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Objectives page 83
Introduction page 83
Metal objects in collections page 83
Common metals page 83
The nature of metals page 84
What are the most common types of damage? page 84
Common causes of damage page 86
Handling, storage and display guidelines page 86
Metals in Australia’s climatic zones page 88
Care of particular metals page 89
Silver page 90
Nickel silver page 92
Copper and copper alloys page 92
Iron and its alloys page 95
Plated iron page 99
Lead and pewter page 99
Tin and its alloys page 100
Aluminium page 100
Gold page 101
MORE ABOUT METALS
Alloys page 102
Corrosion of metals page 102
Electroplate page 104
Zinc carbonate blotter page 105
Brasses page 105
Bronzes page 105
Iron and steel page 107
Bentonite paste page 107
Chloride ions and aluminium and its alloys page 107
Spot-tests page 108
For further reading page 109
Self-evaluation quiz page 110
Answers to self-evaluation quiz page 111
Objectives Metal objects in collections
At the end of this chapter you should: An enormous range of objects in collections are
either made of metal or have metal components.
• have a basic knowledge of the nature of Among them are:
metals;
• weaponry; • sculpture;
• have a basic understanding of what causes
metals to corrode; • clocks and watches; • jugs;
• be able to take steps to minimise the • metal thread; • armour;
corrosion of metals in your collections;
• signs; • coins;
• be able to determine whether corrosion is
active or passive; • plates; • cutlery;
• be aware of when and where not to apply • buttons; • teapots;
chemical treatments to metals;
• pots and pans; • tools;
• know the correct treatments for particular
types of metal; and • zips, hooks and eyes; • aeroplanes;
Metals have been used—either in pure form or • military machinery; • rigging for boats;
combined with other metals—to produce an
enormous variety of objects, including weapons, • screws and bolts; • coatings on CDs; and
tools, machinery, decorative art objects and
• fittings on saddles.
jewellery. Because of the huge range of uses for
metals, objects containing metal, or fully made
from metals, are all around us. They make up a
large part of many collections housed in museums, Common metals
galleries and even some libraries.
The metal objects in your collections will be made
But despite their apparent solidity, metals do from a range of different metals, including:
corrode and can be vulnerable to physical damage.
It is important that those responsible for the care • cast iron; • pewter;
of metal and metal-containing objects are able to
recognise problems when they see them, and take • wrought iron; • lead;
steps to halt them.
• bronze; • tin;
• brass; • aluminium;
Metals 83
• Britannia metal; • galvanised iron; • exposure to the elements; and
• Sheffield plate; • stainless steel; • deliberate steps taken to produce this effect.
For example, sculptors often apply chemicals
• steel; • zinc; and to the surface of a work, to produce a certain
visual effect with the corrosion products.
• electroplated nickel silver.
Before any decision is made to remove this layer of
corrosion products from an object, the nature of
The nature of metals the object and its history must be considered very
carefully. For instance, under no circumstances
should the patina be removed from an ancient
The atoms which make up metals are bonded in a bronze sculpture, whereas a Victorian-era silver
way that is peculiar to metals. A metal becomes a candelabra would have been highly polished and
solid at a certain temperature; and the atoms of so should be cleaned of accumulated tarnish.
the metal settle into a characteristic, well ordered
configuration. In this configuration the atoms are
fixed rigidly in relation to each other. The
configuration is called a crystal lattice or a crystal.
• mechanical strength.
What are the most common
Alloys types of damage?
For centuries, the properties of metals—such as Metals are vulnerable to physical damage and to
their appearance, strength, malleability and chemical deterioration.
chemical reactivity—have been altered by
combining them. These combinations are called Physical damage includes:
alloys. For example, iron combined with carbon
produces alloys such as cast iron and steel; • dents;
whereas the alloying of chromium and nickel with
iron forms stainless steel. • wear of machine parts through repeated
operation;
Similarly, copper can be combined with zinc, to
• wear of metal surfaces through excess
form brass; and with tin, to form bronze.
polishing; and
84 Metals
Chemical deterioration in metals is called corrosion. Because of this, metal objects need to be
Physical damage to metal objects can leave them protected from environmental conditions and
vulnerable to corrosion. For example, a scratch in pollutants which encourage corrosion.
tin plate leads to corrosion of the base metal.
In some cases—as the metal corrodes—the oxide
Corrosion film that forms acts as an insulating barrier, which
slows the rate of corrosion to an acceptable level.
Copper and aluminium are two metals in which
The tarnishing or corrosion of metals will be your oxide coatings form protective layers—called
major problem if you are responsible for the care passivating layers. When iron corrodes, however, it
of metal items. does not usually form a protective film. Iron
continues to corrode until no metal is left, unless
some other protective coating is applied to protect
it from the elements.
Causes of corrosion
Bullets showing copper and lead alloy corrosion Moisture and oxygen are required for metals to
products. corrode.
Photograph courtesy of the Western Australian Museum
Chloride ions, which are found in common salt—
sodium chloride—can speed up the corrosion rate,
and are also capable of penetrating protective
oxide layers.
Metals 85
Corrosion also occurs if dissimilar alloys and • chemical interaction between the metals and
metals come into contact with each other. This other materials, including other metals; or
type of corrosion is called galvanic corrosion.
• a combination of any of the above factors.
Under these circumstances, the more reactive
metal or alloy corrodes while the less reactive The following sections outline general storage and
metal is protected. For example, if iron and copper display principles for metals, as well as giving
were in direct physical contact in the presence of details of the problems, care and treatment of
moisture and oxygen, then the iron would specific metals.
selectively corrode while simultaneously protecting
the copper.
Handling, storage and
This problem can be overcome by avoiding direct
contact between dissimilar metals. This will not be display guidelines
simple if the metals are components of the same
object. When you are handling metal objects, particularly
ones with polished surfaces, always wear clean
The oxide film which forms on particular metals cotton gloves or surgical gloves. This prevents the
acts as an insulating barrier or passivating layer transfer of sweat and fats from the skin to the
barrier, slowing the rate of corrosion to an metal object, and helps reduce the risk of
acceptable level. This type of passivation occurs corrosion.
with copper and aluminium.
Always give your objects adequate support, and
When looking at the way in which artefacts have remember that metals can weaken over time.
corroded and when deciding on management
strategies, it is important to ask these basic Don’t lift metal objects by their handles. The joint
questions: is it necessary to treat an object? or between the handle and the object could be weak.
can the causes of deterioration be controlled?
When displaying a hinged object open, take care
For more information to support it—so that the hinges are not carrying
For more information on the effects the weight of a part or all of the object.
of humidity, dust and pollutants,
please refer to Damage and Decay. Because some of the major contributors to the
deterioration of metals are oxygen, water and air-
borne pollutants, it is important to provide an
For more information on how chloride ions, environment which offers protection against these
fats, oils and sweat can speed up corrosion, factors. This action can prolong the life of your
and on the effects of acids and sulphide metal objects.
pollutants, please see the section
More About Metals, later in this chapter. Simple steps can greatly improve the longevity of
objects. Steps such as:
86 Metals
If you have no choice about the type of shelving Guidelines for outdoor objects
and you must use wooden shelves, we recommend
you take the following steps:
If you are trying to prevent corrosion in an
• coat wood with an epoxy or polyurethane outdoor object:
finish to seal the wood;
• bring the piece inside, or build a roof over it,
• paint chipboard with a solution of 400g of if it is appropriate and possible. In most
urea in 1 litre of water; and cases this won’t be possible;
• allow time for proper drying and curing. • look for areas where water can pool, and
improve the drainage in these areas or remove
water after rain;
Do not seal objects in plastic bags, because the
bags seal in moisture as well. This raises the • don’t allow objects to sit directly on grass—
relative humidity inside the bag, providing a raise them on a plinth;
microclimate which is favourable to corrosion.
• don’t allow the object to sit in water;
CAUTION:
• don’t water the object when you are watering
Avoid polyvinyl chloride—PVC—bags.
the garden—unlike the plants, it won’t grow;
They can give off hydrogen chloride, an acidic and
gas which will corrode most metals.
• clean off bird excrement immediately—it is
If you want to use plastic bags for storage, make corrosive and will quickly etch the surface.
sure you select polyethylene bags, and punch holes
in the bag.
Metals 87
Metals in Australia’s climatic zones
When considering the conservation needs of metals, the environmental conditions associated with the
various climatic regions as well as those of the coastal areas must be taken into account. The moisture, salt
and pollutant levels of the storage environment will have the greatest impact on the rates of corrosion, of
metals. Metals corrode less in dry zones than in areas that have higher average relative humidity.
Metal objects housed in coastal regions are at great risk of corrosion, if steps are not taken to minimise the
impact of salt-laden air.
Arid
This climate is generally very dry, however, in arid areas, it is often very hot during the day and very
cold at night. This wide fluctuation in temperature is matched by wide fluctuations in relative humidity,
for example from 75%–20% in a day.
Steps that can be taken include:
• storing metals in cabinets, boxes and wrappers to buffer the objects against short-term upward
swings in relative humidity. Protection against dust is also achieved in this way.
• using insulation and sensible house-keeping practices which minimise the differences between
internal day and evening temperatures. The corresponding fluctuations in relative humidity should be
minimised.
Note: If your collections of metal objects have been stored in an arid environment for a considerable
period and they are stable—do not try to alter the environment to meet the recommended ideal
conditions. This could do more harm than good. The emphasis should be on long term stability.
Temperate
A temperate climate is considered a moderate climate, however, temperate climates tend to have a
greater range of temperatures than tropical climates and may include extreme climatic variations.
Steps must still be taken to overcome the extreme climatic variations which occur in these areas.
High relative humidity conditions can be counteracted by:
• displaying metal objects in sealed cabinets to overcome short term variations in relative humidity
and temperature;
• store metal objects in cupboards, boxes and wrappers to buffer against variations in external
conditions; and
• protect metals by coating them with water repellents such as CRC, WD-40 or waxes. Consult a
conservator before doing this.
Note: If your collections of metal objects have been stored in a temperate environment for a
considerable period and they are stable—do not try to alter the environment to meet the recommended
ideal conditions. This could do more harm than good. The emphasis should be on long term stability.
88 Metals
Tropical
These climates are characterised by heavy rainfall, high humidity and high temperatures.
To counteract the problems associated with high relative humidity and generally high temperatures that
characterise these regions the following strategies can be adopted:
• place sensitive metals in well-sealed cabinets and maintain the relative humidity at a level below
45%;
• use cabinets, boxes and layers of acid free tissue to create buffer zones which will reduce the impact
of high relative humidity and temperature on metals;
• use portable dehumidification units during periods of high relative humidity; and
• inspect metal objects regularly and maintain high standards of cleanliness.
Note: If your collections of metal objects have been stored in a tropical environment for a considerable
period and they are stable—do not try to alter the environment to meet the recommended ideal
conditions. This could do more harm that good. The emphasis should be on long term stability.
Coastal Regions
Coastal regions generally have more moderate climates than inland areas but they also have high levels
of wind-borne salt. Consideration must be given to counteracting the corrosive effects of salty air.
Steps which can be taken include:
• storing and displaying metals in sealed cabinets to buffer against environmental changes and to
exclude dust and salty air; and
• putting multi-metal vapour phase inhibitors, such as Senson, in sealed storage and display areas.
• sealing buildings to minimise air exchange with the external, salt-rich air, by keeping doors and
windows closed, eliminating drafts and using airlock doors.
• maintain relative humidity below 45% in storage and display areas.
• treat metals with moisture agents—waxes are recommend—and corrosion inhibitors.
Care of particular metals methods for cleaning the metals are quite
straightforward, others involve the measuring,
mixing and application of reactive chemicals. It is
In this section, information is given about a range strongly recommended that:
of metals. The information includes:
• you contact a conservator and discuss the
• a description of the metal and its alloys risks involved in treating metal objects before
where applicable; you proceed;
• the signs and main agents of corrosion of • you do not treat an object unless you feel
that metal and its alloys; confident about carrying out the treatment;
• methods of cleaning the metal; • you do not treat an item if you are unsure
about the type of metal with which you are
• storage and display methods for each metal; and dealing. A conservator can help you with this.
It is also possible to carry out spot-tests to
• protective coatings that can be applied to identify your metals;
objects made from that particular metal.
• if possible, you practise the treatment on
It is important to note that, while some of the another piece of the same metal; and
Metals 89
• you attend a training workshop on the Silver
treatment of metals before attempting some
of the more complex treatments.
Silver’s lustrous appearance and relatively low natural
For more information abundance, its corrosion resistance and ability to be
Spot-tests to identify metals are described in the easily worked have made it a prized metal. Silver is
often used for coins, jewellery and cutlery.
section More About Metals later in this chapter.
Most silver items found in Australia will be either
It is extremely important that you are aware that
sterling silver or plated silver.
some of the chemicals used in these treatments
can also affect you.
Sterling silver
CAUTION:
Thiourea is poisonous, is a suspected carcinogen Sterling silver is the standard alloy used in
and causes goitre. jewellery and cutlery. It is made up of 92.5% silver
and 7.5% copper. The addition of copper to silver
Acetone can cause headaches, depression, nausea
increases hardness of the alloy, without any
and dizziness when inhaled. significant loss of lustre or colour.
Industrial methylated spirits—IMS—is a mixture
of ethanol and methanol and should be used with Plated silver
care. Ethanol can cause headaches, dizziness and
nausea, and methanol is toxic and can cause The two common forms of plated silver are
blindness. Sheffield plate and silver plate/electroplate.
Ammonia can cause severe irritation to the skin and
eyes, breathing difficulties, nausea and vomiting. Sheffield plate is made by fusion-bonding—
Disodium ethylenediamine tetraacetic acid sweating sterling silver to both sides of a copper
EDTA—can be mildly toxic, and can affect unborn or brass sheet; it is then worked to produce the
desired object.
babies.
Citric acid is moderately toxic and irritating. Silver plate or electroplate is formed when a thin
Petroleum spirit is flammable; it removes fats layer of pure or sterling silver is deposited
from the skin, and should be used with care. electrolytically on the surface of a base metal.
Sodium carbonate can cause skin irritation and Common base metals include copper, brass, nickel
ulcers. If it is swallowed, it causes nausea, silver—an alloy of copper, zinc and nickel—and
Britannia metal—a tin alloy with 5–10% antimony.
vomiting and diarrhoea.
If it touches skin, sodium hydroxide causes deep Electroplated materials are often stamped EPNS for
skin burns. If inhaled, it irritates the respiratory electroplated nickel or silver, or EPBM for
tract. If ingested, it can cause burning pain, electroplated Britannia metal.
diarrhoea swelling of the larynx and suffocation.
Silica gel in its granulated form can cause silicosis. As commercial electroplating was developed in the
1840s, it is likely that a lot of the materials in the
collections of local museums in Australia will be
Protect yourself when working with these
made of silver plate.
chemicals—wear gloves and masks. If you buy
any chemicals to mix up your own cleaning For more information
solutions, ask for safety data sheets as well, and For more information on electroplating, please
make sure that you store the chemicals safely. see More About Metals later in this chapter.
You must also remember to take care when Signs of corrosion on silver
disposing of these chemicals—some of them
cannot be flushed down the sink. Silver artefacts tarnish if they are not kept
polished. The silver surface changes through a
90 Metals
faint purplish hue to a deep black. The tarnish is a Then rinse the object in hot water to remove
layer of silver sulphide. residues, and dry it with a lint-free cloth. After
drying, a final polish with a silver cloth will put a
Artefacts excavated from underground or from the thin layer of corrosion inhibitors on the surface of
sea may be coated with grey silver chloride and the silver.
copper corrosion products. If these materials have
been exposed to sunlight, the surface will have a If Sheffield plate is in reasonable condition, it
purplish tinge. needs no further treatment other than being wiped
with a silver cloth and displayed or stored under
Cleaning silver conditions of low relative humidity and away from
wool.
Clean silver only when absolutely necessary, and Although there are commercially available
not as a routine treatment. This is because any solutions which gradually redeposit small amounts
cleaning removes minute amounts of silver. of silver on worn areas, these should be used only
after considering the history and function of the
Take great care to differentiate between tarnish object.
and decorative treatments which are an inherent
part of the object and which would be destroyed On no account should the object be replated. This
by cleaning. For example, a decorative treatment completely devalues the object by removing the
which should not be removed is niello, a black technological evidence of its manufacture.
silver sulphide/silver copper sulphide that is used
deliberately to highlight engraved sections of Electroplated or silver plated objects which are in
silver jewellery. good condition, but on which the silver has been
worn away to reveal underlying metal, can be
Avoid abrasive cleaners. They can cause fine restored by using a solution such as the one
scratching of the surface and remove small described above. This is a better way to rejuvenate
amounts of silver. the surface than the standard electroplating, which
is a lot more costly and not always successful.
There are a number of proprietary brands of silver
dip solutions available, which readily remove If the piece is in good condition, then it is better
tarnish. These are usually made up of thiourea and to maintain it in that condition, rather than
acid mixtures. Silver dips should be used only continually cleaning it and wearing down the silver
when the object is badly tarnished. coating. Wiping with a silver cloth, followed by
storage and display under conditions of low
If you decide to use a silver dip, apply the relative humidity and low pollution levels is the
solution, or dip the object, only for as long as it simplest method of protection.
takes to remove the tarnish.
Despite the best storage, display and care
methods, all electroplated silver will eventually
show pin-pricks of corrosion as the plating wears
thin. Once the plating has been perforated, the
underlying metal is prone to pitting corrosion; and
the surface will gradually become covered with
blotchy, black and green-blue areas of corrosion.
Metals 91
Simple care techniques don’t have much effect on For more information
this type of problem. It needs more complex
treatment. For more information on making a zinc
carbonate blotter, please see
• Immerse the object in a solution of 10g of More About Metals later in this chapter.
thiourea and 50g of citric acid in 1 litre of
water. This treatment will clean the object and
remove the silver corrosion products.
Nickel silver
• After cleaning, the object must be placed in a
diluted bath of sodium carbonate, 1% by
Most 19th and 20th century nickel silver objects
weight in water, and left to soak for an hour or
so to remove any citric acid from beneath the will be found either as the unchanged copper-nickel-
electroplate—to make sure that no further zinc alloy, or with a thin film of electro-deposited
corrosion occurs. Follow this with a final wash silver on the surface.
in fresh, deionised or distilled water.
An easy way to identify nickel—as nickel plating
• If the corrosion damage is not too severe, then or its presence in an alloy—is to look for the
the underlying metal can be re-touched using bright, lemon-green corrosion products which
one of the silver solutions which redeposit characterise nickel (II) compounds.
small amounts of silver on worn areas. Finally,
polish the object with a silver cloth. Australian coins minted before the introduction of
decimal currency in 1966 contain significant
CAUTION: amounts of silver. To remove tarnish from the
Check your chemical safety data sheets, and take imperial pre-1966 coins, follow the procedures for
the appropriate precautions. silver outlined above.
92 Metals
CAUTION: For more information
Spelter bronzes which were popular from the 1850s For more information on the treatment of
to the early 1900s are not bronze at all, but a bronze disease, please see More About Metals
white, zinc-based metal to which various coatings later in this chapter.
have been applied, to give the effect of patinated
bronze. Any attempt to chemically clean these What causes the corrosion of copper?
objects renders them worthless.
Constant high humidity, pollutants such as
Corrosion of copper sulphide gases, acids and careless handling causing
physical damage can all cause deterioration of
copper-based objects. In addition, heating and
The types of corrosion products formed on copper
acidic cleaning solutions can etch the zinc out of
and its alloys depend on the environment and the
brasses—leaving a copper-red discolouration on
metal’s composition.
the surface.
The most common corrosion products are copper
Copper and copper alloys which have been buried
oxides, basic copper sulphates and basic copper
or recovered from a wet site can suffer from the
carbonates. These are generally stable, and protect
effects of chloride salts, resulting in the
the underlying metal from further corrosion.
development of bronze disease.
The corrosion products are sometimes produced
Objects may also have special surface coatings,
artificially—to give the attractive green-brown
such as lacquers, which can be damaged easily by
patina seen on outdoor bronze statues.
scratching or improper cleaning.
The passivating layers of copper corrosion products
tend to break down in the presence of chlorides. Cleaning copper and copper alloys
Whether the chlorides are derived from the sea or
from ground water, the overall impact—accelerated Items which are in good condition need only be
corrosion—is the same. wiped with a dry cloth.
In a humid environment, the presence of chlorides Alcohol, preferably ethanol, may be used to
in copper alloys can cause the development of the remove greasy stains, but only after spot-testing
cyclic corrosion phenomenon known as bronze to ensure there are no surface coatings that will be
disease. This type of corrosion is characterised by affected by this solvent.
the presence of a light blue-green, crumbly
outgrowth on the surface. If this is brushed away, If a badly tarnished copper alloy must be cleaned,
a pit will be evident on the surface. To determine immerse it in a solution of 10g of thiourea and
whether an object is affected by bronze disease, 50g of citric acid in 1 litre of distilled water. This
consult a conservator. treatment will clean the object and remove the
corrosion products.
It is important to note the difference between
bronze disease and a natural patina. Many bronzes The thiourea is an inhibitor which prevents any
are formulated specifically to obtain a certain chemical attack on the metal itself. If thiourea is
coloured patina. If you are not sure, consult a not used in the treatment solution, dissolved
conservator before attempting any treatment. This copper will be redeposited on the surface of the
is particularly important for Japanese and Chinese object, leaving a salmon-pink blush on the surface.
bronzes, and for bronzes from the Renaissance This then has to be removed by polishing.
period onwards, as the patinas of these objects are
intrinsic to the objects and should not be Leave the object in the solution until it is clean.
removed. This can take from several minutes to several
hours, depending on the condition of the object.
Metals 93
You can speed up the treatment by brushing the wash-water should be checked. The pH should be
surface, under running water, with a soft bristle very close to 7, that is, close to neutral.
brush, for example, toothbrush or soft Nylon,
bristle brush. If necessary, a fine pumice powder After washing, and before applying any protective
can be used as a mild abrasive. coating, it is essential to make sure that the
surface is free from grease and water. Any such
If this solution is not effective in removing contamination will show up later as corrosion
tarnish, then the amounts of citric acid and areas.
thiourea used in solution can be increased to up
to twice the strength. Wear rubber gloves when cleaning and coating the
artefacts.
The object must then be thoroughly washed to
remove all traces of acid. This can be done under If oven-drying at 100°C is not appropriate, the
running water, or by immersion in baths of clean object can be dried by painting it liberally with
water. acetone. The acetone drives out water in crevices
and cracks, ensuring that the metal is fully dry.
If the object has been soaking for a considerable
time or is porous, immerse it in a weak sodium The metal is considered dry when there is no
carbonate bath—5g in 1 litre of water—in order longer any smell of acetone.
to neutralise any remaining acid.
It is not appropriate to use acetone on composite
To ensure that washing has been effective, the pH materials or painted surfaces. To dry composite
of the surface of the metal object and that of the objects and painted objects, use a hair drier on a
cold setting.
CAUTION:
Check your chemical safety data sheets and
take the appropriate precautions.
94 Metals
of bronze and copper. Incralac is a commercially Treatment of iron objects
available lacquer which is available in a spray can
or as a brush-on paint. This product can be
Its future role, as either an object on display or in
removed with acetone.
storage, will have a major impact on the treatment
method.
For more information
For a recipe and for information on the To display an object in its working order, it may be
application of microcrystalline-polyethylene wax, that nothing needs to be done other than keeping
please see More About Metals, it in a dry environment or coating it with an
later in this chapter. appropriate protective layer.
Metals 95
coatings. You need approval from local
authorities to sandblast because of the
associated dust problem. An alternative form
of sandblasting, wet sandblasting, uses a
suspension of sand in water combined with a
corrosion inhibitor. This method causes less
pollution, and is more acceptable to local
authorities. Sandblasting should be carried
out by commercial operators, with
conservators close at hand to provide any
necessary advice; and
96 Metals
For more information Subsequent applications further darken the object.
For more information about silica gel,
This coating system results in the formation by
please see the chapter on Humidity and chemical reaction of stable iron tannates, which
Temperature in Damage and Decay. passivate the metal and protect it from further
corrosion.
Large steel objects
Fish oil/white spirit mixture
When treating large objects, it can be difficult to
A mixture of 80 parts white spirit to 20 parts fish
find containers or tubs large enough to immerse
oil can be applied very effectively to freshly
the objects for caustic or citric treatments. If
cleaned iron objects. Thinning the mixture with
sandblasting is inappropriate, the acid or alkaline
white spirit allows it to soak into the steel. It
stripping solution can be applied to the surface by
usually dries within minutes. Several coats can be
using a bentonite paste.
applied and, when dry, it can be painted if
required. This mixture does not change the metal
For more information
colour, and gives good protection. It does not
For more information about the preparation involve chemical reaction with the metal.
and use of bentonite paste, please see
More About Metals later in this chapter. Oil quenching
Finishing techniques for iron objects Blueing is a method applied to many types of
firearms, especially to their barrels, to produce a
lustrous, dark blue finish. Although this is usually
There are many varied methods available to give
done by commercial gunsmiths, a blueing paste is
the object the right colour and protective coating.
available commercially, and can be applied easily.
The type of finish chosen depends on the intended
role of the finished object, with the final decision
After treatment, take care when you’re handling
being a balance between ethical, aesthetic,
the treated object, because acids from hands
practical and personal considerations. The most
readily etch these surfaces.
commonly used techniques are described below.
Paint
Tannic acid
There are numerous enamel and water-based
Rust converters are commercial products which can
paints, which protect and beautify metal surfaces.
be applied to an object which has been cleaned
A range of primers, undercoats and topcoats are
chemically or mechanically, or to one which still has
available. If these are applied correctly to properly
light rusting present on its surface. A rust converter
prepared and cleaned surfaces, adequate protection
will form a thin, black layer on the surface.
should be maintained for many years.
Metals 97
Inorganic zinc primer Natural patina
For iron objects that are displayed outdoors— If an iron object is in a stable condition, with only
particularly in an aggressive, marine a lightly rusted surface, it may be that this is the
environment—an inorganic zinc primer, a high- type of finish you require to demonstrate the
build expoxy top coat and a final clear history and past use of the object. Such finishes
polyurethane coating—with a UV absorbing can be maintained if the storage and/or display
reagent provide good protection. conditions are controlled to prevent further
deterioration.
Lacquer
Storing and displaying iron
Clear lacquers are available in spray cans, or can and iron alloys
be applied by brush. The desired surface finish and
colour must be obtained on the iron before you
apply the lacquer. Follow the manufacturer’s Although the general handling, storage and display
instructions on the product. This finish gives a guidelines apply to iron and its alloys, a few
lasting protection against oxide build-up, provided additional points need to be made.
the entire object is coated. If air or moisture
penetrates this layer, it will lift and the corrosion Once an object has been treated and coated,
will begin again. correct storage or display conditions and careful
monitoring should ensure its stability.
Microcrystalline wax
Large objects such as machinery and horse-drawn
Microcrystalline wax provides both good protection and motor vehicles should be housed, if not in
and finish to an object. The object is immersed in controlled environments, at least with some
a hot liquid-wax solution for up to several hours, protection from the elements. This protection can
depending on the size of the object. It is then be in the form of a shed, a verandah or even a
withdrawn and allowed to cool. Excess wax can be lean-to. Unless some protection is provided,
scraped or wiped off. The wax can also be mixed moisture and dust accumulation will soon restart
with white spirit and applied with a brush or rag. deterioration processes.
This latter method is not as effective as immersion
in the molten wax. If an object is displayed in the open, it should be:
98 Metals
Plated iron replaced in the 19th century with antimony and
some copper. Modern leadless pewters are usually
alloyed tin and Britannia metal.
Iron may be plated with zinc, as in galvanised iron
or tin, copper, chromium or nickel. These coatings Corrosion of lead and pewter
protect the base iron sheet from corroding, and
also provide a bright surface finish.
The main corrosion product on lead and pewter is
Corrosion of plated iron white-grey basic lead carbonate. This provides a
deep, protective patina to the metal surface, which
should not be removed.
Corrosion usually occurs after the breakdown of the
surface plate. This exposes the iron, which then If the pewter and lead have been in a low-oxygen
starts to rust. environment and exposed to sulphide compounds,
a rich, lustrous, grey-black patina of metal
Treatment of plated iron sulphides remains on the surface. These minerals
are stable and should also not be removed.
To remove the rust, a citric acid solution containing
an inhibitor can be used. The inhibitor is included Lead and pewter are particularly susceptible to
to prevent any attack on the plating metal. attack by acids given out by wood. Acetic acid
combines with lead and pewter to form lead
The solution is 10g of thiourea and 50g of citric acetates.
acid in 1 litre of water. Thiourea is the inhibitor.
Both tin and lead are very soft and are susceptible
Test the solution on an inconspicuous area of the to denting and scratching.
object, or on a scrap piece of the same material,
before proceeding with the treatment. Cleaning lead and pewter
Metals 99
fresh water, wipe it with methylated spirits, and Typical examples are:
polish it with a soft cloth.
• Britannia metal which is 93% tin, 5%
A protective surface coating of microcrystalline antimony, 2% copper. It was developed in
wax may be applied after cleaning. England during the mid-1700s in response to
the threat to the pewter utensil industry from
cheap porcelain. Old pewter was dull and,
For more information because of its lead content, was undesirable
For a recipe and for information on the as a food container. Although the new alloy
was brighter and stronger, it eventually lost
application of microcrystalline-polyethylene favour as a metal for the production of
wax, please see More About Metals, household utensils; and
later in this chapter.
• leadless pewter which is alloyed tin.
CAUTION:
Corrosion of tin
Check your chemical safety data sheets,
and take the appropriate precautions.
Although it is normally quite stable, tin reacts
slowly with the atmosphere to form grey, stannous
Storing and displaying lead and pewter oxide and finally stable, white to grey-black
stannic oxide.
Lead and pewter are prone to attack from acetic
acid and other organic acid vapours, which are Many museum objects made of tin or its alloys are
found in poor-quality papers and some fabrics, and covered with a dull, grey coating of corrosion
given off by various woods. products. These form a protective patina. Unless
very pronounced or unsightly, this patina should
Storing lead-based objects in cupboards containing be retained.
these materials contributes significantly to the
deterioration. This type of degradation usually Cleaning tin
shows up when white, powdery crystals form on
these materials. Although tin objects are quite strong, careless
handling will still damage their surfaces.
Because lead and pewter objects are particularly
susceptible to attack by acids emanating from If an object must be cleaned, a pure soap in warm
certain woods, it is very important to store and water can be used to remove dirt and grime. This
display them in enamelled metal cupboards. should be followed by rinsing it with fresh water,
wiping it with methylated spirits and then
The general handling, storage and display polishing it with a soft cloth.
guidelines previously described earlier in this
chapter should be followed. Ask the advice of a conservator before treating
badly deteriorated objects.
100 Metals
Deterioration of aluminium ammonia and ammonium sulphate. This is a long
term treatment which is best left to conservators.
A corroded sea plane float, for instance, was only
stabilised after soaking for a period of 12 months.
Metals 101
Treatment of gold alloying with other metals to produce a wide range
of materials with tailor-made properties.
Because gold is very resistant to corrosion, it
usually requires only polishing with a soft cloth. Alloying changes the corrosion resistance of the
No coating is required on pure gold; but if it is parent metal. Properties such as mechanical
alloyed with copper or silver, a clear acrylic or hardness and melting point also alter dramatically
nitrocellulose lacquer gives protection against with alloying. The microstructure of alloys and
retarnishing. metals is dependent on the rate at which they are
cooled. This subsequently affects the rate of
corrosion.
102 Metals
• an oxidation reaction; and
Mn++ ne- M
• a reduction reaction.
where ‘n’ represents the number of electrons needed
To explain these reactions, it is necessary to give a
simple overview of the structure of atoms. Atoms These electrolytic reactions are used to produce
are made up of a nucleus which contains neutral solid metals from their ionic solutions. The
particles called neutrons and positively charged negative ions can be supplied by a range of
particles called protons. Electrons, which are materials. For example, if the metal object is in a
negatively charged particles, orbit around the seaside location, chloride ions—Cl-—will combine
nucleus of the atom. The number and activity of readily with the metal ions.
the electrons will determine how readily the atoms
will react with other atoms. Many metals, because They will also combine with:
of the way their molecules are structured, can
readily lose electrons. When they do this, they are • sulphides—SO3-—sulphates—SO42—nitrates—
no longer atoms. They are positively charged and NO32-—from atmospheric pollutants; and
are called ions. Because of the charge, ions are not
• oxygen.
stable and combine readily to achieve a stable,
electrically neutral state.
If the metal combines with oxygen, it forms a
metal oxide on the surface of the metal. If this
An oxidation reaction is one in which an atom
metal oxide is continuous, then the overall
loses electrons. This can be represented very
corrosion rate of the underlying metal will slow
simply by the equation:
down and it will become passivated or protected.
where ‘n’ represents the number of electrons lost Corrosion cells are small areas on metal objects
where electrical differences are set up. Electrons
flow between the charged areas, just as an
For example, copper—Cu—can be put into this
electrical current flows between the positively and
equation. In an oxidation reaction:
negatively charged electrodes of a battery.
• Cu Cu+ + e-
A corrosion cell is an electrochemical cell which
acts very much like a battery. The corrosion of
It can be oxidised further:
metals consists of two separate reactions:
• Cu+ Cu2+ + 2e- • oxidation. The oxidation reactions are called
anodic reactions; and
Copper is described as polyvalent, that is, it has
different combining powers: a Cu+ ion needs one • reduction. The reduction reactions are called
negative ion to achieve a stable state, while a Cu2+ cathodic reactions.
ion needs two negative ions to form neutral
compounds. Once these ions combine with other In an electrochemical cell the anodic, oxidation,
substances, they produce cuprous and cupric half of the cell produces electrons as the metal is
compounds respectively. For example, Cu2O is oxidised, while at the cathodic half of the cell,
cuprous oxide or copper (I) oxide and CuO is cupric reduction occurs. The electrons are taken and held
oxide or copper (II) oxide. by the oxidising agent, which in aerated
environments is oxygen.
Iron and zinc are other examples of polyvalent
metals. In a corrosion cell, these reactions can continue in
a cycle. The localised corrosion activity causes
In reduction reactions, atoms gain electrons. pitting in the metal.
A simple representation of this would be:
The rate at which the electrons move out of the
metal and across into the oxygen molecules is the
principal factor controlling the overall corrosion rate.
Metals 103
Fats, oils and sweat • hydrogen sulphide—H2S—from the anaerobic
decay of plant material; and
Organic acids—formed by the oxidation of oils and • carbonyl sulphide—COS—from the
fats—are capable of attacking metals which rely degradation of sulphur-containing proteins,
on a protective oxide coating to produce a good such as those found in wool.
corrosion resistance. To prevent this type of
damage, avoid direct contact between the object Base metals such as zinc and tin are also
and the source of the organic material. Some significantly affected by sulphide pollution and/or
examples of this type of damage are leather contamination. Small concentrations of sulphur
objects with copper fittings. The gradual compounds in damp, oxygenated conditions cause
deterioration of old candle wax in leather- corrosion. The resulting metal sulphides can often
lubricating oils leads to organic acids penetrating form a protective patina, as in the case of tin
the protective copper oxide film, and reacting with sulphides which protect pewter objects.
the underlying metal—to form outgrowths of
bright green organic copper compounds. Adsorption of the sulphur-containing species is an
essential step in the overall corrosion process and
Human sweat on metal objects causes corrosion. any factor which inhibits adsorption helps
Bacterial reactions with sweat can produce minimise attack on the metal. Therefore,
sulphides as metabolic by-products, and convert adsorption of organic materials, such as vapour
inherently inert sulphate ions into reactive phase corrosion inhibitors, greatly decreases the
sulphide ions. corrosion rate.
104 Metals
Source of electricity Brasses
The addition of varying amounts of zinc—Zn—to
copper—Cu—produces a wide range of industrial
brasses of differing physical and mechanical
properties. These include:
Metals 105
Bronze disease sodium carbonate and 10g of sodium bicarbonate
in 1 litre of distilled or deionised water.
Bronze disease is the name given to the type of
A first wash of two to four months, followed by a
corrosion of copper and its alloys in which light
second wash of four to six months in the solution
blue/green, pustular outgrowths form on the
is normally sufficient.
surface. It is due to the breakdown—by chloride
ions—of the passivating layers of corrosion
If the object originally had a bright metal surface,
products which normally protect the surface of
this treatment will produce a green-brown patina
these metals.
which is attractive and stable.
The surface deposits tend to crumble and fall away
If a clean, metal surface is desired, the patina can
when touched. As this loose debris is removed
be removed after treatment—using the citric acid
from the surface, a pitted surface is exposed
stripping process or by polishing.
directly under the corrosion mound.
This method is effective for all cases of bronze
Increased temperatures enhance this form of
disease, but the time required varies greatly from
corrosion. A detailed description of the fundamental
object to object.
processes involved in the bronze disease cycle is
given in an article by MacLeod, 1981.
Remove any protective coating on the object
before treatment.
This type of corrosion problem is most commonly
found with bronzes—hence the name—less
This treatment should be carried out by a conservator,
frequently in brasses, and occurs least frequently
or in close consultation with a conservator.
with copper itself.
After removing the chlorides, apply a finishing
Because of the relatively high background levels of
treatment. Wax impregnation, a coating with
chloride ions in much of the soil in arid Australia,
benzotriazole or a coating with Incralac are
the problems of bronze disease are encountered in
commonly used.
objects that have been recovered from land sites,
as well as those from a marine environment or
Benzotriazole is one of a number of corrosion
coastal areas.
inhibitors for copper and its alloys. The reaction
mechanisms are complex, but the primary
The corrosion problems are much worse when the
protection is due to the formation of a very stable
materials are stored in high humidities. Under
complex with copper, which protects the metal
these conditions, a series of little dots and
from further corrosion. Benzotriazole displaces
pustules will break out over the surface of an
chloride ions from cuprous chloride—this
object. If the humidity is not lowered, or if some
overcomes one of the fundamental causes of
other form of treatment is not given to the object,
accelerated corrosion.
then extensive corrosion and gross disfigurement
of the object is inevitable.
Microcrystalline/polyethylene wax
One of the problems associated with bronze
This is a good recipe:
disease is that after the surface has been pitted, it
is difficult to disguise that area, unless it is in- • 100g of microcrystalline wax
filled with coloured wax or some other suitable
resinous material. • 25g of polyethylene wax
The main aim of treating bronze disease is to Melt the waxes together and stir well to make sure
remove all of the chlorides from the object. they are mixed thoroughly. Quickly pour the
molten mixture into the white spirits and stir it
This is done simply and effectively by immersing constantly while it cools. This makes a smooth,
the object completely in a solution of 10g of white paste. The sheen of the resultant wax film
106 Metals
can be altered by varying either the grades or the of water-dampened tissue paper over the treatment
proportions of the waxes used. When it is dry, the area, and apply the paste on top. It is preferable
wax can be polished, for a shiny finish, or left to cover the poultice of paste with cling wrap, to
untouched for a matt finish. If subsequent prevent it drying out.
treatment is be necessary, this wax can be
removed with white spirit. Repeated applications of the paste may be
required. The paste can be removed by hosing the
surface with water and scrubbing it with a bristle
Iron and steel brush. Then dry the object fully.
Bentonite paste is made by sprinkling bentonite The conservation problem is to remove a relatively
powder into a prepared solution of the alkali or unreactive metal deposit from the surface of a very
acid, and mixing it into a paste. The reactive metal, while at the same time trying to
concentrations of acid and alkali in the paste are remove the chloride ions.
usually higher than if a corresponding solution was
being used. One simple solution to the problem is to use a
solution of ammonia and ammonium sulphate to
For example, an 8% solution—that is, 80g per wash away the chlorides and the metallic copper
litre—of alkali and a 10% solution—that is, 100g from the surface. This produces complex reactions,
per litre—of citric acid are recommended. The paste but is effective.
can be applied directly to the area to be treated.
When a corroded sea plane float was treated this
If the surface is not smooth, residues of the paste way, it took 12 months of steady soaking,
can become clogged, making it awkward to scrubbing and cleaning to stabilise the corroded
remove. To make removal easier, first place a piece metal.
Metals 107
Spot-tests Rinse wet spots of electrolyte, for example, NaCl—
sodium chloride—or other reagents with distilled
water, and dry them.
Spot-tests are used to distinguish different metals
which make up an alloy. Simple instructions and a The battery should be stored disconnected from
list of the tests are provided, to help you identify the tweezers and clip—to avoid accidental
metal objects in your collections. It is important discharging if the two should touch.
to note that these tests are only qualitative in
nature—they will not tell you the relative amounts Tests for identifying metals in an alloy
of the different metals in an alloy.
Antimony—Sb
General instructions
Procedure: dip a small piece of antimony test
paper in diluted HCl—hydrochloric acid—and
9 volt battery apply it to the object.
108 Metals
visible effect on the object. For uncorroded Results: if zinc is present, the edges around the
objects, dip a long piece of dipyridyl test paper in sport turn pink—not orange. Wipe off immediately
NaCl saturated solution so that the paper is wet any NaOH remaining on the metal of the object.
but not saturated—electrolyse. The paper should This can be done with the same filter paper being
be long, to prevent confusion with any colour used for the dithizone reaction. Shiny zinc surfaces
reaction which occurs with the steel of the may be slightly darkened or dulled after
tweezers. electrolysis. There is a small effect on some copper
corrosion products, and the NaOH droplet causes a
Results: if iron is present, the white test paper shiny spot to develop on lead.
turns red after several seconds—for corroded and
uncorroded objects.
If you have a problem relating to the care of
Nickel—Ni metals, contact a conservator. Conservators can
Procedure: dip a small piece of nickel test paper offer advice and practical solutions.
into a saturated solution of NaCl. Electrolyse for
about five seconds.
For further reading
Results: on drying, the following colours may be
observed: pink-red for nickel, brown for iron, green Brown, B.F., Burnett, H.C., Thomas Chase, W.,
for copper and yellow for gold. Goodway, M., Kruger, J., Pourbaix M., eds.
1977, Corrosion and Metal Artefacts—A Dialogue
Silver—Ag between Conservators and Archaeologists and
Procedure: wet a filter paper with 10% potassium Corrosion Scientists, NBS Special Publication
chromate K2CrO4. Electrolyse for one second or 479, U.S. Department of Commerce/National
less. Bureau of Standards, Washington, D.C.
Results: if silver is present, a red silver chromate MacLeod, I. D., 1981, ‘Bronze Disease: An
Ag4CrO4 forms in the spot of the metal. This mark, Electrochemical Explanation’, ICCM Bulletin, VII,
if small, can be polished off very easily. ICCM Inc, Canberra, pp 16–26.
Metals 109
Self-evaluation quiz recovered from the sea;
b) moisture and oxygen enhance corrosion; The presence of brown droplets of moisture on an
iron object indicates:
c) a protective oxide layer forms on the surface
of copper objects; a) there are low levels of chloride ions in the
metal;
d) microcrystalline wax gives good corrosion
protection for iron objects. b) the metal is being attacked by sulphide
pollutants;
Question 2. c) the metal has been buried in a low-oxygen
environment;
Gloves should be worn when handling metal
d) corrosion reactions are still active.
objects so that:
b) the object is less likely to slip from your grip; Select the correct statement from the following:
c) protective lacquers are not damaged by nails; a) wooden cabinets are preferred to painted
metal ones for storing metal objects;
d) your hands are not affected by toxic corrosion
inhibitors. b) metal objects should be wrapped in
unbuffered, acid-free tissue paper;
Question 3. c) storage in plastic bags is acceptable as long
as they are not made of PVC;
Silver cleaning should be carried out only when
d) relative humidities greater than 45% are
absolutely necessary because: essential to help in the release of chlorides
from metals.
a) silver dip solutions are very expensive;
c) cleaning solutions tend to accumulate in Which of the following statements are correct?
indentations and surface cracks;
a) The main corrosion products that form on
d) evidence of historic usage may be lost. lead are stable and protective.
110 Metals
e) Storage of lead in chipboard cupboards is Question 4.
recommended because the resultant lead
acetate patina is protective.
Answer: d).
Question 8.
Question 5.
Which of the following statements is incorrect?
Answer: d).
a) Aluminium may be cleaned with methylated
spirits. Question 6.
b) Caustic soda should be used to remove grease
from aluminium. Answer: b).
Question 9.
Answer: b).
c) silver plate;
Answers to
self-evaluation quiz
Question 1.
Answer: a).
Question 2.
Answer: a).
Question 3.
Answer: b).
Metals 111