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Plate 36 Photomicrographs of two samples of different types of haematite (all in Meltmount of RI 1.662, original magnification 128×). (a): Micaceous haematite from El Brujo, an important Moche site, Peru, viewed under plane-polarized light; (b): same as A viewed under crossed polars; (c): kidney haematite from the British Museum (Natural History) viewed under plane-polarized light; (d): same as (c) viewed under partially crossed polars (photomicrographs: D.A. Scott).

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Plate 37 Photomicrographs of two samples of ochre from the Forbes pigment collection (all in Meltmount of RI 1.662, original magnification 128×). (a): Ochre, Forbes 3.04.12, viewed under plane-polarized light; (b): same as (a) viewed under crossed polars; (c): ochre, Forbes 3.04.11, viewed under plane-polarized light; (d): same as (c) viewed under partially crossed polars (photomicrographs: D.A. Scott).

Plate 38 Iron spalled fragment with akaganéite corrosion.

Plate 39 Deliquescent ‘weeping’ iron with pustules of ferrous chloride, ferric chloride and akaganéite.

Plate 40 Akaganéite on the surface corrosion of a 10th-century iron clench nail from the site of Mosfell, Iceland (photomicrograph: D.A. Scott).

Plate 41 A heavily corroded iron object, disintegrating under ambient conditions.

Plate 42 A view of the akaganéite crystal lattice showing chloride ions trapped in a central tunnel (courtesy of G. Chiari).

Plate 43 Metavoltine growing from pyrite decomposition on waterlogged wood from Los Buchillones, Cuba (ESEM photomicrograph: courtesy of David Carson, Getty Conservation Institute).

Plate 44 Voltine growing from pyrite decomposition on waterlogged wood from Los Bucelliones, Cuba (ESEM photomicrograph: courtesy of David Carson, Getty Conservation Institute).

Plate 45 Roman iron band from Eschenz, Switzerland (excavated by Amt für Archäologie des Kantons Thurgau, www.archaeologie.tg.ch) showing bright blue vivianite (photograph: K. Wüst, Liechtenstein).

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Plate 46 Photomicrographs of samples of different green iron-containing pigments (all in Meltmount of RI 1.662, original magnification 128×). (a): Terra verte from Verona, viewed under plane-polarized light; (b): same as (a) viewed under crossed polars; (c): terra verte from Verona, sample 2, viewed under planepolarized light; (d): same as (c) viewed under crossed polars; (e) Nakbe green earth from Guatemala viewed under plane-polarized light; (f ): same as (e) viewed under crossed polars (photomicrographs: D.A. Scott).

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Plate 47 Photomicrographs of samples of terre verte (all in Meltmount of RI 1.662, original magnification 128×). (a): Terra verde naturale (Italy), viewed under plane-polarized light; (b) same as (a) viewed under crossed polars; (c): terra verde from the Forbes pigment collection, burnt sienna from the Kremer pigment collection, viewed under plane-polarized light; (d): same as (c) viewed under partially crossed polars; (e): Nakbe green earth from Guatemala viewed under plane-polarized light: (f ): same as (e) viewed under crossed polars (photomicrographs: D.A. Scott).

Plate 48 Egyptian cartonnage fragment from the collections of the University of Southern California, Department of Religion. The green earth is the pale green background to the Sphinx (photograph: D.A. Scott).

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Plate 49 (a): Plane-polarized light view of aerinite pigment dispersion in Meltmount of RI 1.662 (original magnification 150×). The aerinite crystals appear as pleochroic laths, well crystallized with clearly defined edges and fractures. The refractive index, which is higher than 1.662, shows the particles in clear relief. (b): Cross-polarized view of the aerinite pigment dispersion shown in (a) (original magnification 150×). The birefringence of the crystalline laths is high, with high order blues, reds and yellows evident in this preparation. Based on this sample of aerinite, its polarized light characteristics should help considerably with its identification, as it is quite distinctive optically (photomicrographs: D.A. Scott).

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Plate 50 Cyanotype made from an X-radiograph of Rearing Horse (c.1610–15) by Adriaen de Vries, Dutch (1545–1626), h. 48.9 cm (86.SB.488). Original X-ray taken at 280 kV, 6mA, 200 sec; cyanotype image formed by iron(III) hexacyanoferrate(II) (Fe4[Fe(CN)6]3.14H2O) on Fabriano Artistico cold-pressed paper 280 gsm, gelatin sized (original bronze statue, J. Paul Getty Museum, Malibu).

Plate 51 Iron tripod (ding) showing pseudomorphic preservation of the steadite ternary iron-carbon-phosphorus phase in a Chinese cast iron from Gansu province (original magnification 180×). The holes in the steadite pseudomorph are now occupied with iron oxides, but originally these would have been pearlitic consisting of finely dispersed ferrite and cementite (photomicrograph: D.A. Scott).

Plate 53 View of the fine layering in the stratified iron oxide corrosion crust shown in Plate 52 (original magnification 480×) (photomicrograph: D.A. Scott).

Plate 52 View of branched iron oxides and precipitation within a field of iron oxide corrosion from a corroded iron artefact from the Icelandic site of Mosfell dating to the 10th century AD (original magnification 280×). These branched structures are very similar to fractal morphologies (photomicrograph: D.A. Scott).

Plate 55 Iron oxide columnar growth forms (original magnification 40×) developing with the corrosion layers of an iron artefact in the collections of the Royal Ontario Museum, Ontario, Canada (photomicrograph courtesy of S. Stock, Royal Ontario Museum, Object ROM 987.276.12).

Plate 54 View of the layered iron oxide corrosion products on the corroded iron artefact shown in Plate 52; this layered structure forms part of the same microstructural field (original magnification 500×). Small perturbations in the conditions of the corrosion events lead to very different morphologies in the same area of the corrosion crust (photomicrograph: D.A. Scott).

Plate 56 Rusticles growing from the corroded surface of the hull of RMS Titanic. These rusticles, of complex microbiological consortia, are slowly eating the iron of the hull of this famous shipwreck (after Cullimore et al. 2002).

Plate 57 Rusticles that have broken away from the hull of the Titanic and are forming a mass of microbial debris on the sea floor. This debris eventually becomes dispersed, so that the iron from the ship eventually becomes part of the food chain as the material disperses across the ocean. Eventually consumed by fish, we are, in a manner of speaking, slowly eating the Titanic!

Plate 58 Chinese white cast iron rhinoceros in the village of Tieniu, 2 km northeast of Kaifeng, Henan, dated to AD 1446 (photograph courtesy of D. Wagner, Department of Asian Studies, University of Copenhagen, Denmark).

Plate 59 Chinese cast iron pagoda, the ‘Eastern Iron Pagoda’ of the Guangxiao Temple in Guangzhou (Canton) Guangdong, cast in AD 967 and now protected by a building from external exposure to the elements (photograph courtesy of D. Wagner, Department of Asian Studies, University of Copenhagen, Denmark).

Plate 60 Eiffel Tower, made of wrought iron beams (photograph: Tony Northrup © licensed for business use and reproduction by www. northrup.org).

Plate 61 An early 18th-century 33-pound cast iron cannonball found in the mouth of Portsmouth Harbour (England) and allowed to dry without any conservation

Plate 62 Conservator cleaning iron with air-abrasive powders. In this photograph glass beads are being used at a pressure of 35 psi to clean the corrosion crust and soil minerals from the surface (photograph: D.A. Scott).

Plate 63 Iron horseshoe before plasma reduction (photograph: K. Schmidt -Ott).

Plate 64 Iron horseshoe after plasma reduction (photograph: K. Schmidt-Ott 2000).

Plate 65 Iron in container with silica gel to keep the RH below 45%. However, such controlled storage may not be enough to keep unstable iron objects from further deterioration (photograph: D.A. Scott).

Plate 66 Iron railings from Waterlow Park, Highgate, London. The photographs show the gradual deterioration to which these painted surfaces are liable. The primer used in the past, a red lead-containing oil based primer finished with 2–3 coats of a carbon black oil paint, provides good corrosion protection when covered with another three layers of paint every so often, but renewed maintenance is essential once the corrosion penetrates through these layers, which start to delaminate. Both top and bottom views show part of the delamination from the same iron railing (photograph courtesy of V.A. Scott).

Plate 67 Iron railings from Hyde Park, London. Newly cleaned and primed with a red-lead or red-lead substitute paint (photograph courtesy of V.A. Scott).

8 Iron carboxylates and cyanides

Compounds of iron with carboxylic acids, such as tannates and gallates, have long been used as inks or stains for paper, barkcloth and leather. The use of iron citrates and oxalates formed a very important part of several early photographic processes, while the cyanides, or rather ferri- and ferrocyanides, achieved prominence as the pigment group known as Prussian blue. Table 8.1 lists some of these compounds, together with the circumstance of their occurrence. There is a rare iron(II) oxalate mineral, humboldtine (Fe2+(–OOC-COO–)∙2H2O), which is related to the calcium oxalate minerals, whewellite and wedellite, better known from their occurrence as the scialbatura on imperial Roman marbles (Monte and Sabbioni 1987), and which are in fact quite widespread. Humboldtine occurs as soft prismatic crystals or as crusts and aggregates with a dull or resinous lustre. First reported by Rivero in 1821 from Kolosuruk in Czechoslovakia, it is also found in Cornwall (England), Bavaria (Germany) and Durango (Mexico) (Eastaugh et al. 2004: 186). Although no examples of its use as a pigment are known, Salter (1869) describes the pigment iron yellow as an ‘oxalate of protoxide of iron’. The Merck Index (2001) gives its use as a ‘pigment for plastics, paints, lacquers’ without further reference. The iron acetates are formed as a result of the immersion of fragments of old iron or rusted scraps in vinegar for long periods of time. The reaction creates dark brown solutions containing iron acetates, which can also be used for staining cloth or wood, or for creating artificial patinas on iron artefacts, and was still in use in 1992 for historic wood restoration and staining projects at the Tokyo National University of Fine Arts in 1992.1 Many historical recipes for the application of iron acetates, especially on wood, often used in combination with other dyes, have been collected by Michaelsen and Buchholz (2006). The structure of these iron acetates may be quite complex; for example Cheng and Reiff (1977) found that the structure of anhydrous ferrous acetate involved a six-coordinate iron(II) atom in non-equivalent positions in the lattice, which was weakly antiferromagnetic. Alcala and Garcia (1973) also worked on the identification of the structure of iron acetate, which showed a complex coordinate crystal structure.
1 Seen during a visit by David A. Scott.

Iron complexes with tannic acids or gallic acids, prominent constituents of plant galls, create brown or black complex iron gallates or tannates, which have been used for black ink (Reiβland and Stijnman 2002) or dye preparation since ancient Mesopotamian times – knowledge of tannins was widespread in ancient Mesopotamia. Often, after soaking in a tannin solution, cotton was run through a solution of a metallic salt such as aluminium or iron sulphate (Levey 1959: 111). An 11th-century Arabic text written by Ibn Badis (Levey 1959: 76), records interesting practical details concerning one such dye recipe: You take a vessel glazed outside and inside. You take nail heads cleaned of rust and put them in the vessel. Fill it with vinegar and leave it two or three days. If pomegranate rind is put into it, it is better. If this is done, take a small stick with a piece of wool or felt wrapped tightly about it, and dip it into (the solution) and dye with it. Take care not to touch your hand or it will get black. If it does (become black), then dip it (your hand) in lemon juice to remove it ... If you want to make it blacker (the dye) then you would have to use yellow myrobalan juice or pomegranate juice obtained by dipping it in water until its color comes out. Immerse it (the leather) in the solution until its color deepens. For the dyeing of wool, the process was almost always carried out on the yarn or the thread. In an Assyrian ritual text, black oxide of iron (magnetite) is put on to make a black thread, a red substance on a red thread and an iron salt on a blue thread. Cassia bark, well known to the Sumerians, contains much tannic acid and when mixed with iron sulphate gives a black-green dye. Another black plant dye from Xanthium atrumarium L., mentioned in Assyrian texts and at present growing near Basra (Levey 1959: 104) produces a gall-like substance. In the same category is the sumach plant which, with ferrous sulphate, produces a black colour on cotton or wool. The iron tannates have found use both as inks and as a conservation treatment for iron objects, where the layer of iron tannates that forms upon treatment with tannic acid is thought 87

Iron and Steel in Ar t
Table 8.1 Some iron carboxylates and cyanides. Name Prussian blue Prussian blue1 potassium ferricyanide potassium ferrocyanide ferric ammonium citrate ferric tannate ferrous acetate ferric acetate, basic ferrous citrate ferrous d-tartrate
1 2

Formula Fe4[Fe(CN)6]3.14H2O Fe4[Fe(CN)6]3.3H2O K3Fe(CN)6 K4Fe(CN)6.3H2O
2

Crystal system cubic cubic monoclinic monoclinic not known amorphous monoclinic not known rhombohedral not known

Colour deep blue deep blue red red-yellow green blue-black light green brown-red white white

Occurrences synthetic pigment synthetic pigment early photography early photography early photography patination processes patination processes patination processes cleaning solutions cleaning solutions

5Fe(Hcit)2(NH4)3(Hclt).NH4(H3cit).2H2O FeC76H46O46 Fe(CH3COO)2.4H2O Fe(OH)(CH3COO)2 Fe[CH2COO. C(OH)COOCH2COOH] Fe[CH(OH)COOCH(OH)COO]

Other variants include ammonium ferric ferrocyanide (NH4)2Fe[Fe(CN)6].xH2O as commercially important pigments. All of these are isotropic. Formula appears unknown: differences exist between the ‘green’ version and the ‘brown’ version. The formula given follows Ware (1999: 157).

to provide some corrosion protection to the iron object. Iron tannates were shown to occur naturally in a buried waterlogged deposit on Roman iron artefacts from the site of Hungate, York, by Farrer et al. (1953), who showed by experimental work that the bacterial activity of Desulphovibrio desulphuricans could be inhibited by iron tannate extract or solutions. In no case was growth of the organism found if concentrations of tannic acid 0.01% or greater were present. This work has been much referred to since its publication, but appears not to have been superseded in an archaeological context. The interaction of iron with tannic acid was investigated by Iglesias et al. (2001) who determined by Mössbauer spectroscopy that the reaction between iron and tannic acid produces two types of iron tannate complexes, but the implications and further characterization of the complexes were not explored in this paper, and further research into the structure and long-term stability of these tannates is required. Tannic acid has become increasingly popular as a corrosion inhibitor or rust converter for use on archaeological ironwork in the UK and in other parts of Europe, although it is hard to assess the success of this treatment. Its counterpart is gallic acid, which has been used for the same purpose. Apart from the work published by Hawley (1996), tannic acid and gallic acid treatments are mostly known from their use on decorative iron objects, although the application of tannic acid as a surface treatment for excavated iron objects in the UK appears quite widespread. Wunderlich (1994) argued that the layer formed between iron and gallic acid was essentially the same complexes of iron(III) with gallic or tannic acid as those found in iron gallate inks. The crystalline structure of iron(III) gallate was determined by Wunderlich et al. (1991). The complexes have a porous structure, are light sensitive, and possess insufficient corrosion resistance. The deep black colour of the complexes prevents visual control of further corrosion and the critical opinion of Wunderlich (1994) is that treatment with tannic acid is a coloristic ‘placebo’ treatment rather than a truly effective conservation measure. This agrees with the assessment of Seeley,2 who recounted observations made on synthetically prepared iron tannate that was finely crystalline, but after several years in storage under benign conditions had polymerized and was clearly unsuitable as an effective conservation treatment for exposed artefacts. It does nothing to stabilize chloride ions nor is it effective in sealing the surface of a heavily rusted object but it may be useful
2 N.J. Seeley, pers. comm. to D.A. Scott, 6 June 1986.

for historic iron objects with coherent oxide surfaces that need to be protected. Matamala et al. (1990), for example, report on the protection of structural steel utilizing tannin extracted from pine tree bark. This rust converter was compared with commercial treatments and with sandblasting. Tests carried out in a salt fog chamber and in acid industrial atmospheres showed that treatment with pine tannin was the most effective. The use of tannins as rust converters has been known for a long time. When a rust converter solution is applied to rusted surfaces, a reaction takes place which is characterized by a blue-black coloration. The reaction has been attributed to the formation of polyphenolic iron complexes in which the formation of magnetite occurs over time by reduction of the ferritannates that are formed. There are many commercial patents for rust converters that make use of tannins. The rust formed on the structural steel samples in an industrial atmosphere used by Matamala et al. (1990) was shown to consist principally of lepidocrocite. The rust layer was relatively uniform and about 60 µm thick, exhibiting small cracks and larger cracks across the rust layer. The pine tannin rust converter was found to react with lepidocrocite, transforming it into an amorphous product, enhancing the corrosion resistance of the treated surface. The results obtained with rust converters are varied. For example, Galván et al. (1992) treated rusted steel with tannic, gallic and phosphoric acid solutions and found that their ability to block the corrosion was quite poor, with some iron being dissolved away.

Iron gall inks
To make common yncke of Wyne take a quart, Two ounces of gomme, let that be a parte, Five ounces of galles, of copres take three, Long standing dooth make it better to be, If wyne ye do want, rayne water is best, And as much stuffe as above at the least: If yncke be to thick, put vinegar in, For water dooth make the colour more dimme (du Beau Chesne and Baildon, A Book Containing Divers Sorts of Hands, 1571; Karnes 2007).

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Iron carboxylate s and cyanide s This recipe from an old English book was replicated by taking 120 ml of cheap white wine, 14 g solid gum arabic dissolved in the wine, 35 g powdered galls3 and 21 g ferrous sulphate, which created a good blue-black ink. There is, in fact, a plethora of recipes for this kind of ink which illustrates how often ancient recipes were recorded if they were well known and extensively used, as iron gall inks were in the Middle Ages. In fact, iron gall inks were already in extensive use by the Roman period, and remained popular until the later Middle Ages. The origins of inks of this type can be traced back to the 3rd millennium BC in China and Egypt. In the 2nd century BC, Philon of Byzantium records a recipe for an invisible ink written in oak gall extract, which could then be made to appear when the letter was brushed with an iron salt solution. Pliny mentions the same reaction as an indicator for iron salt impurities in alum.4 The ancient Egyptians used both carbon black ink and haematite-based inks during the Pharaonic period, with the first evidence for the use of an iron gall type of ink occurring on Greek texts in the collection of the Louvre dating from 252 to 98 BC (Delange et al. 1990). It seems as if the use of an iron-containing ink was connected with the type of writing implement chosen by the scribe, as the Greek texts in iron gall ink were written with a reed pen, while the demotic texts of the same date were written in carbon ink with a rush pen. Leach and Tate (2000) note that the analytical results showed more copper than iron in the ink and no sulphur content. Ménei (1990) speculated that perhaps copper and iron carbonates were used instead of sulphates for making the metallic ink, or that sulphur was incorporated into a gas or liquid component which over time had disappeared. However, it is interesting to note that according to Leach and Tate (2000) examples of papyrus scrolls written in iron-containing inks in the Chester Beatty collection in the British Museum (London) did not show the expected deterioration of the substrate, which is usually associated with iron gall inks on later parchment and paper, as the organic material is degraded by the ink. The speculations of Ménei are not easy to verify and it could also be suggested that acetates or other organometallic salts of iron and copper were mixed with gall extract, which may be as equally practicable in terms of making a useable ink. Seeley5 points out that papyrus presumably still contains a substantial lignin component that may be protective even when degraded due to the phenolic complexes present in lignin. The oxidative degradation of cellulose by a variety of metallic ions is a common problem in the long-term stability of the substrate and many of these inks with metallic ion components have initiated this kind of degradation (Blattner and Ferrier 1985). The Babylonian text, translated by Levey (1959) referred to above, for example, might be used to produce an ink without recourse to an iron sulphate starting material. Further research on this interesting topic is required in order to pursue the matter.
3 4 From Kremer Pigments. The use of iron compounds as spot test reagents is still useful. Poulsen (2002) discusses the use of a ferric spot test for detecting the presence of vegetable tannins in leather. This test is based on the reaction between phenolic-based vegetable tannins and iron salts, which form black or grey reaction products. For the test, two samples of leather fibres are removed, placed on a glass slide, covered with a drop of water and then a cover glass. A drop of a 2% w/v solution of aqueous ferric chloride is applied to the edge of the cover glass and a piece of filter paper applied to the opposite side ensures that the ferric solution is drawn into the sample. A dark coloration of the fibres indicates the presence of vegetable tannins. 5 N. J. Seeley, pers. comm. to D.A. Scott, 27th May 2002.

Around the 7th century AD either the Jews or the Moors introduced the ink to central Europe, and by the time that the German monk, Theophilus, was writing in the 12th century, the procedures were already well known: To make ink, cut for yourself some wood of the hawthorn – in April or May before they produce blossom or leaves – collect them together in small bundles and allow them to lie in the shade for two, three or four weeks until they are fairly well dried out. Then have some wooden mallets, and with them pound these thorns on a hard piece of wood until you can completely peel off the bark, which you immediately put into a barrel full of water. When you have filled two, three, four or five barrels with bark and water, allow them to stand like this for eight days until the water has drawn off all the sap of the bark. Then put this water into a very clean pot or into a cauldron, place it on the fire and heat it. From time to time, put some of this bark into the pot so that, if there is any sap left in it, it can be boiled out, and when you have heated it for a little, take it out and put in some more. This done, boil down what remains of the water to a third, pour it from this pot into a smaller one and continue to heat it until it becomes black and begins to thicken, taking particular care that you do not add any water except that which was mixed with the sap. When you see it become thick, add a third part of pure wine, put it in two or three new pots and continue to heat it until you see that it develops a kind of skin at the top. Then lift these pots off the fire and put them in the sun until the black ink resolves itself from the red dregs. Afterwards, take some small, carefully sewn, parchment bags like bladders, pour the pure ink into them and hang them up in the sun until it is completely dried. When it is dried, take from it as much as you want, mix it with wine over a fire, add a little iron vitriol and write. If, as a result of carelessness, the ink is not black enough, take a piece of iron, an inch thick, put it on the fire until it is red hot and then throw it into the ink (Theophilus, On divers arts XXXVIII: 34–5 [Dodwell 1961]). There are many references to historical recipes for the preparation of iron gall inks, most of which are variants on the same theme. For example, a quotation from the anonymous English ‘Booke of Secrets’ (1596) states: Take halfe a pint of water, a pint wanting a quarter of wine, and as much vineger, which being mixed together make a quart and a quarter of a pint more, then take six ounces of gauls beaten into small pouder, and sifted through a sive, put this pouder into a pot by it selfe, and poure halfe the water, wine, and vineger into it, take likewise foure ounces of vietriall, and beat it into pouder, and put it also in a pot by it selfe, whereinto put a quarter of the wine, water, and vineger that remaineth, and to the other quarter, put foure ounces of gum Arabike beaten to pouder, that done, cover the three pots close, and let them stand three or foure daies together, stirring them every day three or foure times, on the first day set the pot with gaules on the fire, and when it begins to seeth, stir it about till it be thoroughly warme, then straine it through a cloath into another pot, and mixe it with the other two pots, stirring them well together, and being covered, then let it stand three daies, till thou meanest 89

Iron and Steel in Ar t to use it, on the fourth day, when it is setled, poure it out, and it wil be good inke. If there remaine any dregs behind, poure some raine water that hath stand long in a tub or vessell into it, for the older the water is, the better it is, and keepe that untill you make more inke, so it is better than clean water. Another typical recipe from the oldest surviving German language manuscript on painting techniques, dating from the 15th century and known as the Strasburg manuscript (Borradaile and Borradaile 1982: 40) states: If you want black ink for writing letters, take two parts oak apples, one part vitriol of iron and the fourth part gum Arabic. If you wish the ink to be exceptionally black, add one fifth part more vitriol. All these must be ground up fine into powder and this must be put in a cooking pot with some lourinden water and it must not be allowed to boil over. Add to it a small glass of vinegar and take the ink from the fire and stir it until it is cold, for if you let a skin form on it, it will be no good. Note that if the foregoing materials mount up to one pound, a quarter of a pint of lourinden water will be sufficient, but if to only half a pound, less in proportion. If you want to make the ink from oak apples, take as much of the cores (or kernels) as would equal two hens eggs and half mos of wine and a zekel of parchment clippings and boil them up in a glazed pot till well dissolved, then take the size of a walnut of atramentum and heat this over the fire, crush it in a bowl and throw it into the ink and stir it together, taking care that it cooks slowly and does not boil over. When it is cooked enough, go on stirring it until it is cold and it will be good for painting. Iron gall inks continued to be used for ink drawings for several centuries and were employed, for example, by Rembrandt and van Gogh (Feber et al. 2000). The use of these inks frequently causes serious instability problems as the ink slowly rots the paper, often resulting in loss of the lettering altogether (Banik 1997, 2002). This problem has been the subject of several studies in order to try to account for the deterioration and to understand the chemical processes that are at work. Historical iron gall inks are made of iron(II) sulphate, mixed with gallnut extract. These extracts contain gallotannins which form a complex with iron(III) compounds, produced by oxidation, making an ink of a dark brown or black colour, often mixed with gum arabic for application as an ink. Chemically, the ratio of ferrous ions to gallic acid (3,4,5-trihydroxybenzoic acid) should be 1:1 to make a stable ink, but examination of many historical ink recipes reveals that most contain a surplus of ferrous sulphate. By mixing the solutions, a non-coloured water-soluble iron(II)-gallic acid complex forms initially, as shown in Figure 8.1. In the air, this complex is oxidized to form a blue-black Fe(III) complex which is insoluble in water. In this reaction, sulphuric acid is formed (Krekel 1999), which causes the pH of the freshly prepared ink to fall to 1.5–3.0. The chemical structure of these inks has been investigated by Wunderlich et al. (1991), who determined a zeolite, macromolecular 1:1 complex as present by direct reaction of ferric ions with gallic acid in a gel matrix. However, Krekel (1999) maintains that these compounds are not formed if the ink is prepared according to historical recipes. His explanation for 90

Figure 8.1 Iron(III) gallate molecular structure (after Wunderlich et al. 1991).: the darker cluster at each node contains the iron atoms and the gallate groups surround them.

this difference is that small amounts of ferric ions act as a catalyst and take part in a free radical reaction with the carboxylic acid group in the gallic acid. Since most of the historical recipes result in ferrous or ferric sulphate occurring as an impurity in the range of 2–10%, most of the gallic acid is transformed to pyrogallin in the ink. The principal colorant is therefore a 1:1 Fe(III)-pyrogallin complex which is also black and insoluble in water. If the ink recipe calls for iron that is in the III valency state instead of II, a brown ink is formed, and not black. The reason for this is that ferric ions can act as powerful oxidizing agents and they can interact with gallic acid to form a variety of products which have not yet been completely characterized. According to Flieder (1981), these products are purpurogallin and ellagic acid see also Reiβland and Stijnman 2002. Krekel (1999) therefore maintains that black inks are primarily the result of using gallic acids with ferrous ions while with high concentrations of ferric iron, the primary ink colour is brown. Brown inks would also tend to form if ingredients in the recipes result in lowering of the pH, which alum, copper sulphate and vinegar will do, and all of these occur in historical recipes. Some of these effects are dependent on the source of the iron salts used to make the inks, which could contain a variety of other cations such as copper, zinc, potassium, aluminium or manganese. The most common sources were referred to as vitriolum commune or vitriolum goslariensis, originating in mines close to Goslar in the Harz Mountains in Germany. Investigations by Krekel (1999) of ink from manuscripts in the library of the Hildesheim monastery revealed substantial amounts of zinc, suggesting that the less pure vitriolum goslariensis was used as the iron salt. Some authors have even suggested that copper salts may be an important component of these inks, but this is not likely as, when pure copper sulphate is mixed with gallic acid, the complexes are brown and water-soluble. Historic recipes call for a wide range of starting materials: oakgall, oakbark, pomegranate skins, sumach, crushed peachstones,

Iron carboxylate s and cyanide s etc. These different ingredients may have variable tannic and gallic components. Tannic acid is a mixture of different compounds, often with gallic acid and glucose, e.g. pentadigalloylglucose. Moulds such as Aspergillus niger v. Tieghem utilize enzymes to split the tannic acid into gallic acid and glucose, which explains the efficacy of leaving the aqueous extract in a warm environment for a few days. The colour of the ink on many manuscripts is brown rather than black, but this discoloration cannot be related to the age or condition of the documents themselves. Purpurogallin and ellagic acid can be formed even if the correct ratio of iron to gallic acid was used in the recipe. Since these compounds are somewhat soluble this may explain the bleeding of some deteriorated inks. The complete range of deterioration effects seen in iron gall inks remains a chemical puzzle. One possibility put forward by Krekel (1999) is that there is a light-induced charge-transfer process occurring in which one electron is transferred from gallic acid to Fe(III) with the result that the iron is reduced to Fe(II) and the gallic acid is oxidized. If protons are then available during this transfer due to the presence of acidic media, the bond between the gallic acid and iron(III) can be broken irreversibly, forming 1-2 benzoquinone – the starting point for the purpurogallin components. If the manuscript on which the ink is written is well sized, then reaction can occur between calcium carbonate and sulphate ions in the ink to form gypsum, which may maintain the pH of the immediate substrate above 5, and therefore preserve the ink as a good black colour. However, if the pH is too high, in the vicinity of 8, the black complex can be attacked and phenols such as pyrogallin can then be oxidized by the iron content. This consideration should be taken into account when treating documents with ink of this kind, since many conservation methods employ solutions of high pH, which could be very damaging to the iron gall ink. The deterioration effects of iron gall inks is most severe with rag paper, followed by cellulose paper, papers containing wood and finally parchment. The vagaries of the deterioration process have spurred a number of investigations, some of which are more productive than others. For example, Garcia-Guinea et al. (2000) drew attention to the origin of the iron sulphates used in some recipes from iron pyrites. The pyrites are left to soak in water in the open air, and the authors maintain that bacteria such as Thiobacillus ferrooxidans can then assist with the breakdown of the pyrites into melanterite, rozenite or szomolnokite. Their laboratory experiments on synthetic iron gall inks, from 15 to 30 °C, showed that the rate of transition of the ferrous sulphate heptahydrate to ferrous sulphate tetrahydrate is strongly temperature-dependent. However, the extent to which this transition is relevant to the decomposition of actual ink samples remains to be demonstrated. In any event, Neevel (1995) examined more than 100 samples of inks from the 15th to the 19th century and found that most contained more ferrous ions than those needed to form the ink. The surplus of ferrous ions is therefore not completely oxidized and will be present in the paper even after many centuries. Feber et al. (2000) carried out a series of experiments to investigate the effects of these different components on the accelerated ageing of bleached sulphite paper. The authors conclude that the effects of deterioration of ferrous ions can be mitigated to some degree by the tannic acid and gum arabic, helping to slow the process of deterioration to some extent. An interesting study, more concerned with paper degradation than the ink itself, was carried out by Sistach et al. (1999), who made up two groups of inks, one with ferrous ion alone, the other incorporating some ferric ion as well, the other ingredients being gallic acid and gum arabic powder. These authors postulated a chemical reaction between the iron gallic acid complex and the cellulose of the paper support, producing a peroxide-activated compound which loses water and is transformed into a quinone-like structure, capable of abstracting hydrogen ions from cellulose, producing radicals that finally become oxidized cellulose-containing chromophoric carbonyl groups. They suggested that this deterioration may be an example of a Fenton-Hamilton reaction. An alternative hypothesis is related to the observed colour changes of the gallotannates which may involve aerial auto-oxidation. This hypothesis states that radicals formed by auto-oxidation can be captured by polyphenolic compounds such as gallic acid, which is oxidized to compounds of quinonoid type. Quinones formed by oxidation, when irradiated by light, are converted into oxygenated diradicals able to absorb hydrogen from the substrate. The reaction of oxygen and semiquinone radicals and alcoholic groups leads to the formation of hydrogen peroxide, which is also in accordance with a Fenton-type reaction. The authors therefore explained the deterioration of the cellulose substrate by the autooxidation reactions involving hydrogen peroxide in the presence of ferrous ions. Fenton’s reagent produces highly reactive hydroxyl radicals that oxidize the hydroxyl groups of the cellulose and of gum arabic, converting the latter into carbonyl groups. The hydroxyl radicals attack cellulose in a non-selective manner, making the following different types of cleavage possible: • • • • Hydrolytic cleavage of carbon C1, with subsequent oxidation of the remaining aldehyde group to carboxyl, producing gluconic acids. Hydrolytic cleavage at carbon C4, producing glucoside fragments. Oxidation of the carbons, C2 and C3, producing keto groups. Oxidation of C6 to give aldehyde groups and then glucuronic acids.

Sistach et al. (1999) also state that since arabinose units oxidize more readily than glucose, inks containing gum arabic, which contains arabinose, always become darker than those prepared without it. This may help to stabilize the ink to some extent by acting as an oxidation sink. Seeley6 believes that several processes are involved in the degradation, both separately and in combination, and he suggests that acid hydrolysis is the most probable cause due to free sulphuric acid, either from the ink itself, as a result of oxidation, or from the hydrolysis of alum added to the paper in the sizing process. Seeley is of the opinion that energy considerations probably rule out some of the peroxy reactions that have been proposed, but that it would not be surprising if some rather exotic iron complexes were occasionally present in the ink, and that under the right conditions these may be able to locally solubilise the cellulose (cf. cuprammonium: copper compounds dissolved in ammoniacal solution form a soluble cuprammonium complex which can be used to dissolve cellulose) and thus break down the fibres. There actually seems to be some evidence that inks containing traces of copper are more pernicious in this respect.

6 N.J. Seeley, pes. comm. to D.A. Scott, 27 May 2002.

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Conservation issues
A variety of conservation options for treatment is discussed by van Gulik and Kersten-Pampiglione (1994). Cellulose phosphate (fibrous ionite) has been used to absorb iron compounds and is added to the water during the leaf-casting process. Another treatment used is aqueous washing followed by deacidification with a calcium or magnesium compound; in cases where aqueous washing is not possible, a non-aqueous deacidification treatment has been used. However, most deacidification treatments have a bleaching effect on the ink. Various other processes have been tried including treatment with ammonium caseinate, which binds to the ink and the paper; this has given good results in some cases. Work by Liénardy and Van Damme (1991) on deacidification treatment using calcium hydroxide, barium hydroxide or magnesium bicarbonate confirmed the scientific conclusion of Krekel (1999) since the treatments, all with high pH, turned the inks from black to brown. Although not advisable for use on paper containing lignin, Liénardy found that borax treatment gave a good compromise between pH of the ink and colour retention. For these reasons many conservators will not treat iron gall ink with immersion techniques. For example, McAusland (in van Gulik and Kersten-Pampiglione 1994, who provide a survey of different techniques currently employed by conservators for treatment) only carried out local repairs with Tengujo paper or lens tissue with Klucel G in alcohol, often with calcium carbonate addition. Repairs were made with very dry starch paste and Japanese paper. Neevel (1995) was the first to look into the ability of phytates to form insoluble complexes with Fe2+ thus blocking its catalytic activity for the oxidation of cellulose. In 2002, Neevel recommended the use of an aqueous solution of calcium ammonium phytate followed by deacidification with aqueous calcium bicarbonate as most effective in arresting the ink corrosion process, provided that the phytate content is sufficient to complex all iron outside the ink complex. This method is certainly worth further assessment. Snow and Zammit (1987) describe the use of a simple chemical test for the identification of iron gall inks. The usual microchemical test based on potassium ferrocyanide or potassium thiocyanate can only detect the presence of ferric iron, not ferrous. The authors suggest that a better method is to use a 2% w/v solution of 2,2’bipyridyl in ethanol, specific for ferrous ions. This test apparently responds also to ferrigallate inks; Fe2+ must be formed by electron transfer from the ligand. This test should work also on severely faded inks most in need of restoration.

The first written reference to Prussian blue occurs in an anonymous paper in Latin published in 1710; its first synthesis is surprisingly obscure and is credited to the German pigment-maker, Diesbach. By 1724, knowledge of the pigment’s preparation had spread to England (Woodward 1724), and different methods for its preparation were soon developed. The traditional method of manufacture was quite alchemical in nature and involved heating equal amounts of potassium nitrate and potassium tartrate to red heat, followed by the addition of powdered blood of cattle, which was then heated strongly. The resulting mass was washed with water and the aqueous extract treated with alum (potassium aluminium sulphate) and ferrous sulphate. A greenish precipitate formed that turned blue on addition of hydrochloric acid. There are numerous methods of synthesis that give salts of slightly differing compositions and properties. Riffault et al. (1874), for example, cite seven different methods, and devote more than 40 pages to describing them in detail. There are two common chemical routes, the first derived from the reaction of an aqueous ferric salt with potassium ferrocyanide (potassium hexacyanoferrate(II)): Fe3+ + K4Fe(CN)6 → KFe[Fe(CN)6]∙xH2O (8.1)

and the second by the reaction between ferrous sulphate and potassium ferrocyanide, followed by oxidation of the ferrous ferrocyanide with oxidants such as chlorine or chromic acid, producing Prussian blue: 2FeSO4 + K4Fe(CN)6 → Fe2Fe(CN)6 + 2K2SO Fe2Fe(CN)6 → (oxidation) → KFe[Fe(CN)6]3∙xH2O (8.2) (8.3)

At one time it used to be thought that the product of the reaction involving ferrous compounds would produce a different compound, identified as iron(II) hexacyanoferrate(III), which was called Turnbull’s blue. The nature of the difference between Turnbull’s blue and Prussian blue has not proved to be an easy matter to elucidate, and further chemical research on this interesting topic is required. Reaction (8.2) initially produces a white precipitate of iron(II) hexacyanoferrate(II), or ferrous ferrocyanide, often referred to as Berlin white or Williamson’s salt, which is easily oxidized to Prussian blue by air or other oxidants (Berrie 1997). The common method of commercial manufacture is from ferrous sulphate, ammonium salts and sodium ferricyanide: FeSO4 + Na4[Fe(CN)6] + (NH4)2SO4 → (NH4)2Fe[Fe(CN)6] + Na2SO4 (NH4)2Fe[Fe(CN)6] + H2SO4 +NaClO3 → (NH4)Fe[Fe(CN)6] + NaCl + (NH4)2SO4 (8.4) (8.5)

Prussian blue
Prussian blue, an important pigment and type compound for a whole group of chemical substances, sometimes referred to as ‘iron blues’, is essentially ferric ferrocyanide, which in modern terminology is iron(III) hexacyanoferrate(II) hydrate (Fe4[Fe(CN)6]3∙xH2O) or the closely related potassium iron(III) hexacyanoferrate(II) pentahydrate (KFe[Fe(CN)6]3∙5H2O). These are representative of the pigment group known as Prussian blue which has had many acronyms over the years in the pigment trade (for further description of the pigment and the acronyms see Berrie 1997). 92

It is difficult to make Prussian blue in a very pure state, as the finely precipitated freshly made pigment can adsorb a variety of impurities such as aluminium oxide, silicon dioxide, calcium carbonate, etc. In fact this was put to good use in helping to adsorb some of the radioactive fallout from the Russian nuclear disaster of Chernobyl, where large quantities of Prussian blue were spread over Cumbrian and Welsh uplands for the purpose of adsorbing caesium, to prevent it becoming incorporated in the grass, eaten by the sheep and ending up in the human body (Brewer 1993). There are peculiar differences between various types of Prussian blue, some of which are partially soluble while others are practically insoluble. This is largely due to the variation in

Iron carboxylate s and cyanide s chemical formula which the pigment can possess, resulting in some varieties producing a colloidal dispersion more readily than others. Under the microscope, Prussian blue may have very fine particle size, typically 0.01–0.2 µm. The particles appear as small, dark blue fragments or clusters of very fine small blue particles when mounted in Meltmount of refractive index 1.662. Prussian blue crystallizes in the cubic system and is therefore isotropic. The pigment has a low birefringence; it should appear black under crossed polars and show no colour at all if truly isotropic, but it tends to look a deep, dark blue. Schilling and Scott (1989) describe the use of the Chelsea filter as an aid in distinguishing between ultramarine and Prussian blue, ultramarine giving a pink coloration when viewed through the Chelsea filter, while Prussian blue gives only a cool grey. The pigment can usually be distinguished from indigo, since the latter may appear similar, but is anisotropic under crossed polars. However, it may still be difficult to distinguish between some samples of Prussian blue and synthetic ultramarine as the differentiation with the Chelsea filter may not be adequate with some pigment microsamples in which the grain size is very small. In these cases, microchemical tests, Fourier transform infrared (FTIR) spectroscopy or X-ray diffraction (XRD) analysis can be used to obtain a match with known samples. A pigment preparation is shown in Plate 32 (e and f ). The use of Prussian blue spread rapidly as its considerable advantages as a paint became realized. According to Berrie (1997), the earliest examples can be found in Dutch paintings of the early 18th century such as Jacob Blessing the Sons of Joseph by Adriaen van der Werff (1659–1722), which was painted some time before 1722. Later used by Canaletto (Giovanni Antonio Canal 1697– 1768) and by Watteau (1684–1721), it was employed commonly in England and America, continuing throughout the 19th century and into the 20th century. Prussian blue was used extensively during the 19th century by house painters, decorators and manufacturers of paper hangings. However, Riffault et al. (1874: 203) mention that old damp walls were known to destroy the colour of Prussian blue by the nitrate of lime that they contain: ‘There is produced by double decomposition, a ferrocyanide of calcium and a nitrate of iron’, which reveals that some of the environmental factors affecting the stability of the pigment were already known at that time. The pigment was often mixed with chrome yellow to produce a green paint; both pigments are present as very fine particles, making the mixture hard to resolve under the polarized light microscope. some printing processes, such as that of ‘blueprints’ (architectural plans for construction) rapidly falling out of use today, and for historically important printing processes. Plate 50 shows a cyanotype made from an X-radiograph of the painting Rearing Horse (c.1610–15) by Adriaen de Vries (1545–1626): the cyanotype image is formed by the iron(III) hexacyanoferrate(II) (Fe4[Fe(CN)6]3∙15H2O) on Fabriano Artistico cold-pressed paper. The use of iron salts of oxalic and citric acid also have a long and important history of use which have made possible a number of developments in different photographic processes, as Table 8.2 reveals (Ware 1996). The English scientist Sir John Herschel (1842) was the first to discover the use of ferric compounds for making a photographic print, utilizing the development of Prussian blue within the exposed paper or other media to form the image. The first artistic application of the invention was made by a botanist, Anna Atkins (1799–1871) in 1843. The significance of her work was not fully realized until research by Schaaf (1985) stimulated renewed interest in her achievements. The basic steps of making a cyanotype involve preparing an aqueous solution of ferric ammonium citrate and potassium ferricyanide which is used to coat the paper. The negative is then placed against this paper and exposed to bright sunlight for 10–20 minutes until the paper turns green-grey. The image is then formed by developing in water until the details are visible and most of the yellow, unreacted ferric citrate solution has been rinsed away. The prints are then washed in water and dried (see Plate 50). Herschel in 1842 was also responsible for inventing a number of related processes, including the argentotype, which employs ferric ammonium citrate developed with silver nitrate; the Pellet print, which uses ferric ammonium citrate and tartrate, was refined by Pellet in 1878, a British patent already having been issued in 1877. The print was developed with potassium ferrocyanide and gum. A related process was that of the amphitype, which employed ferric ammonium citrate and ferric ammonium tartrate, developed with mercury(II) salts. A large number of ingenious chemical processes utilized the initial cyanotype chemistry and adapted it for different photographic effects. For example, Brown (1902) provides detailed instructions for making cyanotype transparencies on glass and translucent paper. In 1900, the Lumière brothers found that ferric sucrate, made from cane sugar, is light sensitive and that a paper coated with this salt and exposed in the usual way could be developed as a negative or positive cyanotype in potassium ferricyanide or ferrocyanide solutions (Lumière and Lumière 1900). Other historic processes resulted in photographic images being formed from cuprous ferricyanide, ferric gallate and ferric tannate. The use of ferric oxalate solutions made possible the platinum printing process, one of the most successful and permanent early photographic processes, and one which is still in use by aficionados today, since platinum prints are capable of producing a greater range of dark tones than conventional silver halide prints. A summary of the different processes employing iron salts is shown in Table 8.2 (Ware 1996). The essential component of many of these iron-based systems is an iron salt which can undergo a redox reaction upon exposure to UV light. An example is ferric oxalate (Fe2(–OOC-COO–)3), which forms ferrous ions, liberating carbon dioxide on UV exposure: 2Fe3+ + (–OOC-COO–) → 2Fe2+ + 2CO2 (8.6)

Iron salts in historic photographic processes: cyanotypes
Prussian blue is related to the early development of photographic processes, since the precipitation of the pigment formed the basis of several methods of obtaining an image on paper when exposed to ultraviolet (UV) light or sunlight. Light excites electrons from organic molecules which then reduce ferric to ferrous ions to form Prussian blue in the presence of ferricyanide. The formula can vary from KFe[Fe(CN)6]3∙5H2O, the so-called ‘soluble’ Prussian blue to Fe4[Fe(CN)6]3∙15H2O, which is considerably less soluble; this variation is partially dependent on the method of manufacture employed. This may be an important consideration in

The most important photographic process in which ferric oxalate is used is that of the platinotype. The sensitizer consists of a mixture of aqueous solutions of ferric oxalate and potassium 93

Iron and Steel in Ar t
Table 8.2 Alternative photographic processes using iron salts (after Ware 1996). Process argentotype Vandyke brownprint sepiaprint kallitype argyrotype cyanotype blueprint ferroprussiate new cyanotype pellet print chrysotype new chrysotype platinotype sepia platinum POP platinum satista palladiotype amphitype Obernetter’s ferrocupric Phipson’s ferrogallate Colas blackline heliographic Nakahara’s Sensitizer (developer) ferricitrate (silver nitrate) (dev: silver nitrate) ferricitrate + silver nitrate (dev: water) ferric oxalate + silver nitrate (dev: borax or Rochelle salt) ferricitrate + silver sulphamate (dev: water) ferricitrate + ferricyanide (dev: water) ferrioxalate + ferricyanide (dev: dil. nitric acid) ferricitrate/tartrate (dev: ferrocyanide + gum) Ferricitrate (dev: chloroaurate(III)) ferrioxalate + gold(I) complex (dev: carboxylic acids) ferric oxalate + chloroplatinate (dev: oxalate) ferric oxalate + chloroplatinate + mercury(II) salts (dev: oxalate) sodium ferrioxalate + sodium chloroplatinate ferric oxalate + silver chloride + chloroplatinite ferric oxalate + chloropalladite (dev: oxalate ferricitrate/ferritartrate + mercury(II) salts ferric chloride + cupric chloride (dev: thiocyanate) (tone: ferricyanide) ferrioxalate (dev: permanganate) ferritartrate (dev: gallic acid) ferritartrate (dev: tannic acid) Image silver silver silver silver Prussian blue Prussian blue Prussian blue gold gold platinum mercury + platinum platinum silver + platinum palladium mercury cupric ferrocyanide manganese dioxide ferric gallate ferric tannate Inventor(s) Herschel Arndt and Troost Hunt Nicol Ware Herschel Ware Herschel Pellet Herschel Ware Willis Willis Pizzighelli Willis Willis Herschel Obernetter Phipson Colas Nakahara Year 1842 1889 1844 1889 1991 1842 1992 1842 1878 1842 1987 1873 1890 1887 1913 1916 1842 1864 1861 1860 1894

chloroplatinate (potassium tetrachloroplatinate(II)). The ferrous ions formed in equation 8.6 act to reduce the platinum(II) salt to metallic platinum: 2Fe2+ + Pt2+ → 2Fe3+ + Pt (8.7)

dicarboxylate. The dicarboxylate then thermally decomposes to form acetone as the final organic component of the system.7

As Ware (1999) points out, the common alternatives to platinum and palladium in this kind of reaction have been gold (chrysotype and aurotype) or silver (kallitype and argentotype) or gallic acid (ferrogallate process). Ferric citrate and ferric tartrate have been used for alternative processes, as these are also light-sensitive iron salts used in the Van Dyke and Brown photographic processes. The chemistry involved in the cyanotype process is still imperfectly understood (Abrahamson et al. 1994; Lawrence and Fishelson 1999), and has been the subject of numerous studies, a useful reference for further study being the monograph by Ware (1999). Exposure of the ferric ammonium citrate to UV light causes the photoreduction of Fe(III) to Fe(II), the citrate counterion providing the electrons for this reduction. The initial compounds arising from the citrate reduction are carbon dioxide and acetone 94

7

Abrahamson et al. (1994) report that at very low pH values where the iron and citrate are dissociated or form a 1:1 complex, near UV does not produce a photochemical effect. When the pH is from 2-5 the photoreaction does occur with the production of acetone dicarboxylate. These effects are ascribed to changes in speciation of the reaction with dinuclear oxo- or hydroxo-bridged iron citrate species formed by deprotonation of the 1:1 iron citrate complex. The fact that the iron salt used in the cyanotype process is ferric ammonium citrate is significant. The ammonium ion positive charge compensates for the additional deprotonation in the complex further than the three citrate carboxylate groups.

9 Iron corrosion in the soil
We must accelerate the rusting process ... the menace of mechanical litter in the countryside is growing almost everywhere. There is only one word for it, and that is vile ... I am referring to non-disintegrating rubbish of larger proportions, most of it metal ... Perhaps as well as trying to perfect biodegradable plastic, scientists ought to be seeking ways of accelerating rust (Gunston 1980).

Figure 9.1 emphasizes how the many factors that influence the deterioration of metal artefacts in the soil are interrelated. The complexity of these interrelationships makes it difficult to isolate just one component in terms of describing the process of corrosion, since one factor has an influence on several others, which will, in turn feed back into the corrosive environment to which the metallic artefact is exposed. It is interesting to reflect on Gunston’s frustration with ferrous litter, and to compare his sentiments to those of Pliny, who was also relieved that a metal that had been the instrument of so many deaths should itself perish at the hand of natural agencies:

The foe of iron is the customary benevolence of nature which exacts from it this penalty, that it needs must rust and, with equal foresight, decrees that that which inflicts most loss on short-lived humanity shall be of all materials the most short-lived (Pliny, Natural History XXXIV: 141; Bailey 1929(2): 59). The annual cost of all this rusting runs into billions of euros or dollars, and despite Gunston’s despair, still takes with it a sizeable number of iron objects. Many remain however, some to continue

Texture Physical weathering Water permeability Water content Salt concentration Electrical conductivity

Structure Air permeability

Soil porosity Oxygen content Carbonate Organic substances

METAL

Humic substances Soil acidity Microorganisms Ammonium content

Redox potential
Sulphate, nitrate, phosphate, chloride content

Chemical deterioration Leaching Enrichment

Figure 9.1 A diagram showing the numerous factors that influence the corrosion of metal artefacts in the soil (after Gerwin 1999).

95

Iron and Steel in Ar t to decay and others prized for their aesthetic, cultural or scientific importance, which are restored and conserved. According to J. Newton Friend (1911: VIII): ‘The literature on corrosion is so vast and so widely scattered that it has hitherto been exceedingly difficult to become thoroughly acquainted with it.’ The reader may feel that this is even more apposite now, almost 100 years after this statement was made and many thousands of papers later! Much of this corrosion literature is only relevant to the deterioration of modern steel alloys, but some useful information relating to ancient and historic materials can also be gained. pitting or delamination of iron, often with severe loss, with partial or complete conversion to iron corrosion products.

Corrosion product determination in burial environments
There have been numerous studies aimed at identifying the nature of iron corrosion products resulting from burial, although none of these report the nature of the corrosion products before atmospheric oxidation has potentially altered some of the less stable components, such as the green rusts or solutions of ferrous chloride or sulphate. Wolski (1990), for example, examined an iron shield from a late La Tène necropolis, dated to about AD 50, located in the Polish locality of Pyzdry. Three layers of rust were determined to be present: the first layer, closest to the remaining metal, consisted mainly of goethite together with small amounts of lepidocrocite and haematite; the second layer contained goethite and lepidocrocite with small amounts of magnetite; and the principal component of the rust in the third layer was goethite with some lepidocrocite. The zonal formation of the observed corrosion phases are postulated to be due to corrosion processes that proceeded at a slow rate. The kind of layered corrosion exhibited in the corrosion is suggestive of the Liesegang phenomena, in which the slow interdiffusion of different ionic species creates finely layered corrosion structures (Scott 1985, 2005) Shima and Yabuki (1979) examined the corrosion of a number of iron implements from sites in Japan. Iron oxides and iron hydroxides were found to be the principal components of the rusted surfaces with magnetite, goethite and lepidocrocite also present as well as akaganéite. Matsui (2002) examined the micromorphology of the corrosion on some Japanese excavated artefacts including a nail from the 6th century AD, a 5th–6thcentury iron sword and an 18th-century grey cast iron pan. Examination of the surface of the sword revealed large hexagonal plate-like brown corrosion products, about 100 µm in diameter, which consisted of goethite and lepidocrocite. This probably arose from the transformation of GR2 containing sulphate ions, which oxidized upon excavation, producing epitaxially deposited goethite with a surface flecked with acicular crystals of lepidocrocite, releasing sulphate ions to possibly create further corrosion. On another object, a hemispherical red corrosion was shown to consist of two varieties of lepidocrocite, one acicular, and the other in the form of thin plates. Some excavated objects have a black surface resulting from magnetite formation or from iron sulphides, although these are not particularly common. Scharff et al. (2000: 222) found that in most of the finds they sectioned for metallography, the scale present from the smithing operation was still visible microscopically. They mention a light oxide band formed during smithing whose identity is unclear, and which may be magnetite. Only in more heavily corroded samples, where there was no metallic core remaining, could a distinction no longer be discerned between the outer and inner corrosion layers. Some of these smithing scales may indeed be partially composed of magnetite that would assist with the preservation of their shape. Neff et al. (2005) investigated the corrosion of buried iron artefacts from five different sites in France, spanning dates from

Deterioration in the soil
Careful observations have been made concerning the corrosion of iron for many hundreds of years, for example, Sir Thomas Browne writing in 1658, noted that buried iron found surrounded with the bone ash of burnt bodies had only a thin layer of stable corrosion, and thought the ash acted as a preservative, which it may well have done. In the passage below, Browne compares the corrosion of iron with that of bronze, and makes the observation that the iron rivets holding together ivory combs are still not completely corroded, which could be a consequence of vivianite formation, the phosphate corrosion crust being more protective than that found otherwise, especially that due to the ingress of chloride ions: In the Monument of King Childerick, the Iron Reliques were found all rusty and crumbling into peeces. But our little Iron pins which fastened the Ivory works, held well together, and lost not their Magneticall quality, though wanting a tenacious moisture for the firmer union of parts, although it be hardly drawn into fusion, yet that metall soon submitteth unto rust and dissolution. In the brazen peeces we admired not the duration but the freedome from rust, and ill savour; upon the hardest attrition, but now exposed unto the piercing Atomes of ayre; in the space of a few moneths, they begin to spot and betray their green entrals (Patrides 1977: 288). Depending on the environmental factors, there may be considerable variation in the state of preservation of iron objects recovered from archaeological sites. Overall, corrosion rates measured on a corpus of 54 artefacts (Neff et al. 2007a) were below 4 µm per year and tended to decrease with time. They are much lower than those values recorded for modern low carbon steel in soil. But after one or more millennia of corrosion, many objects may either be mineralized beyond recognition or have undergone extensive corrosion. Commonly encountered in this category are unrecognizable fragments, objects which have lost substantial parts of their original shape, and objects concreted in a dense covering of iron oxides that are very heavily corroded beneath this crustal formation. These possibilities account for legions of buried iron and steel artefacts. From sites with extensive microbiological activity or anaerobic burial conditions, the iron objects may be covered with thick layers of various iron sulphides. Heavily chloride-laden soils can be guaranteed to create severe

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Iron corrosion in the soil the 2nd to the 16th century AD. The initial layer of corrosion products (referred to as the dense product layer (DPL) by the authors) consisted of iron oxides, oxyhydroxides, chlorides and/ or carbonates. These phases were generally well crystallized and compact compared with the more external zones of the corrosion. A layer referred to as the ‘transformed layer’ (TL) occurs over the DPL containing both corrosion products and markers from the soil such as quartz grains. The surface between the DPL and the TL corresponds to the original surface of the object, according to the authors, but we know that it is often not possible to specifically locate an ‘original surface’ in iron objects, one reason being topotactic changes, and the growth of the iron corrosion crust tends to disrupt the original surface rather than preserve it. Veined structures in the corrosion crust were identified as either magnetite or maghemite, with the matrix composed of goethite. Some veining of sulphides and carbonates was found from the site of Glinet, and small fissures filled with calcite from the sites of Cabaret and Montbaron. From the 12th–13th-century site of Montbaron, micro-X-ray diffraction (XRD) determined the presence of a relatively unknown iron chloride, β-Fe2(OH)3Cl, ICDD 72-0619, which the authors have identified on other archaeological material. The more usual β-FeOOH was also found from some of the studies, so the significance and role of this newly identified chloride-containing species is of some interest. Scharff and Huesmann (1997) discuss the problems of accelerated corrosion of iron artefacts in Germany based on an assessment of the available evidence. Excavated material can show the presence of akaganéite and a white, highly porous efflorescence, confirmed as rozenite (FeSO4∙4H2O) by XRD. The most typical corrosion found on artefacts exposed to high levels of sulphate in the soil are pale yellow to brown-coloured jarosites as an alteration in aggregates up to 1 cm in diameter, although Scharff et al. (2000: 15) contradict their earlier publication and state that only in some cases was jarosite found to be present. Scharff and Huesmann (1997) conclude that in general very limited sulphateinduced corrosion is found on German iron objects excavated prior to 1960, when industrial regeneration in Germany began to exude high amounts of sulphur dioxide. For example, during 1974 alone, 140 kg of sulphur per hectare is estimated to have been deposited in the industrial ‘Ruhrgebiet’ area. Levels of sulphur dioxide deposition have declined significantly in the West since the mid-1970s, but research suggests that significant damage to buried archaeological iron has already occurred. Gerwin (1999) reported that iron finds excavated from urban sites exhibit the most severe degree of deterioration, heavily corroded artefacts are also excavated from sandy and acid soils, and soil acidity and salt content markedly increase soil aggressivity. Monitoring experiments demonstrated a periodical variability of soil conditions and that considerable variations of the soil corrosion process could be measured. If attempts are made to undertake preventive conservation of archaeological iron artefacts in situ, a detailed examination of the site would be necessary to consider the potential effects of the corrosivity of the soil. Monitoring of iron corrosion at the site of Fiskerton, Lincolnshire in England (Fell and Williams 2004), employed both archaeological artefacts and modern test coupons serving as analogues. A pre-Roman Iron Age causeway situated at Fiskerton was in use from at least 457 to 321 BC, primarily representing an anaerobic waterlogged burial environment that is slightly acidic and reducing. As a result of possible land-use change, survey work included an assessment of the condition of recently excavated archaeological material as well as the deterioration of a range of modern samples buried near the causeway. The excavated iron artefacts showed the presence of ferrous carbonate (siderite, FeCO3), iron sulphides (principally greigite) and calcium carbonate. A separate study by Biek et al. (2003) concluded that the presence of ferrous carbonate and complex calcium iron silicates was a significant factor in the preservation of the iron artifacts. The experimental procedures employed at the site for the iron test coupons and monitoring of the environmental parameters are described in detail by Fell and Williams (2004) and Fell et al. (2005), and forms part of a continuous investigation. Coupons were recovered after 6, 12, 18 and 30 months burial durations. Preliminary study of the coupons after six months exposure showed that goethite – and in some cases, mackinawite and greigite – had formed but that no iron carbonates were detected. The presence of oxygen taken down with the coupons may be one explanation for the iron oxide formed in the anaerobic soil layers. After 12–18 months burial, siderite became more common with iron oxides, iron sulphides (mackinawite and greigite) and calcium carbonate also present (Fell 2005a). After 30 months of burial, siderite was the dominant species. Despite the latter normally conferring some protection to iron, the corrosion rates were found to increase rapidly during the experimental period for those coupons near to and just below the water table (Fell 2006). The explanation for this may be that the corrosion layers on the coupons were not well formed and had become disrupted, allowing rapid corrosion of the modern iron coupons placed near to the water table. The presence of greigite and siderite on the analogue iron coupons provides similar data to that reported by Fell and Ward in 1998, who analysed nine other iron artefacts many years after excavation and found pyrite, greigite and siderite to be present. This probably results from the gradual conversion of mackinawite to other metastable phases such as greigite and finally to pyrite. The presence of siderite may be related to iron sulphide production due to the reducing environment during burial. The extensive presence of siderite corrosion layers on iron artefacts from the site of Nydam Mose in Denmark (Matthiesen et al. 2003), discussed in Chapter 3, presents a different morphology from that seen at Fiskerton. Following the start of experimental work at Fiskerton, the water levels began to rise. This complicated the description of the environment to which the test coupons were exposed and a further series of reports is required to assess the viability of redox potential measurements and other parameters over longer periods of time in understanding the preponderance of greigite and siderite on the iron objects excavated at Fiskerton. Fell (2004) examined the corrosion crusts on a group of iron and other artefacts recovered from an Iron Age cremation site at White Horse Stone, Kent, in southern England, radiocarbon dated to 490–160 BC. The assumption is often made that cremated iron finds should be covered in a bright red haematite patina as a result of burning in an oxidizing atmosphere, and this is what Fell sought to discover. It did indeed appear that haematite was predominantly associated in the burial environment of these artefacts with a burnt context, which is an interesting observation. Leo Biek (1963: 133–4) was one of the first conservation scientists to notice that burnt archaeological iron surfaces composed of firescale contained substantial amounts of haematite. Finds from the White Horse Stone site showed the presence of magnetite, goethite and haematite, and possessed a distinctive grey/black surface that had good corrosion resistance. Fell (2004) notes that this kind of surface is very similar to that found in hammerscale, the by-product of the iron forging process. Burnt iron artefacts can be found as hollowed-out forms, reminiscent of 97

Iron and Steel in Ar t spherical hammerscale with a dark and lustrous skin of variable composition, often containing wüstite, magnetite and fayalite. Samples of hammerscale examined from the 10th-century Icelandic site of Mosfell (Scott and Wärmländer 2006) did not show any fayalite content, so this may not always be a diagnostic feature. In connection with the corrosion of iron objects, since so much loss of original shape can occur and an ‘original surface’ to clean to is so hard to find, one can ask the question – are the deterioration processes of ancient artefacts random, chaotic, structured or periodic? This question is of interest to us because conservation seeks to preserve the object in its present state, as far as possible, without loss of surface detail or of deteriorated parts of the object that may have become very fragile and easily lost if they do not receive proper conservation care. We need to understand the types of deterioration processes that these objects have suffered over time, and it is here that discussion of the types of processes involved in the alteration of artefacts is of relevance. Changes may take place in the solid state to create a completely different lattice structure than the original material, involving topotaxial transformations. In these transformations the ‘original surface’ of the object may be displaced or lost as the alteration front consumes the original material and replaces it with something quite different in composition and lattice dimensions. There are many examples of this kind of transformation in the process of iron corrosion where the alteration of metallic iron to goethite or haematite may disrupt the original surface so that only an approximation of the original shape can be recovered during conservation cleaning (Bertholon 2000). One reason why the use of X-radiographs to reveal the shape of a heavily corroded iron object is so valuable is that, beneath concretions, the corrosion interface between the original shape of the object and the overlying corrosion is often hard to detect by mechanical cleaning. Iron corrosion products may preserve microstructural detail of the original phases within a totally corroded matrix, as illustrated in a Chinese cast iron ding, or tripod, from Li County Museum, Gansu province, probably from the Spring and Autumn period (770–476 BC) (Plate 51). The grey cast iron matrix contains a substantial amount of the ternary eutectic, steadite, whose microstructure, reminiscent of a Swiss cheese, can clearly be seen preserved within the iron oxides or hydroxides that have preserved this structure without any alteration of shape. The lighter regions of iron oxides in the photomicrograph correspond to the ‘holes’ that would have been present in the steadite structure, originally filled with ferrite. Scott (1976, 1989a) attempted to categorize these structures according to the degree of remaining local metallic iron: remnant structures having complete grains or aggregates of metal surviving intact; partial replacement structures with the majority of the structure converted to corrosion products; and fossil structures where the form alone is preserved but with no surviving metallic phase. Interest in remnant or ‘ghost’ images of prior ferrous microstructures has been revived by Notis (2002) and by Scott (2005). There are many examples of pseudomorphic retention of shape in a variety of different materials, not just metallic artefacts, which represent the imposition of order on the subsequent deterioration product by the original material, but this is by no means a universal event and some alterations devise their own types of structures, which may be chaotic and disordered or reveal patterned, branching, cracked or layered morphologies. Iron deterioration processes may also involve fractal structures, an essential part of chaos theory. Fractal geometry deals with the ability of simple models or shapes, such as the grain structure of an iron object, to generate irregular or highly differentiated structures from the starting material. Relationships between solid iron, soil particles, groundwater solutions, temperature, conductivity and dissolved oxygen concentrations may create a series of non-linear relationships forming stable cycles within fields of chaos. The corrosion that forms here may act as its own feedback mechanism which impinges on the process of deterioration as it develops.

Understanding the corrosion process
The concept of ion migration, utilized by Robbiola in several papers dealing with the corrosion of bronze alloys (Robbiola 1990; Robbiola and Pennec 1993; Robbiola et al. 1998) suggested differentiating between corrosion processes that are under anionic control and those which are under cationic control. In processes under cationic control, the cations – in this case the ferrous or ferric ions – diffuse to the surface of the oxide layer, consequently there may be a better retention of shape of the object. In processes under anionic control, for example, where the chloride ions are prevalent, the corrosion crust may be more disrupted and the retention of shape of the original artefact within the corrosion crust may be poor. This is only an analogy in the case of iron compounds, since the original papers dealt with the retention or loss of tin from the patina layers, but the overall picture may still be a useful one. In the majority of buried iron objects, the shape of the material is only roughly preserved within the corrosion products, suggesting that most iron corrosion events are under anionic control compared with bronzes in which the situation is reversed – preservation of shape within the corrosion crust or patina is often very good. The issue is further complicated in the development of the oxide and oxyhydroxide corrosion of iron objects, since in many of these there are topotactic transformations (Bernal and Mackay 1965; Mackay 1961). These topotactic transformations take place in the solid state and result in the replacement of the original phase with a new phase whose structural relationship with the original material may be very different. This kind of transformation can result in volume changes, which disrupt the ‘original surface’ of the object, so that it is often difficult to locate any such original feature within the mass of corrosion products that now constitute the surface of the object. Some of these topotactic transformations result in the alteration of goethite to haematite, akaganéite to maghemite, and lepidocrocite to haematite. Another disruptive process that occurs as a secondary event is the dehydration of the initially formed crust, which allows access to the iron surface of further groundwater solutions, creating septae of additional corrosion that disturb the sedimentarytype bedding of the initial layers and disrupt the slow growth of further corrosion layers. These septae may coalesce to form another corrosion front, which may itself solidify, dehydrate and be liable to generate further corrosion, especially since the most mobile anions, such as chloride ions, are preferentially drawn towards the surface of the iron and may therefore be deep-seated within the corrosion layers, resulting in further corrosion. In some cases this process continues until the iron object is completely mineralized; no metallic iron remains whatever. Upon excavation, these fragile finds may simply disintegrate due to their physical fragility, although chemically they may be quite stable, since the iron has completed the cycle of its existence and returned to the mineral from which it was made. 98

Iron corrosion in the soil Non-linear feedback is an important feature of many systems undergoing deterioration resulting in fractal geometries (Scott 2005). A good example of a fractal structure within the 10th– century wrought iron Icelandic blade fragment from the site of Mosfell in Iceland (already mentioned in Ch. 1) is shown in Plate 52. The iron oxyhydroxides that comprise this branching structure, within a massive matrix of iron oxides, have grown as tree-like forms, fragmenting the space into ever finer variations of treelike branches. This kind of corroded microstructure displays a typically fractal geometry whose branching shapes could be described by a mathematical analysis of the type of branching that this example manifests. The microstructure here is totally dissimilar to that shown in Plate 51, and is not derived in any sense from the microstructure of its wrought iron progenitor, which is a typical wrought iron with very low carbon and phosphorus content consisting of grains of ferrite. We have to look elsewhere to account for this type of structure, which fractal geometry provides in its detailed mathematical description of a variety of forms: fractal tree skeletons are one such form that can aid in understanding the complexity and the order within the chaos of this type of massive corrosion whose structure would otherwise be unaccountable (Mandelbrot 1982). Some iron structures display morphologies suggestive of the Liesegang phenomenon (Scott 1985). First observed by Liesegang in 1896 as a series of banded precipitates within a homogenous diffusing chemical system, they have been the object of considerable scientific curiosity ever since. These self-organizing systems have a number of characteristics. First they are open systems and are part of their own environment. Such systems, in their creation of a new order, are sometimes claimed to run counter to the second law of thermodynamics, which would normally hold that disordered states are more favourable in terms of their energy levels than ordered systems, and that everything would tend to become more disordered upon corrosion and dissolution. The second law really applies to closed systems, but open systems still have a tendency to create disorder, which in the case of the fractal morphologies being considered here is not the case. Formation of patterned or layered deterioration products could be created by self-organizing systems in which reactiontransport and feedback mechanisms result in structured formations (Mandelbrot 1982). That such systems can operate in iron corrosion processes, where both epitactic and topotactic relationships exist between different iron oxides and hydroxides, can be seen from Plates 53 and 54. Plate 54 illustrates a banded periodic structure found in the same iron blade as shown in Plate 53. Plate 53 shows a low magnification photomicrograph of part of the corrosion crust, showing large banded structures passing through the heavily corroded artefact. These structures occur contiguously with the previously described structure in Plate 52, showing that periodic precipitation bands and fractal structures can be closely related to each other within the same object and corrosion crust; small perturbations in the system can result in completely different structures being formed. Liesegang-type structures are not often reported for iron corrosion processes, but other iron metallographic samples do display features of this type.1 Surface corrosion features of iron objects can also present unusual features of growth, as shown in Plate 55, which is a binocular microscopic view of iron corrosion products growing on the surface of an artefact in the collections of the Royal Ontario Museum, Canada. The iron oxides show a columnar growth with radial concentric zoning or growth cycle features around each
1 In David A. Scott’s collection.

of the small columns. This is an unusual morphology for iron corrosion products not reported previously to the best of our knowledge.

Electrochemical approach
Since the corrosion of iron is very much an electrochemical phenomenon, it is useful to examine the corrosion events from this point of view, systematically. The essential equations that outline the reactions of anodic and cathodic regions of the object are shown below. The dissolution of equation 9.1 is usually accompanied by the reduction of oxygen, at the cathode, as in equation 9.2 or 9.3. Reduction to hydrogen, as in equation 9.4, will occur in some bacterial processes or if the pH of the environment is 4 or less: Fe → Fe2+ + 2e– O2 + 2H2O + 4e– → 4OH– O2 + 4H+ + 4e– → 2H2O 2H2O + 2e– → H2 + 2OH– (9.1) (9.2) (9.3) (9.4)

When the iron is freshly buried, anodic and cathodic sites will exist on the surface. As corrosion proceeds, ferrous ions diffuse away from the anodic areas and undergo further reaction, depending on the moisture, pH and oxygen availability in the soil. If oxygen levels are low, compounds such as ferrous hydroxide or ferrous chloride may form which are not particularly stable. These compounds can undergo partial oxidation to form the green rusts, particularly GR1 (discussed in Ch. 4). If oxygen levels are high and the local pH is less than 6, the ferrous ions can remain in solution because the rate of oxidation of ferrous ions to ferric is slow in acidic solution (Selwyn et al. 1999). On the other hand, if oxygen levels are high and the local pH is above 6, any ferrous hydroxide is converted to ferric hydroxide, which can slowly change to form goethite by loss of water. The iron surface becomes further passivated from corrosion as it becomes gradually covered with insoluble iron corrosion products that are often cemented with soil and mineral constituents from the burial environment. The separation between the cathodic and anodic sites led Turgoose (1982b, 1993) to propose that acidity and chloride ion concentration increased as the anodic areas became filled with a ferrous chloride solution. Oxygen reduction by equation 9.2 occurs on the outer surface if there is a conducting oxide corrosion crust. The iron oxides are semiconductors as opposed to the non-conductive oxyhydroxides (Cornell and Schwertmann 2003: 116f.). In finds from Glinet, where goethite was dominant in the DPL, the reduction took place at the metal/ DPL interface as was shown by O18 labelling experiments (Vega et al. 2007: 98ff.). At the anodic sites, iron metal can be oxidized to ferrous ions and the chloride ions maintain charge neutrality.

Corrosion and Pourbaix diagrams: further examples
The Pourbaix diagram for the iron-water system (Fig. 9.2) shows that the stable phase towards the higher regions of pH is goethite. Strictly speaking, goethite is unstable with respect to α-Fe2O3, but the free energy change is small and goethite can persist for 99

Iron and Steel in Ar t geologically significant periods of time, which is why haematite is ignored in this diagram. Magnetite is stable under more reducing conditions, which accounts for the formation of magnetite in corrosion crusts where oxygen availability is restricted or where other corrosion products are susceptible to reduction. At a chloride ion content of an activity equal to unity, the Pourbaix diagram reveals a broad area of stability for goethite, a smaller region for magnetite, and a large area, especially under acidic conditions, where first ferrous chloride, and then ferric chloride are stable, the latter under more oxidizing conditions. During the corrosion of archaeological iron in burial, a whole range of iron oxides may form including goethite, magnetite, ferrihydrite, akaganéite and so on, depending on the pH of the soil solutions and the oxidation-reduction potential, although most of these compounds do not appear on the Pourbaix diagrams for the iron-water system. Turgoose (1982b) held that some of these oxides, such as akaganéite, whose formation is dependent on chloride ions would only be formed as post-excavation products and may not be present at all on unexcavated material. At the time of excavation, most of the chloride ions present in the iron will be in the form of ferrous chloride, but when this ferrous chloride solution is exposed to moist air, a brown solid and a yellow solution are formed. The solid is akaganéite, and the solution will contain ferrous, ferric and chloride ions. In objects that possess a metallic core, the source of ferrous ions can be both from the corroded iron itself and from subsequent corrosion of the iron when it is exposed to the air. The overall reaction proposed by Turgoose (1982a) is: 4Fe2+ + O2 + 6H2O → 4FeOOH + 8H+ (9.5) Turgoose (1982a) states that weeping can be prevented at approximately 18% RH. An RH of– 20% RH is not low enough, but 15% is sufficiently low, so the critical value must lie between 15 and 20% RH. If kept at 15% RH, ferrous chloride dihydrate will be formed, which prevents further reaction from taking place. However, if the relative humidity is between 20 and 44%, reaction may still occur between the ferrous chloride tetrahydrate and metallic iron, resulting in fragmentation or further serious corrosion. Further work on this topic by Watkinson and Lewis (2005) has shown that in the presence of ferrous chloride tetrahydrate the RH would have to be kept at 19% or less; if unwashed akaganéite is present, stability is only achieved below 12% RH. Keeping objects constantly below these RH levels is obviously very difficult to achieve in practice for extended periods of time. Thickett (2005) has confirmed the 19% threshold and shown that the formation rate of akaganéite increases dramatically above 30% RH. This second threshold is important for display situations when achieving 19% RH is extremely difficult and expensive, while 30% is achievable. The presence of both copper ions and humic acid was shown to accelerate the formation of akaganéite and cause this to occur at 16%, but not at 15% RH. Goethite was observed to retard the reaction. In equation 9.5, the production of hydrogen ions is given as one of the causes of continued corrosion. It is also possible to propose a different model, details of which are reviewed by Selwyn et al. (1999) based on research by Askey et al. (1993) who propose that the chloride ions initiate a corrosion cycle, in the same way that hydrochloric acid may do on modern iron and steel surfaces. Their sequence suggests that hydrochloric acid and oxygen react to form ferrous chloride and water, followed by reaction between ferrous chloride, oxygen and water in which akaganéite and hydrochloric acid are generated. 2Fe + 4HCl + O2 → 2FeCl2 + 2H2O 2FeCl2 + 3H2O + O2 → 2FeOOH + 4HCl) (9.6) (9.7)

The acidity produced by this reaction will cause the pH to drop until the solubility of akaganéite becomes significant and the ferric ions remain in solution, giving rise to the problem of ‘weeping’ iron, where dark red hygroscopic pustules form on the surface of the excavated object. Dark brown precipitates of ferric chloride may be seen floating on the surface of the pustules, while the liquid is very acidic, with a pH of 2 or less. This is a serious indication that urgent conservation treatment is required in order to attempt to restore stability to the object, since the weeping iron surface will cause damage to the surface of the object, due to the very low pH conditions, and potential disintegration may result.
Fe2+]TOT=10.00μM
1.0

[C1-]TOT=10.00mM
FeOOH(cr)

0.5

Fe(OH)2.7Cl0.3(c)

0.0
Fe2+

-0.5
Fe(c)

Fe3O4(c) Fe(OH)2(c)

-1.0 2 4 6
pH

t=25˚C
8 10

Figure 9.2 Pourbaix diagram drawn for a chloride activity of 1, with water and iron present. Note the large stability field for goethite together with the occurrence of ferrous chloride and ferric chloride in more acid conditions (after Turgoose 1982b).

The difference between these two theories is that in the Turgoose model, the effect of the chloride ions is indirect, whereas the Askey model proposes a direct role for the chloride ions. The soluble iron(II) chloride is formed in either case. If the chloride ions are precipitated out of solution the cycle would be broken and the reaction would proceed only very slowly. It is well known that chloride ions accelerate the rusting of iron since they interfere with the development of a passive film due to their high charge density, the formation of soluble compounds and ease of transport through the oxide film. The oxidation of the ferrous ions that are produced results in the formation of the iron oxyhydroxides such as goethite or lepidocrocite, with akaganéite being the chloride-containing oxyhydroxide usually associated with continuing instability. The reason why the presence of akaganéite – which encloses chloride ions in its channels so that they cannot be easily removed by washing – speeds up corrosion needs further study (Selwyn et al. 1999: 226; see also below). Work on the intermediate green rusts (Refait and Génin 1993) has shown that akaganéite forms at high chloride ion concentrations, from 2 to 3.6 mol l–1, and that lepidocrocite, goethite and magnetite can form at lower chloride ion concentrations. Two representative Pourbaix diagrams from their work have already been shown in Figures 4.2 and 4.3. In objects that do not possess a metallic core, the only ferrous ions that can take place in reaction 9.7 are those that would be present at the time of excavation. There are therefore a number of possible components that may be oxidized following excavation,

100

ESHE/V

Iron corrosion in the soil such as siderite (FeCO3) or the iron sulphides such as pyrrhotite (FeS), which may lead to the formation of the iron sulphates. Turgoose (1982a) notes that in theory, since the oxidation of pyrite (FeS2) can be prevented by maintaining the RH below 60%, this should not present a major problem in terms of storage, yet the oxidation of pyrite specimens continues to give trouble. The oxidation of siderite to one of the iron oxyhydroxides will not create a volume increase since siderite, with a specific gravity of 3.96, occupies 31 cm3mol–1, while FeOOH, with a specific gravity of 4.3–4.1, occupies 21–22 cm3mol–1, so the amount of damage caused by this transformation should not be significant. The Pourbaix diagram for the iron-sulphur-oxygen-carbonate system is shown in Figure 9.3 as an example of the possible applications of these diagrams to the presence of mixed anions (Garrels and Christ 1965). The diagram is calculated for a total dissolved sulphur content of 10–6 mol l–1, and total dissolved carbonate ion of 1 mol l–1. Note that ferrous sulphide is here eliminated by ferrous carbonate under strongly reducing conditions and the remarkable stability of pyrite in the presence of a small amount of dissolved sulphur. These diagrams, showing mixed anion concentrations and species, are increasingly becoming of use in the study of corrosive environments and the possible nature of the corrosion products that might be expected to be formed.

Orange-brown powdery corrosion
This type of corrosion is due to the slow formation of akaganéite, often on the underside of corroded or partially laminated fragments. The crystallization of the akaganéite may disrupt the surface, forcing off small flakes of corroded metal. Zucchi et al. (1977) appear to be the first researchers who noticed the formation of akaganéite under these circumstances, almost certainly due to the oxidation of ferrous chloride solutions still active within the pores of the iron object. They observed that if these crystals are cleaned away and the object exposed to humid air, more akaganéite appears. This is one of the mechanisms for the continued disintegration of iron objects, as slow changes in the ferrous chloride content within the iron result in further akaganéite formation with the result that the volume expansion cracks the oxide corrosion layers and the mineralized parts of the corrosion crust fall apart. Depending on how the synthetic chemical routes to the formation of akaganéite are conducted, the crystals may form as long narrow spindles or rods, with a length from about 0.2 to 0.5 µm. The crystals that form at room temperature tend to have a square cross-section, as shown by Selwyn et al. (1999), who studied the akaganéite crystals formed on an axe-head from excavations at Discovery Harbour, Penetanguishene, Ontario (Canada). These crystals clearly grow from the substrate iron as striated square-section columns. There has been some difficulty in establishing whether or not the chloride ion content can be reduced by washing, and whether this reduction originates from chloride ions chemisorbed on the surface of the akaganéite, or whether it is chloride ions trapped within the lattice tunnels that can be removed. Ståhl et al. (1998) were of the opinion that only the former chloride ion content could be thus removed. On the other hand Keller (1970) reported that some of the chloride ions could be removed from synthetic akaganéite by repeatedly washing with water, without changing the structure of the material. Akaganéite may act as a catalyst in accelerating the corrosion of iron according to information reviewed by Selwyn et al. (1999)
Figure 9.3 Pourbaix diagram for the iron-sulphur-oxygen-carbonate system. Total dissolved sulphur is here 10–6 M. Total dissolved carbonate is 1 M. Note that ferrous sulphide is eliminated by ferrous carbonate under strongly reducing conditions and the remarkable stability of pyrite in the presence of a small amount of dissolved sulphur (after Garrels and Christ 1965).

who noted that new adherent layers of β-FeOOH formed under synthetic β-FeOOH on iron exposed to daily misting with water. Other researchers have detected a range of chloride ion concentrations in akaganéite on meteoric iron, with the chloride ion concentration being highest contiguous with the remaining iron surface (Buchwald and Clarke 1989). Calculations of the isotropic temperature factor, which reflects the amplitude of vibration of the atom, shows a higher value for chloride ions, 2.0, compared with iron, 0.5, or oxygen, 0.8, which suggests that the chloride ions undergo a greater degree of movement in the tunnels of β-FeOOH.

‘Weeping’ iron
The formation of reddish-brown pustules or droplets exuding from the surface of an iron object is, naturally enough, not a good indication for future preservation. This kind of instability, usually exacerbated by poor storage conditions with fluctuating RH conditions, or no humidity control, is a serious indication that chloride ions are still promoting active corrosion of the iron. The weeping of iron was initially ascribed to the presence of ferric chloride (Organ 1977), but the droplets were later shown to be high in ferrous iron by North (1982), who examined some examples and measured a pH between 1 and 3, with a high concentration of chloride ions and low amounts of ferric iron. Similar results were 101

Iron and Steel in Ar t also obtained by Knight (1982) and Turgoose (1982a). Crystals of either ferrous chloride tetrahydrate (FeCl2∙4H2O), which is pale green, or ferrous chloride dihydrate (FeCl2∙2H2O), which is pale yellow and can form from ferrous chloride solutions; salts of this type have been identified by XRD on iron surfaces exposed to chloride ion corrosion at 50% RH (Selwyn et al. 1999). Turgoose (1982a) found that the dihydrate was stable between 0 and 15% RH, and the tetrahydrate between about 20 and 44% RH, with a yellow solution and a brown solid forming between 55 and 80% RH. The critical relative humidity (CRH) for ferrous chloride tetrahydrate is 55.9% at 25 °C (Richardson and Malthus 1955). Above the CRH, the solution behaves as a deliquescent one, absorbing more water from the atmosphere. Since the solution will also have some ferric iron content, this will influence the CRH. It is difficult to measure the CRH for ferric chloride and various values have been proposed, ranging from 5 to 37% (Selwyn et al. 1999), but regardless of the value, the effect of the presence of any ferric ions will be to depress the CRH to values lower than 55.9%, which may vary from object to object. The weeping pustules often have a thin brown solid film floating on the surface of liquid which, if dried out, can produce a series of hollow shells on the surface of the iron. These films or shells are an indication that oxidation and hydrolysis is occurring within the iron chloride solution. The brown-yellow film is therefore one of the iron oxyhydroxides, usually akaganéite. However Selwyn et al. (1999) examined some of these shells and found goethite and lepidocrocite to be present, but no akaganéite. However, it is possible that akaganéite was the initial product, which then converted to goethite or lepidocrocite in damp conditions, releasing some chloride ions back into solution to continue the corrosion process. Slow conversion of the akaganéite to goethite had been observed in both the laboratory and on artefacts (Thickett 2005). This releases chloride from the akaganéite structure at a slow rate to participate in further corrosion reactions, an observation that confirms the view of Seeley2 regarding this matter. The presence of large amounts of ferrous chloride within the pores usually implies that the weeping occurs on corroded metallic surfaces. The very low pH measured by North (1982) within the pustules suggests that active deterioration of the iron surface is ongoing, with probable dissolution of more iron metal if the objects are not treated.

Sulphate-reducing bacteria
That the activities of the sulphate-reducing bacteria were already known in the early years of the 20th century is evidenced by the review carried out by J. Newton Friend in 1911, which cites research performed by German and English scientists that indicated that some organisms could live by decomposing ferrous carbonate or organic ferrous salts with the precipitation of rust. Friend (1911: 102) notes that the English scientist Richard Gaines, writing in 1910, emphasized the importance of bacterial activity in the corrosion of iron. Gaines found high amounts of sulphur in rusted surfaces of buried steel conduits that could not be accounted for by the sulphur content of the steel itself. During an investigation of the corrosion of a bridge crossing Lake Hauser in Montana (USA) in 1904, the rust was shown to contain bacteria of the species Gallionella ferruginea. Since that time, research has confirmed that the sulphate-reducing bacteria (SRB) are a major factor to be reckoned with in the corrosion of iron. These bacteria invariably produce a biofilm at the metal surface under which anodic dissolution of iron can occur. Lee et al. (1995) consider the process in the following steps: 1 2 3 Transport and accumulation of material from the bulk liquid to the metal surface. Microbial and electrochemical transformations within the biofilm and at the metal surface. Erosion and detachment from the surface of the film.

At ambient temperatures in neutral environments the corrosion of iron is driven by dissolved oxygen and at anodic sites: Fe → Fe2+ + 2e– (9.8)

Spalling and cracking
Knight (1982) distinguishes between two essential disintegration mechanisms for mineralized iron; he describes these as spalling and cracking. In the process of spalling, the object may break up into wedges or flakes. Wedge-like fragments detach themselves from the corroded object as it gradually looses physical cohesion. Cracking, which may be associated with the dehydration of the iron oxyhydroxide crust or with changes in volume due to the reaction of chloride ions within the iron, leaves the surface fissured with deep cracks, which being lines of stress may result in the object falling apart along the crack lines.

The corrosion rate is independent of pH within the range pH 4–10. The usual oxygen reduction reaction occurs at cathodic regions. In waters of low conductivity, the cathodic and anodic sites are in close proximity and therefore OH– ions at cathodic sites are always contiguous with Fe2+ ions at anodic sites, and the resulting film of Fe(OH)2 is relatively adherent, but when sodium chloride is present, the anodic and cathodic sites are further apart and ions can diffuse more readily into the bulk solution and form more porous deposits. Ferrous ions can then oxidize further to ferric ions (Uhlig 1963) as follows: Fe(OH)2 + 1/2H2O + ¼O2 → Fe(OH)3 (9.9)

2

N.J. Seeley, pers. comm. to DA. Scott, 6 June 1986.

The overall result is that the rust layer consists initially of three layers of iron oxide at different levels of oxidation. The innermost layer is largely greenish ferrous hydroxide (Fe(OH)2) while the outer layer comprises orange ferric hydroxide (Fe(OH)3) with magnetite (Fe3O4) formed as a black layer between these two. The corrosion rate is controlled by the rate of oxygen diffusion, which is either diffusion-dependent or mixed (reaction + diffusion). The exact type is dependent on the nature of the corrosion products and the environment. Figure 9.4 illustrates some of the corrosion processes occurring on iron in an environment containing sulphate-reducing bacteria where the situation is totally anaerobic. A biofilm is laid down over the iron by the bacteria and the following events take place: the transport of nutrients to the biofilm; the general anaerobic metabolic processes; the reduction of the sulphate species; the precipitation of ferrous sulphide; and

102

Iron corrosion in the soil

Anoxic bulk liquid Biofilm - bulk liquid interface Anoxic biofilm
FeS1-x H FeS1-x Fe2+ e-

Organic matter 1 2 Organic matter 1 Mass transport process. 2 General anaerobic

metabolic processes.
3 Sulfate reducing process. 4 Ferrous sulfide

Anoxic biofilm scale interface Iron sulfide scale Bulk metal

FeS1-x

4 H

3

precipitation.
5 Electrochemical

Fe2+ H+ 5 e-

corrosion process.

Figure 9.4 Schematic diagram of transport and transformation processes contributing to the corrosion of mild steel in a totally anaerobic biofilm (after Lee et al. 1995: fig. 19).

Oxic bulk liquid Biofilm - bulk liquid interface Oxic biofilm Oxic- Anoxic biofilm interface Anoxic biofilm Anoxic biofilm - metal interface Iron sulfide scale Bulk metal
FeS2 3

Organic matter O2,

1 Mass transport process. 1 2 2 Anaerobic metabolic processes. 3 Ferric hydroxide precipitation. 4 General anaerobic metabolic

6

FeOOH So, 5

sulfate reducing processes.

5 Ferrous sulphide precipitation. FeS1-x Fe HSH
+

6 Sulfide oxidation processes. 4 H 7 Pyrite formation process. 8 Electrochemical

7

2+

corrosion process.

8 e-

Figure 9.5 Schematic diagram of transport and transformation processes contributing to the corrosion of mild steel in a mixed aerobic-anaerobic biofilm (after Lee et al. 1995: fig. 20).

the electrochemical corrosion process. Once sulphate-reducing bacterial activity is established within the biofilm, iron sulphide nuclei form quickly and cover the iron surface. High rates of corrosion by sulphate-reducing bacteria are maintained only where high concentrations of ferrous ions exist. For comparison, the situation pertaining in a mixed aerobic-anaerobic film is shown in Figure 9.5. Here there are more processes involved in the deterioration of the iron. In addition to the formation of ferrous sulphide, the uptake of oxygen in the aerobic part of the system has to be considered to help explain the effects of dissolved oxygen on the sulphate-reducing bacteria part of the corrosion. Oxygen consumption can occur by aerobic respiration, microbial and chemical re-oxidation of sulphides and ferrous compounds, or cathodic depolarization processes. Only the microbial or chemical re-oxidation events or the depolarization of the cathode result in increases in the rate of corrosion. Oxidation of sulphides and ferrous compounds produces sulphates that are more corrosive and thus facilitate the cathodic reaction. The cathodic depolarization can be due to dissolved oxygen reacting with hydrogen atoms adsorbed onto ferrous sulphides. Part of these reactions is shown in Figure 9.5 where the iron surface is covered with an iron sulphide scale, over which an anoxic biofilm exists that is in contact with an oxic-anoxic biofilm which, in turn, is covered with a biofilm and the oxic bulk liquid, such as seawater.

The sulphate-reducing bacteria may also be responsible for the existence of siderite as a corrosion product on buried iron, as the work of Coleman et al. (1993) has shown. Ferrous carbonate may result from the oxidation of fermentation products such as acetate and hydrogen, roughly: 4Fe2O3 + CH3COO– + 7H2O → 8Fe2+ + 2HCO3– + 15OH– (9.10) Fe2O3 + H2 + H2O → 2Fe2+ + 4OH– (9.11) The production of Fe2+, hydroxyl ions and bicarbonate should all favour siderite formation Fe2+ + HCO3– + OH– → FeCO3 + H2O (9.12)

As laboratory studies have shown, Desulfovibrio desulphuricans is indeed capable of reducing Fe2O3 (Coleman et al. 1993: 437f.). This work therefore reveals one of the possible reasons for the formation of siderite on buried iron objects as yet another phenomenon that can be related to the sulphate-reducing bacteria. The opportunity to observe in detail the deterioration of shipwreck sites under the sea has produced significant new data in the case of RMS Titanic, which sank on 15 April 1912. The shattered hull was discovered by R.D. Ballard in 1985 and has since been under regular investigation (Cullimore et al. 2002). 103

Iron and Steel in Ar t Noticing that structures with the appearance of rust-coloured ‘icicles’ were growing all over the hull, Ballard coined the term ‘rusticles’ to describe the phenomenon. Plates 56 and 57 show examples that festoon the wreck of the Titanic. Subsequent investigation of these rusticles revealed that they were complex in structure, were formed as microbially induced concretions and were not composed of a single species of either an animal or plant, but were a complex network of microbial consortia. Consortia are defined as associations of multiple microbial species that are able to function in a synergistic manner. These growths resemble the speleothems observed in limestone caves, which are elongate structures incorporating organic filaments coated by calcite or iron oxides, thought to be over 100,000 years old. The rusticles growing from the iron of the Titanic are complex structures consisting of water channels, reservoirs, complex iron plate-like structures, threadlike spans, porous matrices and ducts to the outside. Within the rusticle structure appear to be a number of different microbial strains occupying specific sites. These strains, identified by Cullimore et al. (2002) include sulphate-reducing bacteria, iron-related bacteria, heterotrophic aerobic bacteria, denitrifying bacteria and archaeobacteria, together with a range of fungi. The supporting structures appeared to be dominated by a mesh-like, heavily mineralized matrix mostly composed of goethite. Interestingly, the sulphate-containing green rust was also found to be present. These bioconcretions can grow to lengths of 3 or 4 m and may eventually be dislodged from the surface of the steel hull, resulting in the iron being dispersed into the oceanic environment as ‘red dust’” or ‘yellow colloids’. An investigation of these features was also carried out by MacLeod and Pennec (2004), who noted that the intense cold, absence of light and low oxygen levels at the ocean bed have slowed the deterioration of the ship and many of the artefacts. The authors found the ship to be covered with drapes of organic structures, built up over the last 90 years, 20–30 cm in length, brittle and approximately 100–200 mm thick. They have a smooth, dark red outer surface covered with microspheres of lepidocrocite. The inner surface is covered with spherical aggregates of goethite together with siderite. Significant amounts of an iron silicate deposit are also present, tentatively identified as hisingerite (Fe2Si2O5(OH)4∙2H2O), which might be a hard compound to detect, but which, according to Gaines et al. (1997) is not especially rare, and was first named by Berzelius in 1828. MacLeod and Pennec (2004) believe that the source of silicon for the formation of this compound comes from the siliceous skeletons of diatoms embedded in the rust flakes. The continued corrosion and dissolution of the iron of the Titanic shipwreck due to this biomineralized rusticle formation may eventually result in the ship effectively being eaten away, so that very little evidence of it may remain on the ocean floor in centuries to come. Emery and Schroeder (1974) carried out a series of experiments with rusting iron powder together with Douglas fir and red oak and showed that direct depolymerization of cellulose and xylan occurred in an acidic environment, probably caused by free radical formation and hydrogen peroxide, which may allow Fenton-type reactions to occur in the wood. The ferrous-ferric transition may involve free radical formation when organic substances are present. Scott (1965) summarizes these reactions in the general form of: Mn+ + O2 → Mn+OO. M OO. + RH → R . + HOO- + M(n+1)+
n+

(9.13) (9.14)

The alternative series of reactions are: Mn+ + O2 → M(n+1)+ + O-O. M(n+1)+ + O-O. + RH → R . + HOO- + Mn+ (9.15) (9.16)

Apart from directly initiating a chain reaction, the metal-oxygen complex can result in the formation of perhydroxyl radicals, which in aqueous solution form hydroxyl radicals: H2O + HOO. → H2O2 + HO. (9.17)

The hydrogen peroxide produced can be decomposed by ferrous ions to form additional hydroxyl radicals: Fe2+ + H2O2 → Fe3+ + OH. + OH– (9.18)

This latter equation forms the basis for the Fenton-type reactions involving a variety of oxidation and free-radical polymerizations. The identification of skin and leather preserved in iron corrosion products is possible, and some examples are given in Cameron (1990) from an Anglo-Saxon cemetery.

Petrification and replacement of organic material in burial environments

Degradation of wood and other organic materials
The deleterious effects of iron on many organic materials has been known for a long time. Bell and Gibson (1957) noted the degradation of cellulosic fibres in contact with rusting iron. MacLean and Gardner (1951) analysed wood degraded by rusting iron and found that the xylan content was easily deteriorated, as evidenced by a decrease in the pentosan content of the timber. 104

Scurfield (1979) discusses some of the processes of the petrification of wood that involves the replacement of some of the cellular tissue of the wood with silica and iron compounds. He found that goethite, like silica, is capable of reproducing cell wall and bordered pit structures in considerable detail and illustrates cell walls clearly demarcated from partially filled cell lumina, lamellated walls of some wood, and a bordered pit preserved in pseudomorphically deposited goethite. The coarse crystallinity of siderite, in comparison with goethite, scarcely preserves any structural detail. Lepidocrocite was found as a secondary component of one of the goethite samples and siderite containing some goethite was also found as a mineral pseudomorph (Scurfield 1979). Heavily deteriorated leather from the remains of a suitcase found on the wreck site of the Titanic from 1912 was examined by MacLeod and Pennec (2004). Fourier transform infrared (FTIR) examination showed the presence of well-defined absorbances in the amide I region (1660–1610 cm–1) amide II, proline and amide III regions (1270–1210 cm–1), indicating well-preserved leather, although reduced absorbances in the 2970–2900 cm–1 region suggested some loss of fatty acids and oils. Interstitial spaces

Iron corrosion in the soil between the leather fibres were filled with lepidocrocite and goethite. Some phosphorus content in other regions suggested the presence of vivianite, although this was not confirmed during the investigation as the phosphorus was present in only very low concentrations. The invasion of iron salts protected the leather to some extent from complete loss in burial. As iron (as opposed to copper and lead) is not a biocide, organic structures are swiftly covered with rust. Such organic material is then consumed by microorganisms. This can leave a negative cast in the rust of, for example, cell walls, as found by scanning electron microscopy (SEM) of wood (Keepax 1975) which can allow determination of species even if there is no longer any organic material present. Roberts (1989) and Fischer (1994) consider some of the problems in dealing with organic remains on metallic objects and emphasize the need for proper analysis and documentation.

105

10 Iron corrosion in the atmosphere

Problems with iron sculpture or ancient iron objects exposed to the elements are considerable, and only the most robust objects have been able to survive for several hundred years without significant conservation measures. Table 10.1 lists some of the common corrosion products found in rust layers, some of which help to reduce the rate of further atmospheric attack, especially in the case of massive cast iron sculptures such as those produced in ancient China. A few of the very impressive objects of this cast iron technology are illustrated in Figure 10.1 and Plates 58 and 59. The huge cast iron oxen from Cangzhou shown in Figure 10.1 represent an astonishing achievement of early white cast iron technology. The Cangzhou lion, another early masterpiece, was cast in AD 953, stands 5.4 m high and weighs 50 tonnes. An early photograph of the lion was taken by American mining engineer, Thomas T. Read, about 1910. Art historians believe that the Cangzhou lion

was originally inside a Buddhist temple, now long gone, and that a bronze statue of the bodhisattva Manjusri rode in the lotus flower on the lion’s back. This was removed in the reign of Shizong (r.954–958), emperor of the minor dynasty of the Later Zhou (951–906) in his campaign against Buddhism. The tail of the lion was missing in 1603 and the lion was toppled over by a storm in 1803. In 1886 Department Magistrate Gong Yu ordered masons to prop the cast iron lion up again and in 1984 the sculpture was professionally restored and placed on a reinforced concrete pedestal 2 m in height. The large cast iron rhinoceros (Plate 58) is situated in the village of Tieniu, 2 km northeast of Kaifeng, Henan, and is dated to 1446. The lines of the piece-moulds used to cast the large sculpture still remain on the surface of the cast iron. In a white cast iron casting, the mould lines are extremely hard and difficult to simply file away to present a smooth surface to the figure. An extraordinary

Table 10.1 Some iron minerals from rust layers (after Graedel and Frankenthal 1990: table 1).

Name ferrous hydroxide magnetite green rust 1 (GR1) green rust 2 (GR2) maghemite ferric oxide ferric hydroxide goethite akaganéite lepidocrocite feroxyhyte szomolnokite rozenite melanterite lawrencite ferrihydrite

Formula Fe(OH)2 Fe3O4 Fe2IIFeIIIOx(OH)y Fe Fe Ox(OH)y
II III

Crystal system hexagonal cubic hexagonal, trigonal/orthorhombic hexagonal trigonal hexagonal cubic orthorhombic monoclinic orthorhombic hexagonal monoclinic monoclinic monoclinic trigonal trigonal

γ-Fe2O3 Fe2O3nH2O Fe(OH)3 α-FeOOH β-FeOOH γ-FeOOH δ-FeOOH FeSO4·H2O FeSO4·4H2O FeSO4·7H2O FeCl2 Fe2O3·O·5H2O

107

Iron and Steel in Ar t

Figure 10.1 Cast iron oxen of Cangzhou. The largest casting is the lion of Cangzhou, cast in AD 953, which is 5.4 m high and weighs 50 tonnes. The oxen are cast in a white cast iron, as is most of the lion, but part of the lion in the lotus area is grey or mottled cast iron, probably due to a slower cooling rate (photograph courtesy of D. Wagner, Department of Asian Studies, University of Copenhagen, Denmark).

α Fe

Fe++ Fe (OH)2 Fe+++

Fe (OOH)

γ Fe (OOH)

Fe (OH)3

Fe 3O4 +H 2O γ Fe 2O3 α Fe2O3 α FeOOH -H 2O

Figure 10.2 Phase relationships in rust layers (redrawn by R. Schmidtling after Hiller 1966).

Chinese cast iron pagoda, in excellent condition, is shown in Plate 59. Known as the ‘Eastern Iron Pagoda’ of the Guangxiao Temple in Guangzhou, Canton Guangdong, it was cast in 967. A building has recently been erected around this pagoda to protect it from atmospheric exposure. The large heat capacity of these massive cast iron objects is thought to be one reason why they have survived outdoor exposure so well for so long. Despite this, increasing atmospheric pollution makes the decision to afford additional protection to this pagoda a wise one. The other reason for the comparative corrosion resistance of these large Chinese cast iron objects is that they are usually made of white cast iron therefore there are no graphite flakes (as there would be in a grey cast iron for example) to act as regions for the absorption of moisture and subsequent cathodic corrosion centres relative to the anodic potential of the surrounding ferrite or pearlite that would normally constitute the other phases of a grey cast iron object. Other famous large, exposed iron structures include the iron pillar of New Delhi, dating from the 5th century AD; the iron bridge at Ironbridge, England, which was the first bridge in the modern era to be made of cast iron employing 376 tonnes of iron, erected in 1777; and the Eiffel Tower, finished in 1889 using 7,300 tonnes of wrought iron (Plate 60). Some of these structures, such as the Eiffel Tower, require considerable conservation maintenance but the same also applies to more humble structures such as iron railings, cast iron grills, wrought iron sculpture, wrought iron gates or Corten steel installations. The formation of rust on iron in the atmosphere has been the subject of innumerable studies. The topic is, of course, of immense importance given the financial burden of the rusting process and the many thousands of archaeological iron objects slowly corroding away in ambient or poor storage conditions. Much research has been devoted to determining the relative amounts of

108

Iron corrosion in the atmosphere different iron oxides and oxyhydroxides in the exposed rust layers. A brief summary of the transitional paths between one form of iron oxide and another in rust layers is shown in Figure 10.2; the role of intermediates, such as lepidocrocite, is highlighted in this chart, where the most stable end products are shown to be goethite and haematite. corrosion rate, the overall heterogeneity of these kinds of objects (due to the presence of slag inclusions or variations in carbon content from one region to the other) would not be helpful in resisting corrosive attack. Slag inclusions may act as cathodic sites in the corrosion process. Some useful data on corrosion rates of 18th-century cast iron cannons were obtained by Croome (2004), from an evaluation of 40 cannons at the Prince of Wales’ Fort near Churchill, Manitoba, Canada. Previous attempts had been made to conserve the cannons including treatment with ethylene diamine followed by coating with Tremclad paint; coating with an aluminium mastic epoxy primer with an aliphatic catalyzed polyurethane top coat; coating with an orthophosphoric acid metal conditioner, epoxy primer and urethane acrylic enamel top coat; and finally a coat of Conquest, a tannic acid-based solution with polymeric coating (Busse 1997). In the sub-arctic conditions of southern Canada, with relatively cold temperatures and high relative humidity (RH), all of these coatings have failed. The Prince of Wales’ Fort grey cast iron cannons have been exposed to the elements since 1782 and as part of the conservation assessment, a testing station was established to monitor the corrosion of grey cast iron test panels. Standard procedures established by the ASTM were followed employing ASTM G50-76, the standard practice for conducting atmospheric corrosion tests on metals (ASTM G50), and the standard practice for characterization of atmospheric test sites (ASTM G92). Test coupons were installed on 9 August 1996. Over the five years of the study, the corrosion rate dropped from an average of 14.5 µm/ year in the first year of exposure to an average of 8.6 µm/year after five years of exposure. Extrapolation of the test data suggests a long-term corrosion rate of 6–7 µm/year, which is quite a low rate of attack. The experimental station is planned to be in operation for another 22 years (until 2024) to assess the true long-term rate of corrosion. Extrapolating the corrosion rate of 7 µm/year would predict that the cannon could lose 3–4 mm from their surfaces in 500 years. The royal ciphers, proof marks and weight marks are 3–5 mm in depth, which suggests that in about 500 years time this information will have been lost.

Rate of atmospheric rusting
In general, research shows that during the first few hours or days of exposure to the atmosphere, a moderately protective film of oxides and hydroxides forms. This is followed by the adsorption of water and deposition of particulate matter and pollutants, which produces an electrolyte that allows the electrochemical corrosion of iron to continue. This corrosion can be perpetuated either by oxidation of the metal or by cycles of oxidation and reduction of ferrous and ferric species. A variety of models has been proposed in the scientific literature in an attempt to explain the events that are occurring during the process of rusting. Primarily, these models may be concerned with the corrosion rates observed in outdoor exposure trials, the range of different compounds determined to be present on the iron surfaces, or the detailed electrochemical investigation of corrosion mechanisms for certain exposure conditions of the environment that can be simulated by laboratory experiment. Some useful atmospheric corrosion rate data for low carbon steels, alloy steels and cast irons are provided by Bryson (1987), Oakwood (1987) and Stickle (1987). Bryson provides information relating to a number of different outdoor exposure trials for low carbon steels, but most of this only relates to exposures carried out for relatively short periods of time, such as 50 days to two years. The corrosion rates over the two-year period can be dramatically different; for example a steel exposed in Phoenix, Arizona, was found to have lost 2.23 g in weight, based on a test panel 10 ×15 cm in size, compared with the same at Galeta Point Beach, Panama, which had lost 336.0 g in weight! The author relates data to the corrosion rate of steel at Bayonne, New Jersey, which varied from 0.075 mm/year to 0.025 mm/year depending on the time of exposure. Recent outdoor trials under the auspices of the UN programme ‘The convention on long-range transboundary air pollution’ are summarized by Kreislova et al. (1997), which covers exposure data coupled with gaseous pollutant measurements. In London, for example, the weight loss after two years was about 234 g m–2, while in Los Angeles the figure was 182 g m–2. Mattson (1988) summarizes data for the corrosion of low carbon steels in general terms as follows: These corrosion rates only apply to the first few years of exposure since the rate of corrosion will generally decline the longer the iron or steel materials are exposed to the atmosphere. The data are therefore of only limited utility for ancient or historic ferrous materials. While the presence of other alloying elements such as phosphorus in ancient objects would initially reduce their
Environment corrosion rate µm/year rural urban industrial marine 4–65 23–71 26–175 26–104

Modelling atmospheric corrosion
Early and useful work on the atmospheric corrosion of iron was carried out in England and Wales, especially by Vernon (1927, 1931, 1935a) and Evans (1930). One of the developments made by Evans is the diagram that still bears his name and which can be used to investigate many types of corrosion events. These are also known as polarization diagrams or mixed potential diagrams. Why should we be interested in these Evans diagrams? It is true that the rate at which a process occurs is generally less applicable to the long-term modelling of corrosion than the stability fields that are predicted under equilibrium conditions by the Pourbaix diagrams. The problem is that it is not sufficient to ascertain if iron will corrode under a given set of environmental conditions. Even though the tendency to corrode may be high, the rate of corrosion may be so low that, in reality, there is no corrosion, or very little. The corrosion currents help us here, and can be investigated with the Evans diagram. The other area of research where this is of use to us is in the application of corrosion inhibitors to metal surfaces. These inhibitors may function to suppress the anodic or cathodic 109

Iron and Steel in Ar t

2 icorr

E0,c i Potential E
1 Ecorr 1 o,c 2 io,c

dic ano
2 Ecorr

cat ho dic 2 cat ho dic 1

Eo,H io,H
1 icorr

Log i
Figure 10.3 Polarization curves for iron showing the derivation of the anodic and cathodic Tafel lines, which are then used in the Evans diagram. The x-axis is the logarithm of the current density and the y-axis is the electrode potential (redrawn by M. Gleeson after Kruger 2005). Two cathodic reactions are shown, the one with the higher cathodic density ‘i20c’ giving the higher corrosion current ‘i2corr’.

E
Eo,c Ecorr Eo,c

E

Ecorr Eo,a icorr (a)

i

Eo,a icorr (b)

i

E
Eo,c Ecorr

Eo,a icorr (c)

i

Figure 10.4 Evans diagrams for three different corrosive situations, reactions under anodic control, shown in (a) those under cathodic control, shown in (b) and those where both the anodic and cathodic reactions are equally important, shown in (c). These diagrams are useful for the investigation of corrosion inhibitors and coatings for iron (redrawn by O.G. Ustun after Kruger 2005).

110

Iron corrosion in the atmosphere reaction, or represent a mixed suppression of both the anodic and cathodic reactions, so their benefit can be measured by using an Evans diagram. This is important if an anodic inhibitor is used in a situation where the major factor in the corrosion process is a very aggressive cathode. The inhibition of corrosion under these circumstances may be inferior compared with the use of a cathodic inhibitor. Any electrochemical reaction can be algebraically divided into separate oxidation and reduction reactions, with no net accumulation of electrical charge. In the absence of an externally applied potential, the oxidation of the iron and the reduction of some species in solution occur simultaneously at the iron/ electrolyte interface and so the measurable current is zero. Data are often presented per unit area as current densities, since this may be a better way to examine the corrosion situation. Different types of diagrams can be drawn up depending on whether the corrosion processes are controlled by some kind of activation potential, or whether the concentration of a reactive species controls the corrosion. Corrosion rates can be determined by applying a current to the iron to produce a polarization curve. When the potential of the iron surface is polarized by the application of current in a positive direction, it is said to be anodically polarized; when in a negative direction, it is called cathodically polarized. The degree of this polarization is a measure of how the rates of the anodic and the cathodic reactions are retarded by different environments. A number of factors need to be considered here such as the concentration of iron ions in solution, the amount of dissolved oxygen, the temperature, the pH and so on, and here we will follow the explanation of Kruger (2005). The variation of potential as a function of current allows the study of the effect of concentration and activation processes on the rate at which anodic or cathodic reactions can give up or accept electrons. Therefore, polarization measurements can determine the rate of corrosion, and we may be especially interested in this rate, particularly if a corrosion inhibitor or coating has been used on our metalwork. Figure 10.3 shows some anodic and cathodic polarization curves. In this figure, the potential ‘E’ is plotted as a function of the logarithm of the current density, ‘i’. When the corrosion reactions are controlled by activation polarization, a straight line plot will be found. On Figure 10.3, ‘Eo,a’ and ‘Eo,c’ are the equilibrium potentials for the anodic or cathodic reactions. These ‘Tafel lines’ are given by the ‘slope’ of the linear part of the polarization curve and by their intercept. The ‘intercept’ is proportional to the logarithm of the exchange current density ‘io’. The values of these figures in the Tafel equation depend on the metal and the environment. It is possible to extrapolate the anodic and cathodic linear portion of these curves to give the corrosion potential ‘Ecorr’. The value of the current at the intersection of these lines will be the rate of corrosion, ‘icorr’ expressed in current density. Parts of the extrapolations shown in Figure 10.3 produce the Evans diagrams in Figure 10.4. The relative values of the slopes of the anodic or cathodic polarization curves determine whether the reaction is under the control of anodic, cathodic or mixed reaction potentials. Not only are these diagrams useful for the study of the effects of corrosion inhibitors, they are also important in the modelling of atmospheric corrosion, where the determination of current densities is relatively straightforward. For example, the decrease in the current density of iron exposed to the atmosphere can be measured as the oxide layer builds up over time. Vernon (1927) was one of the first researchers to demonstrate the effect of the development of a passive oxide film on the surface of iron on the course of subsequent corrosion. Iron specimens exposed indoors to low RH were placed into two different environments: one with the usual dust content of the ambient air and the other screened behind a muslin cloth. Vernon drew attention to the hygroscopic nature of dust particles, as the exposed iron plates began to form discontinuous rust particles, while the screened ones did not rust even when exposed for periods of up to 92 days in duration. These samples were subsequently used in an exposure where the iron plates, previously exposed but screened with muslin for 314 days and still showing no signs of rust, were exposed together with freshly cleaned specimens. The interesting result of this experiment was that, for a time, the screened specimens still preserved their bright appearance, while the rusting of the new specimens proceeded in the usual way. Later, tiny specks of rust appeared, but the subsequent course of attack was then quite different from that obtained in other cases, and consisted in an intensification of existing rust spots rather than in the formation of new ones. The results of this experiment are shown in Figure 10.5 (Vernon 1927: fig. 26) and have been essentially confirmed as valid by more recent work on passivation (Cox and Lyon 1994). The investigations by Evans into metallic corrosion were usefully summarized in his textbook on the subject which was published in 1960, although the diagrams named after him are not featured prominently in the text. Another seminal series of observations by Evans resulted in his description of localized corrosion within a salt water droplet on a steel surface, where he found a ring of rust well within the boundary of the droplet as a result of immunity of the outer region of the droplet as the inner region became anodic. Evan’s explanation, which according to Stratmann (2002) is still valid, is based on the difference in the transport kinetics for molecular oxygen between the outer and inner parts of the droplet. Due to the high rate of oxygen reduction in the outer region, the steel passivates while the inner region becomes anodic and corrodes preferentially. Evans (1960) proposed not only that the reduction of oxygen was important as a cathodic reaction, but that the reduction of ferric rust species must also be considered as important too, and this electrochemical approach to the problem of rusting has been shown to be correct by later research. Evans also pointed out that ‘atmospheric exposure’ may comprise a number of different conditions which he divides into three categories:

Figure 10.5 Relative behaviour on exposure to room atmosphere of iron samples. Curve A represents previously exposed but apparently nonrusted samples while curve B shows the weight gain for freshly prepared samples (redrawn by M. Gleeson after Evans 1960).

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1 2 3

Low RH: below the critical RH level at which attack becomes rapid. Medium and high RH: above the critical RH range and extending up to saturation. Rain, mist and fog: unsheltered exposure in the open air.

The critical level of RH on exposure is often stated to be around 70%. However to define a critical level is somewhat arbitrary; levels above 70% are often very corrosive, but the actual value of the critical RH level is dependent on the type of corrosion products that have formed and the nature of the corrosive environment (for example, Bryson 1987: fig. 4, 2), and as we have seen, levels as low as 15% RH have been proposed as necessary to be below the critical level for hydrated ferrous chlorides (Turgoose 1982b). Vernon (1935b) showed the importance of atmospheric particulates, otherwise known as dust, in the indoor rusting of iron objects, and categorized the particles in terms of their ability to create corrosion: 1 Harmless: producing no rust. Vernon employed pure silica particles for this experiment, although, of course, in longterm exposure, the silica particles may eventually promote corrosion due to differential electrochemical potential as a result of different oxygen diffusion pathways. Intrinsically corrosive: producing rust where the particles settle, typically ammonium sulphate particles, commonly found in industrial areas. Indirectly corrosive: carbonaceous particles which, by absorbing acidic atmospheric gases, can profoundly stimulate corrosion in medium or high RHs.

2 3

which, in turn, heterogeneously catalyzes the oxidation of SO2 to SO42–. Although SO2 readily adsorbs smoke at active sites, the conversion of SO2 to SO32– is quite slow and rapid further conversion to SO42– requires alkaline conditions. Thus, beyond the early stages of corrosion, the longer term effects of smoke may be inhibited by SO2 molecules blocking catalytic sites on smoke particle surfaces. The gaseous pollutants such as ethane, ethylene and acetylene probably interact directly with smoke producing CH3∙ free radicals whose subsequent effects are to alter the structure of the hydrated ferric oxide membranes, enabling the smoke-enhancing corrosion effect to continue. As a result of their experimental work, Skerry et al. were able to conclude that the presence of sulphur dioxide in the air at a concentration of 3.5 ppm significantly enhances corrosion at 85% RH compared with a control with 5,500 ppm of carbon dioxide at the same RH. Schikorr (1963, 1964) examined the rusting of exposed iron based on a cycle involving the initial formation of ferrous sulphate from iron, oxygen and atmospheric sulphur dioxide. Indeed sulphate species are strongly associated with corrosion on exposed steel and iron oxides can act as a store of sulphate ions underneath a layer of FeOOH, forming a semi-permeable membrane. This explanation of the mechanism of atmospheric rusting has become known as the ‘acid regeneration cycle’, the essential feature being the oxidation of ferrous sulphate to ferric sulphate, which subsequently hydrolyzes to a hydrated ferric oxide and sulphuric acid: Fe2+ + SO42– → FeSO4 (10.3) 2FeSO4 → aerial oxidation → Fe2(SO4)2(OH)2 (10.4) Fe2(SO4)2(OH)2 + 2H2O → Fe2O3∙H2O + 2H2SO4 (10.5) The released sulphuric acid then attacks the iron to create more ferrous sulphate, which is converted by hydrolysis to more iron oxide and again releases sulphuric acid. Indeed Schikorr (1964) showed that each molecule of sulphur dioxide adsorbed onto the iron surface produced between 15 and 40 molecules of rust. Evans and Taylor (1972) examined an alternative model to explain this phenomenon known as the ‘electrochemical cycle’. In this model, small amounts of hydrated ferric oxides (rust), together with ferrous sulphate and iron metal produce an electrochemical cell based on Fe/FeSO4/FeOOH. The reaction at the anode being the generation of ferrous ions: Fe → Fe2+ + 2e– (10.6)

Some of these themes have been re-examined in recent years as concerns for the effects of atmospheric pollutants, smoke and dust on the corrosion of metals and the health of human beings has become more prevalent. For example, Skerry et al. (1988a,b) carried out detailed studies of the rusting of exposed iron to smoke, hydrocarbon and sulphur dioxide contaminated air. These authors used a simple smoke aerosol to generate principally carbonaceous particles in conjunction with control air to which various additions of sulphur dioxide were made. The results showed that sulphur dioxide had an overriding effect on the corrosion product characteristics, but addition of smoke gave corrosion products with more pronounced features of plugs and pits. Ethane, ethylene and acetylene only marginally modified the form of the corrosion with a tendency to form filamentous products. As pure iron in pure humid air does not corrode significantly, some assistance is needed. Evans (1960) showed that the oxide layer can be broken down by reductive dissolution: Fe2O3 + 6H+ + 2e– → 2Fe2+ + 3H2O (10.1)

At cathodic regions of the surface these electrons will then be consumed: Fe2+ + 8FeOOH + 2e– → 3Fe3O4 + 4H2O (10.7)

This reaction can be assisted by carbonate or bicarbonate ions, resulting in a corrosion pustule due to the combined effects of oxygen, water and carbon dioxide. The effect of smoke is to help oxidize the ferrous ions catalytically. When a smoke particle is inside an actively corroding protrusion, catalytic reduction of ferric ions at the cathode sites can occur: Fe2+ + 8FeOOH + 2e– → 3Fe3O4 + 4H2O (10.2) During the early stages of corrosion, smoke appears to increase the corrosivity of SO2 by promoting the oxidation of Fe2+ to Fe3+ 112

The magnetite that forms will be rapidly transformed by atmospheric oxygen to the usual products of rust: 3Fe3O4 + ¾O2 + 4½H2O → 9FeOOH (10.8)

Evans and Taylor (1972) make the point that there are now nine molecules of FeOOH instead of the previous eight, due to the additional participation of an extra ferrous ion. The amount of ferrous ions consumed equals that regenerated by the anodic reaction. Since iron enters the liquid at one point and leaves at another, this newly formed rust will not be protective and

Iron corrosion in the atmosphere further corrosion can occur. Initially in the 1960s there was a sceptical response to this idea, which had been suggested by Evans some years before. This was echoed in the response to the model proposed by Evans and Taylor in 1972, partially due to the belief that magnetite, once formed, would be too stable a substance to undergo hydrolysis, but Evans and Taylor found that the newly formed magnetite soon loses its magnetism and undergoes alteration to a rust-red colour when exposed to water with access to air. A qualitative experiment by the authors was carried out using samples kept in closed tubes to air containing specific amounts of moisture and sulphur dioxide. The first change was the appearance of a faint mist of moisture on the surface that could be wiped off with filter paper; it was found to contain ferrous ions. As a result of the work of Stratmann (1990) and Cox and Lyons (1994), the electrochemical cycle of Evans has had to be modified. FeOOH and Fe2+ or Fe(OH)2 comprises the oxidized and reduced species respectively. The reversibility of this reaction depends very much on the pH of the electrolyte. No evidence for the oxidation of Fe3O4 to FeOOH was found by Cox and Lyon, but there is evidence for a redox couple involving Fe3O4 or Fe2O3 and Fe(OH)2 as the oxidized and reduced species, although they offer no set of equations to explain the whole process. One set of possible examples of reactions could be as follows. The reaction at the anode being the generation of ferrous ions, as before: Fe → Fe2+ + 2e– (10.9) typically after two weeks or less in the ambient environment. The corrosion processes may be strongly influenced by other anions such as sulphate and chloride in the surface film which compete for the iron cations and form rust layers that are significantly less protective than the simple oxy anion species. The pH of the moisture on the surface, which is strongly influenced by chloride, sulphur dioxide and nitrogen oxides, is of great importance as this governs the dissolution of the passive oxyhydroxide surface. In situations where the RH exceeds 50%, multilayers of water are absorbed on the surface with increased corrosion rates. The rust layers that form on exposed wrought iron or low carbon steels are poorly adherent and contain many pores, with diameters as large as 15 nm, allowing continual access of oxygen and moisture to the iron surface. The structure of this rust layer on weathering steels is different, as it consists of a double layer with the inner providing a more effective barrier to oxygen diffusion, which limits the extent of corrosion. Music et al. (1993) reviewed the chemical and structural properties of rust formed by the corrosion of steel in the atmosphere. Leidheiser and Music (1982) employed Mössbauer spectroscopy to determine the nature of the rust formed on steel after atmospheric exposure of steel for various periods of time at Bethlehem, Pennsylvania. Lepidocrocite was determined to be the initial corrosion product that converted over time to a mixture of goethite and maghemite after more than 25 years; the rust was found to contain over 90% maghemite. The fact that these products are essentially the same as those that form when steel is exposed to ferrous sulphate solutions under mildly acidic conditions suggest that sulphate ions have played a crucial role in the atmospheric effects. This is supported by the fact that the Bethlehem region is heavily polluted with sulphur dioxide due to the proximity to an ironworks and a coke factory. Mössbauer spectroscopy of the rust formed in the atmospheric corrosion of iron in the presence of sulphate anions showed the presence of lepidocrocite and ferrihydrite after three days (Leidheiser and Czako-Nagy 1984). The presence of maghemite became more pronounced as time progressed, especially after more than six weeks of exposure. Music et al. (1993) continued their study with the exposure of cold-rolled low-carbon steel (JUS-C0146) to solutions of sodium chloride, sodium nitrate and sodium sulphate varying in concentration from 0.05 to 5 mol l–1. The products that formed were all varieties of the iron oxides, frequently magnetite, lepidocrocite and ferrihydrite being determined as present, and, in the case of the chloride ion solutions, akaganéite. Ferrihydrite is more commonly found in oxidation at higher temperatures, and its presence in rust is not dependent on the type of inorganic anion present. Ferrihydrite is poorly crystalline and can transform to goethite or haematite or, in some circumstances, lepidocrocite. Ferrihydrite is therefore thermodynamically unstable and may undergo a topotactic transformation as it alters to haematite through goethite as an intermediary. Ferrihydrite can transform directly to haematite at pH 7–8. The formation of magnetite could be interpreted as the decomposition of iron(II) hydroxide: 3Fe(OH)2 → Fe3O4 + 2H2O + H2 (10.12)

At cathodic regions of the surface these electrons will then be consumed: FeOOH + H+ + e– → Fe(OH)2 (10.10) And electrons and hydrogen ions could be regenerated by the formation of haematite: 2Fe(OH)2 → Fe2O3 + 2H+ + H2O + 2e– (10.11)

The problem is to decide whether the acid regeneration cycle, expressed by equations 10.6–10.8, or the electrochemical corrosion cycle, equations 10.9–10.11, is operative in the case of atmospheric rusting in the presence of sulphate ions. An attempt to form a unified theory of the corrosion of iron in the atmosphere was provided by Graedel and Frankenthal (1990) who list 20 different minerals as possible components of naturally formed rust layers. The only drawback to this comprehensive approach is that some of the compounds listed are not discussed in detail in the article but are only cited as possible rust components, so that the theory appears not to explain all possible events. Nonetheless, this is a useful review of atmospheric corrosion in which three distinct stages of corrosive attack are postulated: 1 The formation of the oxide or hydroxide layer, 1–4 nm thick, which may be stable and passivating in the absence of high RH, atmospheric impurities or liquid water. 2 The alteration of this layer with aqueous media, into one of the green rusts, either GR1 or GR2. 3 The transformation of the green rusts into the typical brown rust layer of iron oxides and hydroxides, which may also contain magnetite. Leidheiser and Music (1982) found lepidocrocite (γ-FeOOH) present in advanced layers of rust which Graedel and Frankenthal (1990) regarded as an indicator of the third stage of rusting,

However the authors state that it is more probable that magnetite forms by the reaction of FeOH+ complexes with Fe3+-hydroxy complexes or amorphous iron(III) hydroxide. A synopsis of the different reaction routes proposed by Graedel and Frankenthal (1990) is shown in Figure 10.6.

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Iron and Steel in Ar t

FeII (bulk)

C1-

C1

FeOC1 FeOOH

[O]

Green rust I & II

[O]

7

D.R.

α

Figure 10.6 Corrosion scheme for exposed iron surfaces during atmospheric rusting (redrawn by R. Schmidtling 2003 after Graedel and Frankenthal 1990).

Another model of atmospheric corrosion was proposed by Stratmann (1990), who tried to re-evaluate the physico-chemical fundamentals of the process, especially on the surface of the iron as a result of alternating cycles of wetting and drying, which were investigated utilizing a number of electrochemical and spectroscopic techniques. Stratmann emphasized the difference in corrosive events that may occur due to the cyclical processes involved in the atmospheric corrosion of iron objects: 1 After wetting a dry corroded metal surface the cathodic partial reaction of the corrosion process is given by the reduction of Fe3+ to Fe2+ within the lattice of γ-FeOOH. If the corrosion potential is rather negative, then magnetite is formed. As a consequence of the formation of the ferrous ions, the electronic conductivity of the oxide layers close to the metal/ oxide interface is increased. This results in an acceleration of the kinetics of oxygen reduction. Oxygen is reduced predominantly at the oxide/electrolyte interface and not at the metal/electrolyte interface. Therefore the rate of oxygen reduction is determined by the electronic properties of the oxide layers, the kinetics of the electron-transfer reaction being very fast on oxide surfaces, especially those containing ferrous ions.

2

3

If the metal surface is covered with a thick electrolyte layer, then the charge transfer reaction is so fast within the reduced oxide scale, that the overall rate of the oxygen reduction is determined by the diffusion of oxygen through the waterfilled pore system of the scale and by the surface area of the oxide scale, which allows an electron transfer to occur at the oxide/electrolyte interface. The size of this effective surface area is determined by the amount of the reduction of the oxide scale immediately after wetting the dry metal surface. Then, during drying, oxygen diffuses rapidly into the pore system of the oxide scale by gas diffusion. The corrosion rate is increased dramatically due to the fast oxygen reduction at the large surface area of the oxide which functions as the cathode. Due to this fast corrosion rate, a dense oxide layer is formed on top of the metal surface and the surface may be passivated. The corrosion stage of drying is terminated by a re-oxidation of the oxide scale by oxygen, which causes the rate of the oxygen reduction to decrease as the electronic conductivity of the oxide scale is reduced. Oxygen is reduced mostly at the phase boundary between the oxide and electrolyte and not at the metal–electrolyte boundary.

114

Iron corrosion in the atmosphere The oxide scale does not function as a simple barrier, but is active electrochemically in cycles of wetting and drying. Electrical charge can be stored within the oxide scale by changing the oxidation level of the cations between +3 and +2, allowing a non-stationary anodic metal dissolution without any reduction of oxygen. As part of this process, ferric ions within the lepidocrocite lattice are reduced to the ferrous state and simultaneously H+ diffuses into the oxygen sublattice of the oxide phase; this reaction is reversible. At more negative potentials, magnetite is irreversibly formed from lepidocrocite and additional redox reactions are possible within the spinel, magnetite, phase. The oxide scale under these conditions functions as a large cathodic zone if the ferrous ions are formed within the ferric sublattice of the oxides. The electronic properties of the reduced oxides determine the rate of electron transfer reactions such as the reduction of oxygen. If the surface is covered with a thick electrolyte layer, the corrosion potential will be more negative and the reduction of the oxide scale will accelerate the charge transfer so that the rate of the oxygen reduction will be determined by the diffusion of oxygen into the pore system of the oxide scale. During drying, the diffusion of oxygen is accelerated (as it has a shorter way to go), the charge transfer reaction is then rate determining and a strong relationship exists between the reoxidation of the ferrous states and the kinetics of the electron transfer reaction. Figure 10.7 summarizes the principal reactions proposed by Stratmann (1990) discussed here. Some of the conclusions of this study were confirmed by subsequent research by Cox and Lyon (1994), which also looked into the different types of processes occurring during wetting and drying. They found that during wetting of the surface, the passivity of the iron surface breaks down and the rust is polarized cathodically by the iron substrate from a comparatively anodic potential of about 0.240 VSHE to a range of –0.460 VSHE to –0.260 VSHE. During this drift in potential in the cathodic direction, and depending on the pH, iron oxyhydroxides are reduced to Fe(OH)2 or ferrous ions. Reduction of Fe2O3 to Fe3O4 may also take place. These reactions are probably supported by the anodic dissolution of iron. When the reducible iron species are exhausted, oxygen reduction then predominates. As the surface dries out, anodic dissolution continues at an increased rate, largely due to oxygen diffusion through the thin electrolyte layer. The potential of the iron/rust electrode drifts in the anodic direction and ferrous ions may be oxidized to Fe2O3 or Fe3O4. No evidence for the oxidation of Fe3O4 to FeOOH was found, but evidence was found for a redox couple involving Fe3O4 or Fe2O3 and Fe(OH)2 as the oxidized and reduced species. The authors note that the importance of this redox cycle during the atmospheric corrosion of iron depends on the volume of available rust that can be reduced, which itself is dependent on the conductivity of both the rust and the electrolyte. Upon wetting of an already corroded surface, the electrolyte will dissolve retained salts, progressively diluting them and reducing electrolyte conductivity. This means that the time during which cathodic reduction of rust is important in supporting a relatively high rate of anodic dissolution of iron may be limited, although in ancient or historic exposed iron objects with thick corrosion layers, cathodic reduction of rust layers may be more significant, since retention of water under thick, permeable layers of rust is so much easier than in laboratory pre-rusted specimens.

5

4

Weissenrieder and Leygraf (2002) studied the initial corrosion of iron and showed that an aqueous adlayer of constant mass was

γ

red surface layer on top of γ

red surface layer on top of α

α

U < U*

γ

[( α

) * = superparamagnetic α crystal size < 240Å]

Figure 10.7 Phase relationships in rust scales (redrawn by R. Schmidtling after Stratmann 1990).

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Iron and Steel in Ar t physisorbed onto the surface at a given RH. This aqueous layer was found to be thicker when compared to previous studies performed on copper. A linear relationship between mass change and the intensity of the water absorption band at 3400 cm–1 was found, as a function of the change in RH. At high RH, a thick aqueous layer formed and the introduction of sulphur dioxide and ozone in the sub-ppm range produced sulphate surface species. membrane is raised; osmotic forces and enhanced electrolytic transport of OH– into the nest help to dilute and localize the solution inside the nest, accelerating the formation of FeOOH and H2SO4. In long-term atmospheric rusting, periods of enrichment of SO42– alternate with those of depletion; the primary reason for the uneven distribution of FeSO4 on the surface however remains unknown (Schikorr 1963). Iron(II) sulphate tetrahydrate, rozenite, is the most abundant sulphate found in these circumstances, with the heptahydrate, melanterite, also being identified.

Atmospheric corrosion and sulphates
Following the usual oxides and hydroxides, the iron sulphates are the most frequently mentioned constituents of rust due to atmospheric exposure. The overall accelerated corrosion of iron in the presence of sulphate ions led Schikorr (1963) to propose a three-stage process: first, the absorption of SO2 onto damp rust; second, the formation of ferrous sulphate by the oxidation of iron with oxygen and SO2; third, the oxidation of ferrous sulphate to create more oxyhydroxide rust, producing free SO42– to maintain the corrosion cycle, which continues until SO42– is removed as insoluble ferric hydroxysulphate. A possible reaction sequence is: Fe + SO2 + O2 → FeSO4 (10.13) 4FeSO4 + O2 + 6H2O → 2Fe2O3∙H2O + 4H2SO4 (10.14) 4H2SO4 + 4Fe + 2O2 → 4FeSO4 + 4H2O (10.15) Since the presence of iron catalyzes the oxidation of sulphite to sulphate, the sulphur dioxide absorbed onto the surface creates HSO3– ions that are rapidly oxidized to HSO4–. Complexes may be formed between sulphate ions and other species such as hydroxyl groups creating Fe(OH)SO4 that precipitates in the range from pH 2.3 to 3.7 and Fe2(OH)4SO4 in the range of pH 3.7–4.9 (Graedel and Frankenthal 1990). If sodium or potassium ions are also present, then sodium or potassium jarosites will form (Lowson 1982) as NaFe3(OH)6(SO4)2 or KFe3(OH)6(SO4)2. Often, sulphate on the iron surface appears to be localized into ‘nests’. The spread of these sulphate nests on iron surfaces was investigated by Barton et al. (1971) using low carbon steels. The leaching of sulphate ions from ferrous sulphate nests containing rusted steel and the consequent weight changes due to water uptake from humid atmospheric conditions and oxidative hydrolysis were studied. The data obtained by Barton suggest an alternative behaviour of an active nest relative to previous studies; the membrane covering the FeSO4 within the nest plays a very important role because in the course of corrosion, this membrane cracks and periodically releases a drop of concentrated ferrous sulphate solution, or even a solid crystal which initiates a new corrosion centre (Schikorr 1963, 1964). Sulphate ions, formed from atmospheric sulphur dioxide, can be transported against the existing concentration gradient only by electrolytic action. This is possible in some rust layers since the rust itself can be a conductor, which means that the metallic surface does not necessarily need to be composed of anodic and cathodic areas; because of this the sulphate ions can still be drawn inwards. Electric field forces may induce SO42– and OH– to move through the anion permeable membrane, so that new Fe(OH)2 and FeSO4 form beneath it. This is then followed by oxidation to red rust from the green rust intermediate products, which after coagulation releases H2O, causing membrane rupture. This process is accelerated when the water activity outside the 116

Atmospheric corrosion and chlorides
The influence of chloride ions, especially in environments exposed near the coast, may be severe. The chloride ions may be easily transported to the corroding metal interface, with the production of GR1, akaganéite, and perhaps some ferric oxychloride, although evidence for the latter is weak. The corrosion cycle discussed above by Askey et al. (1993) for deterioration during burial may also be used as a possible model for continued corrosion in the presence of chloride ions in the atmosphere, where the generation of hydrochloric acid is potentially very damaging: 2Fe + 4HCl + O2 → 2FeCl2 + 2H2O 2FeCl2 + 3H2O + O2 → 2FeOOH + 4HCl (10.16) (10.17)

The complexity of the deterioration of iron in the presence of chloride ions is shown by the longevity of iron pilings used for piers or for sea defences, despite the higher corrosion rates associated with chloride ions. Evans (1960: 504) reviews tests carried out in Nigeria by Ambler, at different distances from the sea, which show how rapidly the corrosion rate falls off as the amount of salts reaching the samples diminishes. In one example, at 50 yards from the sea, the corrosion rate was 5.6 g dm–2/month, but only 0.25 g dm–2/month two miles inland. If rusted surfaces contain ferrous chloride, then enhanced rates of deterioration are found compared with rust without chlorides. For example Buckowiecki (Evans 1960: 505) placed a patch of rust containing about 1% chloride onto a steel specimen exposed to 95% RH at 20 °C for seven days, and then removed the rust by light brushing; further exposure showed fresh corrosion where the rust patch had been placed, but a similar experiment using a patch of rust without chloride ion content showed almost no surface change to the steel specimen after the same exposure. Iron structures in the littoral that can be washed by the sea may exist in a complex zone of tidal corrosion, submersion and aerial oxidation. For example, the erosion and corrosion of the historic iron defences along the Norfolk coast at West Runton, England, produced laminated corrosion layers on a steel bolt whose interior corroded surface had a white deposit associated with the iron oxyhydroxides, shown in the environmental scanning electron micrograph of Figure 10.8. The deposit was shown to be of magnesium hydroxide.1 Seawater contains about 0.05 mol l– of magnesium. One possible explanation is that the iron sea defences are regularly exposed to seawater, which may then dry out in the air before being wetted once more; if continued over long periods of time, this may be enough to allow the magnesium hydroxide to
1 D.A. Scott, unpublished data on Norfolk iron sea-coast defences.

Iron corrosion in the atmosphere 290–400 nm range, which overlaps both the solar spectrum and the spectrum of fluorescent tubes. The Fe3+ complexes undergo charge transfer from the ligand to the metal centre, the result being the production of free hydroxyl radicals to enhance the process of corrosion: [Fe(H2O)5(OH)]2+ + H2O → hν → [Fe(H2O)6]2+ + OH·(10.18) [Fe(H2O)4(OH)2]+ + H2O → hν → [Fe(H2O)5(OH)]+ + OH· (10.19)

Effects of copper and other alloying elements
Small additions of copper, phosphorus, chromium or nickel are usually beneficial for corrosion resistance. Evans (1960: 506ff.) reviews some of the early work related to this issue, dating to around 1913, in which it was already known that addition of 0.15–0.34% copper dramatically reduced the rate of corrosion of iron, and that the presence of both phosphorus and copper was even more beneficial. At the time that Evans was writing it was not clear why these elements were beneficial to the corrosion resistance, and the subject was revisited by Stratmann et al. in 1987. The effect of small quantities of copper on the corrosion of iron is of interest, since many ancient iron alloys contain copper as a minor impurity, often segregated at weld lines or joins. In contrast to pure iron, iron with 0.5% of copper changes its corrosion behaviour with repeating cycles of wetting and drying of the surface. It is not known exactly why copper should have this effect and two different models have been proposed to account for it. In the first model, copper is assumed to alter the kinetics of the cathodic reaction. If oxygen reduction takes place in the rust film itself (the Evans theory already discussed above), then one possibility is that the incorporation of copper into the oxide lattice alters the electrical or electronic properties of the oxide. The alternative hypothesis supposes that the copper influences the kinetics of the anodic reaction. The anodic dissolution of the metal appears to drop in rate from 500 mA cm–2 to less than 100 mA cm–2 after 12 wet-dry cycles for the copper-containing iron, while for pure iron, the rate is more than 1000 mA cm–2 over the same 12 cycles. However, this drop could equally be due to the retardation of the cathodic reduction so it is currently impossible to decide which mechanism is correct.

Figure 10.8 Magnesium hydroxide precipitates on iron from the coast of Norfolk, England (photomicrograph courtesy of the Getty Conservation Institute and D. Carson 2001).

form as a cathodic precipitate as the anodic dissolution of the iron slowly continues under the magnesium hydroxide corrosion layer. Normal seawater will form Mg(OH)2 above a pH of 9.2. If during drying the magnesium concentration increases tenfold, a pH of at least 8.7 would be needed for this precipitation to occur.

Other atmospheric corrosion factors
The corrosion of steel in atmospheres containing small amounts of both sulphur dioxide and nitrogen oxides has been investigated by Johansson (1984) who makes the valid observation that while the importance of sulphur dioxide on the corrosion of iron has received a great deal of attention, there are many other atmospheric pollutants to be considered, such as ozone and the nitrogen oxides. Johansson showed that sulphur dioxide by itself was not very corrosive at low RHs (50%), with less than 2% of the sulphur dioxide supplied being absorbed: 3 ppm of NO2 in air caused rather faster corrosion than SO2, but when both pollutants were added simultaneously, the weight gain was approximately 30 times the value found for sulphur dioxide alone. Photoprocesses involving corrosion of iron exposed to light have been implicated as an additional factor that must be taken into account. Iron oxides absorb photons with wavelengths throughout the visible spectrum, with an absorption maximum close to 400 nm. In the case of haematite, formation of an electronhole pair may be followed by the formation of a surface-bound hydroxyl ion (Graedel and Frankenthal 1990). Ferric ions have mono and dihydroxy complexes prevalent that absorb over the

Corrosion of weathering steels
The modern, so-called ‘weathering steels’ corrode at a much slower rate than wrought iron or low carbon steel. These types of steel have been employed extensively for public sculpture and artistic creations in recent years, and several of them may present unusual conservation problems, such as failure of welded joins or localized corrosion due to bird droppings or stagnant water that were not foreseen when the sculpture was installed, that might lead to laboratory tests with organic coatings (Decker et al. 2008). The first building erected using this kind of steel was in Moline, Illinois, while other important structures include the sculpture by Picasso in front of the Chicago Civic Center. As Pourbaix (1977) 117

Iron and Steel in Ar t notes, these steels do not resist corrosion by stagnant water and because it takes several years before the rust is really protective, severe staining may afflict the sculpture. Pourbaix discusses the problem of forming a protective patina on a low alloy steel in a short period of time. This resolves around the problem of increasing the electrode potential of the steel, in the presence of rainwater with a pH of about 6, to between +450 to +550 mVSHE (see Pourbaix 1977 for more extensive discussion). These weathering steels corrode more slowly than carbon steels, with typical corrosion rates in the urban environment being from 4 to10 µm/year. The most well-known steel for use outdoors is ‘Corten’ steel. Corten is a 400 series stainless steel development by the US Steel Corporation around 1960, in accordance with ASTM A6 specifications. As a result of the development of these special alloy steels, consisting essentially of iron with small alloying additions of chromium, phosphorus, copper or nickel, these weathering steels can be left to corrode in the atmosphere, with the result that a protective film of iron oxides slowly develops that impedes further rusting. This rusted patina allows the iron alloys to be used outdoors for sculpture or architectural purposes, although they cannot be given a bright and polished finish: the usual appearance is a dark red, rusted surface, often with a purple tinge. This approach to dealing with the rusting of exposed steel, by actually allowing protective rusting to take place, has now been in use for over 40 years. These steels have been the subject of much research in order to account for their corrosion resistance. Exel (1977), for example, carried out some studies of corrosion resistance on samples 90 × 90 × 2 mm with two formulations of slightly different chromium and phosphorus content. The samples were exposed to urban (Ljubljana, Slovenia) and rural (Bohinj, Slovenia) localities with the reduction in thickness calculated from the weight loss. The thickness of the Corten steel was reduced by between 0.14 and 0.15 mm after a period of six years, before corrosion ceased. In steels with lower phosphorus and chromium content the reduction in thickness reached 0.155–0.20 mm depending on the corrosivity of the environment and the season of the inception of the exposure programme. However, this study did not consider the corrosion events and the patina formation over a sufficient period of time. A more thorough study along the same lines was carried out by Misawa and Miyuki (1999) over a period of 26 years, who showed that the final protective rust layer consisted of a chromium substituted goethite (α-(Fe1-x,Crx)OOH). This chromium-substituted goethite is preceded by an initial development of an X-ray amorphous iron oxyhydroxide. It was shown by Misawa et al. (1974b) that amorphous ferric oxyhydroxide containing a significant amount of bound water can act as a protective barrier against atmospheric rusting. The amount of the different iron oxide components in the rust layer changes with time. For example, the proportion of lepidocrocite in the total rust layer decreases with time over ten years, which results in a corresponding increase in the amount of X-ray amorphous material such as ferric oxyhydroxide and chromium-substituted ultrafine goethite. When the exposure exceeds ten years, the amorphous material decreases and the amount of goethite increases; after 26 years this rust layer was shown by Raman spectroscopy to be composed of two layers: a dense inner layer possessing a goethite-type oxyhydroxide structure, and an outer layer principally comprised of lepidocrocite. Electron probe microanalysis (EPMA) showed that the chromium from the steel is accumulated in the inner goethite structure and is present to the extent of about 3% by weight. The final, 118 stable protective rust layer of the chromium-substituted goethite impedes the penetration of aggressive corrosive anions such as chloride or sulphate by the formation of a bipolar rust membrane. Misawa and Miyuki (1999: 125, 127) state that contents higher than 3% would be better for the membrane potential working against the diffusion of the anions, thereby reducing the rate of corrosion even further. The corrosion in the atmosphere is also impeded because of the densely aggregated oxide layer which has a typical crystallite size of less than 10 nm. Further work on the evaluation of the protective nature of rust layers on steel bridges has also been carried out by Hara et al. (2001) looking at the relative effects of the different iron oxides on stability. Cook et al. (1998) examined the atmospheric corrosion of a low carbon steel (A36) and a weathering steel (A558) exposed at two sites in Campeche, Mexico, and one site at Kure Beach, USA. For exposure times less than three months, an amorphous oxyhydroxide was predominant, after which lepidocrocite and akaganéite were found, with the amount of akaganéite increasing at sites with higher atmospheric concentration of chloride ions. Over longer exposure periods, goethite was also found and the amount of akaganéite decreased. The patina, which then began to result in a decreased corrosion rate, consisted of an outer layer of lepidocrocite and goethite, overlying a layer of goethite and nanocrystalline maghemite closest to the steel surface. Somewhat different results were found by Yamamoto et al. (2000), who examined the deterioration of weathering steels exposed at rural and marine sites in Japan. These authors found that the initial rust layer formed in rural exposures consisted of multiple layers each with a thickness of less than 2 µm. The layers had different compositions and degrees of enrichment in chromium ions, and consisted essentially of fine particles of FeOOH with crystalline layers of FeOOH between them. However, the rust layers formed in the marine environment did not show well-developed multiple layering; instead crystalline akaganéite and FeOOH were found, but the nature of this latter species is not clear from their paper; perhaps the authors mean amorphous FeOOH. The akaganéite that formed consisted of an aggregation of ordered fine particles. Indeed, the potential problems in using these chromiumcontaining weathering steels for outdoor structures and sculpture has led to further research on different types of weathering steels to find a more resistant alloy. Kihira et al. (2000) report on the development of one such alloy that contains 3% nickel and 0.4% copper, the remainder being iron. The elimination of chromium from the alloy is crucial in marine environments; the new alloy was tested over nine years and exhibited superior resistance to corrosion. Hara et al. (2001) examined the corrosion of weathered steel bridges over periods of time that varied from 2.5 to 18 years, in both mountain and marine environments. The fraction of the rust constituents is described using a ternary diagram consisting of: (a) lepidocrocite + akaganéite + magnetite; (b) X-ray amorphous material; and (c) goethite related oxyhydroxides. In mountain regions (b) was predominant, while in marine environments the amount of (c) compared with (a) decreased due to the enhancement in akaganéite. The somewhat complicated issues related to the relative amounts of lepidocrocite and goethite in iron patinas that have been the subject of several Japanese papers are reviewed by Dillmann et al. (2004), who are concerned principally with rust

Iron corrosion in the atmosphere α-FeOOH and γ-FeOOH with 70% amorphous material and an α/γ ratio of 2.2. The rust from a 400-year-old Chinese cast iron and from more recent steels suggests that the α/γ ratio increases proportionally with the number of years of exposure. The fraction of amorphous material, which is between 20 and 60% during the initial stages of exposure, can increase to 70% with time. After that, the amount of amorphous phase decreases, resulting in an increase of α-FeOOH. Dillmann et al. (2004: 1408) used a range of iron objects in their studies, from a Conques church sample in France (about 150 years old) and an 800-year-old object from the Popes castle in Chateauneuf du Pape, France, to a 1600-year-old artefact from the Temple of Deogarh, India. The change in the α/γ ratio with time can be explained by the progressive transformation of lepidocrocite to goethite with the succession of wet-dry cycles during the atmospheric corrosion process. Because Dillmann et al. also identified magnetite and akaganéite in these rust layers, they proposed a modification of the ratio aspect to factors α*/γ*: α*/γ* = (% α-FeOOH + % Fe3O4 )/ (% β-FeOOH + % γ-FeOOH) (10.20) Despite the fact that magnetite is conductive, it can be considered to be protective because of its high stability. The new stability ratio α*/γ* is a better tool to try to characterize old rust layers, although the general trend of the data is similar to α/γ. The study did not find any amorphous phases to be present in the older rust layers, which could be due to a transformation to densely packed nanoparticles of goethite. The porosity of the rust layers is another important aspect, and appears to be about 10% and principally nanometric (10 nm ≤ D ≤ 50 nm), where D is the pore access diameter. From the results of their study, Dillmann et al. found that the major phases of ancient rust layers exposed to atmospheric corrosion were magnetite, goethite and lepidocrocite, with lepidocrocite present in the outer layers. Goethite appears to predominate in the inner layer and no amorphous phase could be actually found at all. The older the rust layer, the higher the ratios α*/γ* and α/γ become. Significant concentrations of phosphorus, silicon, sulphur or calcium are also detected in these ancient rusts. Monnier et al. (2007) were able to identify ferrihydrite in crosssections from an iron chain exposed for 509 years in the cathedral of Amiens in France. They used micro X-ray absorption spectra (µ-XAS) because the crystalline structure of ferrihydrite gives a poor X-ray diffraction (XRD) signal and the wide band in the Raman spectrum around 700 cm–1 cannot easily distinguish it from feroxyhyte. Thus, the stability α*/γ* must be modified to account also for this phase. Based on electrochemical measurements of the reduction of rust samples from five sites, they gained a reduction reactivity ratio that declined linearly over centuries of exposure. The rust is getting more stable with age and less likely to take part in electron transfer reactions.

crack γ -FeOOH initial rusting

Steel

γ -FeOOH Amorphous oxyhydroxide Steel several years

γ -FeOOH α (Fe1-xCrx)OOH Steel
Figure 10.9 Morphology of development of protective rust layers on weathering steels (after Misawa and Miyuki 1999 © courtesy of the Electrochemical Society, Pennington, NJ, USA).

decades

layers formed on ancient iron artefacts exposed to atmospheric corrosion. Figure 10.9 illustrates the typical layered structure that develops over long periods of time, while Figure 10.10 shows in a ternary plot the relative change in oxide morphology as steel weathers in air. Two typical detailed compositions for Corten steel are shown in Table 10.2 (Central Steel Service 2002). One index of corrosion that has been of some use is the goethite (α) to lepidocrocite (γ) ratio, α/γ. The rust formed on mild and weathering steels was characterized in terms of the presence of α-FeOOH, β-FeOOH, γ-FeOOH, Fe3O4 and amorphous iron oxide content. The α/γ ratio for weathering steels is about 1 during the first 5–10 years of exposure, and is higher than 2 for steels exposed for longer than 10 years. The amount of the amorphous phase is about 53 mass% in the case of rust from a weathering steel exposed for 32 years. Rust analysed from a weathering steel exposed for 41 years to a rural atmosphere contained principally

Table 10.2 Some Corten steel characteristics (after Stainless Steel Information Center 2005). Type 400F 500F A514 Gr B C .12/.16 .25/.31 12–22 Mn 1.55 0.95 .80/1.40 P .025 .25 .035 max S .005 .005 .040 max Si .35/.55 .45/.55 .15/.35 Ni 1 1 Mo .55 .65 .15/.30 Cr .55 .75 .35/.70 B .0005/.005 .0005/.005 .0005/.005 .03 max Ti

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Iron and Steel in Ar t

Figure 10.10 Exposure time dependence of the three major rust components (redrawn by R. Schmidtling after Misawa and Miyuki 1999 © courtesy of the Electrochemical Society, Pennington, NJ, USA).

Deterioration of historic iron structures

We will most likely never realise the full importance of painting the tower, that it is the essential element in the conservation of metal works and the more meticulous the paint job, the longer the tower shall endure (Eiffel 1900). Eiffel’s prognosis is very percipient, and remains as true today as when he wrote those words, concerning his own masterpiece, the Eiffel Tower in Paris. A large number of historic iron structures are exposed to the elements, from the Forth Railway Bridge in Scotland to giant-sized iron castings of bells, pagodas and animals in China. The use of iron in building supports was researched by Hodgkinson in England in 1825 (Bridgwater and Gloag 1948). Hodgkinson determined that the best cast iron beam for buildings was one with a wide bottom and a smaller top flange. This design, together with the misconception that cast iron was fire-resistant, led to its use around the world. Early cast iron columns and support beams were used to construct factories and railway stations. Although the cast iron was strong enough to support heavy machinery, it was defenceless against the fires that occurred frequently on factory floors. Several buildings also collapsed due to brittle fracture of large cast iron beams. The building of the Crystal Palace in London in 1851 was carried out in a functional cast iron which was a good example of its architectural potential (Matero 1994: 199; Muthesius 1970: 58). Other architects tried to imitate, in iron, decorations that were well known in stone and plaster: for example, Bunning’s London Coal Exchange (1847–9) and Paddington Station, designed by Brunel and Wyatt in 1854, which used cast iron columns to support a roof composed of wrought iron arches with some cast iron elements (Bridgwater and Gloag 1948: 172–3). Cast iron sheets, available in the latter half of the 18th century, were used in the construction of lighthouses. The material had several advantages for this use: it was lightweight, could be 120

prefabricated and assembled and disassembled on site, and if constructed correctly, watertight. The disadvantage of cast iron towers is that they swayed in the wind and, in order to reduce this effect, many of them were lined with brick for additional support and insulation. The first cast iron lighthouse was constructed in Wales in 1803, and several, including Gibbs Hill Light built in 1846 in Bermuda, are still in operation. Following the collapse of several buildings during the late 19th and early 20th century, cast iron and wrought iron structural supports were replaced by steel, a practice that has continued to the present day.

The iron pillar of New Delhi
The iron pillar of New Delhi (known as the Delhi pillar) has achieved fame and notoriety as one of the few ancient iron objects that has happily stood outdoors for 1600 years, and yet seems to undergo no obvious deterioration. It has never been painted and is often referred to as the ‘rustless’ iron column. This pillar measures 23 ft 8 in. in height (Hadfield 1912), weighs 6 tonnes and is currently 17 ft above ground level due to the erection of a protective stone base in which the rest of the column is submerged, with a lead cladding around the bottom. The pillar was made of wrought iron during the reign of the imperial Guptas, which can be dated on palaeographic interpretation of the Brahmi script, inscribed into the pillar, to the period from AD 400 to 450 associated with either Samudragupta or Chandragupta II Vikramaditya (probably the latter). The pillar was probably originally erected in the Udayagiri region and removed by 1050 to somewhere near its present location by the Tomar king, Anangapala, later moved by Qutbuddin Aibak, the slave army commander of Muhammad Ghori of Ghazni who erected it in a new Moslem site, a mosque built of stone and wood taken from 27 destroyed Hindu temples, known today as the Qutub Minar.

Iron corrosion in the atmosphere Until 1997, guides earned extra rupees by persuading visitors that good luck would be theirs by encircling their arms backwards around the pillar, the guide usually providing the extra couple of inches of pull needed to complete this contortionistic ritual. However, one consequence of this has been the rubbing away of the iron oxide patina, and shiny iron metal can now be seen in a roughly horizontal band around the pillar. It is debatable how fundamentally damaging this ritual was to the stability of the pillar, but nevertheless, in 1997, the Archaeological Service of India erected iron railings around the pillar to prevent this activity, which has the aesthetic effect of giving the pillar a sepulchral quality that the unencumbered column never possessed. The patina of the pillar has an unusual golden-brown aspect when viewed in bright sunlight, especially at its upper reaches, misleading enough for some observers to mistake the alloy for brass or some other exotic combination of several different metals. Evans (1960) thought that the reason for the remarkable state of preservation was due to an atmosphere free from pollution (certainly not the case in 2005), the low value of the relative humidity, and the very low sulphur content of the iron estimated at 0.006% by Hudson (1953). Several chemical analyses of the pillar have been published, summarized by Balasubramaniam (2002a) as 0.15% carbon, 0.25% phosphorus, 0.005% sulphur, 0.05% silicon, 0.02% nitrogen, 0.05% manganese, 0.03% copper, 0.05% nickel and the remainder iron. The microstructure of the wrought iron is fairly typical for such bloomery products with entrapped slag inclusions. Balasubramaniam’s basic hypothesis is that the extraordinary state of preservation is due to a self-passivating iron oxyhydroxide layer in which phosphorus plays a key role (Balasubramaniam 1999, 2002b; Balasubramaniam and Ramesh Kumar 2003). Craddock (1995: 206), on the other hand, writes: … the truth is that western metallurgists are just not familiar with the behaviour of very large masses of iron that have been standing for millennia in relatively dry climates. There is certainly nothing unusual about the composition of the iron. Many people favour the ‘heat capacity’ theory in which the rapid evaporation of dew or rain on the warm iron surface would severely limit the extent of corrosion. The nature of the iron oxide corrosion crust was studied by Dillman et al. (2002), employing micro X-ray diffraction (µ-XRD) and micro particle-induced X-ray emission (µ-PIXE) techniques. This study showed a higher amount of phosphorus to be present in the corrosion crust, which was up to 800 µm thick, at the scale/metal interface. The oxide film on the Delhi pillar is layered and previous studies on weathering steels, rusted over 26 years, using reflected polarizing light microscopy (PLM) has shown that the layer could be divided into two parts: an outer layer that is optically anisotropic and an inner layer which is isotropic. On the other hand, surface rust formed on mild steel consists of a mottled structure consisting of a mixture of isotropic and anisotropic components. It is therefore thought that weathering steels obtain their protection from this isotropic layer (Ramesh Kumar and Balasubramaniam 1998; Yamashita et al. 1994). In the corrosion layers from the Delhi pillar, Dillmann et al. (2002) found that there were three different layered features present. In the first region, close to the metal surface, no XRD pattern could be obtained at all, showing that the features are amorphous. From the second region, magnetite and goethite were found, while the third region showed the presence of goethite. At one location close to the metal/scale interface the diffraction study showed both magnetite and goethite with additional weak XRD peaks matching those of satterlyite (Fe2(PO4)(OH), ICDD 35-0622), showing the presence of small amounts of crystalline phosphoruscontaining material close to the remaining metallic surface. The presence of phosphorus alters the crystallization of the oxyhydroxides, with feroxyhyte (δ-FeOOH), being amorphous and compact in the presence of phosphorus, which over long exposure times may lead to the precipitation of insoluble phosphates, enhancing the corrosion protection of the resulting film. Strangely, this article makes no reference to the previously assigned compound ICDD 45-0500 found in the same corrosion crust, which has the formula FeH3P2O8∙4H2O, reported by Balasubramaniam (2002a). This latter compound, unknown as natural mineral, can only be synthesized with phosphoric acid! How significant then, is the effect of the environment on the stability of the pillar? In order to try to answer this question Halder et al. (2004) sought to model the time of wetness (TOW) of the pillar by applying a non-steady state heat transfer model. The predicted wetting times were then used to estimate the anticipated rust thickness on the surface of the pillar. The results of this study suggested a TOW of two hours per year, which is a very low figure. The aqueous corrosion rate of a piece of the Delhi pillar was estimated at 28 µm/year in 0.001% sodium chloride and 252 µm/year in 0.003% sulphurous acid solution. Using these data Halder et al. estimate that the thickness of the corrosion crust should have been between 6,400 and 72,000 µm. That this is not the case, as the corrosion crust was only 800 µm thick, is taken as additional proof of the protective passive film theory of protection of the pillar. However, we would expect the presence of thick layers of ordinary rust on an exposed, massive iron object, to result in a progressive diminution of the corrosion rate with time, as transport through the oxide film results in the slower penetration of moisture and oxygen, and would never attain a corrosion penetration of even 10,000 µm on a wrought iron object. If the TOW of the pillar is only two hours per year, this must be a contributory factor in the preservation of the pillar. As Craddock states, there are plenty of iron objects made from bloomery iron that contain small amounts of phosphorus, yet few of these have been only exposed outdoors in so massive a form as the pillar, so there is a lack at present of comparative data. The final word on the mystery of the Delhi pillar has not yet been written.

Iron corrosion in cement and concrete structures
The presence of iron in historic buildings has resulted in various forms of deterioration, such as spalling, loss of material and cracking within cement, concrete and stone structures. Carbonation or chloride ingress can induce physiochemical conditions favourable to corrosion (Neff et al. 2007b). When the active corrosion of iron supports develops, the corrosion layers expand, which provokes mechanical damage to the concrete matrix. This type of corrosion has been described by Neff et al. as occurring in two phases. In the first phase, the high alkalinity of the concrete passivates the iron. The second phase involves 121

Iron and Steel in Ar t carbon dioxide from the atmosphere penetrating through the stone or concrete, generating both water and alkaline salts, with carbonation of the cement. The presence of this carbonated cement induces a decrease in the pH, and if enough water and oxygen are present, then the iron will actively corrode (Neff et al. 2007b). Laboratory experiments demonstrated that iron oxyhydroxides such as goethite and lepidocrocite form a complex layer resulting in spalling and associated damage. Neff et al. (2007b) describe this corrosion in terms of three stages, the first of which corresponds to an original alteration layer that appears before the iron is submerged in the concrete. This first layer is probably magnetite or wüstite. The second layer is thicker, consisting of the same corrosion products with the addition of goethite on the inner and outer parts of the corrosion layer. The third stage is the appearance of goethite and lepidocrocite on the outer surface of the iron. In colloquial building terms, this is sometimes referred to as ‘oxide jacking’ (Harris 1992: 242). In the disastrous case of the Athenian Acropolis, Belanos substituted ancient iron clamps used to fasten the Pentelic marble blocks with I-shaped steel implants, which corroded within a few years of the restoration, since the untreated steel implants were simply grouted into position (Harris 1992: 244). Another interesting example of the exacerbation of corrosion by restoration is that of Castle Cooke, Enniskillen, Ireland, an 18th-century house that originally suffered from ‘oxide jacking’ from the wrought iron clamps set in lead. During restoration, all the wrought iron clamps were removed and replaced with 304 stainless steel turn-down clamps set in a generous amount of lead, which became anodic in relation to the stainless steel clamps, resulting in a 50% volume expansion caused by the formation of lead(II) oxide (Harris 1992: 245). Sagoe-Crentsil and Glasser (1993) examined some of the corrosion phenomena when steel rods begin to corrode embedded in cement. Studies of the corrosion of wrought iron showed green rust formation of approximate composition Fe42+Fe23+(OH)12(Cl,OH)2. This type of rust is stable under conditions of high pH and low Eh in the presence of chloride ions. The authors derived a stability diagram relevant to the corrosion of iron in cement, constructed for a pH of 12, that reveals the stability fields of green rust, α-FeOOH, δ-FeOOH and β-FeO(OH,Cl), which is useful for further studies of this form of corrosion. Low chloride ion concentrations, such as 15 mmol l–1, enhance the solubility of iron at pH 12–13 due to the formation of the green rust, and its subsequent migration and precipitation in the more oxygen-rich regions of the cement destabilize the passive layers on the steel. The chloride ions that are liberated can then continue the cycle of corrosion. Therefore, chloride-induced corrosion can occur even under anoxic conditions provided the soluble corrosion products can migrate towards more oxygen-rich environments. Renewed interest in the corrosion of iron has been initiated by a number of French researchers, ostensibly for the purpose of investigating the suitability of iron and iron reinforcements in concrete and cement for the storage of contaminated nuclear waste materials (Antony et al. 2005; Chitty et al. 2005; Hœrlé et al. 2004; Neff et al. 2005; Vega et al. 2005). Chitty et al. (2005) undertook a study of the long-term corrosion resistance of metallic reinforcements in cement and concrete utilizing samples dating from the Gallo-Roman period of AD 300 to the early 20th century. On a prima facie basis, one might suppose that the following regions would be found: remaining sound iron metal; a corrosion front extending below the original surface of the iron, consisting principally of iron oxides and oxyhydroxides; a corrosion crust above the original surface consisting of iron oxides and concrete and cement components, and, relatively unaltered cement or concrete layers. This is essentially what the new study found to be the case. Of interest are the corrosion rates that these authors determined from their studies: from less than 1 µm per year for the Gallo-Roman sample of about AD 300 to 7.5 µm/year for samples from the Conciergerie Hotel, Paris, from 1550. Most of the other samples were from buildings a few hundred years old and many had a corrosion rate from 2 to 3.5 µm/year. Historic mortars are mainly composed of portlandite (Ca(OH)2) in which interstitial solutions may have a pH of about 13. Carbonation leads to a decrease in the pH value from 13 to about 8. When aggressive elements such as chloride ions reach the iron reinforcements, the second step, called by Chitty et al. (2005) the ‘active stage’, begins and corresponds to a fast rate of growth of rust, which can burst through or crack the concrete covering. The microstructure of the iron corrosion products is often layered (referred to as ‘marblings’ by the authors!) and the detailed investigation of these using micro-Raman spectroscopy enabled the determination of the mineral composition of these layered corrosion products on a cross-section of an object from the site of St Gervais church, Paris, dated to about 1645. Goethite and magnetite (and/or maghemite) were found in the bulk corrosion; the veins are made only of iron oxides such as maghemite and/or magnetite, while the matrix is composed principally of iron oxyhydroxides such as lepidocrocite, goethite and akaganéite. Only in the case of the Gallo-Roman sample was siderite found in one of the layers, in some areas contiguous with the metal/primary corrosion interface. In these matrices, some veins of maghemite and/or magnetite occur. The green rusts, which were a prominent feature of the studies carried out by Sagoe-Crentsil and Glasser (1993), are not mentioned at all by Chitty et al., probably because they would have been transformed to more stable products between the dates of the two studies (1993 and 2005) and would no longer be present.

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11 Iron corrosion in freshwater and marine environments

There is an apocryphal tale of the European museum scientist who was dispatched many years ago by UNESCO to an American shipwreck site in Florida to advise on the conservation of the marine finds. Among these finds were small cannons, still with an explosive charge. Conventional wisdom often calls for such marine objects to be dried out before storage to prevent further deterioration, and so it was suggested that the small cannons should be dried out in the oven. As you can surmise, this course of action was ill-advised, and, as so often in the history of the treatment of iron artefacts, the objects themselves may have the last laugh on our efforts to preserve them for posterity. Two survey papers that discuss the corrosion of metals in seawater – North (1987) and North and MacLeod (1987) – are highly recommended for further background. As the number of shipwreck sites that have been salvaged and conserved has grown over the past 40 years, so too has an understanding of the conservation needs and limitations inherent in dealing with objects perhaps as large as the Titanic, or as small and numerous as iron nails – or as potentially hazardous as a cannon.

Many archaeological and historic artefacts from shipwrecks to standing structures are exposed to corrosion as a result of marine or freshwater burial. In severe cases, total loss of the iron artefacts from marine sites may occur, although a common event that prevents total loss is the development of a concretion over the corroding object, which produces a local microenvironment for the object independent of the bulk pH and Eh of the environment. The principal reason for this heavy concretionary corrosion is that, unlike copper and bronze artefacts, iron is not biologically toxic therefore such artefacts may be rapidly colonized by a variety of marine organisms. These organisms secrete layers of skeletal material, mostly calcium carbonate, with ferrous and ferric ions incorporated from the subsequent corrosion of the iron. North (1976) provides an example from the wreck of the Batavia that sank at the Wallabi group of the Houtman Abrolhos islands, about 35 km off the coast of Western Australia during her maiden voyage in June 1629. During the first few years, exposed iron was covered with a layer of coralline algae that provided a substrate for secondary growth of seaweeds, molluscs and hard coral. Subsequent marine growth entrapped sand and

Figure 11.1 Schematic cross-section of concreted iron object corroding in seawater (redrawn by R. Schmidtling after North and MacLeod 1987).

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Iron and Steel in Ar t other marine detritus, which promoted further concretionary marine excrescence. The oxygen content of the entrapped water contiguous with the iron surface started to fall. Corrosion under these conditions generates an acidic solution of about pH 4.8, rich in ferrous and ferric ions. A schematic cross-section of a typical corroded marine iron artefact is shown in Figure 11.1 (after North and MacLeod 1987). The sound metallic core, if any remains, is followed by a zone of internal corrosion, a thick crust of corrosion products, and a concretionary layer that has built up around the artefact. Typical molar variations in chloride ion content may range from 1.5 mol l–1 towards the metal surface, while only averaging 0.5 mol l–1 in seawater. Similarly, the acidity is higher towards the metallic surface, reaching 4.8 pH contiguous with sound metal, and 8.2 in the particular seawater itself. Misawa et al. (1974a) carried out a study on the formation of the oxyhydroxides in water at room temperature. The green rusts were also found to form in addition to Fe3O4, α-FeOOH, β-FeOOH, γ-FeOOH, δ-FeOOH, and amorphous FeOOH. The formation processes upon which end products are dependent are strongly affected by the oxidation rate, the pH, and the structure and composition of initial and intermediate species of iron. A systematic diagram of the formation process of the above species is given both for dissolved and solid species (Misawa et al. 1974a: 132, fig. 1). A great deal of iron corrosion in water is connected with microbiological processes and a number of different environmental milieux need to be considered: • • • A totally aerobic biofilm where oxygen is present in the water and also penetrates through the entire biofilm. An anaerobic biofilm, where oxygen is absent from both water and the biofilm. An aerobic/anaerobic biofilm, where oxygen is present in the water and where anaerobic microniches and/or an anaerobic layer exists in the biofilm. In aerobic processes the corrosion of iron is dependent on the dissolved oxygen content (which decreases with depth). At the anodic areas the following reaction takes place. Fe → Fe2+ + 2e– (11.1)

The rate of corrosion is actually independent of the pH within the range 4–10. At the cathode, the usual oxygen reduction reaction occurs: O2 + 4e– + 2H2O → 4OH– (11.2) Supply of oxygen, which decreases with increasing depth, is the main factor determining corrosion rates. In waters of low conductivity, the anodic and cathodic sites are close to each other so that a compact film of Fe(OH)2 forms an adherent layer. Such a film provides an effective diffusion barrier to dissolved oxygen penetration. But in dilute salt solutions that have high electrical conductivity, the anodic and cathodic sites are farther apart and the iron corrodes much faster (Uhlig 1963). The ferrous ions that form can be further oxidized to ferric: Fe(OH)2 + 1/2H2O + ¼O2 → Fe(OH)3 (11.3)

The end result is a rust layer composed of at least three layers of iron oxides of different stages of oxidation: the innermost layer is largely greenish composed of a green rust; the outer layer is mostly orange ferric hydroxide and magnetite may form as an intermediate layer between the ferrous and ferric hydroxides. An aggressive form of corrosion of iron in water is tuberculation which, according to Herro (1991) originates from differential oxygen concentrations. Oxygen reduction occurs around the base of the tubercle and at the inner magnetite shell. Anodic iron dissolution may take place underneath the tubercle: the ferrous iron generated in the anodic region can migrate through the overlaying material producing an anion flux opposite to the

Fluid filled cavity (Fe++, CI-, SO4 =)
2–

Water

Crust (friable) • Hematite - red, brown, orange (ferric oxide) • Carbonate - white • Silicates - white Shell (brittle) • Magnetite - black Core (friable) • Ferrous hydroxide greenish-black • Iron carbonate grey-black (siderite) • Phosphates, etc.

Fracture in crust

Corroding floor

Metal loss region

Metal
Figure 11.2 A typical tubercle of corrosion resulting from differential oxygen concentration. Oxygen reduction takes place around the base and at the inner magnetite shell, while iron dissolution occurs underneath the mound of corrosion. Ferrous ions are generated that migrate outwards, with chloride or sulphate being drawn inwards (after Herro 1991).

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Iron corrosion in fre shwater and marine env ironments outward flow of ferrous ions. Eventually, the pH falls within the pit as anions such as chloride accumulate, a common event in pits formed within archaeological ironwork. An illustration of the typical cross-section through such a pit is illustrated in Figure 11.2. If bacteria form an aerobic biofilm over part of the iron surface, corrosion underneath this film may be restricted if the film is uniform and rates of corrosion may be reduced to between 2.5 and 7 µm per year. The anodic behaviour of iron or steel in neutral or alkaline waters with dissolved sulphide ions was investigated by Shoesmith et al. (1980). This was found to be dependent on the sequential chemisorption and anodic discharge of hydrogen sulphide: Fe + H2S → Fe SH–ads+ H+ Fe SH–ads → FeSH+ads+ 2e– (11.4) (11.5) A detailed review of the effects of sulphate-reducing bacteria on the corrosion of low carbon steels is provided by Lee et al. (1995). They break the process down into the following stages: 1 The transport and accumulation of materials from the bulk liquid to the metal surface. These materials can be soluble, such as microbial nutrients and corrosive chemicals, or particulate, in the form of viable microorganisms or inorganic particles. Microbial and electrochemical transformation processes within a biofilm and at the metal surface. The extracellular polymers excreted by the microorganisms contribute to the biofilm deposit and promote adherence of corrosion products. Erosion and detachment from the surface of the film.

2

3

Subsequent to reaction 11.5, FeSH+ads may be incorporated directly into a developing layer of mackinawite (Shoesmith et al. 1980: 1013): FeSH+ads → FeS1-x+ xHS -+ (l-x)H+ (11.6)

Reaction 11.5 is the rate-limiting step exercising control over charge transfer, while the cathode reaction is governed by hydrogen sulphide reduction: 2H2S + 2e– → H2 + 2HS – (11.7)

If oxygen is absent and hydrogen sulphide is present, Wikjord et al. (1980) found that the corrosion proceeded from an iron-rich to a sulphur-rich phase in the following sequence: (1) mackinawite (tetragonal) FeS1-x is formed, followed by (2) ferrous sulphide (cubic FeS), then (3) troilite FeS (hexagonal) (4) pyrrhotite (hexagonal Fe1-xS), and finally (5) pyrite (cubic FeS2) with the film becoming increasingly protective as it evolves from mackinawite to pyrite. The iron sulphides tend to act as local corrosion initiators because of their good electron conductivity, low overvoltage for hydrogen reduction, noble electrode potential and defect structure. These properties cause iron sulphides to be effective cathodes in galvanic cells with uncorroded iron, resulting in severe corrosion of iron artefacts.1
1 Elemental sulphur could be present as well, resulting in a potential hazard to other copper or silver alloy objects via the gas phase if not removed (Eggert and Sobottka-Braun 1999).

The sulphate green rust 2 (4Fe(OH)2·2FeOOH·FeSO4·nH2O) can also be generated by corrosion of iron in marine environments as it is more stable than chloride GR1. Génin et al. (1993) reported on the subject during a study of the corrosion of steel piles at the harbour of Boulogne, France. After only a few years of service (they were anticipated to last for at least half a century), the 15 m high steel sheets displayed huge holes. These lie under a fouling crust about 10 cm thick comprising seashells, sand, mud and rust at a specific level – that of the lowest tide at the solstices (i.e. where anoxic conditions are prevalent but where aerobic conditions might also occur). Similar phenomena were later detected in other harbours on the Atlantic, the North Sea and the Baltic Sea. Besides GR2, magnetite was also found but no sulphide was present at all. As Génin et al. (2002) were able to demonstrate by laboratory experiments that iron-reducing bacteria (e.g. Shewanella putrefaciens) are able to reduce lepidocrocite to green rust, magnetite and green rusts are seen as indicators for microbially influenced corrosion (MIC) cycles, triggered by the tides, which induce periodic changes of the oxygen content in the environment of the steel. Ferric oxyhydroxides such as lepidocrocite are formed under aerobic conditions. These partially protective ferric rusts tend to peel off when reduced by bacteria to green rust under anoxic conditions.

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12 Introduction to the conservation of iron objects
In the museum where I was initially trained some thirty-odd years ago, I was perplexed to see that most of the Saxon iron artifacts had what appeared to be ochre-coloured sawdust adhering to the surface corrosion layers. I wondered if Saxon burials had been sprinkled with coloured sawdust or woodchips in the way prehistoric burials were sometimes covered with a layer of ochre. In actuality, the iron artifacts had been thrown into a vat of boiling wax coloured with ochre. Those artifacts that survived were then tossed into a cauldron of heated sawdust to absorb the surplus wax (Arthur 1987: 2).

Different attempts and approaches to the conservation and storage of iron objects span a large territory of needs, opinions, institutional priorities, chemical techniques and human perceptions. Knight (1997), for example, stated at the conference Metal 95 that conservation methods which involve the uncontrolled removal of all the corrosion products, resulting in the total loss of evidence preserved in corrosion, are now not considered to be acceptable by most British conservators. He explicitly included methods such as alkaline reduction and plasma treatment, methods for whose usefulness others at the same conference were arguing. The

danger of the situation reported by Knight is that large numbers of iron objects may simply deteriorate to rust over the years, while the risk of the approach by Oswald (1997) is that microstructural details may be compromised, surface finishes may be destroyed or go unrecognized, and there may be a heavy cost factor involved in treating iron artefacts by plasma techniques. Other problems arise when dealing with large marine iron objects, for which another set of priorities might be more appropriate, such as long washing or desalination treatments, with strenuous mechanical removal of concretions and rust.

Figure 12.1 The ‘prisoner of choice’ (after Black 1982).

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Iron and Steel in Ar t The aims of the proposed conservation treatment need to be addressed before a decision is made concerning the most appropriate course of action. The cheapest short-term solution to the problem is to do nothing, except to place the iron objects into controlled relative humidity (RH) conditions in storage. This, however, is not a final solution, for many iron objects have a nasty habit of disintegrating in storage, even when stored below 45% RH, and since research has suggested that unstable objects require a RH of less than 12%, how viable is that level, and how can it be achieved in storage over long periods of time? Some of the historical approaches to the conservation of iron objects have had drastic consequences for the appearance and metallographic structure, which is important for the history of the objects themselves, and for any further conservation treatments. (e) The original surface is retained by an internal surface of thick overlying concretion, the centre is a complete void; no metal remains at all. This kind of complete disappearance is usually only found in anaerobic, oxygen-deficient environments. Casts of such spaces can be taken to preserve information on object shape.

Morphological states
Before we begin to review some of the methods employed for the conservation and protection of iron objects, it is worthwhile trying to answer the question: what do old iron objects look like? Depending on exposure or burial conditions some of the objects will have rusted away altogether, and so nothing is left of them. Those that do survive span the following range (adapted after Cronyn 1990): (a) The iron object is well preserved and the surface covered with a thin patina or a superficial layer of corrosion products. In some cases even ancient objects of this type may require no special storage conditions; others may show ‘weeping’, cracking, spalling and lamination of parts of the surface. The use of the term ‘patina’ in connection with iron objects is often restricted, since usually the corrosion products do not form a uniform alteration layer that retains the shape of the original object. There is a surface of the iron object that is still preserved, in a metallic form, covered by corrosion products. This may include marine artefacts, covered with thick layers of concretionary material. Pseudomorphic preservation of wood and other organic materials may be found within the corrosion product layer or patina. The preservation of an ‘original surface’ analogous to that found in copper alloy objects is rare. The artefact is liable to deteriorate in the same way as (a). There is an interface in the corrosion, which marks the shape of the original object, although there may be little or no metal actually remaining. These objects may be deceptively fragile and simply break like biscuits, with fragmentation and loss. Metallographic examination of the fragments may reveal from which type of iron the object was originally made, as tiny specks of metal or pseudomorphic preservation of the metallographic structure of the original ferrous phases is not uncommon. A thick layer of corrosion products covers the entire object of which little remains: the centre may now be a void where the object once existed. These products may be very light in weight and their density is often a guide to their poor state of preservation; they may also be very fragile.

Examples of types (a) and (b) may include objects that are surprisingly stable, for example, iron nails from the site of Inchtuthil, Scotland, dated to AD 791 have undergone no further corrosion, despite being stored in uncontrolled RH for the past 30 years. This stability is probably due to the unusual circumstances of burial of these nails, found in a large pit, many hundreds of thousands in extent, rusted over with a crust of deteriorated nails that has kept the bulk of the buried iron in exceptionally good condition for nearly 2,000 years. However, unstable objects are more common in any category, as we have seen. Also relatively stable are those objects which have reverted to the mineral form from which they were originally summoned, such as those in category (c) and (d), although they may be less dense, friable and liable to dehydration and powdering. Watkinson (1983) discusses how these changes in density might be of use in assessing the degree of mineralization of the iron in question. The density was measured for 35 iron objects by immersion in ethanol, and the total amount of extractable chlorides was then measured. With few exceptions, those objects with a density of less than 2.9 contained less chlorides than those with a density greater than 3.0. Almost all artefacts that were totally mineralized contained less than 1000 ppm of chloride ion. This density measurement can therefore be used to determine whether or not the iron object is completely mineralized, thereby helping to predict post-excavation stability and the appropriate storage conditions for the objects; those being mineralized requiring less carefully controlled conditions.

Surface appearance
Obviously we expect a miraculous transformation of a 4000 year old object into its original form, a resurrection of metallic life that long ago transpired into a fragile oxide ghost. This being impossible, are we satisfied with a relatively accurate reconstruction of the original surface? (Oswald 1997). Debate concerning the appearance of treated and untreated iron objects is not at least an aesthetic issue of some complexity, given the competing demands of cleaning, stabilization, impregnation or controlled storage. As Oswald (1997) remarks, it is quite possible that the conserved iron object is still sick, suffering from dry, rusty patches or perhaps watery, gold-yellow pimples. Can we put up with X-radiographic pictures and threedimensional tomograms of gold and silver engravings inside a formless clump of an object? Do we want a stable, sandblown surface reconstructed according to the best knowledge, intuition and imagination of the conservator, or do we want an ‘original’ but fragile surface whose metallic skeleton must be reinforced? These are the questions that Oswald asks, to which there are a
1 In D.A. Scott’s collection.

(b)

(c)

(d)

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Introduction to the conser vation of iron objects

Figure 12.2 Chinese gilded cast iron lion from the collections of the Royal Ontario Museum, Canada, showing disastrous swelling and delamination of the surface following damp storage conditions (photograph courtesy of the Royal Ontario Museum, Canada).

Figure 12.3 Cannon from the wreck of the Riksäpplet, which sank in 1676 and was salvaged in 1953. The cannon was soaked in water and placed in a vat of boiling paraffin wax before being put on display. The photograph shows the cannon shortly after treatment (left) and the poor appearance in 1976 (right), after 20 years on display. The slow corrosion due to the presence of chloride-containing species is evident (after Barkman 1977b).

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Iron and Steel in Ar t whole range of answers possible, depending on the requirements of the object, curator and conservator. It is true that the nature of the appearance of some iron objects can be dispiriting, but this is the nature of the beast, so we should try to view them as dispassionately as possible and classify the types of surface appearance as best we can. The different types of surface colour and texture usually represent variations on the following colour themes: • Blue-black, black or brown colours on sound iron objects. These are typical patina finishes, much used on swords and ornamental work. Some of these colours are due to the deliberate corrosion of the surface or heat treatment of the iron or steel to create different oxide coatings or temper colours. • Brown or red powdery surface, with no soil or other minerals. This appearance can either represent fresh corrosion of the iron or a heavy concretion of haematite and other iron oxides. • Brown or red surface with attached soil minerals, very common in excavated iron objects often with loss of shape and voluminous covering of the object, which is completely obscured by corrosion. • Green or whitish crusts. These are often associated with marine burial environments and the green rusts. Such crusts may be unstable in normal air and convert to brownish surfaces. • Black or brown-black surface, often associated with waterlogged or marine anaerobic burial conditions, usually due to thick layers of iron sulphides. are seen merely in terms of paint, which they may have been. In fact, lead-based paints have been used until the early decades of the last century for much the same effect. The recognition of the ‘antipathia’ of rust to its opposite, iron metal, and the means for preventing this inexorable conversion, is part of the subject of conservation, where iron objects of all kinds provide a constant reminder of their essential instability. Iron objects provide a source of endless problems for the conservation and museum community as soon as they are lifted from the soil, retrieved from under water or put outside to weather. No other material can be so intractable or so time-consuming to conserve and so difficult to stabilize against further decay or deterioration as archaeological iron and steel. The problem is compounded by the sheer quantity of excavated iron objects and their frequent association with organic materials that may be degraded or only present as pseudomorphic remnants. The conservator dealing with iron objects is truly the ‘prisoner of choice’ as the drawing shown in Figure 12.1 humorously depicts (Black 1982). Since the time that Black was writing, some of the methods that had been proposed have since been shown to be ineffective, and others have emerged among the prisoner’s options. It is, nevertheless, critical to review these methods, since an understanding of the history of how iron objects have been conserved is essential to their preservation. The often undocumented conservation to which the objects may have been subjected in the past could have resulted in treatment residues, surface alterations, patina loss, or microstructural change to the iron object concerned. Plate 61 shows an untreated cast iron cannonball retrieved from the sea, placed on exhibition on a polystyrene mount: the acidic ooze from the cannon is shown staining and partially dissolving the mount as active corrosion proceeds. Figure 12.2 shows what can happen to otherwise stable iron objects which have become damp in storage. It is a Chinese inlaid cast iron lion in the collections of the Royal Ontario Museum, Canada, which has suffered from water damage in storage and continually loses parts of the surface as corrosion slowly continues to occur. The iron cannon illustrated in Figure 12.3 (left) was treated some years previously to remove chloride ions, judged to be stabilized, and placed on display in the left-hand photograph. The cannon is from the wreck of the Riksäpplet, which foundered in 1676 and was salvaged in 1953. After being soaked in water, the cannon was then placed in a vat of boiling paraffin before being put on display in 1954. The appearance of the same cannon some 20 years later can be seen in Figure 12.3 (right). Expansion caused by the slow, continual rusting has caused the surface to crack and some of the ornamentation has delaminated and been lost completely, despite the care that was taken to treat and display the cannon in the first place (Barkman 1977b).

Methods of protection
[Iron] can be protected from rust by means of cerussa, gypsum and vegetable pitch: rust is called by the Greeks ‘antipathia’ the natural opposite to iron (Pliny, Naturalis historia XXXIV: 43). The protection technique described by Pliny is essentially to cover the surface of the exposed iron completely with another material, an obvious and often necessary recourse to prevent rusting. Covering the iron with lead white (cerussa) or with calcium sulphate (gypsum) is hardly ideal, unless these coverings

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13 Conservation of iron from the soil

Historical and early conservation treatments
The problem for restorers and craftspeople during the 19th and 20th centuries was that they were working largely in isolation with no help from chemists or corrosion scientists, the latter group being practically non-existent even by 1900. Indeed, it is only in recent years that methods have become available for treatments that provide long-term stability for iron objects excavated from many different site contexts and therefore different burial conditions. Buried iron objects have been excavated in their millions from all parts of the world over the past 300 years. Many of these have fallen into piles of assorted rust, rendering them quite useless as a source of archaeological or metallurgical information. Some may have been better left unexcavated rather than removed to uncontrolled storage without conservation facilities. In Europe, the discovery that buried metallic objects are sometimes in worse condition than their excavated counterparts because of environmental contamination of the soil means that leaving objects buried or even reburial of them is not necessarily a viable option. The simplest treatment used in an attempt to stabilize these artefacts was to wash them with water, the concept of washing an object to help keep it clean and free from contaminants being one with a long and commendable history, since it was first described by Krause in 1882 as a ‘novel conservation method for iron antiquities’. Krause was, however, over-optimistic in stating that ‘possibly remaining insoluble iron compounds are safe’. Salzer (1887), on discovering that even after 15 one-day treatments with water, chloride ions still remained in the artefacts, suggested the removal of soluble salts from iron with repeated treatment with spirits of wine. He wanted to extract calcium and iron chlorides, ‘the most dangerous foe of our iron antiquities.1 Some of the earliest documented attempts to deal with the instability problem took place in Scandinavia, where Norwegian,
1 It is not clear exactly how this was carried out. There is no information as to whether the spirits were warmed, for how long, whether washed or steeped, etc. Because calcium was found to be present, Krause had the strange idea that calcium chloride, being more hygroscopic than iron chloride, was the true culprit.

Danish and Swedish investigators were at the forefront of attempts to stabilize excavated iron artefacts. During the 1860s it was possible to ‘excavate’ as many as 66 grave barrows from an Iron Age graveyard in Ringerike, Norway, in ten days (Hansen 2001), amassing thousands of iron objects in need of treatment once removed from the soil. Hansen reviews the evidence for the early forms of treatment applied to these objects in Norway. The Danish photographer, Peter Petersen (1835–1894), introduced a boiling method that was used in Norway shortly before 1870, which involved impregnating the iron objects with a mixture of oil and wax, heated in a bath held in a steam boiler. The objects were held in the boiling mixture for 5–10 minutes (Jakobsen 1988). This impregnation mixture changed during 1870, and consisted of 75% linseed oil with 25% wax, most probably yellow beeswax. By 1877, Oluf Rygh (1833–1899) replaced the wax with copal varnish, keeping the proportions the same, after he noted that objects treated seven years earlier had began to corrode once again. In Eastern Prussia, Blell (1883) had cleaned iron artefacts by heating to red hot with subsequent quenching in water, followed by prolonged treatment in dilute sulphuric acid for up to several weeks. This resulted in both the delamination of corrosion crusts and the stripping of remaining corrosion from the objects. Besides aesthetic considerations he also had conservation (i.e. the removal of dangerous rust) in mind. Records in the National Museum of Denmark prove that the method goes back to M.R. Schmidt in the 1850s (Jakobsen 1988: 53). As denuded as they look to our modern eyes, many of these bare objects which have been stripped of rust and the information it once contained, have survived without much new corrosion remarkably well following this (mal)treatment. By the 1880s it began to be noticed that some of the corroded Viking swords had been made by pattern welding using different constituents of iron, steel or phosphoric iron, and that beneath the heavily waxed or oil encrusted surfaces, large Roman letters and signs were hidden. This discovery resulted in a sudden surge of interest in these rusted iron objects, whose surfaces were obscured with caked deposits of wax and oil. Axel Krefting (1859–1932), an engineer from Trondheim, began to undertake some research into the conservation problems posed by these artefacts around 1883. Krefting came to the conclusion that the best approach would be 131

Iron and Steel in Ar t to remove the corrosion layers, preventing further rusting (Gilberg and Vivian 2001; Krefting 1892a,b). The rust layers were stripped away using electrochemical or electrolytic reduction and molten paraffin wax was then applied to the surface of the bare iron to afford some protection. The use of boiled or molten paraffin wax has continued in conservation laboratories for the impregnation of iron ever since, although as more has been learnt about the corrosion processes, the limitations of such an approach to surface preservation is now understood. The approach taken in Denmark also involved drastic alteration of the patina in an attempt to create stability; the technique was described by Rosenberg (1917) and reviewed by Christensen (1967). The corroded iron artefacts are superficially cleaned and carefully wrapped in moistened asbestos paper and the packages heated to a temperature of about 800 °C for one hour; from the red-hot state the objects are then plunged into a cold solution of potassium carbonate. The packages are then boiled in frequent changes of distilled water until samples of the water reveal no trace of chlorides after which they are boiled in paraffin wax or microcrystalline wax, when the objects are at last ready for manual cleaning. The technique was especially recommended for finds from Iron Age funeral pyres by Christensen (1967). For large iron objects recovered from the sea, Eriksen and Thegel (1966) utilized eight hours at 850 °C, with slow heating and cooling. The method is now obsolete, although surprisingly it was still in use in the National Museum of Denmark, Copenhagen as recently as 1980.2 One of the more shocking consequences of this method is that in the process of quenching some of the corroded iron objects may disintegrate completely, resulting in lacuna or holes in the object which then have to be infilled in coloured wax to make good the loss. Any original metallurgical structure of the iron object is completely lost in this process of heating to 800 °C and then effectively quenching in aqueous potassium carbonate, a treatment that may create entirely new metallographic features distinctly different from that of the original iron object. also experimented with dammar resin in solvents, linseed oil and animal fat in the form of tallow. Boissonnas3 and Studer (2006) report that between 1900 and 1905, hundreds of graves dating from the 12th century BC to the Roman period were found in the region of Giubiasco, Switzerland. These constituted the first large-scale ‘excavations’ in Switzerland and over 2000 bronze and iron finds were taken for conservation and restoration to the Swiss National Museum, which had just been built. The objects were first dried at 70 °C and then immersed in hot linseed oil. Ten years later, after the initial treatment was shown to be unsatisfactory, they were reheated in a mineral fat similar to Vaseline. While re-treating these objects in the last few years (c.2000), it became apparent that the use of alkaline sulphite solutions, besides desalinating the artefacts, had the practical side effect of completely dissolving the aged oil films, and so therefore no pretreatment was necessary. The alkaline sulphite re-treatment also dissolved all the animal glue used to glue fragments together; the advantages or possible disadvantages of this deconstruction would have to be assessed prior to treatment. Sir William Flinders Petrie (1853–1942) was one of the first archaeologists to take a serious interest in the preservation of antiquities, particularly from his excavations in Egypt, where the destructive effects of salts within the excavated material was particularly problematic (Gilberg 1997; Petrie 1888, 1904). At an early stage he recognized the advantages of soaking artefacts in water to eliminate soluble salts. Some of his work is usefully reviewed by Sease (2001). Petrie employed a long period of immersion in water for treatment of iron objects, followed by baking them dry and saturating with wax (Petrie 1904). Alexander Scott, working at the British Museum from 1920 to 1940, carried out several investigations designed to improve the conservation of metallic antiquities (Scott 1921, 1926), and originated the use of sodium sesquicarbonate solutions to try to reduce the chloride ion content of buried metals, particularly bronze and iron. This method had a period of extensive use at the British Museum (Oddy and Hughes 1970). In 1933, Scott tried to improve on the use of natural rubber in solution and advocated the use of chlorinated rubber, sometimes with the addition of graphite powder. The addition of graphite powder may not have been advisable, as graphite can act as a cathode in an electrochemical cell with iron, especially if the coating is fractured or incomplete. A number of other more recent suggestions, such as that of Barton (1960), continued to expand the range of materials that has been tried without apparent success, such as the use of ketone resins, or Paraloid B-72. It is interesting that some polymeric materials can be adversely affected by iron surfaces, such as CMC (sodium carboxymethyl cellulose), which will crosslink in the presence of iron ions or cellulose nitrate (Horie 1987: 129, 132).

Early impregnation techniques
Molten wax, vegetable pitch and lead white have been used for thousands of years as a surface coating, as the reference to Pliny above, reveals. In more recent times impregnation with paraffin wax has been much employed, partly because it helps to disguise the rough and undulating surfaces of corroded objects. Salzer (1887) mentions its use as a consolidant. Harder, microcrystalline waxes such as Cosmoloid 80H are used today instead of paraffin wax, since they form a less brittle coating with a smaller particle or crystal size. Despite this continued use of wax, the moisture barrier properties of wax coatings or impregnation is poor and continued slow deterioration cannot necessarily be halted. In Germany, a variety of different methods was tried, with one approach being impregnation with water glass (a solution of sodium silicate, formerly used as a preservative for eggs) and rubber (Gilberg 1987; Krause 1882; Rathgen and Borrman 1905), neither of which proved to be very effective. Rathgen and Borrman tried using solutions of natural rubber as a consolidant for iron, but natural rubber in this form is not particularly stable; they
2 Seen by D.A. Scott during a visit to the laboratories.

Examination techniques
The identity of heavily rusted or concreted objects may be in doubt, since visual examination may be misleading and exploratory mechanical probing or cleaning may simply fragment the object, so that often the original shape is still not evident, especially those objects that may be totally mineralized. The most useful examination technique in these circumstances is X-radiography,
3 V. Boissonnas, pers. comm. to D.A. Scott, 27 November 2005.

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Conser vation of iron from the soil which can enable scores of small finds to be identified without the necessity of cleaning them at all during the process of conservation. As Corfield (1982) observes, the conjunction of the lack of understanding of the nature of the material being conserved and the drastic nature of conservation treatments employed during the 1950s and 1960s resulted in a legacy of ironwork in many museums from which all of the corrosion has been removed and from which all decorative surfaces incorporating inlay or overlay used on the iron have been lost, events that have seriously damaged the value of the objects as archaeological records in their own right. The use of X-radiography in the conservation of iron has therefore many functions including: • Determination of the size and shape of the object under the concretion or corrosion. The X-radiograph will also reveal the extent of mineralization of the iron object. In some cases mineralized fragments may be simply lumps of corrosion. • The presence of welded parts, especially of iron and steel, as in pattern-welded sword blades. The different elemental compositions result in density variation in the radiograph, with the result that the pattern of the welding parts may even be visible, enhanced by selective corrosion. • The presence of metal coatings of tin, bronze, copper or silver over the iron, either as inlay or overlay. These can sometimes, but not always, be seen as thin bright lines on the X-radiograph, as they are much more X-ray opaque than iron. The ability to determine if any object survives at all under the concreted lump is often crucial to decisions regarding the conservation procedures that may be appropriate to individual objects. For example, if the radiograph reveals that little, if any, metallic iron remains in the object, then the use of strong reducing techniques would not be appropriate, since the entire lump would probably disintegrate. If the metallic plating used on the iron has survived, a thin bright line might show on the X-radiograph. This line may be within the corrosion products and help to locate the ‘original surface’ of the object. Care has to be taken in drawing finds on the basis of the X-radiograph. Plated objects may appear larger because of the volume increase due to corrosion of the iron beneath. If the remaining metallic core of unplated objects is mistaken for the position of the former original surface, the drawn object would then be much smaller in size than the original size of the actual object, where the outline is now often lost within the corrosion products. The accelerating voltages used for iron X-radiographs are less than that required for their bronze counterparts, and most exposures are in the range from 80 kV, 5 mA to 240 kV, 10 mA at a distance of 100 cm from the source. These values may be different, depending on the tube and other parameters; for example, English Heritage, during the period from 1990 to 2006, commonly employed 3 mA, 80 kV for 60–300 seconds for such items as knives and keys, while larger items such as barrel padlocks and thicker blades were often examined at 3–5 mA, 120–160 kV for 60–300 seconds. More substantial objects such as axe heads may require 5 mA, 120–160 kV for 120–300 seconds.4 Above 120 kV the use of lead screens helps to intensify the image and even at 80–90 kV there is improvement in image clarity through the elimination of X-ray scatter. The beneficial effects of using lead screens or copper or aluminium filters over the X-ray tube
4 V. Fell, pers. comm. to D.A. Scott, 14 December 2005.

itself to reduce the amount of scattered radiation is illustrated in Figure 13.1; the two X-radiographs are of a mediaeval English barrel padlock, taken with and without lead screening. In England during the late 1960s and early 1970s, the use of Xradiographs for drawing small finds for excavation reports became increasingly common as the accumulation of archaeological material began to overwhelm the conservation resources available for treatment. Many excavated iron objects may simply have to be given a lower priority for treatment or examination during this process, as Corfield (1982) remarks: It is important that the process of selection [of the iron objects] is carried out on a consultative basis; the archaeologist, the curator and the finds assistant should meet with the conservator, and select the objects destined for conservation making full use of the radiographs which have been taken. This small expenditure of time and thought will rescue many objects otherwise destined for oblivion.

Figure 13.1 The X-radiography of a barrel padlock illustrating the advantage of using lead screen intensifiers used in the image above and not used for the same exposure conditions for the radiographic image shown below (after Corfield 1982).

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Iron and Steel in Ar t However, there is a limit to the amount of information that can be revealed by X-radiography and Corfield (1982) draws attention to these limitations in terms of decisions made regarding possible conservation options, illustrating an example of an Anglo-Scandinavian key where the bronze inlay on the handle was not revealed; a mediaeval arrowhead with a thin coating of copper that was only revealed by mechanical cleaning; and organic materials or pseudomorphs on iron objects that could not be detected. There is therefore a problem of selectivity, in deciding on what conservation strategy to adopt in the face of thousands of small, corroded iron artefacts requiring treatment if they are selected for conservation. Knight makes the point that the illustrator must have access to the object itself as well as to the X-radiographs, since with the two-dimensional representation of these three-dimensional lumps, parallax effects could result in quite large errors; if the mass is completely corroded, there is a problem of deciding on the orientation of the object (Corfield 1982: 14). Corfield states that stereoradiography may help, and Price notes that the position of the object vis-à-vis the X-ray beam is important, and cites as an example the X-radiograph of a clock, 5–7 cm either side of the main beam, and then trying to compare the position of the cogs. He advises positioning the X-ray plates in the centre of the beam and not attempting to expose too many plates at one time (Corfield 1982: 14). Modern X-ray computer tomography (Fachhochschule Aalen 2004) can overcome the problem of loss of the third dimension in a conventional radiograph. It allows one to take individual sections of a rotating object at every desired height; these can then be combined to create a three-dimensional model of the object (two-dimensional tomography). A further development is three-dimensional tomography that allows the whole object to be scanned in one run. Such data can also be used for industrial rapid prototyping processes such as stereolithography: Unlike conventional moulding, there is no need to touch the object so the surfaces of even the most fragile objects will remain undamaged. Replacements and reconstructions for physical copies can be achieved by data processing in the computer. Three-dimensional scanning using visible light is another option for generating such data, as demonstrated by Fürhacker and Markart (2006) with a reconstruction of a La Tène iron fibula. on finds first consolidated to prevent wholesale loss of rusted surfaces. They are still useful for removing the outer dense layers, for example, those with embedded stones. Air-abrasive cleaning is still commonly employed and a wide variety of cleaning agents is now available ranging from aluminium oxide to walnut shells. Since many of the iron surfaces are encrusted with mineral grains cemented to the object, the use of harder abrasive materials such as aluminium oxide and glass beads are generally necessary to clean away these from the surface of the object. These techniques are skilful processes in which experience has to be gained in order to carry out this part of the conservation treatment effectively. A conservator using typical air-abrasive cleaning equipment employing binocular magnification to more carefully delimit excessive removal of the corroded surface is shown in Plate 62. Fendel (1994) discusses tools useful for mechanical cleaning in more detail. Fragile layers may be temporarily consolidated with a volatile binder such as cyclododecane (Scharff et al. 2000: 331), which is removed later by evaporation. Uhlig (2002) draws attention to the problems of consolidating fragile iron objects when cleaning them. Plastic polymers are not especially suited for the purpose as the corrosion layers become adhered together causing possible future damage to any original surface. It is very difficult to examine impregnated objects. A series of trials using cyclododecane on Roman iron surface finds was carried out to assess the possibility of using this alternative. Particularly fragile, partially hollow objects proved easier to clean after consolidation with cyclododecane however there was one drawback: the waxlike lubrication created by cyclododecane during polishing made it more difficult to recognize corrosion layers. If objects are cracked and fractured, additional consolidation can be carried out by applying the cyclododecane with a heated spatula. If packed in plastic foil and polyethylene bags, Uhlig found that the objects could then be worked on over a period of several months. Laser cleaning allows safe removal of fragile layers without physical contact when they absorb the respective wavelength highly and the substrate does not. A number of applications on metals have been studied in the last decade (Fotakis et al. 2006: 306–13), as well as different types of lasers for use on archaeological iron (Koh and Sárady 2003). Old organic coatings are best removed with the far infrared (IR) pulses of a TEA CO2-laser, which are only poorly absorbed by metals. A rust crust on Byzantine mail armour soaked with an oil/resin mixture in a previous treatment has been successfully removed by a pulsed Nd:YAG laser that allowed improved control of the cleaning than the air-abrasive method (Heinrich 1998). Klotzbach et al. (2008) presented the laser removal of rust and coatings from a 16th-century harness. In a project studying the laser cleaning of archaeological iron. Hildenhagen et al. (2004) showed that it can be useful to first reduce the corrosion layer mechanically. Results obtained by laser cleaning revealed surface details more clearly than by air-abrasive methods. Moistening with ethanol to speed up the process risks the particles chipping off. The self-limiting effect of the laser application does not work here because the layers over and beneath the original surface do not absorb the light differently. The process has therefore to be carefully controlled by the operator visually while wearing protective goggles to protect against the strong flashes of light (laser plasma). Traditional techniques of chemical cleaning have relied on vinegar, lemon juice, oxalic acid or other fruit acids. Entwistle (2001) records that Maynard, working as a restorer in London in the 1880s, employed a strong solution of potassium cyanide using about half an ounce to a wineglass full of water in which

Mechanical and chemical cleaning
Many iron objects are so badly encrusted that a considerable amount of mechanical cleaning is required to reveal something of the shape of the object (Scott 1989b). The tools used can range from large pincers and pliers to hammers and chisels, and from picks and dental tools to scalpels and small scrapers. Much of this work is either self-explanatory or reliant on the experience of the user to break away part of the concretion or corrosion crust without undue damage to the object itself. Tools used in carrying out cleaning operations include the cavitron, the vibrotool and the air-abrasive unit. Both the cavitron (a small cleaning tool employing ultrasonic vibration in a water mist), and the vibrotool (which uses adjustable vibrational impact to break up the corroded surface) were much used from the 1960s to the 1980s, but have now been relegated for the most part as being old-fashioned and undesirable. In Germany and elsewhere in Europe, rotating abrading tools have been used, frequently 134

Conser vation of iron from the soil the iron object was immersed and subsequently scrubbed with a toothbrush. A paste was also used for cleaning consisting of a mixture of Castile soap, potassium cyanide and water which was beaten into a creamy consistency. Chemically the cyanide would react with iron oxides to form soluble cyanides that were washed away. Entwistle notes that by 1905, Rathgen had experimented with a method of treatment for iron that involved boiling the objects in molten potassium cyanide. The treatment was employed both for small silver and iron artefacts, which were briefly immersed in the molten potassium cyanide and then quenched in water. All traces of cyanide were then removed by repeated boiling in distilled water followed by impregnation in molten paraffin wax. Though efficacious for the treatment of large numbers of small objects, Rathgen cautioned against the use of this method because of the toxicity of potassium cyanide, and he later employed a fused mixture of potassium and sodium carbonate with some success (Rathgen 1903; Rathgen and Borrman 1905). Cyanides were much in use at the turn of the 19th century, even being employed as electrolytes for electrolytic reduction of various metals, however they would never be used for these purposes now given the highly poisonous nature of potassium cyanide solutions although chemical cleaning still has its place in such cases when mechanical cleaning would do more harm by damaging the surface. Nevertheless, chemically removing more or less protective (‘passivating’) rust may make the underlying metal more vulnerable to corrosion. It can, therefore, be wise to add an inhibitor to the solution (see Ch. 14). Complexing agents are used as their free electron pairs can form strong bonds with metallic cations; they often contain carboxylate groups. The concentration of the active free deprotonated anion is strongly pH-dependent: the higher the pH, the more complexing anions are present. This allows the strength of a solution to be adjusted by means of the pH; for example, by the addition of sodium hydroxide or the direct use of a salt instead of the acid. For archaeological finds, the disodium salt of ethylene diamino-tetraacetic acid (EDTA) has been found useful for cleaning plated objects (Emmerling 1969). Jourdain-Treluyer (1990) also recommended EDTA for effective chelation of Fe3+ at a concentration of 5–10% w/v and pH of about 5.5. However, there are real dangers that the object itself may be attacked if heavily deteriorated. Farke (1992) made the discovery that mineralized textile fragments on iron objects can be uncovered and microscopically studied after controlled application of a 10% solution of Na2EDTA, which dissolves other rust more readily than the fibre pseudomorphs. The detection of the presence of iron salts due to staining or in the form of mordants or pigments has recently been shown to be facilitated by the use of bathophenanthroline test strips. Vuori and Tse (2005) showed that these strips are effective for identifying iron in cellulosic textiles. They can be used to detect iron in acidic collagen and silk fibres, however, they were unable to detect iron in keratin-derived material. The removal of iron salts from waterlogged wooden materials was shown by MacLeod et al. (1990) to be facilitated by the use of different grades of polyethylene glycol, which can act as a chelating agent for the removal of iron from these types of materials. A series of experiments involving PEG solutions and a variety of chelating agents under neutral and mildly acidic conditions demonstrated the beneficial effects of heating, stirring and ‘chemical surface activation’ in the removal of iron from archaeological waterlogged timbers, which can be cleaned of iron contaminants quite effectively without damage to the wooden object itself.

Techniques based on reduction and heating
We have seen that there was an early introduction of both electrolytic reduction and heating techniques to effect stabilization to the iron artefacts under treatment. The raison d’être of most of these techniques was either oxidation, through heating of the object, or reduction, to remove the corrosion crust entirely. Developments in reduction techniques that followed on from these early approaches to conservation include hydrogen reduction, alkaline sulphite reduction and plasma reduction. Of these three, the hydrogen reduction process was developed first, based on the known chemical techniques of transformation of metallic oxides to metal by heating in a stream of hydrogen gas.

Electrolytic reduction
Electrolytic reduction as a conservation treatment has its origins during the zenith of the electrotyping and electrochemistry developments of the late 19th century; Rathgen (1889, 1898) employed electrolytic reduction on a variety of artefacts using 2% potassium cyanide solution in water as an electrolyte and platinum anodes for the treatment of chlorides in ancient bronze artefacts. He used a variety of techniques depending on the object concerned, and would also use grinding wheels and mechanical cleaning during his conservation treatments. A good example of the skilful work achieved is shown in Figure 13.2.

Figure 13.2 Iron inlaid dagger shown before cleaning (left) and after cleaning with the silver inlay revealed (right) (after Rathgen and Borrman 1905).

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Iron and Steel in Ar t The early application of electrolytic reduction for the treatment of iron objects generally employed aqueous sodium hydroxide as the electrolyte with iron or molybdenum stabilized stainless steel anodes. As Plenderleith and Werner (1971: 286) observe, it is sometimes difficult to make a good electrical connection with corroded iron, and it may be necessary to scrape away some of the rusted surface to expose uncorroded metal beneath. In preparing large objects, such as cannons, for electrolytic reduction, electrical contact may have to be made in several areas along the length. A cautionary note that is always necessary when dealing with reduced iron objects is exemplified by this quotation from Plenderleith and Werner (1971: 286): As a matter of interest, electrolytically reduced iron often steams when first rinsed after removal from the tank. This is due to the rapid oxidation of pyrophoric iron, and a case is on record where a large piece of black reduced rust, when picked off, actually glowed and burned through the French polish on the bench! When reduction was considered to be complete, or when sufficient rust and debris had accumulated in the tank to suggest that reduction had gone far enough, the object was removed, rinsed in cold water to remove any adhering sludge of reduced iron compounds, and then boiled in successive changes of distilled water until the wash-water was free of chlorides. This washing process had to be carried out as rapidly as possible to prevent further surface rusting of the iron. The iron object was then dried under an IR heater or in a warm oven for at least 24 hours, brushed and then waxed or lacquered. The process of electrolytic reduction is still used but it is mostly restricted to large marine finds rather than buried archaeological material. The reasons for this are many, but essentially there is too much loss of surface and lack of control over how much of the corrosion products are, essentially, stripped away from the iron object by evolving hydrogen bubbles in the process of reduction, not to mention the occasional pyrophoric conflagration! A 17thcentury hinge plate, shown in Figure 13.3, displays a stripped appearance after electrolytic reduction, despite the limited extent of rusting before cleaning, so there has been a loss of surface even here. Iron objects treated in this way in the past may possibly still be stable on display, but have suffered so much loss of shape or information that the inherent archaeological record that they represent has been compromised by the conservation treatment. It is still possible to examine the metallographic structure of iron objects that have received this treatment, which is some consolation, but as a method for smaller, often important archaeological material it has been superseded by other techniques. Electrolytic reduction to iron metal and de-rusting by gas bubbles can be avoided when the object is not too strongly polarized cathodically. The negatively charged metal repels the anions in solution (‘electrolytic desalination’ – see Wihr 1972, 1975) and the rate of chloride removal can be enhanced (Beaudoin et al. 1997). The use of electrophoresis (placing the iron objects between electrodes without actually effecting an electrical contact to them) is no more effective than simple washing (Höhn 1980). An important aspect to bear in mind in connection with electrolytic reduction is the different behaviour of cast iron and wrought iron. Wrought iron suffers badly from any hydrogen bubbling between the metallic core and the corrosion products, while similar electrolytic treatment of cast iron causes much less disruption of the surfaces and may produce acceptable results in conservation treatment.

Hydrogen reduction
Hartwich in 1887 was already reducing iron objects in a current of hydrogen, although it is difficult to discover how effective this treatment really was, and whether some of the iron objects might not have simply disintegrated during the treatment or even exhibit pyrophoric behaviour when removed from the treatment chamber. The dangers of using heated streams of hydrogen gas for the reduction of iron artefacts are illustrated by the apocryphal story of one such treatment by an English conservation scientist, many years ago, who managed to blow up part of the laboratory during the experiment. As a result, research into this method of conservation was halted and had to wait until laboratory facilities, properly equipped to handle heated hydrogen gas, became available. Hartwich (1887) claimed that his technique was highly successful and he admired the newly formed metallic appearance of the treated artefacts. Nearly 80 years later, the successful utilization of hydrogen reduction for the treatment of archaeological iron, especially for marine artefacts, was carried out in Sweden in 1964. Among the important finds that were treated were the iron objects from the Swedish warship, Vasa, which sank on her maiden voyage in Stockholm Harbour on 10 August 1628, and which was salvaged 333 years later in 1961. The conservation treatment consisted of passing pure hydrogen over the objects that were contained within a cylindrical furnace, at a temperature between 600 and 700 °C for 76 hours, followed by cooling to ambient temperatures over a 48-hour period (Arrhenius et al. 1973; Barkman 1977a,b). After hydrogen reduction, the objects were coated with molten paraffin wax under vacuum in order to prevent renewed conversion to rust. The authors were aware of the drawbacks of the process and ensured that composite objects with wood or other organic material were not treated, that a prior investigation with radiography was undertaken, and that any laminated object was carefully studied before treatment. The principal problems with the hydrogen reduction process

Figure 13.3 Iron hinge piece cleaned with electrolytic reduction showing slight surface pitting as a result of loss of the surface during the cleaning process (photograph: D.A. Scott).

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Conser vation of iron from the soil are the loss of metallographic structure of the ferrous material (Tylecote and Black 1980), the dangerous nature of the hydrogen reduction process, demanding industrial safety precautions, and the high cost of the installation. There have even been occasions where the iron removed from the reduction furnace proved to be pyrophoric, as finely divided iron can be ignited and burnt to iron oxide. Prior work on the hydrogen reduction of two grey cast iron cannon from an 18th-century shipwreck carried out in Finland around 1995/7 failed as the cannons fell from their supports and one trunnion was broken.5 As a consequence of these drawbacks, the hydrogen reduction process has become limited in its application, principally during the 1970s and 1980s to large-scale marine objects such as cannon, cannonballs and ships’ fittings and fixtures that would otherwise have presented an insurmountable conservation problem at the time (Blackshaw et al. 1982; although it is true that electrolytic reduction could have been employed instead, perhaps with less damage to the various material states comprising some of the corroded objects (Barker et al. 1982). As concerns for the metallographic integrity of the iron objects have grown – and indeed for the safety of the objects themselves – this drastic treatment is now seen as less than desirable, and alternative approaches to the reduction of archaeological iron have led to both less damaging and less invasive treatment options being developed. The limitations of the hydrogen reduction process, particularly the need to employ high temperatures in order to achieve reduction, has led naturally to the investigation of more sophisticated techniques without the total loss of metallographic structure of the original material, and without the difficulties posed by electrolytic reduction, where large tanks full of caustic solutions are required. One of the last notable applications of the hydrogen reduction process was used to treat the cannons from the wreck of the Mary Rose in Portsmouth. One practical advantage of its application was that it allowed a rapid display of the treated finds, which ensured public interest and helped to raise the necessary funds for the conservation of the rest of the ship6. of samples before, during and after treatment. However this work was based on experiments using the iron chlorides FeCl2∙4H2O and FeOCl (!) as model compounds. The complete reduction of the oxide turned out to be rather undesirable because of the brittle nature of the resulting porous metal. The principal advantage is the ‘softening’ of the corrosion crust, which allows the revelation of even tiny details of the ‘original’ surface such as file markings and other surface features, in a short period of time and of a quality hitherto unimaginable. Müsch (1997) achieved a similar effect without plasma by simply heating objects in a closed chamber filled with charcoal to temperatures between 250 and 350 °C. Apart from the unacceptable temperatures to which the iron objects were exposed during these treatments, there are other issues that need to be addressed in assessing their efficacy. The microstructural details of the iron will be irreversibly affected so part of the scientific and historical value of the treated material will be compromised in the course of the treatment, an indignity that iron has often had to endure during some conservation treatments to survive at all. The use of plasma treatments for iron has been reassessed by Schmidt-Ott and Boissonnas (2002). Some of these conserved objects were re-examined eight years after treatment, revealing that the apparent long-term stability that had been expected following plasma reduction had not been achieved. Many artefacts manifested corrosion, ranging from active pitting corrosion to total disintegration of the object. It is possible that much longer treatment times, of the order of 190 hours at temperatures of 300–400 °C, would be required to remove most of the chlorides. According to Ståhl et al. 2003 (see also below), the akaganéite should long be destroyed. The attempt to render the surface passive with carbon or nitrogen was also unsuccessful, and the use of these elements entailed colour changes and possible chemical changes to the surface which were undesirable. Instead of being regarded as a universal panacea, Schmidt-Ott and Boissonnas (2002) decided to make use of plasma reduction as one treatment in a series of possible conservation measures that aimed to respect the integrity of the object as far as possible while improving stability. The National Swiss Museum in Zurich has been involved with research into the application of plasmas for conservation treatments since 1984 and has operated its own unit since 1990. The hydrogen plasma used is produced by an electrical discharge in a radio frequency field using a 27.12 MHz, 4 kW generator, with the objects to be treated held on glass grids in the centre of a large reaction tube. As a safety measure, the environment is shielded from high-frequency radio waves by enclosure in a Faraday cage. A mixture of hydrogen and argon gases is used at a pressure of 20–90 Pa. Temperatures employed during reduction are measured with a liquid thermometer, an IR pyrometer, and a thermocouple, all of which recorded temperatures less than 140 °C, avoiding any gross changes in microstructural morphology of the treated objects. Ehrenreich and Strahan (1987) verified that no microstructural changes took place to quenched martensitic structures by boiling in distilled water, while Archer and Barker (1987) maintained that hydrogen reduction processes were safe to use, even up to a temperature of 250 °C. The same conclusion was reached by Perlík (2004) who reported on the influence of low-pressure hydrogen plasma on changes in the metallographic structure of iron and found none affected under 250 °C. In Perlík’s work it was found that plasma treatment at about 200 °C did not affect phase composition. Changes in the structure of tempered martensite were insignificant, although a decrease in hardness by approximately 150 HV was found to occur. No measurable effects on the microstructure and properties were found until applying 137

Gas plasma reduction
The use of gas plasmas for the conservation of metalwork was first explored at the British Museum Research Laboratory by Daniels et al. in 1979, although the temperatures used in these early plasma applications had the drawback of potential microstructural alteration of the iron artefact during treatment. The work of Vepřek and co-workers in Switzerland has helped to sustain interest in plasma reduction as a workable method for treatment. Patscheider and Vepřek (1986), for example, describe a plasma apparatus employing gas mixtures of hydrogen, methane, nitrogen and argon, using temperatures as high as 400 °C, which could take up to 20 hours of treatment time. To passivate the iron object against post-treatment corrosion, the surface was enriched with carbon and nitrogen in the plasma and a wax impregnation was applied as additional protection. A number of papers were published by this group of workers describing the apparent success of the new treatment (Eckmann et al. 1988; Vepřek et al. 1987, 1988) using a high-frequency, low-pressure plasma system. The equipment employed and the conditions required for the reduction of iron oxides and removal of chlorides were evaluated by XRD analysis
5 C. Degrigny, pers. comm. to D.A. Scott, 19 June 2002. 6 V. Boissonnas, pers. comm. to D.A. Scott, 27 November 2005.

Iron and Steel in Ar t temperatures in the region of 250 °C and tempering at 300 °C or 250 °C. At these temperatures the microstructure transforms into bainite as the needles of martensite shorten and carbide areas begin to form. At 350 °C, further tempering of martensite and bainite leads to the formation of some ferrite and the particles of cementite coagulate; the structure begins to show the presence of some troöstite. Although not addressed in Perlík (2004), it is also possible that subgrain boundary features in cold-worked wrought iron may be affected, and that this subtle change can even be initiated by temperatures as low as 150 °C. From all of these perspectives, it can be concluded that an ideal temperature limit for treatment would be below 150 °C, a limit that now appears possible to meet in practice. In the temperature range from 50 to 200 °C, internal stresses are relieved and some of the carbon can be ejected as ε-carbide. As these are probably not Arrheniustype processes, we cannot be sure that what occurs in a short time at high temperatures has already occurred in 2000 years at soil temperatures. The persistence, for example, of the metastable beta phase in high tin bronzes over 3000 years indicates that some transitions simply require greater activation energy than storage at room temperature for long periods of time would be able to provide (Scott 2002). The only disadvantage of this low-temperature hydrogen plasma treatment is that it is not removing chloride ions, but is inducing a series of microcracks in the corrosion crust that greatly facilitates the removal of chloride ions using an aqueous method such as the use of alkaline sulphite, which then has to be employed as a secondary conservation process. After the plasma reduction treatment, the iron objects are cleaned using the air-abrasive technique with aluminium oxide powders of about 37 µm diameter or with glass beads of less than 50 µm diameter. The treated and cleaned objects are then further treated with alkaline sulphite reduction (Rinuy and Schweizer 1981, 1982). The plasma treatment was found to substantially decrease the time needed for desalination compared with treatment of the same group of objects without plasma reduction. Measurements of chloride extraction proved that 10 instead of 12–14 weeks are sufficient for plasma-treated objects (Schmidt-Ott and Oswald 2006). Instead of using microcrystalline wax to impregnate the treated surface, Schmidt-Ott and Boissonnas (2002) employed Paraloid B-44 (Acryloid B-44), an ethyl acrylate-methyl methacrylate copolymer which, according to Down et al. (1996), retains a stable pH over time, whereas Paraloid B-72 tends to become more acidic. Paraloid B-44 has also been used as a coating for mineralized organic remains after prior analysis by reflectance electron microscopy (REM) during treatment with alkaline sulphite (Schmidt-Ott and Oswald 2006), where B-72 failed because of its lower glass transition temperature as the baths were kept at 50 °C. The treated objects are then stored at low RH using silica gel or oxygen absorbers, such as the RP system from the Mitsubishi Gas Chemical Company (Becker 1999). If the iron objects preserve organic mineralized material, they should not be treated by plasma reduction as they will become more brittle and easily damaged. If non-mineralized organic material is treated it becomes desiccated and tends to crack, so these composite materials cannot be treated using this method either. If the iron objects are composite with copper alloy components, the reduction of the copper oxides and other minerals of the patina or crust will result in unacceptable alteration to the copper alloys. Other groups have also investigated the application of plasma reduction to iron objects. For example, Kotzamanidi et al. (1999) describe the application of a reducing, low pressure, radio frequency plasma at temperatures in the range 138 240–400 °C. During this investigation, steel oxidized either in a salt spray cabinet or in the soil together with excavated objects from Mount Athos (Greece) were treated. Post-corrosion experiments were carried out including electrochemical polarization studies and exposure in a humid atmosphere. These tests confirmed greater stability for specimens treated in a hydrogen plasma diluted with nitrogen and methane. Using instrumental neutron activation analysis, measurements were made of the chloride ion removal from the corrosion layer following the plasma treatment; this suggested that the removal was an effect of heat rather than the plasma treatment per se. Akaganéite decomposes to chloridefree haematite above 200 °C (Ståhl et al. 2003), which would imply higher corrosion stability of heat-treated objects. The issue of the preservation of microstructural integrity of the iron objects was not addressed in this research – potentially a severe problem, as we have seen, since temperatures in excess of 250 °C were being employed. On the other hand, the use of the hydrogen plasma reduction technique, if limited to low temperatures, cannot be employed as a method for removal of chloride ions directly, therefore the efficacy of the treatment is severely restricted. Further studies, again in Switzerland, by Schmidt-Ott (2004) were undertaken to ascertain if the temperature employed in the process could be reduced still further, below the temperature of 120 °C used with the hydrogen/argon mixed plasma. It was discovered that temperatures of 80 °C could be efficacious if a pure hydrogen plasma was employed rather than the hydrogen/argon mixture. The applied plasma was produced by a 27 MHz generator in a 0.7 m³ quartz vessel at a gas pressure of about 15–50 Pa (0.1–0.4 Torr). The use of a pure hydrogen plasma, which was previously only employed in the treatment of silver artefacts, was utilized on pre-dried iron objects, reaching a temperature of 80 °C. Metallographic examination of a group of 20 Roman nails from the site of Wetzikon-Kempten, Hinwilerstrasse was chosen for evaluation of possible microstructural alteration. A series of controls suggested that the process of pre-drying of iron objects before plasma reduction at 80 °C did not lead to any improvement in removal of external corrosion layers of the nails. Both pure hydrogen plasma and the hydrogen/argon plasma previously used show similar effects on the metallographic samples so far examined. In both cases a clear separation between the outer corrosion layers and the original surface could be observed, which helps to explain why mechanical cleaning following plasma reduction is facilitated so easily. An example of an iron object before and after this kind of low-temperature plasma treatment is shown in Plates 63 and 64. Recent analyses with Raman microscopy (Schmidt-Ott and Hug 2007) demonstrated that the reduction is limited to a thin outer layer and the separation at the original surface even appears in an argon plasma without any hydrogen. Like modern electrolysis or other treatments, the RF-plasma application on iron may no longer be seen as reduction in a strict sense. The observed loosening might instead be due to the RF-field and the current passing through the samples.

Techniques based on aqueous extraction
The boiling of ancient iron objects in water – or at least the washing of them in water to remove salts – is a historic treatment used for many years. The reasons why this simple method was

Conser vation of iron from the soil ineffective in the long term is only now evident from the scientific investigations into the processes of corrosion discussed in this book. Because of the potential fragility of archaeological iron, the attempt to wash the objects is often better than doing nothing at all, although even more sophisticated washing techniques cannot hope to remove all the chloride ions principally responsible for the problem. For example, Scott and Seeley (1987) proposed the use of a modified Soxhlet extraction process for the removal of chlorides from fragile iron artefacts employing automatic cycles of hot distilled water, the whole apparatus being purged with nitrogen to prevent corrosion from occurring during washing in hot water as a result of aerial oxidation in wet conditions. A diagrammatic view of the apparatus is shown in Figure 13.4. Several small objects can be treated at the same time, but the utility of the method is dependent on the size of the Soxhlet apparatus, which tends to become stained with iron hydroxides, and since not all the chloride ions can be removed by washing in water, the general utility of the method is only moderate. It was adopted, however, by Aoki et al. (1993) who concluded that initially, only about 50% of chloride or sulphate ions was extracted by the Soxhlet process. However, by preceding the Soxhlet extraction with a hydrogen plasma treatment, the effective removal of the chloride ions was increased to about 80%, although it remains doubtful if this is any guarantee of increased stability over many years of storage. A reassessment of the treated objects would be of interest.

Aqueous reduction techniques
If the application of gas reduction methods involves the application of too much heat or too complex an apparatus, then would immersion techniques in aqueous-based reducing solutions be preferable? Can such techniques be used successfully on all iron artefacts? Will some objects simply disintegrate if immersed in strong reducing solutions? The answers to these questions have slowly become apparent as a result of research carried out over the last 25 years. The use of aqueous reduction methods first became a practical proposition as a result of the use of alkaline sulphite for reduction of marine cast iron artefacts by North and Pearson in 1975. The artefacts were treated by immersion in 0.5 mol l–1 sodium hydroxide/0.5 mol l–1 sodium sulphite solution at 60–70 °C for periods up to three months in sealed containers. Schmidt-Ott and Oswald (2006) found, after four years of experience, that more diluted solutions such as 0.01 mol l–1 NaOH/0.05 mol l–1 Na2SO3 at 50 °C were sufficient. Iron is stable in alkaline environments (although in highly alkaline environments we would expect dissolution of the iron in the form of ferrates, according to the Eh-pH diagrams), even when chloride ions are present. It was thought that this reduction treatment would result in the reduction of all ferric oxyhydroxides to magnetite. The half reaction for the oxidation of sodium sulphite under alkaline conditions is: SO32– + 4OH- → SO42– + 2H2O + 4e– (13.1)

Gas bubblers

Reflux condenser

Soxlet container

Stopcock for removal of washwater sample

To nitrogen cylinder

Flask filled with distilled water Heating mantle

Figure 13.4 Iron washing with the Soxhlet extractor under nitrogen to prevent aerial oxidation during washing. While useful for fragile artefacts and other delicate washing processes, its utility is limited due to the usual problems associated with washing of iron artefacts (after Scott and Seeley 1987).

Excess reagent remaining at the conclusion of the treatment was fixed by washing in barium hydroxide solution that will form barium sulphite and sulphate, which are insoluble. The alkaline sulphite reduction treatment proved to be very successful in the elimination of chloride ions and has been usefully employed for the conservation of marine iron artefacts. The utility of the method has resulted in its application to iron objects from all types of environments. Rinuy and Schweizer (1982) adopted the alkaline sulphite treatment for the conservation of several kilograms of excavated Roman nails from the Württembergisches Landesmuseum, in Stuttgart, Germany. At the time that this study was made, the Württembergisches Landesmuseum was using the electrophoresis desalination treatment (Eichhorn 1975), which allowed a comparison to be made with the sulphite reduction treatment as well as with intensive washing (Plenderleith and Werner 1971), immersion in a solution of 10% formic acid followed by intensive washing and with washing in distilled water at 40 °C with daily changes of water (Wihr 1975). The alkaline sulphite desalination treatment released twice as much chloride ions as the other techniques, and artefacts decorated with silver or brass appeared to suffer no visible damage during treatment (Rinuy and Schweizer 1982: 45). Schmidt-Ott and Oswald (2006: 128), however, observed the reduction of green copper corrosion products to cuprite or copper that could even be deposited on other objects in the bath. They were unable to find a suitable protective coating to prevent this from occurring.

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Iron and Steel in Ar t Skinner and Bryce (c.1982) employed the alkaline sulphite method to treat over 100 cannonballs and grenades from the site of the wreck of HMS Dartmouth. The problem with assessing the efficacy of some of these treatments however is the lack of any review of how the treatment has performed over time. An account of comparative treatment efficiencies for iron objects is given by Watkinson (1982, 1996; Watkinson and Neal 1998). The 1982 paper examines the use of lithium hydroxide and sodium hydroxide as methods for desalination. Lithium hydroxide had been enjoying a short vogue at the time, but doubts about its efficacy were confirmed by Watkinson, and the method is now considered obsolete. Sodium hydroxide continues to be a useful storage medium and does accomplish some desalination. Watkinson (1996) compared the chloride extraction efficiency of the following aqueous washing methods: alkaline sulphite, Soxhlet extraction, repeated boiling and pressurized water. Absolute extraction efficiencies were determined by digestion of the objects following treatment. Alkaline sulphite was shown to be a more efficient chloride extractor than the other three treatments examined, either separately or combined. The chloride extraction rate is 87% as compared to 72% for the combined treatments. Beaudoin et al. (1997) provide a critique of the problem of the renewal of corrosion of archaeological objects previously stabilized by the alkaline sulphite method. The objects studied were from a homogeneous body of protohistorical iron axes. The physicochemical study of the corroded structures allowed the nature of the compounds and the corrosion structures before and after the resumption of corrosion to be determined. Results showed the presence, at the corrosion/iron interface, of new chloride compounds that were interpreted as the chemical precursors of renewed corrosion. An evaluation of re-treatment options was carried out using a two-step treatment: a simple immersion in an alkaline sodium sulphite solution followed by an electrochemical treatment under cathodic polarization. The first results established a relation between the higher rate of chloride extraction observed at the initial part of the immersion phase. The use of cathodic polarization enhanced the chloride extraction rate. Stawinoga (1996) simplified the method for mass treatment by working at room temperature in unstirred plastic containers. Results so far are promising and the efficacy of this variant is currently being investigated at the State Academy of Art and Design Stuttgart (Schmutzler and Ebinger-Rist 2008). Stawinoga (1996) and Schmidt-Ott and Oswald (2006) also omitted the barium hydroxide treatment. If this step really precipitates all potentially corrosive anions as insoluble barium sulphite or sulphate in the object, as has been suggested, has never been proven experimentally. Wang (2006), at least, could detect barium sulphite in a treated object in one case. Apparently, simple washing with deionized water after treatment is sufficient to leave no harmful levels of sulphite/ sulphate in the object. A detailed review of all theoretical and practical aspects of the alkaline sulphite treatment is given by Greiff and Bach (2000). Magnetite is not formed as a result of the direct reduction of ferric oxyhydroxides by sodium sulphite (Gilberg and Seeley 1982) as was originally thought by North and Pearson (1975), but oxygen is scavenged by sulphite and the oxidation of ferrous to ferric ions is prevented, thus no new rust precipitates in the pores. This helps in the desalination by diffusion. Greiff and Bach discuss some further issues which may affect the efficacy of the alkaline sulphite treatment, such as whether the desalination of freshly excavated artefacts could be improved if the formation of akaganéite after excavation could be prevented. 140 More insight into the mechanism of chloride removal can be expected from the Odefa project (Optimisation de la Déchloruration des Ferreux Archéologiques) funded by the French Ministry of Culture (Reguer et al. 2007; Guilminot et al. 2008). Dillmann and his co-workers and partners, whose advanced microanalytical tools (µ-XRD and µ-XAS in addition to µ-Raman, µ-FTIR and SEM–EDS) proved to be so fruitful in gaining new insights into the corrosion processes, will now apply them to study the effects of sodium hydroxide alone, alkaline sulphite, and electrolysis. Of particular concern is whether, for ferric (or even ferrous compounds), alkaline sulphite is a viable reducing method. Hydroxylamine (NH2OH) is an alternative alkaline reducing agent and oxygen scavenger which has the advantage of leaving only volatile residues in iron artefacts, and allows shorter treatment times. At first, promising results were obtained by Wunderlich (2000), but later research was unable to confirm its efficacy (Greiff and Bach 2000: 336; Wiesner et al. 2007). Fe2+ is a stronger reducing agent than hydroxylamine and gets oxidized, and brown ferric rust precipitates in the solution; the corrosion stabilization is not reliable and akaganéite is not destroyed. Even magnetite seems to get attacked by hydroxylamine (Wiesner et al. 2007). Hydrazine (NH2NH2) is a powerful reducing agent and can transform akaganéite powder in four days quantitatively to magnetite (Scharff et al. 2000: 302). However, the practicality of using it in conservation treatments is effectively prevented since hydrazine is a known carcinogen: it is therefore too dangerous. At present, it seems that the only relevant effect of reducing agents is not to reduce ferric to ferrous compounds but to scavenge oxygen during desalination and avoid further oxidation/corrosion. As a result of this, no fresh iron (II/III) hydroxides are precipitated in the pores which lower the diffusion rate dramatically as was observed by Andersen (2006). Interestingly, in a small test utilizing 10 nails, Al-Zahrani (1999) found that desalination with sodium hydroxide, de-aerated with nitrogen, was even more efficient than alkaline sulphite. In a project funded by Deutsche Bundesstiftung Umwelt (DBU), Schmutzler will try to reproduce this result in order to develop a badly needed, viable route for the mass treatment of iron finds (Eggert 2008). Some of these approaches to treatment have been used for storage. For example, sodium sulphite or the hazardous hydrazine, added to enclosed containers housing iron objects in aqueous solution such as those from marine burials, effectively scavenge oxygen from the system and act as cathodic inhibitors: 2SO32– + O2 → 2SO42– N2H4 + O2 → N2 + 2H2O (13.2) (13.3)

Harrison (1988) investigated the effectiveness of three amines at removing iron chlorides and reducing iron oxyhydroxides to stabilize archaeological iron. The amines employed were 1,2 diaminoethane (ethylenediamine or en), triethenolamine (tea), and vak iv (8% formaldehyde, 6% isopropanol, 5% NaOH, 5% tea). Test procedures on iron nails from aerobic sites were carried out and changes in appearance are described, together with graphs showing the rate of chloride extraction. The treated samples were aged at about 100% RH for eight weeks and found to be stable. It is suggested that either 1,2 diaminoethane or the vak iv mixture is a safe and effective iron treatment. However, vak iv contains formaldehyde, which is a hazardous substance. Argyropoulos et al. (1997), working at the Canadian Conservation Institute (CCI), report that the combination of

Conser vation of iron from the soil sodium hydroxide and ethylenediamine as a treatment appears to be more effective than the use of sodium hydroxide alone. Through trial and error, the conservators at CCI had evolved a treatment protocol using an immersion time of three to four months in a 5% v/v solution of ethylenediamine in deionized water. After a period of ten years, results showed that using ethylenediamine as part of a conservation treatment was one of the most effective means of stabilization compared with other treatments. The iron artefacts were first immersed in a 2% w/v aqueous solution of sodium hydroxide at room temperature. The solution was monitored for chloride content weekly for the first month, and then monthly until chloride ion levels typically fell below 50 ppm. Following this, the sodium hydroxide solution was replaced with aqueous ethylenediamine at 5% v/v and heated during working hours to 50 °C using a hotplate. The chloride ion concentration was again monitored and treatment stopped when chloride levels fell to between 10 and 20 ppm, usually after three to four months. After treatment, the objects were hot-washed in successive baths of deionized water; washing was considered complete when the surface pH of the object was between 6.5 and 7.5. This took about six weeks, after which the water was removed by immersion in acetone for about three days, and tannic acid was applied to convert their surface colour to black. The treatment appears laborious, but has been judged as reasonably effective for these artefacts. Ethylenediamine is used in industry as a corrosion inhibitor in acid solutions as well as for the pickling of steel (Agryropoulos et al. 1997). The mechanism whereby ethylenediamine could behave as a corrosion inhibitor is perhaps that it forms insoluble iron complexes at the oxide-covered metal surface, which is presumably the modus operandi occurring here. On the other hand, ethylenediamine could also behave as a corrosion stimulator if it formed soluble iron complexes, so it is not entirely clear that the effect will entail corrosion inhibition in all cases where treatment is attempted. Indeed, Selwyn and Argyropoulos (2005) found that immersing archaeological iron, which had a substantial amount of remaining iron metal, in ethylenediamine solutions can be dangerous because of the ability of ethylenediamine to form soluble complexes with iron(II) ions. Despite these problems, there is now a Chinese patent (CN 1796616A, 2006-9-5) for a desalination solution containing sodium hydroxide and EN with the addition of surfactants and phosphate which has proved to be more effective in removing chloride and protecting cast iron against further corrosion than sodium hydroxide alone (Liu and Li 2008). consuming and may need pretreatment of solutions. This also holds true for the classical titrations with silver nitrate indicated by chromate (Mohr titration), with NaSCN as back titration of excess silver ions (Volhard titration), or with mercuric nitrate (see North 1987: 248–52). Schmidt-Ott and Oswald (2006) used a ready-made commercial mercurometric testkit (Aquamerck 1.11106.0001) but their protocol is still time consuming. Wunderlich (2000) determined the chloride concentration using Hg(SCN)2 (Cl– sets SCN– free which reacts with Fe3+ to form an intense red complex) but this needs a spectrophotometer. An informal workshop conducted by a group of American conservators searched for cheaper and faster methods for chloride determination, the results of which are summarized in Wellmann (2002). However it is not clear if sulphite ions, the major cause of interference problems, were present. Evaluated during this workshop were LaMotte titration tests, Quantab strips, the Hach titration kit, the Jenway chloride meter, and a chloride specific ion meter with an Accumet pH/mV meter. Large amounts of sulphate, the oxidation product of sulphite, interfere with the determination of small chloride contents by ion chromatography (Schmidt-Ott and Oswald 2006). Ion chromatography is a modern instrumental method for quantitative measurements of ions. It has been applied to corrosion samples (Wang 2007a) and combined with inductively coupled plasma mass spectroscopy (ICP-MS) to sodium hydroxide wash solutions from the conservation of DC mode hydrogen plasma treated Scandinavian artefacts (Andersen 2006). From a conservation point of view, to compare the efficiency of desalination methods, the amount of chloride remaining in the object is even more interesting than the amount extracted. If the non-destructive but costly instrumental neutron activation analysis (INAA; Kotzamanidi et al. 1999, Selwyn and Argyropoulos 2006) cannot be referred to, measurement requires dissolution of desalinated iron finds in strong acids, e.g. nitric. Fortunately, the Romans left enough iron nails in European soils to provide sufficient test samples for this. Unfortunately, dissolution is normally performed in open systems with considerable loss of chloride evaporating as hydrochloric acid in the atmosphere. Ellis et al. (1976) found a 99% (!) loss of chloride from synthetic akaganéite if the sample is warmed in a beaker with 30% HNO3 just long enough to dissolve the solid. This seems to have been totally unnoticed in the conservation community. Therefore, if values for remaining chloride are reported at all, they might be too low! Schmutzler7 is in the process of developing a protocol using digestion in closed systems.

Measuring chloride ion concentration
An important and related issue in the conservation of works of art is the measurement of chloride ion concentration in the treatment of corroded iron objects, where ferrous chloride and ferric chloride may be important corrosion products, as well as sodium chloride from burial or marine environments. If only the endpoint of a washing process needs to be determined (no more chloride extracted by fresh solution) a qualitative test for chloride with silver nitrate is sufficient (Plenderleith and Werner 1971: 201). If a process is to be optimized (e.g. to find the right time for the change of washing solutions), quantitative data are needed. The conventional potentiometric titration of chloride is rather time

Composite iron objects
The problem of treatment of artefacts composed of iron and other materials is to find a treatment which is beneficial to all. For example, long-term storage in alkaline solutions is prohibited for many materials. Berger (2004) treated the anchor with attached wooden stock from a shipwreck site by electrolytic means employing cathodic polarization in an electrolyte compatible with both the wood and the iron, a 1% solution of potassium nitrate being chosen. The process of chloride ion removal using electrolytic treatment generally entails loss of the original surface
7 B. Schmutzler, pers. comm. to G. Eggert, 6 April 2008.

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Iron and Steel in Ar t if hydrogen is evolved. The problem was minimized by using voltammetry to monitor the current at –1.3VSHE (–0.642VSSE) which gave promising results, although the author does state that further research would be necessary to understand the efficiency of his proposed treatment. Polyethylene glycol (PEG) is the most common consolidant employed for wet archaeological wood, but it attacks iron by dissolving rust, especially when used for a prolonged period of time in heated solutions (this issue is discussed in greater detail in Ch. 15). Other wood consolidants such as sucrose or lactitol (Imazu and Morgós 1999: 615) allow the treatment of iron-wood composites without disassembling them or using corrosion inhibitors. a perforated polyethylene bag. When closed tightly, the RH in the box can be maintained at less than 45% for several months before the silica gel needs to be changed. This storage option has been superseded to some extent by the availability of plastics less permeable to oxygen and water vapour, as well as oxygen scavengers. While 12% RH would be safe from a corrosion point of view, Thickett (2005) identified a second threshold around 30%, above which the akaganéite corrosion rate increased significantly; hence the recommendation for the 30% level which is given as option (b). Wang (2007b) found a similar increase of the corrosion rate with RH. Keeping the RH below or at 30% (e.g. by changing the silica gel frequently enough – Wang (2007a) recommends yearly – ) seems to be a good strategy to avoid major damage in a short time. Modified commercial display cases with low air exchange rate and a large amount of silica gel are even able to keep the RH below 20% with only one annual exchange (Thickett and Luxford 2007). Option (c), reburial, may be a possibility in some sites if careful use of geotextiles and filling materials are employed, but since the exclusion of oxygen and moisture cannot be assured, the use of reburial for iron objects is rarely employed at the present time. Leaving objects in situ is a related possibility and this is frequently utilized with underwater wrecks or very large exposed structures that cannot be moved indoors. When extrapolating the progress that has been made in archaeology, science and conservation over the few last decades into the future, it seems wise to leave as much material as possible unexcavated for the benefit of future generations, whose solutions to current problems may be so much more sophisticated. Brewer (1990) examined the use of deoxygenated solutions and biocides for the storage of iron artefacts. The study expanded upon previous work initiated by CCI in which chemically deoxygenated solutions were tested on iron cannonballs as well as test coupons. These solutions were previously thought to be adequate for iron artefact storage, but microbial corrosion in the low-oxygen levels used in these storage conditions still promoted corrosion of some of the objects. In order to address this problem, a number of chemical biocides were tested as additives to the storage solutions. Samples of 20 mild steel coupons and 10 archaeological nails were immersed in ten different test solutions. The solutions consisted of various combinations of two chemical deoxygenators and three biocides, as well as two control solutions of plain tapwater and distilled water. The iron samples were immersed in the solutions for a period of four and a half months during which time weekly observations were made. The preliminary results suggest that sodium sulphite is a satisfactory deoxygenator and that all three biocides tested – formaldehyde, glutaraldehyde and a commercial quaternary ammonium compound by the name of Quat’s Disinfectant – worked well to inhibit microbial corrosion. Diethylhydroxylamine was found to be ineffective as it failed to reduce the dissolved oxygen content of the solutions sufficiently to inhibit further corrosion. A further evaluation of the storage of archaeological iron objects in aqueous solutions at CCI is that of Costain (2000). Here, six different regimes were investigated: 1% w/v sodium hydroxide; deionized water; 2% v/v ethylenediamine; alkaline sulphite (0.5 M sodium hydroxide with 0.5 M sodium sulphite); 1% w/v sodium carbonate and synthetic seawater conforming to ASTM D1141-75. Three different treatment protocols were subsequently employed. The study was carried out between 1983 and 1985. Samples were wrought iron nails from Red Bay, Labrador (a 16th-century Basque occupation), and Gaspe Bay, Quebec, a 17th-century underwater site. Nails were placed in the various solutions and

Storage strategies
A typical storage protocol is shown in Plate 65, where a polyethylene box with a tight-fitting lid filled with suitable inert packing material to cushion the iron object is closed with a bag of silica gel and an RH indicator strip to monitor the RH inside the box. This protocol may, however, prove inadequate to protect many iron artefacts if instability due to ferrous chloride and akaganéite is present. The storage of archaeological iron either before treatment or after conservation presents an endless series of difficulties. To avoid post-excavation corrosion of iron, its cause – the chloride content - has to be removed by interventive conservation. If this cannot be achieved, preventive conservation has to use storage conditions that slow down or totally stop corrosion. The principal factors are temperature, humidity and oxygen (Rosenberg 1933), as well as control of atmospheric pollutants such as sulphur dioxide. Reaction rates normally decrease with temperature therefore finds are often stored cold or frozen. While this may be preferable than doing nothing, experience with iron artefacts (e.g. nails) and meteorites in Antarctica has shown that even below 0 °C considerable corrosion can occur. There are a number of different possible approaches to the problem of storage, dealing either with the water or the oxygen content of the environment: Keep at a very low RH, i.e. under 12%. Keep at a controlled RH of about 30%. Reburial of objects from terrestrial sites. Store in deoxygenated aqueous solution. Keep in oxygen-free or low-oxygen conditions either with the use of an inert gas or oxygen scavengers in sealed cases. (f ) Deep-freeze the objects. Of these various options, the only one commonly available is (b). All the other possibilities involve complications of one kind or another. For example, the very low RH option of (a) may involve some objects undergoing dehydration with the attendant risk of lamination or fracturing. Even if successful, this option cannot be achieved without considerable costs in the long term. An example is the storage of finds in plastic containers with silica gel (Watkinson 1987), which has since been further researched by this author to investigate the efficacy of low RH storage (Watkinson and Lewis 2005). In the storage box shown in Plate 65, the iron objects are cushioned on acid-free tissue paper in individual containers and the polyethylene box contains a substantial packet of silica gel in 142 (a) (b) (c) (d) (e)

Conser vation of iron from the soil monitored for one year. The results showed that the alkaline sulphite and sodium hydroxide storage solutions resulted in comparatively stable artefacts. Other solutions mentioned above, or even freezing, were less successful. Interestingly, since ethylenediamine has been used in other contexts, the Gaspe Bay nails corroded and lost weight in ethylenediamine through every 3-month period of the storage evaluation; this is now explained by Selwyn and Argyropolous (2005). The use of inert gas storage will halt further oxidative deterioration of iron objects and has occasionally been used as a preventive conservation measure. One of the first examples of the use of dry nitrogen for storage of an unstable iron artefact is that used in the British Museum (Natural History) for the storage of the 3.5 tonne ‘Cranbourne’ meteorite. This massive meteorite was found in Victoria, Australia in 1854 and began to rust badly when removed to the British climate in 1863. During storage at the British Museum, the meteorite has lost 25 kg of rust. In 1936 the meteorite was placed in a sealed glass case under a continual supply of dried nitrogen. This treatment, according to Howie (1992: 98), has dramatically reduced the rate of atmospheric rusting, although it has not stopped deterioration completely and there appears to be slow, continual rusting of this object even in dry nitrogen. The credit for the first use of nitrogen as a preventive conservation measure for a conserved object on display belongs to Albert France-Lanord, who in 1949 described the conservation treatment of a Merovingian iron helmet from Baldenheim, discovered in 1902, now in the collections of the Musée Archéologique in Strasbourg. This helmet was mounted in a Plexiglas (Perspex) case which was sealed after being completely purged with nitrogen. This treatment was well in advance of its time, even though condensation did occur on the surface of the object as it was kept in the sealed case. Further developments in the use of anoxia treatments had to await a more sophisticated understanding of the design of display, storage and treatment facilities for this purpose. Spriggs (1992) gives an account of an inert atmosphere system for another helmet, this time an Anglian helmet from the excavations in York, England, where a large number of Viking and mediaeval iron finds have been conserved over the past 30 years. Routine application of anoxia treatments in the storage of iron artefacts has been a notable and useful advance, an example being that of Mathias et al. (2004) in their attempts to stabilize the iron objects excavated from the Colony of Avalon, founded by Lord Baltimore in Newfoundland, Canada, in 1621. More than one million artefacts have been excavated from this site, with 20% of finds being made of iron. Continued corrosion and disintegration of the iron artefacts prompted the intervention, which used the RP/ESCAL system of low oxygen storage, developed by Mitsubishi Gas Chemical Company. The RP agent is available in two different forms: the RP-A system for use with metallic artefacts and the RP-K system for non-metals; RP-A results in a microenvironment with a RH of less than 10% and an oxygen concentration of less than 0.1%. Unlike metallic foils, ESCAL is transparent, yet remains an excellent barrier to most gases such as oxygen and water. The outer layer of the ESCAL barrier film is polypropylene. The barrier layer is a vacuum-deposited ceramic film on a PVA substrate. The inner (sealing) layer is polyethylene, which can then be heatsealed to form small enclosures. The microenvironment created using ESCAL and RP-A can last from four to six years. With the purchase of $3,000 of materials, Mathias et al. (2004) were able to treat more than 200 iron objects and still have a reasonable quantity of materials left for further treatment. Guggenheimer and Thickett (2008) proved that no akaganéite forms from synthetic mixed powder samples of Fe and FeCl2∙4H2O for six months when packed with RP-A in ESCAL bags. RP-K (which does not lower the humidity) needs more time (up to three days) until the oxygen in the bag is consumed; the observed slight corrosion possibly took place in this initial phase. The use of an active oxygen scavenger is an advantage over simply packing iron objects (Meier and Tegge 1996) or even wet, fresh finds (Höpfner 1999) under nitrogen, because no plastic is 100% impermeable to gases. The excavated artefacts are covered in fresh soil and then vacuum-sealed in multilayered plastic bags. These are flushed with nitrogen, creating an oxygen-depleted environment. The method has been in use since 1996 and over a period of three years has proved to be an effective passive technique. The Ageless oxygen absorber (Grattan and Gilberg 1994) has also been tested for iron storage (Matsuda et al. 1997). Matsuda et al. tested various combinations of bags and anticorrosive agents including RP agent, Ageless and silica gel. Sealed bags of samples were kept at 25 °C and 60% RH or at 60 °C and 95% RH for one year. Many of these combinations proved effective: the weight of rusted iron plates kept in ESCAL bags with RP agent, Ageless or silica gel over a year remained unchanged. Long-term evaluation of the efficacy of these treatments must await further study. Dehydration and cracking of some artefacts may present a possible danger and disadvantage of this system, but since the majority of untreated iron artefacts are disintegrating in storage in any event, this approach looks to be very promising. Storing iron finds from Baden-Württemberg routinely in deep freeze cells at –20 °C before treatment has already been described by Eichhorn in 1975. Scharff et al. (2000: 82) consider that it stops corrosion temporarily because the water in the pores freezes. Experience with short-term storage shows that the usual flaking found in untreated finds is prevented. To avoid frost wedging, finds to be frozen should not be too wet. Observations of finds stored for long periods in deep-freeze conditions are not convincing, but there has been no systematic long-term evaluation of this energyconsuming strategy. As much as 16 tonnes of iron are currently stored in Baden-Württemberg using this approach. Experience with metallic corrosion in historic buildings in Antarctica (Hughes et al. 2002) indicates that corrosion is astonishingly active even below 0 °C. This therefore casts doubt on the overall effectiveness of long-term deep-freeze storage. All nails stored frozen by Costain (2000) for one year showed clear signs of new corrosion in cross-section. First results of experiments by Kuhn with FTIR (using Thickett’s (2005) method) with mixed Fe/FeCl24H2O powder samples stored at –20 °C showed no akaganéite formation after one year although the samples slightly changed colour in the red-brown direction within weeks (Eggert 2008). Further measurements over the coming years will show if the formation of akaganéite really can be prevented in this way. Green and Bradley (1997) assessed strategies for the longterm storage of archaeological iron in the collections of the British Museum. The assessment was based on the examination of a large number of British and European archaeological iron objects. The results of this particular assessment were somewhat inconclusive.

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14 Conservation of exposed ironwork

Ironwork exposed to the atmosphere represents a considerable conservation problem in terms of protection due to the size and variety of the ancient and historic iron artefacts that require treatment and maintenance. These objects range from large cast iron objects from ancient China to historic bridges of wrought iron, industrial relics, outdoor sculpture and buildings that incorporate iron fittings and fixtures. A considerable amount of exposed ironwork is undergoing active corrosion with tremendous economic impact on costs of replacement and maintenance. Structures such as the Forth Bridge in Scotland are reputed to require continual painting – when the painters have finished at one end of the bridge, it is time to start repainting the bridge at the other. A full account of the treatment of bridges, cranes, ships and industrial heritage is beyond the scope of the present text, which is more concerned with objects of art. A number of initiatives have been underway in recent years to try to address the corrosion protection of artistic and historic artefacts. For example, Seipelt and Brüggerhoff (1997) report on an interdisciplinary working group, AG-KORR, established in Germany in 1993, consisting of corrosion specialists and conservators. The aim of this group is to transfer knowledge from corrosion science to conservation work by adapting industrial protection techniques. An old charging machine from the mining industry is discussed by the authors and different approaches for the conservation of the equipment proposed, dependent on the available options for its intended display in a technical museum. A meeting held in 2006 with the topical question ‘Is sustainable conservation/restoration possible?’ dealt with the preservation of technical and museum heritage (Brüggerhoff 2008). Some of the papers from this meeting were published in the journal, Materials and Corrosion (e.g. Decker et al. 2008; Klotzbach et al. 2008; Schmutzler and Ebinger-Rist 2008).

Inorganic coatings for iron
Rust never sleeps, but some options to prevent its rise which are used in engineering are not viable for the conservator. We

cannot change the alloy or the construction of our objects. And man’s ability to change the outdoor climate is limited; however the reduction in sulphur dioxide air pollution in industrialized countries has proved to be helpful. Despite storage options for smaller objects, it is vital to isolate the iron from the corrosive atmosphere. In other words, coatings are needed for corrosion protection. A large range of coatings and inhibitors is available for the treatment of iron objects although most have rather limited applicability to the conservation of historic and archaeological materials. Technical advances have been made in inorganic coatings, employing metals such as nickel or chromium, metallic oxides, cements and enamels but these drastically change the appearance of the object, and would obscure any traces of use on the surface. Their applicability for the conservation of historical objects is limited to special cases, e.g. when objects are already covered with a non-transparent coating. For example, Bathy (1989) gives an account of a protective method for gate fittings, railings and other outdoor ironwork developed in the Fine Mechanical Institute, Warsaw, Poland. Due to an increase in atmospheric pollution, the author considers that increased protection of these objects is essential. The new method aspires to offer protection for 30 years and includes dismounting, cleaning and coating with tin. After this, the objects are painted and re-mounted in their original location. Generally, it may not be appropriate to tin-coat the iron objects as this alters the nature of the surface rather drastically and may confuse later technical examination. This approach to conservation is heavily interventionist and would probably not be followed for the treatment of gates of special historic interest, but it tells us something about the dissatisfaction with organic coatings. Nishimura et al. (2002) give another example of the use of a metallic coating on the large outdoor steel sculpture, The Wind of May, erected in the severe marine atmosphere of Quingdao in China. The protective coating applied was thermally sprayed aluminium with a thickness of 120 µm. This was then sealed with a zinc-rich epoxy paint, coated with a micaceous iron oxide epoxy and then given a top coat of acrylic-modified polyurethane paint. After five years the only noticeable deterioration was a slight loss in surface gloss. This approach to the preservation of such sculpture may be seen as a drastic attempt to achieve enhanced stability as the surface of the original sculpture is now embedded in several 145

Iron and Steel in Ar t layers of organic polymers and paint, seriously impinging on the artist’s intent in some cases. the coating, mechanical rupture of the coating, or the presence of subcoating surface impurities that may generate soluble products. In the early stages of the deterioration, anodes and cathodes form in proximity to each other and as iron goes into solution, it is rapidly precipitated as a hydroxide due to the concentration of OH– ions at the cathode. These hydroxide products form into a hollow cone, which ultimately becomes a barrier to the free transport of neutral species such as oxygen. In the anodic regions, the ferrous hydroxide undergoes hydrolysis to produce additional solid corrosion products containing Fe3+ together with H3O+ ions. These ions require negative balance; this is supplied either by chloride ions diffusing through the coating or the OH– ions from the cathode. But these latter ions are mostly trapped near their cathode sites by the organic coating, allowing the chloride ions to diffuse inwards, resulting in an increase in chloride ion concentration underneath the coating film. The migration of these chloride ions would result in an excess of positively charged sodium ions in the bulk, except that these ions will readily penetrate the coating at the cathodic sites and act as counter-ions to the OH– ions present. After this process there are distinct regions on the iron surface with very different chemical compositions. The anodes will be quite acidic, while the cathodes will be very alkaline. As the coating system deteriorates, a breakthrough between anodic and alkaline areas may occur with neutralization reactions taking place between hydrogen ions and hydroxyl ions as well as dilution of the chloride ion concentration. Surface roughening and disruption of the coating film are consequences of this type of corrosive failure. Acrylates are generally more stable than cellulose nitrates and do not necessarily need a plasticizer because of their lower glass transition temperature; they have replaced cellulose nitrates in most conservation applications. Paraloid (Acryloid) types widely used in metal conservation (CAMEO 2006; Down et al. 1996) include: B-44 (methyl methacrylate/ethyl acrylate copolymer); B-48 (methyl methacrylate/butyl acrylate copolymer; contains an adhesion promoter and probably the plasticizer dibutyl phthalate); B-67 (isobutyl methacrylate; contains a crosslinking inhibitor); B-72 (70% ethyl methacrylate/30% methyl acrylate copolymer). Paraloid B-67 yellows slightly with age and is a little softer than Paraloid B-72. Paraloid B-44 retains a stable pH, according to Down et al. (1996), whereas Paraloid B72 tends to become more acidic over time. In comparative laboratory trials (100% RH, 40 °C, 28 days), the Paraloids (except B-48) worked reasonably well on clean steel coupons but not on pre-rusted ones (Brüggerhoff 2001). But in this test regime, other products have their problems, too. Microwaxes are used both in and outdoors as intermediate range protection. Paraffins have shorter and less branched or cyclic chains (see Table 14.1) and solidify as a macrocrystalline solid. They tend to lose n-alkanes by sublimation and become brittle. Although somewhat more stable against oxidation (less iso-alkane content), they are nowadays mostly replaced by the microwaxes. Compared with lacquers, wax coatings have the advantage of less gloss; often lacquers are top coated with wax. Because of their low glass transition temperature they are ‘self-healing’ when scratched but are also tackier and tend to incorporate dust. Corroding waxed iron reminds us that these coatings are not a very efficient water

Organic coatings for iron
A great deal of work has been carried out on the subject of organic coatings for iron, which historically has involved the use of wax, resin, oil, epoxy, acrylic, polyurethane, polyamide and practically every other class of polymer. Opaque, multi-coated polymers over primed metal surfaces used in the car industry for the protection of iron and steel components of cars often perform very well over 20–30 years, but this kind of opaque polymer system cannot be used on ancient objects or on rusted surfaces. Over long periods of time, coatings on iron fail due to their (low) permeability to gases (oxygen etc.), moisture or pollutants, and the inherent vulnerability of the object itself to anions, particularly chloride ions, which break down the passivity of the surface layer, promoting coating failure. This difficulty has led to extreme measures being employed by conservators in the past (such as the attempted encapsulation of the iron object in a polyester resin block) in an effort to stabilize the corroded object from further decay. This misguided conservation treatment is doomed to failure, as the inherent instability of heavily corroded objects begins to affect the polyester resin as diffusion of air and moisture takes place and cracks slowly open up, with the result that one is left with a hideous mess to re-conserve after 5–10 years of encapsulation. Coating failure may lead to potentially severe corrosion on an iron surface; the coating may indeed be doing more harm than good. Under-rusting, sometimes in the form of filiform corrosion, is a typical example starting from defects (pores, scratches etc) in the coating. Coatings should be seen more as a temporary measure requiring maintenance than a permanent solution. They are akin to a sacrificial layer with a shorter life than the more permanent material beneath. The situation in conservation terms is often worse than in everyday corrosion protection, which also fights an uphill battle against rust. It may not be appropriate to clean historical objects down to the bare metal and coat with a thick pigmented anticorrosive primer as this would compromise their documentary value. A detailed review of the organic coatings used in metal conservation is given by Koller and Baumer (2000a,b); earlier conservation applications are referenced by Horie (1987). A wealth of current useful information can be found online.1 Plasticized cellulose nitrate (e.g. Frigilene, Agateen or the German Zaponlack) was the preferred choice in conservation in the first half of the 20th century for many applications, including the coating of iron. Its use slowly declined because of their inherent instability at room temperature, their tendency to yellow and increased brittleness created by loss of plasticizer. Failure of cellulose nitrate coatings over iron were studied by Ritter and Rodriguez (1982). Coated iron samples were immersed in 0.05 mol l–1 sodium chloride solution and the extent of failure of the coating studied using in situ techniques. The authors found that any number of causes could initiate corrosion such as a defect in
1 CAMEO 2006; see also BCIN (www.bcin.ca/) and AATA (http://aata.getty.edu/NPS/).

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Table 14.1 Composition of macrocrystalline (‘paraffins’) and microcrystalline waxes (‘microwaxes’) (after Koller und Baumer 2000b: tables 10, 11). Hydrocarbon type Hard paraffin % w/w Ø n-alkane iso-alkane cyclo-alkane dicycloalkane/tricyclo alkane 82-92 9–4 9–4 – Ø number of C-atoms 25 27 29 – Plastic microwax % w/w 10–25 38–45 38–45 – Ø number of C-atoms 35–42 35–50 35–50 – Hard microwax % w/w 25–35 20–28 20–28 20 Ø number of C-atoms 35–45 35–50 35–50 45–55

barrier. Brüggerhoff (2001) found commercial products containing inhibitors to be more protective than pure microwaxes. Polyethylene waxes can be made water-dispersible by copolymerization with (meth)acrylic acid which then is neutralized with a base. This forms an inbuilt surfactant similar to soap. In accelerated ageing tests in a climatic chamber and by electrochemical measurements in chloride and in sulphate containing electrolytes, one such product, Poligen ES 91009, has been found to provide protect iron from corrosion better than Paraloid B-72 (Argyropoulos et al. 2007; Siatou et al. 2007). Commercial corrosion inhibitors do not improve the performance. To confirm these very promising results for improved indoor protection independently, various Poligen types are currently being evaluated (including the effects of sulphur dioxide polluted atmospheres) by Wolfram in a joint project of the State Academy of Art and Design Stuttgart and the Deutsches Bergbau-Museum Bochum. The shorter the hydrocarbon chain the more fluid the waxes become – until we come to the mineral oils. These are irreplaceable as temporary corrosion protection agents in industrial applications. Commercial products contain additives to improve the anticorrosive effect. Products that are formulated to be used on wet metals contain an emulgator to form an emulsion. The weapon oil Ballistol – recommended by Rathgen (1924) – is still in use in Germany and is easily discerned by its aroma of aniseed in armouries following a fresh application. The strongsmelling anethol component hides the less desirable smell of the ammonia, which this formulation also contains. The paraffin oil is emulgated with potassium oleate in this product (Eggert 1994; Koller and Baumer 2000b). Lanolin, the grease derived from the sheep’s fleeces, is, after thousands of years, still employed as a corrosion-inhibiting coating on iron objects (Horie 1987: 153). The soft waxy material, purified from the grease, is a complex mixture of high molecular weight alcohols, fatty acids, sterols, steroids and wax esters. Koller and Baumer (2000b) warn that both the terminology (‘wool fat’, ‘wool wax’) and the composition vary widely. One of the unique properties of lanolin is that it can incorporate up to 25–30% of water.

Comparative studies of modern organic coatings
Hallam et al. (2004) discuss conservation of iron objects in the collections of the National Museum of Australia, prior to its opening in March 2001. An evaluation of coatings for iron was initiated with comparison to some widely used wax coatings such as BeSq195 and TWA2095. This research continued from

the discovery that some commercial coatings applied to bronzes imparted greater protection than conventional microcrystalline waxes, in which delamination from the surface of the object tended to occur. During the study, the tested materials were ranked by their mode of failure, relative resistance to a corrosive environment and their physical film characteristics. The coated coupons were tested according to ASTM 117 and artificially aged in an environmental chamber at 50% RH, 30 °C, using a 0.1 mol l–1 sodium chloride spray. Among the coatings tested, CRC SoftSeal, Tectyl, Dinol AV30 and Dinol AV8 possessed a dark yellow to brown colour therefore would be unsuitable for many types of external application. Heated or hot-dip waxes could be used only for small objects and their use is restricted by the thermal stability of any paint or other original coating on the object. Coldwaxing was found to be ineffective, resulting in a porous layer of semi-fused wax that does not impart much protection. CRC SoftSeal, CRC Long Life, Tectly and Dinol AV30 produced tacky films unsuitable for most exposed surfaces. PX115, ACF50 and WD40, although useful for parts storage, were not recommended for exterior use. Dinol AV4010, a petroleum-based product used in the aviation industry for applying to the exterior surface of aircraft, is described as a colourless corrosion inhibitor that leaves a tack-free film. These films can be easily removed with white spirit even after heat exposure. Dinol AV4010 thinned down with a 10% addition of white spirit was used to good effect in the conservation treatment of the Francis Birtles Bean Car, an unrestored historic vehicle from the 1920s. PX115 and Penrite Shelsley Medium were used to treat internal mechanical components. Shelsley Medium is formulated to provide corrosion protection and lubrication to infrequently operated engines. PX115 is a high-wax content thixotropic military storage oil for the long-term storage of non-operational engines. The results of this work were useful in showing that there are many possible alternatives to traditional microcrystalline waxes, and that, in some situations where microcrystalline waxes may fail due to pitting corrosion, there are a number of other possibilities. Another useful series of studies of coatings for use on historicalperiod iron and steel exposed structures and artefacts was carried out by Brüggerhoff (2001) and Mottner et al. (2004). Outdoor industrial monuments need to be preserved in their present physical condition, to respect their original appearance or the appearance they have acquired during their exposure outdoors, as far as practicable. Previous investigations by the authors had resulted in the testing of a single-component polyurethane resin (EK-PUR from Conrads, Germany), a ketonic resin (Laropal K80, BASF, Germany), a polyester resin (Kydal 50L, Tedden, Germany), an oil (Owatrol, Voss Chemie, Germany) and the inorganic-organic hybrid system, Ormocer (Fraunhofer Institute for Silicate Research, Germany). The test regime utilized mild steel coupons treated by: (1) dipping in 5% sodium chloride solution; 147

Iron and Steel in Ar t (2) exposure to 100% RH for eight hours at 40 °C; (3) drying for 16 hours at room temperature; (4) five repetitions of steps 2 and 3; (5) exposure to outdoor weathering for three weeks; (6) desalination by immersion in water; (7) air-abrasive cleaning with walnut shells at 8 bar pressure, distance 50 cm and then coating and drying. This regime differs substantially from the testing protocol employed by Hallam et al. (2004) in the evaluation of their coatings. Mottner et al. (2004) examined the performance of different Ormocer formulations with the addition of glass flakes as a transparent filler. The systems OR1-GF (4), OR1-GF (4;7:1) and OR1-GF (5; 7:1) proved to be the most successful. The nomenclature here uses the terms 4 or 5 to refer to the number of layers applied, GF = glass flakes and 7:1 is the ratio between the resin and glass flakes as a w/w ratio. In climate testing of these coatings a modified version of the DIN 50018 standard was used. The results of the study showed that very poor protection was afforded by the tested polyurethane and ketonic resins. Performance of the Ormocer resins was dependent on coating thickness. Comparison of the behaviour of Ormocer with different wax formulations such as Tecerowax, Cosmoloid and Vestowax showed that Ormocer provided reasonable protection, although Tecerowax in particular was also adequate. The authors stress the importance of outdoor exposure trials in addition to laboratory experiments, and intend to evaluate these materials again after 3–5 years. Definitive answers are only possible by long-term observation of real applications in model projects (Brüggerhoff 2001: 38). An interesting use of amine-quinone resins for corrosion protection was reported by Nikles and Warren (1998) and Vaideeswaran et al. (1999) who found that the novel polymer, which they had made, bonded ferociously to rust. The authors found that amine-quinone polymers with a 2,5-diamino-1,4-benzoquinone functional group, adhered strongly to iron and inhibited further corrosion. However, the polymers were only investigated as corrosion protection films for iron particles used in magnetic tape, and further field trials would be needed to determine whether the polymer coatings would be of use on exposed iron structures or archaeological material. Since these polymers – in common with many others used on iron – cannot be easily removed once they are applied, their utility may be limited to more recent historic artifacts. Another recent development in coatings technology is that of conducting polymeric coatings based on polyacetylene or polyaniline. Reaction of polyacetylene with iodine results in a polymeric compound with high conductivity. Wessling (2001) reported that steel coated with polyaniline showed excellent corrosion resistance. Remarkably, the position of polyaniline in the galvanic series is slightly below that of silver, but above both iron and copper, making the behaviour of polyaniline that of a true organic metal. The polymer was able to oxidize iron or copper and attain a relatively stable, reduced so-called leuco-emeraldine (LE) form, which can be re-oxidized by oxygen back to the organic metal (PAni). In corrosion studies, the polyaniline coating was found to alter the corrosion process as it replaces iron as the cathode. The surface potential of the iron is shifted from about –400 mV to between +250 mV to +400 mV; in this oxidizing environment, ferrous ions are exclusively formed: Fe →Fe2+ + 2e– (14.1) PAni + n2e– → (LE) (14.2) Oxygen then oxidizes ferrous to ferric ions and the (LE) back to the normal oxidation state, generating hydroxide ions in the process. A stoichiometric amount of the Fe3+ and OH– ions is now available to form haematite: 2Fe3+ + 6OH– → Fe2O3 + 3H2O (14.3)

This haematite develops on the iron surface at the interface between the iron and the polyaniline coating. It has strong adherence and provides a barrier to further rust formation. The reaction mechanism requires a two-layer paint system, which may again limit its use on historic structures, but corrosion trials reveal exceptional protective properties. Electrochemical impedance spectroscopy (EIS) provides information about the barrier properties of a coating. Most coatings measured by this technique reveal an increase in the dielectric constant, a number that is independent of coating thickness. A vacuum has a dielectric constant of 1, with water ranked at 75. The polyaniline coatings do not exceed a dielectric constant of 12 when first applied and hardly alter over time, while conventional coatings all show a continual rise in the dielectric constant on weathering. These coatings are already in use in marine environments, chemical plants and in public construction in towns, parks and sport arenas, and may prove useful for exposed iron statuary. New varieties of these polyaniline-based coatings are currently under development. For example, De Souza et al. (2001a,b) describe the use of an acrylic polymer formed by sulphonatedoped polyaniline and polymethylmethacrylate, which have been employed to protect iron surfaces exposed to chloride ions. The research carried out suggests that the polymer coating has a double-acting protection mechanism: forming a passivating complex with the anion of camphorsulphonate and as a physical barrier to avoid chloride anion penetration. Bernard et al. (2001b) examined the protection of iron surfaces coated with a polyaniline polymer potentiostatically polymerized in solution. The passive layer is strengthened by phosphate incorporation and sulphonated aniline is inserted in the chain to give a copolymer. The polymer is able to protect iron from corrosion over several weeks of accelerated corrosion testing. In related research, Bernard et al. (2001a) examined the films formed by electrochemical copolymerization of aniline and metanilic acid (3-aminobenzenesulphonic acid) in phosphoric acid solutions and found that these gave better corrosion protection than pure polyaniline. The coatings were tested under standard salt-spray conditions and found to perform well compared with controls. Although experience tells us to be wary of new developments, there is real cause for optimism in the conservation world that the future may bring improved products!

Restoration of the Statue of Liberty
The problems encountered during attempts to restore the Statue of Liberty in New York provide an interesting example of the difficulties of dealing with large outdoor works of art. The statue was conceived and initially sculpted at a reduced scale by Auguste Bartholdi and the full-scale version, created between 1874 and 1884 by Monduit & Cie, was paid for by the French people who had supported America against the British during the American

while the organic metal (PAni) is reduced to its leuco form (LE):

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Conser vation of e xposed ironwork Revolution. Copper sheets, 2.37 mm (3/32 in.) thick, were hammered into moulds to form the shape. Three hundred copper panels were needed, which were then riveted together and held in place on a wrought iron armature. This iron armature was then attached to an iron flame made of commercial angle-iron that was attached to a central ‘A’ frame of wrought iron made of four vertical girders. The iron support system was probably designed by Alexandre Gustave Eiffel (1832–1923). To support the statue, the American public paid for a concrete plinth covered in polished granite blocks. The weight of the hammered copper sheet was 81,300 kg, while 113,400 kg of wrought iron was employed. The 46.84 m (152 ft 2 in.) high statue on its five-storey plinth was inaugurated on 28 October 1886, on the island originally called Minnissais by the Mohegan Indians, the autochthonous inhabitants, and which changed names several times before being called Liberty Island in 1956 by which time there were no Mohegan Indians left. The skilled French engineers were well aware of the problems of galvanic corrosion and the wrought iron armature was attached to the copper sheets by a series of copper strips placed over the iron armature and riveted to the copper sheets. A layer of asbestos soaked in shellac was inserted between the iron bars and the copper strips and sheets, separating the two metals in order to avoid galvanic corrosion. The copper surface on the inside of the statue was originally left uncoated, but in 1911 was covered in a coal-tar emulsion sealing compound, later to be covered with a total of 11 layers of paint: aluminium flake paint in 1932, leadbased enamel in 1947, alkalyd paint and vinyl paints applied during the 1970s. A conservation assessment carried out in 1982 identified a number of problems: in many areas the asbestos had degraded and absorbed saltwater spray, creating galvanic corrosion, with the result that some of the iron armatures were badly corroded. The iron corrosion products were distorting the copper skin and the retaining strips. In some areas there was severe corrosion of the copper sheets where water had accumulated. As a result of this assessment an extensive and expensive restoration programme was undertaken. When the monument was restored in 1988–94, a stainless steel armature, steel type 316L (UNS S3160) was employed to replace the wrought iron and a layer of Teflon was placed between the copper and steel. The use of this stainless steel as a replacement for the wrought iron should ensure that the statue continues to stand with no further instability, apart from the weathering of the copper panels, which are predicted to last for about 1000 years before they need to be replaced (see Baboian et al. (1986) for a variety of papers on this topic). of protective coatings, which have failed to prevent further corrosion. Since the ship is 322 feet in length, it is difficult to imagine that an aqueous treatment regime could be feasible. The use of sacrificial anodes would also be impractical since some parts of the vessel are already very heavily corroded and impressed electrical current or anodic protection would be unevenly distributed throughout. Watkinson and Lewis (2004) therefore came to the conclusion that the RH surrounding the ship should be reduced to about 20% using forced air driers. The crucial aspect of this argument is that iron does not corrode in the presence of FeCl2∙2H2O if the RH is kept low enough. As was mentioned in Chapter 4 , Watkinson and Lewis (2004, 2005) found that at 19% RH, a mix of iron powder and FeCl2∙2H2O did not gain weight after 13.9 days. In contrast, FeCl2∙4H2O and iron power gained weight at 22% RH, while in order to prevent corrosion in the presence of β-FeOOH, an RH of 12% would be required. Desiccating the 322-ft long hull of this ship to 12% RH would be impractical and involve very high maintenance costs. Since the rate of corrosion of iron in the presence of FeCl2∙4H2O and βFeOOH is much slower at 20% RH than 25% or 30%, the proposal made by Watkinson and Lewis (2004) is that the stability of the iron hull could be significantly enhanced and its lifespan prolonged by storage environments that control the RH to 20%. A giant dehumidification chamber for the chloride-infested lower hull was built by constructing a glass roof between the dry dock edge and the waterline of the hull. The exterior of the relatively uncorroded upper hull was stripped to the metal surface and treated using a rigorous coating regime (Watkinson and Tanner 2008). As we have illustrated, the general shift in conservation away from interventive treatments, which often fail to provide adequate protection, to preventive storage solutions does not negate the possibility of providing preventive strategies for the treatment of very large objects.

Historic iron railings, fences and building components
A common group of iron objects that causes problems is iron railings, which are usually made from wrought iron but can also be made from cast iron. When these railings begin to deteriorate, unsightly iron corrosion products flow over and stain stone or brick walls into which they are inset, and continued rusting leads to splitting and disruption of the mounted parts as the iron expands, eventually resulting in spalling of part of the facade. Iron railings are often painted, with several layers of paint providing some protection, although penetration of this painted layer can result in severe anodic dissolution under the paint, producing a hollowed effect to some heavily corroded examples. A study of iron fittings was carried out by Ashurst (1988), who undertook the conservation of wrought iron railings dating from 1733 attached to an historic townhouse, Vault Hall, in Nottingham, England. This study formed part of a conservation and research project at the Ornamental Smiths’ Workshop of English Heritage where ironwork that had once been deemed irreparable was conserved and restored. The conservation involved dismantling, sorting, labelling and documenting each of the component parts and their condition. The iron was then heated with a blowtorch in a process called ‘flame cleaning’, which was judged to be the 149

Preservation of the SS Great Britain
A good example of the conservation problems associated with large exposed iron objects is the study carried out by Watkinson and Lewis (2004) in dealing with the preservation of the 1843 wrought iron steamship, the SS Great Britain, which was salvaged off the Falkland Islands in 1970 and placed in a dry dock at the Great Western Dockyard in Bristol, England. The RH around this wrought iron ship rarely drops below 70% with the consequent problems of stabilization. Early attempts to conserve this structure involved 10.00 psi aqueous pressure blasting and the application

Iron and Steel in Ar t best way to obtain a cleaned surface, free of old paint layers and grime. The primary aim of the intervention was to conserve as much of the original ironwork as possible, even when corroded, unless it could no longer fulfil its function. It was found important to maintain an even coat of paint on the iron (two coats of zinc phosphate epoxy primer plus one alkyd undercoat and two alkyd topcoats). Seeley2 states that his personal preference for architectural ironwork has been the use of a lead-based paint, although this is prohibited in the USA, but in Austria the traditional minium with linseed oil may still be applied for conservation purposes and is often the preferred choice (Krebs 2008). In the UK, the National Trust has used this method to restore (at considerable expense) various elaborate wrought iron gates such as the magnificent Davie Gates at Chirk Castle, Wrexham in Wales. Weaver (1988) used fertan, a chemical compound based on tannin derivatives, phosphoric acid and wetting agents, which reacts with the corrosion products of iron and steel and converts unstable iron oxides or rust to a more stable ferric tannate. The potential problems with tannic acid derivatives are cited in Chapter 8. Texier (1997) carried out a scientific study in Paris during the recent restoration of the Alexandre III bridge, which was constructed in 1900. The focus of this study was the cast iron and the reattachment and restoration of the various fittings with which the bridge was decorated. Different types of structural epoxy adhesives were tested for their mechanical properties, tensile strength and applicability, and epoxy resins were used for the reattachment of the ornamental fixtures. It is not clear, however, whether ageing experiments were performed on these materials to assess their performance with cast iron and brass over the long term. The use of sacrificial anodes or impressed current to protect iron beams, rods and supports within historic buildings has only recently been put to use, despite the principles being well known for the last 100 years or so; reinforced concrete bridges and steel pipelines have been protected by cathode current for decades (Blackney 1997; Blackney and Martin 1998a,b). A cathodic protection system was also used by Farrell et al. (2001: 42), who report that sacrificial anode systems are suitable for small metal components embedded in masonry, where the pore water within the building acts as an electrolyte. The impressed current system is more suitable for larger supports such as I-beams and columns in buildings where the masonry has higher electrical resistance. Turnpenny and Tappin (2003) discuss the application of cathodic protection to steel-framed masonry-clad buildings, particularly because of the prominence of ‘Regent Street Disease’ in England, first recognized in the late 1970s. The ‘Regent Street Disease’ problems arose from a form of construction employed in the early 20th century, where the external masonry was tightly placed around a steel frame with cavities infilled with mortar, brick or rubble. Corrosion due to moisture penetration rusts the steel, expanding the members and cracking the masonry, creating yet further moisture penetration and still more rusting. Steel-framed construction began in Chicago during the 1890s according to Turnpenny and Tappin (2003), although Seeley3 notes that Sir William Siemens (1823–1883) possessed a billiards room in his house in England whose roof was entirely supported by steel beams, i.e. long before 1890. Major steel-framed buildings erected in the UK in the 1900s included the Ritz Hotel (1904–05)
2 3 N.J. Seeley, pers. comm to D.A.Scott, 15 January 2003. N.J. Seeley, pers. comm to D.A.Scott, 27 May 2002.

and Selfridges (1908–09), both in London, while sheds built at Cressnonk Tidal Dock, Glasgow, completed in 1895, have the honour of being the first examples of this construction in the UK. The Second World War and the consequent shortage of steel in the UK led to the demise of this type of steel-framed masonry construction. The first installation of a cathodic protection system in a historic structure was in 1991, for the entrance colonnade to the government buildings in Dublin, a limestone structure supported by two steel I-section beams. More recently this technique was applied to iron staircase supports embedded in brickwork at Kenwood House, Hampstead Heath, England. Most cathodic protection systems use impressed current cathodic protection (ICCP). The ICCP system comprises a set of anodes, a DC power supply, cabling and a monitoring system. The positive terminal of the power source is connected to the anodes, and the negative terminal to the steel reinforcement (cathode) and a small current passed. The passage of this DC current forces the steel to become cathodic relative to the external anode, which must be designed to resist corrosive attack. Three current varieties are: mixed metal oxide-coated expanded titanium mesh ribbon and discrete rod anodes of platinized titanium in a graphite paste backfill or conductive ceramic cylinder or mixed metal oxide-coated titanium mesh tubes. Because of variation in current, reference electrodes also need to be installed as close to the steel as possible in order to evaluate the performance of the system. One critical factor affecting ICCP is that the entire steel structure should be continuously conductive. Failure to ensure that all steel components are electrically connected could result in non-ICCP members becoming increasingly anodic or corroding while the rest of the structure is under cathodic protection, so there are dangers associated with the application of ICCP to historic structures. Turnpenny and Tappin (2003) successfully employed ICCP on a c.1915 four-storey office building in a conservation area of the city of Birmingham, England. Cathodic protection of iron objects can also be used during cleaning in acid solutions (de Groot et al. 2004). Experiments were conducted with mild steel sheets, placed outdoors for 33 days to form a corrosion layer. For the cathodic protection, a stainless steel mesh was used as an anode, with a DC power supply. Citric acid, sulphuric acid and orthophosphoric acid solutions were used to strip back the corrosion crust using a cathodic potential of –650 mV Ag/AgCl (–450 mVSHE), which was sufficient to provide cathodic protection for the steel surfaces during acid stripping. Cathodic reduction produces hydrogen due to the following reaction in acid media: 2H+ + 2e– → H2 (14.4)

Since hydrogen produced at the cathode may result in hydrogen embrittlement, fragile objects or those subjected to stress should probably not be treated with this form of protection during acid cleaning. Such methods can be applied only to historic iron objects where corrosion stripping is possible without loss of important evidence. In the case of the historic structures, routine and careful maintenance, as Eiffel cautions, is needed, while ancient objects often have to learn to take care of themselves. For wrought iron and steel structures such as the 300 m-high Eiffel Tower, the amount of effort required to preserve the structure from the effects of rusting are considerable; this is achieved by multiple coats of paint. The Tower has been repainted 17 times since its construction in 1889,

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Conser vation of e xposed ironwork an average of once every seven years. According to the aesthetic taste of the time, it has changed colour on several occasions, from the original red-brown colour to a yellow ochre, then a chestnut brown and finally to the bronze-coloured paint in use in 2002. This colour is shaded off towards the top of the Tower to create the illusion that the same colour is used throughout as the Tower is contrasted with the sky. Sixty tonnes of paint are used and 25 painters are employed for more than a year. Failing old paint layers are removed conventionally by sand blasting, torches or steel brushes. Blasting with ‘dry ice’ pellets (i.e. solid carbon dioxide at –79 °C) is a new alternative modern industrial technique for cleaning and paint stripping. The pellets are quite soft (Mohs hardness 2–3) and sublime without leaving any residue on the object. Coatings are cooled abruptly and crack. The large volume increase during sublimation of carbon dioxide particles entering cracks aids in the cleaning effect. Compared to blasting with corundum or conventional cleaning with a steel brush, this method reduces attack of the original oxide scales from casting (Blumer et al. 2007). Blumer et al. tested the application on cast iron, a Renaissance stove plate and a small 19th-century bridge. Lemos et al. (2007) employed his technique to remove previous conservation coatings from a rusting 15th-century Portuguese cannon. The Eiffel Tower is under almost continuous restoration (rather like the perennial painting of the Forth Bridge). This has resulted in the removal of over 1,340 tonnes of extraneous materials, which had been added to it over the last 120 years. This material included superfluous railings, barriers, pipes and girders that did not form part of the original conception. An appraisal of the restoration issues involved in the continued work on the tower and the reasons for the continual change in colour would be of interest, but have not yet been addressed as far as we are aware. It is amusing to recall that the original plans for the Eiffel Tower called for its demolition only 20 years after its completion, which would have been 1905 – a demolition that fortunately was never carried out. The same longevity sadly has not been bestowed on the West Pier at Brighton, Sussex, England. The loss of this famous pier due to its destruction by storms and fires during 2003 and 2004, is the first example of the demise of a Grade I listed building in England since 1973. Constructed by Eugenius Birch of cast iron and timber from 1863 to 1866, the pier was the apogee of pleasure-pier development. During the Second World War, the pier was partially demolished to prevent its possible use by invading German forces. Little or no maintenance was carried out after that time. The loss of this structure highlights the importance of maintenance to prevent the further degradation of historic buildings (Morrice 2005). The building-at-risk strategy, formulated in the late 1990s by English Heritage to deal with cases of this kind, came too late to apply to the Brighton pier, for which the lack of any local or national consensus on conservation intervention has proved to be disastrous. Attention is beginning to be focused on many aspects of our rusting architectural heritage that formerly were ignored. For example, Thomson and Banfill (2005) discuss the preservation issues associated with corrugated iron-clad buildings, their history and construction, and conservation requirements due to their cultural significance, particularly in some remote areas of the UK. From a survey of 72 such structures in the Scottish Highlands and Islands, it is apparent that there is a risk that the remaining stock of these buildings will disappear entirely from the Scottish landscape. Nearly half were in poor condition, empty and deteriorating or in ruins, and only five of these are currently protected as listed buildings.

Conservation of painted iron surfaces
Historically, iron objects have often been coated, not only for protection, but also to improve their appearance or to imitate other materials. When historic paint layers begin to fail, allowing iron corrosion products to disrupt the paint, a difficult conservation problem arises. An example of historic 19th-century iron railings in Waterlow Park, Highgate, London, is illustrated in Plate 66, revealing the typical problems of surface preservation created by blistering and exfoliation of the paint layers and underlying rust. Recently maintained railings from Hyde Park in London are shown in Plate 67. Ankersmit et al. (2004) studied the problem in relation to the cleaning of a work of art, Espaces Virtuels: Jaune et Blanc (1965) by the Venezuelan artist, Jesús Rafael Soto. They decided, after consultation with the artist, to leave the historic paint intact. The deteriorated iron plates were treated with different chelating agents: ethylenediamine tetraacetic acid (EDTA); diethylenetriamine pentaacetic acid (DTPA); diammonium citrate (DAC); triammonium citrate (TAC); and phytic acid (PA). These experiments showed that extraction of the iron ions using these reagents produced considerable paint disruption, but blocking an excess of iron ions inside the polymer by phytate did not disrupt the paint layer, and the transformation of the brown rust spots into a white iron-phytate complex helped to mask the effects of the corrosion products in the white and yellow paint matrix of the artwork. This approach certainly deserves further study. In general terms, the usual approach in the past has been the complete removal of the overlying paint layers, wire brushing of the rusted surfaces, the provision of a primer (which in former times used to be a lead-based paint) and finally re-coating with two or three layers of polyurethane-, alkyd- or epoxy-based paint. To avoid removal, the options to conserve the original paint on baroque period iron bars in cathedrals were investigated in an extensive research project (Königsfeld and Brüggerhoff 2002), funded by Deutsche Bundesstiftung Umwelt (DBU). As laboratory tests showed, it was impossible to achieve good penetration into the coated rust layers, sufficient consolidation and effective isolation from the corrosive environment with reversible acrylates. The choice was therefore the otherwise superior, but irreversible, polyurethane (BOB® from Vosschemie).

Corrosion inhibitors
An inhibitor is a substance that retards the rate of corrosion of a metal. It acts to retard the electrochemical interaction of the metal with the environment by suppressing the anodic reaction, the cathodic reaction, or both. The problems with the use of inhibitors in conservation is that they are frequently hazardous materials such as chromates, benzoates, nitrites, aromatic organic materials, and other substances that should not come into contact with the skin or inhaled. There is also the problem of trying to inhibit the corrosion of heavily deteriorated iron objects where the inhibitor is unable to penetrate to the metal/oxide interface and carry out any beneficial inhibition. However, inhibitors do have some applicability to marine artefacts and historic iron objects.

151

Iron and Steel in Ar t An early use of chromates has recently been discovered in the Swiss National Museum (Studer 2006). During recent air-abrasive cleaning of some swords excavated in Giubiasco and restored some 100 years ago, a liquid was found seeping out of cracks. It gave a Fourier transform infrared (FTIR) spectrum similar to a concoction of an aqueous dichromate solution with lanolin and mineral fat, which was patented by the engineer B. Zschokke in the 1910s; at the time he was providing advice on iron conservation as reported in the museum’s annual report. and NaOOC(CH2)nCOONa. These inhibitors may be useful as they are relatively inexpensive, environmentally benign, nontoxic and readily biodegradable. They have the potential to treat several metallic composite artefacts, although they are probably only suitable for historic or lightly rusted types of iron object. In the experimental work reported by Otieno-Alego et al. (2003) and Thurrowgood et al. (2004), corroded coupons were immersed in citric acid stripping solutions. Addition of the corrosion inhibitors in the wash solution following stripping over three-day immersion periods was found to give comparable corrosion protection to the steel surface as prior trials using chromate solutions. The protectiveness of the initial hydrophobic layer formed using the disodium salt of secacic acid on iron surfaces was confirmed using cleaned and polished mild steel coupons treated in 1 g l–1 ethanol solutions of the inhibitors for one hour followed by air drying and exposure to 100% RH for 24 hours; whereas the blank coupon showed severe corrosion, the secacic acid-treated surfaced remained free of any attack. Sodium decanoate or long-chain saturated free acids extracted from vegetable oil also showed promising results as invisible and environment friendly inhibitors against atmospheric corrosion of iron surfaces in recent laboratory experiments (Hollner et al. 2007). The same is true for extracts of cactus seeds (Hammouch et al. 2007), also tested within the framework of the PROMET project.4 Otieno-Alego et al. (2004) also investigated how thiourea, used as a corrosion inhibitor added to citric acid stripping baths for historic iron objects, could be replaced with something less toxic. Although used extensively in silver-cleaning recipes, it has been known for some time that thiourea is hazardous to human health, especially on repeated exposure, and is damaging to aquatic life. Thiourea also acts as a corrosion inhibitor only in rather high concentrations and may actually stimulate corrosion at concentrations not within a prescribed range. Experimental studies found that a suitable replacement was a non-toxic thioamino acid derivative, L-methionine methyl ester hydrochloride, employed as a 0.01 mol l–1 additive in a 5% citric acid solution for the cleaning of ferrous artefacts. Polarization studies showed that L-methionine methyl ester hydrochloride functioned as a dual anodic and cathodic corrosion inhibitor. The citric acid solution inhibited with L-methionine methyl ester hydrochloride successfully removed goethite and haematite layers on heavily mineralized mild steel coupons. Repetitive cycles of stripping and washing showed that cleaning of the surface could be achieved within three hours. Another environmentally friendly approach for stripping could be the use of siderophores (Kunz et al. 1996). These are compounds such as hydroxamates, for example, desferrioxamine B, which are excreted by organisms to complex iron for use as a nutrient. Siderophores are under investigation for industrial de-rusting applications and are said to not attack the metal itself and therefore incorporate some inhibiting properties themselves (Kunz et al. 1996).

Anodic inhibitors
The anodic inhibitors help to passivate the anodic iron surface. Some of these are oxidizing agents which, in near neutral solutions, can function with or without oxygen and include sodium nitrite and sodium chromate (Walker 1982). The possible interactions are as follows: 2Fe + NaNO2 + 2H2O → Fe2O3 + NaOH + NH3 (14.5) 2Fe + 2Na2CrO4 + 2H2O → Fe2O3 + Cr2O3 + 4NaOH (14.6) The difference between these is that the nitrite only produces an insoluble oxide film, while the chromate produces a film consisting of both ferric oxide and chromium oxide. Both inhibitors are effective at concentrations as low as 0.1 g l–1. Other inhibitors can only function when dissolved oxygen is present (Walker 1982) including phosphates, borates and benzoates. The care needed to optimize the conditions under which inhibitors are used is well illustrated by the research on aminecarboxylic acid inhibitors on iron carried out by Bommersbach et al. (2005). They found that the mixed inhibitor forms a threedimensional film on mild steel surfaces first of all by using some of the corrosion products formed. It acts principally as an anodic inhibitor and is efficient from 0.3% w/w after two hours of immersion. The influence of temperature was assessed and for temperatures below 50 °C the film-forming ability of the inhibitor was conserved. The good effectiveness of the film obtained at 80 °C for 5% w/w of inhibitor proved the existence of a critical ratio between the quantity of iron oxides-hydroxides and inhibitor molecules for the formation of a satisfactory film. The authors regard these developments as evidence that it might be possible to use more environmentally friendly compounds for iron corrosion inhibition than the chromates or nitrites formerly employed. The use of citric acid to strip rust from iron has a long tradition. Plitnikas (1999) successfully employed a citric acid gel with spot electrolysis to clean inlaid iron swords from the collection of Brigadier-General Herbert Colborne Nanton of the Royal Engineers. The swords (both decorated with koftgari inlay) were presented to him by the Maharajah of Cooch Behar, a frontier state in north-eastern Bengal. Otieno-Alego et al. (2003) report on the use of the disodium salt of secacic acid (1,8-octane-dicarboxylic acid) as a corrosion inhibitor for iron in citric acid wash solutions. The development of these dicarboxylate salts as corrosion inhibitors has also been spurred by the hazardous nature of the chromate and nitrite alternatives that have been used in the past. One group of corrosion inhibitors that shows good inhibitory properties for mild steel, copper, magnesium and aluminium alloys in aerated nearneutral solutions are the compounds based on the linear saturated sodium mono- and α,ψ-dicarboxylates such as CnH2n+1COONa 152

4

PROMET is a European 6th Framework funded project from 2004 to 2008 with 21 partners from 11 countries of the Mediterranean basin which, among other research goals, tested new materials, corrosion inhibitors, coatings and vapour-deposited barrier films as alternative methods of protecting metallic collections.

Conser vation of e xposed ironwork

Cathodic and mixed inhibitors
Some cations can act in neutral solution and diffuse to the surface of the cathode and react with the hydroxyl ions produced to form insoluble precipitates, which act as a barrier and slow down the process. The ions that are important here include calcium, magnesium, zinc, nickel and manganese. Some typical reactions include: Zn2+ + 2(OH)– → Zn(OH)2↓ Ca + CO2 + 2OH– → CaCO3 ↓ + H2O
2+

(14.7) (14.8)

Some metal ions such as arsenic or antimony may form a surface film on the cathode and reduce the rate or amount of hydrogen evolution. Large colloidal cations, such as polyphosphates, (Na5CaP6O18)nn+, can form thick barrier films that impede the cathodic reaction, and some substances such as zinc chromate can ionize in solution and influence both the anodic and cathodic reactions, as can some polyphosphates and silicates (Walker 1982).

buildings. Porter et al. (1998) examined the behaviour of cast iron components of a building following a fire and came to the conclusion that the behaviour of structural cast iron in buildings in fires has been little understood and subject to ill-informed prejudices over the years. Consequently passive fire protection methods employed when rehabilitating historic structures have been onerous and often detrimental to the special architectural interest and appearance of listed buildings. A survey conducted in the archives and among fire officers showed that cast iron behaves well in fires and is much less prone to collapse in the early stages of a fire than unprotected steelwork. This allows a more sophisticated engineering approach to be taken towards risk assessment, which can strike a benign balance in building conservation terms.

Iron staining and associated deterioration
A great deal of damage can be caused by the rusting of iron components of objects or buildings; this is a common problem, particularly with ceramic, brick and stone objects. For example, Jensen (1989) draws attention to the potential damage caused to furniture by old iron nails that corrode thereby rupturing and splitting of the wood. In this case, the author provides a series of illustrations to show how the old nails can be removed with a minimum amount of damage to the furniture concerned. Rusted core pins, hinge components or fittings embedded in stone must sometimes be drilled out to eliminate the rusting component and save the object as a whole. In cases where this is not possible or desirable, the removal of iron stains may be the major concern due to the ubiquity of iron and its often ill-advised use for repair or strengthening of large objects. Removal of these stains without further damage to the principal material can be difficult. Traditional recipes have included: the use of lemon juice, whose active agent is essentially citric acid; a 10% w/v aqueous solution of oxalic acid; a 5% w/v solution of the disodium salt of EDTA; and a 3% v/v solution of hydrogen peroxide for ferric stains, either as a poultice or as a solution in which small objects can be immersed. Some commercial preparations that have also proved to be useful include Renaissance De-Corroder, which is a nontoxic cleaning solution based on an ‘amine complex of hydrooxycarboxylic acid’. There are also biological rust removers that can be efficacious such as Biox, which is available as either a gel or liquid, and which is considered safe for general purpose use although fragile objects should never be immersed or treated with solutions of this kind without careful prior evaluation. Rockliff and Tait (1989) describe the conservation of a Second World War summer uniform jacket, which had been recently acquired by the Provincial Museum of Alberta, Canada. It had apparently been folded away, in damp conditions, with a metal coat hanger inside, and was extensively stained with iron as well as watermarks. All buttons and insignia capable of easy removal were taken off the cotton twill jacket. For removal of the iron stains, sodium hydrosulphite or oxalic acid were considered. The former was proving unsuccessful, but the latter did have some efficacy. A 1% solution of oxalic acid has a pH of 0–1, so minimal contact and complete removal was necessary. Treatment, using 3% and 5% solutions at 80 °C, was carried out over a vacuum suction area on the previously washed, wet garment. After application the areas were well rinsed (neutral pH) then the whole garment was 153

Vapour phase inhibitors
Traditional vapour phase inhibitors include dicyclohexylamine nitrite and cyclohexylamine carbonate, usually applied to the wrappings placed around modern iron objects or inhibited directly by immersion in a 5% w/v solution. The utility of these vapour phase inhibitors is limited by health and safety concerns and by volatilization of them in the museum environment. Leng and Stratmann (1993) investigated the inhibition of the atmospheric corrosion of iron with ammonium benzoate. This was shown to be effective, as an insoluble layer of iron benzoates forms over the clean iron surface, inhibiting corrosion. In museum use however, the health and safety issues of using these kinds of materials are important and were not addressed in this article. This concern is the principal problem with using vapour phase inhibitors: how to protect museum staff and visitors from the diffusion or leaking of these inhibitors into the atmosphere, since many are potential carcinogens. A conference was held on the subject of corrosion inhibitors in conservation in 1985 (see Keene 1985 which can be consulted for further information), but continual advances in the field mean that some of the information from this conference has been superseded, and relevant advances have been reviewed here. The use of vapour phase inhibitors, while a good idea in principle, is generally considered too much of a health risk to use in the conservation of metallic antiquities, as exposure of conservation personnel to any chemical reagents in the vapour phase needs to be heavily restricted.

The behaviour of cast iron during a fire
Cast iron has a poor reputation among modern architects (who, perhaps, have no experience of its properties, design and use) and yet was used extensively in the 19th century for many fine

Iron and Steel in Ar t washed at a neutral pH. Some stains remained, although they were considerably lightened. There was no colour loss or any apparent weakening of the fibres. The removal of iron staining from marble and calcite is often necessary due to the rusting of armatures and other fittings. Thorn (2005) notes that many unbuffered acidic compounds will also dissolve calcite. He found that the most effective reagent for iron stain removal was ammonium thioglycollate. Thioglycollic acid with suitable buffering agents can also be employed and the treatment can be adjusted to provide some consolidative effect with the incorporation of limewater. Thioglycollates have also been used for treating actively decaying pyrites (see Ch. 5). The removal of iron staining from painted surfaces has also been investigated by Ankersmit et al. (2004) (as mentioned in the text above in relation to painted iron surfaces above).

154

15 Conservation of iron from marine sites

Iron objects buried or recovered from the sea present one of the most acute needs for conservation treatment. The invariable presence of chlorides and active deterioration when removed from their marine environment results in often expensive and time-consuming conservation treatment being necessary. Plain carbon steel is today the most important alloy used for shipping and construction, but in the past cast iron and wrought iron were of even greater importance. Mild steel corrodes in the marine atmosphere at rates that vary from 25 to 750 µm/year with similar rate ranges for wrought iron and cast iron although as time proceeds the rate of corrosion usually diminishes as the corrosion crust develops. Washing, hydrogen reduction, electrolytic reduction, alkaline sulphite reduction and storage in sodium hydroxide solutions are all methods that have been used on marine iron by a number of researchers.

Electrochemistry and electrolytic reduction
For marine finds, the use of the electrolytic reduction process has never really gone out of use for want of any practical alternative, but it has been considerably refined as a result of the research of conservation scientists during the period from 1990 to 2000. Modern electrochemistry now uses a reference electrode in addition to the anode and cathode through which the current flows. This avoids polarizing effects at the counter electrode and allows direct control of the potential and with that the energetics of reactions occurring at the working electrode. This has resulted in a more sophisticated approach to the application of electrolytic reduction techniques. An example is the treatment of a large iron cannon (excavated in January 2001) from the wreck of the Swedish warship, Kronprins Gustav Adolf, which sank in 1788. Some years previously, a cannon from the same wreck had been lifted and conserved using hydrogen reduction, but the treatment had not been very successful: one of the trunnions fell apart during the treatment and there was a noticeable decrease in the hardness of the cannon’s surface, probably due to damage to the corroded grey cast iron

surface, in which graphite tends to act as the cathode in corrosion events, resulting in a heavily oxidized exterior surface layer which is often referred to as a graphitized layer. Consequently, a different conservation technique – electrolytic reduction – was selected to be applied on the newly excavated cannon. Once lifted from the sea, the cannon was immersed in water with the pH raised by the addition of potassium hydroxide. The cannon was placed in a stainless steel tank and inspected. It was found to be heavily concreted in some areas with stones so mechanical cleaning was employed as a preliminary step to remove the worst excrescences. A stainless steel mesh cage was constructed to enclose the cannon which will act as the anode (+). This cage cannot touch the cannon or the tank itself and supports, where required, were made from high density polyethylene. The cannon was placed in the tank upside down to prevent damaging of any markings on the top surface during initial polarization; it was turned later during treatment to remove all concretions. Two holes were drilled into the cannon and steel rods attached with copper wire to make the cathode connection to the object (–). Contact points were kept outside of the electrolyte to prevent them from corroding during the treatment. Potassium hydroxide was used as the electrolyte as a 1% w/v solution. The corrosion potential (Ecorr) of the cannon was measured before treatment to check on the contacts between the cannon and steel rods.

Defining and measuring corrosion potential
For the purpose of electrolytic reduction, how can Ecorr be defined? Ecorr is the potential of the metal immersed in a solution at the equilibrium value for which the anodic current and the cathodic current counterbalance each other (Ia + Ic = 0). Now, since Ecorr is a relative value and cannot be measured directly, it is always measured in comparison to a reference electrode (see Ch. 2 for a discussion on the types of reference electrodes commonly used). To measure the Ecorr value, the metallic object is connected to the V output of the multimeter, and the reference electrode is placed in the electrolyte close to the metallic object and connected 155

Iron and Steel in Ar t to the COM output. The metal has to be cleaned at the connection point to ensure contact with the metallic surface. If the contact point is immersed, no protection of the contact is necessary for iron alloys in basic solution. For copper alloys in neutral or slightly basic solution, the contact has to be embedded in an epoxy resin to prevent any oxidation of the metal. A cathodic potential (Ec) of –0.95 V Ag/AgCl (–750 mVSHE) was applied during treatment. This value was chosen as it favours the extraction of chlorides but avoids hydrogen evolution – strong hydrogen bubbling must be prevented as it may fracture the graphitic corrosion layer that preserves the archaeologically important surface of the object. As the corrosion layers are not strongly conductive, it was necessary to increase the initial current by adjusting the power supply to obtain the desired potential at both contact points. MacLeod (1981, 1986, 1988, 1989a,b, 1992, 1995, 1996a,b, 1998a,b, 2002) has undertaken a considerable amount of work in the areas of electrochemistry and the conservation of iron in seawater. On-site Ecorr and pH measurements on the wreck site of HMS Sirius (1790) on Norfolk Island (located in the South Pacific Ocean) confirmed that the rate-determining step in corrosion is the flux of dissolved oxygen to the concreted object. Data collected from a number of wreck sites have shown that corrosion potentials are linearly dependent on water depth; that systematic differences exist between wrought and cast iron; and that Ecorr data combined with water depths may provide a rough dating tool for cast iron objects. The use of sacrificial anodes for the protection of marine iron is also discussed here and has been put to use by MacLeod in a number of wreck sites. Heldtberg et al. (2004) discuss the site of the snow brig SS James Matthews, which sank off the coast of Western Australia in 1841. A pre-disturbance electrochemical survey of the major iron structures on the predominantly wooden ship was carried out prior to the attachment of sacrificial zinc anodes to a number of these fittings. After attachment, the surrounding sediment was monitored to assess the impact of dissolved zinc salts on the local environment. The anodes were commercial zinc blocks connected to the iron with insulated copper cable, silver-soldered and covered with heat-shrink epoxy mastic. Interpretation of the results is interesting in terms of comparison with other shipwreck sites. The SS Xantho, an iron steamship excavated by the Western Australian Maritime Museum in Fremantle, Australia, had a mean Ecorr of 25 measurements of –0.268 V at an average water depth of 3.5 m (MacLeod 1986). This value is slightly more cathodic than the mean values from the SS James Matthews, where Ecorr was –0.258 V, not unexpected given the deeper site conditions of the SS Xantho. After attachment of the zinc anodes, the potential drop was between 0.236 and 0.417 V, which indicates a greater degree of protection than that seen with the SS Xantho, where the drop in Ecorr was only 0.115 V but the anode was protecting a much larger surface area. The SS Resurgam, the world’s first powered submarine built in 1878 – which sank on its maiden voyage in 1880 off the North Wales coast –had an average Ecorr of –0.393 V which fell by 0.040 V after attachment of zinc anodes (Gregory 2000), indicating a good connection, but poor protective capacity. The voltage drops on the SS James Matthews exceeded the nominal value of 0.150 V considered necessary for reasonable protection. Full cathodic protection is attained at voltages more negative than –0.610 V, the beginning of the field of immunity in the Pourbaix diagrams. Only the Ecorr/pH data for deck knee 6 and windlass 10 were shifted below this value and can, therefore, be assumed to be completely protective. But all the data from the James Matthews confirmed that the overall rate of iron corrosion had been dramatically reduced by the zinc anode attachments. 156 Analysis of zinc corrosion products that had accumulated in the sediments near the ship showed that concentrations near the anodes exceeded the 410 mg/kg limit of the Australian and New Zealand Environmental and Conservation Council Interim Ocean Disposal Guidelines. However, the impact of such localized concentrations of zinc on the marine ecology would require further ecotoxicological assessment and it may be that much of this zinc is not biologically available. A corrosion protection similar to that of zinc anodes can be achieved by an impressed current system as was demonstrated for parts of the USS Monitor, the US navy’s first ironclad warship featuring a rotating gun turret which was built (and sunk) in 1862. Nordgren et al. (2007) used an impressed current system in order to reduce the rate of corrosion of the wrought iron turret while stored in fresh water tanks (this allowed excavation of the interior to proceed and avoided damage to any buried artifacts). MacLeod et al. (2008) found that in-situ use of sacrificial anodes prior to excavation had a dramatic impact and saved the turret from significant corrosion once it had been recovered. They now recommend in-situ pretreatment with anodes for all marine iron. McCarthy (1989) illustrates further work in Australasian maritime conservation with an account of work on the SS Xantho. In close collaboration, conservators, conservation scientists and archaeologists carried out physical and chemical analyses on the iron wreck, which was lodged on the seabed. In this way, the corrosion potential of different parts of the ship was assessed and conservation and management measures taken accordingly. The most important feat was the cutting free, study and conservation of the huge engine and its subsequent display at the West Australian Museum in Fremantle. The author stresses throughout the text the importance of the joint role of the archaeologist and conservator in such projects. Some of the treatment times involved in the conservation of large marine iron artefacts can be lengthy, for example, Logan (1989), recounts that the Canadian Conservation Institute (CCI) employed slow electrolysis for six years and undertook about 450 hours of manual work to conserve one heavily corroded, 2.27 m-long cast iron cannon, thought to be of French origin from the late 17th–early 18th century, recovered from the sea off the Canadian coast. Radiography was carried out by Hawker-Siddeley Canada Inc., having ensured that the cannon was not loaded. The conservation treatment was the usual method employed at CCI for underwater corroded iron. Electrolysis was carried out in a plasticlined tank using 1% w/v sodium hydroxide and 1.5 A current. Washing in deionized water was carried out for 21 months until no more chlorides could be extracted. Following desalination, the cannon was dried, rust blisters were mechanically removed and tannic acid treatment employed in an attempt to stabilize the surface. When treating cast iron objects by electrolysis, it is important to keep the current density as low as practicable to avoid undue damage to fragile graphitized layers caused by the evolution of hydrogen. Therefore, one should start with a current in the microampere range and slowly increase the current until a very slight evolution of hydrogen occurs. In some cases, the current can then be turned down slightly below that level, but in any event vigorous evolution of hydrogen is to be avoided at all costs, since irreversible damage to the cast iron artefact under treatment may result. In the case of the CCI cannon, recommendations were made that it should be displayed in a case with low relative humidity (RH) to help to keep the object stable for the foreseeable future.

Conser vation of iron from marine sites Since the required RH is now suspected to be as low as 12%, a reassessment of this kind of object and the aftermath of its attempted stabilization would be of interest. was finally raised in 1982, being sprayed with water when first excavated. Spraying with PEG 200 was begun in late 1994 and continued until 2006, when a higher grade of PEG (PEG 2000) was introduced to the spray system for the next five years to render the outer decayed zones of the oak timbers less hygroscopic. Sandström et al. (2005) employed XANES analysis to determine the nature of the sulphur species in the oak, which revealed the presence of thiols (R-SH); disulphides (R-SS-R’) and elemental sulphur (S8). Some areas showed the presence of iron pyrites (FeS2). XRD studies showed the presence of pyrite, mackinawite (Fe8S9) together with the hydrated iron sulphates, rozenite (Fe2+SO4∙4H2O) and melanterite (Fe2+SO4∙7H2O) in addition to some natrojarosite (NaFe3+3(SO4)2(OH)6). Studies of the wood timbers in cross-section revealed reduced sulphur species in high concentration in lignin-rich parts, especially in the middle lamella between wood cells, but no iron. However, iron does occur in the vessels and lumina and is responsible for the reaction: FeS2 + 7/2O2 + (n+1)H2O → FeSO4∙nH2O + H2SO4 (15.1) In order to prevent the recycled PEG solutions used in the conservation treatment of the Mary Rose from becoming too acidic, 0.8 tonnes of sodium bicarbonate had to be added to the PEG to neutralize the acidity developed from the oxidation of sulphides during the ten years of treatment (1994–2004). Sandström et al. (2005) are contemplating the possible benefits of removal of as many iron ions as possible with a potential candidate chelating agent being EDMA, ethylenediiminobis(2hydroxy-4-methyl-phenyl) acetic acid, which forms especially strong bonds as a complex (Fe(EDMA)–, previously developed as a water-soluble iron micronutrient to increase the productivity of citrus trees. Gilberg et al. (1989) investigated treatments designed to preserve objects possessing both wood and iron metal components. Previous methods such as separating the wood from the metal using PEG proved impracticable because of the cementing action of the iron corrosion products and the fragility of the objects. PEG also has a complexing ability to remove rust from the surface of objects under treatment, enhancing the corrosion of the exposed metal. In an attempt to find a suitable alternative that would render treatment with PEG non-corrosive, the authors started preliminary trials to evaluate certain water-soluble corrosion inhibitors. They also tested various resins, which were similar to PEG but which possessed corrosion inhibitive functional groups. Visual examination of sample composite objects showed that Pluracol 824, an amine substituted polypropylene glycol, and a combination of PEG 400 with Hostacor KS1, a commercial corrosion inhibitor, suppressed the corrosion of iron metal. Since this time, standard weight loss tests have been included in the project in order to measure quantitatively the corrosivity of these two mixtures towards wood/iron composite materials. Lanagan et al. (1997) investigated the problems of corrosion of iron components while using PEG 400 solutions for treatment. The name ‘polyethylene glycol’ is, in fact, a misnomer, since the polymer is actually a polyether of general formula: HOCH2(CH2OCH2)nCH2OH. As some of the chloride ions are washed out of the iron objects during treatment, it is important to establish the effect of using PEG 400 in the presence of corroding iron. The behaviour of iron in solution was shown to be complex: there is an apparent change from chloride being an inhibitor of iron corrosion at some concentrations and an accelerant at others, which explains why the in-treatment corrosion of iron composite 157

Iron and polyethylene glycol (PEG)
Jespersen (1987) was one of the first conservators to draw attention to the problems of deterioration caused by the precipitation of iron-corrosion products on PEG-treated wood. This was noticed at the time of conserving one of the five Viking ships from Roskilde Fjord, Denmark. The iron, which was completely transformed into a soft black substance, was removed. It was many years before any indications of renewed corrosion emanating from the wood was observed, but eruptions of iron corrosion around the holes formerly occupied by the corroded iron was noted; by the end of the 1970s, white spots appeared in many places around the original nail-holes. The deterioration worsened with time: blistering, powdering and fragments falling from the sides of the planks were observed. Experimental work and analysis identified the iron corrosion products on these Viking ships as ferrous sulphate tetrahydrate, the formation being due to the RH levels that exceeded 60%. The corrosion displaces the PEG with hydrated crystals of the ferrous salt. Jespersen (1987) considers that the corrosion processes occurring with these iron salts cannot be controlled and that conservation efforts must concentrate on methods to remove the iron salts during the conservation treatment. A similar story was reported for the Vasa shipwreck by Sandström et al. (2002), who pointed out the potentially degradative reactions that may take place due to the large amount of elemental sulphur within the oak timbers. The environment of the Vasa burial, being nearly anoxic, favoured the sulphate-reducing bacteria, producing large quantities of hydrogen sulphide. The Vasa sank in 1628 and was salvaged in 1961. After treatment with various grades of PEG and intermittent spraying for 17 years, the ship was placed on display in 1990. In July 2000, salt formation and pH values below 2 were found in more than 600 locations. X-ray diffraction (XRD) established that the salts were of gypsum (CaSO4∙2H2O), natrojarosite (NaFe3(SO4)2(OH)6), melanterite (FeSO4∙7H2O) as well as elemental sulphur (S8). Dissolved hydrogen sulphide from the sulphate-reducing bacterial action penetrates the wood and reacts to precipitate the elemental sulphur within the waterlogged timbers depending on their state of degradation. Subsequent studies revealed elemental sulphur beneath every surface of the Vasa, which if oxidized was estimated to be able to produce as much as 5000 kg of sulphuric acid. The presence of about 8500 corroded iron bolts which hold the ship together increases the oxidation rate of sulphur and catalyzes the oxidative degradation of cellulose as well as PEG, producing formic acid. Metallic iron corrodes rapidly in PEG solutions and forms bonds with the ether oxygens and hydroxy groups of the PEG polymer. The increased acidity of the Vasa shows that the oxidation of sulphur to sulphuric acid is not halted by the current conditions of display (about 20 °C and 55% RH), and the continuing decay due to iron oxidative processes is of major concern. This discovery has spurred a similar investigation into the timbers of the Mary Rose, King Henry VIII’s warship, the first ship able to fire a broadside, built in 1509–1511, and which sank in 1545. The wreck site was discovered in 1968 and the ship

Iron and Steel in Ar t materials changes with time and with the concentration of the PEG solution. During conservation treatment, there is a simultaneous outward flow of chloride and an inward flow of PEG, and as these relative concentrations change, different corrosion characteristics are observed. Under acidic and low oxygen conditions, the ethylene glycols, including PEG 400, all inhibit the corrosion of iron by screening active sites on the surface. In the absence of glycol, chloride ions are inhibitory at concentrations greater than 0.1 mol l–1, but lose their inhibitory characteristics at concentrations of about 10–2 mol l–1 under anodic polarization and they then assist in the anodic dissolution of iron. Addition of glycol increases the apparent activity of the chloride ions in the following order: 40% v/v PEG 400; greater than 4% v/v PEG 400; greater than 5% v/v EG . The mechanism of corrosion of iron in PEG 400 continues to be a subject of interest. Studies by Guilminot et al. (2002) have confirmed that the presence of PEG (or the PEG- anion) modifies the iron corrosion mechanisms observed in aqueous solution. PEG and/or the HO(CH2CH2O)n– anion is adsorbed onto the iron surface. This adsorption constitutes the first stage in the corrosion process. Diffusion of the iron ions/PEG complexes is then promoted by the aqueous solution. Guilminot et al. determined that there were three parameters that govern the corrosion of iron in aqueous PEG 400 solutions: • The amount of dissolved oxygen. The dissolved oxygen reduction current, which induces corrosion, decreases as the PEG 400 concentration increases. • The complexation of iron ions by the PEG 400. This factor controls the degree of iron corrosion in solutions of PEG 400 between 10% and 50% v/v PEG. • The nature of the protective surface film on the iron artifact. Since PEG molecules are adsorbed onto the metal surface, when the PEG content of the solution is high, the active area for corrosion is reduced. The decrease in the dissolved oxygen reduction current and the decrease in the active surface of the artefact limit iron corrosion, while the complexing nature of PEG promotes corrosion. These opposing effects may help to explain why the maximum degree of iron corrosion was observed in 20% PEG 400 solutions. When the water content is reduced, corrosion also decreases, becoming negligible in solutions with over 60% PEG 400. The observation of pitting corrosion in artefacts under treatment may therefore be due to local breakdown in the adsorbed PEG film. Doorninck in 1966 using a polysulphide rubber. Muncher (1988) carried out the same technique using an epoxy compound known by the trade name HySol. A partially degraded ship’s fastener was treated at the Florida Research and Conservation Laboratory using partial replication then subjected to electrolytic reduction; after completion of the treatment, a composite HySol casting and wrought iron artefact remained that accurately represented the original fastener. After evaluating these two approaches for the conservation of a French pistol from the wreck of the Le Cygne (1808), Mardikian and David (1996) came to the conclusion that neither of the two previously published approaches to this problem was going to be satisfactory, as the pistol had too complex a construction. From examination through the end of the barrel of the French pistol, it was apparent that the iron of the barrel had completely disappeared. In order to obtain clear X-radiographs of parts of the pistol no longer extant, a contrast medium was made up by softening 50 g gelatin in a litre of hot water and adding 200 g of barium sulphate. The pistol concretion was placed in the refrigerator for several hours beforehand and then the barium contrast medium was poured in. After successful X-ray examination, the concretion was warmed in water and the gelatin contrast medium washed away. Mardikian and David rejected the use of polysulphide rubber, polyurethane or epoxy products as being unreliable in the damp interior of the pistol cavity. As they had only one chance to get the casting to work they used a silicone elastomer (Dow Corning 3481 with slow-curing catalyst Silastic 81R). The concretion was pierced in selected areas with a 2 mm diameter tungsten drill and the iron oxides rinsed away as much as possible. During pouring of the silicone, a partial vacuum was used for limited periods and the silicone set for 24 hours. The method successfully revealed inscriptions in the iron metal, preserved now in resin. The wood, which was still partially intact when the concretion was cut to remove the silicone cast, was treated with sodium citrate at 2% w/v for 45 days, then placed in an agitated solution of sodium dithionite at 5% w/v and protected from oxygen in this way for ten days. After washing it was treated in 15% v/v PEG 200 for 90 days before being frozen at –21 °C for 48 hours then freeze-dried. The brass mountings of the pistol were treated in disodium EDTA 10% w/v for two weeks. The different parts were stabilized by electrolysis in an agitated sodium sesquicarbonate 2% w/v solution at a cathodic potential of –0.80 VSHE. After controlled rinsing, these were placed in 1% w/w benzotriazole in distilled water at 60 °C for 24 hours then coated with Cosmolloid 80H mineral wax in white spirit. The conservation of this complex composite pistol was successfully accomplished, and the entire object was reconstructed and exhibited as a stable artefact.

Reconstruction of the form of totally corroded iron objects
Some iron objects recovered from sea burial may be effectively covered by marine growth, such as the RMS Titanic, and become so degraded through corrosion that there is nothing left of the object at all. The concretion may preserve the cast of the original object however, and with skilful conservation work, it may be possible to clean the inside surface of the concretion without disturbing the marks created by the original surface of the iron object, fill it with a suitable resin, break the concretion away, and preserve in a cast resin a replica of the original iron artefact. The first report of this technique was made by Katzev and Van 158

Submarines
Barker et al. (1997) discuss the conservation of the submarine, Holland 1, which was recovered from the seabed in 1981 and subjected to a robust form of cleaning. This removed all the marine deposits but not the chloride residues present in the many interfaces of the submarine’s structure. These were subsequently sealed under a paint scheme that failed to prevent chloridesponsored corrosion. In 1993, Hampshire County Council Museums Service, England, was asked for advice on a suitable course of action and a conservation steering group was formed

Conser vation of iron from marine sites comprising the authors of this paper. Engineering consultants were then engaged to carry out a study based on the preferred option of washing the submarine in situ. The consultants’ brief proposed the construction of an insulated glass reinforced plastic tank that would envelop the submarine and which, at the end of the programme, could be modified to display the vessel under environmentally controlled conditions. Another interesting submarine conservation problem is that of H.L. Hunley, a submersible fashioned from a cylindrical iron steam boiler during the era of the American Civil War, which was recovered from the harbour at Charleston, South Carolina after nearly 140 years of immersion in seawater. Drews et al. (2004) have carried out initial investigations to try to determine the most effective treatment to mitigate chloride-induced corrosion. It was found possible to correlate the extent of corrosion with the density of the iron plates making up the submarine. Chloride ion was, not unexpectedly, higher in areas where the visible corrosion was most severe. In areas where the iron plates overlapped, the corrosion was found to be less severe. Data regarding whether the corrosion was higher in the interior or exterior of the hull plates and the rivets were inconclusive. Study of chloride release involved a number of different solutions. Once again, this work showed the efficacy of soaking in dilute solutions of sodium hydroxide (here a 1% w/w solution was used). Drews et al. (2004) also investigated the use of high pressure water washing using temperatures ranging from 130 to 230 °C using deionized water or 0.5% w/w sodium hydroxide. Treatment at 180 °C with 0.5% w/w sodium hydroxide for 24 hours showed the same efficacy of chloride removal as that obtained by soaking and electrolysis at room temperature for 60 days. Recent research has shown that akaganéite transforms into more stable phases under such conditions, releasing bound chloride (de Vivies et al. 2007). It appears that essentially, all the chlorides can be removed from archaeological iron from wet sites if the iron is kept wet and not exposed to air before using sodium hydroxide as a treatment solution (Watkinson 1987).

In-situ monitoring
Marine sites with potentially massive iron artefacts or ship’s parts present an ideal setting in which to attempt either in-situ conservation treatment or in-situ monitoring of the site or find, before any excavation attempt is made. An example of in-situ conservation work is provided by the treatment of a wrought iron anchor and a cast iron carronade from the wreck of the HMS Sirius, dating from 1790, carried out by MacLeod (1996a). The artefacts received in-situ electrolysis treatment using sacrificial anodes in the shallow waters off Norfolk Island. This pretreatment helped to stabilize the artefacts and ensured that they could be safely recovered and transported. Monitoring on the seabed and in the laboratory showed that approximately 80% of the chlorides had been removed from the cannonade before excavation, highlighting the benefits of this kind of pretreatment should it prove practicable to carry it out. This cathodic pretreatment can also result in the significant improvement in the quality of the surface of the excavated artefact after treatment. It is possible to maintain artefacts on the seabed by the continued use of the sacrificial anode method. A Pourbaix diagram for this wreck is shown by MacLeod (1989a) and reproduced here as Figure 15.1. The cathodic protection of the cannonade changes the Eh to a slightly more negative value, helping to suppress corrosion, as the measurements detailed on this diagram show. Stewart et al. (1997) usefully discuss the design of an in-situ monitoring programme for 27 shipwrecks in the vicinity of the northern tip of the Bruce Peninsula, near Lake Heron in Ontario, Canada. MacLeod (2002) reports on the in-situ monitoring of the City of Launceston, which sank in 1865 in Port Phillip Bay, Melbourne, Australia. Scientific studies of the wreck were made during 1991, 1994, 1998, 1999 and 2001, using more than 175 sets of pH and corrosion potential measurements, as well as estimates of the depth of graphitization. The depth of graphitization refers to the extent of loss of the iron-containing phases in the cast iron, which are now completely mineralized, and is roughly equivalent to the depth of corrosion of the cast iron. Based on the assumption that the wreck has been in a relatively constant environment since 1865, the mean depth of graphitization was found to be 15.4 mm, which equates to a corrosion rate (dg) of 0.119 mm per year. Using the values of the

On-site packing
Jensen et al. (1996) described their method of treatment of iron objects from waterlogged sites which introduced new techniques for the overall packing of waterlogged finds, including wood. Waterlogged wood is cleaned thoroughly and sealed in perforated polyolefin film, Cryovac, for wet storage. Iron objects are vacuum-packed in airtight bags after flushing with an inert gas. A refrigerated container on site ensures safe storage and transport to the laboratory. The packing procedures are designed to be compatible with the subsequent conservation processes. Different impregnation methods followed by freeze-drying of the waterlogged wood and dehydration and vacuum impregnation of metals, were also used.

0.2 cathodic protection of carronade 0.0

Fe2+ FeOOH

inner anchor

outer anchor -0.43 -0.5 -0.62 Fe3O4

-0.9

Fe

pH 2 4 6 8 10 12 14

Figure 15.1 Iron Pourbaix diagram for seawater conditions (redrawn by R. Schmidtling after MacLeod 1989a).

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Iron and Steel in Ar t corrosion potentials and associated corrosion rates for individual cast iron objects, the following relationship describes the average corrosion environment for this site: log dg = 3.25Ecorr + 0.202 (15.2) plate being completely mineralized. Based on the estimated rate of corrosion derived from these measurements, the wreck was expected to collapse around 2007–09, a prognosis to be checked by diving campaigns. Monitoring of marine iron artefacts during storage or stabilization has been discussed by Degrigny and Spiteri (2004), employing electrochemical techniques. Hjelm-Hansen et al. (1992) reported on iron artefacts immersed in sodium hydroxide and sodium sesquicarbonate solution. In sodium hydroxide solution, the Ecorr decreased to –0.560 to –0.760 VSHE, rising towards 0.040 to –0.060 VSHE after several days. This effect was confirmed by Degrigny and Spiteri (2004) who measured Ecorr values of iron artefacts in potassium hydroxide and sodium hydroxide solutions. Ecorr values provide information on the thickness of the corrosion layer and the accessibility of chlorides to the wash solution. The monitoring of Ecorr is proposed as an aid in evaluating the storage and stabilization of iron objects in hydroxide solutions. Degrigny and Spiteri suppose that some reduction reactions are occurring in the corrosion crust with ferric ions being reduced to ferrous.

This linear relationship between the log of the corrosion rate and the corrosion potential has been previously studied by MacLeod in a number of papers (e.g. 1989a, 1992, 1995, 1996a,b, 1998a,b, 2002). This relationship provides a direct method for the interpretation of the corrosion potential data. MacLeod states that the primary rate-controlling step is the flux of dissolved oxygen to the artefact, with Ecorr values being more anodic (less negative) when the oxygen flux increases. Initial voltage of the cast iron engine was –0.289 V vs Ag/AgClsea (= –0.539 VSHE), indicating extensive deterioration had already occurred. The Ecorr of the cast iron propeller from the City of Launceston was 264 mV more negative at –0.553 V and retained significant amounts of uncorroded metal. The conclusion of the in-situ monitoring research was that the upper regions of the vessel were seriously deteriorated with several ribs, frames, the capstan and a deck

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16 Conservation and decision-making

In discussing the nature of decision-making in conservation treatment, Caple (2000) uses as an example a decision tree for the conservation of 100 heavily rusted iron objects retrieved from a mediaeval excavation. The objective of the archaeologist is to identify the objects to facilitate interpretation of the site, to produce accurate drawings of the objects and to conserve the objects, if possible: In any situation a number of possible options are possible. These can be drawn as the first branches of the tree … Each action will have a number of outcomes … [I]n monetary terms, the outcome is a simple series of potential profits or losses. The route with the greatest profit can be selected, and is referred to as the highest EMV (expected monetary value). Alternatively the route with the least risk or the greatest return for the least investment can be selected. The objectives for conservation are invariably more complex (Caple 2000: 27). In the example discussed, the cost per object for X-radiography is assumed to be $3.00, for complete air-abrasive cleaning, $25.00 and for partial cleaning $10.00. Given plausible upper and lower limits for positive results depending on the conservation technique employed, decision trees can be produced showing the choice of outcomes. These provide a good example of the application of this kind of decision-tree analysis to the conservation of a large group of iron objects.

Assessing the efficacy of treatment
One of the major problems confronting the existence of thousands of treated and untreated iron objects in storage is how can we determine whether or not the conservation treatment was effective. Do treatments intended to reduce the level of chloride ion in ancient iron delay the onset of re-

corrosion, make no difference or even hasten it? These questions are important, especially since in many countries decisions are taken not to treat archaeological ironwork at all but to rely on passive storage measures. One of the first workers to take an interest in this subject was Keene, then working at the Museum of London. Keene and Orton (1985) report on their assessment of the condition of a large number of iron objects from Winchester, England, excavated between 1961 and 1971 and treated during the period from 1969 to 1977. The objects concerned were from a variety of different types of burial contexts which, at the inception of the conservation programme in 1969, were treated using electrolysis and boiling. Later treatments utilized electrophoresis with 5% sodium benzoate, continuous washing close to boiling, washing in a circulation bath with Amberlite MB-1 ion-exchange resin, steaming in a pressure cooker with a 15 lb weight applied to the pressure valve of the cooker, and soaking in aqueous 5% sodium benzoate solution. After treatment some objects were consolidated with 10% polyvinylacetate solution, while others were consolidated using vacuum impregnation with Araldite AY103 with hardener HY951: quite a concoction of different substances! Some desalination treatments were carried out after consolidation or repair and finally all objects were lacquered, mostly with Ercalene (a cellulose nitrate coating). The results of the statistical evaluation showed that treatments which aim to remove chloride ions make the re-corrosion of archaeological iron less likely. During the assessment, it was noticed that the treated objects were in much better condition than the untreated controls; most of the latter had split and flaked to the point of disintegration while the treated artefacts had no more than a few detached small flakes. An assessment of real-time survival rates for treated iron was carried out in London by Keene (1994). The samples used in this assessment consisted of four batches of iron from the Swan Lane site, iron from the same site which was not treated, iron from other Museum of London sites, some batches stored in desiccated conditions, some in ambient conditions, and iron from completely different areas and types of sites, excavated by the Passmore Edwards Museum and stored under reasonable conditions. The results of this survey showed that in real-time assessments after long periods in storage, active treatment aimed at removal of chloride ions did improve the survival rate of iron 161

Iron and Steel in Ar t artefacts. Treatment appears to have a much greater effect than controlled storage at low relative humidity (although as we have seen, these RH levels have to be very low, less than 12%; this level was not employed in the study by Keene since in 1994, this information was unknown, and RH levels of below 45% would have been typically achieved by the use of silica gel in closed containers over long periods). A further reassessment of the condition of treated iron objects at the Museum of London took place in 2000. This assessment also included a survey in which a large number of museums and other organizations in England, Scotland, Ireland and the Netherlands were asked to report on the kinds of treatment they were using for archaeological iron (Heywood 2000: 7–11). English Heritage1 established the Management of Archaeological Projects (MAP2) guidelines in 1991, which call for: Museum requirements must be established and appropriate resources allocated. The United Kingdom Institute for Conservation (UKIC)’s Guidelines for the preparation of excavation archives for long term storage (Walker 1990) and the Museums and Galleries Commission’s Standards in the museum care of archaeological collections … should be referred to when planning for curation. According to Heywood’s (2000) survey, the implementation of these recommendations, as far as iron artefacts are concerned, leaves much to be desired and she notes that the highly ‘cost sensitive’ environment in which archaeology in the UK is currently embedded has resulted in virtually no iron treatments being undertaken because iron is too low down on the list of priorities due to the treatment processes being labour intensive and expensive: This situation seems to be justified through the misinterpretation of ‘appropriate selection’ in MAP2 and reinforced by the preventive treatment recommendations coming from the Ancient Monuments Laboratory. The majority of U.K. laboratories seem to follow the passive treatments recommended by English Heritage. Therefore, without knowing whether or not ‘passive treatments’ are truly successful in the long-term the majority of
1 See www.english-heritage.org.uk.

laboratories in the U.K. rely upon dry storage (usually in sealed polyethylene boxes with a conditioned silica gel desiccant) (Heywood 2000: 1–2).. Heywood traces the genesis of this lack of treatment to the economic recession of the mid-1980s, which has had a long-term effect on the conservation budget at the Museum of London and has probably had similar consequences throughout the UK. Certainly the effect at the Museum of London was immediate and continues at the time of writing in 2008: all desalination treatments of archaeological iron ceased. Heywood writes that: The long-term consequences of this are becoming apparent. During an iron condition survey conducted by Ganiaris and Hogg (1996) it was shown that iron objects found on sites in 1986 until the early 1990’s were in worse condition than previously excavated objects. A site excavated in 1974 (SH74) had 40% of objects treated versus only 2% of a similar site of a similar size (BOY86). On the continent, the situation appears to be mixed. In France and Switzerland, desalination using the most efficient alkaline sulphite method seems to be widespread, perhaps a legacy of Rinuy and Schweizer’s (1981, 1982) seminal adoption of this technique for the conservation of iron from the soil. The Swiss National Museum in Zurich routinely applies this method for all mostly low temperature plasma treated finds (Schmidt-Ott and Oswald 2006). A representative survey among German conservators in charge of the conservation of archaeological iron (Schmutzler 2007) found that only 40% were using any kind of desalination treatment – and only half of this group was employing treatment with alkaline sulphite. Given that the electrochemistry of iron corrosion is accepted universally, it is hard to understand these apparently different national attitudes for its prevention. Man’s first known iron may have fallen from heaven but now the fate of our ferrous heritage is in our own hands: what we preserve for future generations to study, wonder and enjoy remains and depends upon the decisions that we make today. And it might take nerves of steel to succeed!

Sine Ferro Nihil

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Glossary of some technical terms and descriptions

Acicular Possessing an elongated or needle-shaped morphology. In steels, cementite and pearlite are the most common phases that could develop an acicular structure. Anode The surface area where oxidation takes place. In corrosion, the metal is oxidized to cations at anodic sites, and the electrons flow away through the metal to react at cathodic sites. In electrolysis, when iron objects are connected to the negative pole of a power supply as cathodes, the plus pole is connected to an inert counter electrode, the anode. The problem is to find anodes that are not too quickly attacked in alkaline or acidic solutions, as the cathodic reduction proceeds. Molybdenumstabilized stainless steels are suitable for use as anodes under these circumstances and only tend to be blackened or discoloured on the surfaces exposed as anodes in solution. Austenite The face-centred cubic form of iron, known as γ-iron, which is stable above 695 °C. It is softer than the lower temperature form of iron (ferrite). Ferrite and cementite separate out of austenite as the temperature falls to the eutectoid point of 0.8% carbon at 695 °C. Bainite The time-temperature-transformation (TTT) diagrams for steels show that there is a wide range of intermediate temperatures within which neither pearlite or martensite form. Instead fine aggregates of ferrite plates or laths and cementite particles form. The generic name for these intermediate structures is bainite. There are two main types: upper bainite and lower bainite. Upper bainite consists of fine plates of ferrite each about 0.2 µm thick and 10 µm long, which grow in sheaves. Lower bainite is very similar except that cementite particles also precipitate inside the plates of ferrite. There are therefore two kinds of cementite precipitation: those that grow from the carbonenriched austenite which separates the plates of bainitic ferrite and others which appear to precipitate from supersaturated ferrite. Body-centred cubic (BCC) A unit cell in which atoms are situated at each corner of a cube with one atom in the centre of the cube. Each atom at the corners is shared by each neighbour. BCC metals such as barium, chromium, α-iron, molybdenum, tantalum, vanadium and tungsten cannot be heavily cold-worked because of their low ductility and greater toughness (compared with metals of face-centred cubic (FCC) structure; see below). Boudouard equilibrium When reducing iron ore in the form of iron oxide using carbon as the reducing agent, the

carbon is oxidized into carbon monoxide and carbon dioxide. The equilibrium relationship between these carbon compounds is known as Boudouard’s equilibrium: C + CO2 ↔ 2CO. It is temperature-dependent: the higher the temperature the higher the concentration of carbon monoxide. When the concentration of CO is below the equilibrium value, the reaction with carbon proceeds in the direction to make more CO, this being called the carbon solution reaction or solution-loss reaction. Carburization The process of increasing the carbon content of the surface layers of wrought iron by heating the iron surrounded with carbonaceous material such as wood charcoal. Related to case-hardening in which heat treatments are used for producing a hard surface layer. Cast iron An iron-carbon alloy that usually contains 2–4% carbon. Generally divided into three groups: (1) grey cast iron in which free carbon occurs as flakes of graphite – this has excellent casting properties and can be machined; (2) white cast iron in which all of the carbon is taken up as cementite (Fe3C) and pearlite, usually hard and brittle; (3) malleable cast iron which is usually obtained by heat-treating white cast irons, converting the combined carbon into free carbon or temper carbon; in the whiteheart process, a certain amount of carbon is removed from the surface by oxidation. Cathode In an electrochemical cell, reduction takes place at the cathode. In many corrosion processes, the cathodic regions are protected during corrosion, while attack takes place at anodic regions. In the reduction processes used in the treatment of iron objects, the object itself functions as the cathode. Electrons are transferred from the cathode to chemical species in solution, for example, water is reduced to hydrogen and hydroxyl ions. Curie temperature Named after Pierre Curie (1859–1906), it is the temperature at which a ferromagnetic material loses its characteristic ferromagnetic behaviour. For iron, this temperature is about 776 °C; above this temperature iron is paramagnetic, i.e. essentially non-magnetic. Cyanotype A form of photographic process using iron salts. The cyanotype is made with an aqueous solution of ferric ammonium citrate and potassium ferricyanide used to coat a 163

Iron and Steel in Ar t sheet of paper. The negative is then placed against this paper and exposed to bright sunlight for 10–20 minutes until the paper turns green-grey. The image is then formed by developing in water until the details are visible and most of the yellow, unreacted ferric citrate solution has been rinsed away. The prints are then washed in water and dried. Damascening An ancient process of ornamenting a metal surface with a pattern. In the early Middle Ages swords with this pattern were said to be from Damascus, made by repeatedly welding, drawing out and doubling up a bar composed of a mixture of iron and steel. The surface was later treated chemically to darken the steel areas, with ferrite remaining bright. In the West, this is closely associated with the technique of pattern welding (see below), which was used to make composite iron and steel artefacts. Another meaning of damascening refers to the process of inlaying metal on another metal which is common particularly in parts of Iraq and India where it is known as Kuft work. Decarburization A steel production technique first practised in China from the 5th century BC onwards. Thin plates of cast iron were heated to oxidize them into a steel containing spheroidal carbide without any formation of graphite. In general, the method or effect of the loss of carbon from the surface of a steel is also a (sometimes undesirable) decarburization. Etchants (for iron) Chemical reagents used to reveal grain boundaries and differences in microstructure visible under the microscope due to differential attack. The most generally useful is nital, made from 100 ml ethanol with the addition of 2 ml concentrated nitric acid (2% nital), or 4 ml concentrated nitric acid (4% nital). The polished iron sample or section is immersed in the solution for 2–10 seconds. For yellow staining of cementite to help distinguish between ferrite and cementite, picral is useful, made from 100 ml ethanol and 2 g picric acid. A variant is alkaline sodium picrate, made with 2 g picric acid, 25 g sodium hydroxide and 100 ml water. Used as a boiling solution into which the iron sample is immersed, the ferrite is unaffected and cementite darkened. Vilella’s reagent is made from 1 g picric acid, 100 ml ethanol and 5 ml hydrochloric acid. Useful for exposing the needles of plate martensite and for exposing the austenitic grain structure of quenched and tempered steels. Klemm’s reagent is an interference tint etching agent for iron and steel made from a saturated solution of sodium thiosulphate to which 1 g per 100 ml of sodium or potassium metabisulphite is then added. This is known as Klemm’s 1 reagent. Klemm’s 3 reagent is made in the same way, but with the addition of 3 g potassium or sodium metabisulphite to the stock thiosulphate solution. The iron or steel is held in the solution for a long time, perhaps 3–10 minutes, until a dark surface film forms over the alloy composed of a complex oxide-sulphide-sulphate film. This interference film is then ready to reveal surface microstructure. Gives useful and colourful results on a wide range of different alloys. Eutectic In binary alloys the composition with the lowest melting point. The eutectic is a fixed composition in binary alloys and is often a fine intimate mixture of two phases. Eutectoid In binary alloys, the decomposition from a solid phase into two finely dispersed solid phases. In iron and steel, the most common is the eutectoid of ferrite and pearlite formed from the decomposition of austenite at the eutectoid point at 0.8% carbon and 695 °C. Face-centred cubic (FCC) An atomic arrangement in crystals where the atoms can be imagined as spheres at the corners and middle of the faces of a set of cubic cells. FCC metals such as gold, silver and copper can be readily drawn out into a wire (are ductile) and can be cold-worked to shape. Iron at high temperatures as 164 austenite (see above) is face-centred cubic, which accounts for the use of red-hot temperatures for working iron, as it is then in the FCC lattice arrangement, rather than the body-centred cubic (see above) arrangement, which pertains at lower temperatures. Fayalite The most common component of ancient iron slags, fayalite is an iron silicate of formula 2FeO∙SiO2 which melts at about 989 °C and crystallizes in the orthorhombic system. Usually takes the form of broken, elongated grey laths in a glassy silicate matrix. Ferrite Substantially pure α-iron occurring in iron-carbon alloys. This is iron in a body-centred cubic form. Ferromagnetic The characteristic of materials which are strongly attracted when subject to a magnetic field. The magnetic moment of atoms are aligned in domains. Iron and steel are the most common ferromagnetic materials. When heated above the Curie temperature (see above) they lose their ferromagnetism and behave as paramagnetic (see below) substances. Graphite One form of carbon, occurring in the trigonal system as grey, soft lustrous plates. It is the form of carbon found in cast irons and usually occurs as thin flakes or nodules in the pearlite and ferrite matrix. HV The microhardness of an alloy or metal obtained using the Vickers diamond pyramid hardness test. The hardness is obtained by indenting the alloy with a diamond pyramid of 136° angle under a specified load and measuring the size of the impression produced. The retention of this scale is perhaps more than Vickers deserved, as they gave up making microscopes in favour of tanks many years ago. Industrial scales of hardness include the Rockwell scale and the older Brinell scale, which can be converted approximately to match the Vickers hardness scale. Hypereutectoid In steels, alloys with more carbon than is contained in pearlite. In carbon steels, a hypereutectoid steel contains more than 0.8% carbon and consists of pearlite and cementite. Hypoeutectoid In steels, alloys with less carbon than is contained in pearlite. In carbon steels, a hypoeutectoid steel contains less than 0.8% carbon and consists of pearlite and ferrite. Iron electronic configuration Iron atoms have six electrons in the 3d and two electrons in the 4s shell (configuration 3d64s2). When iron has a valency of two, in the ferrous state, it is referred to as the (d6) configuration, as two 4s electrons are shared or donated to another species. Similarly, when three electrons from the iron atom are involved, known as the ferric state, the configuration drops another electron to (d5). The geometry of iron compounds tends to be tetrahedral or octahedral. Kurdjumov-Sachs relationship A number of orientation relationships occur on phase transformations. One of these is the Kurdjumov-Sachs orientation, which results in the precipitation of iron carbide phases along certain preferred crystal planes in the solid, as the alloy changes from one crystal form to another. The other well-known relationship is called the Nishiyama-Wasserman orientation. These two relationships are of importance in the detailed study of martensitic transformation in steels and the types of plessite formations in meteorites. Malleabilizing A method of heat treatment of cast iron first used in China in the early centuries BC, in which a white or grey cast iron is packed in charcoal and kept at red heat for several days before cooling. The graphite, normally present as flakes, tends to form nodules, sometimes referred to as spheroidal graphite cast iron (SGCI). Graphite in the form of nodules in a grey cast iron is considerably less brittle and can be worked to some extent: it has been made malleable by heat treatment.

Glossar y of some technical terms and descriptions Martensite A constituent (usually in steels) formed when the alloy is cooled at a rate sufficiently rapid to suppress the change from austenite to pearlite. Also results from the decomposition of austenite at low temperatures. Consists of a solid solution of carbon in iron. The phase is very hard and can be softened to some extent by tempering to form epsilon-carbide that is also very hard but less brittle, so that it can be used for cutting edges without fracture of the edge, which could be a problem if the martensite was left untempered. Paramagnetic Materials that are paramagnetic are weakly attracted when subjected to a magnetic field. Paramagnetism requires that atoms retain permanent dipole moments even without an applied field. This usually implies a partially filled electron shell with unpaired electrons. In pure paramagnetism these atomic dipoles do not interact with one another and are randomly oriented in the absence of an external field, resulting in zero net moment. If they do interact they can align or anti-align, resulting in ferromagnetism or antiferromagnetism respectively. Paramagnetic behaviour can also be observed in ferromagnetic materials that are heated to above their Curie temperature. Pattern welding The method of making a sword from iron and steel by twisting the components together in the form of long bars, which are then hammered and welded to another collection of composite bars. When finished, the surface can be ground and polished to reveal the pattern created by the welding of the iron and steel components. The starting materials are usually wrought iron and a low carbon steel. Puddled steel A kind of steel, first made in ancient China, which appeared in the 2nd century BC and became very popular by the 2nd century AD. In the puddling process, the cast iron is first heated in air while being stirred. When preferential oxidation of the carbon content of the cast iron occurs, the temperature at which the mass remains molten rises, resulting in a pasty mass. If the stirring was continued in the semi-solid state, the result was a low carbon wrought iron, but it was also possible to stop the process before decarburization was complete to obtain a medium or high carbon steel. Steadite The ternary phosphide eutectic between ferrite (usually with a little phosphide content), cementite and iron phosphide (Fe3P), which occurs in cast irons. The eutectic has a melting point of about 960 °C so is the last constituent to form as the cast iron cools down. It is a very brittle phase but is usually only present in small amounts scattered as isolated islands. Tempering Usually applied to steels in which some of the hardness is removed by heating at moderate temperatures, from 200 to 650 °C, depending on the type of tempering required. In ancient metals, tempering (or self-tempering) of martensite would have been carried out to reduce the brittleness of the fully quenched steel cutting edges of blades used for knives and swords. Time-temperature-transformation (TTT) diagrams Most useful in considering the nature of the quenched microstructure to be found in steels and high tin bronzes. The quenching rate and composition results in a whole series of TTT diagrams that are commonly used to investigate transformation effects on components found during the quenching of different types of steels or other alloys. A related diagram is the continuous cooling temperature diagram, or CTT, which may be of more practical utility. Troöstite The name given to structures in steel consisting of very fine aggregates of ferrite and cementite, which cannot be resolved under the optical microscope, which etch rapidly, and may appear very dark blue. Such structures may be very fine pearlite or the product of tempering martensite at temperatures lower than those that give the very fine dispersion of cementite in ferrite, previously known as sorbite. Weld A term used to describe a join made between two or more metallic components by heating them together without the addition of any solder. Welding was an essential part of the early use of bloomery iron, in which parts of the bloom can be heated and joined together. The oxide scale that forms on iron does not prevent the welding process as it would with, for example, bronze alloys, which cannot be welded together. The fact that welding can occur so easily in iron and low carbon steels, substantially helped in the development of iron technology, since in the West, cast iron was not developed until the 13th century AD. Widmanstätten A general term for structures resulting from changes in solid alloys when one constituent forming from another solid constituent crystallizes along the crystallographic planes of the parent phase. First observed in the structure of iron meteorites, the Widmanstätten structure is commonly encountered in ancient iron objects due to the hot forging in the austenitic field and consequent decomposition of the austenite on cooling into pearlite and ferrite. In steels with over 0.8% carbon, the decomposition is into pearlite and cementite. Wrought iron Essentially ferrite or ferrite with a small amount of carbon content and entrapped slag stringers from working and hammering to shape. Wrought iron is relatively soft when heated to the austenitic region, allowing the blacksmith to shape the metal, as in the production of wrought iron gates and fences.

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