Primary crust Secondary crust

THE EFFECTIVENESS OF CHLORIDE REMOVAL FROM ARCHAEOLOGICAL IRON USING ALKALINE DEOXYGENATED DESALINATION TREATMENTS MELANIE RIMMER1, QUANYU WANG2 and DAVID WATKINSON1
Cardiff University, School of History and Archaeology, Humanities Building, Colum Road, Cardiff, CF10 3EU, United Kingdom. rimmermb@cardiff.ac.uk; watkinson@cardiff.ac.uk 2 The British Museum, Department of Conservation and Scientific Research, Great Russell Street, London, WC1B 3DG, United Kingdom. qwang@thebritishmuseum.ac.uk
1

Introduction Desalination treatments for archaeological iron have not been in general use by British conservators for many years. The reasons for this include time and resource constraints, concerns about the effects of treatments on fragile mineral-preserved organic remains, and a lack of reliable quantitative data on desalination efficiency. Storage in reduced relative humidity (RH) has been adopted as the primary method of corrosion prevention for archaeological iron collections. A lack of adequate availability and maintenance of such storage often leads to RH levels that allow corrosion processes to occur, particularly those relating to chloride-containing β-FeOOH (akaganéite) which begins to induce iron corrosion above 12% RH (Watkinson and Lewis 2005). There is a growing worry among conservators that leaving chloride ions in objects poses significant risks if controlled RH storage fails. Research design As part of a collaborative research project with Cardiff University and The British Museum, desalination treatments were re-examined by determining chloride extraction rate from a statistically significant number of archaeological samples. Two treatments were selected based on previous research (Watkinson and Al-Zahrani 2008), which suggested that chloride extraction of over 95% could be achieved using sodium hydroxide (0.5M NaOH) deoxygenated either with sulphite ions or nitrogen gas. In the study reported here, both treatments were modified to use 0.1M NaOH at room temperature; the sulphite ion concentration was also reduced to 0.05M, based on the method employed at the Swiss National Museum (Schmidt-Ott and Oswald 2006). Both treatments were tested using a large number of archaeological iron nails exhibiting varied corrosion morphologies and chloride ion content, originating from three British sites. The nails were desalinated for up to 96 days at room temperature, with up to six solution changes. Treatment was terminated when chloride levels in the treatment solution were less than 10 ppm for two consecutive solutions, although due to time constraints a small proportion of the objects did not complete the treatment. Chloride concentration was measured using a specific ion meter. After treatment, the nails were acid digested at room temperature in covered containers, and their residual chloride ion content determined.

Chloride extraction efficiency Neither of the two treatments as tested achieved the >95% average extraction rate reported by Al-Zahrani. Both achieved similar results in terms of the average chloride extraction (c. 75%), and both treatments displayed significant variability in the extraction (11-99%). Alkaline sulphite treatment heated to 60°C resulted in shorter treatment times and slightly improved overall average extraction rate, although the extraction range remained large. Although this makes treatment appear to be an unpredictable process, in the majority of cases (c. 80% for all three treatments), over 60% of the total chloride present could be extracted. Although it is difficult to determine the precise reasons for poor extraction rates where these occur, several factors were identified: bulky corrosion products and/or adhering soil retarding the diffusion rate, bound chloride, most likely held within the structure of β-FeOOH, or chloride trapped deep within inaccessible pores and surrounded by metal (Figure 1).

Figure 1: Scanning electron microcope image (top) and energy-dispersive spectroscopy map of Cl, showing Clcontaining corrosion products surrounded almost completely by metal.

Statistical analysis of results Due to the fact that large numbers of objects were treated and digested, statistical analyses of the results is possible. This shows that there is no significant correlation between the total chloride extracted during treatment and the residual chloride remaining in the object. A correlation was found between the final solution concentration and the residual chloride concentration, indicating that where objects did not reach the specified completion criteria (<10 ppm solution concentration), residual chloride levels tended to be high. This demonstrates that some objects require longer treatment times than others, and that monitoring of the chloride concentration in the desalination solution is important if treatments are to be completed. The level of residual chloride which induces significant post-excavation corrosion is an unknown quantity. North and Pearson (1978) suggest that objects containing <200 ppm may be considered ‘stable’, while those containing >1000 ppm are at significant risk. Using these boundaries, approximately 80% of the objects had their chloride levels reduced to less than 1000 ppm by treatment, while 40% of the objects fell below the ‘stable’ 200 ppm boundary. It

must be stressed that these limits do not have any empirical basis; the level of chloride in objects which may be considered ‘safe’ is not known, and is the subject of further research. Conclusion The treatment of large numbers of archaeological samples in alkaline deoxygenated solutions has resulted in a significant body of data, providing statistically sound information about the extraction efficiency that can be expected when treating objects. Both nitrogen-deoxygenated 0.1M sodium hydroxide and 0.1M/0.05M alkaline sulphite were capable of extracting significant quantities of chloride ions from objects in the majority of cases. Although it is not known how much needs to be extracted from objects to prevent rapid and destructive postexcavation corrosion, it is considered that any reduction of chloride ion content is beneficial to an object in terms of reducing its susceptibility to corrosion, particularly where storage RH exceeds the recommended 12% limit. It is hoped that this new data will lead to the consideration of desalination treatments as part of iron conservation strategies in the UK. References
North, N. A., and Pearson, C. (1978) ‘Methods for treating marine iron’, in ICOM Committee for Conservation 5th Triennial Meeting, Zagreb, 78/23/3. Paris: International Council of Museums, 1-10. Schmidt-Ott, K., and Oswald, N. (2006) ‘Alkaline Sulfite Desalination: Tips and Tricks’, in VDR conference handbook, "Archaeological Metal Finds - From Excavation to Exhibition". October 1113th 2006, Mannheim, Germany. Watkinson, D., and Al-Zahrani, A. (2008) ‘Towards quantified assessment of aqueous chloride extraction methods for archaeological iron: de-oxygenated treatment environments’, The Conservator 31: 75-86. Watkinson, D., and Lewis, M.R.T. (2005) ‘Desiccated Storage of Chloride-Contaminated Archaeological Iron Objects’, Studies in Conservation 50: 241-252.

SIMPLIFYING SODIUM SULPHITE SOLUTIONS – THE DBU-PROJECT “RETTUNG VOR DEM ROST” BRITTA SCHMUTZLER1, GERHARD EGGERT1 State Academy of Art and Design, Am Weißenhof 1, D-70191 Stuttgart, Germany b.schmutzler@abk-stuttgart.de; gerhard.eggert@abk-stuttgart.de Motivation Especially in the field of archaeological heritage preservation, archaeologists and conservators are confronted with masses of iron finds and almost all of them suffer from the characteristic post excavation corrosion induced by chloride ions under uncontrolled storage conditions: the orange akaganéite needles growing vertically up from an iron object’s metal core after the surface was flaking off. To investigate the best possibility of conserving masses of iron finds under restricted personnel and budget facilities, the research project “Rettung vor dem Rost” was funded by the DBU (Deutsche Bundesstiftung Umwelt, Osnabrück/Germany). Closely connected to these questions is the aspect of saving our environment by reducing the needed amount of chemical agents or energy. Starting point of the project is the Alkaline Sulphite Desalination Method (North and Pearson 1975). The urgency of the research project was highlighted in 2006 by a German mail survey (Eggert and Schmutzler 2009). In this framework, the effort of time and budget were identified as main counter argument against the application of alkaline sulphite desalination. Only 20 % of all interviewed German conservators (nearly 40) applied the Alkaline Sulphite Method at this time. In this extended abstract, experimental results regarding the aspect of the simplification of the method and reducing the required budget are reported. Aim of research in detail From a theoretical point of view the Alkaline Sulphite Method should be successful (Cornell and Giovanoli 1990), and accordingly many comparing experiments show that caustic solutions are the most efficient desalination solutions (e.g. Rinuy 1979; Rinuy and Schweizer 1982; Watkinson 1996). Initially, sodium sulphite was thought to reduce iron(III)compounds mainly to magnetite. In fact, no reduction takes place at completely dried out iron finds from the soil, but the role of sulphite is as an oxygen scavenger in the bath solutions (Gilberg and Seeley 1987). Actually, the passivating power of the concentrated sodium hydroxide is enough to stabilize the soaked iron (Hjelm-Hansen et al. 1993). Nevertheless, the de-aeration function is welcome, since freshly precipitated iron(III)hydroxides are suspected to plug up the pores of the corrosion product layers which can inhibit in turn the diffusion of the desalination solution respectively chloride ions.
1

From this outline it can be deduced that de-aeration of desalination solutions is relevant and can be reached by chemical strategies - or alternatively by physical strategies. First, Al Zahrani tried in 1999 de-aeration by nitrogen atmosphere, but his experimental results based on 10 nails only (Al Zahrani 1999; Watkinson and Al Zahrani 2008). The role of sulphite for desalination success or more alternatives for chemical de-aeration in addition to nitrogen, e.g. vacuum and heat are to be considered. Furthermore, iron finds from the soil are not as much chloride contaminated as finds from the sea, that's why the diminishing of the sodium hydroxide and the sulphite component are also to be investigated (Stawinoga 1996; SchmidtOtt and Oswald 2006). The subsequent aspect is to investigate the potential of omitting sulphite respectively any de-aeration method. These approaches offer the opportunity to reduce the costs of active conservation as well as the diminishment of environment pollution by chemical agents. Methodology of research The concept of the research project was to identify the most effective desalination method under consideration of the above mentioned criteria by comparing experiments, conducted using archaeological finds. The chloride content of the desalination solutions and the residual chloride content of the desalinated objects were measured. Of course, working with archaeological iron finds at this large scale needs a courageous and generous contributor, which could be won in the Landesamt für Denkmalpflege BadenWürttemberg. Roman nails from the archaeological site “Köngen” were used as specimens. The desalination experiments were conducted using around 100 g nails in one litre desalination solution (alkaline sulphite (each 0.5 mol/l), diluted alkaline sulphite (NaOH 0.1 mol/l, Na2SO3 0.05 mol/l), sodium hydroxide NaOH 0.5 and 0.1 mol/l) at room temperature (20 °C ± 1 °C); all chemicals used were of high quality purchased for analytical purpose. One bath ran 60 days, and desalination was finished when little or no chloride could be detected in the bath solution (around 4 baths). Results In case of the Köngen finds, the contamination with chloride was quite low compared to finds from the sea. Nevertheless, this small amount of chloride is able to stimulate post excavation corrosion. Hence, as main criterion for an effective desalination, the residual chloride content is to be considered. The less chloride is inside the metal core and the more chloride was extracted, the more efficient was the desalination method, and the lower is the risk of post excavation corrosion. A clear ranking of the varying desalination solutions can be worked out regarding their sodium hydroxide concentration: in 75 % of cases the 0.5 molar sodium hydroxide solutions extracted more chloride and left less inside the objects than desalination solutions with 0.1 mol/l NaOH. In contrast, in case of de-aeration the picture is less clear: the most effective desalination solutions are de-aerated by vacuum, nitrogen or sulphite (0.5 mol/l). But maybe

this impression is only caused by the cold desalination temperature, and is independent from de-aeration. Because one of the most efficient solutions is cold sodium hydroxide 0.5 mol/l without any de-aeration – it simply stood at room temperature in a box with an air-tight lid. This phenomenon was replicated in a second experiment. In contrast, reproducing this experiment at 55 °C, a result obtained which is quite contrary to expectations: cold desalination (with and without de-aeration) is more efficient than warm desalination (only deaerated with sulphite, 0.5 mol/l and 0.05 mol/l). The initially planned enhancement of diffusion of the desalination solution as well as the chloride ions seems not to take place. Furthermore, the combination of physical de-aeration with sodium sulphite does not improve the desalination. Discussion The efficiency of extraction by treatment in our experiments varies between 79 % and 46 %, i.e. every object still contained chloride after desalination. However, how important are these differences in efficiency regarding long-term stability? This question has to be answered by systematic survey of desalinated objects. Conclusions As things are now, it is recommended to use 0.5 molar solutions – but all other approaches to save money work well: Cold desalination allows working with plastic containers, it saves energy, and it extracts chloride more efficiently. De-Aeration with sulphite is cheap, with nitrogen cheaper, but with vacuum it is “for free”. A disadvantage to be mentioned is the equipment needed for mass treatment under vacuum or nitrogen, since air-tight vacuum drying ovens are recommended. However, smaller quantities can also be desalinated using exsiccators and pressure control. Finally, no other chemical agents are needed for disposal of sulphite, whereby the requirements for environment protection are matched. Perspectives The project will end in autumn 2010, so more results will be gained in the next months. It is planned to ensure the reported preliminary results by analysing finds from a second archaeological site. Furthermore, it is to be investigated, if the high efficiency of cold deaerated desalination solutions is caused by de-aeration or temperature. Results from experiments with hot caustic solutions are still to be evaluated. At least, it has to be investigated the relevance of the desalination efficiency rank. Then it can be concluded, if diluted sodium hydroxide concentration is another way for low-cost mass conservation treatment. All these other aspects of the research project and the detailed experimental results will be published in near future.

Acknowledgements We are grateful to DBU, Deutsche Bundesstiftung Umwelt, Osnabrück/ Germany for funding. For support with archaeological iron samples and lab space we are deeply indebted to Landesamt für Denkmalpflege Baden-Württemberg, especially Nicole Ebinger-Rist. Further, we thank all conservators participating at the survey. References
Al Zahrani, A.N. (1999), Chloride ion removal from archaeological iron and β-FeOOH, unpublished PhD Thesis, Universitiy of Wales, Cardiff Cornell, R.M., and Giovanoli, U. (1990), 'Transformation of akaganeite into goethite and hematite in alkaline media', Clays and Clay Minerals 38: 469-476. Eggert, G. and Schmutzler, B. (2009), `Lässt sich die Konservierung von Eisenfunden ‚auf Standard’ bringen?´ In kulturGUTerhalten, ed. U. Peltz and O. Zorn, Mainz: Philip von Zabern: 91-95. Gilberg, M.R., and Seeley, N.J. (1982), `The alkaline sodium sulphite reduction process for archaeological iron: a closer look´, Studies in Conservation, 27(2): 180-184. Hjelm-Hansen, N., Van Lanschot, J., Szalkay, C.D., and Turgoose, S. (1993), `Electrochemical assessment and monitoring of stabilisation of heavily corroded archaeological iron artefacts`, Corrosion Science 35: 767-774. North, N.A., and Pearson, C. (1975), `Alkaline sulfite reduction treatment of marine iron´ in Icom committee for conservation, 4th Triennial Meeting, Venice, 13-18 October 1975. Preprints, Paris: International Council of Museums: 75/13/ 3/ 1-14. Rinuy, A. (1979), `Vergleichende Untersuchungen zur Entsalzung von Eisenfunden´, Arbeitsblätter für Restauratoren, Gruppe 1: 130-140. Rinuy, A., and Schweizer, F. (1982), `Entsalzung von Eisenfunden mit Alkalischer Sulfitlösung´, Arbeitsblätter für Restauratoren, Gruppe 1: 160-174. Schmidt-Ott, K., and Oswald, N. (2006), `Neues zur Eisenentsalzung mit alkalischem Sulfit´, Beiträge zur Erhaltung von Kunst- und Kulturgut 2: 126-134. Stawinoga, G. (1996), `Ein Beitrag zur Eisenentsalzung´, Arbeitsblätter für Restauratoren,

Gruppe 1: 293-294.
Watkinson, D. (1996), Chloride extraction from archaeological iron: comparative treatment efficiencies`, in Archaeological conservation and its consequences, Preprints of the Contributions to the Copenhagen Congress, 26-30 August 1996, ed. A. Roy and P. Smith, London: International Institute for Conservation: 208-212. Watkinson, D. and A. Al Zahrani, (2008), `Towards quantified assessment of aqueous chloride extraction methods for archaeological iron: de-oxygenated treatment environments´, The Conservator 31: 75-86.

Gerhard Eggert and Britta Schmutzler (Eds.)

Archaeological Iron Conservation Colloquium 2010

Extended Abstracts

Archaeological Iron Conservation Colloquium 2010

State Academy of Art and Design Stuttgart 24th to 26th June 2010

Extended Abstracts

Session 4 Marine Finds

EFFECT OF DECHLORINATION IN NaOH OF IRON ARCHAEOLOGICAL ARTEFACTS IMMERSED IN SEA WATER FLORIAN KERGOURLAY1,4, DELPHINE NEFF1, ELODIE GUILMINOT2, CELINE REMAZEILLES3, SOLENN REGUER4, PHILIPPE REFAIT3, FRANCOIS MIRAMBET5, EDDY FOY1, PHILIPPE DILLMANN1 LAPA/SIS2M, CEA-CNRS et IRAMAT LMC UMR5060 CNRS, CEA Saclay bat 37, 91191 Gif/Yvette, France, florian.kergourlay@cea.fr and delphine.neff@cea.fr 2 Laboratoire ARC’ANTIQUE, 26, rue de la haute forêt, 44000 Nantes, France, elodie.guilminot@arcantique.org 3 Laboratoire d’Etudes des Matériaux en Milieux Agressifs (LEMMA), Université de La Rochelle, Avenue Michel Crépeau, F-17042 La Rochelle cedex 01, France; celine.remazeilles@univ-lr.fr, philippe.refait@univ-lr.fr 4 Synchrotron SOLEIL, Saint Aubin, France, solenn.reguer@synchrotronsoleil.fr 5 Centre de Recherche et de Restauration des Musées de France (C2RMF), Paris, France
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Introduction The aim of the dechlorination treatments is to remove the chloride and the Cl-containing phases present inside the corrosion layers. Dechlorination of iron artefacts has been widely studied in order to understand the physico-chemical mechanisms involved. The final goal is to optimise the various dechlorination treatments tested by the conservation laboratories. A general tendency to agree on the fact that dechlorination is more efficient on artefacts freshly excavated stands in the literature (Drews et al. 2004). Treating an artefact after excavation stops or reduces the corrosion phenomena. The consequence is a limitation of the activation of the corrosion processes when artefact is exposed to air through the migration of chloride ions inside the corrosion layers. The precipitation of akaganeite (β-FeOOH) is often associated to these phenomenons (Selwyn 2004) specifically on the artefacts stored during long periods. Our methodology initiated by the Odefa project was to characterise the evolution at a microscopic scale of the corrosion layers during a dechlorination treatment consisting in soaking of the artefacts in NaOH 2%. Treatments in basic solutions are the most common in conservation workshop. Artefacts excavated from the marine site of Les Saintes Maries de la Mer were chosen to establish the set of samples. Some of them were freshly excavated while others were excavated and stored without any protection against air two years before applying the treatment. In a first time the entire ingots were treated and transverse sections were analysed.

Two complementary analytical protocols have been followed. The first one is based on the treatment of entire iron ingots in basic medium with or without cathodic polarisation. Transverse sections of the treated ingots were afterwards analysed. The second consists in characterising the structural evolution of the phases in situ in solution during the treatment. For this last protocol the treatment in soda 2%wt has been given priority. Characterisation of the corrosion products on transverse sections were based on a combination of microbeam analytical tools: µraman spectroscopy (532 nm, Ø 2 µm), X-ray microdiffraction (µXRD, 17 keV and 30x600 µm²) and Energy Dispersive Spectroscopy coupled to Scanning Electron Microscope). Before treatment The observations highlighted by the Odefa project are briefly reminded in this paragraph. One freshly excavated ingot stored only nine weeks in tap water has been analysed. Corrosion products of several millimetres thickness were present and a concretion layer (mainly calcite or quartz) was partly present on the external surface. The inner part of the corrosion layer was mainly composed of an iron hydroxychloride (β-Fe2(OH)3Cl). On the external part a thin layer of magnetite (few 10 µm thickness) almost continuous has been observed. Its presence has been attributed to the first stage of corrosion. Between the β -Fe2(OH)3Cl and the magnetite layer a thin layer of akaganeite (few 10 µm thickness) was also observed. Its presence could be explained by a weak release of chloride during the storage of the ingot in aerated tap water. This process provoked an oxidation of the superficial part of the β-Fe2(OH)3Cl and induced the precipitation of akaganeite on the ingot during the immersion in the tap water or during the drying of the ingot when it was prepared for the analyses. The average Cl content of the layer is about 18%wt. The corrosion layers of the ingot stored during two years at ambient RH and temperature were completely different. The corrosion products were mainly composed of iron oxy-hydroxides. Goethite (α-FeOOH) was the main constituent but akaganeite (βFeOOH) was present in veins more or less parallel to metal/corrosion product interface. Moreover marbles were observed by optical microscope and were correlated to less crystallised phases as feroxyxhyte (δ-FeOOH)/ferrihydrite (5Fe2O3, 9H2O). The average Cl content of the layer is about 4%wt. After treatment on entire ingots Cathodic polarisation in KOH 1%wt and soaking in NaOH 2%wt have been applied on fresh and stored ingots. On the freshly excavated ingots chlorides extracted from the Cl containing phases were not detected anymore. The corrosion products have evolved towards a system composed of goethite and less crystallised ferrihydrite and/or feroxyhyte. Moreover a layer of magnetite has been detected at the metal/corrosion product interface. On the two-year stored ingots goethite and ferrihydrite and/or feroxyhyte were present in the layer but akaganeite is not completely removed from the external part of the corrosion layer.

In situ dechlorination To determine how the crystalline phases transform inside the corrosion layer during a treatment and identify the intermediate phases formed in solution, partial treatment in 2%wt NaOH on samples cut on a freshly excavated ingot have been conducted. Sample was put in a cell so that µXRD could be performed on the transverse section allowing the transformation of the phases inside the corrosion layer to be followed. The samples were carefully selected in order to present both akaganeite and β-Fe2(OH)3Cl allowing to compare the behaviour of both phases in the same conditions. Firstly it has been noticed that akaganeite contrary to βFe2(OH)3Cl could not be dechlorinated during treatment lasting at the most 35h. Secondly after 8h of treatment the dechlorination front is located at about 600 µm of the surface in the β-Fe2(OH)3Cl zone. Magnetite has been mainly observed in situ in the dechlorinated zone but Fe(OH)2 was also detected during the dechlorination process. Observations have been completed using raman microspectroscopy of the sample after the interruption of the treatment. On the dried sample the dechlorinated zone is composed of a mix of goethite and magnetite and the dechlorination front have been correlated to the presence of akaganeite, goethite, magnetite and ferrihydrite. The presence of akaganeite on the dried sample and not in situ could be explained by the interruption of the treatment that induced its precipitation. Last in the not dechlorinated zones the β-Fe2(OH)3Cl was still the main phase detected by raman spectroscopy but some akaganeite was also present under the dechlorination front in the corrosion layer. Dechlorination mechanisms The E-pH equilibrium Pourbaix diagram of iron in concentrated chloride aqueous solution was recently established (Remazeilles et al. 2009). It shows that an equilibrium exists between the two ferrous phases β-Fe2(OH)3Cl and Fe(OH)2. This equilibrium is more favourable for Fe(OH)2 under alkaline conditions. In consequence, immersing objects containing βFe2(OH)3Cl in the rust layer leads to the release of chlorides, according to the chemical reaction: β-Fe2(OH)3Cl + OH- → 2 Fe(OH)2 + ClFe(OH)2 was detected in situ in the reactor. Magnetite was also detected and may result from the oxidation of Fe(OH)2. Consequences for conservation The dechlorination rate of β-Fe2(OH)3Cl in alkaline media proved to be higher than that of akaganéite. So, for artefacts that remained in anoxic conditions, the dechlorination was more efficient for freshly excavated objects. In this case, the rust layer more likely contained only β-Fe2(OH)3Cl, even if a small amount of akaganéite could have been present as the result of a slight oxidation of the β-Fe2(OH)3Cl layer.

Finally, when Fe(OH)2 forms from β-Fe2(OH)3Cl, the next steps of the treatment will have an influence on the final corrosion products because this phase is very reactive towards O2. A step favouring a slow oxidation process of Fe(OH)2 (long treatment, soft drying) should lead to the formation of magnetite (and possibly goethite), while a step favouring a fast oxidation process (rinsing in ethanol for instance) should lead to poorly crystallized phases such as δFeOOH.

References Drews, M., de Viviés, P., González, N., and Mardikian, P. (2004), `A study of the analysis and removal of chloride in iron samples from the Hunley´, in Metal 2004, Proceedings of the Int. Conference on Metals Conservation, Canberra, Australia, 4-8 October 2004, Canberra: National Museum of Australia, 247-260. Selwyn, L. (2004), `Overview of archaeological iron: the corrosion problem, key factors affecting treatment, and gaps in current knowledge´, in Metal 2004, Proceedings of the Int. Conference on Metals Conservation, Canberra, Australia, 4-8 October 2004, Canberra: National Museum of Australia, 294-306. Rémazeilles, C., Neff, D., Kergourlay, F., Foy, E., Conforto, E., Guilminot, E., Reguer, S., Refait, Ph., and Ph. Dillmann (2009), `Mechanisms of long-term anaerobic corrosion of iron archaeological artefacts in seawater´, Corrosion Science 51(12): 2932-2941

EVOLUTION OF pH IN THE SOLUTIONS OF DECHLORINATION CHARLENE PELÉ1, STEPHANE LEMOINE1, ELODIE GUILMINOT1 Laboratoire Arc’Antique, 26 rue de la Haute Forêt, 44300 Nantes, France Elodie.guilminot@arcantique.org Introduction Archaeological iron artefacts are usually stabilized by electrolysis or by immersion in alkaline sulphite. For the two treatments, measurements of the chloride concentration are taken every week by argentimetry – potentiometry. The treatment solution is changed when the chloride concentration “stops” increasing. In Arc’Antique, the monitoring of the dechlorination treatment also includes the pH measurement over 2 years. For the electrolysis, the solution of KOH (1%w) initially has a pH of 13.3. The pH decreases during the treatment. The value is approximately 10.5 at the end of each bath. These evolutions of the pH seem to be correlated with those of chloride concentrations. When the chloride concentration stops increasing, the pH decreases. For the dechlorination by immersion in alkaline sulphite, with the high concentrations (NaOH 0.5M + Na2SO3 0.5M), the pH of the solution remains at 13.5 during all the treatment. But if we use the lower concentrations ((NaOH 0.1M + Na2SO3 0.05M) concentration advised in the Wang’s paper), the pH decreases during the treatment and it can reach a value of 10 at the end of the bath. In this presentation, we’ll try correlating the evolution of the pH with the impacts of dechlorination. The dechlorination of iron artefacts The ferrous archaeological artefacts contain chlorinated corrosion products. After excavation, the chloride corrosion cycle can provoke the rapid destruction of the archaeological object. For this reason, the objects are currently treated to remove chloride ions. Desalination methods have been employed for several decades in order to stabilize iron archaeological artefacts. Electrochemical and immersion treatments are currently used. In literature (North 1978, North 1987, Mardikian 2005, Selwyn 2001), it is mentioned that the immersion methods extract the chloride by diffusion; and the electrolysis favours the extraction of chlorides by reducing the CPs. In the electrolysis, the electric field applied to the iron artefacts also accelerates the chloride removal. The solution of the desalination treatments is chosen so that the artefact remains in the passive zone of the Pourbaix diagram, it’s an alkaline solution. For the electrolysis, the objects are polarized at -1.45V/SSE (or -0.8V/NHE) with a stabilised generator in an alkaline solution (as KOH 1%) maintained at room temperature and stirred every week. For the immersion in the alkaline sulphite, the objects are immersed in a closed tank, and the solution is regularly stirred and heated (50°C). The alkaline sulphite solution is made of soda (NaOH, 0.5M) and sodium sulphite (Na2SO3, 0.5M) (North 1978), but in a
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recent paper (Wang 2008), the treatments are also effective in less concentrated solutions (0.1M NaOH and 0.05M Na2SO3). During the stabilisation treatments, the main parameters of the treatment solution (temperature, pH and chloride content) were monitored for this paper. The chloride content was quantified using argentimetry / potentiometry and the pH was measured by a glass electrode (with corrections of the temperature). Results and discussion Electrolysis During the treatments of the archaeological artefacts, only the chloride rate was measured. But since a research program on the comparison of the iron stabilization, several parameters have been monitored: chloride rate, pH, temperature, conductivity. For this study, a Roman iron ingot (from “Saintes Maries de la Mer”, near Marseille in France) was treated by electrolysis in 10L of KOH (1% (w/w)). The results of pH and chloride rate are showed in Fig. 1. We notice the decrease of pH from 13 to 10.5 in each bath. In the first bath, the pH has remained to 13 for 3 days, whereas it has remained to 13 for 8 days in the third bath. The evolution of pH wouldn’t depend on time but on the evolution of the chloride rate. The pH decreases when the chloride rate increases, and the pH stabilizes at 10.5 when the chloride rate reaches its maximum value (whatever the value).

Fig. 1: Evolution of pH and Cl contents during electrolysis of an iron ingot in 10L of KOH (1%w/w).

During the treatments of large objects (for example, cannons), the bath time is longer and the volume of solution is bigger. However the same evolutions of pH and chloride rate are noted (Fig 2.).

Fig. 2: Evolution of pH and Cl contents during electrolysis of 2 cast cannons (1 cannon from “Breles” and 1 cannon from ”Le Juste” shipwreck (France)) in 3500L of KOH (1%w/w).

In theory, the pH of KOH solution (1 %(w/w) = 0.1782M) is 13.25. With the pH of 10.5, the concentration of OH- is 3.10-4M. If the pH decreases from 13.25 to 10.5, 0.1779M of OH- are consumed, or 2.994.10-11M of H3O+ are produced. During the electrolysis, the production of H3O+ could come from the oxidation of water on the anode (stainless steel grid): 6 H2O → O2 + 4 H3O+ + 4 eThe reactions of carbonation can also produce H3O+ ions. Carbonation occurs when carbon dioxide dissolves in water: CO2 + 2 H2O → H2CO3 + H2O H2CO3 + H2O → HCO3- + H3O+ HCO3- + H2O → CO32- + H3O+ (pKA=10.3) The consumption of OH- could be due to the penetration of anions OH- in the corrosion products of the archaeological object. But normally this phenomenon is limited because the cathodic polarization of the object supports the anions mobility from the object to the solution (the anode). Currently we don’t know which the predominant phenomenon is and how we explain exactly the pH evolution. However the production of H3O+ ions (or consumption of OH- ions) is closely dependent on the end of the chloride extraction. Thus it would be possible to use the pH in the monitoring of electrolysis

Immersion treatments in alkaline sulphite solutions For a research program on the comparison of the iron stabilization, a Roman iron ingot (from Saintes Maries de la Mer, near Marseille in France) was also treated by immersion in 10L of alkaline sulfite (0.5M NaOH and 0.5M Na2SO3) at 50°C. The results of pH and chloride rates are showed in the Fig. 3. The pH remains constant and it doesn’t depend on the chloride rate. In theory, the pH of the alkaline sulfite solution is 13.7. The measured pH is between 13.1 and 13.7. The variations could be due to the monitoring of solution level (because of the evaporation).

Fig. 3: Evolution of pH and Cl contents during immersion treatments of an iron ingot in alkaline sulphite solutions (0.5M NaOH and 0.5M Na2SO3).

Another Roman iron ingot (from Saintes Maries de la Mer, near Marseille in France) was treated by immersion in less concentrated alkaline sulfite (0.1M NaOH and 0.05M Na2SO3) at 50°C. The results of pH and chloride rate are showed in Fig. 4. In this solution, the pH decreases from 13 to 10.5. In theory, the pH of the alkaline sulfite solution (0.1M NaOH) is 13. If the pH decreases from 13 to 10.5, 0.0997M of OH- will be consumed, or 2.99.10-11M of H3O+ will be produced. We noticed the same evolution of pH during the monitoring of the archaeological artefacts (from The Natière site, France) (Fig. 5). During the immersion in alkaline sulfite, the reactions of carbonation could produce H3O+ ions (cf Electrolysis). The diffusion of Cl- from the object to the solution favours the penetration of anions OH- in the corrosion products of the archaeological object (Selwyn 2004). If the consumption of OH- is too big, the concentration of OH- will not be sufficient to protect iron.

Fig. 4: Evolution of pH and Cl contents during immersion treatments of an iron ingot in alkaline sulphite solutions (0.1M NaOH and 0.05M Na2SO3).

Fig. 5: Evolution of pH and Cl contents during immersion treatments of marine iron artefacts from The Natière site (France) in alkaline sulphite solutions (0.1M NaOH and 0.05M Na2SO3).

Conclusion Our measurements showed the pH could change during the dechlorination treatments. In the case of the immersion treatments, the pH only decreases for the less concentrated solutions (0.1M NaOH and 0.05M Na2SO3). For the solutions more concentrated (0.5M NaOH and 0.5M Na2SO3), the pH is maintained around 13.5. Thus, the quantity ions OHwould be sufficient. On the other hand, in the less concentrated solutions, the pH decreases to 10. Consequently, this solution would risk to not keeping the domain of iron passive. So, the immersion treatments should be used in higher concentrations (0.5M NaOH and 0.5M Na2SO3). As regards the electrolysis, even if the pH decreases (13 to 10.5), the object is always protected by cathodic polarization. Furthermore, we notice the pH evolution is linked to the rate of chloride extracted: the pH decreases when the chloride rate reaches its maximum value. Thus, it will be possible to use the pH as a means of treatments monitoring. The pH measurement is easiest to use for a routine monitoring of the electrolysis treatments. References
Mardikian, P., Gonzalez, N., Drews, M. and De Vivies, P. (2005) ‘New perspectives regarding the stabilization of terrestrial and marine archaeological iron’ Proceedings of Williamsburg conference The Conservation of Archaeological Materials: Current Trends and Future Directions. North, N. A. and Pearson, C. (1978) ‘Washing methods for chloride removal from marine iron artifacts’ Studies in Conservation 23: 174-186. North, N.A. (1987) ‘Conservation of metals’ in Conservation of Marine Archaeological Objects, Ed. Colin Pearson, Butterworths, London, 207-232. Selwyn, L.S., (2004) ‘Overview of archaeological iron: the corrosion problem, key factors affecting treatment, and gaps in current knowledge’ Proceeding of Metal 2004 – Ed. National Museum of Australia, Canberra: 294-306. Wang, Q., Dove, S., Shearman, F., and Smirniou, M. (2008) ‘Evaluation of methods chloride ion concentration determination treatments and effectiveness of desalination treatments using sodium hydroxide and alkaline sulphite solutions’ The Conservator 31: 65-74.

CONSERVATION OF IRON ARTIFACTS FROM THE USS MONITOR (1862) ERIC NORDGREN1
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The Mariners’ Museum, 100 Museum Drive, Newport News, Virginia, USA enordgren@marinersmuseum.org Over 200 tons of metal artifacts have been recovered from the wreck of the USS Monitor (1862), including the ship’s engine, condenser, Dahlgren shell guns, and the world’s first ship-mounted rotating gun turret. More than 75 percent of this material is composed of wrought or cast iron resulting in the need for large scale evaluation and conservation of iron artifacts at The Mariners’ Museum’s (TMM) Batten Conservation Lab. The approach taken is a practical one, endeavoring to make optimal use of established treatments and work towards adopting newer, more efficient options when possible. Conservation of Monitor iron artifacts begins with maintaining wet storage conditions from the moment of recovery from the sea until the objects can be safely dehydrated during conservation treatment. Owing to the tremendous volume of material, some of it of a very large weight and volume (engine, 30 tons, turret, 120 tons) this is not an insignificant task. Artifact handling and lifting is a significant challenge due to the size, weight and fragility of many of the Monitor components, requiring that an artifact handler with extensive rigging experience is included in the conservation team. Large numbers of artifact tanks are required, some with volumes up to 300,000 liters. Extensive support services such as plumbing and electrical and drainage systems are also needed, as well as fresh water for the storage solutions. In the absence of other complicating factors such as the presence of organic materials, iron artifacts are stored in 1-2% solutions of sodium hydroxide at a pH of 11-13, which serves to prevent significant iron corrosion as well as to begin the process of chloride extraction. Large artifacts have initially been stored in caustic solutions based on tap water for reasons of economy and availability of water purification facilities. Smaller iron artifacts are stored in sodium hydroxide solutions based on de-ionized water. As larger facilities for the production of de-ionized water become available and treatments progess, the large artifacts such as the engine and turret will also be stored in de-ionized water/sodium hydroxide solutions, allowing more effective desalination and reducing the possibility of calcium deposition on the artifacts due to reduced solubility at high pH. In the case of the gun carriages and turret, current storage is in tap water with the addition of an impressed current cathodic protection system which polarizes the metal sufficiently to prevent significant further corrosion without the addition of an electrolyte. This was done to protect wood elements of the composite gun carriages and to prevent damage to organic artifacts formerly contained within the turret. Now that excavation of artifacts from the turret has been completed, future treatment stages for the turret will be conducted in sodium hydroxide.

The pH, condition and level of the storage solutions are monitored to ensure the best storage conditions possible. The objects are also monitored for signs of corrosion during storage. Frequently, significant amounts of chloride salts are extracted into solution from the objects during wet storage, leading Monitor conservators to term this phase of conservation as ‘active storage’. Documentation and cataloguing is continued at this stage, starting with the archaeological context and continuing with pre-treatment, digital photography, computed radiography, measurements and descriptions. Radiography is very important in ascertaining the morphology and level of preservation of the artifact, allowing for careful planning of the conservation and handling. As the appearance changes and true dimensions are revealed during conservation, documentation continues throughout the process concluding with after treatment reports. The vast majority of marine recovered iron artifacts are covered with a thick layer of ‘concretion’ (Memet 2007) consisting primarily of calcium carbonate, biofouling, and corrosion products, which must be removed for effective desalination treatment. This is normally accomplished physically with a combination of hand tools and small pneumatic chisels. In some cases the Garcia Method of flame deconcretion has been used successfully on iron artifacts as well (Carpenter 1990). Particular care must be taken when deconcreting objects made of graphitized cast iron, as these have typically lost nearly all of their mechanical strength and may suffer loss easily. It should be noted that disassembly of multi-component iron artifacts can promote effective release of chlorides from confined spaces, and can also be of great benefit when treating composite artifacts of iron and other metals or organic materials. Disassembly is done when it is possible to do so without causing damage to the artifact (Krop and Nordgren 2010). Once concretion has been removed and disassembly started, desalination proceeds at a more rapid pace. In some cases this involves passive soaking in 1-2% sodium hydroxide solutions with chloride monitoring at regular intervals of one week, with the solution being changed when chloride concentrations in solution reach a plateau. More often, electrolytic reduction in sodium hydroxide solutions is employed. As well as promoting the release of chlorides, this functions to reduce iron corrosion products and loosen small fragments of remaining calcareous concretion. The treatment solution is often circulated with a pump to promote a rinsing effect and to mix the treatment solution thoroughly before solution samples are drawn for chloride testing. Chloride testing during iron desalination treatment is normally accomplished by testing samples of the treatment solutions with methods such as chloride ion specific electrodes, potentiometric titration, or ion chromatography. The goal of the iron conservation treatments is to proceed until levels of chloride below 1ppm (mg/L) are measured for at least 3 consecutive weeks. While it is felt that this gives a good indication of the effectiveness of the treatment, it is realized that solution analysis does not tell the whole story and in selected

cases destructive sampling followed by digestion has been performed to look at the quantity of chlorides which may still remain in the metal. While sodium hydroxide soaking with and without electrolytic reduction are the primary methods currently used for desalination of monitor artifacts, alternative treatments are being evaluated. A study comparing these methods with hot and cold alkaline sulfite washing of Monitor iron artifacts was performed by former TMM employee Laura Reid and will be presented separately at this Colloquium. Conservators working on the Monitor have followed with interest the development of subcritical extraction of chlorides (de Vivies, Cook, Drews, Gonzalez, Mardikian, and Memet 2007) by the team working on the submarine HL Hunley at the Clemson University Restoration Institute and have submitted a sample of wrought iron from the Monitor’s turret for subcritical testing. The use of nitrites for corrosion inhibition, storage and treatment of archaeological iron artifacts is also being investigated and will be reported in a poster session at the Metal 2010 Conference (Sangouard, Nordgren, and Spohn 2010). The test material, sodium nitrite, has the potential to prevent corrosion of iron and other metals such as copper alloys at a near neutral pH, making it an attractive possibility for storage of composite artifacts containing organics or multiple metal alloys. Testing is also underway to determine how well nitrites may function as a medium for extracting chlorides. Following the removal of concretion, corrosion and significant amounts of chlorides, Monitor iron artifacts are thoroughly rinsed in de-ionized water and dried under controlled conditions. A coating of 2-10% tannic acid is applied to protect the surface with an iron tannate layer, followed by coating with clear acrylic coatings. When necessary, components are reassembled and given supportive mountings to relieve stress on the material. The artifacts are carefully monitored in storage and on display, in which the climate is controlled to approximately 5060% relative humidity (RH) and 20-25 degrees Celsius. It is anticipated that some Monitor components may require special display environments such as low RH or modified atmosphere, depending on the extent of desalination treatment that has been achieved. The general methods and practices described above are used to conserve iron artifacts from the USS Monitor. Although this list is not exhaustive, and other methods are utilized depending on certain conditions, these techniques have proved quite effective at stabilizing artifacts recovered from the shipwreck for long term storage and display.

References
Carpenter, J., (1990) ‘A Review of Physical Methods Used to Remove Concretions from Artefacts, Mainly Iron, Including Some Recent Ideas’, Bulletin of the Australian Institute for Maritime Archaeology 14 (1), 25-42. De Vivies, P., Cook, D., Drews, D., Gonzalez, N., Mardikian, P., and Memet, J.B., (2007) ‘Transformation of akaganeite in archaeological iron artefacts using subcritical treatment’ in: Degrigny, C., ed, Metal 07: Interim meeting of the ICOM-CC Metal WG, Amsterdam, 17.-21.

September 2007, Amsterdam: ICOM-CC Metal Working Group, 26-30.
Krop, D.S, and Nordgren, E. (2010) ‘Disassembly of USS Monitor’s complex mechanical components.’, in: Metal 2010: Interim meeting of the ICOM-CC Metals Group, Charleston, South Carolina, 11-15 October 2010. (forthcoming) Memet, J.B., (2007) ‘The corrosion of metallic artefacts in seawater: descriptive analysis’, in Corrosion of Metallic Heritage Artifacts, ed. P. Dillmann, G. Beranger, P. Piccardo, and H. Matthiesen, Woodhead Publishing, Cambridge, 152-169. Sangouard, E., Nordgren, E., and Spohn, R., (2010) ‘Evaluation of Sodium Nitrite as a Corrosion Inhibitor for USS Monitor Artifacts’ poster submission for Metal 2010: Interim meeting of the ICOMCC Metals Group, Charleston, South Carolina, 11-15 October 2010. (forthcoming)

RETREATMENT OF ARCHAEOLOGICAL IRONS TEMPORARILY SUBMERGED IN BRACKISH FLOODWATERS KENYA BROWN1 Maryland Archaeological Conservation Laboratory, 10515 Mackall Road, St. Leonard, Maryland, USA, kbrown@mdp.state.md.us Abstract Irons artifacts excavated at Jamestown, Virginia, USA, (Fig. 1) between 1930 and 1950 led chemists to coat the artifacts with layers of parrafin wax. Salt from the floodwaters entered into the abraded wax layers and on the surfaces of the irons causing ferrous oxide corrosion. Treatment precluded dewaxing in 20 liters of xylene in a solvent still heated at 350°F, 176°C for 6 to 8 hours; desalination in 1 percent of NaOH and deionized water; application of 5 percent tannic acid mixed with deionized water; and a coating of 10 percent paraloid in a solution of 50 percent each xylene and ethanol. Challenges throughout the phases of treatment included wax on the surface of the irons after the dewaxing process. Residual wax forced conservators on the project to retreat the artifacts by xylene immersion at room temperature for 24 to 48 hours. Desalination often yielded weekly volatile chloride readings in treatment batches; the objective being the stabilization of the level of chlorides in the solution at 10 parts per million (ppm) over a four week period. Two four week periods of abherrant readings delegated immersion into plain deionized water instead of the NaOH solution. The immediate results revealed the desired level of 10 ppm between a 1 to 4 week period. Tannic acid application acted as a stabilizer to the corrosion resulting in the change of the orange rusted color of the irons to their original black appearance. Some objects, however, were resistant initially to the first application and required spot mechanical removal before a secondary tannic acid application.
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Fig. 1: Historic Jamestown, Virginia map and site guide. Courtesy of the National Park Service.

Extended Abstract In 2003, Jamestown staff members prepared the site storing the object for the onslaught of Hurricane Isabel in accordance to its emergency plan. Unfortunately, the combination of the hurricane and its related storm surge brought in waters from the nearby Pitch and Tar Swamp (which takes in waters from the James River) measuring 5 ft, 152 cm deep at the National Park Service (NPS)Visitor Center. A significant number of the 900,000 artifacts were affected. 42,500 of them, including approximately 20,000 iron objects, were sent to the lab as an agreement between the National Park Service and the MAC lab in 2004. The iron artifacts were treated with paraffin wax applied as both a consolidant and protective coating by the Civilian Conservation Corps (CCC) and National Park Service in 1935. The original wax treatment would remain on the irons until their retreatment at the Maryland Archaeological Conservation Laboratory (MAC) in St. Leonard, Maryland. Although the wax from the previous treatment offered some protection, the irons suffered corrosion from the fissures in the wax that developed over several decades. Consequently, these openings allowed salt laden waters to enter the surfaces of the objects. The James River situated near 540 km to the southern portion of the Chesapeake Bay, is a large watershed stretching from New York to Virginia. Salinity levels in the James river are affected by the urbanization and farm land use around the bay (Benke, et al., 2005) Runoff waters originating from the rainfall in these areas create groundwater containing nitrates and chemical contaminants adversely changing its saline properties. Studies conclude that 48 percent of the nitrates found in groundwater contribute to the contamination of the James River. Hurricane Isabel brought 1,190 billion gallons of groundwater between September 19-25, 86.9 billion gallons per day (329.4 billion liters), which is 8 times more than the normal amount of rainfall to enter the Chesapeake during a 7 day period in September (USGS, 2003). The James's highest saline counts were recorded at 15 ppm on September 24, 2003 based on information from a stationed buoy in the river (Virginia’s Department of Environmental Quality, 2003). In March 2004, samples were taken at Jamestown by NPS staff members showing readings between 40–88 ppm, a significant increase from the readings taken during the storm. The Pitch and Tar swamp adjacent to the visitor center measured 157-276 ppm during the same time period. Irons submerged for a minimum of 24 hours into floodwaters from the swamp were made susceptible to these same contaminants and augmented salinity which ultimately led to their corrosion. Jamestown staff and NPS volunteers rinsed the irons in distilled water and bagged them in two other holding facilities before the objects were sent to the MAC lab.Upon their arrival, conservators commenced the first phase of treatment, dewaxing followed by desalination. A typical batch of irons consisted of 200-300 objects per bin. Chloride readings taken from these batches concluded a range of 10-15 ppm during the first week immersion.

Alkaline solutions tend to dissolve both organic and inorganic material while producing an environment where corrosion substances are pliable, allowing an easier removal of Clֿ ions High temperature in alkaline solutions increases the solubility of iron oxides forcing more of the corrosion products to dissolve (Selwyn and Argyropoulos, 2005). The lab's relative humidity (RH) averaged at 65 degrees farenheit, 18 degrees celsius daily, however, there are periods of increased RH during the summer season. A majority of the chloride readings were heightened for several months possibly indicating continued states of corrosion caused by an attraction between Clֿ and Fe +² ions. The adsorption of Clֿ ions is also contingent on the pH of the solution. If corrosion is passivated at a high pH, the presence of Fe +² ions are decreased minimizing the attraction between the two. In acidic conditions, Clֿ ions are adsorbed into iron oxide surfaces of the object at a retarded rate because the charge on the Fe +² becomes Fe -2, repelling the Clֿ ions. (Selwyn and Argyropoulos, 2005) In these cases, the results were lower chloride readings. Because chloride test results fluctuated weekly revealing both high and low readings, questions regarding the pH of the lab's deionized water became a factor. It was found that the pH level was measured above 7.0. Furthermore, 1 percent NaOH solutions exhibited ranges between 12.0 and 18.0pH. 60 percent of the objects in desalination contained chlorides ranging 30-64 ppm weekly. Irons were removed from these solutions and placed in deionized water in an effort to deactivate any remaining chlorides. Weekly test results yielded lower chloride readings. The initial treatment proposed by lab conservators stipulated a final coating of paraloid. In order to prevent reactivation of corrosion within a microenvironment, objects in high chloride solutions did not receive an application of paraloid. The wax layers that remained on some of the irons prevented tannic acid application from being effective. About 2 percent of the last 3,000 objects remaining in treatment required additional xylene immersion at room temperature for 24, 48, and 72 hours. Most of these objects responded to the second xylene treatment and reacted positively to the tannic acid application. In other cases where the wax remained on the surfaces, tannic acid applications were again unsuccessful. It was not advisable to perform a tertiary xylene treatment due to the fragile and mineralized state of the objects.

References
Argyropoulos, V., and Selwyn L.S. (2005) ‘Removal of Chloride and Iron Ions from Archaeological Wrought Iron with Sodium Hydroxide and Ethylenediamine Solutions’, Studies in Conservation 50: 81-100. Benke, A.C., Smock, L.A., and Wright A.B. (2005). Rivers of North America. Burlington, Massachusetts: Elsevier Academic Press. Keene, Suzanne. (1984) ‘The Performance of Coatings and Consolidants used for Archaeological Iron,’ in Adhesives and Consolidants: Contributions to the Paris Congress, 1984. London: International Institute for Conservation, 104-6. "U.S. Geological Survey: Impacts of High River Flow and Tropical Storm Isabel on the Chesapeake Bay and its Watershed." U.S. Geological Survey. 06 October 2003. Web. 22 Jan. 2010. Virginia Department of Environment Quality (2003). James River Water Quality Data. Richmond, Virginia: Roger Stewart.

Gerhard Eggert and Britta Schmutzler (Eds.)

Archaeological Iron Conservation Colloquium 2010

Extended Abstracts

Archaeological Iron Conservation Colloquium 2010

State Academy of Art and Design Stuttgart 24th to 26th June 2010

Poster Session

IDENTIFICATION OF ORGANIC REMAINS ON IRON FINDS USING VARIABLE PRESSURE SCANNING ELECTRON MICROSCOPY (VP - SEM) ANDREA FISCHER1 1 Staatliche Akademie der Bildenden Künste, Am Weißenhof 1, D-70191 Stuttgart, Germany. a.fischer@abk-stuttgart.de The remains of organic material, which have been preserved in the corrosion products, can be observed on many iron finds. Recent systematic and methodical approaches have increased the understanding of the original function and use of textiles, leather and other organic materials. Identification of these materials depends on their condition and state of preservation and has greatly improved because of the introduction of the SEM in the 1980s. Using a Zeiss EVO 60, investigations at the State Academy of Art and Design in Stuttgart have revealed the potential of VP- SEM to study organic remains. Alternative applications of the microscope were tested on iron finds lifted in a block. The microscope facilitates the analysis of samples without prior preparation and the sample chamber can accommodate small archaeological finds such as fibulae, fittings or knifes. It is possible to study surface details of fragile and brittle materials which had not been recognized before. The non-destructive observations provides a more thorough insight into organic remains, showing the state of preservation of disintegrated substances and preserved morphological characteristics, thereby enabling identification of the material. It must be recorded that the capacity of the cooling stage is limited as far as both weight and size are concerned. Furthermore, using the VP - SEM accelerates the drying process and therefore the exposure time for in situ examinations of waterlogged organic remains is limited. To some extent, damp samples can be examined, because water vapour can be introduced into the chamber and the (1)highly degraded fibre, the cuticle is lost temperature of a Peltier cooling stage (2) negative cast of fibre Image: A. Fischer, SABK can be controlled. Organic remains from hydrated soil blocks were lifted in small sections and placed on the cooling stage for examination. Excellent results have been achieved, distinguishing highly degraded textile and leather remains used perhaps as belts, bags or wrappings.

THE LABORATORY PROCESSING OF BLOCK – LIFTED FINDS FROM GRAVES ANDREA FISCHER1; CHRISTINA PEEK2 Staatliche Akademie der Bildenden Künste, Am Weißenhof 1, D-70191 Stuttgart, Germany a.fischer@abk-stuttgart.de 2 Landesamt für Denkmalpflege, Berliner Str. 12, D-73728 Esslingen, Germany, christina.peek@rps.bwl.de To reconstruct and gain knowledge about early medieval clothing, archaeological research relies on the examination of the organic remains preserved in close proximity to metal burial finds. Lifting the finds at archaeological sites as a block enables the recognition and identification of all preserved information, ensuring safe excavation and careful investigative cleaning in the conservation laboratory. This „excavation en miniature” is a particular challenge to conservators and is well suited to the didactical imparting of the basic principles and skills of archaeological conservation. For this reason, practical studies in processing block-lifted finds are of significant value in the curriculum of the Objects Conservation Course at the State Academy of Art and Design Stuttgart. The cleaning of metal finds with associated organic remains is an irreversible process, determining whether information is preserved or irrecoverably lost. Only a systematic examination and treatment, including a stratigraphical excavation of all structures and layers, comprehensive documentation and the identification of the nature of organic remains, can provide optimal basic data for research. The careful documentation is of scientific importance, because most of the organic remains will be destroyed Documentation of iron finds with mineral preserved textile after the objects are taken out remains Image: K. Bott, SABK of the block. The process of drawing several plana trains one to recognise delicate and sophisticated details. Drawing details is learning to see - and learning to see is learning to understand!
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THE IRON COLLECTION OF ANCIENT MESSENE: A METHODOLOGICAL CONSERVATION APPROACH MARIA GIANNOULAKI1, VASILIKE ARGYROPOULOS1, GEORGE MICHALAKAKOS1, THEODOROS PANOU2, ANTIKLEIA MOUNDREA-AGRAFIOTI3, PETROS THEMELIS4 Department of Conservation of Antiquities & Works of Art, TEI of Athens, Ag.Spyridonos 12 210 Egaleo, Athens, Greece mgiann@teiath.gr; bessie@teiath.gr; 2 Department of Medical Radiologic Technologists, TEI of Athens, Ag.Spyridonos 12 210 Egaleo, Athens, Greece thpanou@teiath.gr 3 Department of History, Archaeology and Social Anthropology, University of Thessaly, Argonafton & Philellinon 38 221 Volos, Greece eagraf@ha.uth.gr 4 Society of Messenian Archaeological Studies, Psaromiligou 33, 10 553Athens, Greece pthemelis@hotmail.com In Greece, but also in other Mediterranean countries, in museums that house archaeological collections next to sites and/or excavation areas, iron finds of every day use may be stored for many years after excavation without proper conservation or maintenance programs. To compound this problem, wide temperature and RH fluctuations during the year create further damages to metal artifacts. Thus, the nature of these collections in terms of typology, technology and condition is unknown and it is difficult to design an effective conservation plan to preserve the collection. Furthermore, the current legislation does not easily permit the transportation of artifacts to a scientific laboratory or sampling for further diagnostic examination. Consequently, a “re-excavation” and a damage assessment of the collection should be carried out in-situ. Under the auspices of the 6th Framework funded project, PROMET, the T.E.I. of Athens has developed a systematic methodology approach based on statistics for surveying quickly the technology and condition of large metals collections prior to treatment and possibly many years from excavation, so as to identify treatment priorities. Such an approach requires also the application of diagnostic techniques in-situ, in order to identify the value and condition of each artefact and determine their treatment priority. A technology survey was performed using the variables that describe the type, such as morphological characteristics. Burt frequency tables and classification trees were produced according to the defined variables presenting the characteristic technological types of the collection. A condition survey was carried out to determine treatment priority levels using the
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prediction-answer of the question: Which objects are in urgent need of treatment, would benefit from treatment, do not require treatment? Variables affecting the condition (such as burial environment, environment and time after excavation, technological characteristics, type of corrosion products) and the ‘value’ were used. With the assistance of a statistical package SPSS12.0 (SPSS 2004), frequency tables were produced showing how all the probable values of a variable(s) are correlated in the sample. From here, Multinomial Logistic Regression was chosen to predict the answer to the question. X-ray Radiography was applied in the entire sample of 549 wrought iron objects, as it is an essential non-destructive technique for revealing hidden clues as to the methods of manufacturing, decorative detail, as well as the overall condition of the artifacts (amount of remaining metal core, presence of cracks, extent of corrosion layers). The process of the results helped to design an effective conservation program for the preservation and the protection of the collection, including management after excavation, storage and treatment and was applied experimentally on a sample of 16 wrought iron artifacts that retained the original metal core but exhibited clear signs of ‘active’ corrosion (akaganeite formation, spalling), so as to evaluate the efficiency of the application. This poster presents the overall results from the application of a systematic methodology approach for surveying the technology and the condition and from the design and application of an efficient conservation program for the iron artifacts collection of Ancient Messene. References
Argyropoulos V., M. Giannoulaki, D. Anglos, P. Pouli , MA. Harith, A. Elhassan, AG. Karydas, Ch. Zarkadas, V. Kantarelou, A. Arafat, N. Haddad (2007) ‘Developing Innovative Portable Diagnostic Techniques and Approaches for the Analysis of Metal Artefacts from Museum Collections’ in 7th European Commission Conference Safeguarded Cultural Heritage. Understanding & Viability for the Enlarged Europe, Prague, Czech Republic. Giannoulaki M., V. Argyropoulos, Th. Panou, A. Moundrea-Agrafioti and P. Themelis (2005) ‘The feasibility of using portable X-Ray radiography for the examination of the technology and the condition of a metals collection housed in the Museum of Ancient Messene, Greece’ in ART CONSERVATION-RESTORATION – STUDIES AND PRACTICE, Volume VII, VII Conference of Art Conservation-Restoration, Students and Graduates, 13-15 October 2005, Torun, Poland, 163-176.

FREEZING CORROSION – A VIABLE STORAGE OPTION? CHARLOTTE KUHN1, GERHARD EGGERT1 State Academy of Art and Design, Am Weißenhof 1, D-70191 Stuttgart, Germany charlotte@charlotte-kuhn.de; gerhard.eggert@abk-stuttgart.de Introduction Several authors assume a good corrosion stability of archaeological iron stored at deep-freeze temperatures, but systematic studies about the efficiency of this conservation method are missing. The corrosion of iron in Antarctica (e. g. Buchwald and Clarke 1989), following the same mechanisms as post excavation corrosion, raises doubts about the stability of iron artefacts under such conditions. Experimental and Results To study the process of post excavation corrosion at deep-freeze temperatures, powder samples consisting of iron and iron(II)-chloride-tetrahydrate (Watkinson and Lewis 2004) in similar weight proportions were stored at maximum -20 °C and under common working room climate as a reference. To observe the transformation of the initial powder samples, FTIR spectroscopic measurements were carried out at regular intervals. The intensity of the band at 852 cm-1, which is specific for akaganéite, can be referred to for a quantitative evaluation of the akaganéite content in each measured sample. Therefore, a calibration line was created by measuring pellets with known amounts of akaganéite (Thickett 2003). Experimental results show, that significant amounts of akaganéite can form within days under uncontrolled environmental conditions. Concerning samples stored at deep-freeze temperatures slight changes in colour as well as minimal changes in the IR spectra also indicate ongoing chemical reactions after just few days. However, corrosion reactions are significantly delayed. The deep-freeze storage of archaeological iron finds thus seems to be maintainable for short periods to minimize active corrosion, but can not be recommended as a long-term storage solution. References
Buchwald, Clarke (1989) “Corrosion of Fe-Ni alloys by Cl-containing akaganéite (β-FeOOH): The antarctic meteorite case”, American Mineralogist 74: 656-667 Watkinson, Lewis (2004) “SS Great Britain iron hull: modelling corrosion to define storage relative humidity”, Proceedings of Metal 2004, National Museum of Australia, Canberra: 88-103 Thickett (2003) “Analysis of Iron Corrosion Products with Fourier Transform Infra-red and Raman Spectroscopies”, IRUG 6, Padua: Il Prato: 86–93
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METAL 2010: ICOM-CC WG ‘METALS’ INTERIM MEETING IN CHARLESTON, SOUTH CAROLINA FROM OCT. 11-15, 2010 PAUL MARDIKIAN1 1 Clemson University Conservation Center, Warren Lasch Laboratory, School of Materials Science and Engineering, 1250 Supply Street Bldg. 255, North Charleston, SC 29405, USA. pmardik@clemson.edu

ARCHAEOLOGICAL IRON AFTER EXCAVATION (AIAE): A SUB-WORKING GROUP WITHIN THE ICOM-CC METALS WORKING GROUP ERIC NORDGREN1 Co-ordinator ICOM-CC Metals WG Sub-Working Group Archaological Iron After Excavation (AIAE); The Mariners’ Museum, 100 Museum Drive, Newport News, Virginia, USA; enordgren@marinersmuseum.org Archaeological Iron After Excavation (AIAE) is an international forum for scientists, conservators, archaeologists and other researchers interested in the investigation and conservation of iron artifacts after they have been recovered from archaeological contexts. The objectives of AIAE are: 1. 2. 3. 4. To identify research groups working on any aspects of post excavation changes and storage conditions of archaeological iron excavated from land or marine sites To compile and maintain an exhaustive and accessible bibliography of these topics To identify research areas that need to be further developed To promote research and disseminate relevant information
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AIAE was initiated in 2003 as a sub-working group of the International Council of Museums Committee for Conservation Metal Working Group (ICOM-CC Metal WG), and encourages participation by ICOM-CC Members. AIAE is a partner with the State Academy of Art and Design, Stuttgart, Germany in the 2010 Iron Conservation Colloquium in Stuttgart. For more information please contact Eric Nordgren, AIAE Sub working group co-ordinator.

CORROSION PROTECTION WITHOUT RED LEAD: A CONTRADICTION IN TERMS? MARTINA RAEDEL1, MICHAEL BÜCKER1, MARTIN SABEL1, MANDY REIMANN2, GEORG HABER2, THOMAS BALDAUF2
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BAM Federal Institute for Materials Research and Testing, Richard-Willstätter-Strasse 11, 12489 Berlin, Germany, martina.raedel@bam.de 2 Haber & Brandner GmbH, Lichtenfelserstrasse 4, 93057 Regensburg, Germany When restoring historic iron and cast-iron objects, the selection of a suitable anti-corrosive protective coating is often a key concern. A drawback of most modern anti-corrosion systems is that they have been developed for use in industrial applications. As a consequence, these systems have a monochrome appearance, and short drying times often do not allow for the artistic embellishment of the object’s surface. Another challenge posed by the conservation of historic objects is that the surface to be treated typically displays a residual level of rust (according to ISO surface preparation standard St 2). The corrosion protectant frequently used in the past, red lead, is an environmental and health hazard. A two-year research project, titled Korrosionsschutz in der Denkmalpflege (“Corrosion protection in the preservation of historic monuments”), funded by the German Federation of Industrial Research Associations (AiF), aims to contribute to the investigation, evaluation and modification of modern anti-corrosion systems for historic iron and cast-iron objects. Together with the metal conservation workshop Haber & Brander, BAM will evaluate the performance of modern anti-corrosion systems in comparison with red lead. A key aim is to adapt commercial anti-corrosion systems to the requirements associated with the conservation of historic objects. At the start of the project, a comparative study of red lead and modern anti-corrosion systems will be performed. Numerous sample materials will be tested: new and artificially corroded low-alloy steel; historic cast and wrought iron; as well as materials already treated with red lead or featuring other residual coatings. After applying various commercially available anticorrosion systems, the samples will be subjected to an accelerated aging process in a controlled-humidity atmosphere, under exposure to UV light and, as the case may be, corrosive gasses. Using a range of optical and physical methods, the researchers hope to evaluate the performance of the various anti-corrosion systems. The adaptation of the anticorrosion substances as well as the preparation of advisory guidelines for conservation practice are two additional goals of the project.