A Practical Guide to the

Care and Conservation

of Metals

Gordon Turner-Walker
To Andreas
Gordon Turner-Walker
Gordon Turner-Walker is Associate Professor of Cultural Heritage Conservation at the Graduate
School of Cultural Heritage Conservation, National Yunlin University of Science and Technology,
Taiwan where he has worked since 2003. He graduated with a BSc in physics and astrophysics
from the University of London before becoming involved in field archaeology. Since then
he has worked on excavations covering a broad range of dates and cultures in Britain and
the Mediterranean. He took the Diploma in Archaeological Conservation at the University of
Durham where he later studied for a PhD in the decay and characterization of ancient bone.
His interests lie in the survival of chemical and forensic information in ancient bone and other
cultural materials, and the interaction of archaeological materials with the burial environment.

Prior to taking up his present position, Dr Turner-Walker worked at the Norwegian University
of Science and Technology in Trondheim, Norway where he undertook research into the
preservation processes leading to the formation of bog bodiess and the in situ monitoring of
prehistoric rock art sites. For three years he joined the University’s Department of Medicine
as a post-doctoral fellow where he pursued a joint research project with English Heritage into
the diagnosis of osteoporosis in the medieval populations of Norway and England. His current
interests include the corrosion and conservation of ancient metals, the deterioration of skeletal
hard tissues and aspects of forensic archaeology. He is a Fellow of the International Institute
for Conservation of Historic and Artistic Works (IIC) and an Individual Affilliate of the Asian
Academy for Heritage Management.
 Preface
There are innumerable textbooks dedicated to understanding the corrosion and corrosion
protection of metals – two crucially important subjects in many aspects of engineering and
technology. There are also several excellent books in existence related to the corrosion and
conservation of ancient metals. The question must therefore be asked as to why there is a
need for yet another book about the deterioration and preservation of ancient metals. In
this volume I have tried to write the book that I wished was available to me as a student of
conservation and as a recently qualified conservator embarking on a career in archaeological
conservation. Lately, having worked as a conservation educator I have identified the need
for a textbook written at an appropriate level for undergraduate and graduate students of
conservation that combines in a single volume a basic guide to the structure and chemistry
of metals, the nature of the problems that arise when striving to preserve metal cultural
artefacts for the future, and possible solutions to those problems. These are difficult and quite
specialised fields of expertise which I have striven to explain in simple and practical terms but
without oversimplifying the science to the point of dishonestly representing reality. This book
does not pretend to be the last word on metals conservation, but rather hopes to serve as
a foundation on which interested parties can build a greater understanding of the problems
facing our common tangible cultural heritage, and formulate appropriate strategies for its
preservation.

In the past there has been a perceived polarisation in approaches to cultural heritage
conservation between Asia and western countries – particularly in terms of the symbolic
meaning of tangible cultural heritage and how it relates to preserving the intangible aspect of
cultural objects and buildings. Happily, recent years have seen a convergence of philosophies
and approaches towards heritage conservation, such that preservation of cultural heritage is
increasingly seen in terms of its social and cultural contexts, as well as in terms of its physical
condition. Having spent almost six years in Taiwan, teaching cultural heritage conservation and
working with museum professionals, I have become increasingly aware of the need for suitable
literature which presents current conservation issues in an accessible format and language.
The decision to publish this book in both English and Chinese is an attempt to bridge the
barriers arising from differences in language and culture and make its content available to a
wider audience – after all, the nature of metals and the problems their preservation presents
are global in character.

I am indebted to all those who have made this book possible: the Headquarter Administration
of Cultural Heritage, Council for Cultural Affairs who funded this publication and the research
that preceded it, especially Ms Yin-Ing (Janet) Tung and Mr Rei-How Chu for their continued
support throughout this project; my employer, the Graduate School of Cultural Heritage
Conservation, National Yunlin University of Science & Technology; my research assistant
Mr Chih-Hua (Edward) Hsieh; and all those in Taiwan’s museum community who patiently
answered my innumerable questions.

Writing a book of any kind is as harrowing for those close to the author as it is for the author
his/herself and this book was no exception. I wish to extend my heartfelt gratitude to family,
friends and colleagues who helped in this endeavour and who graciously shared its burden.
I am especially grateful to those individuals and institutions that throughout my career both
encouraged and assisted me by allowing access to historical and archaeological sites, artefacts,
materials and analytical facilities. Thanks are also due to those who have kindly allowed me
to use images or data arising from their own work. However, I take full responsibility for any
errors or misunderstandings that may arise from my use of this information.
 Introduction
The history of human civilization is closely
linked to the story of mankind’s exploitation
of metals. Almost no aspect of the modern
world could function without an intimate
knowledge of the extraction, purification and
use of metals. Despite the fact that the past
century has been described as the "Plastic Age"
– following in the tradition of the classification
of technological development into the Stone
Age, Bronze Age, Iron Age and Steel Age
– there can be no doubt that the world today
exploits metals more extensively than at any
other time in history. Although many everyday
objects and structures that would have
traditionally been made from wood have today
often been replaced by synthetic alternatives,
notably plastics derived from petroleum,
many of them have been replaced with larger,
stronger and more durable metal alternatives.
Wooden ships have been replaced by steel
ships, wooden carriages and carts have been
replaced by steel cars, trucks and trains. Wood
and fabric aeroplanes have been replaced
by aluminium jumbo jets. Buildings that in
previous generations would have contained
large structural elements made of wood are
now constructed of steel-reinforced concrete.
Traditional household objects such as ceramic
cooking vessels have been gradually replaced
with metal pots and pans, beginning with
the transition from pottery to copper alloys,
then cast iron, and now aluminium and
stainless steel. The importance of metals
grew exponentially with the development of
electricity and electrical engineering. Here
metals did not replace traditional materials
since non-metals are characterized by being
non-conductors of electricity. The whole of
the electrical revolution that took place in
the 1800s and 1900s – power generation and
distribution, lighting, heating and the operation
of large industrial machines – would have
been impossible without the unique electrical
properties of metals, principally copper. The
transition from an agricultural economy to an
industrial one would not have been possible
without a sophisticated understanding of the
properties of metal and improved methods
of extracting and refining metals. Our
energy supplies are entirely dependant upon
advanced knowledge of metallurgy, since high
performance steels are required in the mining
of coal and the drilling and pumping of oil and
natural gas. These in turn provided the energy
to increase metal production, mining, smelting
and refining, which then brought down the
prices of metals. The agricultural revolution
would not have been possible without steel
ploughs and tractors to till the soil and plant
the seeds. Nor could the fertilizers, on which
modern agriculture rely, have been developed
without steel metallurgy – early artificial
calcium phosphate fertilizers produced by the
Thomas-Gilchrist converter process were a by-
product of steelmaking, and the Haber-Bosch
process which converts hydrogen and nitrogen
to ammonia (a precursor to nitrate fertilizers)
relies upon an iron catalyst. Furthermore, the
very high temperatures and pressures (400-
450 oC and over 200 atmospheres) under
which the Haber-Bosch process takes place
themselves require high performance steels.
Since metals have played such an important
role in humanity’s past it is hardly surprising
that objects fabricated from metals constitute
a significant proportion of the world’s cultural
heritage. Without doubt they would feature
even more prominently were it not for the fact
that metals can be recycled and that apart
from objects placed in graves and tombs, or
lost in shipwrecks, the economic pressure
on societies to recycle and reuse metals has
meant that a large portion of metal cultural
heritage has been deliberately destroyed. Our
surviving metal heritage takes many forms.
The earliest objects necessarily come from
the archaeological record and include grave
goods, jewellery, weapons and examples of
treasure trove – object deliberately buried in
the ground either for safe-keeping or as part
of ritual offerings to the gods. As a result of
their antiquity and the corrosion that affects
most metals buried in soils, archaeological
objects are both fragile and susceptible to
accelerated deterioration once removed from
the relative stability of the ground. This makes
archaeological objects of any material class
difficult to preserve and archaeological metals
represent one of the hardest classes of object
to conserve. Younger, historical metalwork can
be found in the form of art, sculpture, arms
and armour, architectural elements, working
machines and industrial heritage. Each class
of artefact has its own characteristic problems
but working machines and industrial heritage
present especially challenging ethical and
practical issues. Should working machinery be
restored to a working condition, for example?
If so, then at what point in their working
history should they be restored to and how
much non-original material is it appropriate
to incorporate? Machinery such as motor cars
and industrial heritage are frequently made treatments but not least suitable trained
from iron and steel – metals which corrode conservation professionals. The role of this
quickly when not continuously maintained. guide is to provide museum staff, conservators
The advanced stage of deterioration seen in and managers of cultural heritage in Asia with
these objects is an additional challenge to the tools to understand metal cultural heritage
those seeking to preserve 19th and 20th century and practical advice on how to care for objects
heritage. made entirely of metal or composite objects
containing both metallic and non-metallic
By their very nature, metals are susceptible to elements.
corrosion. Except for rare finds of native copper
and the noble metals gold and silver, metallic
elements are not found on the surface of the
Earth. Metallic iron can occasionally be found
alloyed with nickel in the form of meteorites
and these are known to have been used to
fashion tools in antiquity. However, by far the
vast majority of metals are extracted from
rocky ores, in which the element is chemically
combined with sulphides, carbonates or oxides
(see Chapter 1). To extract the metal it is
necessary to put in a large amount of energy,
usually in the form of heat. Corrosion is the
process in which the metal returns to a more
thermodynamically stable state as an oxide, or
carbonate. In energy terms this oxidation can
be seen as a reversal of the reduction reactions
that took place during the smelting process.
Because corrosion proceeds so slowly at room
temperatures it is not possible to easily detect
the energy released when metals oxidise.
However, in special circumstances such as the
thermite reaction, the reaction is extremely
rapid and liberates spectacular amounts of
heat. In the thermite reaction powdered
aluminium metal reacts with iron oxide to
give aluminium oxide in a reaction that is
sufficiently exothermic to melt the reduced iron
liberated in this redox reaction. The reaction
finds practical application in the in situ welding
of railway lines.

The details of metal smelting and oxidation

processes will be discussed in more detail
in Chapters 2 and 3, respectively. To briefly
summarise the deterioration of metals
here, corrosion is an oxidation reaction
that is catalysed by liquid water. Like most
chemical reactions it is accelerated by
rises in temperature. South East Asia has
a climate that is both hot and humid, two
conditions that are therefore detrimental to
the survival of most metals. The resulting
rapid corrosion means that, although many
metal cultural heritage objects from this area
may not be old by European standards, their
accelerated deterioration means that they
are seriously threatened. The future survival
of metallic cultural heritage relies upon many
interdependent factors – appropriate storage,
care and, where necessary, conservation
 Chapter 1 The Nature & Properties of Metals
1.1 What is a Metal?
Before discussing metal artefacts in any
depth it is relevant to examine what exactly
we mean by metals, to look at their physical,
chemical and mechanical characteristics and
how they in turn have influenced how metals
have been used. We all imagine that we can
identify metals from non-metals by a simple
evaluation. However, these evaluations are
often empirical; we recognise a copper coin for
what it is because we have seen one before and
we have been taught that it is a copper coin.
On the other hand, engineers, physicists and
chemists have a quite different understanding
of what constitutes a metal and use often quite
precise criteria with which to characterise
and describe metals and their behaviour.
Metals are a class of chemical elements with
very special properties determined by their
electronic structure. There are many metals in
the periodic table (out of 94 naturally occurring
elements only 17 are classed as non-metals)
but of these, only gold, silver and copper occur
naturally on Earth in the pure form. Metallic
iron can occasionally be found in the form
of meteorites in which the iron also contains
crystalline inclusions of iron-nickel alloys which
can be either iron-rich (90-95% Fe) or nickel-
rich (up to 65% Ni). Nickel-iron meteorites of
course are extra-terrestrial in origin and their
metal content can corrode once exposed to
Earth’s atmosphere. Usually, iron and all other
metals occur in the Earth’s crust in combination
with other elements (usually oxides, sulphides
or carbonates) in the form of ores. The
chemical affinity between these non-metals
and the metal in the ore is extremely strong.
Metals can only be extracted from their ores
by the input of large amounts of energy – be it
thermal, chemical or electrochemical.
1.2 Basic Chemistry of Metals
and Non-metals
Each metal has characteristic properties but
all metals have specific properties in common:
They are tough but can be bent or shaped
by hammering (i.e. they are ductile). This
distinguishes them from many inorganic non-
metals such as glass, stone and ceramic which
are generally very brittle and cannot be shaped
by hammering. Metals are good conductors
of electricity and heat and polished metals
often have shiny, light-reflecting surfaces.
All of these characteristics result from the
unique bond between metal atoms. In the
metallic bond each atom loses one or more of
its outer electrons which then form a diffuse

Figure 1.1: A) In metals each atom loses one or more of its outer electrons to form a diffuse sea of
negative charge pervading the spaces between the remaining lattice of positive ions. In copper, theoretical
and experimental evidence suggests that, on average, each copper atom contributes approximately one
electron to this conduction band. Note the hexagonal close packing of atoms common in metals. B) This
hexagonal pattern is also seen in ultra-high resolution scanning tunnelling microscope images of metals.
True image of a single plane of copper atoms with 20 lead atoms embedded into the lattice structure. The
field of view is 10 nm x 8.5 nm. (Image taken from Schmid and Varga, 2002). The ragged “noisy” edge of
the image in the left of the picture is an artefact of the scanning method.
sea of negative charge pervading the spaces
between the remaining lattice of positive ions
(Figure 1.1). It is the strong electrostatic
forces between these delocalised electrons
and the positively charged metal ions that give
metals both their strength and ductility. Unlike
covalent and ionic bonds the metallic bond
is effectively equal in all directions. Because
there are no rigid covalent bonds binding
individual atoms they are free to slide over one
another when an external force is applied and
this accounts for the ductility of metals. The
free movement of the electron sea explains the
conductivity of metals and their ability to reflect
electromagnetic radiation. Many metals have a
lower melting point than non-metallic, mineral
materials where covalent bonds dominate.
Non-metals are frequently brittle, hard and
inflexible, and do not conduct electricity or heat
well. Metallic elements exhibit an extraordinary
range of physical properties. Two examples
serve to illustrate this point. The lightest
metal, lithium, has a density of 0.534 g·cm-3,
or about half that of water; while osmium has
a density of 22.62 g cm-1, making it more than
40 times heavier than lithium, and yet both
lithium and osmium are metals. Tungsten has
a melting point of 3410 oC whereas mercury
has a melting point of -39 oC ,making it a liquid
at room temperature.
Figure 1.2: Phase diagram for alloys of copper and tin (bronze). The area above the bold line represent
molten alloy. Different mixtures of copper and tin form many kinds of solid phases represented by the
patchwork of regions below the curve. Note that the melting point falls sharply as the tin content exceeds
90%.
When heated until it melts a metal can be
combined with other metals (but rarely non-
metals) to form alloys which may have very
different properties to the pure metals on
their own. An alloy does not necessarily have
properties that are intermediate between those
of the two component metals. For example,
copper has a melting point of 1084.6 oC and
tin a melting point of 232 oC. Bronze, which is
an alloy of copper and tin can have a melting
point that is intermediate between these
two extremes depending upon their relative
proportions, although the relationship with
composition is far from linear and the melting
point falls sharply as the tin content exceeds
90% (see Figure 1.2). To further complicate
matters, alloys of copper and tin can form one
or more of a multitude of different "phases" as
the molten metal cools, leading to a complex
internal microstructure.
In sharp contrast the melting points of alloys
of copper and silver do not behave in an
expected fashion. Silver has a melting point
of 962 oC. Silver alloyed with 28% copper has
a melting point of 779 oC which is almost 200
o
C lower that that of pure silver and over 300
o
C lower than that of pure copper (Figure 1.3).
Some metals are totally soluble in each other,
Figure 1.3: The behaviour of copper-silver alloys is extremely non-linear. The lowest melting point is
achieved with a composition of 28.1% copper and 70.9% silver. A practical exploitation of this is that a
range of silver solders with different melting points is possible with high silver contents.

for example gold and silver form a single solid

solution called electrum over the entire range
of compositions. In contrast, silver and copper
are only completely soluble in each other in all
proportions when molten. Copper-silver alloys
which have copper contents between 2% and
27% segregate into two discrete phases when
cooling and solidifying. These two discrete
constituents are nearly 100% silver pure silver
and a silver-copper "eutectic" (71.9% silver;
28.1% copper). This eutectic is the composition
with the lowest melting point seen in Figure 1.3.
The presence of two phases in the alloy breaks up
the regular crystalline microstructure and causes
an increase in hardness. Most silver objects are
made from "sterling" silver composed of 92.5%
silver and 7.5% copper, and with a greater
hardness than pure silver. This more complex
microstructure of different crystalline phases
affects both the mechanical properties of the
alloy and its resistance to corrosion.

1.3 The Microstructure of Metals

Metals are crystalline materials. The crystals
in metals are generally referred to as grains
and in pure metals these can be described
as similar to the multi-faceted bubbles found
in detergent foam. Figure 1.4 shows copper
crystals grown by electro-deposition on the
surface of a copper block.
Figure 1.4: A) Copper crystals grown by electro-
deposition onto the surface of a copper block. B)
At higher magnifications it is possible to see linear
striations on the crystal facets which reflect the
regular alignment of atoms in the crystal lattice.
When pure molten metals are cooled and
solidify, individual crystals grow from the
melt and these eventually join up to make
the characteristic grains seen in many metals.
When cross-sections are viewed under a
microscope these grains appear as polygons,
especially if the polished section is briefly
etched in acid to reveal the grain boundaries
(Figure 1.5).

When alloys of two or more metals are cooled

from the melt the situation is more complicated
and many different structures can be formed.
As seen in Section 1.2 different alloy
compositions have different melting points and
thus form at different times during the cooling
of the molten metal. Often the initial solid
phase takes the form of characteristic tree-like
structures called dendrites. The "branches" of
these dendrites look similar to ice formation in
a snowflake but in the metal these are three-
dimensional in form. These dendrites are most
clearly seen in metallographic sections of cast
metals but occasionally can be seen in the
corroded surfaces of archaeological copper
alloys such as the Bronze Age axe shown in
Figure 1.6. Dendrites are definitive markers of
cast objects but they are usually destroyed by
subsequent heating and mechanical working
so that not all cast objects retain a dendritic
structure.
1.4 The Value of Metals –
Elemental Abundances
The economic value of certain metals has
changed quite dramatically through history
whilst the precious nature of other metals has
remained constant. This reflects the complex
interplay between their relative abundances,
ease of extraction (mining, smelting, etc.) and
their date of discovery. For example, aluminium
is the most abundant metal in the earth’s crust
Figure 1.6: Bronze Age axe from northern England
(U.K.) showing dendrites revealed by corrosion in
the soil. This is good evidence that the axe was
cast.
but it was not used as a metal until 1825 when
Hans Christian Oersted isolated it for the first
time. The newly discovered metal was so
rare that it was more valuable than gold and
Emperor Napoleon III had dinner plates made
from the metal. By 1884 the price had fallen
to be equal to that of silver. Today total annual
world production of aluminium is over 25 million
tonnes and the price has fallen to 1/200th
that of silver, making it one of the cheapest
metals. In stark contrast to the recent history
of aluminium, gold is extremely rare but was
one of the first metals to be used by man. Why
is this? The answer lies in how it is found on
the Earth’s surface and the relative difficulties
involved in extracting the raw metal.

Figure 1.5: A small cast copper alloy incense bowl before and after etching with alcoholic ferric chloride. The
etching reveals the complex pattern of grain boundaries in the metal shown in detail in the third image.
Before looking at the early use of metals it
would be relevant to examine the composition
of the Earths crust which is the principal source
of mankind’s raw materials. The relative
abundances of metals and other elements
in the Earth’s crust is a reflection of two
processes: the synthesis of "heavy" elements
in the interiors of stars and the fractionation of
the primordial gas and dust that took place as
the solar system formed.
The two major elements in the universe are
hydrogen and helium, comprising 75% and
25% respectively. These proportions were
effectively fixed shortly after the "Big Bang"
13.7 billion years ago. All heavier elements
such as carbon, oxygen, iron, etc. (with the
exception of trace amounts of lithium created
in the Big Bang) are created by nuclear
reactions in the cores of stars and are released
into interstellar space during supernovae,
enormous explosions which accompany the
deaths of massive stars and during which
the heaviest elements, such as gold, lead
and uranium, are also synthesised. During
formation of the Solar System there was a
modification of the composition of the original
gas and dust cloud as lighter elements such as
hydrogen and helium were driven to the outer
regions by the heat of the young Sun. This left
the inner planets with a higher proportion of the
heavier elements, including the metals. Based
on the chemistry of meteorites and knowing
the relative volumes of the crust, mantle and
core, the average composition of the Earth
has been estimated as 34.63% iron, 29.53%
oxygen, 15.20% silicon, 12.70% magnesium,
2.39% nickel, 1.93% sulphur, 1.13% calcium
and 1.09% aluminium by weight.
However, the early Earth endured a period of
heavy meteoric bombardment that heated the
planet until the whole mass became liquid.
This allowed further elemental segregation of
the molten rock with the heaviest elements
sinking to the centre to form a metallic core.
The core has been estimated to be composed
of approximately 85% iron with about 5%
nickel and the remaining mass made up of
other metals, phosphorus, carbon and sulphur
(McDonough 2000). Other dense metals, such
as lead and uranium, are either too rare to be
significant or tend to bind to lighter elements
and remain in the crust. The elements found in
the Earth’s continental crust, i.e. the rocks that
we can readily mine and exploit, are therefore
depleted in heavy elements and enriched in the

Element Symbol Abundance Element Symbol Abundance

Hydrogen 1
H 3.088 Iron 26
Fe 1.949
Helium 2
He 0.000 Cobalt 27
Co 7.76 x10-4
Lithium 3
Li 0.006 Nickel 28
Ni 2.45 x10-3
Carbon 6
C 0.031 Copper 29
Cu 1.55 x10-3
Nitrogen 7
N 0.003 Zinc 30
Zn 1.95 x10-3
Oxygen 8
O 61.624 Arsenic 33
As 4.89 x10-5
Fluorine 9
F 0.062 Strontium 38
Sr 7.76 x10-3
Sodium 11
Na 2.453 Molybdenum 42
Mo 3.09 x10-5
Magnesium 12
Mg 1.548 Silver 47
Ag 3.89 x10-6
Aluminium 13
Al 6.162 Cadmium 48
Cd 3.89 x10-6
Silicon 14
Si 19.487 Tin 50
Sn 3.31 x10-5
Phosphorus 15
P 0.062 Antimony 51
Sb 3.09 x10-6
Sulphur 16
S 0.015 Barium 56
Ba 0.062
Chlorine 17
Cl 0.008 Tungsten 74
W 1.55 x10-5
Calcium 20
Ca 1.948 Platinum 78
Pt 9.77 x10-8
Titanium 22
Ti 0.195 Gold 79
Au 3.89 x10-8
Vanadium 23
V 0.005 Mercury 80
Hg 7.76 x10-7
Chromium 24
Cr 0.004 Lead 82
Pb 1.23 x10-4
Manganese 25
Mn 0.031 Uranium 92
U 1.55 x10-5

Table 1.1 Elemental abundances (in atomic %) of the commonest elements in Earth’s continental crust
(n.b. 10-4 at.% is equivalent to 1 ppm).
lighter metals and non-metals. The segregation
of metals between the Earth’s crust and the
interior is also influenced by the relative
affinities between each metal and non-metals,
principally oxygen. Those metals which bind
readily with oxygen form minerals with a lower
density than the pure metals and these lighter
compounds subsequently rise to the surface,
being found in the earth’s crust. Luckily for
us, weathering and other geological processes
result in the concentration of commercially
important metal-bearing minerals into ores
that can be more readily collected, processed
and exploited.
Table 1 shows the atomic abundances of
the commonest elements and economically
important metals in the Earth’s continental
crust. The values are expressed in atomic
percent (relative numbers of atoms) rather than
weight percent. Note that oxygen, silicon and
aluminium together make up over 87% of the
crustal rocks. The next most abundant metals
are sodium, iron, calcium, and magnesium in
that order. Although iron has been smelted and
used for approximately 4000 years, sodium,
calcium and magnesium were not isolated
as metals until 1807-1808 when Humphry
Davy used electrolysis on molten salts. Thus,
the availability of metals for exploitation by
humans was not limited to their abundance in
rocks found at the surface of the Earth.
Table 1 shows that the native metals, ones that
occur on the Earth’s surface in their metallic
form, are exceedingly rare – iron is two million
times more abundant than silver and two
hundred million times more abundant than
gold. At current prices gold is a little over 30
thousand times more expensive than sponge
iron, a reflection on the greater ease of mining
and refining iron ore compared to gold deposits.
Although a thousand times more abundant
than silver, copper and tin are still relatively
rare, which is ironic considering that copper
and bronze both featured at the beginning of
the pyro-metallurgical revolution1.
1.5 Native Metals & Metal Ores
On Earth, only three metals occur naturally un-
combined with non-metals. The "native" metals
- gold, silver and copper - were the earliest to
be recognised and used by ancient man. Gold
is the simplest native metal to find since it does
not corrode or tarnish and therefore appears
as a bright yellow nugget on the ground or in a
riverbed. It is very soft when pure and is easily
shaped into simple but attractive objects such
as beads and pendants. Pure gold can also be
hammered into thin sheets and thus a small
1
The pyro-metallurgical revolution was the connection between the use fire and metals.
amount of metal can make a spectacular piece
of jewellery. Native silver also occurs naturally
as a metal but often acquires a dark patina of
sulphide or chloride. This silver often forms as
a tangle of wires and crystals, is soft and can
be hammered into lumps or sheets. However,
native silver is comparatively rare and there
is evidence that the refinement of silver from
lead began early in the history of metallurgy.
Slag heaps found in Asia Minor and on the
islands of the Aegean Sea indicate that silver
was being separated from lead as early as the
4th millennium BC. Native copper usually has
a coating of red copper I oxide or is covered
in green corrosion products and it is possible
that green or blue copper corrosion products
were used as pigments long before they were
recognised as potential sources of useful
metal. Native copper is relatively common in
North America and there are important sources
in Bolivia. The technological transition from the
low-temperature hammering of native metals
into jewellery, to the melting and casting of
gold, silver and copper was an important step
in the pyrotechnic revolution that led to the
large-scale smelting of metals from their ores
(Gale et al. 1985).
Oxides of the transition metals are frequently
brightly coloured; iron (red or black), copper
(green or blue), cobalt (pink). Sulphides of
metals often have a shiny metallic surface and
can be substantially heavier than other rocks.
Sulphides of iron, copper, lead and nickel have
this characteristic metallic lustre. It seems
probable therefore that some metal ores were
actively collected by Stone Age peoples for
use as pigments long before their connection
with metals was understood. Cave art from
southern Europe employing red- and yellow
ochre (Fe2O3 and Fe2O3·H2O) as pigments date
back as far as 32,000 years and "ochre burials"
attest to the decoration of bodies (or clothing)
with red pigments as far back as the dawn of
human societies.
The Australian burials at Lake Mungo contain
the earliest known ochre burial dating back
approximately 40,000 years. It is also known
that Neanderthals used red ochre to decorate
carved mammoth tooth objects. We now have
ample evidence that Neanderthals used ochre
in burial rituals, and recent evidence from
excavations in Zambia suggest that Homo
heidelbergensis, the common ancestor of
Homo neanderthalis and Homo sapiens, also
used coloured pigments – possibly for body
painting – as early as 350,000 years ago
(Barham 2002).
 Chapter 2 Working with Metals
2.1 Smelting Metals
As stated in Chapter 1, apart from the native
metals; gold, silver, copper and rare instances
of native tin, all metals in the Earth’s crust
occur in combination with non-metals as stony
ores. The most common ores occur as oxides,
hydrated oxides, carbonates and sulphides.
These compounds are found in various
concentrations in soils, sedimentary rocks,
metamorphic rocks and minerals deposited
from hot waters around hydrothermal springs.
Metal ores can also become concentrated by
the weathering of parent rocks containing
more widely dispersed metal compounds. The
term ore is usually restricted to economically
important rocks bearing a high proportion of
one or more metals that may be extracted
commercially. Other rocks, for example
limestone, represent large deposits of the metal
calcium in the form of carbonate but limestone
is not considered an ore since calcium is not
readily extracted from it. In many metal oxides
and oxy-hydroxides the bond between the
metal and oxygen can be broken by the high
temperature reaction of the ore with carbon
monoxide. This can be generalized as follows:
MeO + CO " Me + CO2 where Me is a metal.
This is a redox reaction involving the exchange
of one or more electrons – the metal oxide
is reduced (it gains an electron) and carbon
monoxide is oxidised to carbon dioxide (by
losing an electron). The process of reducing
metal ores using carbon is technically called
the carbothermic reaction but more generally
it is referred to as smelting. Note that the
production of aluminium is also often called
smelting although this is a very different
process that requires large amounts of
electrical energy. The reduction of metal oxides
with carbon is not possible with all metals
because they have different electrochemical
behaviours. Most metals are electropositive
in nature and readily give up electrons in
a chemical reaction. However, they do not
all react with the same readiness or speed
– metals display different reactivities. The
greater the ease with which an element loses
its electrons and acquires a positive charge,
the greater is its reactivity. Thus, metals may
be placed in a reactivity series that reflects
the ease of reaction (oxidation) of different
elements.
Table 2.1 arranges metals in order of their
decreasing chemical activity. As one goes down
the activity series from potassium to platinum
the ease with which a metal loses electrons
decreases. Note that both carbon and hydrogen
are placed in the series despite not normally
being considered metals. This is because these
two elements have special relevance to the
reduction of metals from their ores and their
subsequent corrosion respectively.
The higher the metal in the series, the more
reactive it is – its reaction is faster and more
exothermic. The metal is also more susceptible
to corrosion with oxygen and water. This also
implies that the reverse reaction becomes
more difficult – the more reactive a metal, the
more difficult it is to extract from its ore. As
a general rule it is possible to predict redox
reactions from the reactivity series, or more
precisely, the electrochemical or galvanic
series (see Chapter 3). Those metals lower in
the series have a greater affinity for electrons
than metals above them. In redox reactions
this means that metals higher in the series
will lose one or more electrons to those below
them.
Thus, metals above hydrogen will give up
electrons to the hydrogen ion (H+) which will
be reduced – the metal will react with water,
steam or an acid to release metal ions and
hydrogen gas. Those metals below hydrogen –
copper, silver, gold and platinum – do not react
with dilute acids and are generally resistant to
corrosion in aqueous environments:
Fe + 2H+ " Fe2+ + H2 (gas)
Cu + 2H+ ≠ Cu2+ + H2 (gas)
The mechanisms behind these phenomena are
explained in greater detail in Section 3.2 and
3.3 below. By similar reasoning, metals above
carbon cannot be extracted from their ores
by heating with carbon, whereas those below
carbon can be reduced with charcoal, coal or
coke. Generally, the further down the series
the easier it is to extract the metal from its
ore, which explains why gold and silver occur
as native metals. It also explains why iron
and zinc were exploited as metals long after
the metals copper, tin, lead and mercury were
discovered.
The inability to reduce aluminium, magnesium,
etc. with carbon explains why it was impossible
to isolate the pure metal before the advent of
electricity. Table 2.1 shows the traditional
layout of the reactivity series with the more
reactive metals at the top of the table and the
 Element Symbol Notes
Potassium K
Sodium Na
Lithium Li

INCREASINGLY ELECTROPOSITIVE ____

Calcium Ca

INCREASINGLY REACTIVE ____

Magnesium Mg
Aluminium Al Above not reduced by Carbon
Carbon C ------------------------------------
Zinc Zn Below are reduced by Carbon
Iron Fe
Tin Sn
Lead Pb Above react with dilute acids
Hydrogen H ------------------------------------
Copper Cu Below do not react with dilute acids
Silver Ag
Gold Au
Platinum Pt
Table 2.1 Relative reactivities of different metals. Electropositivity refers to the tendancy of an element to
donate electrons and thus form positive ions.

less reactive, more noble metals at the bottom
of the list. A more technical way of expressing
the relative reactivities of metals and their
ease of reduction is given by an Ellingham
diagram. Figure 2.1 shows a simplified
Ellingham diagram which includes some of
the more important metals used in antiquity
together with commercially important metals
such aluminium and titanium.
In Ellingham diagrams the more noble metals
appear at the top and the more reactive
metals at the bottom, which is the reverse of
how the reactivity series is usually expressed.
An Ellingham diagram shows the relative
stabilities of metals and their oxides (or other
compounds). Above each labelled diagonal
line the element is thermodynamically stable
as the metal. Below that line it is stable as
the oxide. The scale on the left gives the
standard free energy change when the metal
is oxidised, such that increasingly negative
values represent more energetic reactions that
will occur spontaneously in the presence of
oxygen. This is why metals that appear higher
up on the diagram are more stable than those
metals that appear lower down, and are more
likely to be found in their pure metallic form.
The right hand scale shows that reduction
of the metal oxide to the metal increases
towards the top right of the diagram. In a full
Ellingham diagram this scale shows the partial
pressure of oxygen, with one atmosphere of
O2 at the top, decreasing logarithmically down
to 10-38 atmospheres O2 (an extremely reducing
atmosphere) at the lower end of the scale.
The heavy diagonal line represents the
equilibrium for the oxidation of carbon to
carbon monoxide:
C + 1⁄2O2" CO
For a metal oxide to be reducible by carbon
monoxide it must lie above the heavy line at
any particular temperature. Silver is very easily
reduced at fairly low temperature, although in
practice it must be smelted in a hot fire because
the ignition temperature of charcoal of around
300-400 oC (Ellern 1968) must be exceeded
in order to produce the carbon monoxide gas
which is the reducing agent. Gold lies off the
top of the diagram because it has positive free
energy of formation and is therefore found in
the metallic state.
As one moves from the top left of the Ellingham
diagram to the bottom right the metals
become increasingly difficult to separate
from their oxides, requiring higher and higher
temperatures to achieve the reduction. Those
metals that lie completely below the line for
carbon (titanium, aluminium, magnesium,
Figure 2.1: Simplified Ellingham diagram which includes some of the more important metals used in
antiquity together with commercially important metals such aluminium and titanium. The circles at the
ends of the lines represent the melting points of the metals. The squares represent their boiling points.

etc.) cannot be reduced by carbon monoxide at
any temperature achievable by burning carbon.
The sequence of metals as one moves from the
top left of the Ellingham diagram gives the
approximate sequence of their first utilization
by man, and gives a further explanation of why
the isolation of aluminium, magnesium and
calcium had to wait until the development of
galvanic reduction.
Today, as in antiquity, most metals are obtained
by the reaction of an oxide with carbon at high
temperature. In the past the usual source of
carbon was charcoal (in 9th-10th century China
and 17th century England coal was used) but
since the industrial revolution the usual fuel has
been coke, especially for iron smelting. Coke is
made by baking coal at high temperature in the
absence of oxygen in a process analogous to
the making of charcoal from wood. Water, coal
tars and other volatiles are driven off from the
coal leaving a porous residue of fused carbon.
In the smelting furnace two reactions are
possible and both may take place concurrently
depending upon local conditions in the hot
zone of the furnace.
These are reduction by carbon monoxide gas
– for example copper oxide:
CuO + CO " Cu + CO2
through the reaction with reducing furnace
gasses, or reduction by elemental carbon if
the oxide is in direct contact with incandescent
fuel:
2CuO + C " Cu + CO2
Similar reactions are found in the reduction of
the metals of antiquity as shown below:
Ag2O + CO " 2Ag + CO2
HgO + CO " Hg + CO2
SnO2 + 2CO " Sn + CO2
Fe2O3 + 3CO " 2Fe + 3CO2
Malachite Cu2CO3(OH)2 (basic copper carbonate)
can be reduced at around 700-800 oC. An open
fire will reach approximately 700 oC. However,
an open fire allows too much oxygen to the
fuel - producing CO2 in rather than CO. An
enclosed atmosphere and a forced draught to
raise the temperature are required. This leads
to a fire with an oxidizing zone close to the
source of the air and a reducing zone deeper
in the furnace where the ore can be reduced to
metal. As one would expect from the historical
development of metallurgy, copper is easier
to smelt than iron. Crushed copper carbonate
can be reduced to a bead of molten copper in
two terracotta bowls (one inverted) by placing
them in a simple hearth with burning charcoal
and blowing with hand bellows. This process
is often replicated in the laboratory as an
instructive exercise for students of archaeology
and ancient technology (Yee et al. 2004).
In these experiments it is usual to first roast the
ore in air to convert the carbonate into copper I
oxide and it seems likely that this was also done
in antiquity. Sulphide ores (of iron, copper or
silver) must also be roasted before they can be
smelted. This drives off SO2 gas and converts
the sulphide to a more easily reduced oxide.
It is likely that the earliest smelting was done
on a very small scale, perhaps a development
of melting and casting native copper, and that
several people with blowpipes were used to
supply the forced draught (Fasnacht 1999).
This is seen in several Egyptian wall paintings
(Figure 2.2). This crucible smelting of high
grade oxide ores in an open hearth fed by
blowpipes is essentially a non-slagging process
(Craddock 1999) and is therefore quite difficult
to identify in the archaeological record.
When smelting copper from lower grade ores
the oxide, carbonate or sulphide is usually
Figure 2.2: Drawing based on Egyptian wall painting
showing several metalworkers using blowpipes to
supply the forced draught to a small hearth. The
blowpipes are reeds with clay moulded around the
ends to form simple tuyeres and avoid charring of
the reed.
combined in a rock containing silicate minerals.
These have a very high melting point but must
be made liquid so that the copper metal and
slag can be separated. To reduce the melting
point of the unwanted slag minerals a flux
must be added to the crushed ore.
In metal fabrication (see Chapter 2.3 below)
a flux is compound which facilitates joining
two metals in a soldering or welding operation
by removing oxides from the surfaces of the
metals to be joined and by helping the melted
metal to flow easily. In extractive metallurgy a
flux is used to remove unwanted elements for
the furnace reaction products and bind them
into a slag which is then made more fluid. In
copper smelting the process can be fluxed with
iron oxide which combines with silicate to form
a separate, low-melting point phase (fayalite):
2FeO + SiO2 " 2FeO.SiO2
(sometimes given as Fe2SiO4)
Fayalite has a melting point of 1150 oC
compared to 1083 oC for pure copper and
~1650 oC for SiO2. The molten copper runs
through the slag since it is denser and forms
a pool at the bottom of the furnace. This can
be collected when the furnace has cooled. In
large-scale operations the slag was run out of
the furnace after the smelting but before the
furnace cooled. Archaeological investigations
of probable smelting sites and practical
experimental smeltings show that production
of quite large volumes of copper were possible
with relatively primitive technology (Figure
2.3).
Depending upon the ratios of fuel to ore and
flux, and the sophistication of the furnace it
is quite conceivable that iron ore could have
been reduced in a copper smelting operation,
although the resulting metal would have been
in the form of small prills or blooms mixed with

Figure 2.3: Experimental smeltings such as the
one shown here show that production of useful
amounts of copper are possible using relatively
primitive technology. Note the operation of the bag
bellows.
slag and un-reacted charcoal. Whatever the
nature of the discovery of iron smelting, and it
appears to have been discovered independently
in several regions of the Old World, the first
iron produced was by the direct process in
bloomery furnaces.
Although iron can be reduced with charcoal at
a temperature of around 800 oC the melting
point of pure iron is 1538 oC which is far
in excess of the temperatures achieved in
even a large prehistoric furnace. Thus it was
impossible to produce metallic iron in the same
way as copper. Because iron is more reactive
(electropositive) than copper it is necessary to
work much harder to win the metal from its
ore. This translates into higher temperatures,
a more reducing atmosphere and a greater
length of time – which in turn require a much
larger ratio of fuel to ore. In the case of copper
it was sufficient to melt the metal which would
then run free from the slaggy residue which
has a much higher melting point. In the case of
iron it was necessary to melt the slag so that
this ran free from the remaining solid metal.
Practical smelting experiments have shown
that in a very small bowl furnace (i.e. a clay-
lined hole in the ground) fed by bellows iron ore
could be reduced to a small bloom which could
be forged to a compact mass by further heating
and hammering. This process required 1.6 kg
of charcoal for each 100 g of iron, produced
a draught of 70 litres of air per minute for 5
hours and achieved a temperature of 1250 oC
(quoted in Tylecote 1962). This made iron a
very expensive commodity in antiquity.
Greater yields became available with the
development of shaft furnaces fed by natural
draught, often supplemented by hand-powered
or mechanically-powered bellows. Many iron
smelting furnaces have been identified on
archaeological excavations in the Old World
and these seem to display a great deal of
variation in form depending upon period and
geographical location. However, since the
upper parts of the furnace rarely survive above
the original ground level any reconstructions of
how they looked in use are largely conjectural
(McDonnell 2005). Some clues are available,
however, in examples of recent ethnographic
smelting practices such as those of the Dogon
people in Mali, West Africa (Serneels 2005).
2.2 The Physical Properties of Metals
Because there are so many different metals,
because they can be alloyed in a wide range
of compositions, and because they may be
subsequently modified by mechanical and
thermal treatments, metal objects can be
produced with a huge range of physical and
chemical characteristics. As a general rule pure
metals are softer and more easily deformed
than alloys. The ductility of metals, that is the
extent to which they can be deformed without
fracturing, can be attributed to the metallic
bond and the ability of metal atoms to slide
over one another along planes in the crystal
lattice.
Even a pure metal will become harder if it is
hammered at room temperature because "cold
working" introduces defects into the crystal
lattices which inhibit the sliding of atomic
planes over one another. This can be overcome
quite simply by heating the metal above a
certain temperature that depends upon the
metal and the amount of deformation it has
received. This introduces sufficient thermal
vibration to allow the crystal lattices to relax
and rearrange themselves into a more ordered
arrangement. This process is called annealing
and was discovered very early in the history
of metallurgy. Metallographic analysis of
copper beads from Aşikli in Central Anatolia
demonstrates that they were made from native
copper by cold working and annealing (Maddin
et al. 1999). Cold working and annealing of
copper alloys results in smaller, flattened
crystal grains with characteristic twinning.
These are readily identified during microscopic
examination of polished and etched sections.
This hardening by cold working is enhanced in
alloys of two or more metals.
Alloys are generally harder than pure metals
because the presence of atoms of different
ionic radii (metal lattices are composed of
metal ions in an electron sea) also disrupt the
sliding of lattice planes. Where metals are not
totally soluble in each other to give a single
solid solution, they segregate into different
phases and these also increase the hardness
of the resulting alloy. In modern materials
science these effects are very well understood
and today alloys are carefully selected for
their casting, machining and other mechanical
properties. Metals can also form alloys
with non-metals such as carbon, nitrogen,
phosphorus and silicon. Of these, perhaps the
most important is carbon which is introduced
into iron in varying proportions during the
smelting process.
2.2.1 Ferrous Alloys (Iron & Steel)
Carbon is readily soluble in liquid iron and at
high temperatures will diffuse into iron in the
solid state to form steel. The initial diffusion of
carbon appears to be along the grain boundaries
(Bokshtein et al. 1961). Even small amounts of
carbon can significantly increase the hardness
of iron and the range of carbon contents found
in steels can give rise to a number of different
micro-structures, with very different properties.
Iron has several different crystal structures or
allotropes. Pure iron below 912 oC has a body
centred cubic crystal structure known as alpha-
iron (α-iron) or ferrite. Above this temperature
and below 1394 oC it changes to a face centred
cubic structure called gamma-iron (γ-iron) or
austenite.
An understanding of the properties of the
different allotropes of iron is essential to
the manufacture of good quality modern
steels, although in antiquity blacksmiths and
swordsmiths were able to make excellent
tools and weapons based only on tradition and
experience. The switching from face centred to
body centred structures as iron cools can be
arrested by the incorporation of small amounts
of carbon in the crystal lattice. Ferrite is a
fairly soft metal that can dissolve only a small
concentration of carbon (no more than 0.021%
by mass at 910 °C). Above the austenising
temperature of 912 °C, however, the metal can
accommodate much larger concentrations of
carbon in its structure (up to 2.04% by weight
at 1146 °C).
Steel is an alloy of iron and carbon, with carbon
contents that range between 0.20 and 2.04%
by weight. Carbon acts as a hardening agent,
preventing atomic planes and dislocations in
the iron atom crystal lattice from sliding past
one another. Varying the amount of carbon
and alloying elements and carefully controlling
whether these additional elements are present
as solutes or precipitated phases allows careful
control over the mechanical qualities of the
resulting steel, such as its hardness, ductility
and tensile strength. The addition of carbon
to iron lowers its melting point and alloys with
carbon contents between 2.04% and 4.00%
are known as cast irons because this lower
melting point allows them to be cast easily.
Above 3.50% carbon the melting point falls
below 1200 °C, a temperature achievable in
the furnaces of antiquity. However, a higher
temperature maintained for long periods is
required to allow sufficient carbon to diffuse
into the reduced iron and produce a liquid
product – cast iron.
The hardness of steels can be increased
enormously by correct heat treatment of the
finished tool or weapon, usually involving
rapid cooling. The heat treatment process for
most steels involves heating the alloy until
austenite forms, then quenching the hot metal
in water or oil, cooling it so rapidly that the
transformation to ferrite (or pearlite) does not
have time to take place. When austenite is
quenched the carbon is "frozen" in place when
the cell structure changes from face centred to
body centred cubic. The carbon atoms are too
large to fit in the interstitial vacancies between
iron atoms and thus the crystal structure is
distorted. The structure that forms is called
martensite which has a lower density than
austenite, so the quench hardening of steels
results in a change of volume. Martensitic
structures are extremely hard but brittle. Some
of this brittleness can be reduced by reheating
the steel briefly to relax some of the internal
stresses – a process called tempering.
Stainless steels represent an immensely
important class of ferrous metals. Despite the
strength, low cost and wide-ranging applications
of iron and steel they are very prone to rapid
corrosion when exposed to moist air. This is
accelerated in the presence of dissolved salts
– as in sea water (see Chapter 3). During the
latter part of the 19th century several alloys
of steel containing manganese and nickel
were discovered to have corrosion resistant
properties, following work in Britain, Germany
and the USA. However, the development of
true stainless steels seems to have been a
spin off from the search for alloys with superior
mechanical and wear resistance properties.
In 1913 researchers at Sheffield, a traditional
steel-producing city in England, found that
a sample of steel developed for rifle barrels
were remarkably resistant to the acids used to
reveal its microstructure during metallographic
examination. This steel had a composition of
12.86%, chromium, 0.24% carbon and 0.44%
manganese (Street and Alexander 1989). Soon
afterwards the process of producing stainless
steel alloys was commercialised and in January
1915 the discovery of "non-rusting steel" was
announced in The New York Times.
Many kinds of stainless steels are now available
for a variety of applications and these fall
into four major groups depending upon their
microstructure: ferritic, austenitic, martensitic
and duplex (a combination of ferritic and
austenitic structures). The stainless properties
arise from a microscopically thin layer of
chromium oxide that forms spontaneously on
the surface. One of the best known stainless
steel compositions is 18-8 stainless with 18%
chromium, 8% nickel and less than 0.1%
carbon. Although simple chromium-nickel
stainless steels are used for cutlery and
tableware this steel is not hard enough to hold
a sharp edge. Stainless steel kitchen knives
are often an alloy containing molybdenum and
vanadium which con be hardened and tempered
like carbon steel, for example "CROMOVA 18"
which consists of 18% Chromium (Cro) as well
as some Molybdenum (Mo) and Vanadium
(Va).
2.2.2 Copper Alloys (Bronze & Brass)
Unlike iron, copper melts at the temperatures
easily reached in a simple furnace. Therefore,
alloys of copper and tin could be made
directly at the smelting stage. The earliest
copper artefacts were of almost pure copper
(98-99% Cu in Ireland). Some copper ores
naturally contain traces of arsenic (<1%)
and when smelted these produced arsenical
bronzes which were harder than pure copper.
However, since arsenical oxide is volatile
much arsenic is lost in the smelting process.
There is good archaeological evidence that
early bronze metal smiths intentionally added
supplementary arsenic (over 3%) to improve
the hardness of their tools and weapons. A 4%
arsenical bronze is twice as hard as a 4% tin
bronze after cold working.
1
hV = Viker’s hardness, a standard measure of the hardness of (usually) metals
The earliest bronzes may have been made
accidentally by smelting copper and tin ores at
the same time. They first appear around 3,200-
3,100 BC. Metal smiths realised around 1,800-
1,500 BC that by adding controlled amounts of
tin to their copper they could produce metals
with a wide range of properties. Chemical
analyses of later bronzes show that scrap
was often included in the manufacture of new
objects and this resulted in a deviation of the
alloy composition from standard recipes. In
Europe the tin contents ranged from 5-15%
with hardness ranging from 60-70hV1 when
annealed to 262hV when cold worked. Lead
is immiscible in copper in the melt and solid
phases. However, lead reduces the melting
point of a copper alloy, makes casting easier
and works as a lubricant in the solid phase to
make working the metal easier. Chinese and
Japanese bronzes tend to have a higher Pb
content.
In China the production of bronzes for specific
purposes was highly developed. The Book of
Diverse Crafts, or Kao Gong Ji in Chinese,
represents the earliest existing book on
handicrafts and technology. Dating from the
Spring and Autumn Period (770-476 BC) and
the Warring States Period (476-221 BC), the
book contains a great deal of scientific and
technical information, including how to make
carts, weapons, ritual articles, and bells, as
well as information on dyeing processes,
construction, irrigation, and other handicrafts.
The Book of Diverse Crafts contains recipes
for the casting of various tools, weapons and
functional objects to achieve the appropriate
physical properties (Table 2.2). Thus,
increasing amounts of tin were added to the
alloy to increase the hardness of the cutting
edge but this was accompanied by increasing
brittleness. Tools that received repeated heavy
shocks such as axes have a low tin content.
Conversely, tin-rich mirrors achieved a highly
reflective surface but were extremely brittle
and if dropped tended to shatter like glass.
Artefact Type Cu:Sn Melting point (oC)
Cauldrons &
5:1 930
Bells
Axes 4:1 900
Spears 3:1 800
Swords &
2:1 750
Knives
Arrowheads 3:2 740
Mirrors 1:1 700
Table 2.2 Quoted historical compositions of different
Chinese bronzes.
 Artefact Type (Source) Cu (%) Sn (%) Pb (%) Zn (%) Cu:Sn
Wine Jug (Li 2007) 77.97 20.46 0.52 0.10 3.8:1
Dagger Axes
(*Lin et al. 1997) 78.60 17.10 4.20 n.a. 4.6:1
(Li 2007) 83.15 13.26 1.01 n.d. 6.3:1
Spearheads
(*Lin et al. 1997) 82.80 11.60 5.20 n.a. 7.1:1
(Li 2007) 86.26 n.d. 6.91 0.51 -
Swords (Collins 1934) 77.83 19.25 1.93 4.0:1
Arrowheads (*Lin et al. 1997) 75.40 15.60 8.40 4.8:1
Mirrors
Tang Chinese (Collins 1934) 71.00 23.11 2.50 - 3.1:1
Han Chinese (Collins 1934) 73.52 24.56 1.47 - 3.0:1
Han Korean (Collins 1934) 70.50 26.97 1.93 - 2.6:1
Han Korean (Collins 1934) 72.64 24.16 2.06 - 3.0:1
Han Chinese (Li 2007) 70.06 22.16 6.12 n.d. 3.2:1
Han Chinese (Li 2007) 74.32 19.87 4.81 n.d. 3.7:1

Table 2.3 Measured compositions of different bronze (various authors) * averages of several analyses

However, actual chemical analyses of cementation process by smelting ground ore

archaeological objects demonstrate that
these are idealised compositions and in reality
metalsmiths used a range of alloy compositions
which included lead and other non-ferrous
metals. Table 2.3 shows the results of different
chemical analyses of Chinese bronzes and
illustrates that in reality bronze smiths in
antiquity used a variety of metals compositions
which probably included reused scrap.
Today bronze as a material is largely restricted
to decorative uses such as sculpture,
architectural features and medals. By contrast
brass, the alloy of copper and zinc, is still used
extensively in a wide range of objects – both
because of its relative cheapness compared to
bronze and because of its excellent mechanical
properties and corrosion resistance. The
manufacture of brass began in the area around
modern Iran and Pakistan and dates to early
part of the first millennium BC. The production
of brass presents interesting problems. The
smelting temperature of zinc ores is higher than
the boiling point of the pure metal. Therefore
the metal should be lost in the smoke from
the furnace as soon as it forms. There are two
ways to solve this problem and both were used
in antiquity.
The melting point of zinc is 420 °C and the
boiling point 950 °C. Smelting ZnCO3 with
charcoal requires a temperature of 1000
°C. Brass can be made by what is called the
together with copper metal granules. As the
zinc metal is created it is adsorbed onto the
surface of the copper granules to form brass.
At 20% zinc the melting point of the alloy has
fallen to 1000 °C and the molten alloy collects
at the bottom of the furnace. The other method
is to smelt the zinc separately, a technique that
was not achieved in the West until the 18th
century. However, zinc has been smelted in
Pakistan since the 4th century BC. The zinc
vapour is collected in clay retorts suspended
upside down above the charcoal and drips
down to be collected below. Production of brass
saw a rapid expansion in the Roman period and
most Roman copper alloys are in fact brass or
ternary alloys of copper, tin and zinc, possibly
reflecting a high proportion of recycled scrap.
Brass is a very versatile alloy. It is easily cast
into complex shapes and will accept fine detail.
It can also be cold worked by hammering to
form hollow vessels and complex shapes. It can
be joined by rivets or by soldering with lead-tin
alloys (soft solders). It is still widely used today
in many parts of the developed and developing
world, seeing applications in electrical
appliances as switches and connectors, water
supplies as valves, connectors and faucets
(taps), architectural features such as door and
window handles, as well as more traditional
uses in decorative candlesticks, etc. The good
casting qualities, corrosion resistance and ease
of machining (such as the cutting of screw
threads) means that many plumbing fittings
continue to be made from brass, although the
finished objects are frequently chrome plated
to give a decorative finish that does not tarnish
or discolour. Brass continues to be used for its
mechanical and corrosion-resistance qualities
in maritime equipment on ships and for bullet-
and shell casings in military ordinance. Naval
brass contains trace amounts of tin (60.0%
Cu, 39.25% Zn, 0.75% Sn) whereas cartridge
brass is a true brass (70% Cu, 30% Zn). Brass
is the traditional metal for making clocks and
precision scientific instruments. High zinc brass
is called spelter and was used extensively in
the late 19th to early 20th centuries to make
decorative sculptures, lamps and interior
design objects in the Art Deco and Art Nouveau
styles.
2.2.3 Other Copper Alloys
Modern metallurgy has produced a wide
range of different copper alloys with differing
mechanical and corrosion characteristics.
Phosphor bronze is an alloy of copper with
3.5-10% tin and a phosphorus content of up to
1%. The phosphorus is added as a deoxidizing
agent during melting. Phosphor bronzes are
employed for their toughness, strength, low
coefficient of friction, wear resistanjce and
fine grain. The phosphorus also improves the
fluidity of the molten metal, making casting
easier and enhancing the mechanical properties
of the finished casting. Further increasing the
phosphorus content leads to formation of a
very hard compound copper phosphide (Cu3P),
resulting in a brittle alloy. Phosphor bronze is
used for springs, bolts and various other items
used in situations where resistance to fatigue,
wear and chemical corrosion are required,
for example, in ship propellers and in objects
exposed to a marine environment. Phosphor
bronze is also used in some “brass” wind
instruments.
Gunmetals are a class of copper alloys which as
the name suggests were used in the casting of
cannons. The so-called 88-10-2 alloy is the U.S.
Government bronze specification “government
bronze,” composed of 88% copper, 10% tin,
and 2% zinc. The percentages of the three
elements vary slightly in gunmetals produced
for different purposes. These ternary alloys
of copper, tin and zinc may also contain small
amounts of lead to improve castability – the
leaded gunmetals. Another important class
of copper alloys is the cupronickels, including
"nickel silver". These see wide application in
the manufacture of tablewares such as knives,
forks and spoons, as well as teapots and similar
teawares. Today, nickel silver also forms the
basis of many coins. A typical alloy (Alloy No.
752) has the composition 65% copper, 18%
nickel, and 17% zinc – making it technically
a nickel brass. The white alloy of 75% copper
and 25% nickel used in coins is also known
as cupronickel. Some nickel silver alloys,
especially those containing high proportions
of zinc, are corrosion-resistant. However,
because of the potential for copper leached
from the surfaces of tablewares tainting the
flavour of foods, most nickel silver objects
are electroplated with silver – so that many
teapots, cutlery etc. carry the stamp EPNS:
electroplated nickel silver (Figure 2.4). Nickel
silver was first developed in China as an alloy
called paktong (白銅 bei-tong) literally "white
copper".
Figure 2.4: Most nickel silver objects are electroplated
with silver – so that many teapots, cutlery etc. carry
the stamp EPNS or electroplated nickel silver. Once
this layer is breached, for example by excessive
polishing or impacts, the underlying copper alloy
can corrode leading to green spots.
There is evidence for cupronickel alloys being
used for weapons during the Warring States
period in China (China Today website 2002).
This rare Chinese alloy was imported in small
quantities during the eighteenth century and
was used by European craftsmen to make
domestic objects in imitation of sterling
silverware. In 1770 German metalworkers
were able to produce a similar alloy and in
1823 a competition was initiated to perfect
the production process by creating an alloy
that possessed the closest visual similarity to
silver. A similar metal called German silver
was developed by English silversmiths in
Birmingham in 1832. Cupronickel is today used
to make musical instruments such as cymbals
and wind instruments.

A group of copper alloys used to make
small decorative objects, especially in the
Orient, are called shakudo. These are alloys
containing trace amounts of gold with a typical
composition close to 95% copper and 5% gold
although the gold content may range from 2%
to 7%. These alloys were artificially coloured
or patinated to give a range of colours from
purple to black. The alloy was first used in Han
China but was exploited extensively by the
Japanese for the creation of sword furniture.
Patinated shakudo was frequently the base
metal for gold inlays since the dark surface
provided a perfect contrast to the bright gold.
Traditionally, shakudo was chemically treated
with a paste of daikon radish and then boiled
in a patinating solution called rokushô until the
desired colour was achieved. A similar copper
alloy, Corinthian bronze, was known in the West
during the classical period. It is thought to have
been an alloy of copper and gold or copper and
silver and was considered to be precious. The
Roman natural philosopher, Pliny the Elder,
distinguished it into three kinds, depending on
the metal that is added to the copper base:
in the first, gold is added (luteum); in the
second, silver (candidum); in the third, gold,
silver, and copper are equally blended. Other
classical authors commented that Corinthian
bronze, unlike many other copper alloys,
was resistant to tarnishing. Pliny also refers
to a fourth, alloy, known as hepatizon that
seems related to Corinthian bronze (Craddock
1982, Jacobson and M. P. Weitzman 1992,
Jacobson 2000). Bronze jewellery pieces with
a compact black patina and dating from the
early medieval period in Europe have also
been found to contain trace amounts of gold
(Caple and Clogg 2001). Another decorative
alloy used in Japan is shibuichi, which can
be patinated into a range of shades of blue
or green. In Japanese shibuichi means “one-
fourth” and indicates the standard formulation
of one part silverto three parts copper, though
this composition can be varied to give slightly
different shades of colour. The alloys shakudo,
shibuichi, and kuromido – an alloy of copper
and arsenic- can be combined in a layered
structure called mokume-gane which was also
used decoratively in Japanese sword fittings.
The different colours of these alloys were
revealed by patination with rokushô to give an
appearance likened to wood grain.
2.2.4 Silver Alloys
Silver alloys fall into two groups. Alloys with a
silver content over 90% are used in coinage,
tableware, candlesticks, etc. and in jewellery.
Those with silver contents below 66% are
classified as silver solders. Fine or pure silver
is too soft to make into large or delicate objects
and thus pure silver is restricted to coinage
and to electronic components where its low
electrical resistance is exploited. The most
common silver alloy is Sterling silver, which
has a minimum millesimal fineness of 925.
Thus, Sterling silver contains 92.5% pure silver
and 7.5% other metals, usually copper. The
word "sterling", used in reference to the 92.5%
grade of silver, arose in England in the 13th
century, although the standard alloy purity was
used in Germany in the 12th century. Britannia
silver is an alloy containing 95.84% silver, with
the remaining ~4% made up usually by copper.
Britannia standard silver was introduced by
the British government in 1696 as part of the
modernization of coinage by King William III,
when hand struck silver coins were replaced
by more standard coins minted by mechanised
production of "milled" coins.
Silver solders are used to make strong joins in
silver and copper alloys where use of a "soft"
lead-tin solder would devalue the object or be
too weak. There are two basic types of silver
solder: those with composition 66.6% silver,
22.2% copper and 11.1% zinc, and those with
50% silver, 33% copper and 17% zinc. Those
with a higher silver content are used in making
silver jewellery, whereas the low-silver solders
are used in joining base metals such as brass
and bronze. Silver solders used in making
jewellery and silverwares have a variety of
melting points since there may be a need for
several successive soldered joints and the last
solder used must have a lower melting point
than the first solder used to prevent collapse of
the object. These different solders are termed
hard flow, medium flow and easy flow. Table
2.4 shows the different silver content and
melting points of these solders.
Solder Type % Ag Melting Pt. (oC)
Very Hard Flow 75 1005
Hard Flow 75 741-788
Medium Flow 70 691-738
Easy Flow 65 671-718
Super Flow 56 618-652
Table 2.4 Silver solders and their melting points.
2.2.5 Lead and Tin Alloys
Lead has been used by man for millennia. The
earliest lead artefact known was excavated
at Jarmo (Northern Iraq) and a lead bracelet
was also found at Yarim Tepe I dating to the
6th millennium BC. Here the lead must have
been smelted from the ore (probably the
heavy sulphide ore galena) since native lead
is practically unknown. Lead is a soft grey
metal known for its density and resistance to
corrosion. It has been used in weights and for
fabricating water pipes, etc. since antiquity.
Today, lead is used in building construction,
lead-acid batteries, bullets and shot, weights,
and as part of lead-tin solders. In past centuries
lead was alloyed with tin to make pewter
for use in tablewares and drinking vessels.
However, lead is soluble in a range of organic
acids found in foodstuffs and is cumulatively
toxic. Roman recipes for fruit sauces specified
cooking in lead pots since the resulting lead
acetate [Pb(C2H3O2)2] – called sapa – gave
the food an artificial sweetness (Lesser 1988).
The serious danger that lead products posed
to health were recognised in the Medieval
period and laws relating to the adulteration of
wines with lead represent some of the earliest
consumer protection and health and safety
legislation. As early as 1348 the London Guild
of Pewterers issued ordinances that attempted
to prevent the adulteration of pewter by the
addition of high proportions of lead. However,
this seems to have been aimed at protecting
the reputation of Guild members rather than
the health of its customers (Richardson 2005).
The soft, malleable nature of lead and
the fact that its annealing temperature is
room temperature means that lead can be
extensively cold worked without cracking. A
skilled craftsperson can easily form hollow
forms from lead sheet using wooden mallets
of various shapes. Lead sheet is very easily
joined using soft (lead-tin) solders. As a result,
lead sheeting is used in making decorative and
watertight features on roofs (Figure 2.5). Tin
is a soft, malleable white metal with natural
corrosion resistance and a softer shine than
silver. In antiquity tin was used for jewellery,
and for imparting a decorative and corrosion
resistant surface coating to iron and copper
alloys. Today it has been replaced by chrome
and zinc as a corrosion resistant plating but
it is still used in the manufacture of plated
containers for canned foodstuffs – tinned food.
Because of its low melting point (232 oC) tin
forms the basis of many types of "soft solder".
2.2.6 Gold and Platinum
Alloys of the precious metals gold and platinum
have a variety of uses and are commonly found
in jewellery and in situations where extreme
resistance to chemical corrosion are required.
Gold still forms the basis of much of the world’s
economic system. Pure gold is the softest and
most malleable of metals and it can be beaten
out into extremely thin sheets of "gold leaf".
One gram of gold can be beaten into a sheet
measuring one metre square and with a
thickness of only 50 nanometres – thin enough
to allow light to penetrate the metal. Gold and
platinum are resistant to most acids and do not
oxidise in air. However, both metals are soluble
in aqua regia (a mixture of concentrated
nitric and hydrochloric acids) and in cyanide
solutions. Apart from their uses in jewellery
gold and platinum are used as catalysts in
industrial chemical processes. Gold is used
in the microelectronics industry as a highly
conductive and corrosion resistant connector.
Gold in jewellery is rarely used in a pure form
because it is so soft and easily deformed. It
is frequently alloyed with copper, silver or
nickel, to increase its hardness, alter its colour
or simply as a dilutent to reduce the cost of
the raw material. Alloying with copper gives a
reddish hue to “rose gold”. Addition of silver
in appreciable amounts will give the alloy a
yellow or greenish colour. Blue tinged gold
can be made by adding iron, and alloying with
aluminium gives a purple colour. White golds
are made by alloying with nickel or palladium.
Gold alloys are usually assigned carat values to
denote the proportion of pure gold. The best
known assignation is the carat (or karat) value
in which the purity is expressed in terms of
24ths by weight. Thus 24-carat gold is 24/24
or pure gold (w/w). Similarly 18-carat gold is
18/24 or 75% gold; 12-carat gold is 50% gold;
and 9-carat contains barely 38%.
2.2.7 Aluminium Alloys
Over the past 100 years aluminium and its
alloys have become one of the most important
metals in mass production. It is the most
widely used non-ferrous metal and world-wide
production is second only to that of iron. It is
produced by electrolysis of molten cryolite salt
– requiring large quantities of electricity. It is
used to make objects as varied as aircraft,
where it is used for its high strength to weight
ratio, and aluminium cooking foils. Although it
has a natural corrosion resistance it is prone to
corrosion by salts and is therefore frequently
given an artificial, protective oxide coating
by a process known as anodising. In 1884,
aluminium was selected to be used for the
top of the Washington Monument a time when
aluminium had about the same value as silver.
The 1893 statue of Eros (more accurately that
of his twin brother, Anteros) in Picadilly Circus,
London was one of the first statues to be cast
in aluminium.
An important class of aluminium alloys is those
Figure 2.5: Lead sheet is very easily joined using soft (lead-tin) solders. As a result, lead sheeting is used
in making decorative and watertight features on roofs such as these roof fixtures on the Musee d’Orsey,
Paris.

containing copper, including duralumin – an 2.3 Making Metal Artefacts

alloy of aluminium, copper and magnesium
– developed in Germany in 1903. This alloy is
slowly self-hardening after heat treatment and
quenching, leading to a strong light material
that was used in airship- and aircraft frames.
Modern aircraft construction employs a range
of aluminium alloys which include magnesium
and silicon, or zinc.
Metal objects can be made using a wide range of
techniques depending upon the metal alloy used
and its intended purpose. In general, metals can
be made by one – or a combination of – four
techniques: casting, shaping, cutting and joining.
The first metal artefacts were cold worked from
native metals or the small blobs of metal produced
by crude furnace smelting. Later, casting was
introduced for gold and copper alloys.
Figure 2.6: Successive stages in the casting of brass incense burners from clay moulds. This small village
in northern Vietnam has been a centre for brass casting for centuries and the surrounding area is littered
with broken and discarded mould fragments.
2.3.1 Casting Metals
The simplest moulds are flat stones with the
form carved out of the upper surface. After the
metal was pored into the recess in the mould,
which was then covered with a flat stone to
prevent oxygen dissolving into the molten
metal. Today there are several approaches to
casting of metal objects from delicate jewellery
pieces to giant ship’s propellers. Clay can
be made into relatively simple or complex
multiple piece moulds, and then fired to give
a rigid form capable of withstanding the high
temperatures of molten alloys. These clay
moulds can be taken from a metal or wooden
master copy so that several, identical objects
can be cast from different moulds (Figure 2.6).
In the "lost wax" or cire perdue technique wax
is carefully modelled around a wax original
which is melted out when the mould is fired.
Modern lost wax casting of jewellery used high
temperature investment plasters rather than
clay to make the moulds. For larger objects
such as sculptures, where a solid casting would
use too much metal, cored castings were
developed (Figure 2.7). Both copper alloys and
ferrous metals can be cast into sand moulds,
usually from a metal or wooden master that is
used repeatedly (Figure 2.8).
Figure 2.7: Large cast sculptures in bronze would be extremely heavy and use excessive amounts of
valuable metal. As a result hollow castings were developed with a clay core that was later removed. The
images show a two-piece mould for a brass bust cast with a clay core.
2.3.2 Shaping Metals
Metal objects can be fashioned by the reshaping
of cast sheets, rods or ingots. This reshaping can
be done using simple hammers used together
with an anvil or stake on which to strike the
metal. More sophisticated techniques include
pressing in which malleable sheet is driven
into a hard, pre-shaped mould and spinning in
which sheet is forced over a wooden or metal
form whilst both form and sheet are spun at
high speed on a lathe. Spinning is a technique
that is suitable for the forming of open forms
such as plates and bowls in soft metals such as
pewter, copper, brass and aluminium. Metals
and their alloys can be hammered or forged to
reduce their thickness and change their form.
This can be done hot or cold depending upon
the metal. Copper and lead are especially soft
and can be routinely shaped cold using simple
metal, horn or wooden hammers, and a small
anvil. Copper alloys, chiefly bronze and brass or
silver suffer considerable work-hardening when
hammered and require frequent annealing to
soften the metal and prevent the formation of
stress cracks when they are raised into hollow
forms such as bowls, vases, etc.
Pressing in a machine press is a technique that
lends itself to the mass production of thin, sheet
metal artefacts as diverse as aluminium drinks
cans to automobile bodywork. The sheet metal
Figure 2.8: Both copper alloys and ferrous metals can be cast into sand moulds, usually from a wooden or
metal master that is used repeatedly. The sequence shows the casting of a brass bell in a three-piece sand
mould.

is pressed under considerable load between a
mould and die and is permanently deformed.
There may be successive pressing operations
until the final required shape is achieved. The
technique is related to stamping and modern
metal coins are produced from sheet metal in
a die press. A simple type of machine press is
a set of adjustable rollers. Metal is fed into the
rollers, which are turned to pull the material
through. The space between the rollers is
smaller than the metal fed into it and thus
the metal is made thinner and longer or wider.
Successive hot rolling procedures are used to
turn billets of steel into sheet. Small iron and
steel artefacts are hot forged into shape using
variously shaped hammers and anvils. The
hot iron is relatively plastic and can be cut
and pierced using hardened steel chisels, and
punches. In the hands of a skilled blacksmith
iron and steel can be manipulated into a wide
variety of shapes and "wrought iron" is a
traditional component of architectural features
such as gates and railings. Larger objects and
engineering components where great strength
is required are usually hot forged from cast
billets using power hammers. Examples of this
work include anchors, propeller shafts for large
ships, crankshafts for engines, etc.
2.3.3 Cutting Metals
In shaping metal objects the form is created by
cutting away and removing unwanted material
until the desired shape is achieved. This is in
many ways analogous to a sculptor removing
stone from a rough block until the final form
is revealed. Metal sheet and wire can be cut
with simple shears and chisels. Thicker metal
requires either mechanical presses or must be
sawn with a hardened and tempered blade.
Further shaping can be done by abrading the
metal surface with files or abrasive stones.
All of these techniques are known from
antiquity and many ancient metal artefacts
retain characteristic toolmarks that allow us
to understand how an object was created.
With only slightly more sophisticated tools
metal can be drilled or incised with decorative
designs. In modern engineering practice
complex components such as engine parts
are produced using a combination of casting,
forging and cutting of crude metal forms to
achieve a complex shape with extremely
precise dimensions and with the appropriate
properties of hardness, strength and wear
resistance.
The most basic tool in machining metals is
the lathe, on which a piece is rotated on
a horizontal axis and metal is removed by
bringing a hardened blade against the spinning
surface. This is exactly the same principle
that a woodworker uses when turning wood
on a lathe, except that because of the forces
involved in turning engineering steels the
cutting tool is manipulated mechanically rather
than held in the hand. Typical applications
Figure 2.9: Turning the cast brass bell on a lathe to give a smooth, easily-polished surface. Metals turned
on a lathe often still exhibit the closely spaced spiral grooves characteristic of this process.
include the turning of cast bronze and brass
bells and the boring of cannons. Metals turned
on the lathe often still exhibit the closely
spaced spiral grooves characteristic of this
process (Figure 2.9).
2.3.4 Joining Metals
There are a multitude of methods available for
joining one or more pieces of metal. Perhaps
the earliest and simplest methods of joining
thin sheets of metal are by folding, stitching or
riveting. All are seen in archaeological artefacts
of gold, silver and bronze. Folded joints or
seams are sometimes seen in Bronze Age
gold cups or bronze cauldrons and require no
solder. In a folded seam the edges to be joined
are folded back on themselves and aligned
so that the folds interlock. The seam is then
hammered flat, closing the joint (Figure 2.10).
A more secure joint can be made by folding
the edges over twice and hammering flat. In
the case of thin gold and tin sheet these folded
seams can be made effectively watertight.
Folded and soldered seams are used in the
manufacture of some tin cans. Stitched joints
are rather crude approaches to joining metals
that mimic the stitching of textiles or skins (for
example see the the 8th century BC gold collar
from Gleninsheen in Ireland). However, this
method probably represents the beginnings
of riveting which is now a high art with many
applications. A rivet is a short metal pin or bar
hammered over at both ends that is used to
join two pieces of sheet metal, or an additional
feature, such as a handle, to a sheet metal
object (Figure 2.10). This rivet may be made
of the same metal as the pieces joined or a
dissimilar one. Rivets may also be used to join
metals to non-metal elements such as leather
and textile – something that is not possible
with soldering for example.
Rivets can be used in joining metals in delicate
objects and in small repairs or in very large
steel constructions. During the early industrial
period rivets were used extensively where
strength was a premium such as in shipbuilding,
bridges and boilermaking (Figure 2.11). Today
rivets are used extensively in the aerospace
industry where the stressed aluminium skins of
the wings and fuselage may contain hundreds
of thousands of rivets. In many engineering
applications, especially heavy construction,
rivets have been superseded with bolts.
Another traditional way of joining metals
is to use a soldered or welded joint. Both
techniques describe the joining of two pieces of
solid metal by running a liquid metal between
them that subsequently cools and solidifies
– the exception being the solid state welding
of metals such as iron by forge welding and
explosive welding. Soldering is almost as old
as the working of metals themselves. The
earliest soldered joints were achieved using
one of two techniques. The simplest is to use
small pieces of alloy with a lower melting point
than the metals to be joined – a solder. When
the piece is heated, either in a charcoal fire
or with a blowpipe, the melted solder is drawn
into the joint by capillary forces. To achieve a
secure joint the pieces to be joined must be in
good contact (to facilitate capillary forces), be
free of oxides and other contaminants such as
grease, and be heated evenly so that solder
flows the whole length of the joint. Obviously,
careful heating is essential to prevent collapse
of the whole object into a molten mass. A flux
of some sort is frequently used which combines Figure 2.10: Two kinds of seam in a Medieval copper
cauldron from Trondheim, Norway. The vertical seam
with any oxides produced by heating the metal
was double-folded and then was hammered flat,
surfaces and helps the melted solder to flow closing the joint. The base is riveted into place, as are
into the joint. A slightly more sophisticated the loops for the handle. These were probably riveted
method of soldering that was frequently used cold since copper is soft and ductile.
with ancient gold jewellery was to create the
solder in situ by local reduction of a base cementation of brass, forming a local alloy with
metal such as copper in a technique known as a lower melting point than the surrounding
colloid soldering. This method is described by gold. This technique was ideally suited to the
Maryon (Marion 1941) but was also know to creation of filigree and granulation jewellery
the ancients, being described by the authors where very fine wires and beads are soldered
Pliny, Thophilius and the noted jeweller Cellini onto a base.
(Ogden 1982). Here, powdered copper oxide
or malachite is mixed with an organic glue and Brazing is the term given to soldering non-
applied to the surfaces to be joined. When precious metals with a copper alloy or silver
heated in a small furnace the organic matter alloy solder to give a stronger joint than that
is charred to carbon which then reduced the possible with a lead-tin "soft solder". Brazing
finely divided copper oxide to metallic copper. may be used to join ferrous metals and cast
The reduced copper diffuses into the surface iron. In the latter a nickel alloy solder is
of the gold by a mechanism similar to the commonly used.
Figure 2.11: Iron rivets in the boiler of a steam traction engine at the Racine County Fair in Wisconsin,
U.S.A. Iron and steel sheets are riveted while the rivets are red hot – later contraction of the metal closes
the joint even tighter.

True welding refers to the joining of iron and available, depending upon the situation. Most
steel without the use of a non-ferrous metal of them rely on filling a joint space with a
filler. Up until the end of the 19th century molten steel alloy which is heated by an electric
this was always achieved by heating the arc, gas flame or laser beam. The weld metal
pieces to be joined in a blacksmith’s hearth is supplied ready-fluxed in the form or rods or
and hammering them together at white heat wires and the welded joint may be surrounded
– around 1350 to 1450 oC at which point in an inert atmosphere by flooding the work
the hot metal "sparkles". This forge welding with argon gas.
process makes extremely strong joints since
it has a continuous microstructure across the
weld and there is no filler material as in a
soldered or brazed joint. Today this traditional
technique is restricted to smaller items such as
wrought ironwork, etc. and to specialist forging
operations such as making Damascus steels
and sword blades where a composite, layered
structure of alternating high and low carbon
steels is created to combine the properties
of strength, toughness and the ability to be
hardened to give an extremely sharp edge.
The complex folding and twisting operations
employed by swordsmiths in fashioning
Damascus and "pattern welded" blades has
the advantage of producing a decorative grain Figure 2.12: The pattern in these knife blades
or watered effect in the resulting steel (Figure were created by sandwiching layers of high- and
2.12). low carbon steel by fire welding. For the knife in
the foreground the blade was hammering with
In modern engineering projects there are a a patterned punch before the final shaping and
wide variety of different welding techniques grinding.
2.4 Protective Coatings for Metal
Artefacts
Apart from the precious or noble metals, most
metals and their alloys are prone to corrosion
when exposed to water and air. For this reason
many metal objects receive a protective coating
that insulates the metal surface from the
surrounding environment. This protective layer
may be purely functional in working objects
and machinery, or it many also be decorative.
The most obvious protection for machine parts
is the very visible layer of grease covering and
lubricating the moving parts (Figure 2.13). For
those objects that do not represent moving
parts to be lubricated one cheap and efficient
protective barrier to air and water is provided
by a layer of paint. Since it is important that
there is a very close bond between the surface
of the metal and the paint layer it is usual to
first coat the metal with a primer that reacts
chemically with the surface – an etch primer.
For example a modern automobile may be
finished with several coats of paint with
different properties do ensure good adhesion
to the underlying steel. In non-ferrous metals,
for example silver and brass artefacts, it is not
uncommon for a colourless lacquer or varnish
to be applied to prevent tarnishing in a damp
Figure 2.13: The most obvious protection for machine parts is the very visible layer of grease covering and
lubricating the moving parts on this steam engine. Those parts that are not greased are protected by a
thick coat of paint.
or polluted atmosphere. This is particularly
common in museum collections and exhibition
objects.
Another approach to surface coatings is to
cover the surface of a reactive metal that is
susceptible to corrosion with a second metal
that is resistant to corrosion – a metal plating.
This can be both functional and decorative and
a wide range of different metals can and have
been used: tin, silver, gold, chromium and zinc.
The use of silver plating over copper and nickel
alloys has already been discussed. Today, gold
coatings are applied by electroplating from
cyanide solutions but in the past a variety of
methods were used. By far the most common
method for applying gold coatings in antiquity
was by fire gilding, also known as amalgam
gilding. In fire gilding gold dust or foil is placed
in liquid mercury in the proportions one part
gold to eight parts mercury and then ground
together in a mortar and pestle. The resulting
paste is then applied to the surface to be
gilded. When the metal object is heated the
mercury is driven off as vapour, leaving behind
a layer of gold that adheres very strongly to the
underlying metal. The method is described in
detail by several Medieval authors (Hawthorne
and C.S. Smith 1979). Because of the inherent plating and is used to give a corrosion resistant
dangers in handling mercury, especially finish to steels, as in nickel plated guns, and
mercury vapours, this technique is now rarely to die cast zinc- or copper alloy components
used outside the developing world. such as electrical connectors, door hinges and
decorative items.
Base metal platings fall into two main
categories, those that are more reactive than
the underlying metal and those that are less
reactive than the underlying metal. One of
the earliest metal platings used is tin. Tin has
a low melting point and small objects can be
dipped into a bath of molten tin to acquire a
thin coating of this soft, shiny, white metal.
Tin plating was often applied to small iron and
steel object such as spurs and keys to prevent
corrosion. It is also used to coat the interiors
of copper and copper alloys vessels, especially
where copper may react with foodstuffs and
taint the flavour. Tin plating is still used today
in the manufacture of the tinplated steel used
in canned foods (Figure 2.14).

Figure 2.14: Tin is used to coat the interiors of
copper vessels and cooking utensils where the
copper would react with foodstuffs and taint the
flavour. Tin plating is also commonly used in canned
foods, especially fruit which is acidic.
Figure 2.15: Electroplated chromium plating on
steel, cupronickel and aluminium alloy laboratory
equipment. Acid vapours and high humidity have
caused the plating to break down, allowing corrosion
of the various underlying metals.

Tin has the disadvantage that it is less reactive

than iron and if the thin layer is scratched
or penetrated then the underlying steel will
corrode rapidly due to galvanic corrosion
stimulated by the contact of two dissimilar
metals (see Section 3.5 and Figure 3.3). In
most applications tin plating has been replaced
by chromium, nickel or zinc plating and the
protective metal barrier is usually applied
by an electroplating process rather than hot
dipping. Although "hard" chromium platings
can be applied to give a wear-resistant finish
to machine bearings and gun barrels it is
usually used decoratively or to provide a
corrosion resistant finish to ferrous metals and
die cast copper or zinc alloys (Figure 2.15).
Nickel plating is less common that chrome
 Chapter 3 Principles of Metal Corrosion
3.1 The Corrosion of Metals that remains in the surface and the second
All the metals, except the noble metals gold, layer that lies within the water but the majority
platinum and silver, are thermodynamically of which remains held close to the surface
unstable at the surface of the Earth. The by electrostatic forces. A small part of the
so-called base metal react with water and solubilised layer will diffuse into the bulk of
atmospheric or dissolved gasses to form the liquid under the influence of the thermal
oxides, sulphides and carbonates; depending motion of the water and solute molecules. In
upon which gasses or dissolved salts are an ionic solid such as a sodium chloride crystal
present. Where volatile organic gasses have this is easy to visualise. Ions of both positively
access to a metal surface they may form charged Na+ and negatively charged Cl- will
metal salts of organic acids which are highly slowly diffuse away from the surface of the
soluble or deliquescent (they adsorb sufficient crystal into the bulk solution such that both
water vapour to form a liquid solution). In the solid surface and the liquid immediately
almost all cases, water is the catalyst for these surrounding it remain electrically neutral – if
reactions. These reactions between metals equal numbers of positive and negative ions
and their environment fall under the general leave the surface the charges must balance
term corrosion and the corrosion of metals and there is no net electrostatic charge. In
has an enormous impact on industry and the case of a metal surrounded by water the
society, as well as the conservation of cultural situation is made a little more complicated. The
property. The financial costs associated with metallic bond differs from ionic bonding in that
the corrosion of metals are considerable. It the positive metal ions are not held together by
is estimated that in the USA alone the costs a lattice of counterbalancing negative ions but
arising from the corrosion of metals in 1998 by a diffuse and delocalised sea of electrons.
was $276 billion, or approximately 3.1% of
the country’s gross domestic product (Federal
Highway Administration Report Number:
FHWA-RD-01-156). These costs included
destruction of infrastructure, maintenance
and the financial costs of measures to prevent
corrosion. It is hardly surprising, therefore,
that a considerable literature exists on the
mechanisms of corrosion and its prevention
– textbooks and journals on this subject fill
library shelves across the world. Many books
and papers relating to the conservation
of cultural heritage similarly discuss the
principals of electrochemical corrosion but
few discussions describe what actually takes
place when a metal corrodes. In this section
an attempt will be made to describe in simple
terms the corrosion of metals without deviating
too far from the truth.

3.2 Metals and Water

In simple terms the corrosion of metals may
be seen as a specialised case of the dissolution
of a solid in water. When any solid is placed
in water, even those materials normally
considered extremely insoluble, surface atoms
or molecules will leave the surface and enter
the liquid – a polar solvent such as water has
the capacity to surround charged ions and Figure 3.1: Diagramatic representation of the
concentration of charged ions close to a metal
effectively solubilise them. This leads to the
electrode. In this case the charged ions are metal
formation of an electrical double layer that ions leaching from the surface of the metal. Each
surrounds the surface of the solid (Figure 3.1). charged sphere represents a single metal ions
As the name suggests, the double layer is surrounded by its hydration layer – a bound shell of
composed of two layers of charged ions, one water molecules.
If a metal ion leaves the surface and enters
the surrounding water it cannot be followed by
a free electron (or two or three electrons in
the case of divalent and trivalent ions) – the
electron is tightly bound within the atomic
lattice.
Thus, although the positively charged metal
ion is surrounded by water molecules and
moves into solution the negative charge
remains trapped in the solid. A better way to
imagine this is that thermal motion in the solid
kicks a naked metal ion into the surrounding
solution and retains its electron(s) in the bulk
of the metal. Since many millions of metal ions
may pass into solution a considerable electrical
potential builds up between the metal and the
layer of solvated ions immediately surrounding
it – the metal becomes negatively charged
and the solution becomes positively charged.
Positive ions are prevented from diffusing into
the bulk solution because of the electrostatic
attraction presented by the negatively charged
metal surface. Very quickly a state of dynamic
equilibrium is achieved where metal ions
leaving the surface are balanced by an equal
number re-entering it. The thickness of the
resulting layer of positively charged cations is
typically in the order of nanometres.
This situation is the fundamental mechanism
behind the standard electrode potential
Eo quoted so often in discussions of metal
corrosion. For example the oxidation of iron is
frequently expressed as the half-reaction:
Fe Fe2+ (aq) + 2e- (Eo = -0.44 volts)
Here, oxidation refers to loss of one or more
electrons from an atom or ion. The "aq" in
brackets denotes that the ion is in aqueous
solution and the double arrow shows that the
reaction is reversible. The quoted standard
electrode potential in volts refers to the
measurable potential difference between the
metal and a standard solution of its ions at
one mole per litre, one atmosphere and 25 oC.
Since two electrodes are needed to measure
the potential, obviously some kind of second
electrode is needed in the solution to complete
Alkali Metal Ionic Radius (pm)
Lithium 80
Sodium 100
Potassium 160
Rubidium 180
Caesium 210
Table 3.1 Relationships between ionic radii, hydrated ion size and electronegativity.
a circuit, by convention Eo is measured with
respect to hydrogen. The reasons for this will
become clear later.
Obviously the more metal ions that go into
solution, and the higher the electric charge on
each ion the greater the voltage between the
metal and the surrounding solution of metal
ions. Solutions of different metals give rise to
different standard electrode potentials, giving
rise to the concept of the galvanic series (or
electropotential series) which is used when
determining the reactiveness or nobility of
metals.
3.3 The Galvanic Series
As we we saw in table 2.1 some metals are
chemically more reactive than others. Gold
does not usually corrode but iron corrodes
relatively quickly. Sodium reacts so quickly
that it may burn in moist air. Once again this
can be related to the ease with which metal
ions leave the surface of the metal and enter
aqueous solution. The energy involved in
when an atom shifts from the solid metal into
solution is dependant upon a large number
of thermodynamic and physical criteria. One
is the ionisation energy required to remove
electrons from the outer orbitals of the atom.
Another factor is the energy released when
water molecules cluster around the ion once
it enters solution. The free energy of solvation
is the energy released when ions in a lattice
associate with molecules in a solvent. Among
other things this depends upon the size and
charge of the ion in question. Generally
speaking smaller, more highly charged ions
become hydrated by a larger number of water
molecules and are associated with larger
free energy of solvation. Thus, they are less
likely to re-join the metal surface and greater
numbers can enter solution. This, in turn, leads
to a higher electrode potential. Of the Group I
alkali metals shown in Table 3.1 the ionic radii
increase down the series but the size of the
hydrated ion (i.e. the ion surrounded by bound
water molecules) decreases.
The electronegativity shown in table 3.1
refers to the affinity different atoms have to
Hydrated Radius (pm) Electronegativity
600 0.98
450 0.93
300 0.82
250 0.82
250 0.79
Half-reaction E° (V) extremely insoluble in water compared to ionic
solids. For example the solubility of copper
Li+ + e$ Li(s) -3.05 in water at pH 8-11 is less than one part per
K+ + e$ K(s) -2.93 million (400 ppb) and the solubility of nickel is
less than one part per billion. By comparison
Ca2+ + 2e$ Ca(s) -2.76
the solubility of sodium chloride at 20 oC is
Na+ + e$ Na(s) -2.71 approximately 360 gL-1. The low solubilities of
Mg 2+
+ 2e $
Mg(s) -2.38 most metals in oxygen free, neutral water is a
reflection of the local potential difference at the
Al 3+
+ 3e $
Al(s) -1.66 electrical double layer which inhibits diffusion
Ti 2+
+ 2e $
Ti(s) -1.63 of solubilised metal ions into the bulk solution.
-1.21 Since obviously many metals do corrode
Ti3+ + 3e$ Ti(s)
in water some mechanisms must exist in
Mn2+ + 2e$ Mn(s -1.03 the real world that neutralise this potential
Zn2+ + 2e$ Zn(s) -0.76 difference and allow ions to enter solution in
large numbers.
Cr 3+
+ 3e $
Cr(s) -0.74
Fe 2+
+ 2e $
Fe(s) -0.44
3.4 Corrosion Made Simple
Ni 2+
+ 2e $
Ni(s) -0.25 Clearly, if the potential difference at the
Sn2+ + 2e$ Sn(s) -0.13 electrical double layer can be neutralised then
metal ions are free to diffuse into the bulk liquid
Pb2+ + 2e$ Pb(s) -0.13 and the metal can continue to "dissolve". One
2H+ + 2e$ H2(g) -0.00 way to achieve this is to remove electrons from
Cu2+ + 2e$ Cu(s) +0.34 the metal and since metals are conductors it
is not necessary that the electron be removed
O2(g) + 2H2O + 4e $
4OH (aq)
$ +0.40 locally, i.e. at the same place that the metal
Cu + e+ $
Cu(s) +0.52 ions are dissolving. If the water in which the
metal is immersed is acidic then hydrogen ions
Fe 3+
+e$
Fe 2+ +0.77
in solution can accept electrons from the metal
Ag+ + e$ Ag(s) +0.80 and be reduced to hydrogen according to the
Pt2+ + 2e$ Pt(s) +1.19 following half-reaction:

Au3+ + 3e$ Au(s) +1.52 2H+ + 2e- " H2(g)

Au+ + e$ Au(s)
Table 3.2 The electrochemical series – a
simplified list of standard electrode potentials.
(aq) = aqueous; (s) = solid; (g) = gaseous.
electrons. High values of electronegativity such
as those seen in oxygen (3.44) or the halogens
chlorine (3.16) and fluorine (3.98) mean that
the neutral atom readily accepts an electron to
become a negatively charged ion. Low values
of electronegativity mean that the neutral
atom readily gives up one or more electrons
to become a positive ion. Thus lithium, with
the lowest value of electronegativity in the
periodic table is easily oxidised and will react
vigorously with any highly electronegative
atom. All metals can be ranked according to
their electronegativity, or the ease with which
they lose or gain electrons (Table 3.2).
From the electrochemical series it is clear that
when a metal such as lithium is placed in pure
water the standard voltage implies that more
lithium ions enter solution than for example tin
ions enter solution when metallic tin is placed
in water. In general however, metals remain
+1.83 Since the atomic hydrogen created forms
bubbles that escape from the water the
action of hydrogen ions is to effectively pump
electrons from the metal into the atmosphere.
As long as there are free hydrogen ions
in solution then the metal can continue to
dissolve. Many metals will react with acids to
evolve hydrogen. The reaction of a metal with
acid can be understood in terms of the two
complimentary half-reactions:
2H+ + 2e- " H2(g)
Fe (s) " Fe2+ (aq) + 2e-
or by combining the two half-reactions:
Fe (s) + 2H+ " Fe2+ (aq) + H2(g)
However, those metals that lie below hydrogen
in Table 3.2 have a greater affinity for electrons
than hydrogen atoms and H+ ions are unable
to snatch electrons from the surfaces of these
metals. Metals such as copper, silver, gold
and platinum do not react with weak mineral
acids. However, in the case of the alkali metals
sodium and potassium the charge density near
these small, highly charged ions is sufficiently
strong to tear free hydrogen ions from the
solvating water molecules. Consequently, these
metals react vigorously even with pH neutral
water to evolve hydrogen gas. The reaction
with potassium is sufficiently exothermic for
the hydrogen to ignite once it reaches the
air. The resulting aqueous solution of positive
potassium ions is highly alkaline because of
the removal of H+ ions from the system and
the resulting OH- ions provide a counterion to
the K+. It is now clear why hydrogen is used as
the reference when defining standard electrode
potentials – it neatly divides those metals
which react with acids from those that do not.
However, experience tells us that many metals
will corrode when exposed to water even if that
water is pH neutral.
Some other mechanism must be responsible
for removing electrons from the system. That
other mechanism involves oxygen – and it is
extremely difficult to exclude oxygen from any
real situation. Air contains approximately 21%
oxygen and water exposed to air at 20 oC will
dissolve approximately 9 mgL-1 of oxygen. The
solubility of oxygen in water is higher than the
solubility of nitrogen such that the air dissolved
in water contains approximately 35.6% oxygen
compared to 21% in air.
The reduction of dissolved oxygen provides the
complimentary half-reaction to the oxidation of
the metal (here reduction is defined as the gain
of one or more electrons by an atom or ion):
O2 (g) + 2H2O + 4e -
4OH (aq)
- of toxic copper salts from mine water. The
Fe (s) " Fe 2+
(aq) + 2e-
to give:
2Fe (s) + O2 (g) + 2H2O " 2Fe2+ (aq) + 4OH-(aq)
Since oxygen can continue to dissolve into the
water this reaction will continue indefinitely
until all the iron is oxidised or reaches
equilibrium with the dissolved Fe2+ ions. In fact
Figure 3.2: If a cleaned sheet of iron or mild steel is placed in a solution of copper sulphate then the surface
becomes coated in a thin layer of pink, copper metal. The reaction runs more quickly if the solution is
slightly acidified with sulphuric acid.
corrosion is accelerated by two further factors:
the extreme insolubility of iron hydroxides,
the precipitation of which leads to the removal
of Fe2+ ions from the system; and the further
oxidation of Fe2+ ions to Fe3+ ions which, being
small highly charged ions are also capable of
hydrolysing water to give acid solutions:
Fe3+ + 3H2O " Fe(OH)3 (s) + 3H+
Iron corrosion will be described in more detail
in section 3.6 below.
There is a third way in which electrons can be
removed from a metal corroding in water. If
there is a second metal ion in solution that has a
greater affinity for electrons than the corroding
metal then it can also snatch electrons from
the metal surface and be reduced to a metal
atom (note that the half-reactions in Table
3.2 are reversible). Thus if a rod of iron is
placed in a solution of copper sulphate the
surface becomes coated in a thin layer of pink,
copper metal (Figure 3.2). The reaction runs
more quickly if the copper sulphate solution
is slightly acidified. The two reactions taking
place are:
Fe (s) " Fe2+ (aq) + 2e$
Cu2+ (aq) + 2e$ " Cu (s)
or, by combining the two half-reactions:
Fe (s) + Cu2+ (aq) " Fe2+ (aq) + Cu (s)
These reactions are exploited in the removal
mine runoff is passed through shallow pools
containing steel sheets and the soluble copper
salts are replaced by the environmentally
friendlier iron salts which oxidise and precipitate
out as hydroxides downstream.
3.5 Galvanic Corrosion
The different affinities for metal atoms to their
outer electrons illustrated in Table 3.2 explain
the phenomenon of galvanic corrosion. Galvanic
corrosion is the electrochemical process in
which one metal corrodes preferentially when
in electrical contact with a different type of
metal and both metals are immersed in an
electrolyte – usually water. Galvanic corrosion
is important in two fields of engineering: one
negative – the corrosion of metals; and one
positive –the design of electrochemical cells
or batteries for electricity generation. Both
phenomena arise from the same principles.
Where two dissimilar metals are in contact and
in a corrosive environment, the more noble
metal will corrode less than it would alone and
the less noble metal corrodes more rapidly. The
noble metal is cathodically protected and the
less noble metal acts as a sacrificial anode. The
reason zinc is used to coat iron is that it acts as
a sacrificial anode to the iron – preventing the
rapid corrosion seen in unprotected steels.
Zinc forms a compact layer of oxide that acts
as a barrier to the penetration of oxygen and
water to the metal below. If the zinc layer is
Figure 3.3: Tin plating on steel has the disadvantage
that it is more noble (electropositive) than iron and
if the coating scratched or penetrated then the
underlying steel corrodes rapidly due to galvanic
corrosion stimulated by the contact of the two
dissimilar metals.
Figure 3.4: A simple battery can be created by
inserting a steel wire and a copper wire into an
orange. The multimetre shows that a voltage is
generated between the dissimilar metals.
scratched the iron below still does not rust
quickly because the zinc corrodes preferentially.
Furthermore, the increase in volume
experienced as the zinc oxidises can close
small scratches and pits in the zinc coating. Tin
plating is also used to prevent the corrosion of
iron and steel – as in canned food. However,
because tin is more electropositive or noble
than iron it does not corrode preferentially.
Instead the iron experiences rapid corrosion
that penetrates beneath the tin plating (Figure
3.3). The same galvanic corrosion is responsible
for the spotting and flaking of chromium-plated
parts on automobiles and bicycles as the steel
continues to corrode under the plating.
Although the design of electrical batteries is an
extremely complex science, in simple terms the
voltage to be expected from a battery stems
from the difference between the standard
electrode potentials of the two dissimilar
metals used. A simple battery can be created
by inserting a copper wire and an iron wire into
an orange (Figure 3.4). When the two wires are
connected into a circuit the iron wire is oxidised
and Fe ions are released into the orange juice
– the iron wire becomes the anode. Electrons
flow through the wire to the copper terminal
where hydrogen ions in the acidic orange juice
are reduced to hydrogen. Current flows in the
juice in the form of hydrogen and Fe ions. The
maximum voltage to be expected is 0.96 volts
(the voltage difference between:
Fe Fe2+ + 2e- (Eoi = -0.44 V) and
Cu Cu2+ + 2e- (Eo = +0.34 V).
The current – the number of electrons flowing
in the external wire – can be increased by
substituting copper and steel plates for the
wires, thereby increasing the available surface
area for the redox reactions to take place.
However, the maximum voltage remains 0.96
volts.
A simple way to understand cathodic protection
is to visualise what happens to electrons in the
two-metal system. In the case of the galvanic
couple between zinc and iron the dissolution
of the more reactive zinc in an aqueous
environment leaves an excess of electrons in
the metal lattice. However, since iron has a
greater affinity for electrons than the zinc the
electric charge tends to migrate into the iron
lattice. This excess negative charge inhibits loss
of positive ions from the surface of the iron – it
inhibits corrosion. For this reason zinc blocks
are attached to steel structures in corrosive
environments such as ships and oil platforms
that are immersed in seawater (Figure 3.5).
As we saw in Section 2.4, tin plating is also
used to protect iron and steel from corrosion
– especially in tin cans. Unfortunately in the
case of tin- and chrome-plated steels it is the
plating that is cathodically protected and the
underlying steel acts as the sacrificial anode.
If the plated coating is scratched or broken
that the underlying steel corrodes rapidly,
the corrosion even penetrating below the
chromium or tin coating.
Figure 3.5: Zinc blocks attached to the hull of a
cargo ship. The zinc in more electropositive than the
steel of the hull and acts as a sacrificial anode when
immersed in seawater which acts as an effective
electrolyte in the galvanic cell.
Gold - Silver - Bronze - Copper - Brass - Tin - Lead - Pewter - Cast Iron - Wrought Iron - Chromium - Zinc
>>> Increasing rate of corrosion
Noble (Electropositive)
Table 3.3: Relative reactivities of common metals and alloys.
3.6 The Corrosion of Metals in
Practice
It is only partially true that the corrosion
of metals is related to their positions in the
electrochemical series. It is as much related
to their environment and the type of oxide (or
other corrosion product) films they form. Few
metals are used in their pure form. Copper
is the exception to this rule, seeing wide
applications in copper water pipes, copper
wires for electrical distribution and in beaten
copper cooking pans, etc. Most metal objects
are composed of one or more alloys and, as
we saw in Section 1.3, an alloy is frequently
composed of several phases with different
compositions. Each of these phases may have
a different a different electrode potential and
therefore galvanic corrosion cells are set up
within the surface of the alloy itself. This
complicates discussions of alloy corrosions
considerably. Some common metals and their
alloys can be arranged according to their
effective reactivity as in Table 3.3.
In theory, metals on the right should corrode
more quickly than those on the left. However,
this would mean that chromium and zinc should
corrode faster than iron. In fact, as we saw
previously in Section 2.4 zinc and chromium
are used as plating metals to give iron a more
corrosion-resistant coating. So, how do we
explain what is going on here? The answers
lie in the chemical and physical properties of
the corrosion product that forms on the metal
and the environment in which that corrosion
product is created.
3.6.1 The Corrosion of Metals in Air
Metals have a natural affinity with oxygen.
If a perfectly clean metal surface is exposed
to gaseous oxygen then a proportion of the
molecules that strike the surface will stick
irreversibly. When a metal is exposed to dry
air oxygen molecules adsorb onto the surface
forming a layer several molecules thick and
some molecules may diffuse into the metal
lattice – i.e. the surface becomes coated with
the metal oxide. In some metals, notably the
shiny white metals tin, silver and chrome
the oxide layer forms a very coherent film
with a lattice structure that conforms to the
underlying metal atoms – an epitaxial layer
>>>
Base (Electronegative)
that binds strongly to the metal below. These
films are only a few molecules thick and visible
light easily penetrates to the metal below and
is reflected back out. These metals appear
shiny and when polished can act as mirrors.
Copper I oxide (Cu2O) is red in colour and when
exposed to air the pink shiny surface of freshly
polished copper slowly turns brown as the oxide
layer increases in thickness. When metals are
heated in air or in an oxidising environment
then oxidation is considerably accelerated
and higher oxidation states of the metal are
achieved. Copper heated in air develops a
layer of black copper II oxide (CuO). When iron
is heated in an oxidising environment, such as
a blacksmith’s forge, a compact layer of black
magnetite (Fe3O4) forms on the surface. This
oxide layer is a mixture of iron oxidation states
sometimes written as FeO·Fe2O3 which adhere
strongly to the underlying metal. Wrought iron
objects typically retain this dark grey oxide
finish which to some degree protects the metal
from normal rusting. Many other metals will
react with polluting gasses to form insoluble
compounds. Silver reacts with trace amounts of
hydrogen sulphide (H2S) in the air and develops
a tarnish as a result. Silver sulphide is black,
and silver left in air polluted with hydrogen
sulphide slowly passes through a range of
colours from yellow, through browns to black
as the thickness of the black sulphide layer
increases and visible light reflected from the
metal surface diminishes. Household objects
made of silver appear to tarnish more rapidly
near pointed and sharp edges, suggesting that
corona discharge at these points is involved in
the adsorption of hydrogen sulphide which is a
polar or electrically charged gas (Figure 3.6).
Epitaxial oxide layers inhibit the penetration
of oxygen and water to the underlying metal
and thus prevent further corrosion. In moist
air water vapour will also be adsorbed onto
the surface of the metals and once this layer
builds up to several molecules in depth it
begins to act as a liquid and this has two
effects – electrochemical cells are set up
which accelerate the rate of dissolution of
the metal, and the presence of water permits
transformations of the corrosion products into
more complex forms, often accompanied by a
significant change in volume. A good example
of atmospheric corrosion is that of copper since
copper sheeting is often used as a covering for
the roofs of buildings. Copper has two oxidation
states Cu+ and Cu2+ of which Cu2+ is more stable
at room temperature. Copper metal reacts
with atmospheric oxygen at room temperature
to give an epitaxial layer of Cu2O. This epitaxial
layer follows the underlying copper lattice and
any lattice defects are concentrated on the outer
surface at the boundary of Cu2O and O2. When
this layer becomes thicker than 200 nm it no
longer follows the underlying lattice and cracks
develop, exposing the copper metal below. The
bottom of the crack becomes the anode and
the top of the Cu2O layer becomes the cathode
– thus setting up a corrosion cell. Further
oxidation results in an outer layer of CuO. Both
of these copper oxides are semiconductors
and will carry an electric current, so that the
reduction of oxygen at the surface of the oxide
layer continues to remove electrons from
the metal, allowing further dissolution at the
metal-oxide interface. Copper I (Cu+) ions are
insoluble except when in the presence of very
large concentrations of Cu2+ ions, Cl- ions, or
when complexed with ammonia.
In the absence of other atmospheric gasses
the copper roof will gradually change colour
from red to black. However, the atmosphere
contains traces of CO2 and many cities have
polluted air which may contain oxides of
nitrogen and sulphur. Carbon dioxide, sulphur
and nitrogen oxides are all soluble in rainwater
and can therefore react with copper sheeting
on roofs according to the following reactions:
At the anode (i.e. the metal-oxide interface):
Cu " Cu2+ + 2e-
At the cathode (i.e. at the oxide water
interface):
O2 + 2H2O + 4e- " 4OH- (aq)
The accumulation of OH- ions in the surface
film causes the formation of basic copper
carbonates through the reaction with dissolved
atmospheric CO2.
2Cu2+ + CO32- (aq) + 2OH- (aq)
" Cu(OH)2·CuCO3
Basic copper carbonate occurs in two forms:
the green malachite and the blue azurite. The
dominant form depends upon the concentration
of available CO2. High levels of carbon dioxide
lead to azurite. Higher temperatures and
available water tend to favour malachite
formation. Low water or low carbon dioxide
levels also favour malachite:
3 CuCO3·Cu(OH)2 + CO2
2 Cu3(CO3)2(OH)2 + H2O
malachite azurite
In low hydroxyl ion concentrations azurite is
Figure 3.6: (above) Household silver is often
cleaned regularly to a high lustre to remove blue or
brown tarnishing due to formation of silver sulphide.
Tarnishing seems accelerated on points and edges,
suggesting the coronal discharge or electrostatic
effects are involved in attracting the polar hydrogen
sulphide gas.

Figure 3.7: (right) Bronze outdoor statues in

Gothenburg, Sweden. Acid rain has reacted with
the patina to produce soluble copper salts that
have washed away with the rain leaving a streaked
appearance.

favoured (Frost et al. 2002). In polluted cities

rain acidified with dissolved SO2 or SO3 leads to
further possible corrosion products:
4CuO + SO42- + 2H2O + 2H+
" Cu4(OH)6SO4 (brochantite)

3CuO + SO42- + H2O + 2H+

" Cu3(OH)4SO4 (antlerite)

Copper sulphate is a soluble salt and will
normally be washed from the surface of
corroded copper and copper alloys. However,
in outdoor bronze sculpture this corrosion
product may form in areas inaccessible to rain,
leading to a very uneven or streaked patina
(Figure 3.7).
Cuprite and brochantite tend to dominate on
rain-washed light green areas, while antlerite
and the hydroxyl-chlorides atacamite and
paratacamite are more often found in dark rain-
sheltered areas (Strandberg 1998). Pollution in
the atmosphere can lead to other corrosion
products. In NO2 or NO3 the patina contains
Cu(NO3)2·3Cu(OH)2. The patina that forms on
copper alloys in city centres often contains a
considerable proportion of particulate matter
in the form of dust, asphalt particles and soot,
often making the colour quite dark.
When iron and steel corrode in air the corrosion
that forms is frequently less complex than
those seen on copper alloys, but the corrosion
can be much more serious. Although there is
only one possible anodic reaction there are
several possible cathodic reactions depending
upon local pH and oxygen availability.
The anodic reaction is:
Fe " Fe+2 + 2e-
The Fe+2 ion is small and highly-charged so that
at the anode local pH falls due to hydrolysis of
water and precipitation of hydroxides:
Fe+2 (aq) + H2O " FeOH+ (aq) + H+ (aq)
FeOH+ (aq) + H2O " Fe(OH)2 (s) + H+ (aq)
Possible cathodic reactions are:
Hydrogen evolution:
2H+ (aq) + 2e- " H2 (g)
2H2O + 2e- " H2 (g) + 2OH- (aq)
Oxygen reduction:
O2 + 4H+ + 4e- " 2H2O
O2 + 2H2O + 4e- " 4OH-
In both cases local pH rises at the cathode due
either to removal of H+ ions or production of
OH- ions, whereas pH falls at the anode where
the metal is actively corroding. The factors
that decide which part of the metal acts and
the anode and which the cathode include
local inhomogeneities in the carbon content
of the steel, imperfections in any protective
coating or local variations in the availability of
water and oxygen. If a single drop of water is
placed on a clean piece of steel the air-water
interface acts as the cathode and the metal in
the centre of the drop acts as the anode. A pit
develops in the steel at the middle of the drop
and a ring of rust forms at the border of the
water drop where the diffusing ferrous ions
(Fe+2) meet the hydroxyl ions (OH-) to form
insoluble ferrous hydroxide (Fe(OH)2). Ferrous
hydroxide forms initially as a greenish gel
but this is further oxidised by the interaction
with dissolved oxygen to give a hydrated solid
corrosion product:
2Fe(OH)2 + O2 " Fe2O3·H2O
The reaction product, rust, is a hydrated form
of the iron oxide haematite – Fe2O3 which can
also be written as 2FeO·OH of which there are
several crystalline forms– α-FeO.OH, β-FeO·OH
and γ-FeO·OH. In normal conditions the most
common form is goethite – αFeO·OH. Unlike
the compact patina that forms of copper
alloys, there is a considerable volume change
as iron oxidises and hydrates so that iron
corrosion does not adhere to the underlying
metal surface. Successive phases of wetting
and drying lead to a layered structure in the
rust which then frequently cracks and falls off
the surface, exposing the underlying metal
to further corrosion. The porous nature of
the corrosion also allows water to collect and
provide a pool of electrolyte so that close to the
metal surface the pH can attain very low levels.
If there is a more noble metal, such as a tin
or chrome plating, to act as the cathode then
corrosion of the iron is accelerated because
there is no build up of oxide on the noble metal
and oxygen has ready access to a clean surface
rather than having to diffuse slowly through a
heavy layer of iron corrosion. Such metals are
also better conductors of electricity than iron
corrosion products so the corrosion cell acts
very efficiently.
An additional reaction is possible but slow in
normal conditions – the dehydration of the
oxy-hydroxide to haematite:
2α-FeO·OH " Fe2O3 + H2O where FeO·OH acts
as a cathode to the metal anode, oxygen is
reduced and the metallic iron is oxidised.
3.6.2 The Corrosion of Metals in
Water
If metals are permanently, or occasionally,
immersed in water – as opposed to simply
exposed to moist air – then the corrosion
can often become extreme. Metal structures
exposed to seawater, ships, bridges, pipes
and pump components are especially prone
to rapid corrosion. It is the high concentration
of chloride ions, and the consequent high
conductivity, in seawater that accelerates
corrosion of metals. Most metal chlorides are
soluble and a high volume of available water,
combined with the presence of counter-ions
allows solubilised metal ions to diffuse far
from the site of dissolution of the metal.
When a metal is immersed in water galvanic
corrosion cells are set up even in the absence
of two dissimilar metals. The geometry of the
object has a strong influence on the pattern
of corrosion it experiences. Crevices, corners
and joints where local oxygen concentrations
are easily depleted become anodic and pitting
corrosion takes place. More open areas
where there is free access to oxygenated
water become cathodic and are protected
from corrosion at the expense of the anodic
regions. If water flows rapidly over the surface
of the metal then metal ions are scoured from
the surface and swept away into the bulk
water. In high speed components such as
pumps, propellers and turbines where water
turbulence creates temporary bubbles in the
liquid, this so-called cavitation corrosion is a
major problem that leads to severe pitting of
the surfaces (Figure 3.8).
Here it is worthwhile to discuss corrosion
seen in sunken shipwrecks. Metals exposed
on the sea bed for several hundred years
experience severe corrosion. Even in very
Figure 3.8: Severe cavitation corrosion in a cast
steel water pump. The steel has been eroded where
bubbles have formed and collapsed on the metal
surface.
deep, cold waters steel ships undergo quite
rapid corrosion as the iron is converted into
"rusticles" similar to those found on the wreck
of the Titanic (Cullimore et al. 2000). Many
shipwrecks contain objects made from a wide
variety of metals, many of which suffer serious
corrosion in seawater. Copper alloys, especially
the marine brasses are somewhat resistant
to corrosion. Iron and steels corrode quite
rapidly. Cast iron, particularly massive objects
such as cannons appear to survive quite well
but appearances are deceptive here. In a
marine environment cast irons, particularly
the grey cast irons which contain flakes of free
graphite, can suffer severe internal corrosion
and become completely graphitised. Here
the extremely stable graphite is an excellent
conductor of electricity and acts as a noble
metal, becoming cathodic to the pearlite
and cementite which corrode to oxides, oxy-
hydroxides and carbonates. This porous mass
of corrosion products is held together by the
remaining network of graphite flakes and the
object does not disintegrate in the same way
as carbon steels and exquisite details of the
cannon are frequently preserved beneath a
crust of marine concretions. However, when
these objects are raised from the seabed
and exposed to air the porous structure dries
out and atmospheric oxygen penetrates into
the corrosion. Here renewed corrosion, of
un-reacted metal coupled with oxidation of
partially oxidised species in the corrosion
products can lead to catastrophic fracturing
in the corrosion and destruction of the object.
There are even reported cases of cannon balls
recovered from the sea bed becoming so hot
as oxidation proceeds that the graphite begins
to burn and the cannon balls spontaneously
combust (Nature News 29 Apr 2002 doi:
10.1038/news020429-17). Post-excavation
corrosion of archaeological metals is discussed
in greater detail below.
The corrosion of tin and lead alloys is discussed
in Section 3.8 below.
3.6.3 Corrosion of Archaeological
Metals
Archaeological objects – that is objects that
are buried in soil or tombs for many hundreds
of years experience different environments
than normal engineering metal structures or
art objects. When one considers the rate of
corrosion seen in many metals above ground
one might expect that metal artefacts should
not survive in the archaeological record at
all – having long ago been converted back
to stable compounds resembling metal ores.
The truth is that in many cases that is exactly
what happens. Some corroded objects may be
unrecognisable as having once been metal,
while others may have disappeared completely.
That so many archaeological metal objects are
found is testament to the fact that burial deep
underground considerably slows degradation
reactions and helps preserve ancient objects
made from a wide variety of inorganic and
organic materials.
The rate of corrosion in any burial environment
is limited by six main factors:
1) The chemical reactablility of the metal or
alloy (its standard electrode potential)
2) The availability of oxygen (or other electron
acceptor)
3) The conductivity of the surrounding soil
(which is related to its water content and
the concentration of dissolved ions)
4) The permeability to water and oxygen of the
corrosion layers formed between the metal
and the environment
5) The local pH
6) Contact with dissimilar metals
Temperature is also a factor that influences
rate of corrosion and it is generally true that
temperature falls off quite quickly with burial
depth. In oxidising environments, that is in
environments where the soil solution contains
dissolved oxygen, the mechanisms of corrosion
follow the same reaction as those seen in the
corrosion described in Sections 3.6.1 and 3.6.2
above. The main difference is that unlike in
atmospheric and underwater corrosion the
metal ions released by corrosion are not readily
washed away from the corroding object. As
metals corrode, positive ions are released from
the surface and migrate into the surrounding
soil until the local pH rises to a level where
they are insoluble and they precipitate out as
solid corrosion products. These solid corrosion
products cement together soil particles to form
a hard crust around the archaeological object.
The thickness of this corrosion crust depends
upon the rate of corrosion and the solubility of
the released ions.
The solubility of the ions depends upon pH
and the redox potential Eh (effectively the
amount of dissolved oxygen or other electron
acceptors) of the soil. When excavated,
archaeological metals are often surrounded
by a thick encrustation of corrosion combined
with sand or soil particles and any other
organic matter lying close to the object.
Generally, ferrous objects have a much thicker
and more porous crust of external corrosion
than copper alloys, silver of lead objects. The
presence of reinforcing sand particles together
with pressure of surrounding soil supports
this external corrosion and prevents it from
fracturing and falling away from the corroding
surface as is seen for example in the corrosion
of iron objects in air. The metal in the oxide
that forms this internal corrosion originally
formed part of the object and as the corrosion
front moves inwards from the original surface
it leaves a porous pseudomorph of internal
corrosion which normally has a lower oxidation
state than the external corrosion. The original
surface lies at the boundary between the
external and internal corrosion and it is this
surface that preserved the original shape of
the object and any technological evidence
– tinning, gilding, tool marks, wear surfaces,
etc. The recognition of this original surface
is in many ways an act of faith – the surface
revealed by the removal of external corrosion
is frequently blistered and cracked so it is
possible that there are considerable changes
in volume during the formation of the internal
corrosion. The corrosion of archaeological
metals can best be summarised by dealing
with each common alloy in turn.
3.6.3.1 Corrosion of
Archaeological Iron
The corrosion of iron can be summarised
as follows. Assuming the soil solution has
neutral pH dissolved oxygen is reduced to the
hydroxyl ion at the cathode which is often the
outer surface of the internal corrosion. Inside
the corroding object, at the interface of the
internal corrosion and the metal core Fe2+ ions
are released at the interface between the oxide
and the metal and the high concentration of
positive ions there attracts chloride ions
deep into the oxide layer. The presence of
these negatively charged ions changes the
electrostatic balance between the metal surface
and the Fe2+ ions which then begin to diffuse
outwards through the internal corrosion to the
surrounding soil where they may be oxidised
to Fe3+ ions. Diffusion and mixing of Fe2+ ions
and Fe3+ ions gives rise to the formation of
magnetite (Fe3O4) which is an oxide of mixed
iron I and iron II oxidation states – sometimes
written Fe2O3·FeO. This leads to a generalised
situation where in cross section a residual
metallic iron cores is surrounded by a shell of
black magnetite internal corrosion, which is
then overlain by a more porous, brown jacket
of external corrosion containing soil particles
and associated detritus infiltrated with iron
III corrosion products. Since magnetite is an
electrical conductor it frequently acts as the
cathode in the corrosion cells, although oxygen
availability is limited by the diffusion through
the external corrosion layers which can be very
thick. If the corrosion continues to completion
the iron core may dissolve completely,
production of Fe2+ ions stops and in the absence
of a potential gradient the Cl- ions diffuse
out from the corrosion into the surrounding
environment. In extreme cases, the magnetite
core may also dissolve leaving a void in the
shape of the original object, surrounded by
external corrosion. This situation is sometimes
encountered in iron objects from shipwrecks
and the only way to identify the original artefact
is to fill the void with silicone rubber and break
off the surrounding corrosion crust (Cronyn
1989). The cathode may be a dissimilar metal
such as tin plating or, at a microscopic level, a
metal grain of different composition. If there is
a more noble metal to act as the cathode then
corrosion of the iron is accelerated because
there is no build up of oxide on the noble
metal. Such metals are also better conductors
of electricity than magnetite. Depending upon
the chemistry of the burial environment other
more exotic corrosion products may form.
If CO2 is present in the groundwater or
seawater then the corrosion product siderite
(FeCO3) is stable at low Eh and high-to-neutral
pH. This also forms as a corrosion product in
post-excavation corrosion. In anoxic conditions
iron and other metals are protected against
corrosion. However, where there are high
sulphide levels and high levels of organic
matter in the sediment then sulphate-reducing
bacteria (SRBs) may influence the local
soil environment. These primitive bacteria
use sulphate as an electron acceptor in the
oxidation of simple organic compounds,
releasing hydrogen sulphide (H2S) into the
local environment. This can combine with
Fe2+ ions to form iron pyrite (FeS). This leaves
some metals with a false gilding of shiny "fool’s
gold" that results in excellent preservation of
surface details. Alternatively, where phosphate
levels are high, such as in rubbish pits and
graves then vivianite (FePO4·2H2O) a bright
blue mineral may form together with the more
usual rust.
3.6.4 Post-excavation Corrosion
of Archaeological Iron
Chloride ions play a key role in the corrosion
of archaeological metals and are one of the
main reasons for post-excavation corrosion
of archaeological objects. Once excavated,
archaeological iron is exposed to much greater
concentrations of oxygen than in the burial
environment. One might think that corrosion
would be much slower because now the iron
is in a dry environment but that is far from
true for two reasons. Firstly, once water
has evaporated from the porous corrosion
products surrounding the remaining metal
core the inward diffusion of gaseous oxygen
is much more rapid. The shrinking reservoir
of salt-containing water retreats into the
smallest pores, close to the metal surface and
this drives chloride ions close to the metal
surface. Archaeological iron has a very fine
pore structure and this also acts as a moisture
trap, drawing water vapour from the air and
condensing it as liquid within the smallest
pores. Secondly, the fact that archaeological
iron contains high concentrations of chlorides
in the corrosion pits – close to the metallic
core – increases the moisture content of the
iron corrosion products. Ferric chloride is very
hygroscopic and attracts moisture from the air.
It also forms very acidic solutions in water due
to hydrolysis:
FeCl3 (s) " Fe3+ (aq) + 3Cl- (aq)
Fe3+ (aq) + 3H2O " Fe(OH)3 (s) + 3H+ (aq)
Fe(OH)3 is very insoluble and pumps hydroxyl
ions out of solution, lowering the pH further.
The following reactions show that water can be
generated by post-excavation corrosion with
only the addition of oxygen if free ferrous ions
are available.
Fe2+ (aq) + 2OH- (aq) " Fe(OH)2 (s)
6Fe(OH)2 (s) +O2 (g) " 2Fe3O4 (s) + 6H2O
2Fe(OH)2 (s) + 11⁄2O2 (g) " Fe2O3·H2O (s) + H2O
Oxygen is the driving force in this corrosion,
which can continue in only small quantities
of water. Corrosion is further catalysed by
chlorides:
2Fe (s) + 11⁄2O2 (g) + 6HCl (aq)
" 2Fe2+ (aq) + 6Cl- (aq) + 3H2O
Fe2+ (aq) + 2H2O + 3Cl- (aq)
" FeO·OH + 3H+ (aq) + 3Cl- (aq)
4Fe2+ + O2 + 6H2O " 4 β−FeO·OH + 8H+
Metallic iron continues to corrode and local pH
falls by production of H+ ions.
Chlorides have four detrimental effects:
1) They affect which solid corrosion product
forms, giving rise to β-FeO·OH. Sites of
FeO·OH production occur where outward
diffusing Fe2+ ions meet inward diffusing
O2. The production of hydrogen ions is
counteracted at the iron core by reaction
with the metal to produce hydrogen:
2H+ (aq) + 2e- " H2 (g)
But in the corrosion crust the pH can fall
low enough to make FeO·OH soluble. This
is weeping iron where drops of very acidic
orange water form on the corrosion crust.
2) Local HCl concentrations dissolve more
stable iron oxides.
3) Chlorides lower the relative humidity (RH) at
which corrosion can take place. This should be
at an RH above 44% but because β-FeO·OH is
very hygroscopic and absorbs water between
15% RH and 44% RH archaeological iron is
unstable at all RH values above 15%.
4) Chlorides increase the conductivity of the
concentrated solutions within the corrosion
crust.
Current approaches to the care of
archaeological ironwork follow one (or both) of
two philosophies. Removal of all chlorides from
the corrosion products, and maintaining the
storage and display environment below an RH
value of 15%. Both approaches have severe
limitations in their practical applications as is
explained in Chapter 5.
3.6.5 Corrosion of Archaeological
Copper Alloys
Copper alloys corrode less quickly than iron
objects, both on land and in seawater. Copper
and copper alloys are more electropositive
than iron and the external corrosion layers are
more compact, coherent and protective than
those that form on iron and its alloys. As a
result copper and bronze artefacts dating from
the very beginnings of man’s exploitation of
metals several thousand years ago have been
discovered on archaeological excavations.
In most archaeological deposits, either on
land or underwater, water, oxygen and carbon
dioxide are present in the environment. Often
the corrosion products seen on archaeological
copper alloys are superficially similar to those
patinas that form during atmospheric corrosion.
However archaeological environments also
contain dissolved salts which accelerate
corrosion and influence the corrosion products
formed. Once again, of these ions the chloride
ion is the most common and most damaging.
Copper has two oxidation states. All copper
I compounds are highly insoluble except for
CuCl which is soluble in concentrated HCl
where it forms a co-ordinately bonded anionic
complex. The usual copper I compound formed
on archaeological copper alloys is Cu2O. The
chloride ion acts as a catalyst in the production
of Cu2O:
2Cu + 1⁄2O2 + HCl " Cu2O + HCl
Note that the HCl is recycled at the end of
the reaction. If the pH falls to approximately
2 then Cu2O becomes soluble in the HCl and
Cu+ ions may migrate until the rise in pH
causes precipitation of CuCl as crystals. Local
corrosion cells may then be set up between
Cu2O, CuCl and copper metal:
2Cu + 2HCl + 1⁄2O2 " 2CuCl +
H2O
2CuCl + H2O Cu2O + 2HCl
(Nantokite Cuprite +
hydrochloric acid)
as the pH falls then Cu2O " CuCl
Also, copper disproportionates: 2Cu+ Cu
+ Cu2+ so that Cu+ only exists in high Cu2+
concentrations at the expense of the dissolution
of Cu metal. So in high Cu2+ concentrations such
as those found at the bottom of corrosion pits,
Cu+ can dissolve the un-oxidised metal. Thus
at the bottom of a crack in the patina and in
pits in the corroding metal local concentration
cells produce rapid corrosion according to the
following reactions:
Cu " Cu2+ + 2e-
Cu + Cu2+ " 2Cu+ (aq)
Cu+ (aq)+ Cl- (aq) " CuCl (s)
2CuCl + H2O " Cu2O + HCl (aq)
4CuCl + 4H2O + O2
" CuCl2 3Cu(OH)2 + 2HCl (aq)
Rather surprisingly, the corrosion product
CuCl2 3Cu(OH)2 has been identified on copper-
rich dental amalgams (Marshall et al 2004).
The low pH can be further maintained by the
hydrolysis of water by solvated highly charged
Cu2+ ions according to the reaction:
[Cu(H2O)4]2+ (aq)
[Cu(H2O)3OH]+ (aq) + H+ (aq)
The pH at the bottom of corrosion pits (anode)
is very low but as the copper ions migrate
away from the sites of active corrosion the pH
rises and they precipitate out as basic copper
carbonates, sulphates and chlorides.
This is bronze disease and can be seen on many
museum objects as a bright green, powdery
corrosion product that can appear very rapidly
if the RH rises above 50%. (Compare this with
the threshold of 15% for archaeological iron
containing chlorides).
The deterioration of copper alloys from bronze
disease can be very rapid and outbreaks of
fresh corrosion can occur within 24-48 hours if
the RH rises too high.
4CuCl + O2 + 4H2O
" 2Cu2(OH)3Cl + 2Cl- + 2H+
The final corrosion product is a hydroxy-chloride
or basic copper chloride. The basic copper
chlorides occur in one of two forms: black/
green atacamite or dark green paratacamite
of which paratacamite is most common on
archaeological bronzes. The presence of these
corrosion products makes archaeological
bronzes inherently unstable.
The corrosion of alloys of copper is a little
more complicated than the reactions above
suggest. At the microscopic level, the corrosion
of bronzes and brasses develops along
grain boundaries. For bronzes with <10%
tin the alpha phase corrodes preferentially
because tin is more electronegative than
copper, leading to inter-granular corrosion.
For >10% copper and >1% zinc the tin rich
delta phase corrodes preferentially. For >10%
tin and <1% zinc the corrosion begins with
the copper-rich alpha phase. For alloys of
leaded gunmetals the alpha and delta phase
corrode preferentially and metallic copper
may re-deposit electrochemically. Because
of the differential rates of corrosion in multi-
phase alloys the metallographic structures are
frequently preserved even in severely corroded
copper alloys (Chase 1994).
Corrosion of thin copper alloys such as raised
vessels and coins can continue until there is
no remaining metal. The object is left as a
mineral copy of the original metal shape and
will be extremely fragile. Such objects may
break up into small sections and will have
none of the ductility normally associated with
metals (Figure 3.9). However, such objects are
extremely stable once excavated because any
excess chlorides will have diffused out of the
corrosion products into the surrounding soil.
Even so, some hydration of corrosion products
might take place and there may be some colour
changes in the external patina.
3.7 Corrosion of Silver Alloys
At room temperature silver reacts with
atmospheric oxygen to get a thin film of Ag2O.
This is a thin white coating that is epitaxial to
the underlying metal structure and protects
against further oxidation. However, in the
presence of water from moist air both O2 and
H2O are adsorbed and together form H2O2.
The peroxide promotes lattice defects in
the Ag2O layer that allow Ag+ to move from
the base of cracks to the oxide-air interface

Figure 3.9: Raised bronze bowl during excavation
in Cyprus. Severe corrosion has left the object as
a mineral copy of the original metal shape and
extremely fragile as a result. Such objects may
break up into small sections and have no ductility
normally associated with metals. The bowl is shown
after conservation below.
where they react with any polluting gasses
in the atmosphere. Of these polluting gasses
hydrogen sulphide is the most important:
2Ag +H2S + 1⁄2O2 " Ag2S + H2O
or possibly
Ag2O + H2S " Ag2S + H2O
Silver sulphide is a black insoluble compound
and is responsible for the black or brown
tarnish on silver objects. Tarnishing only occurs
in the presence of water and oxygen.
In the soil silver usually gets a thick layer of
silver chloride AgCl, especially if there are high
chloride concentrations in the environment
(e.g. in seawater or near human burials). This
silver chloride is very insoluble and immediately
forms a pink or grey, waxy precipitate on the
metal surface. This upsets the balance between
Ag+ and silver metal and drives more silver
into solution. The AgCl is open and spongy
and therefore allows electrolytes and oxygen
to penetrate easily to the metal surface. It
forms thick corrosion layers and thus can also
obscure the details on silver objects such as
coins.
Pure silver is too soft to make artefacts and
is therefore usually alloyed with 5.5-20%
copper. Over time this copper migrates to the
grain boundaries of the microstructure and
is preferentially oxidised during corrosion,
weakening the bond between the metallic
grains. For this reason archaeological silver
can be extremely brittle and fracture easily.
Intergranular corrosion of the copper rich
phase releases Cu2+ ions into the soil around
the corroding silver object, potentially covering
the object with green corrosion products. As
a consequence some archaeological silver is
sometimes mistaken for corroded bronze.
3.8 Corrosion of Lead and Tin
Alloys
Lead and tin are Group IV metals forming
ionic Sn2+ and Pb2+ compounds but can also
form covalent tin IV and lead IV compounds,
some of which may hydrolyse in water. This is
especially true in the presence of chlorides.
Tin is more stable as SnIV but lead is more
stable in the Pb2+ form. Both tin and lead
form amphoteric oxides which react with both
acids and alkalis, and this is important to their
stability in the ground and in the museum
environment. Both tin and lead are stable
in acid reducing environments but will form
soluble compounds in acid oxidising or in any
alkaline conditions. Because production of
hydrogen is chemically difficult for lead in acid
conditions the usual cathodic reactions are:
O2 + 4H+ + 4e- " 2H2O
and at the anode:
Pb " Pb2+ + 2e-
Pb2+ compounds are stable in air but SnII
compounds react with atmospheric oxygen
to give SnIV compounds or SnO2. SnO2 is an
electrical conductor so that O2 reduction can
take place at the oxide surface and not only at
the bare metal, thus accelerating corrosion.
Both lead and tin alloys are generally very
stable in the outdoor environment and react
with the atmosphere to form a grey patina.
Lead roofs are even stable against the sulphuric
acid in polluted rainwater since lead sulphate is
extremely insoluble. Because all ground waters
contain dissolved CO2 the most common
corrosion products on archaeological lead
objects are lead carbonate PbCO3 (cerussite),
basic lead carbonate Pb3(OH)2(CO3)2, and
less commonly lead sulphate PbSO4 and lead
chloride PbCl2. Lead carbonate is white, but
the corrosion products formed on lead can
range from yellow to orange or red due to the
presence of various lead oxides. Lead oxides
were previously widely used as paint pigments
in historical times because of their range of
stable colours.

3.8.1 Organic Acids and the

Corrosion of Lead
In burial, storage and display environments
polluted with organic acids: formic, acetic, etc.
corrosion of lead can be rapid and catastrophic.
The acetate ion acts as a catalyst in lead
corrosion by forming the extremely soluble
lead acetate Pb(CH3COO)2. The acetate ion
may be introduced from decaying organic
matter in the ground, from wooden (especially
oak) storage or display cases, from handling
with bare hands or even from vapours arising
from foodstuffs. It may also be introduced by
previous conservation treatments. Acetic acid
will dissolve metallic lead and also convert
stable oxides into more soluble forms. The
solution formed carries Pb2+ ions outwards
from the metallic core where they react with
atmospheric CO2 or dissolved CO32- ions. There
is an ionic exchange of CO32- for CH3COO, which
is thus released to react further with lead metal.
The resulting corrosion products show a large
change in volume and they no longer protect
the underlying metal from further oxidation.
 Chapter 4 Documenting Historic and Archaeological Metals
All conservation projects begin and end with
documentation and the care and conservation
of metals are no exception. Before any
conservation strategy can be decided and
implemented it is essential to know exactly
what the problems are. Thus all historical and
archaeological metalwork, from a steamship
to a Roman coin, are carefully documented to
establish their condition – a condition report
– only then can a conservation proposal be
formulated and costs estimated. The condition
report should aim to investigate and document
the objects function, use, materials, state of
deterioration, nature of deterioration products,
evidence of manufacturing methods (tool-
marks, casting seams, etc.) and traces of use
such as wear-marks. Replaced parts in the
case of composite objects such as machines
should be recorded and evidence of previous
treatments must be documented where
possible. The condition report serves many
functions. In conjunction with a museum’s
collections policy it may be used to determine
whether an object fulfils the criteria for
acceptance into the collection: Is the object
authentic? Does the intrinsic interest of the
object outweigh the costs and risks of its
subsequent conservation or restoration?
Does the object pose any significant health
risk to museum staff or public, for example
does a steam engine contain any asbestos
insulation? The condition report also forms the
essential foundation for informed conservation
– treatment decisions made and implemented
on the basis of the best available evidence.
The condition report also forms a baseline
assessment of the objects condition before any
conservation. This can be thought of as similar
to a doctor’s medical examination and diagnosis
of a patient’s health prior to treatment. Not
only does this examination lead to a diagnosis
but also a treatment regime and choice of
medications. Reference back to the initial
examination allows the doctor to see whether
the patient is improving or deteriorating. By
pooling this knowledge doctors can determine
which treatments are successful in the long
term and which are not. Similarly, museums
and institutions with large collections of similar
materials can re-evaluate different treatment
regimes by examining treated objects many
years after conservation. One example
is the re-examination of archaeological
ironwork to evaluate the success or failure
of different desalination methods (Keene
1994). Obviously, this is impossible without
complete documentation of prior condition
and conservation treatments. Ideally, this
documentation should be readily accessible
to future conservators and researchers –
archived either as traditional treatment cards
or as part of an electronic database. Taken
collectively, condition reports for a group of
objects or a collection – a condition survey
– helps formulate conservation strategies at
a higher level. Assessing the condition of a
museum’s collections is an essential part of
collections care and management. It identifies
any fundamental problems in the storage
environment, helps prioritise objects for
conservation and allows budgets to be set and
applied for.
Documentation of metalwork can take many
forms, from written descriptions, through
drawings and photographs, to X-radiography.
These non-destructive methods can be
supplemented by various scientific analyses,
some of which can be non-destructive such
as X-ray fluorescence (XRF) spectrometry or
Raman spectrometry, while others may require
the taking of a small sample, for example X-ray
diffraction (XRD) studies of corrosion products
or the taking of a paint sample to establish
the original colour scheme on a repainted
vehicle or industrial machine. The types of
documentation and analyses selected depend
largely on the nature of the object under study.
For working machines the documentation may
be similar to a log book where hours of use,
routine maintenance, major overhauls and
replaced parts are recorded in detail. For
archaeological objects the documentation may
be more forensic in its approach, recording
trace evidence that helps in the interpretation
of the object, its function, use and eventual
deposition in the archaeological record.
One of the most common and potentially useful
methods of documenting archaeological metal
objects is the use of radiography, usually X-
radiography.
4.1 X-radiography of Archaeological
Metals
Iron objects and some copper alloys such
as coins are routinely radiographed in
archaeological conservation laboratories and
English Heritage provide excellent guidelines
for radiography of archaeological metalwork
(English Heritage 2006). X-radiographs reveal
the shapes of objects hidden under several
millimetres of external corrosion and act as
Figure 4.1: X-radiography is a fast and effective means of primary documentation for a large group of
corroded iron objects. The archaeological objects are laid out on a photographic plate (above) and the
exposed radiograph (opposite) records both their morphology and condition.

Figure 4.2: Radiography not only helps in the identification of objects it also documents the degree of
corrosion in a metal object. Here a Medieval knife has been sectioned for metallographic analysis and
radiography was used to locate areas where metallic iron was well preserved.
a way of identifying what is otherwise an
unremarkable and shapeless lump of corrosion.
Frequently, radiography is the fastest and most
effective means of primary documentation for
a large group of corroded iron objects or coins
(Figure 4.1). Radiography not only helps in
the identification of objects it also documents
the degree of corrosion in a metal object
– especially in corroded iron objects where the
voluminous corrosion products are much less
opaque to X-rays than the surviving metal core
(Figure 4.2).
The corrosion products in non-ferrous
metals are frequently more compact than
iron corrosion products and therefore are
barely less opaque to X-rays than the metal
itself. Nevertheless, radiography of smaller
copper- or silver alloy objects such as coins
and jewellery is often advisable since this can
reveal otherwise hidden details. For example
the Anglo-Saxon brooch in Figure 4.3 has been
repaired in antiquity, using a small iron plate
and iron rivets. Corrosion of the iron in the
repair has caused the brooch to break once
again but all evidence for the repair is hidden
from the naked eye by corrosion products.
The nature of the repair was revealed only by
radiography. The relative contrast in absorption
of X-rays by ferrous corrosion products and
non-ferrous metals means that metal plating
on corroded iron objects are often quite
visible in X-rays while being invisible in visible
light, even under magnification. As we saw
in Section 3.5 corrosion of iron can continue
beneath a tin or noble metal plating, while
the tin is cathodically protected until all the
associated iron is oxidised. Thus, tin plating or
copper alloy and silver inlays on iron objects
often remain un-corroded even in severely
degraded objects.
These platings and inlays lie at the original
surface of the object and are surrounded on the
outside by external corrosion – predominantly
goethite – and on the inside by internal
corrosion – predominantly magnetite and
unstable, chloride-containing oxy-hydroxides.
In smaller objects such as keys the presence
of a tin plating acting as the cathode results
in very serious corrosion, to the extent that
almost all metallic iron is dissolved from the
object. In these cases the tin plating is the
only surviving record of the original surface
and because of the extreme fragility of iron
corrosion products it may be impossible to
mechanically clean the artefact (see Section
5.2.4). In such cases radiography in several
orientations allows a drawing to be made
of the object’s original shape and it may be
possible to open a small "window" in the
external corrosion to allow identification of
the non-ferrous metal using XRF or a similar
technique. Keys and similar objects may also
contain brazed joints where several composite
parts have been joined. Brazing can sometimes
be distinguished by identifying bubbles in the
dense metal on X-rays (Figure 4.4).
Because of the different corrosion characteristics
of wrought iron and steel it is sometimes possible
to interpret X-rays to determine whether an
ancient ferrous object has been created by
welding together several pieces of metal with
different carbon compositions. Wrought iron
usually contains long, parallel filaments of
slag from having been repeatedly hammered
Figure 4.3: Anglo-Saxon brooch that has been repaired in antiquity using a small iron plate and iron rivets.
These are only visible on the radiographs.
and folded – slag stringers. Corrosion often
follows these stringers so that X-rays of very
corroded objects show a "grainy" texture. Steel
frequently does not show these slag stringers
but is prone to pitting corrosion. Thus, in
thin objects such as knives and swords, steel
cutting edges can sometimes be distinguished
from a wrought iron core. In antiquity blades
were made by fire welding together iron and
steels of different hardness and toughness
to give a durable blade with good cutting
characteristics. Repeated heating in the forge
can cause trace elements such as phosphorus
and nickel in the steel to become concentrated
in the surface so that weld lines may be slightly
cathodic with respect to the surrounding iron.
As a result weld lines may be visible in X-
radiographs of corroded blades. Swords from
the later Roman period and Migration Period
Figure 4.4: Brazing can sometimes be distinguished
on X-radiographs of corroded archaeological objects
by identifying bubbles in the denser brazing metal
– usually brass. In this Medieval key tin plating is
visible as a dense white outline (white arrow). The
brazing with bubbles can be seen in the red boxes.

were frequently made by a complex process

of folding and twisting iron and steel bars to
achieve a springy, resilient blade with hard,
steel cutting edges – the co-called "pattern
welding" process. In the finished blade the
beautiful and complex pattern was a testament
to the skill of the swordsmith and a guarantee
of quality. Many surviving blades bear inlaid
inscriptions and makers’ names. This technique
of sword making was common to many pre-
industrial cultures as smiths sought to solve
similar problems, and Damascus blades join
those from India, Southeast Asia and China
in sharing these patterned steels. Figures 4.5
and 4.6 show stereo pairs of X-rays illustrating
pattern welding and inlayed inscriptions
revealed by differential corrosion in the blades Figures 4.5: Stereo pairs of X-radiographs
of these Viking swords from Norway. Use of illustrating pattern welding and inlayed inscriptions
stereo radiography can help is distinguishing revealed by differential corrosion in the blade of this
inscriptions on two sides of an iron object or Viking sword from Trondheim, Norway.
in understanding the internal mechanisms of a
lock for example. health and safety can be avoided. High energy
X-rays are used, typically over 100 kV and
Radiography of archaeological metals usually films may be used in combination with a lead
involves conventional industrial X-ray films in intensifying filter that screens out much of
a reusable cassette, although in some of the the scatter and increases the image contrast
larger laboratories digital radiography is being by stimulating photoemission of electrons in
introduced. If the X-ray plates are exposed in a the lead which is pressed into close contact
sealed cabinet X-ray source such as a Faxitron with the emulsion. Industrial X-ray films are
machine (Figure 4.7) then many issues with available with extremely fine grain emulsions
Figure 4.6: Digitally enhanced detail of the radiograph seen in Figure 4.5. By crossing ones eyes it is
possible to visualise a 3-dimensional, stereoscopic view of the twisted rods and inlayed pattern. To the
right is a reconstruction of a 9th century AD Viking sword by Czech swordsmith Patrick Bárta showing similar
pattern welding and inlay. The hilt is inlaid with copper and silver wires.

Figure 4.7: Closed cabinet industrial X-ray machines

are available for the routine radiography of small
objects. The multiple safety features means that
many issues with health and safety of the operator
can be avoided.

such that in very small, delicate objects such

as jewellery it is possible to cut out the area
of the image of interest and view it through a
conventional transmitted light microscope to
document fine details of manufacturing.

4.2 Microscopic Analyses of

Archaeological Metals
The conservation of archaeological metals
– in fact of almost all archaeological materials
except large structural timbers – is undertaken
under a low-power binocular microscope. This
allows the conservator to distinguish slight
differences in colour and texture that signify
changes in corrosion product as well as identify
potentially useful forensic information relating
to the object, its use or its burial environment.
Careful note should be made (and documented
in text, photographs or samples) of any
tool-marks, soldered joints, wear-marks or
Figure 4.8: Microscopic examination, combined
with mechanical cleaning and X-radiography can
reveal how objects have been made and assist the
archaeologist in interpreting ancient technologies.
A) shows a radiograph of several Roman writing
styli with a detail of two with decoration. B) shows
three styli that have been cleaned by air-abrasion
revealing brass inlay on two and a grooved grip on
a third.

associated organic materials preserved in

corrosion products. All these pieces of trace
evidence may help in the interpretation of the
object itself or its archaeological context.
The examination of tool-marks such as punches
used in the decoration of silver or copper alloys
vessels can lead to a better understanding
of manufacturing techniques in antiquity and
even shed light on the number of artisans
working in a workshop (Larsen 1987; Wicker
1994; Nielsen et al. 2005).

Microscopic examination, in conjunction

with close examination of X-rays can reveal
how objects have been made and assist
the archaeologist in interpreting ancient
technologies (Figure 4.8). When metal
objects have been buried quickly in controlled
circumstances, for example by being included
in a tomb or grave to accompany the dead into
the next world, the corrosion products may
preserve organic material in contact with the
corroding metal. These metal salts released by
corrosion can have a remarkable preserving
effect on materials that might usually decay
rapidly in the soil. Copper salts are naturally
toxic and work as biocides – killing bacteria
that would normally quickly degrade organic
materials like wool, linen, leather and wood.
Iron usually corrodes rapidly in the soil,
especially in combination with copper alloys
or noble platings, and this corrosion releases
soluble ions that penetrate organic matter.
Capillary forces draw aqueous metal salts
deep into porous organic materials such a
leather, textile, wood and horn. Metal salts are
known to react chemically with proteins and
carbohydrates and salts of iron, copper and tin
are used as mordants to help organic dyes bind
to textile fibres. Mineral preservation seems to
be facilitated if the organic matter is slightly
chemically degraded prior to infiltration with
soluble metal salts. Traces of organic matter
preserved in association with metal grave
goods are called mineral preserved organics
(MPOs) or mineral pseudomorphs. The most
commonly encountered pseudomorphs are
those that have been preserved with iron
or copper corrosion products, although
preservation by silver chloride is also known.
The detail preserved by metal corrosion is
remarkable, with microscopic details of fibre
and other cellular structures preserved. The
quality of detail preserved is demonstrated by
the preservation of insect remains on some
Anglo-Saxon grave goods (Figure 4.9).

Figure 4.9: The detail preserved by metal corrosion is remarkable, with microscopic details of fibre and
other cellular structures preserved. The quality of detail preserved is demonstrated by the preservation of
insect remains on these Anglo-Saxon grave goods from East Anglia, U.K.
 Chapter 5 The Conservation of Metals
5.1 Strategies for Conservation
of Metals
With the exception of gold alloys of high
purity all historic and archaeological metals
will have some form of external corrosion and
some will have extensive internal corrosion.
Even gold can acquire a thin coating of brown
or red staining after centuries of soil burial
– possibly representing a fine layer of cuprite.
Gold alloyed with copper or silver may become
surface enriched as copper or silver ions are
leached from the outer few microns of the
metal - leaving the surface dulled.
In some metal objects this corrosion is
relatively harmless and will not promote
further deterioration of the artefact. For
examples some bronze and brass objects have
an aesthetically pleasing patina that is valued
by collectors and the museum public alike. In
most cases this patina will be preserved during
the cleaning of a copper alloy object. Instead
of removing this corrosion the surface may be
stabilised with a chemical passivator and the
cleaned copper patina coated with a protective
lacquer to prevent water condensing on the
surface and changing the nature or colour of
the corrosion film.
All copper alloys should be stored or exhibited
in an atmosphere that is below 45% RH and
has no polluting gasses such as SO2 or H2S. In
other metals, especially iron, the thick layers
of corrosion hide the shape of the original
artefact. The shape of the object can be
revealed by X-radiography and drawings for
publications and reports may be made from
X-ray plates. However, if the artefact is to
be displayed in a museum then the external
corrosion may be removed to allow the object
to be seen and fully understood by the public.
The artefact will also have to be cleaned if it has
decorative platings or inlays of another metal
so that the pattern can be seen. Some lead and
silver alloys can also become covered in a thick
layer of corrosion that hides the shape of the
artefact and obscures surface decoration. In
the case of silver, this thick corrosion – usually
silver chloride – can be removed to show the
shape and decoration below. The corrosion
layer itself is not a danger to the long-term
survival of the object or to museum specialists
handling the objects. After removal of the
silver chloride crusts the exposed surface may
be restored to a bright, shiny finish or may
be left dull depending upon the preference of
the museum specialists or in accordance to an
accepted conservation ethical code. It is ironic
that although "bronze" objects are commonly
considered acceptable whilst still corroded and
green in colour silver is not viewed favourably
by the museum public if it is blackened by
corrosion – a situation commonly encountered
in both archaeological and historical silver. The
cleaning and subsequent care of metal cultural
heritage is as much about cultural preferences
and ethical codes as it is about practical
conservation. Clearly, before any interventive
treatment is undertaken the conservation
strategy and its intended outcomes should be
fully discussed and agreed amongst all relevant
parties – the owner or curator, the conservator
and any specialists involved in researching that
class of objects concerned.
5.2 Cleaning and Stabilisation of
Corroded Metals
The cleaning and conservation of metals differs
from the cleaning of other cultural material in
the nature of the material removed. Cleaning
usually involves the removal of "dirt". Dirt can
be interpreted in many ways but usually the
term refers to foreign particulate or oily matter
sitting on top of, or permeating into, the original
surface. There are various ethical approaches to
the removal of such dirt from many classes of
historical and cultural artefacts. If the dirt has
got there through the normal use of the object,
for example grease by repeated handling during
the use of a tool, then it can be argued that the
dirt represents part of the object’s history and
should not be removed in the same way that
dust accumulated in poor storage or display
should be removed. In the case of metals
the situation is more complicated. Corrosion
does not represent foreign matter deposited
on top of the original surface. Corrosion is
the original material transformed into another
form. Removal of the corrosion will not reveal
the original surface – removing the corrosion
is actually removing part of the object itself.
Very often this is not understood correctly. In
the case of corroded coins there is often the
desire on the part of some collectors to clean
the coin to reveal the underlying detail. In the
case of severely corroded archaeological coins
the original surface may no exist, having been
converted to voluminous corrosion products.
Any attempt to "clean" the coin by physical
of chemical methods only makes the situation
worse. In fact, amongst serious coin collectors
there is an understanding that cleaning should
only be attempted in very special circumstances
and that cleaning a coin will most often destroy
its aesthetic and monetary value. Thus, no
cleaning of a historical or archaeological
metal artefact should be considered without
a clear evaluation by curators, owners and
conservators of the ethical issues involved.
5.4 Types of Cleaning
There are four approaches to the cleaning of
corroded historical and archaeological metals.
1) Mechanical cleaning to remove, or modify
the appearance of, external corrosion.
2) Chemical cleaning to remove corrosion.
3) Electrochemical cleaning to reduce and/or
remove corrosion.
4) Thermal reduction.
These four traditional approaches are now
supplemented by laser cleaning of metals
where pulses of high energy laser light are
directed at the surface and rapid heating either
decomposes the corrosion product or thermal
shock blows off the outer layer by a principle
called laser ablation. Often, several methods
will be used separately or in combination on
one object to get the best results.
5.3.1 Mechanical Cleaning
Mechanical cleaning is the term used when
foreign matter or corrosion is physically
removed from the surface of an object using an
external force. There is no requirement that a
machine is used and most mechanical cleaning
is done by hand using simple small tools with no
moving parts. The simplest act of mechanical
cleaning is the removal of superficial dust or
particulate matter using a soft, dry cloth. No
chemical interaction takes place between the
cloth and the object’s surface, nor between the
cloth and the particulate matter – apart from
perhaps a temporary electrostatic attraction.

Method Tools
Air movement Vacuum cleaner
Rubber bulb
Breath
Compressed air jet
Brushing Natural bristle (watercolour brush)
Nylon bristle
Glass bristle brush

____ INCREASING ENERGY ____

Brass wire brush
Steel wire brush
Peeling/Pulling Adhesive tapes
Flexible adhesive
Rubbing/Polishing Cotton swabs (without a polishing compound)
Cotton swabs (with a polishing compound)
Soft pencil eraser
Hard pencil eraser
Scraping/Scratching Bamboo sticks
Needle Probe
Scalpel
Cutting Scalpel
Abrading/Grinding Polishing compounds
Sandpaper
Rotary grindstone
Impact Air-abrasion
Vibrotool
Sandblasting
Hammer
Table 5.1 Methods of mechanical cleaning summarised. The energy applied to the surface increases as one
moves down the table. It is important to select the correct energy to use when mechanically cleaning any
object and to use tools of the appropriate hardness.
There are, of course, many different ways of surface reflects light differently from a rough
applying an external force and some are more surface covered in particulate matter and looks
gentle (or aggressive) than others. The table "cleaner" as a consequence (Figure 5.1).
below describes the most common types of
physical interaction between a dirt or corrosion
layer and the tool used to remove, or reduce it
(Table 5.1).

Obviously the gentlest cleaning method

is using the drag caused by moving air to
remove dust. This is hardly effective against
hard corrosion but is useful in removing dust
and particulate matter created by other, more
aggressive, mechanical cleaning methods.
Brushing involves direct physical contact
between the cleaning tool and the dirt or
corrosion. The stiffer and more resilient the
fibre used in the brush the more energy can
be transferred to the particulate matter on the
surface and the more effective the cleaning. If
a harder, as opposed to stiffer, bristle is used
then as well as removing particulate matter
from the surface small pieces of hard material
may be dislodged from the surface. Thus some
corrosion can be physically removed by the
use of a glass bristle or wire brush. In softer
materials – metal as opposed to the minerals
which make up corrosion – then the surface
may be permanently damaged in the form of
scratches, so these brushes are hardly ever
used on soft metals such as silver and copper,
or where tin plating or gilding is present.
Brushing implies that a shear force is applied
parallel to the surface of the object.

It may be possible to remove some unwanted
materials such as flaking paint from the
surface by applying a force at right angles to
the surface – i.e by pulling the paint off the
surface. Adhesive tapes are useful for removing
old overpainting from some industrial heritage
objects without damaging the original paint
below. As unlikely as it seems, it is possible
to remove some corrosion products using a
variation of this technique. Silver chloride
corrosion can be physically removed from
the very fragile underlying silver by carefully
peeling off a layer of cellulose nitrate adhesive
applied previously (see Section 5.8.1).
Polishing is a term often used in connection with
the "cleaning" of historical metals, especially
silver and copper alloys. This implies rubbing a
cloth or cotton wool swab repeatedly back and
forth parallel to the object’s surface. Polishing
has a two-fold action: loose particles are
removed from the surface are entangled in the
fibres of the cloth or swab; and material that
is securely bound to the surface is burnished
to give a smoother surface. This smoother
Figure 5.1: Gently cleaning superficial corrosion
from an aluminium rice steamer using a scalpel.
Removing the white powdery corrosion leaves a
darker, smoother and more even surface finish.
The effectiveness of the cleaning depends upon
the hardness of the material in contact with
the surface, the force applied, and the duration
of the polishing. The aggressiveness of the
polishing action can be modified by using a
polishing compound that contains hard, sharp
particles of differing sizes. These particles
usually come in some kind of carrier liquid
that wets the surface of the object and allows
even distribution of the polishing compound.
This can be simply a water- or spirit-based
wetting agent (detergent) or may also contain
some chemical reagent specific to the metal
being polished – for example, copper, brass
and silver polishes frequently contain ammonia
which forms soluble complexes with copper
corrosion products. Silver polish may contain
thiosulphate which helps to reduce silver
sulphide. Another useful tool for the removal of
particulate matter and softer corrosion products
is a pencil eraser. These come in a variety of
rubber and plastic compositions of various
hardnesses. Putty rubbers are soft and sticky
and good at binding loose particulate matter
such as rust but may leave an oily residue on
the surface cleaned. Plastic (PVC) rubbers bind
up particulate matter into the rubbings created
and leave the surface looking cleaner without
disrupting the underlying corrosion layer.
Harder erasers (usually grey in colour) contain
abrasive particles which will actually remove
or smooth metal corrosion products as well as
removing particulate matter from the surface
(Figure 5.2). It is possible to buy large abrasive
rubber erasers for cleaning and polishing the
aluminium engine blocks on motorcycles and
these are often useful in cleaning historical iron
tools and small pieces of industrial heritage.
Figures 5.2: A cast iron rotary cutter (used as a
mortar for chopping Chinese medicinal plants) with
one quadrant cleaned using a hard pencil eraser
(PentelTM Hi-Polymer Super-Hard).
So far, the mechanical cleaning methods that
have been described are general ones where
the point of contact with the surface is relatively
large. When cleaning metal objects under a
low-power binocular microscope only a small
are is visible at one time and it is possible to use
very precise methods where areas of around
one millimetre square are cleaned at one time.
Foreign matter and corrosion may be dislodged
or broken free very gradually using very small
tools such as needle probes and scalpels.
This kind of cleaning is called investigative
cleaning and any interesting corrosion
products, technological evidence or platings
should be photographed and documented by
the conservator before a decision is made
to remove or retain them (English Heritage
2008). Extreme care must be taken so as not to
remove important trace evidence that may give
clues to how the artefact was made, used and
discarded. Cleaning at this level of observation
is an absolute necessity when conserving any
archaeological metal artefact. Since corrosion
products are frequently hard and brittle when
compared to the underlying metal it is possible
to use crushing forces to break them up and
remove them. This can be done using sharp
needles and scalpels to introduce cracks in
the corrosion by applying pressure vertically
or obliquely with respect to the metal surface.
With care it is possible to slice through even
hard corrosion using a scalpel (see Figures 5.3
and 5.4).
With archaeological iron object it is difficult to
remove the hard, concreted external corrosion
without risk of damage to the underlying
internal corrosion which may be equally
brittle and fragile. One traditional method is
to use rotary burrs or grinders mounded on
a flexible drive similar to a dental drill. This
however creates a lot of dust which can hide
the surface being worked on and may present
a health or nuisance hazard to the conservator.
Vibrating needle probes – vibrotools – are
also used in cleaning corrosion from small
objects but the vibration involved can also
fragment fragile objects. A more delicate
approach is to use an air-abrasive machine
where a small jet of compressed air containing
abrasive powder is directed at the surface to
be cleaned. Commercial air-abrasive machines
are available and are used in a glove box with
protective gloves and vacuum dust extraction
(Figure 5.5). The jet nozzle of an air-abrasive
Figure 5.5 Commercial air-abrasive machines are
available and are used in a glove box with protective
gloves and vacuum dust extraction.

can be extremely small – less than a millimetre
in diameter – so that the work can be both
delicate and precise. Cutting strength is
varied by altering the powder flow and the air
pressure so that a very gentle effect can be
achieved. Air-abrasive machines can be used
with a variety of abrasive powders of different
cutting strengths. On larger objects and
industrial heritage commercial sandblasting or
shot blasting is used to clean corroded metals
but this is usually done in a sealed room
where the surface cannot be observed as it is
revealed. It in normal to use sandblasting on
large objects when the desired objective is to
remove all corrosion and paint down to a bare
metal surface. The most extreme mechanical
cleaning of historical and archaeological
metalwork is reserved for marine iron objects
where external concretions deposited by
marine organisms are sometimes removed
with a hammer or pneumatic chisel (Cronyn
1989).
5.3.2 Chemical Cleaning
The chemical cleaning of metals refers to the
use of a chemical reagent, often in aqueous
solution, to solubilise otherwise insoluble metal
salts. As mentioned in Section 5.3.1 above
many commercial copper and silver polishes
contain chemical regents that either reduce a
metal ion to a more soluble oxidation state or
form soluble complexes with them. Cleaning
with acids or alkalis also constitutes chemical
cleaning. Some corrosion products, particularly
the hydroxyl-carbonates are soluble in acids.
Figures 5.3: Mechanical cleaning of iron corrosion
products from the clasp of a Chinese balance case.
The micrographs show how a scalpel can be used
horizontally to cut through the corrosion crust,
slicing down to a darker, more compact layer; or
held vertically so that brittle corrosion products can
be broken free, parting naturally at the interface
with the more compact layer. Figures 5.4: For more
delicate work a sharpened sewing needle held in
a propelling pencil is very useful in cleaning fine
detail.
The oxides of tin, zinc and aluminium are
amphoteric and will react with alkalis to form
soluble salts. Common chemical cleaning
reagents for copper and silver artefacts may
include organic acids such as formatic and
citratic acid. Other approaches to the chemical
cleaning of corroded metals involve chelating
agents that form strong ligands with metal
ions. These include ethylene diamine tetra-
acetic acid (EDTA) and similar compounds that
will surround and solubilise divalent ions such
as those of copper, lead and iron. Aqueous
ammonia also forms soluble complexes with
copper and silver and as stated above may
be included in commercial metal polishes
– although ammonia compounds can also find
application in the conservation laboratory.
Chemical cleaning is often combined with
mechanical cleaning, as when a corroded
metal object is rubbed with a cotton wool swab
dampened with a solution of chemical reagent
or when the object is immersed in an ultrasonic
tank and physical vibration combined with
cavitation at the surface disrupts the corrosion
crust.
5.3.3 Electrochemical Cleaning
Electrochemical cleaning, as the name
suggests, makes use of an impressed electrical
potential to either reduce the oxidation
state of a corrosion product in situ or drive
a charged species (usually chlorides) from
the surface of the metal. Frequently these
two aims are achieved simultaneously.
Electrochemical cleaning is used extensively
in the desalination of marine ion objects but
is also used in the conservation of terrestrial
archaeological ironwork. The impressed
potential can be applied from an external
DC source and controller so that voltage and
ampage can be carefully adjusted to reduce
the corrosion product in question without
generating hydrogen gas bubbles that would
otherwise disrupt and remove the corrosion.
Alternatively, a potential can be generated in
situ by connecting the iron to a more reactive
metal such as aluminium or zinc. When placed
in a suitable electrolyte the reactive metal
becomes anodic and pumps electrons into the
iron object where nacent atomic hydrogen
generated at the metal core locally reduces
the internal or external corrosion. This reaction
is however much more difficult to control and
corrosion crusts are frequently disrupted,
broken up and lost by the formation of bubbles
of hydrogen gas between the remaining metal
core and the corrosion layers. By employing
the more controlled reduction possible with
an external DC current however, the local
reduction of compact corrosion products
surrounding the metallic iron core, to which
chloride ions are assumed to be closely bound,
has the advantage of opening up the pore size
and therefore facilitating the outward diffusion
of Cl- ions. Coupled with the electric potential
difference between the negatively charged
core and an external anode this means that
treatment times for the desalination of chloride-
contaminated objects is dramatically reduced.
One of the main disadvantages with these
stripping or electrolytic reduction methods is
that tin platings are removed by the alkaline
electrolytes used and any inlaid non-ferrous
metals are likely to be damaged or destroyed
during prolonged treatment.
5.3.4 Gaseous Reduction of
Archaeological and Marine Iron
Since it can be argued that the corrosion of
iron artefacts is simply the thermodynamically-
favoured reversion of metallic iron back to its
original state as an ore, it is not surprising that
several treatments have been developed that
in some ways mimic the gaseous reduction of
metal ores to metal at elevated temperatures.
Early attempts to remove presumed sodium
chloride contamination from cannons recovered
from the sea involved placing the objects in an
industrial annealing furnace for several hours to
drive off chlorides in gaseous form (Eriksen and
Thegel 1966). These attempts were ultimately
unsuccessful and more technical solutions were
sought. Heating in a reducing environment at
temperatures of 600-850 oC has had considerable
success with marine iron objects, especially cast
iron cannons which contain free graphite (North
and Pearson 1977). The reducing atmosphere is
usually hydrogen created by cracking ammonia
at high temperature and pressure in special
retorts or furnaces. This is, of course, extremely
dangerous and special precautions must be
taken. The oxy-hydroxides in the corroded
cast iron are reduced to magnetite and metallic
iron. The finished objects are very stable and
have a good aesthetic appeal – looking black
and compact. A major disadvantage is that
all corrosion products are reduced to black
magnetite, including external corrosion so
wrought iron objects from terrestrial sites should
be mechanically cleaned of external corrosion in
advance to preserve the original shape.
A recent fairly development in the treatment
of unstable iron is the use of low-temperature
plasma (Veprek 1989, Aoki et al. 1989).
Plasma reduction is undertaken at much
lower pressures than in traditional hydrogen
reduction and consequently is considerably
safer with regards potential explosion risks.
Plasma reduction of corroded iron objects
simultaneously reduces oxy-hydroxides to
more stable magnetite and removes chloride
contamination. Treatment temperatures
are typically of the order of 300 oC which is
considerably lower than the range used in
conventional reduction furnaces. However,
it should be made clear that all thermal
treatments will radically alter the internal
microstructures of all metals exposed and
therefore may negate any future possibility of
metallographic or chemical analyses.
5.3.5 Passivation and Coating of
Metals
After a metal surface has been cleaned it is
also usual to apply some kind of chemical
treatment to stabilize or pacify the surface
of the newly cleaned object or provide an
impenetrable barrier to oxygen and water.
Pacifying treatments aim to chemically alter
the outer surface of the metal to reduce the
susceptibility to future corrosion using either
organic molecules which form stable organo-
metallic compounds, or other inorganic
compounds such as phosphates. A wax
or lacquer barrier may then be applied to
prevent future corrosion. Wax impregnation
of cleaned archaeological iron objects is often
used and involves immersing the hot object in
melted paraffin wax under vacuum to ensure
penetration of this water-repelling barrier into
the fine pore structure of the corrosion layers.
The current approaches to cleaning of specific
metals and their alloys will be introduced
below.
5.4 Cleaning of Copper Alloys
With historical copper alloys that have never
been buried in soil, corrosion is frequently
superficial – the shape is clearly seen but the
metal may look dull, tarnished or spotted with
light corrosion. Outdoor copper alloy sculpture
may be more seriously corroded since they
are often displayed in city centres with high
levels of pollution. In the case of household
items and scientific instruments the cleaning
of copper alloys is mostly cosmetic and may be
done with mild abrasives or chemical polishes.
After the surface has been cleaned care must
be taken to remove all traces of polishing
compounds and chemical reagents. Residues
of polishing abrasives contain finely divided
metal particles and may be hygroscopic, and
thus attract moisture to the cleaned surface,
stimulating fresh corrosion. Many commercial
copper and silver polishes contain ammonia or
other compounds which can also catalyse fresh
corrosion. In a museum context the cleaned
surface may be protected against further
corrosion by the application of a clear lacquer
or microcrystalline wax. Once again, care must
be taken to ensure a complete and even coating
since any thin areas or gaps in the coating
will corrode or tarnish preferentially, leaving
dark streaks on the object corresponding to
brush strokes. With historical metals with
complicated shapes it is easier to spray the
surface with lacquer rather than risk leaving
brush strokes.
With archaeological copper alloys the situation is
considerably more complex since the corrosion
is often considerable, with some areas covered
by thick corrosion and some pitting or erosion
of the surface details. In extreme cases the
corrosion forms unsightly warts or spots which
need to be carefully removed to reveal the
original shape of the object, even if the original
surface is lost. This approach can be an ethical
minefield since it relies upon the conservator’s
judgement as to where the original surface
lies. In most archaeological copper alloys the
internal corrosion is predominantly the red/
brown cuprite, while the external corrosion is
usually a mixture of blue/green basic copper
carbonates – although the corrosion may also
contain iron and tin oxides that may introduce
browns and greys into the patina. Strictly
speaking, the original surface should lie at the
interface of the cuprite and the green external
corrosion (Figure 5.6) but it is considered
Figure 5.6: (below) The original surface on a
corroded copper alloy objects should strictly lie
at the interface of the red cuprite and the green
external corrosion. In this cast Chinese bronze
sword the depth of penetration of the cuprite layer
can be seen clearly. The original surface (arrowed)
lies between this and the external corrosion.
unacceptable to clean down to this cuprite layer. can be achieved (Figure 5.7). Aluminium oxide
To do so would risk removing important surface is very hard and sharp and cuts corrosion very
detail and leave the bronze object red in colour quickly. It is useful for removing iron corrosion
rather than green – a situation tantamount to but is far too hard for copper alloys that have
the destruction of cultural property. Instead, much softer and less coherent corrosion
the conservator seeks a coherent and compact products. Microscopic glass beads or sodium
surface, whatever the colour, which preserves bicarbonate powder are, however, excellent
the shape, texture and decorative features of for cleaning copper alloys. It is quite possible
the perceived original. to safely remove the external green corrosion
products to reveal tinned surfaces on copper
5.3.1 Mechanical Cleaning of alloys without destroying the fine patina below
Copper Alloys the external corrosion (Figure 5.8).
Cleaning of archaeological copper alloys is
most often done mechanically and under a
low-power microscope. Small tools such as
needles, bamboo probes, surgical scalpels,
paintbrushes and glass fibre brushes are the
common tools used. Gloves should, wherever
possible, be worn to protect the object from
grease and sweat on the conservator’s fingers
but also protect the conservator’s hands from
irritating or toxic dust. A sharp scalpel may be
used to carefully remove soil encrustations
from the underlying patina since a sharp
scalpel requires less force than a blunt blade
and there is less chance of scratching the
surface or inadvertently tearing a piece of
corrosion out of the metal. Sometimes it is
necessary to use a dentist’s drill with small
abrasive burrs to clean off hard concretions
that cannot be removed with a scalpel without
destroying the metal below. With considerable
practice and good a microscope it is possible
to remove the external corrosion from copper
alloys with an abrasive air-abrasive machine
with suitably sized nozzles and a careful
selectrion of an abrasive powder. This is a
technique usually restricted to the cleaning of
archaeological iron but will care, patience and
sufficient practice good results on copper alloys

Figure 5.7: With considerable practice and good
a microscope it is possible to remove the external
corrosion from an archaeological copper alloy object
using an air-abrasive machine with suitably selected
powder and pressure. Here a small key has been
partly cleaned down to the “original surface”.
Figure 5.8: It is possible to remove the external
green copper corrosion products from an
archaeological object to reveal the gilded surface
without destroying the fine patina below the
external corrosion. An Anglo-Saxon square-headed
brooch from Lindsey in Lincolnshire.
One caveat when cleaning copper alloy objects
created by the combination of different
parts. Tin- or lead-rich solders may corrode
faster than the bronze or brass surfaces they
are joining and as a result the joints in an
archaeological object may fail while in the
ground. The remaining solder residue may
be completely corroded and may look like a
powdery corrosion product. This should not
be removed in mistake for external corrosion
since this will destroy important technological
evidence and make it unclear exactly where,
for example, a soldered handle was attached
(Figure 5.9). Furthermore, red enamel inlay in
the form of a glass coloured by copper I oxide
can deteriorate in the burial environment and
turn into green powdery material containing
copper carbonate. Once again, this represents
important technological and art historical
evidence and should not be removed, having
been mistaken for ordinary corrosion.
Clearly, the cleaning and conservation of
archaeological copper alloys requires good
powers of observation, good comprehension
of art historical and technical issues relating to
the class of objects treated, and a high level of
training and experience.
5.4.2 Chemical Cleaning of
Copper Alloys
Copper alloys can be cleaned chemically if
the original surface is too fragile to survive
mechanical cleaning. Usually, chemical cleaning
is used in combination with mechanical
cleaning to soften hard encrustations or
to remove copper corrosion overlying gold
plating. Dilute formic acid may be applied to

Figure 5.9: Roman bronze flagon from a grave in East Anglia. The handle has become detached after
hundreds of years of soil burial but the original location of the handle is indicated by the corroded remains
of the solder. The detail shows the solder “scar” and how the surface of the flagon was roughened with a
file to help the solder bond strongly.
external corrosion using cotton wool swabs.
The acid reacts with carbonates in the basic
copper carbonate corrosion products and these
copper II compounds become soluble copper
formates. Objects must be well rinsed with
water and/or ethanol afterwards to remove
excess acid. Conservators should be very
careful when using acids to clean corrosion
products. Formic acid turns the green patina
to a red/brown surface by exposing the cuprite
(copper I oxide) surface below. Furthermore,
with gilded objects, acid decomposition of basic
copper carbonates below the gold plating can
create bubbles of carbon dioxide that may lift
and detach the thin gilded surface. In the past,
chemical stripping of corrosion using organic
acid solutions – formic, citric, tartaric or oxalic
acids has been used in the cleaning of copper
alloys, especially the bulk cleaning of many
objects such as in coin hoards, etc. Certain alkali
salts have also been used – 15% NaKTartarate
/ 5% NaOH (pH 13), NaOH/Glycerol (pH 13) or
Na2EDTA at pH 8. However this runs the risk of
removing or radically altering the patina and
de-zincifies or de-stannifies the metal below.
Simple electrolytic stripping of archaeological
bronzes has been used by wrapping Cu wire
around bronzes and immersing them in NaOH
and a closely related method is electrochemical
stripping using zinc granules and warm NaOH.
Here the method relies upon the generation of
bubbles above the remaining metal to disrupt
and weaken the external corrosion. However,
there is a danger that zinc metal may plate
out onto the objects being cleaned. Sodium
sesquicarbonate washing in 5% aqueous
solution has also been used in the past in an
attempt to reduce the chloride content of the
corrosion crusts. The reaction targets cupper I
chloride:
2CuCl + H2O Cu2O + 2HCl
The HCl created is neutralized by the carbonate
to give off carbon dioxide, thus driving the
reaction to the right and leading to the slow
removal of CuCl from the object. However, very
pure chemicals must be used and the treatment
can cause colour changes in the patina.
5.4.3 Stabilisation of Copper
Alloys
For any archaeological copper alloy it is
usually necessary to chemically stabilize the
corrosion products in the patina to prevent
future corrosion (bronze disease). Problems
with post-excavation corrosion usually result
from chlorides closely bound to the metal
surface below the patina and most chemical
stabilization aims to prevent reactivation of
chloride catalysed corrosion. Bronze disease
is recognised by rapidly growing, bright green,
powdery corrosion normally associated with
pits in the surface patina. If bronze disease
is limited to a few bright green spots in an
otherwise stable patina then these spots can
be excavated mechanically and the chlorides
immobilized. After removing the loose, bright
green paratacamite the pit is packed with Ag2O
and the object exposed to a high humidity.
Under high humidity the chlorides become
mobile but react with the silver to form highly
insoluble AgCl:
2CuCl + Ag2O " Cu2O + 2AgCl
However, exposure to ultraviolet light can
reduce the AgCl to metallic silver, in a reaction
analogous to the exposure of a photographic
emulsion, and release the chlorides again. As
an alternative treatment, the copper object can
be exposed to ammonia vapour that complexes
with copper chloride by forming a strong
ligand. The object is then put in a saturated
acetone vapour leading via a condensation
reaction to triacetone amine that encloses
the AgCl. However, once again there is the
danger of colour changes in the patina and any
cyclic copper acetylene compounds formed are
intrinsically unstable.
Most conservators now use treatment with
benzotriazole (C6H5N3) to stabilize all but the
most unstable bronzes and copper alloys.
Benzotriazole is commonly referred to as
BTA and can act as either an electron donor
or electron acceptor - having three lone pair
electrons that can form coordinate bonds with
copper. It is thought to form three different BTA
compounds with copper to give a thin film over
the whole metal surface – although it remains
unclear to what extent it binds to copper within
the corrosion layer. This film is less than 500
nanometres thick and therefore quite fragile.
In practice, objects are degreased in acetone
and then immersed under vacuum in a 3%
aqueous solution of BTA or 3% in ethanol. If
the object is too large to completely immerse
in liquid or to fit into a vacuum chamber then
a 3% solution in alcohol dripped on a tissue
and placed in an airtight storage box acts as a
vapour phase inhibitor – BTA being carried as a
vapour into the pore structure of the corrosion
where it undergoes reaction with copper
compounds. As an important health and safety
note, BTA is a suspect carcinogen and should
be treated with the respect accorded to all
reagents in the conservation laboratory.
To further protect copper alloy objects they
are usually lacquered with IncralacTM or
B44, a methylmethacrylate with a glass reducing the amount of dust that is frequently
transition temperature of 60 oC. It is soluble created when using wire brushes. Care should
in toluene, xylene, dichloromethane, acetone be taken when using wire brushes that brass
and butanone but insoluble in heptane and bristle brushes are not overused since hard
alcohols. A mixture of acetone and toluene brushing will result in a layer of yellow brass
is a common solvent for IncralacTM but in hot being deposited on the cleaned surface
humid climates lower boiling point solvents – a situation that can be avoided by using
must be used because acetone is hygroscopic specially made phosphor bronze brushes. After
and absorbs atmospheric water. Once superficial surface cleaning the metal parts of
water becomes dissolved in the solvent the tools can then be protected against further
methacrylate is precipitated as a white, stringy corrosion with a thin application of oil or wax
mass that fails to bond to the object’s surface which does not look out of place on a working
and is disfiguring. This adsorption of water implement (Figure 5.10).
can also occur once the lacquer is painted on
the object and in such cases a white bloom
forms on the surface. IncralacTM is specifically
designed for use with copper and copper alloys
and contains both BTA and a ultraviolet filter to
prevent degradation of the BTA.
To avoid a shiny surface that looks obviously
artificial, a matting agent such as fumed
silica or wax is usually added to the lacquer.
Another way of matting the surface is to blow
gently on the lacquer as it is drying. Moisture
in the breath condenses on the drying lacquer
because the evaporation of solvent cools the
surface. This condensed moisture leaves a
layer of water droplets on the surface which
later evaporates, leaving the finished surface a
matt texture when dry.

5.5 The Cleaning of Ferrous

Metals
As with copper alloys, there is a very big
difference in the preservation states between
historical iron or steel that has never been
buried in soil and archaeological iron that
may have spent many centuries underground.
There is therefore a clear divergence in both
conservation problems and solutions between
historic and archaeological iron objects. Iron
objects that have stood outside in the open
air may remain relatively un-corroded for
hundreds of years, such as the case of the
iron pillar in Delhi. Iron and steel tools that are
used or regularly handled tend to survive well
since surface wear removes corrosion products
that may promote further corrosion and grease
from frequent handling acts as a water-
repelling barrier. Fairly recent or historical
hand tools and agricultural implements that
had no original decorative surface are often
quite easily cared for. Such objects can usually
be "cleaned" quite simply with stiff brushes
or mild abrasives to remove loose surface
corrosion down to a compact layer of more
stable corrosion products. Smaller tools can be
cleaned more gently using hard pencil erasers
that contain a fine abrasive material. The use
of erasers has the additional advantage of
Figure 5.10: After simple mechanical cleaning
this object has been coated with a thin layer of
microcrystalline wax (Renaissance WaxTM).
Larger objects and tools can be sand- or shot
blasted to remove corrosion down to the
bare metal. This is often done in the case of
historic vehicles such as steam locomotives
where the object is to repaint the metal as
new – restoration as opposed to conservation.
Obviously if a working machine or large vehicle
is to be restored to its original use then almost
by definition any corrosion will be superficial
and the underlying metal in good condition.
The restoration of working machines is a
controversial issue involving a complex web of
practical, historical and ethical questions which
will not be discussed here but are covered
in several excellent papers (Dessaint 1995,
Magnin et al. 1995).
There is a large body of historical decorative
ferrous alloys from Old World historical
contexts and ethnographic sources. These
objects fall into three broad classes – arms and
armour; architectural features and household
items; and religious iconography. Even entirely exhibition it is frequently the case that small
functional objects such as armour may be "windows" are opened in the corrosion to
elaborately decorated with inlays, engravings reveal detailed information not obtainable from
and gilding. These artefacts fall somewhere X-radiography alone (Figure 5.12).
between historical objects and archaeological
metalwork and require specialist care by
appropriately trained conservators. Once
again the borderline between conservation and
restoration can become blurred and frequently
conservators working on historical decorative
metalwork have a background in fine metalwork
as well as conservation training.

5.5.1 Conservation of Archaeological

Iron
The conservation of archaeological iron objects
is more problematic than the conservation
of historical artefacts and requires a very
different approach. To begin with, most
archaeological iron objects are small compared
to some historic objects. Apart from some very
large wrought iron objects such as forged iron
structural beams from Roman bathhouses
(Wacher 1971) and large marine iron objects
such as wrought anchors and cast cannons,
the vast majority of archaeological iron objects
are small – nails and door fittings, knives
and small hand tools, weapons and military
equipment, etc. (Fulford et al 2005).The
treatment of archaeological iron poses some
of the most difficult and intractable problems
in conservation. The problems arise from two
key aspects of the nature of archaeological iron
and steel – the extreme nature of the corrosion
which simultaneously leads to the relative
fragility of iron objects compared to copper
alloys and the voluminous corrosion products
surrounding the artefact; and the presence
of chlorides beneath the corrosion crust.
Both these issues need to be addressed when
dealing with their conservation. The highly
corroded nature of archaeological iron objects
leads to them being surrounded by a thick and
often extremely hard jacket of corrosion that
obscures the shape of the object and makes
identification impossible (see Figure 5.11). The
actual object hidden beneath the corrosion
may be very fragile since much of the original
metallic iron has migrated into the external
corrosion, leaving behind a more porous and
brittle pseudomorph in magnetite. Attempts
to mechanically remove the hard, external
corrosion risk breaking the object within.
Perhaps the gentlest method of cleaning this
heavily encrusted ironwork is by the use of
air-abrasion using aluminium oxide powder
at high pressure. This is undertaken under
low-power binocular microscope and is both
time consuming and expensive. Because of
this, unless the object is destined for museum
Figure 5.11: The highly corroded nature of
archaeological iron objects leads to them being
surrounded by a thick and often extremely hard
jacket of corrosion that obscures the shape of the
object and makes identification impossible. Here X-
radiography allows the object to be recognised and
drawn, even without cleaning.
The problem with chlorides, however, remains
the most serious threat to the future integrity
of archaeological iron, especially marine
archaeological iron. The chloride-containing
corrosion products found in archaeological
iron are extremely hygroscopic and can
absorb atmospheric moisture at RH levels
down to 15%. As we saw in Section 3.6.3,
in aqueous solutions these chlorides catalyse
rapid corrosion of the remaining metal and the
transformation of stable oxides into unstable
forms. When the objects were in the soil
this corrosion occurred much more slowly
due to limited oxygen availability and lower
temperatures. More importantly perhaps,
since the corrosion products surrounding the
surviving iron core were filled with water,
ferrous and ferric ions were able to diffuse
outwards until they precipitated in the soil
surrounding the object – forming the external
corrosion. During post-excavation corrosion
the temperatures are higher than in the ground
and access to plentiful atmospheric oxygen
can lead to rapid rates of fresh corrosion.
To exacerbate the problem, the diffusion of
Figure 5.12: Cleaning of archaeological iron objects is both time consuming and expensive. Here small
windows in the corrosion overlying these Roman styli have been opened up by air-abrasion to reveal
technological details not resolved by X-rays.

soluble ions is extremely limited because the shape of the object. In the early days of the
pore structure is now full of air – there are conservation of archaeological iron objects
no capillary forces to draw ions-rich water both problems were dealt with quite simply by
away from the core and diffusion is limited removing all of the corrosion products down to
by the small reservoir of water within the the bare metal. This was frequently done using
corrosion. As a consequence, oxy-hydroxide electrolytic stripping where the evolution of
corrosion products form at the interface of the hydrogen at the surviving metal surface broke
metallic core and the internal corrosion, and up the corrosion crust and simultaneously set
a considerable change in volume is involved. up a potential gradient that drove off negatively
This expansion of corrosion products within the charged chloride ions. This electrolytic stripping
internal structure of iron objects or "corrosion was achieved either by wrapping the iron object
jacking" is responsible for the fragmentation
of some archaeological metals if stored in a
poor environment (Figure 5.13). In fact, this
destructive corrosion can be quite rapid and
is often accompanied by the formation of
deliquescent drops of bright orange liquid that
oozes up from beneath the corrosion crust – so
called "weeping iron". As a simple experiment,
solid ferric chloride (FeCl3) sealed in a glass
flask with a piece of dampened cotton wool will
rapidly draw water vapour from the wool and
turn from a crystalline solid into a thick, brown
liquid with a pH of around 3. (Figure 5.14)

Conservation treatments thus focus on two

problems – the first of which is the question
of chloride-stimulated post-excavation
corrosion, and the second is the removal of
external corrosion products that obscure the
Figure 5.13: The expansion of corrosion products,
or corrosion jacking, within the internal structure of
iron objects is responsible for the fragmentation of
ancient metals stored in an environment with high
humidity.
Figure 5.14: A crude but effective demonstration of the dangers of free ferric and chloride ions in
archaeological ironwork. Solid FeCl3·6H2O is sealed in a conical flask with damp cotton wool. After three
hours 30 minutes the ferric chloride has absorbed sufficient water to become partially liquid. After 48 hours
the salt is completely dissolved and the cotton wool is dry.

in zinc ribbon and placing it in a bath of alkali
such as caustic soda (NaOH) or by the use of
an applied external dc current. The stripped
metal core was then treated with hot wax to
prevent future corrosion.
0.02-0.05 Amp cm-2 to give a satisfactory
result. All residues of electrolytes should be
carefully removed by long rinsing in tap water
and then distilled water and the objects dried
in an oven at 60 oC.

5.5 Conservation of Lead 5.5.2 Consolidative Reduction

In the case of lead corrosion – usually mixed
oxides and carbonates – the corrosion products
are frequently voluminous and powdery. Dust
from this corrosion is a health hazard to those
handling lead objects and furthermore can
attract moisture and organic acid vapours
from a poor storage or display environment.
Lead is extremely toxic and lead corrosion
products are usually removed until a more
compact surface is revealed. Cleaning of lead
objects must always be done so as to minimise
the conservator’s exposure to toxic dust. One
way to minimise dust is to use electrochemical
methods.
5.5.1 Normal Reduction
Lead objects that obviously still contain a large
amount of metallic lead but which have a thick
crust of powdery carbonates and oxides can be
made the cathode in a 5% NaOH or 10% H2SO4
electrolyte. The anode should be stainless
steel. Because lead is soluble in alkalis an
external current must be applied before the
object is lowered into the electrolytic bath if
NaOH is used. This current should be around
In the case of thin lead objects, or objects
such as coins and seals which have fine detail,
there may not be enough metal left for the
object to survive normal electrolysis. However,
if the electric field is carefully controlled it is
possible to reduce basic lead carbonated back
to metallic lead. A current of 1-2 mA cm-2 in an
electrolyte of 10% H2SO4 gives good results but
the anode and all connecting wires should be of
lead and lead wire or sheet should be wrapped
around the object to be treated. This treatment
can take several weeks during which time the
object should be inspected regularly. When
the reduction process is complete the object
should be rinsed and dried as described above.
This treatment is quite successful in treating
lead objects that have corroded in poor storage
conditions containing organic acids.
Lead has also been cleaned with chemicals to
sequester or chelate lead corrosion products.
This type of treatment is risky because most
corrosion products of lead are very insoluble
and any chemical agent powerful enough
to remove the corrosion will also attack the
remaining metallic lead. Disodium EDTA has
been used to remove lead corrosion products
but objects must be very well rinsed afterwards
because acetic acid residues are extremely
damaging to lead objects. After cleaning
and rinsing lead objects must be stored or
displayed in a low-humidity environment
where all organic acids are excluded. Silica gel
will remove both moisture and organic acids
from air in the storage or display case.
5.5.3 Reshaping Lead Objects
Lead is a soft metal and its annealing
temperature is below room temperature.
Metallic lead can be shaped easily and bent at
room temperature without becoming brittle.
Ancient and archaeological lead can, however,
be very much more brittle than recent lead and
thus lead objects should only be reshaped where
there is a clear need to do so – for example
unrolling thin lead sheet to read inscriptions
as in the case of Roman lead curses. If this is
done the metal must be examined to see how
much metal remains or consolidative reduction
must be used to convert corrosion back to
metal before any reshaping is attempted.
5.6 Conservation of Tin Objects
Although a base metal, some tin and pewter
(lead tin alloy) objects can have a very fine
bright surface or attractive patina, even after
many years. This is because of the thin,
epitaxial layer of protective tin IV oxide.
However, in some case there may be ugly
corrosion warts, powdery crusts and a flaking
surface. In pewter this seems to depend
upon the alloy composition as much as the
environment. In some archaeological tin objects
the corrosion has gone so far as to make any
metal unrecognisable. Tin finds from marine
sites are especially vulnerable to corrosion and
fragmentation (Figure 5.15).
Figure 5.15: A collection of heavily fragmented tin
alloy spoons recovered from a marine archaeological
site off the coast of Sweden.
5.6.1 Cleaning Tin Alloys
Tin and pewter should be mechanically cleaned
with great care. On historical objects the
darkened patina should never be removed by
polishing or stripping. In the middle of the 20th
century tin coins and medals were cleaned
electrochemically using NaOH and aluminium,
zinc or magnesium powder. This example of
galvanic reduction has fallen out of favour in
recent years as the standard approach to the
conservation of tin and its alloys.
5.7 Silver Alloys
The conservation and cleaning/restoration of
silver poses a number of ethical problems.
Silver is both a precious metal and has a
beautiful appearance when polished. In the
west many people expect silver objects to be
bright and shiny and think objects are less
attractive and less valuable if dull or tarnished.
Opinions vary from country to country, from
museum to museum and from collector to
collector. For example in China it is acceptable
for silver to have a deep tarnish of silver
sulphide. Coin collectors usually leave silver
coins un-cleaned if the details are readable.
Thick corrosion, especially copper corrosion
products will usually be removed because a
green colour makes them look like bronze
coins and therefore gives a false impression.
Similarly, thick corrosion crusts of silver
chloride or bromide are usually removed to
make coins and other small objects more easily
readable and the resulting matt surface may,
or may not, be polished to a high lustre.
5.7.1 Cleaning Silver Alloys
Thick corrosion crusts are usually removed
mechanically using sharpened bamboo probes
rather than needles or scalpels since steel
may well damage the soft metal below. If the
external corrosion comes away from the original
surface easily then a thin layer of adhesive can
be spread on the corrosion and when that has
dried the corrosion can be peeled back (Figure
5.16). This can be dangerous because the silver
can be very fragile. Intergranular corrosion
may make thin silver objects like coins break
or crumble. Commercial silver cleaners should
never be used on archaeological or ancient
silver objects. Organic acids, such as citric
acid or complexing agents such as ammonia
or ammonium thiosulphate [(NH4)2S2O3] are
often useful for removing the final layers of
corrosion from silver. These complexing agents
are useful because they prevent metallic silver
plating back onto the corrosion products or
underlying metal of the object – any silver
in solution being more noble than the object
which may contain copper. Sometimes it is
Figure 5.16: A thin layer of cellulose nitrate adhesive has been spread on the corrosion and when that has
dried the corrosion has been carefully peeled back to reveal a clean metal surface. Note the brittleness
arising from intergranular corrosion. The clean surface has been burnished gently with glass beads in
ethanol.
easier to chemically reduce the overlying silver method is suitable for batch cleaning of several
corrosion to metallic silver that can then be coins at one time and is useful in cleaning coins
brushed off from the original surface. This can from marine sites and shipwrecks.
be done with sodium dithionate (Na2S2O4). This
 Chapter 6 Appropriate Packing and Storage of Metals
While metal artefacts are in use it can be
assumed that deterioration in relatively slow
because continual care is taken to preserve
their function – iron railings on buildings are
scraped repainted, machine parts are oiled
or greased, worn or rusted components are
replaced with new ones. In open air museums
where vehicles are in almost constant
operation all the component parts, metals and
non-metals are usually in excellent condition
– perhaps more so than when they originally
left the factory (Figure 6.1). Static exhibits
displayed outside in the open air museums are
more likely to suffer deterioration since they
are relatively neglected compared to working
exhibits. Nevertheless, it is possible to maintain
even large objects in good condition with quite
simple measures to keep off the worst of the
elements that promote corrosion of metals.
Obviously in the open air it is impossible to
exclude oxygen from the display environment.
However, it is possible to exclude liquid water
even if ambient humidity is entirely dependant
upon the local climate. A simple rain cover over
a parked vehicle or piece of industrial heritage
can vastly prolong its useful life as a display Figures 6.2: A simple rain cover over a steam engine
object (Figures 6.2 and 6.3). Preventing rain displayed at the Norwegian University of Science
and Technology, Trondheim, Norway.
from falling on a complex piece of machinery
means that water is unable to pool in hollows
and crevices in the structure, and this in military heritage should be routinely monitored
turn prevents the build up of blown dust or since birds and small animals may find the
soil particles from allowing plants to become exhibit a perfect, well-protected, location to
established. The combination of water, soil and set up home (Figure 6.4).
plant matter provide a reservoir of conductive
electrolyte that promotes rapid corrosion of 6.1 Display Strategies for Metal
metals. However, even covered industrial or Objects
Historical metals, that is metal artefacts that
have not been recovered from archaeological
sites, and sculpture are generally more
stable, less fragile, and consequently easier
to care for and curate than archaeological
finds. Most ferrous and copper alloy objects
can be displayed inside a building with just a
light covering or oil, wax of clear lacquer to
prevent water from gaining access to the metal
surface. They should be regularly dusted since
dust is hygroscopic and will attract moisture
to the surface – something that may lead to
spotting corrosion or breakdown of a polymer
coating on lacquered objects. Most museum
dust is composed of human skin cells and
fibre particles shed from visitors. This is easily
controlled by vacuuming or dusting with a soft
brush or cloth. However, if the museum or
Figure 6.1: Enthusiasts and amateurs may restore gallery is located in an area with heavy traffic,
historic cards and other vehicles to an unrealistic or if there has been building work in the vicinity
level of perfection. Classic car owners at a car show of the gallery, then the dust is likely to contain
in Trondheim, Norway.
Figures 6.3: A permanent textile rain cover protects part of the mine ventilation pump equipment at the
Gold Ecological Park museum in Taipei County, Taiwan.
grit or asphalt particles, soot and other oily
residues. Removal of this particulate matter
requires more care because the dust in this
case may be sticky or may scratch the surface
of objects if a simple cloth is used to rub over
the surface. Open display of silver objects is
more problematic and not only in terms of
security. Pollution in the form of hydrogen
sulphide gas will lead to rapid tarnishing of a
polished silver surface and the silverware will
slowly turn brown and then black.
Dust and other pollution is much reduced if
the objects are displayed within a glass case
because it is much easier to control a small,
enclosed environment. Some glass cases can
be extremely sophisticated in design with
dry air piped into the airspace to maintain
an overpressure that prevents dust and other
pollutants from entering the display case.
These are useful for extremely valuable or
sensitive metal artefacts but in most instances
a well sealed case will buffer displayed objects
from extremes in temperature and humidity.
In many museum cases cold sources of light
are used by having spotlights located outside
1
Human hair contains 5% cysteine by weight.
the display case or by using fibre optic lights.
For sensitive metals such as silver and lead
especial care must be taken to prevent
enclosing the objects for very long periods with
a source of pollution such as hydrogen sulphide,
ammonia or organic acids. Materials used
in the construction of museum cases should
always be regularly tested to see if they are in
danger of releasing reactive gasses that may
damage metal. Potential sources of problem
gasses include: woollen textiles that release
hydrogen sulphide from the decomposition of
the sulphur containing amino acid cysteine
present in keratin1; rubber seals for glass cases
that contain sulphur and may also release
hydrogen sulphide; ammonia vapour evolved
from paints and silicone rubber sealants used
in cases; formic and acetic acids vapours given
off by poor quality wood, particle boards and
papers used in displays. All materials used in
the construction of storage and display cases
should be tested for suitability, for example
using the simple Oddy test of accelerated aging
at elevated temperatures (Green and Thickett
1995).

Figure 6.4: Large objects displayed in the open air
can attract small animals and birds. This bird’s nest
is built amongst the tubes and pipes of a rocket
motor on outdoor display at the Kennedy Space
Centre, Florida, U.S.A.
In a sealed museum case it is possible to exert
some control over the enclosed atmosphere.
Relative humidity can be both lowered and
buffered to reduce the potential for water
condensing on the surfaces of metal objects or
within the corrosion products of archaeological
objects. Dry silica gel can reduce the RH within
a case to levels below 35% – the ideal storage
level for historical metals and archaeological
metals other than iron and the most unstable
of copper alloys. Silica gel is highly porous
with porosity of below 100 nm in diameter.
As a result it has an enormous surface area of
around 800m2g-1. Because silica gel contains
a large number of polar groups it has the
ability to adsorb substantial mounts of water
vapour form the air. For example, silica gel in
equilibrium with air at 34% RH will hold 20-
25% of its dry weight in adsorbed water. Since
the cage-like structure of silica gel is polar it
will also adsorb polar gasses such as hydrogen
sulphide, acetic acid and formic acid in small
quantities. There are commercial alternatives
to silica gel such as Artsorb, which appears to
contain a combination of silica gel and lithium
chloride. This has a higher equilibrium moisture
content at RH values above 65% and therefore
shows better performance at buffering cases
where high humidities are required. However,
there seem to be no advantages with using this
product when the requirement is to maintain
a low humidity and the potential presence of
chloride-containing dust in a case for metal
artefacts may pose an additional threat. For
display cases containing silver it is possible to
purchase textiles containing activated charcoal
which acts as a scavenger for hydrogen
sulphide and other trace pollutants. However,
care should be taken that other display objects
in the case are not a significant source of
damaging gasses, however unlikely that may
seem. For example Green (1992) reports
hydrogen sulphide evolution from low-fired
archaeological ceramics.
6.2 Storage Strategies for Metal
Objects
Long-term or permanent storage of metal
artefacts can be problematic. Unlike artefacts on
display in a public gallery that may be checked
regularly by curators and conservation staff,
those held in storage may be hidden from view
and unavailable for routine visual inspection.
Many objects are stored in closed boxes and a
problem may only be detected when the box is
opened to reveal that corrosion has resulted in
catastrophic fragmentation of an object (Figure
6.5).
Figure 6.5: This Anglo-Saxon spear has fragmented
due to post-excavation corrosion during long-term
storage, despite packing with silica gel.
Figure 6.6: Fragments of a Viking sword that has
been electrochemically stripped of corrosion and
waxed. It can be safely stored in a tailor-made
etherfoam mount in a climate controlled store (R.H.
less than 35%).
Open storage of objects is one option but this
is extremely expensive in terms of space used.
For historical metals and stable archaeological
objects storage in acid-free cardboard boxes
within custom made etherfoam packing is quite
satisfactory if the store has adequate climate
control and RH can be maintained at 35% or
below (Figure 6.6). For archaeological copper
alloys where the humidity must be maintained
below 35% and especially for archaeological
ironwork which are unstable above 15% RH it
is necessary to reduce the volume of available
air considerably, thereby increasing the ratio of
silica gel desiccant to air. Small finds such as
coins can be stored in individual polyethylene
self-seal bags and then stacked in hermetically
sealing polyethylene food storage boxes,
together with dried silica gel. It is usual to place
a humidity indicator strip in the box where it
can be read without disturbing the seal, and to
label the box with the date on which the silica
gel was regenerated (Figure 6.7).
This approach is useful for short term storage
of less than a year or so and is an ideal
solution for transporting small metal finds
from site to the conservation laboratory. For
long term storage that may last up to several
years during which time the objects will not be
looked, at storage in an anoxic environment
is a potential solution. Corrosion of metals
usually requires the presence of both oxygen
and water. Traditionally the approach for
passive stabilisation of archaeological metal
has involved exclusion of water, either using
a water impermeable barrier such as wax or
oil, or by storage in a desiccated environment.
Figure 6.7: Simple and cheap solutions for the
packing of small archaeological and historic metal
artefacts. Inert packaging – such as self-seal
polyethelene bags, polyether foam and low-density
polyethelene airtight boxes should be used and any
labelling materials should be of archival quality.
Polyethelene bags for objects and silica can be
perforated using a spiked wheel tracing tool. The box
should be of the correct size to avoid overcrowding
but minimise enclosed volume of air. Make sure
when sealing the box to place an RH indicator
strip where it can be readily seen. Each box should
contain at least 75 g of freshly regenerated silica gel
for every litre capacity (Watkinson and Neal 2001).
The introduction of oxygen scavengers such
as AgelessTM has raised the possibility of
generating oxygen free atmospheres on a
small scale. A range of water and oxygen
impermeable, metallised polyethylene bags are
available, together with tablets or sachets of an
oxygen absorber and telltales to generate and
monitor an anoxic environment respectively.
Objects are heat sealed into the bags, which
must be carefully labelled since some bags
have no window through which to identify the
object inside. These can then be stored in a
cool dark place for long periods of time, with
routine monitoring for failure of the seal.
 Acknowledgements
The author expresses gratitude to all the many people who assisted in the production of this
volume, especially the following: Mr Hsieh, Chih-Hua; Mr Ole-Bjørn Pedersen; Dr Yu, Ying-Da; Mr
Eddie Daughton and the Experimental Archaeology Students from Strode College, U.K. Thanks
are also due to the following institutions: the Department of Materials Science, Norwegian
University of Science and Technology, Trondheim; Vitenskapsmuseum, Norwegian University of
Science and Technology, Trondheim; Nidaros Metalvarefabrik, Trondheim, Norway; West Sweden
Conservator’s Studio, Gothernburg, Sweden.

The image in Figure 1.1b is taken from Schmid and Varga (2002) Segregation and surface
chemical ordering - an experimental view on the atomic scale. Chapter 4 in: The Chemical
Physics of Solid Surfaces, Volume 10: Alloy surfaces and surface alloys. D. P. Woodruff (ed.),
Elsevier: 118-151, and appears courtesy of Elsevier. The photographs in Figure 2.3 are used
with the permission of Eddie Daughton. Photographs in Figure 2.10 were taken by Kari Dahl with
permission of Vitenskapsmuseum, Norwegian University of Science and Technology, Trondheim.
The photograph and X-radiograph in Figure 4.10 appear courtesy of Dr Jean-Bernard Memet.
Radiographs in Figures 4.5 and 4.6 are courtesy of Vitenskapsmuseum, Norwegian University
of Science and Technology, Trondheim. The photograph of Patrick Bárta’s sword in Figure 4.6
was taken by Tomáš Balej. Figure 5.8 is courtesy of Doncaster Museums Service, U.K. The
photograph in Figure 6.6 was taken by Hsieh, Chih-Hua. All other photographs and drawings are
by the author.
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