(a) (b)

(a) (b)

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).
 (a) (b)

(c) (d)

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 Plate 41 A heavily corroded iron object, disintegrating under ambient
from the site of Mosfell, Iceland (photomicrograph: D.A. Scott). 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 Plate 44 Voltine growing from pyrite decomposition on waterlogged wood
wood from Los Buchillones, Cuba (ESEM photomicrograph: courtesy of David from Los Bucelliones, Cuba (ESEM photomicrograph: courtesy of David
Carson, Getty Conservation Institute). 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).
 (a) (b)

(c) (d)

(e) (f)

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 plane-
polarized 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).
 (a) (b)

(c) (d)

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).

Plate 49 (a): Plane-polarized light view of

(a) 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).

(b)
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. 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.
 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 Formula Crystal system Colour Occurrences

Prussian blue Fe4[Fe(CN)6]3.14H2O cubic deep blue synthetic pigment
Prussian blue1 Fe4[Fe(CN)6]3.3H2O cubic deep blue synthetic pigment
potassium ferricyanide K3Fe(CN)6 monoclinic red early photography
potassium ferrocyanide K4Fe(CN)6.3H2O monoclinic red-yellow early photography
ferric ammonium citrate 2
5Fe(Hcit)2(NH4)3(Hclt).NH4(H3cit).2H2O not known green early photography
ferric tannate FeC76H46O46 amorphous blue-black patination processes
ferrous acetate Fe(CH3COO)2.4H2O monoclinic light green patination processes
ferric acetate, basic Fe(OH)(CH3COO)2 not known brown-red patination processes
ferrous citrate Fe[CH2COO. C(OH)COOCH2COOH] rhombohedral white cleaning solutions
ferrous d-tartrate Fe[CH(OH)COOCH(OH)COO] not known white cleaning solutions
1
Other variants include ammonium ferric ferrocyanide (NH4)2Fe[Fe(CN)6].xH2O as commercially important pigments. All of these are isotropic.
2
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, 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
 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).

88

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 galls 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.
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. Seeley 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.
 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.
 N. J. Seeley, pers. comm. to D.A. Scott, 27th May 2002.
Iron carboxylate s and cyanide s
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
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,

90

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
Iron carboxylate s and cyanide s
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 auto-
oxidation 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. Seeley 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.
 N.J. Seeley, pes. comm. to D.A. Scott, 27 May 2002.
91
Iron and Steel in Ar t
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.
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
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 (8.2)
Fe2Fe(CN)6 → (oxidation) → KFe[Fe(CN)6]3∙xH2O (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 (8.4)
(NH4)2Fe[Fe(CN)6] + H2SO4 +NaClO3
→ (NH4)Fe[Fe(CN)6] + NaCl + (NH4)2SO4 (8.5)
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

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.
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
Iron carboxylate s and cyanide s
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)
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 Sensitizer (developer) Image Inventor(s) Year

argentotype ferricitrate (silver nitrate) silver Herschel 1842
(dev: silver nitrate)
Vandyke ferricitrate + silver nitrate silver Arndt and 1889
brownprint (dev: water) Troost
sepiaprint
kallitype ferric oxalate + silver nitrate silver Hunt 1844
(dev: borax or Rochelle salt) Nicol 1889
argyrotype ferricitrate + silver sulphamate silver Ware 1991
(dev: water)
cyanotype ferricitrate + ferricyanide Prussian Herschel 1842
blueprint (dev: water) blue
ferroprussiate
new cyanotype ferrioxalate + ferricyanide Prussian Ware 1992
(dev: dil. nitric acid) blue
pellet print ferricitrate/tartrate Prussian Herschel 1842
(dev: ferrocyanide + gum) blue Pellet 1878
chrysotype Ferricitrate gold Herschel 1842
(dev: chloroaurate(III))
new chrysotype ferrioxalate + gold(I) complex gold Ware 1987
(dev: carboxylic acids)
platinotype ferric oxalate + chloroplatinate platinum Willis 1873
(dev: oxalate)
sepia platinum ferric oxalate + chloroplatinate mercury + Willis 1890
+ mercury(II) salts platinum
(dev: oxalate)
POP platinum sodium ferrioxalate + platinum Pizzighelli 1887
sodium chloroplatinate
satista ferric oxalate + silver chloride + chloroplatinite silver + platinum Willis 1913
palladiotype ferric oxalate + chloropalladite (dev: oxalate palladium Willis 1916
amphitype ferricitrate/ferritartrate + mercury(II) salts mercury Herschel 1842
Obernetter’s ferric chloride + cupric chloride cupric Obernetter 1864
ferrocupric (dev: thiocyanate) ferrocyanide
(tone: ferricyanide)
Phipson’s ferrioxalate manganese Phipson 1861
(dev: permanganate) dioxide
ferrogallate ferritartrate ferric gallate Colas 1860
Colas (dev: gallic acid)
blackline
heliographic ferritartrate ferric tannate Nakahara 1894
Nakahara’s (dev: tannic acid)

chloroplatinate (potassium tetrachloroplatinate(II)). The ferrous dicarboxylate. The dicarboxylate then thermally decomposes to
ions formed in equation 8.6 act to reduce the platinum(II) salt to form acetone as the final organic component of the system.
metallic platinum:

2Fe2+ + Pt2+ → 2Fe3+ + Pt (8.7)

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
 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 posi-
tive charge compensates for the additional deprotonation in the
complex further than the three citrate carboxylate groups.

94
 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 Structure

Physical weathering Air permeability

Water permeability Soil porosity

Water content Oxygen content

Organic substances
Carbonate
Salt concentration
Humic substances
METAL
Electrical conductivity
Soil acidity

Redox potential Microorganisms

Sulphate, nitrate, phosphate, chloride content Ammonium 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.
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
96
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–6th-
century 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

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 sulphate-
induced 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 corrosion in the soil
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.
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 sedimentary-
type 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
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.

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 tree-
like 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 reaction-
transport 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.
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
 In David A. Scott’s collection.
Iron corrosion in the soil
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– (9.1)
O2 + 2H2O + 4e– → 4OH– (9.2)
O2 + 4H+ + 4e– → 2H2O (9.3)
2H2O + 2e– → H2 + 2OH– (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+
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 [C1-]TOT=10.00mM
1.0
FeOOH(cr)
Fe(OH)2.7Cl0.3(c)
0.5
ESHE/V
0.0
Fe2+
Fe3O4(c)
-0.5
Fe(OH)2(c)
Fe(c)
-1.0
2 4 6 8 10
pH
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).
100
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
(9.5) 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 (9.6)
2FeCl2 + 3H2O + O2 → 2FeOOH + 4HCl) (9.7)
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
t=25˚C
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,
 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 Seeley 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.
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.
 N.J. Seeley, pers. comm. to DA. Scott, 6 June 1986.
102
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 Transport and accumulation of material from the bulk liquid
to the metal surface.
2 Microbial and electrochemical transformations within the
biofilm and at the metal surface.
3 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)
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)
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
 Iron corrosion in the soil

Anoxic bulk liquid Organic matter

Biofilm - bulk liquid interface 1 1 Mass transport process.

2 2 General anaerobic
Anoxic biofilm metabolic processes.
Organic matter
FeS1-x H 3 Sulfate reducing process.
4 Ferrous sulfide
FeS1-x Fe2+ e- precipitation.
4
FeS1-x 3
5 Electrochemical
Anoxic biofilm -
Fe2+ H+ H corrosion process.
scale interface

5
Iron sulfide scale
Bulk metal e-

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 Organic matter

1 Mass transport process.
O2,
Biofilm - bulk liquid interface 1 2 Anaerobic metabolic processes.
3 Ferric hydroxide precipitation.
Oxic biofilm 3 2
4 General anaerobic metabolic
FeOOH
6 So, sulfate reducing processes.
Oxic- Anoxic biofilm interface 5 Ferrous sulphide precipitation.
5 6 Sulfide oxidation processes.
Anoxic biofilm FeS2 FeS1-x HS- 4 7 Pyrite formation process.
7
Anoxic biofilm - metal interface Fe2+ H + H 8 Electrochemical
corrosion process.
Iron sulfide scale 8
Bulk metal 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.
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
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. (9.13)
M OO. + RH → R . + HOO- + M(n+1)+
n+
(9.14)
The alternative series of reactions are:
Mn+ + O2 → M(n+1)+ + O-O. (9.15)
M(n+1)+ + O-O. + RH → R . + HOO- + Mn+ (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
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

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
Iron corrosion in the soil
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 Formula Crystal system

ferrous hydroxide Fe(OH)2 hexagonal
magnetite Fe3O4 cubic
green rust 1 (GR1) Fe2IIFeIIIOx(OH)y hexagonal, trigonal/orthorhombic
green rust 2 (GR2) Fe Fe Ox(OH)y
II III
hexagonal
maghemite γ-Fe2O3 trigonal
ferric oxide Fe2O3nH2O hexagonal
ferric hydroxide Fe(OH)3 cubic
goethite α-FeOOH orthorhombic
akaganéite β-FeOOH monoclinic
lepidocrocite γ-FeOOH orthorhombic
feroxyhyte δ-FeOOH hexagonal
szomolnokite FeSO4·H2O monoclinic
rozenite FeSO4·4H2O monoclinic
melanterite FeSO4·7H2O monoclinic
lawrencite FeCl2 trigonal
ferrihydrite Fe2O3·O·5H2O trigonal

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).

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
α Fe 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.
Fe++ 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
Fe+++
Fe (OH)2 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.
Fe (OOH)
γ Fe (OOH) Fe (OH)3 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,
Fe 3O4 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
+H 2O but the same also applies to more humble structures such as iron
railings, cast iron grills, wrought iron sculpture, wrought iron
γ Fe 2O3 α Fe2O3 α FeOOH gates or Corten steel installations.
The formation of rust on iron in the atmosphere has been the
-H 2O
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
Figure 10.2 Phase relationships in rust layers (redrawn by R. Schmidtling corroding away in ambient or poor storage conditions. Much
after Hiller 1966). research has been devoted to determining the relative amounts of

108

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.
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 4–65
urban 23–71
industrial 26–175
marine 26–104
Iron corrosion in the atmosphere
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.
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

icorr
2

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

Ecorr
1
cat
ho
dic 2

cat
ho
dic 1

Eo,H

io,H icorr
1

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 E
Eo,c
Eo,c
Ecorr

Ecorr

Eo,a Eo,a
i i
icorr icorr
(a) (b)

Eo,c

Ecorr

Eo,a i
icorr
(c)
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

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
Iron corrosion in the atmosphere
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 non-
rusted samples while curve B shows the weight gain for freshly prepared
samples (redrawn by M. Gleeson after Evans 1960).
111
1 Low RH: below the critical RH level at which attack becomes
rapid.
2 Medium and high RH: above the critical RH range and
extending up to saturation.
3 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 long-
term exposure, the silica particles may eventually promote
corrosion due to differential electrochemical potential as a
result of different oxygen diffusion pathways.
2 Intrinsically corrosive: producing rust where the particles essential feature being the oxidation of ferrous sulphate to ferric
settle, typically ammonium sulphate particles, commonly
found in industrial areas.
3 Indirectly corrosive: carbonaceous particles which, by
absorbing acidic atmospheric gases, can profoundly stimulate
corrosion in medium or high RHs.
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)
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
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
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)
At cathodic regions of the surface these electrons will then be
consumed:
Fe2+ + 8FeOOH + 2e– → 3Fe3O4 + 4H2O (10.7)
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

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)
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,
Iron corrosion in the atmosphere
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)
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.
113
Iron and Steel in Ar t
FeII (bulk)
C1-
[O]
Green rust I & II
[O]
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.
114
C1 FeOC1
FeOOH
7
2 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 water-
filled 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.
3 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.

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.
4 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 re-
oxidation 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
γ α
red surface
layer on top
of γ
U < U*
[( α
Figure 10.7 Phase relationships in rust scales (redrawn by R. Schmidtling after Stratmann 1990).
Iron corrosion in the atmosphere
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.
5 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.
Weissenrieder and Leygraf (2002) studied the initial corrosion
of iron and showed that an aqueous adlayer of constant mass was
red surface
layer on top
of α
) * = superparamagnetic α
crystal size < 240Å]
115
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 per-
formed 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.
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
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 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 (10.16)
2FeCl2 + 3H2O + O2 → 2FeOOH + 4HCl (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. 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
 D.A. Scott, unpublished data on Norfolk iron sea-coast
defences.

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 electron-
hole 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
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.
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 chromium-
containing 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

crack
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
γ -FeOOH proportionally with the number of years of exposure. The fraction
of amorphous material, which is between 20 and 60% during the
initial rusting initial stages of exposure, can increase to 70% with time. After
Steel 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
γ -FeOOH
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
Amorphous oxyhydroxide several years
the ratio aspect to factors α*/γ*:
Steel
α*/γ* = (% α-FeOOH + % Fe3O4 )/ (% β-FeOOH + % γ-FeOOH)
(10.20)

Despite the fact that magnetite is conductive, it can be

γ -FeOOH
α (Fe1-xCrx)OOH decades
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).
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
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 cross-
sections 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.

Table 10.2 Some Corten steel characteristics (after Stainless Steel Information Center 2005).

Type C Mn P S Si Ni Mo Cr B Ti
400F .12/.16 1.55 .025 .005 .35/.55 1 .55 .55 .0005/.005
500F .25/.31 0.95 .25 .005 .45/.55 1 .65 .75 .0005/.005
A514
12–22 .80/1.40 .035 max .040 max .15/.35 .15/.30 .35/.70 .0005/.005 .03 max
Gr B

119
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 Qutbud-
din 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.

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.
Iron corrosion in the atmosphere
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 phosphorus-
containing 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
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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
122
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.
 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.
Figure 11.1 Schematic cross-section of concreted iron object corroding in seawater (redrawn by R. Schmidtling after North and MacLeod 1987).
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
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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.
Fluid filled cavity
2–
Water
(Fe++, CI-, SO4 =)
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).
124
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
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.
 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+ (11.4)
Fe SH–ads → FeSH+ads+ 2e– (11.5)
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.
 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).
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.
2 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.
3 Erosion and detachment from the surface of the film.
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.
125
 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.
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.
(b) 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).
(c) 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.
(d) 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.
128
(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.
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 79 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 three-
dimensional 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
 In D.A. Scott’s collection.
 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.
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
130
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).
 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.
Some of the earliest documented attempts to deal with the
instability problem took place in Scandinavia, where Norwegian,
 It is not clear exactly how this was carried out. There is no infor-
mation 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.
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.
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
 Seen by D.A. Scott during a visit to the laboratories.
132
also experimented with dammar resin in solvents, linseed oil and
animal fat in the form of tallow.
Boissonnas 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).
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,
 V. Boissonnas, pers. comm. to D.A. Scott, 27 November 2005.
 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.
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 X-
radiographs 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.

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. 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 Figure 13.1 The X-radiography of a barrel padlock illustrating the
the elimination of X-ray scatter. The beneficial effects of using advantage of using lead screen intensifiers used in the image above and
lead screens or copper or aluminium filters over the X-ray tube not used for the same exposure conditions for the radiographic image
shown below (after Corfield 1982).
 V. Fell, pers. comm. to D.A. Scott, 14 December 2005.

133
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.
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
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 wax-
like 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
 Conser vation of iron from the soil

the iron object was immersed and subsequently scrubbed with Techniques based on reduction and heating
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 We have seen that there was an early introduction of both
react with iron oxides to form soluble cyanides that were washed electrolytic reduction and heating techniques to effect stabilization
away. Entwistle notes that by 1905, Rathgen had experimented with to the iron artefacts under treatment. The raison d’être of most
a method of treatment for iron that involved boiling the objects of these techniques was either oxidation, through heating of
in molten potassium cyanide. The treatment was employed both the object, or reduction, to remove the corrosion crust entirely.
for small silver and iron artefacts, which were briefly immersed Developments in reduction techniques that followed on from these
in the molten potassium cyanide and then quenched in water. early approaches to conservation include hydrogen reduction,
All traces of cyanide were then removed by repeated boiling in alkaline sulphite reduction and plasma reduction. Of these three,
distilled water followed by impregnation in molten paraffin wax. the hydrogen reduction process was developed first, based on the
Though efficacious for the treatment of large numbers of small known chemical techniques of transformation of metallic oxides
objects, Rathgen cautioned against the use of this method because to metal by heating in a stream of hydrogen gas.
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, Electrolytic reduction
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 Electrolytic reduction as a conservation treatment has its origins
cyanide solutions although chemical cleaning still has its place during the zenith of the electrotyping and electrochemistry
in such cases when mechanical cleaning would do more harm by developments of the late 19th century; Rathgen (1889, 1898)
damaging the surface. Nevertheless, chemically removing more or employed electrolytic reduction on a variety of artefacts using
less protective (‘passivating’) rust may make the underlying metal 2% potassium cyanide solution in water as an electrolyte and
more vulnerable to corrosion. It can, therefore, be wise to add an platinum anodes for the treatment of chlorides in ancient bronze
inhibitor to the solution (see Ch. 14). artefacts. He used a variety of techniques depending on the object
Complexing agents are used as their free electron pairs can concerned, and would also use grinding wheels and mechanical
form strong bonds with metallic cations; they often contain cleaning during his conservation treatments. A good example of
carboxylate groups. The concentration of the active free the skilful work achieved is shown in Figure 13.2.
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 Figure 13.2 Iron inlaid dagger shown before cleaning (left) and after cleaning
timbers, which can be cleaned of iron contaminants quite with the silver inlay revealed (right) (after Rathgen and Borrman 1905).
effectively without damage to the wooden object itself.

135
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 17th-
century 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.
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).
136
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

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. 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 ship.
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
 C. Degrigny, pers. comm. to D.A. Scott, 19 June 2002.
 V. Boissonnas, pers. comm. to D.A. Scott, 27 November 2005.
Conser vation of iron from the soil
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
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 Arrhenius-
type 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 chloride-
free 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

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
Gas bubblers
Reflux condenser
Soxlet container
Stopcock for
removal of wash-
water 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).
Conser vation of iron from the soil
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)
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.
139
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 physico-
chemical 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– (13.2)
N2H4 + O2 → N2 + 2H2O (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

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).
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
Conser vation of iron from the soil
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! Schmutzler is in the process of developing a protocol
using digestion in closed systems.
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
 B. Schmutzler, pers. comm. to G. Eggert, 6 April 2008.
141
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.
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:
(a) Keep at a very low RH, i.e. under 12%.
(b) Keep at a controlled RH of about 30%.
(c) Reburial of objects from terrestrial sites.
(d) Store in deoxygenated aqueous solution.
(e) 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 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

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 heat-
sealed to form small enclosures. The microenvironment created
using ESCAL and RP-A can last from four to six years. With the
Conser vation of iron from the soil
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 energy-
consuming 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 long-
term 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.
143
 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.
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.
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
 CAMEO 2006; see also BCIN (www.bcin.ca/) and AATA
(http://aata.getty.edu/NPS/).
146
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

Table 14.1 Composition of macrocrystalline (‘paraffins’) and microcrystalline waxes (‘microwaxes’) (after Koller und Baumer 2000b: tables 10, 11).
Hydrocarbon type Hard paraffin
Ø number of
% w/w Ø
C-atoms
n-alkane 82-92 25
iso-alkane 9–4 27
cyclo-alkane 9–4 29
dicyclo- – –
alkane/tricyclo alkane
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 strong-
smelling 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
Conser vation of e xposed ironwork
Plastic microwax Hard microwax
Ø number of Ø number of
% w/w % w/w
C-atoms C-atoms
10–25 35–42 25–35 35–45
38–45 35–50 20–28 35–50
38–45 35–50 20–28 35–50
– – 20 45–55
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. Cold-
waxing 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 historical-
period 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)
while the organic metal (PAni) is reduced to its leuco form (LE):
148
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 sulphonate-
doped 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

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, lead-
based 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).
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
Conser vation of e xposed ironwork
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 β-
FeOOH 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
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).
Seeley 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 Seeley 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)
 N.J. Seeley, pers. comm to D.A.Scott, 15 January 2003.
 N.J. Seeley, pers. comm to D.A.Scott, 27 May 2002.
150
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,

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.
Conser vation of e xposed ironwork
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.
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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.
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 amine-
carboxylic acid inhibitors on iron carried out by Bommersbach
et al. (2005). They found that the mixed inhibitor forms a three-
dimensional 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 near-
neutral solutions are the compounds based on the linear saturated
sodium mono- and α,ψ-dicarboxylates such as CnH2n+1COONa
152
and NaOOC(CH2)nCOONa. These inhibitors may be useful as
they are relatively inexpensive, environmentally benign, non-
toxic 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.
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 thio-
amino 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).
 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.

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↓ (14.7)
Ca + CO2 + 2OH– → CaCO3 ↓ + H2O
2+
(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).
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
Conser vation of e xposed ironwork
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 non-
toxic cleaning solution based on an ‘amine complex of hydro-
oxycarboxylic 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
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
154
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).
 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 plastic-
lined 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.

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.
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
Conser vation of iron from marine sites
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(2-
hydroxy-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
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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.
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
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.
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 chloride-
sponsored 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

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).
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.
Conser vation of iron from marine sites
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
0.2
inner
Fe2+
anchor
cathodic FeOOH
protection of
0.0
carronade
outer
anchor
-0.43 Fe3O4
-0.5
-0.62
Fe
-0.9
pH
2 4 6 8 10 12 14
Figure 15.1 Iron Pourbaix diagram for seawater conditions (redrawn
by R. Schmidtling after MacLeod 1989a).
159
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)
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
160
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.
 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
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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
Heritage 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
 See www.english-heritage.org.uk.
162
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
 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. Molybdenum-
stabilized 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 carbon-
enriched 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
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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.

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
Glossar y of some technical terms and descriptions
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.
165
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