Professional Documents
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METAL OBJECTS
Jan Gullman
189
reactions balance each other so that all produced for determination of whether there is high potential
electrons must be consumed and vice versa. Elec- corrosivity in a given soil or not. The second one
trochemical corrosion can therefore be limited or concerns development of cheap and reliable corro-
controlled byintroducing restrictions in one ofthree sion countermeasures, such as coatings or cathodic
phenomena: protection. Therefore soil corrosion technology is
mainly concerned with problems in environments
- the anodic reaction where only relatively young iron artifacts are not
- the cathodic reaction or completely corroded.
- the electrical current which unite the reactions
The technological criteria used in estimating soil
The anodic reactions convert the metals from ele- corrosivity are based on measurements of electrical
ments to metal ions and electrons. The most im- resistivity, pH and concentration of some ions such
portant cathodic reaction, for corrosion processes, is ashydrogen carbonate and chloride (German Stand-
the reduction of oxygen dissolved in water to form ard DIN 50 929) in the soil. Sulphur content of the
hydroxide ions by taking up the electrons generated soil is also considered to have a gre,at influence on
by the anodic reactions. corrosion rates in soil. The most important factor for
the corrosion rate of iron in soil is, however, whe-
The soil environments from which archaeological ther the corroding object in question is above or
objects are excavated are more or less wet. In the below the ground water table. Below the ground
temperate climatic zone the prerequisites for wet water table the transport rate of oxygen is the step
corrosion are almost always fulfilled in unfrozen that determines the rate for the corrosion of iron
soils. In spite of this, corrosion rates vary a great (Iversen 1988, Camitz and Vinka 1989).
deal between different soil environments. Corrosion
problems with technical equipment such as steel Archaeological metals in soil
pipes and poles have necessitated the development
of a field of soil corrosion technology. The conditions which are prevalent at the time of
the excavation may often be very different from the
Soil corrosion technology ones that prevailed some time after the deposition of
the material. The objects may have been placed in
Corrosion research can be divided into the scientific containers made of organic materials which created
and technological areas. There isno clear distinction a microclimate. This should have resulted in cor-
between these two fields. rosivity similar to a den in the earth rather than soil
conditions. In other cases, the environment might
Corrosion technology usually avoids complicated have been dominated by organic material from, for
theoretical models and is mainly based on experi- example, a decaying body in a grave or waste mate-
ence and evaluations of relatively simple experiments rials in a compost heap. In order to gain knowledge
and standard measurements. about the possible changes in the environment over
time and their nature, archaeological evidence from
In corrosion science theories and hypotheses are excavations should provide valuable information.
formulated and tested. For these purposes corrosion Physical conditions, such as particle size of the soil
conditions in liquids or atmospheres are easier to and factors influencing the water flow around the
work with than soil conditions (which are difficult to object can be expected to influence the corrosion
define and reproduce). This is probably the reason rate. As well, as various chemical factors such as the
for the relatively little work done on soil corrosion chemical composition of the soil constituents, the
science compared to soil corrosion technology. An- pore water composition and the pH levels can also
other reason for this situation is that the need for affect corrosion rates.
knowledge concerning soil corrosion emanates from
technology. Corrosion rates in soils of the magnitude It might be assumed that biological processes can
0. l millimeter per decade or more are considered to also have an important influence on corrosion pro-
be of technical importance and require countermea- cesses in soil. There are at least two kinds of pro-
sures. cesses which seem to have great potential influence.
The first is oxygen-consuming and carbon dioxide-
The technological aims of corrosion research in soil producing fermentation of organic materials. This
can be taken up in one of two fields. The first one can on one hand lower the availability of oxygen so
concerns the construction of a set of reliable criteria that the corrosion processes are slowed. On the
190
other hand carbon dioxide dissolved in water in- The literature describes several cases of bronze
creases the solubility of certain corrosion products. artifacts with banded structures of malachite and
The second kind ofprocesses are caused by sulphur cuprite in the stannic oxide layer. These have been
bacteria of different kinds which promotes transfor- found covering the remaining metal core. The me-
mation of sulphur between the oxidation states -II chanisms of formation of these banded structures
and +VI which may have influence on corrosion does not seem to be completely understood, but the
mechanisms. interpretation of the so called Liesegang type pat-
terns indicate influence of diffusion in the tin hy-
droxide gel (Scott 1985,Robbiola et al 1988).
Bronze corrosion
In soils with high chloride content, copper(I) chlo-
Archaeological bronze objects are attacked to a ride (nantokite) is often formed in the inner parts of
lesser degree by corrosion than iron objects. The the corrosion product layer.
corrosion products usually consist almost entirely of
cuprite, malachite and stannic oxide (Nöggerath Itshould be remembered that archaeological brass
1825, Becquerel 1832, Fink and Polushkin 1936, objects are often referred to as bronze. The corro-
Gettens 1951, Geilmann 1956, Otto 1961, Walker sion of brass objects is similar to that of bronze
1980, Ullrich 1985, Tylecote 1979, Grauer 1980). objects with the main difference being that no tin
Malachite is typically expected to form a protective oxide hydrogel layer can then be formed. There
layer under appropriate conditions. This can also be seems to be very little known regarding details of
true of cuprite. The stannic oxide is amorphous and influence by humic and fulvic acids or other soil
can probably be described as a hydrogel. It should components with high ion exchange capacities on
therefore not be expected to act as a protective corrosion mechanisms.
barrier.
Iron corrosion
The stannic oxide is precipitated within the bound-
aries of the original shape of the object. This often
The details of the corrosion process of iron objects
allows even completely corroded bronze objects to
in soil seem to be more complicated than those of
keep their original shape.
bronze. According to Stambolov (1985), who quotes
many publications, the most commonly found corro-
According to the classical article by Geilmann sion products in soil are magnetite and goethite. The
(Geilmann 1956) bronze artifacts can be completely reason for this is explained by Turgoose (1982), who
corroded in sand with high organic content. They also proposes a model for corrosion of iron in soil.
can even be transformed so extensively that they This model includes the anodic reaction of iron oxi-
become white objects of tin oxide. This shows that dation to ferrous ions and the cathodic reduction of
leaching - or using the pedological term "eluviation" oxygen to hydroxide ions. These two reactions are
- ofsoluble copper compounds from bronze objects, assumed to occur spatially separated by a layer of
is an important factor for the deterioration mecha- "largely magnetite and goethite with perhaps some
nisms of bronze in soil. Low pH from carbonic acid other stable ferrous-compounds". A water solution
and substantial water transport are bound to pro- which may contain high concentrations of ferrous
mote this process. These circumsiances are also ions is assumed to be contained in pores of the
known from the field of corrosion technology. Con- deposited corrosion products. The counter ion is
ditions which lead to dense coatings of corrosion usually chloride. The accumulation of chloride ions
products on copper alloyslead to lowcorrosion rates is explained by the flow of ionic current between
(Linder 1984). Unsuitable pH values ie below pH 7 anodes on the metal surface and cathodes on the
lead to relatively rapid corrosion attacks. surface of the deposited corrosion products. These
are assumed to possess electronic conductivity.
It can therefore be concluded that the most detri-
mental factors for copper alloys in soil seem to be The corrosion model described above is in accor-
those which promote eluviation of inter alia mala- dance with established corrosion theory and seems
chite and cuprite. These processes include lowering to givea reasonable explanation in qualitative terms.
the carbonate activity (eg by lowering the pH) and However, a semiquantitative treatment of the accu-
lowering the copper(Il) ion activity (by reactions mulation of ferrous chloride raises some questions.
such as complexation). Ion exchange with clay Corrosion rates on archaeological iron objects with
minerals can also play a role. chloride enrichments are usually on the order of
191
millimeters per millennium. The corrosion current products and the metal surface. With small pores rn
density for a corrosion rate of 1 mm/millennium can the layer, ion selective properties should be expected
be calculated by considering I cm' of an iron sur- in ferric hydroxide membranes. This has been in-
face. vestigated by N. Sato and co-workers (eg Sakashita
et al 1984). In these studies it was found that ferric
- 1 mm penetration corresponds to O.786155.847 : hydroxide membranes are anion selective below a
0.014moles of iron. pH ofabout lO.This property leads to an electro-os-
motic flowof chloride ions. Sato et al concluded that
- In the corrosion reaction electrons are delivered to these play a significant role in the corrosion of
generate the charge 2x0.014x9650F 2700 As. metals. Perhaps these matters deserve additional
attention in research regarding corrosion in soils.
- Division by the number of seconds in 1000 years,
31536000000,gives as a result that it is equivalent There has so far been limited interest in these
to a current density of 0. 1 pAlcm'. questions among those who work with corrosion
problems in soil. This is in contrast to the great
This is a very low current density. From the above development in similar fields described in modem
we can also calculate the case if all anionic charge literature on surface and soil science (Lindsay 1979,
transfer is accomplish"d by chloride ions. There Stumm 1987). Many examples can be found of fruit-
would then be a flow of: ful approaches to phenomena in soil that also should
be possible to apply on questions regarding corro-
2x0.014/1000 : 28x10" mole sion in soil.
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References
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