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Nick Umney
The reactions for lead may be: (click image for larger version)
Wood and metal are used together for so many purposes that they are usually
regarded as highly compatible materials. However, interactions between certain
metals and woods can take place under adverse conditions, or as a result of using
unsuitable materials. Such interactions can occur through direct contact of metal
fastenings and fittings with wood or indirectly, through the environment when metal
objects are transported, stored, or displayed in wooden containers. This has long
been known but is still sometimes forgotten. Damage to metal objects in the Burrell
Collection was reported during the day on Storage at the UKIC conference,
Restoration '91. This article briefly reviews ways in which wood may contribute to
the corrosion of metal objects.
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The object is a 19th Century bronze statue of Nandi, the Kneeling bull of Shiva.
(Museum no IM 69-1914) (click image for larger version)
Wood can act as a source of water for corrosion processes. Under stable
conditions an equilibrium is reached in which water is distributed between air and
wood in certain definite proportions. The position of equilibrium depends on the
relative humidity and temperature of the surrounding air, and on the wood species.
At 20°C and 55%RH both a cubic metre of air and a 6 cm cube of wood contain
about 10 ml of water. Increasing the temperature causes a reduction in the
moisture content of the timber and an increase in the relative humidity of the
surrounding air.
The approximate moisture content of wood that will produce a relative humidity
of 80% inside a wooden container over a range of temperatures is shown in the
graph below.
2
therefore important that any wood used should have a suitable moisture content
and that steps are taken to minimise temperature variations in service.
Table to show the Approximate Moisture Content of wood required to give 80%
relative humidity inside a wooden box (click image for larger version)
Besides moisture, many woods contain volatile alcohols, esters, and oils that have
a solvent action on some protective coatings applied to metal objects, thereby
making the metal more susceptible to the effects of moisture or other chemicals.
Examination by Farmer1 in 1962 of cadmium plated radio sets that had corrode in
storage showed that corrosion had been caused by the birch wood in their cabinets
rather than by other materials present. Many species of timber can produce small
amount of volatile corrosive substances and this is more pronounced under warm,
damp conditions. These substances include many molecular weight carboxylic
acids particularly acetic and formic acids. The tendency to cause corrosion under
these conditions is not directly related to the acidity of the wood and its pH value is
not a reliable guide to the extent of corrosion that it might cause.
Farmer measured the amount of free acid produced by various woods under
controlled conditions at intervals up to two years. For all timbers examined,
including oak, Douglas fir, Sitka spruce, beech, birch, obeche and Parana pine,
there was a progressive increase in free acid. More than 90% of the acid was
volatile and was identified chemically and chromatographically as acetic acid.
The production of acetic acid is believed to result from a process of slow hydrolysis
of combined acetyl groups present in hemicelluloses. In support of this, the
amounts of acetic acid produced by several timbers are balanced with reasonable
accuracy by the losses of combined acetyl groups.
The rate at which acetic acid is liberated depends on the chemical constitution of
the wood from which it is derived. This varies with species and largely accounts for
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the considerable differences in rates of production of acetic acid between timbers.
The proportion of acetyl groups capable of liberating acetic acid is higher in
hardwoods than in softwoods. In practice, kiln dried wood is much more likely to
cause corrosion than air dried wood.
Most metals are attacked by acetic acid, which can cause corrosion at
concentrations as low as 0.5 ppm in air. Serious damage can occur through long-
term storage, especially in damp conditions. Lead objects can be rapidly destroyed
by being stored in cases made of wood, the lead being converted into lead
carbonate. Zinc and bronze are also affected but not as strongly as lead.
Table showing the measured pH values of some common timbers (click image for
larger version)
4
For some metals, the extent of corrosion is limited by the formation of an oxide or
hydroxide surface layer. In these cases, corrosion may be accelerated by the
presence of acids and certain salts that increase the solubility of the primary
corrosion product. The aqueous extracts of most common woods are acidic and
can act in this way. Acidity in wood results from complex mixtures of organic acids
and their salts. Sugar acids formed by hydrolysis of hemicelluloses are strong acids
and their salts are soluble in water and neutral solutions. When salts are present
that can act as electrolytes, the chemical reactions that cause corrosion are
reinforced by electrochemical reactions and mineralisation is greatly accelerated.
Oak, sweet chestnut, Western red cedar and Douglas fir are the woods most
commonly associated with corrosion of metals in contact with them under damp
conditions. Iron and steel are much more susceptible to the corrosive influence of
wood than aluminium, copper or brass.
Sometimes, corrosion of metals occurs in contact with woods that are not unduly
acidic and this is often due to the presence of common salt. For example, salt can
promote bi-metallic corrosion of nickel plated steel and coppered iron. Cases have
been observed where alkali produced by the corrosion of coppered iron nails
holding canvas to a wooden frame has caused rotting of the canvas. Salt is not a
normal constituent of wood but it can be introduced into wood by logs being floated
to the sea or being exposed to sea spray. Also, in North America, a salt seasoning
process is used for drying certain hardwoods including maple.
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There are also specific reactions that occur between particular timbers and metals.
For example, Western red cedar contains tropolones that react with metallic copper
to form a stable chelate that appears as a green coating on the metal.
Recognition of interactions such as those described has led to the search for more
passive materials for the construction of sealed environments, particularly for
permanent displays. However, the circumstances under which wood and metal can
come together and interact are many and varied, and vigilance is required to
prevent damage. It is hoped that this short paper will help to keep this problem in
focus.
Reference