Professional Documents
Culture Documents
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 prices of metals. The agricultural revolution
linked to the story of mankind’s exploitation would not have been possible without steel
of metals. Almost no aspect of the modern ploughs and tractors to till the soil and plant
world could function without an intimate the seeds. Nor could the fertilizers, on which
knowledge of the extraction, purification and modern agriculture rely, have been developed
use of metals. Despite the fact that the past without steel metallurgy – early artificial
century has been described as the "Plastic Age" calcium phosphate fertilizers produced by the
– following in the tradition of the classification Thomas-Gilchrist converter process were a by-
of technological development into the Stone product of steelmaking, and the Haber-Bosch
Age, Bronze Age, Iron Age and Steel Age process which converts hydrogen and nitrogen
– there can be no doubt that the world today to ammonia (a precursor to nitrate fertilizers)
exploits metals more extensively than at any relies upon an iron catalyst. Furthermore, the
other time in history. Although many everyday very high temperatures and pressures (400-
objects and structures that would have 450 oC and over 200 atmospheres) under
traditionally been made from wood have today which the Haber-Bosch process takes place
often been replaced by synthetic alternatives, themselves require high performance steels.
notably plastics derived from petroleum,
many of them have been replaced with larger, Since metals have played such an important
stronger and more durable metal alternatives. role in humanity’s past it is hardly surprising
Wooden ships have been replaced by steel that objects fabricated from metals constitute
ships, wooden carriages and carts have been a significant proportion of the world’s cultural
replaced by steel cars, trucks and trains. Wood heritage. Without doubt they would feature
and fabric aeroplanes have been replaced even more prominently were it not for the fact
by aluminium jumbo jets. Buildings that in that metals can be recycled and that apart
previous generations would have contained from objects placed in graves and tombs, or
large structural elements made of wood are lost in shipwrecks, the economic pressure
now constructed of steel-reinforced concrete. on societies to recycle and reuse metals has
meant that a large portion of metal cultural
Traditional household objects such as ceramic heritage has been deliberately destroyed. Our
cooking vessels have been gradually replaced surviving metal heritage takes many forms.
with metal pots and pans, beginning with The earliest objects necessarily come from
the transition from pottery to copper alloys, the archaeological record and include grave
then cast iron, and now aluminium and goods, jewellery, weapons and examples of
stainless steel. The importance of metals treasure trove – object deliberately buried in
grew exponentially with the development of the ground either for safe-keeping or as part
electricity and electrical engineering. Here of ritual offerings to the gods. As a result of
metals did not replace traditional materials their antiquity and the corrosion that affects
since non-metals are characterized by being most metals buried in soils, archaeological
non-conductors of electricity. The whole of objects are both fragile and susceptible to
the electrical revolution that took place in accelerated deterioration once removed from
the 1800s and 1900s – power generation and the relative stability of the ground. This makes
distribution, lighting, heating and the operation archaeological objects of any material class
of large industrial machines – would have difficult to preserve and archaeological metals
been impossible without the unique electrical represent one of the hardest classes of object
properties of metals, principally copper. The to conserve. Younger, historical metalwork can
transition from an agricultural economy to an be found in the form of art, sculpture, arms
industrial one would not have been possible and armour, architectural elements, working
without a sophisticated understanding of the machines and industrial heritage. Each class
properties of metal and improved methods of artefact has its own characteristic problems
of extracting and refining metals. Our but working machines and industrial heritage
energy supplies are entirely dependant upon present especially challenging ethical and
advanced knowledge of metallurgy, since high practical issues. Should working machinery be
performance steels are required in the mining restored to a working condition, for example?
of coal and the drilling and pumping of oil and If so, then at what point in their working
natural gas. These in turn provided the energy history should they be restored to and how
to increase metal production, mining, smelting much non-original material is it appropriate
and refining, which then brought down the 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.
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 When heated until it melts a metal can be
(Figure 1.1). It is the strong electrostatic combined with other metals (but rarely non-
forces between these delocalised electrons metals) to form alloys which may have very
and the positively charged metal ions that give different properties to the pure metals on
metals both their strength and ductility. Unlike their own. An alloy does not necessarily have
covalent and ionic bonds the metallic bond properties that are intermediate between those
is effectively equal in all directions. Because of the two component metals. For example,
there are no rigid covalent bonds binding copper has a melting point of 1084.6 oC and
individual atoms they are free to slide over one tin a melting point of 232 oC. Bronze, which is
another when an external force is applied and an alloy of copper and tin can have a melting
this accounts for the ductility of metals. The point that is intermediate between these
free movement of the electron sea explains the two extremes depending upon their relative
conductivity of metals and their ability to reflect proportions, although the relationship with
electromagnetic radiation. Many metals have a composition is far from linear and the melting
lower melting point than non-metallic, mineral point falls sharply as the tin content exceeds
materials where covalent bonds dominate. 90% (see Figure 1.2). To further complicate
Non-metals are frequently brittle, hard and matters, alloys of copper and tin can form one
inflexible, and do not conduct electricity or heat or more of a multitude of different "phases" as
well. Metallic elements exhibit an extraordinary the molten metal cools, leading to a complex
range of physical properties. Two examples internal microstructure.
serve to illustrate this point. The lightest
metal, lithium, has a density of 0.534 g·cm-3, In sharp contrast the melting points of alloys
or about half that of water; while osmium has of copper and silver do not behave in an
a density of 22.62 g cm-1, making it more than expected fashion. Silver has a melting point
40 times heavier than lithium, and yet both of 962 oC. Silver alloyed with 28% copper has
lithium and osmium are metals. Tungsten has a melting point of 779 oC which is almost 200
a melting point of 3410 oC whereas mercury o
C lower that that of pure silver and over 300
has a melting point of -39 oC ,making it a liquid o
C lower than that of pure copper (Figure 1.3).
at room temperature. Some metals are totally soluble in each other,
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%.
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.
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 regions by the heat of the young Sun. This left
would be relevant to examine the composition the inner planets with a higher proportion of the
of the Earths crust which is the principal source heavier elements, including the metals. Based
of mankind’s raw materials. The relative on the chemistry of meteorites and knowing
abundances of metals and other elements the relative volumes of the crust, mantle and
in the Earth’s crust is a reflection of two core, the average composition of the Earth
processes: the synthesis of "heavy" elements has been estimated as 34.63% iron, 29.53%
in the interiors of stars and the fractionation of oxygen, 15.20% silicon, 12.70% magnesium,
the primordial gas and dust that took place as 2.39% nickel, 1.93% sulphur, 1.13% calcium
the solar system formed. and 1.09% aluminium by weight.
The two major elements in the universe are
However, the early Earth endured a period of
hydrogen and helium, comprising 75% and
heavy meteoric bombardment that heated the
25% respectively. These proportions were
planet until the whole mass became liquid.
effectively fixed shortly after the "Big Bang"
This allowed further elemental segregation of
13.7 billion years ago. All heavier elements
the molten rock with the heaviest elements
such as carbon, oxygen, iron, etc. (with the
sinking to the centre to form a metallic core.
exception of trace amounts of lithium created
The core has been estimated to be composed
in the Big Bang) are created by nuclear
of approximately 85% iron with about 5%
reactions in the cores of stars and are released
nickel and the remaining mass made up of
into interstellar space during supernovae,
other metals, phosphorus, carbon and sulphur
enormous explosions which accompany the
(McDonough 2000). Other dense metals, such
deaths of massive stars and during which
as lead and uranium, are either too rare to be
the heaviest elements, such as gold, lead
significant or tend to bind to lighter elements
and uranium, are also synthesised. During
and remain in the crust. The elements found in
formation of the Solar System there was a
the Earth’s continental crust, i.e. the rocks that
modification of the composition of the original
we can readily mine and exploit, are therefore
gas and dust cloud as lighter elements such as
depleted in heavy elements and enriched in the
hydrogen and helium were driven to the outer
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 amount of metal can make a spectacular piece
of metals between the Earth’s crust and the of jewellery. Native silver also occurs naturally
interior is also influenced by the relative as a metal but often acquires a dark patina of
affinities between each metal and non-metals, sulphide or chloride. This silver often forms as
principally oxygen. Those metals which bind a tangle of wires and crystals, is soft and can
readily with oxygen form minerals with a lower be hammered into lumps or sheets. However,
density than the pure metals and these lighter native silver is comparatively rare and there
compounds subsequently rise to the surface, is evidence that the refinement of silver from
being found in the earth’s crust. Luckily for lead began early in the history of metallurgy.
us, weathering and other geological processes
result in the concentration of commercially Slag heaps found in Asia Minor and on the
important metal-bearing minerals into ores islands of the Aegean Sea indicate that silver
that can be more readily collected, processed was being separated from lead as early as the
and exploited. 4th millennium BC. Native copper usually has
a coating of red copper I oxide or is covered
Table 1 shows the atomic abundances of in green corrosion products and it is possible
the commonest elements and economically that green or blue copper corrosion products
important metals in the Earth’s continental were used as pigments long before they were
crust. The values are expressed in atomic recognised as potential sources of useful
percent (relative numbers of atoms) rather than metal. Native copper is relatively common in
weight percent. Note that oxygen, silicon and North America and there are important sources
aluminium together make up over 87% of the in Bolivia. The technological transition from the
crustal rocks. The next most abundant metals low-temperature hammering of native metals
are sodium, iron, calcium, and magnesium in into jewellery, to the melting and casting of
that order. Although iron has been smelted and gold, silver and copper was an important step
used for approximately 4000 years, sodium, in the pyrotechnic revolution that led to the
calcium and magnesium were not isolated large-scale smelting of metals from their ores
as metals until 1807-1808 when Humphry (Gale et al. 1985).
Davy used electrolysis on molten salts. Thus,
the availability of metals for exploitation by Oxides of the transition metals are frequently
humans was not limited to their abundance in brightly coloured; iron (red or black), copper
rocks found at the surface of the Earth. (green or blue), cobalt (pink). Sulphides of
metals often have a shiny metallic surface and
Table 1 shows that the native metals, ones that can be substantially heavier than other rocks.
occur on the Earth’s surface in their metallic Sulphides of iron, copper, lead and nickel have
form, are exceedingly rare – iron is two million this characteristic metallic lustre. It seems
times more abundant than silver and two probable therefore that some metal ores were
hundred million times more abundant than actively collected by Stone Age peoples for
gold. At current prices gold is a little over 30 use as pigments long before their connection
thousand times more expensive than sponge with metals was understood. Cave art from
iron, a reflection on the greater ease of mining southern Europe employing red- and yellow
and refining iron ore compared to gold deposits. ochre (Fe2O3 and Fe2O3·H2O) as pigments date
Although a thousand times more abundant back as far as 32,000 years and "ochre burials"
than silver, copper and tin are still relatively attest to the decoration of bodies (or clothing)
rare, which is ironic considering that copper with red pigments as far back as the dawn of
and bronze both featured at the beginning of human societies.
the pyro-metallurgical revolution1.
The Australian burials at Lake Mungo contain
1.5 Native Metals & Metal Ores the earliest known ochre burial dating back
On Earth, only three metals occur naturally un- approximately 40,000 years. It is also known
combined with non-metals. The "native" metals that Neanderthals used red ochre to decorate
- gold, silver and copper - were the earliest to carved mammoth tooth objects. We now have
be recognised and used by ancient man. Gold ample evidence that Neanderthals used ochre
is the simplest native metal to find since it does in burial rituals, and recent evidence from
not corrode or tarnish and therefore appears excavations in Zambia suggest that Homo
as a bright yellow nugget on the ground or in a heidelbergensis, the common ancestor of
riverbed. It is very soft when pure and is easily Homo neanderthalis and Homo sapiens, also
shaped into simple but attractive objects such used coloured pigments – possibly for body
as beads and pendants. Pure gold can also be painting – as early as 350,000 years ago
hammered into thin sheets and thus a small (Barham 2002).
1
The pyro-metallurgical revolution was the connection between the use fire and metals.
Chapter 2 Working with Metals
2.1 Smelting Metals the ease with which a metal loses electrons
As stated in Chapter 1, apart from the native decreases. Note that both carbon and hydrogen
metals; gold, silver, copper and rare instances are placed in the series despite not normally
of native tin, all metals in the Earth’s crust being considered metals. This is because these
occur in combination with non-metals as stony two elements have special relevance to the
ores. The most common ores occur as oxides, reduction of metals from their ores and their
hydrated oxides, carbonates and sulphides. subsequent corrosion respectively.
These compounds are found in various
concentrations in soils, sedimentary rocks, The higher the metal in the series, the more
metamorphic rocks and minerals deposited reactive it is – its reaction is faster and more
from hot waters around hydrothermal springs. exothermic. The metal is also more susceptible
Metal ores can also become concentrated by to corrosion with oxygen and water. This also
the weathering of parent rocks containing implies that the reverse reaction becomes
more widely dispersed metal compounds. The more difficult – the more reactive a metal, the
term ore is usually restricted to economically more difficult it is to extract from its ore. As
important rocks bearing a high proportion of a general rule it is possible to predict redox
one or more metals that may be extracted reactions from the reactivity series, or more
commercially. Other rocks, for example precisely, the electrochemical or galvanic
limestone, represent large deposits of the metal series (see Chapter 3). Those metals lower in
calcium in the form of carbonate but limestone the series have a greater affinity for electrons
is not considered an ore since calcium is not than metals above them. In redox reactions
readily extracted from it. In many metal oxides this means that metals higher in the series
and oxy-hydroxides the bond between the will lose one or more electrons to those below
metal and oxygen can be broken by the high them.
temperature reaction of the ore with carbon
monoxide. This can be generalized as follows: Thus, metals above hydrogen will give up
electrons to the hydrogen ion (H+) which will
MeO + CO " Me + CO2 where Me is a metal.
be reduced – the metal will react with water,
This is a redox reaction involving the exchange steam or an acid to release metal ions and
of one or more electrons – the metal oxide hydrogen gas. Those metals below hydrogen –
is reduced (it gains an electron) and carbon copper, silver, gold and platinum – do not react
monoxide is oxidised to carbon dioxide (by with dilute acids and are generally resistant to
losing an electron). The process of reducing corrosion in aqueous environments:
metal ores using carbon is technically called
Fe + 2H+ " Fe2+ + H2 (gas)
the carbothermic reaction but more generally
it is referred to as smelting. Note that the Cu + 2H+ ≠ Cu2+ + H2 (gas)
production of aluminium is also often called
smelting although this is a very different The mechanisms behind these phenomena are
process that requires large amounts of explained in greater detail in Section 3.2 and
electrical energy. The reduction of metal oxides 3.3 below. By similar reasoning, metals above
with carbon is not possible with all metals carbon cannot be extracted from their ores
because they have different electrochemical by heating with carbon, whereas those below
behaviours. Most metals are electropositive carbon can be reduced with charcoal, coal or
in nature and readily give up electrons in coke. Generally, the further down the series
a chemical reaction. However, they do not the easier it is to extract the metal from its
all react with the same readiness or speed ore, which explains why gold and silver occur
– metals display different reactivities. The as native metals. It also explains why iron
greater the ease with which an element loses and zinc were exploited as metals long after
its electrons and acquires a positive charge, the metals copper, tin, lead and mercury were
the greater is its reactivity. Thus, metals may discovered.
be placed in a reactivity series that reflects
the ease of reaction (oxidation) of different The inability to reduce aluminium, magnesium,
elements. etc. with carbon explains why it was impossible
to isolate the pure metal before the advent of
Table 2.1 arranges metals in order of their electricity. Table 2.1 shows the traditional
decreasing chemical activity. As one goes down layout of the reactivity series with the more
the activity series from potassium to platinum reactive metals at the top of the table and the
Element Symbol Notes
Potassium K
Sodium Na
Lithium Li
less reactive, more noble metals at the bottom Ellingham diagram this scale shows the partial
of the list. A more technical way of expressing pressure of oxygen, with one atmosphere of
the relative reactivities of metals and their O2 at the top, decreasing logarithmically down
ease of reduction is given by an Ellingham to 10-38 atmospheres O2 (an extremely reducing
diagram. Figure 2.1 shows a simplified atmosphere) at the lower end of the scale.
Ellingham diagram which includes some of
the more important metals used in antiquity The heavy diagonal line represents the
together with commercially important metals equilibrium for the oxidation of carbon to
such aluminium and titanium. carbon monoxide:
In Ellingham diagrams the more noble metals C + 1⁄2O2" CO
appear at the top and the more reactive
metals at the bottom, which is the reverse of For a metal oxide to be reducible by carbon
how the reactivity series is usually expressed. monoxide it must lie above the heavy line at
An Ellingham diagram shows the relative any particular temperature. Silver is very easily
stabilities of metals and their oxides (or other reduced at fairly low temperature, although in
compounds). Above each labelled diagonal practice it must be smelted in a hot fire because
line the element is thermodynamically stable the ignition temperature of charcoal of around
as the metal. Below that line it is stable as 300-400 oC (Ellern 1968) must be exceeded
the oxide. The scale on the left gives the in order to produce the carbon monoxide gas
standard free energy change when the metal which is the reducing agent. Gold lies off the
is oxidised, such that increasingly negative top of the diagram because it has positive free
values represent more energetic reactions that energy of formation and is therefore found in
will occur spontaneously in the presence of the metallic state.
oxygen. This is why metals that appear higher
up on the diagram are more stable than those As one moves from the top left of the Ellingham
metals that appear lower down, and are more diagram to the bottom right the metals
likely to be found in their pure metallic form. become increasingly difficult to separate
from their oxides, requiring higher and higher
The right hand scale shows that reduction temperatures to achieve the reduction. Those
of the metal oxide to the metal increases metals that lie completely below the line for
towards the top right of the diagram. In a full 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 carbon was charcoal (in 9th-10th century China
any temperature achievable by burning carbon. and 17th century England coal was used) but
The sequence of metals as one moves from the since the industrial revolution the usual fuel has
top left of the Ellingham diagram gives the been coke, especially for iron smelting. Coke is
approximate sequence of their first utilization made by baking coal at high temperature in the
by man, and gives a further explanation of why absence of oxygen in a process analogous to
the isolation of aluminium, magnesium and the making of charcoal from wood. Water, coal
calcium had to wait until the development of tars and other volatiles are driven off from the
galvanic reduction. coal leaving a porous residue of fused carbon.
In the smelting furnace two reactions are
Today, as in antiquity, most metals are obtained possible and both may take place concurrently
by the reaction of an oxide with carbon at high depending upon local conditions in the hot
temperature. In the past the usual source of zone of the furnace.
These are reduction by carbon monoxide gas
– for example copper oxide:
In these experiments it is usual to first roast the Fayalite has a melting point of 1150 oC
ore in air to convert the carbonate into copper I compared to 1083 oC for pure copper and
oxide and it seems likely that this was also done ~1650 oC for SiO2. The molten copper runs
in antiquity. Sulphide ores (of iron, copper or through the slag since it is denser and forms
silver) must also be roasted before they can be a pool at the bottom of the furnace. This can
smelted. This drives off SO2 gas and converts be collected when the furnace has cooled. In
the sulphide to a more easily reduced oxide. large-scale operations the slag was run out of
It is likely that the earliest smelting was done the furnace after the smelting but before the
on a very small scale, perhaps a development furnace cooled. Archaeological investigations
of melting and casting native copper, and that of probable smelting sites and practical
several people with blowpipes were used to experimental smeltings show that production
supply the forced draught (Fasnacht 1999). of quite large volumes of copper were possible
This is seen in several Egyptian wall paintings with relatively primitive technology (Figure
(Figure 2.2). This crucible smelting of high 2.3).
grade oxide ores in an open hearth fed by
blowpipes is essentially a non-slagging process Depending upon the ratios of fuel to ore and
(Craddock 1999) and is therefore quite difficult flux, and the sophistication of the furnace it
to identify in the archaeological record. is quite conceivable that iron ore could have
been reduced in a copper smelting operation,
When smelting copper from lower grade ores although the resulting metal would have been
the oxide, carbonate or sulphide is usually in the form of small prills or blooms mixed with
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.
2.2.1 Ferrous Alloys (Iron & Steel) The hardness of steels can be increased
Carbon is readily soluble in liquid iron and at enormously by correct heat treatment of the
high temperatures will diffuse into iron in the finished tool or weapon, usually involving
solid state to form steel. The initial diffusion of rapid cooling. The heat treatment process for
carbon appears to be along the grain boundaries most steels involves heating the alloy until
(Bokshtein et al. 1961). Even small amounts of austenite forms, then quenching the hot metal
carbon can significantly increase the hardness in water or oil, cooling it so rapidly that the
of iron and the range of carbon contents found transformation to ferrite (or pearlite) does not
in steels can give rise to a number of different have time to take place. When austenite is
micro-structures, with very different properties. quenched the carbon is "frozen" in place when
Iron has several different crystal structures or the cell structure changes from face centred to
allotropes. Pure iron below 912 oC has a body body centred cubic. The carbon atoms are too
centred cubic crystal structure known as alpha- large to fit in the interstitial vacancies between
iron (α-iron) or ferrite. Above this temperature iron atoms and thus the crystal structure is
and below 1394 oC it changes to a face centred distorted. The structure that forms is called
cubic structure called gamma-iron (γ-iron) or martensite which has a lower density than
austenite. austenite, so the quench hardening of steels
results in a change of volume. Martensitic
An understanding of the properties of the structures are extremely hard but brittle. Some
different allotropes of iron is essential to of this brittleness can be reduced by reheating
the manufacture of good quality modern the steel briefly to relax some of the internal
steels, although in antiquity blacksmiths and stresses – a process called tempering.
swordsmiths were able to make excellent
tools and weapons based only on tradition and Stainless steels represent an immensely
experience. The switching from face centred to important class of ferrous metals. Despite the
body centred structures as iron cools can be strength, low cost and wide-ranging applications
arrested by the incorporation of small amounts of iron and steel they are very prone to rapid
of carbon in the crystal lattice. Ferrite is a corrosion when exposed to moist air. This is
fairly soft metal that can dissolve only a small accelerated in the presence of dissolved salts
concentration of carbon (no more than 0.021% – as in sea water (see Chapter 3). During the
by mass at 910 °C). Above the austenising latter part of the 19th century several alloys
temperature of 912 °C, however, the metal can of steel containing manganese and nickel
were discovered to have corrosion resistant The earliest bronzes may have been made
properties, following work in Britain, Germany accidentally by smelting copper and tin ores at
and the USA. However, the development of the same time. They first appear around 3,200-
true stainless steels seems to have been a 3,100 BC. Metal smiths realised around 1,800-
spin off from the search for alloys with superior 1,500 BC that by adding controlled amounts of
mechanical and wear resistance properties. tin to their copper they could produce metals
In 1913 researchers at Sheffield, a traditional with a wide range of properties. Chemical
steel-producing city in England, found that analyses of later bronzes show that scrap
a sample of steel developed for rifle barrels was often included in the manufacture of new
were remarkably resistant to the acids used to objects and this resulted in a deviation of the
reveal its microstructure during metallographic alloy composition from standard recipes. In
examination. This steel had a composition of Europe the tin contents ranged from 5-15%
12.86%, chromium, 0.24% carbon and 0.44% with hardness ranging from 60-70hV1 when
manganese (Street and Alexander 1989). Soon annealed to 262hV when cold worked. Lead
afterwards the process of producing stainless is immiscible in copper in the melt and solid
steel alloys was commercialised and in January phases. However, lead reduces the melting
1915 the discovery of "non-rusting steel" was point of a copper alloy, makes casting easier
announced in The New York Times. and works as a lubricant in the solid phase to
make working the metal easier. Chinese and
Many kinds of stainless steels are now available Japanese bronzes tend to have a higher Pb
for a variety of applications and these fall content.
into four major groups depending upon their
microstructure: ferritic, austenitic, martensitic In China the production of bronzes for specific
and duplex (a combination of ferritic and purposes was highly developed. The Book of
austenitic structures). The stainless properties Diverse Crafts, or Kao Gong Ji in Chinese,
arise from a microscopically thin layer of represents the earliest existing book on
chromium oxide that forms spontaneously on handicrafts and technology. Dating from the
the surface. One of the best known stainless Spring and Autumn Period (770-476 BC) and
steel compositions is 18-8 stainless with 18% the Warring States Period (476-221 BC), the
chromium, 8% nickel and less than 0.1% book contains a great deal of scientific and
carbon. Although simple chromium-nickel technical information, including how to make
stainless steels are used for cutlery and carts, weapons, ritual articles, and bells, as
tableware this steel is not hard enough to hold well as information on dyeing processes,
a sharp edge. Stainless steel kitchen knives construction, irrigation, and other handicrafts.
are often an alloy containing molybdenum and The Book of Diverse Crafts contains recipes
vanadium which con be hardened and tempered for the casting of various tools, weapons and
like carbon steel, for example "CROMOVA 18" functional objects to achieve the appropriate
which consists of 18% Chromium (Cro) as well physical properties (Table 2.2). Thus,
as some Molybdenum (Mo) and Vanadium increasing amounts of tin were added to the
(Va). alloy to increase the hardness of the cutting
edge but this was accompanied by increasing
2.2.2 Copper Alloys (Bronze & Brass) brittleness. Tools that received repeated heavy
Unlike iron, copper melts at the temperatures shocks such as axes have a low tin content.
easily reached in a simple furnace. Therefore, Conversely, tin-rich mirrors achieved a highly
alloys of copper and tin could be made reflective surface but were extremely brittle
directly at the smelting stage. The earliest and if dropped tended to shatter like glass.
copper artefacts were of almost pure copper
(98-99% Cu in Ireland). Some copper ores Artefact Type Cu:Sn Melting point (oC)
naturally contain traces of arsenic (<1%) Cauldrons &
5:1 930
and when smelted these produced arsenical Bells
bronzes which were harder than pure copper. Axes 4:1 900
However, since arsenical oxide is volatile
Spears 3:1 800
much arsenic is lost in the smelting process.
There is good archaeological evidence that Swords &
2:1 750
early bronze metal smiths intentionally added Knives
supplementary arsenic (over 3%) to improve Arrowheads 3:2 740
the hardness of their tools and weapons. A 4% Mirrors 1:1 700
arsenical bronze is twice as hard as a 4% tin
bronze after cold working. Table 2.2 Quoted historical compositions of different
Chinese bronzes.
1
hV = Viker’s hardness, a standard measure of the hardness of (usually) metals
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
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.
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 steel artefacts are hot forged into shape using
mould and die and is permanently deformed. variously shaped hammers and anvils. The
There may be successive pressing operations hot iron is relatively plastic and can be cut
until the final required shape is achieved. The and pierced using hardened steel chisels, and
technique is related to stamping and modern punches. In the hands of a skilled blacksmith
metal coins are produced from sheet metal in iron and steel can be manipulated into a wide
a die press. A simple type of machine press is variety of shapes and "wrought iron" is a
a set of adjustable rollers. Metal is fed into the traditional component of architectural features
rollers, which are turned to pull the material such as gates and railings. Larger objects and
through. The space between the rollers is engineering components where great strength
smaller than the metal fed into it and thus is required are usually hot forged from cast
the metal is made thinner and longer or wider. billets using power hammers. Examples of this
Successive hot rolling procedures are used to work include anchors, propeller shafts for large
turn billets of steel into sheet. Small iron and ships, crankshafts for engines, etc.
2.3.3 Cutting Metals include the turning of cast bronze and brass
In shaping metal objects the form is created by bells and the boring of cannons. Metals turned
cutting away and removing unwanted material on the lathe often still exhibit the closely
until the desired shape is achieved. This is in spaced spiral grooves characteristic of this
many ways analogous to a sculptor removing process (Figure 2.9).
stone from a rough block until the final form
is revealed. Metal sheet and wire can be cut 2.3.4 Joining Metals
with simple shears and chisels. Thicker metal There are a multitude of methods available for
requires either mechanical presses or must be joining one or more pieces of metal. Perhaps
sawn with a hardened and tempered blade. the earliest and simplest methods of joining
Further shaping can be done by abrading the thin sheets of metal are by folding, stitching or
metal surface with files or abrasive stones. riveting. All are seen in archaeological artefacts
All of these techniques are known from of gold, silver and bronze. Folded joints or
antiquity and many ancient metal artefacts seams are sometimes seen in Bronze Age
retain characteristic toolmarks that allow us gold cups or bronze cauldrons and require no
to understand how an object was created. solder. In a folded seam the edges to be joined
With only slightly more sophisticated tools are folded back on themselves and aligned
metal can be drilled or incised with decorative so that the folds interlock. The seam is then
designs. In modern engineering practice hammered flat, closing the joint (Figure 2.10).
complex components such as engine parts A more secure joint can be made by folding
are produced using a combination of casting, the edges over twice and hammering flat. In
forging and cutting of crude metal forms to the case of thin gold and tin sheet these folded
achieve a complex shape with extremely seams can be made effectively watertight.
precise dimensions and with the appropriate Folded and soldered seams are used in the
properties of hardness, strength and wear manufacture of some tin cans. Stitched joints
resistance. are rather crude approaches to joining metals
that mimic the stitching of textiles or skins (for
The most basic tool in machining metals is example see the the 8th century BC gold collar
the lathe, on which a piece is rotated on from Gleninsheen in Ireland). However, this
a horizontal axis and metal is removed by method probably represents the beginnings
bringing a hardened blade against the spinning of riveting which is now a high art with many
surface. This is exactly the same principle applications. A rivet is a short metal pin or bar
that a woodworker uses when turning wood hammered over at both ends that is used to
on a lathe, except that because of the forces join two pieces of sheet metal, or an additional
involved in turning engineering steels the feature, such as a handle, to a sheet metal
cutting tool is manipulated mechanically rather object (Figure 2.10). This rivet may be made
than held in the hand. Typical applications of the same metal as the pieces joined or a
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.
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 or polluted atmosphere. This is particularly
common in museum collections and exhibition
Artefacts objects.
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 Another approach to surface coatings is to
many metal objects receive a protective coating cover the surface of a reactive metal that is
that insulates the metal surface from the susceptible to corrosion with a second metal
surrounding environment. This protective layer that is resistant to corrosion – a metal plating.
may be purely functional in working objects This can be both functional and decorative and
and machinery, or it many also be decorative. a wide range of different metals can and have
The most obvious protection for machine parts been used: tin, silver, gold, chromium and zinc.
is the very visible layer of grease covering and The use of silver plating over copper and nickel
lubricating the moving parts (Figure 2.13). For alloys has already been discussed. Today, gold
those objects that do not represent moving coatings are applied by electroplating from
parts to be lubricated one cheap and efficient cyanide solutions but in the past a variety of
protective barrier to air and water is provided methods were used. By far the most common
by a layer of paint. Since it is important that method for applying gold coatings in antiquity
there is a very close bond between the surface was by fire gilding, also known as amalgam
of the metal and the paint layer it is usual to gilding. In fire gilding gold dust or foil is placed
first coat the metal with a primer that reacts in liquid mercury in the proportions one part
chemically with the surface – an etch primer. gold to eight parts mercury and then ground
For example a modern automobile may be together in a mortar and pestle. The resulting
finished with several coats of paint with paste is then applied to the surface to be
different properties do ensure good adhesion gilded. When the metal object is heated the
to the underlying steel. In non-ferrous metals, mercury is driven off as vapour, leaving behind
for example silver and brass artefacts, it is not a layer of gold that adheres very strongly to the
uncommon for a colourless lacquer or varnish underlying metal. The method is described in
to be applied to prevent tarnishing in a damp detail by several Medieval authors (Hawthorne
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.
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 Figure 2.15: Electroplated chromium plating on
copper vessels and cooking utensils where the steel, cupronickel and aluminium alloy laboratory
copper would react with foodstuffs and taint the equipment. Acid vapours and high humidity have
flavour. Tin plating is also commonly used in canned caused the plating to break down, allowing corrosion
foods, especially fruit which is acidic. of the various underlying metals.
Table 3.1 Relationships between ionic radii, hydrated ion size and electronegativity.
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:
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.
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. Figure 3.4: A simple battery can be created by
Where two dissimilar metals are in contact and inserting a steel wire and a copper wire into an
in a corrosive environment, the more noble orange. The multimetre shows that a voltage is
generated between the dissimilar metals.
metal will corrode less than it would alone and
the less noble metal corrodes more rapidly. The
noble metal is cathodically protected and the scratched the iron below still does not rust
less noble metal acts as a sacrificial anode. The quickly because the zinc corrodes preferentially.
reason zinc is used to coat iron is that it acts as Furthermore, the increase in volume
a sacrificial anode to the iron – preventing the experienced as the zinc oxidises can close
rapid corrosion seen in unprotected steels. small scratches and pits in the zinc coating. Tin
plating is also used to prevent the corrosion of
Zinc forms a compact layer of oxide that acts iron and steel – as in canned food. However,
as a barrier to the penetration of oxygen and because tin is more electropositive or noble
water to the metal below. If the zinc layer is 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.
Gold - Silver - Bronze - Copper - Brass - Tin - Lead - Pewter - Cast Iron - Wrought Iron - Chromium - Zinc
>>> Increasing rate of corrosion >>>
Noble (Electropositive) Base (Electronegative)
Copper sulphate is a soluble salt and will those seen on copper alloys, but the corrosion
normally be washed from the surface of can be much more serious. Although there is
corroded copper and copper alloys. However, only one possible anodic reaction there are
in outdoor bronze sculpture this corrosion several possible cathodic reactions depending
product may form in areas inaccessible to rain, upon local pH and oxygen availability.
leading to a very uneven or streaked patina
(Figure 3.7). The anodic reaction is:
Fe " Fe+2 + 2e-
Cuprite and brochantite tend to dominate on
rain-washed light green areas, while antlerite The Fe+2 ion is small and highly-charged so that
and the hydroxyl-chlorides atacamite and at the anode local pH falls due to hydrolysis of
paratacamite are more often found in dark rain- water and precipitation of hydroxides:
sheltered areas (Strandberg 1998). Pollution in
the atmosphere can lead to other corrosion Fe+2 (aq) + H2O " FeOH+ (aq) + H+ (aq)
products. In NO2 or NO3 the patina contains
FeOH+ (aq) + H2O " Fe(OH)2 (s) + H+ (aq)
Cu(NO3)2·3Cu(OH)2. The patina that forms on
copper alloys in city centres often contains a Possible cathodic reactions are:
considerable proportion of particulate matter
Hydrogen evolution:
in the form of dust, asphalt particles and soot,
often making the colour quite dark. 2H+ (aq) + 2e- " H2 (g)
When iron and steel corrode in air the corrosion
2H2O + 2e- " H2 (g) + 2OH- (aq)
that forms is frequently less complex than
Oxygen reduction: 2α-FeO·OH " Fe2O3 + H2O where FeO·OH acts
as a cathode to the metal anode, oxygen is
O2 + 4H+ + 4e- " 2H2O
reduced and the metallic iron is oxidised.
O2 + 2H2O + 4e- " 4OH-
In both cases local pH rises at the cathode due 3.6.2 The Corrosion of Metals in
either to removal of H+ ions or production of Water
OH- ions, whereas pH falls at the anode where If metals are permanently, or occasionally,
the metal is actively corroding. The factors immersed in water – as opposed to simply
that decide which part of the metal acts and exposed to moist air – then the corrosion
the anode and which the cathode include can often become extreme. Metal structures
local inhomogeneities in the carbon content exposed to seawater, ships, bridges, pipes
of the steel, imperfections in any protective and pump components are especially prone
coating or local variations in the availability of to rapid corrosion. It is the high concentration
water and oxygen. If a single drop of water is of chloride ions, and the consequent high
placed on a clean piece of steel the air-water conductivity, in seawater that accelerates
interface acts as the cathode and the metal in corrosion of metals. Most metal chlorides are
the centre of the drop acts as the anode. A pit soluble and a high volume of available water,
develops in the steel at the middle of the drop combined with the presence of counter-ions
and a ring of rust forms at the border of the allows solubilised metal ions to diffuse far
water drop where the diffusing ferrous ions from the site of dissolution of the metal.
(Fe+2) meet the hydroxyl ions (OH-) to form When a metal is immersed in water galvanic
insoluble ferrous hydroxide (Fe(OH)2). Ferrous corrosion cells are set up even in the absence
hydroxide forms initially as a greenish gel of two dissimilar metals. The geometry of the
but this is further oxidised by the interaction object has a strong influence on the pattern
with dissolved oxygen to give a hydrated solid of corrosion it experiences. Crevices, corners
corrosion product: and joints where local oxygen concentrations
are easily depleted become anodic and pitting
2Fe(OH)2 + O2 " Fe2O3·H2O
corrosion takes place. More open areas
The reaction product, rust, is a hydrated form where there is free access to oxygenated
of the iron oxide haematite – Fe2O3 which can water become cathodic and are protected
also be written as 2FeO·OH of which there are from corrosion at the expense of the anodic
several crystalline forms– α-FeO.OH, β-FeO·OH regions. If water flows rapidly over the surface
and γ-FeO·OH. In normal conditions the most of the metal then metal ions are scoured from
common form is goethite – αFeO·OH. Unlike the surface and swept away into the bulk
the compact patina that forms of copper water. In high speed components such as
alloys, there is a considerable volume change pumps, propellers and turbines where water
as iron oxidises and hydrates so that iron turbulence creates temporary bubbles in the
corrosion does not adhere to the underlying liquid, this so-called cavitation corrosion is a
metal surface. Successive phases of wetting major problem that leads to severe pitting of
and drying lead to a layered structure in the the surfaces (Figure 3.8).
rust which then frequently cracks and falls off
Here it is worthwhile to discuss corrosion
the surface, exposing the underlying metal
seen in sunken shipwrecks. Metals exposed
to further corrosion. The porous nature of
on the sea bed for several hundred years
the corrosion also allows water to collect and
experience severe corrosion. Even in very
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.
Figure 3.8: Severe cavitation corrosion in a cast
An additional reaction is possible but slow in steel water pump. The steel has been eroded where
normal conditions – the dehydration of the bubbles have formed and collapsed on the metal
oxy-hydroxide to haematite: surface.
deep, cold waters steel ships undergo quite unrecognisable as having once been metal,
rapid corrosion as the iron is converted into while others may have disappeared completely.
"rusticles" similar to those found on the wreck That so many archaeological metal objects are
of the Titanic (Cullimore et al. 2000). Many found is testament to the fact that burial deep
shipwrecks contain objects made from a wide underground considerably slows degradation
variety of metals, many of which suffer serious reactions and helps preserve ancient objects
corrosion in seawater. Copper alloys, especially made from a wide variety of inorganic and
the marine brasses are somewhat resistant organic materials.
to corrosion. Iron and steels corrode quite
The rate of corrosion in any burial environment
rapidly. Cast iron, particularly massive objects
is limited by six main factors:
such as cannons appear to survive quite well
but appearances are deceptive here. In a 1) The chemical reactablility of the metal or
marine environment cast irons, particularly alloy (its standard electrode potential)
the grey cast irons which contain flakes of free
2) The availability of oxygen (or other electron
graphite, can suffer severe internal corrosion
acceptor)
and become completely graphitised. Here
the extremely stable graphite is an excellent 3) The conductivity of the surrounding soil
conductor of electricity and acts as a noble (which is related to its water content and
metal, becoming cathodic to the pearlite the concentration of dissolved ions)
and cementite which corrode to oxides, oxy-
4) The permeability to water and oxygen of the
hydroxides and carbonates. This porous mass
corrosion layers formed between the metal
of corrosion products is held together by the
and the environment
remaining network of graphite flakes and the
object does not disintegrate in the same way 5) The local pH
as carbon steels and exquisite details of the
6) Contact with dissimilar metals
cannon are frequently preserved beneath a
crust of marine concretions. However, when Temperature is also a factor that influences
these objects are raised from the seabed rate of corrosion and it is generally true that
and exposed to air the porous structure dries temperature falls off quite quickly with burial
out and atmospheric oxygen penetrates into depth. In oxidising environments, that is in
the corrosion. Here renewed corrosion, of environments where the soil solution contains
un-reacted metal coupled with oxidation of dissolved oxygen, the mechanisms of corrosion
partially oxidised species in the corrosion follow the same reaction as those seen in the
products can lead to catastrophic fracturing corrosion described in Sections 3.6.1 and 3.6.2
in the corrosion and destruction of the object. above. The main difference is that unlike in
There are even reported cases of cannon balls atmospheric and underwater corrosion the
recovered from the sea bed becoming so hot metal ions released by corrosion are not readily
as oxidation proceeds that the graphite begins washed away from the corroding object. As
to burn and the cannon balls spontaneously metals corrode, positive ions are released from
combust (Nature News 29 Apr 2002 doi: the surface and migrate into the surrounding
10.1038/news020429-17). Post-excavation soil until the local pH rises to a level where
corrosion of archaeological metals is discussed they are insoluble and they precipitate out as
in greater detail below. solid corrosion products. These solid corrosion
products cement together soil particles to form
The corrosion of tin and lead alloys is discussed
a hard crust around the archaeological object.
in Section 3.8 below.
The thickness of this corrosion crust depends
3.6.3 Corrosion of Archaeological upon the rate of corrosion and the solubility of
Metals the released ions.
Archaeological objects – that is objects that The solubility of the ions depends upon pH
are buried in soil or tombs for many hundreds and the redox potential Eh (effectively the
of years experience different environments amount of dissolved oxygen or other electron
than normal engineering metal structures or acceptors) of the soil. When excavated,
art objects. When one considers the rate of archaeological metals are often surrounded
corrosion seen in many metals above ground by a thick encrustation of corrosion combined
one might expect that metal artefacts should with sand or soil particles and any other
not survive in the archaeological record at organic matter lying close to the object.
all – having long ago been converted back Generally, ferrous objects have a much thicker
to stable compounds resembling metal ores. and more porous crust of external corrosion
The truth is that in many cases that is exactly than copper alloys, silver of lead objects. The
what happens. Some corroded objects may be presence of reinforcing sand particles together
with pressure of surrounding soil supports thick. If the corrosion continues to completion
this external corrosion and prevents it from the iron core may dissolve completely,
fracturing and falling away from the corroding production of Fe2+ ions stops and in the absence
surface as is seen for example in the corrosion of a potential gradient the Cl- ions diffuse
of iron objects in air. The metal in the oxide out from the corrosion into the surrounding
that forms this internal corrosion originally environment. In extreme cases, the magnetite
formed part of the object and as the corrosion core may also dissolve leaving a void in the
front moves inwards from the original surface shape of the original object, surrounded by
it leaves a porous pseudomorph of internal external corrosion. This situation is sometimes
corrosion which normally has a lower oxidation encountered in iron objects from shipwrecks
state than the external corrosion. The original and the only way to identify the original artefact
surface lies at the boundary between the is to fill the void with silicone rubber and break
external and internal corrosion and it is this off the surrounding corrosion crust (Cronyn
surface that preserved the original shape of 1989). The cathode may be a dissimilar metal
the object and any technological evidence such as tin plating or, at a microscopic level, a
– tinning, gilding, tool marks, wear surfaces, metal grain of different composition. If there is
etc. The recognition of this original surface a more noble metal to act as the cathode then
is in many ways an act of faith – the surface corrosion of the iron is accelerated because
revealed by the removal of external corrosion there is no build up of oxide on the noble
is frequently blistered and cracked so it is metal. Such metals are also better conductors
possible that there are considerable changes of electricity than magnetite. Depending upon
in volume during the formation of the internal the chemistry of the burial environment other
corrosion. The corrosion of archaeological more exotic corrosion products may form.
metals can best be summarised by dealing
with each common alloy in turn.
If CO2 is present in the groundwater or
seawater then the corrosion product siderite
3.6.3.1 Corrosion of (FeCO3) is stable at low Eh and high-to-neutral
Archaeological Iron pH. This also forms as a corrosion product in
The corrosion of iron can be summarised post-excavation corrosion. In anoxic conditions
as follows. Assuming the soil solution has iron and other metals are protected against
neutral pH dissolved oxygen is reduced to the corrosion. However, where there are high
hydroxyl ion at the cathode which is often the sulphide levels and high levels of organic
outer surface of the internal corrosion. Inside matter in the sediment then sulphate-reducing
the corroding object, at the interface of the bacteria (SRBs) may influence the local
internal corrosion and the metal core Fe2+ ions soil environment. These primitive bacteria
are released at the interface between the oxide use sulphate as an electron acceptor in the
and the metal and the high concentration of oxidation of simple organic compounds,
positive ions there attracts chloride ions releasing hydrogen sulphide (H2S) into the
deep into the oxide layer. The presence of local environment. This can combine with
these negatively charged ions changes the Fe2+ ions to form iron pyrite (FeS). This leaves
electrostatic balance between the metal surface some metals with a false gilding of shiny "fool’s
and the Fe2+ ions which then begin to diffuse gold" that results in excellent preservation of
outwards through the internal corrosion to the surface details. Alternatively, where phosphate
surrounding soil where they may be oxidised levels are high, such as in rubbish pits and
to Fe3+ ions. Diffusion and mixing of Fe2+ ions graves then vivianite (FePO4·2H2O) a bright
and Fe3+ ions gives rise to the formation of blue mineral may form together with the more
magnetite (Fe3O4) which is an oxide of mixed usual rust.
iron I and iron II oxidation states – sometimes
written Fe2O3·FeO. This leads to a generalised
situation where in cross section a residual 3.6.4 Post-excavation Corrosion
metallic iron cores is surrounded by a shell of of Archaeological Iron
black magnetite internal corrosion, which is Chloride ions play a key role in the corrosion
then overlain by a more porous, brown jacket of archaeological metals and are one of the
of external corrosion containing soil particles main reasons for post-excavation corrosion
and associated detritus infiltrated with iron of archaeological objects. Once excavated,
III corrosion products. Since magnetite is an archaeological iron is exposed to much greater
electrical conductor it frequently acts as the concentrations of oxygen than in the burial
cathode in the corrosion cells, although oxygen environment. One might think that corrosion
availability is limited by the diffusion through would be much slower because now the iron
the external corrosion layers which can be very is in a dry environment but that is far from
true for two reasons. Firstly, once water But in the corrosion crust the pH can fall
has evaporated from the porous corrosion low enough to make FeO·OH soluble. This
products surrounding the remaining metal is weeping iron where drops of very acidic
core the inward diffusion of gaseous oxygen orange water form on the corrosion crust.
is much more rapid. The shrinking reservoir
2) Local HCl concentrations dissolve more
of salt-containing water retreats into the
stable iron oxides.
smallest pores, close to the metal surface and
this drives chloride ions close to the metal 3) Chlorides lower the relative humidity (RH) at
surface. Archaeological iron has a very fine which corrosion can take place. This should be
pore structure and this also acts as a moisture at an RH above 44% but because β-FeO·OH is
trap, drawing water vapour from the air and very hygroscopic and absorbs water between
condensing it as liquid within the smallest 15% RH and 44% RH archaeological iron is
pores. Secondly, the fact that archaeological unstable at all RH values above 15%.
iron contains high concentrations of chlorides
4) Chlorides increase the conductivity of the
in the corrosion pits – close to the metallic
concentrated solutions within the corrosion
core – increases the moisture content of the
crust.
iron corrosion products. Ferric chloride is very
hygroscopic and attracts moisture from the air. Current approaches to the care of
It also forms very acidic solutions in water due archaeological ironwork follow one (or both) of
to hydrolysis: two philosophies. Removal of all chlorides from
the corrosion products, and maintaining the
FeCl3 (s) " Fe3+ (aq) + 3Cl- (aq)
storage and display environment below an RH
Fe3+ (aq) + 3H2O " Fe(OH)3 (s) + 3H+ (aq) value of 15%. Both approaches have severe
limitations in their practical applications as is
Fe(OH)3 is very insoluble and pumps hydroxyl
explained in Chapter 5.
ions out of solution, lowering the pH further.
The following reactions show that water can be 3.6.5 Corrosion of Archaeological
generated by post-excavation corrosion with Copper Alloys
only the addition of oxygen if free ferrous ions Copper alloys corrode less quickly than iron
are available. objects, both on land and in seawater. Copper
and copper alloys are more electropositive
Fe2+ (aq) + 2OH- (aq) " Fe(OH)2 (s)
than iron and the external corrosion layers are
6Fe(OH)2 (s) +O2 (g) " 2Fe3O4 (s) + 6H2O more compact, coherent and protective than
those that form on iron and its alloys. As a
2Fe(OH)2 (s) + 11⁄2O2 (g) " Fe2O3·H2O (s) + H2O
result copper and bronze artefacts dating from
Oxygen is the driving force in this corrosion, the very beginnings of man’s exploitation of
which can continue in only small quantities metals several thousand years ago have been
of water. Corrosion is further catalysed by discovered on archaeological excavations.
chlorides:
In most archaeological deposits, either on
2Fe (s) + 11⁄2O2 (g) + 6HCl (aq) land or underwater, water, oxygen and carbon
" 2Fe2+ (aq) + 6Cl- (aq) + 3H2O dioxide are present in the environment. Often
the corrosion products seen on archaeological
Fe2+ (aq) + 2H2O + 3Cl- (aq)
copper alloys are superficially similar to those
" FeO·OH + 3H+ (aq) + 3Cl- (aq)
patinas that form during atmospheric corrosion.
4Fe2+ + O2 + 6H2O " 4 β−FeO·OH + 8H+ However archaeological environments also
contain dissolved salts which accelerate
Metallic iron continues to corrode and local pH
corrosion and influence the corrosion products
falls by production of H+ ions.
formed. Once again, of these ions the chloride
Chlorides have four detrimental effects: ion is the most common and most damaging.
1) They affect which solid corrosion product Copper has two oxidation states. All copper
forms, giving rise to β-FeO·OH. Sites of I compounds are highly insoluble except for
FeO·OH production occur where outward CuCl which is soluble in concentrated HCl
diffusing Fe2+ ions meet inward diffusing where it forms a co-ordinately bonded anionic
O2. The production of hydrogen ions is complex. The usual copper I compound formed
counteracted at the iron core by reaction on archaeological copper alloys is Cu2O. The
with the metal to produce hydrogen: chloride ion acts as a catalyst in the production
of Cu2O:
2H+ (aq) + 2e- " H2 (g)
2Cu + 1⁄2O2 + HCl " Cu2O + HCl
Note that the HCl is recycled at the end of
the reaction. If the pH falls to approximately
4CuCl + O2 + 4H2O
2 then Cu2O becomes soluble in the HCl and
" 2Cu2(OH)3Cl + 2Cl- + 2H+
Cu+ ions may migrate until the rise in pH
causes precipitation of CuCl as crystals. Local
corrosion cells may then be set up between The final corrosion product is a hydroxy-chloride
Cu2O, CuCl and copper metal: or basic copper chloride. The basic copper
chlorides occur in one of two forms: black/
2Cu + 2HCl + 1⁄2O2 " 2CuCl +
green atacamite or dark green paratacamite
H2O
of which paratacamite is most common on
2CuCl + H2O Cu2O + 2HCl archaeological bronzes. The presence of these
(Nantokite Cuprite + corrosion products makes archaeological
hydrochloric acid) bronzes inherently unstable.
as the pH falls then Cu2O " CuCl
The corrosion of alloys of copper is a little
Also, copper disproportionates: 2Cu+ Cu more complicated than the reactions above
+ Cu2+ so that Cu+ only exists in high Cu2+ suggest. At the microscopic level, the corrosion
concentrations at the expense of the dissolution of bronzes and brasses develops along
of Cu metal. So in high Cu2+ concentrations such grain boundaries. For bronzes with <10%
as those found at the bottom of corrosion pits, tin the alpha phase corrodes preferentially
Cu+ can dissolve the un-oxidised metal. Thus because tin is more electronegative than
at the bottom of a crack in the patina and in copper, leading to inter-granular corrosion.
pits in the corroding metal local concentration For >10% copper and >1% zinc the tin rich
cells produce rapid corrosion according to the delta phase corrodes preferentially. For >10%
following reactions: tin and <1% zinc the corrosion begins with
the copper-rich alpha phase. For alloys of
Cu " Cu2+ + 2e-
leaded gunmetals the alpha and delta phase
Cu + Cu2+ " 2Cu+ (aq) corrode preferentially and metallic copper
may re-deposit electrochemically. Because
Cu+ (aq)+ Cl- (aq) " CuCl (s)
of the differential rates of corrosion in multi-
2CuCl + H2O " Cu2O + HCl (aq) phase alloys the metallographic structures are
frequently preserved even in severely corroded
4CuCl + 4H2O + O2
copper alloys (Chase 1994).
" CuCl2 3Cu(OH)2 + 2HCl (aq)
Rather surprisingly, the corrosion product Corrosion of thin copper alloys such as raised
CuCl2 3Cu(OH)2 has been identified on copper- vessels and coins can continue until there is
rich dental amalgams (Marshall et al 2004). no remaining metal. The object is left as a
The low pH can be further maintained by the mineral copy of the original metal shape and
hydrolysis of water by solvated highly charged will be extremely fragile. Such objects may
Cu2+ ions according to the reaction: break up into small sections and will have
none of the ductility normally associated with
[Cu(H2O)4]2+ (aq)
metals (Figure 3.9). However, such objects are
[Cu(H2O)3OH]+ (aq) + H+ (aq)
extremely stable once excavated because any
excess chlorides will have diffused out of the
The pH at the bottom of corrosion pits (anode)
corrosion products into the surrounding soil.
is very low but as the copper ions migrate
Even so, some hydration of corrosion products
away from the sites of active corrosion the pH
might take place and there may be some colour
rises and they precipitate out as basic copper
changes in the external patina.
carbonates, sulphates and chlorides.
This is bronze disease and can be seen on many
museum objects as a bright green, powdery 3.7 Corrosion of Silver Alloys
corrosion product that can appear very rapidly At room temperature silver reacts with
if the RH rises above 50%. (Compare this with atmospheric oxygen to get a thin film of Ag2O.
the threshold of 15% for archaeological iron This is a thin white coating that is epitaxial to
containing chlorides). the underlying metal structure and protects
against further oxidation. However, in the
The deterioration of copper alloys from bronze
presence of water from moist air both O2 and
disease can be very rapid and outbreaks of
H2O are adsorbed and together form H2O2.
fresh corrosion can occur within 24-48 hours if
The peroxide promotes lattice defects in
the RH rises too high.
the Ag2O layer that allow Ag+ to move from
the base of cracks to the oxide-air interface
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.
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 of X-rays by ferrous corrosion products and
unremarkable and shapeless lump of corrosion. non-ferrous metals means that metal plating
Frequently, radiography is the fastest and most on corroded iron objects are often quite
effective means of primary documentation for visible in X-rays while being invisible in visible
a large group of corroded iron objects or coins light, even under magnification. As we saw
(Figure 4.1). Radiography not only helps in in Section 3.5 corrosion of iron can continue
the identification of objects it also documents beneath a tin or noble metal plating, while
the degree of corrosion in a metal object the tin is cathodically protected until all the
– especially in corroded iron objects where the associated iron is oxidised. Thus, tin plating or
voluminous corrosion products are much less copper alloy and silver inlays on iron objects
opaque to X-rays than the surviving metal core often remain un-corroded even in severely
(Figure 4.2). degraded objects.
The corrosion products in non-ferrous These platings and inlays lie at the original
metals are frequently more compact than surface of the object and are surrounded on the
iron corrosion products and therefore are outside by external corrosion – predominantly
barely less opaque to X-rays than the metal goethite – and on the inside by internal
itself. Nevertheless, radiography of smaller corrosion – predominantly magnetite and
copper- or silver alloy objects such as coins unstable, chloride-containing oxy-hydroxides.
and jewellery is often advisable since this can In smaller objects such as keys the presence
reveal otherwise hidden details. For example of a tin plating acting as the cathode results
the Anglo-Saxon brooch in Figure 4.3 has been in very serious corrosion, to the extent that
repaired in antiquity, using a small iron plate almost all metallic iron is dissolved from the
and iron rivets. Corrosion of the iron in the object. In these cases the tin plating is the
repair has caused the brooch to break once only surviving record of the original surface
again but all evidence for the repair is hidden and because of the extreme fragility of iron
from the naked eye by corrosion products. corrosion products it may be impossible to
The nature of the repair was revealed only by mechanically clean the artefact (see Section
radiography. The relative contrast in absorption 5.2.4). In such cases radiography in several
orientations allows a drawing to be made and folded – slag stringers. Corrosion often
of the object’s original shape and it may be follows these stringers so that X-rays of very
possible to open a small "window" in the corroded objects show a "grainy" texture. Steel
external corrosion to allow identification of frequently does not show these slag stringers
the non-ferrous metal using XRF or a similar but is prone to pitting corrosion. Thus, in
technique. Keys and similar objects may also thin objects such as knives and swords, steel
contain brazed joints where several composite cutting edges can sometimes be distinguished
parts have been joined. Brazing can sometimes from a wrought iron core. In antiquity blades
be distinguished by identifying bubbles in the were made by fire welding together iron and
dense metal on X-rays (Figure 4.4). steels of different hardness and toughness
to give a durable blade with good cutting
Because of the different corrosion characteristics characteristics. Repeated heating in the forge
of wrought iron and steel it is sometimes possible can cause trace elements such as phosphorus
to interpret X-rays to determine whether an and nickel in the steel to become concentrated
ancient ferrous object has been created by in the surface so that weld lines may be slightly
welding together several pieces of metal with cathodic with respect to the surrounding iron.
different carbon compositions. Wrought iron As a result weld lines may be visible in X-
usually contains long, parallel filaments of radiographs of corroded blades. Swords from
slag from having been repeatedly hammered the later Roman period and Migration Period
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.
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.
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 that although "bronze" objects are commonly
considered acceptable whilst still corroded and
of Metals green in colour silver is not viewed favourably
With the exception of gold alloys of high
by the museum public if it is blackened by
purity all historic and archaeological metals
corrosion – a situation commonly encountered
will have some form of external corrosion and
in both archaeological and historical silver. The
some will have extensive internal corrosion.
cleaning and subsequent care of metal cultural
Even gold can acquire a thin coating of brown
heritage is as much about cultural preferences
or red staining after centuries of soil burial
and ethical codes as it is about practical
– possibly representing a fine layer of cuprite.
conservation. Clearly, before any interventive
Gold alloyed with copper or silver may become
treatment is undertaken the conservation
surface enriched as copper or silver ions are
strategy and its intended outcomes should be
leached from the outer few microns of the
fully discussed and agreed amongst all relevant
metal - leaving the surface dulled.
parties – the owner or curator, the conservator
In some metal objects this corrosion is and any specialists involved in researching that
relatively harmless and will not promote class of objects concerned.
further deterioration of the artefact. For
examples some bronze and brass objects have 5.2 Cleaning and Stabilisation of
an aesthetically pleasing patina that is valued
by collectors and the museum public alike. In
Corroded Metals
The cleaning and conservation of metals differs
most cases this patina will be preserved during
from the cleaning of other cultural material in
the cleaning of a copper alloy object. Instead
the nature of the material removed. Cleaning
of removing this corrosion the surface may be
usually involves the removal of "dirt". Dirt can
stabilised with a chemical passivator and the
be interpreted in many ways but usually the
cleaned copper patina coated with a protective
term refers to foreign particulate or oily matter
lacquer to prevent water condensing on the
sitting on top of, or permeating into, the original
surface and changing the nature or colour of
surface. There are various ethical approaches to
the corrosion film.
the removal of such dirt from many classes of
All copper alloys should be stored or exhibited historical and cultural artefacts. If the dirt has
in an atmosphere that is below 45% RH and got there through the normal use of the object,
has no polluting gasses such as SO2 or H2S. In for example grease by repeated handling during
other metals, especially iron, the thick layers the use of a tool, then it can be argued that the
of corrosion hide the shape of the original dirt represents part of the object’s history and
artefact. The shape of the object can be should not be removed in the same way that
revealed by X-radiography and drawings for dust accumulated in poor storage or display
publications and reports may be made from should be removed. In the case of metals
X-ray plates. However, if the artefact is to the situation is more complicated. Corrosion
be displayed in a museum then the external does not represent foreign matter deposited
corrosion may be removed to allow the object on top of the original surface. Corrosion is
to be seen and fully understood by the public. the original material transformed into another
The artefact will also have to be cleaned if it has form. Removal of the corrosion will not reveal
decorative platings or inlays of another metal the original surface – removing the corrosion
so that the pattern can be seen. Some lead and is actually removing part of the object itself.
silver alloys can also become covered in a thick Very often this is not understood correctly. In
layer of corrosion that hides the shape of the the case of corroded coins there is often the
artefact and obscures surface decoration. In desire on the part of some collectors to clean
the case of silver, this thick corrosion – usually the coin to reveal the underlying detail. In the
silver chloride – can be removed to show the case of severely corroded archaeological coins
shape and decoration below. The corrosion the original surface may no exist, having been
layer itself is not a danger to the long-term converted to voluminous corrosion products.
survival of the object or to museum specialists Any attempt to "clean" the coin by physical
handling the objects. After removal of the of chemical methods only makes the situation
silver chloride crusts the exposed surface may worse. In fact, amongst serious coin collectors
be restored to a bright, shiny finish or may there is an understanding that cleaning should
be left dull depending upon the preference of only be attempted in very special circumstances
the museum specialists or in accordance to an and that cleaning a coin will most often destroy
accepted conservation ethical code. It is ironic its aesthetic and monetary value. Thus, no
cleaning of a historical or archaeological decomposes the corrosion product or thermal
metal artefact should be considered without shock blows off the outer layer by a principle
a clear evaluation by curators, owners and called laser ablation. Often, several methods
conservators of the ethical issues involved. will be used separately or in combination on
one object to get the best results.
5.4 Types of Cleaning
There are four approaches to the cleaning of 5.3.1 Mechanical Cleaning
corroded historical and archaeological metals. Mechanical cleaning is the term used when
foreign matter or corrosion is physically
1) Mechanical cleaning to remove, or modify
the appearance of, external corrosion. removed from the surface of an object using an
external force. There is no requirement that a
2) Chemical cleaning to remove corrosion. machine is used and most mechanical cleaning
3) Electrochemical cleaning to reduce and/or is done by hand using simple small tools with no
remove corrosion. moving parts. The simplest act of mechanical
cleaning is the removal of superficial dust or
4) Thermal reduction.
particulate matter using a soft, dry cloth. No
These four traditional approaches are now chemical interaction takes place between the
supplemented by laser cleaning of metals cloth and the object’s surface, nor between the
where pulses of high energy laser light are cloth and the particulate matter – apart from
directed at the surface and rapid heating either 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
It may be possible to remove some unwanted Figure 5.1: Gently cleaning superficial corrosion
materials such as flaking paint from the from an aluminium rice steamer using a scalpel.
surface by applying a force at right angles to Removing the white powdery corrosion leaves a
darker, smoother and more even surface finish.
the surface – i.e by pulling the paint off the
surface. Adhesive tapes are useful for removing
old overpainting from some industrial heritage The effectiveness of the cleaning depends upon
objects without damaging the original paint the hardness of the material in contact with
below. As unlikely as it seems, it is possible the surface, the force applied, and the duration
to remove some corrosion products using a of the polishing. The aggressiveness of the
variation of this technique. Silver chloride polishing action can be modified by using a
corrosion can be physically removed from polishing compound that contains hard, sharp
the very fragile underlying silver by carefully particles of differing sizes. These particles
peeling off a layer of cellulose nitrate adhesive usually come in some kind of carrier liquid
applied previously (see Section 5.8.1). that wets the surface of the object and allows
even distribution of the polishing compound.
Polishing is a term often used in connection with This can be simply a water- or spirit-based
the "cleaning" of historical metals, especially wetting agent (detergent) or may also contain
silver and copper alloys. This implies rubbing a some chemical reagent specific to the metal
cloth or cotton wool swab repeatedly back and being polished – for example, copper, brass
forth parallel to the object’s surface. Polishing and silver polishes frequently contain ammonia
has a two-fold action: loose particles are which forms soluble complexes with copper
removed from the surface are entangled in the corrosion products. Silver polish may contain
fibres of the cloth or swab; and material that thiosulphate which helps to reduce silver
is securely bound to the surface is burnished sulphide. Another useful tool for the removal of
to give a smoother surface. This smoother particulate matter and softer corrosion products
is a pencil eraser. These come in a variety of cleaning and any interesting corrosion
rubber and plastic compositions of various products, technological evidence or platings
hardnesses. Putty rubbers are soft and sticky should be photographed and documented by
and good at binding loose particulate matter the conservator before a decision is made
such as rust but may leave an oily residue on to remove or retain them (English Heritage
the surface cleaned. Plastic (PVC) rubbers bind 2008). Extreme care must be taken so as not to
up particulate matter into the rubbings created remove important trace evidence that may give
and leave the surface looking cleaner without clues to how the artefact was made, used and
disrupting the underlying corrosion layer. discarded. Cleaning at this level of observation
Harder erasers (usually grey in colour) contain is an absolute necessity when conserving any
abrasive particles which will actually remove archaeological metal artefact. Since corrosion
or smooth metal corrosion products as well as products are frequently hard and brittle when
removing particulate matter from the surface compared to the underlying metal it is possible
(Figure 5.2). It is possible to buy large abrasive to use crushing forces to break them up and
rubber erasers for cleaning and polishing the remove them. This can be done using sharp
aluminium engine blocks on motorcycles and needles and scalpels to introduce cracks in
these are often useful in cleaning historical iron the corrosion by applying pressure vertically
tools and small pieces of industrial heritage. 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).
Figure 5.7: With considerable practice and good Figure 5.8: It is possible to remove the external
a microscope it is possible to remove the external green copper corrosion products from an
corrosion from an archaeological copper alloy object archaeological object to reveal the gilded surface
using an air-abrasive machine with suitably selected without destroying the fine patina below the
powder and pressure. Here a small key has been external corrosion. An Anglo-Saxon square-headed
partly cleaned down to the “original surface”. brooch from Lindsey in Lincolnshire.
One caveat when cleaning copper alloy objects evidence and should not be removed, having
created by the combination of different been mistaken for ordinary corrosion.
parts. Tin- or lead-rich solders may corrode Clearly, the cleaning and conservation of
faster than the bronze or brass surfaces they archaeological copper alloys requires good
are joining and as a result the joints in an powers of observation, good comprehension
archaeological object may fail while in the of art historical and technical issues relating to
ground. The remaining solder residue may the class of objects treated, and a high level of
be completely corroded and may look like a training and experience.
powdery corrosion product. This should not
be removed in mistake for external corrosion
since this will destroy important technological 5.4.2 Chemical Cleaning of
evidence and make it unclear exactly where, Copper Alloys
for example, a soldered handle was attached Copper alloys can be cleaned chemically if
(Figure 5.9). Furthermore, red enamel inlay in the original surface is too fragile to survive
the form of a glass coloured by copper I oxide mechanical cleaning. Usually, chemical cleaning
can deteriorate in the burial environment and is used in combination with mechanical
turn into green powdery material containing cleaning to soften hard encrustations or
copper carbonate. Once again, this represents to remove copper corrosion overlying gold
important technological and art historical 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. stabilization aims to prevent reactivation of
The acid reacts with carbonates in the basic chloride catalysed corrosion. Bronze disease
copper carbonate corrosion products and these is recognised by rapidly growing, bright green,
copper II compounds become soluble copper powdery corrosion normally associated with
formates. Objects must be well rinsed with pits in the surface patina. If bronze disease
water and/or ethanol afterwards to remove is limited to a few bright green spots in an
excess acid. Conservators should be very otherwise stable patina then these spots can
careful when using acids to clean corrosion be excavated mechanically and the chlorides
products. Formic acid turns the green patina immobilized. After removing the loose, bright
to a red/brown surface by exposing the cuprite green paratacamite the pit is packed with Ag2O
(copper I oxide) surface below. Furthermore, and the object exposed to a high humidity.
with gilded objects, acid decomposition of basic Under high humidity the chlorides become
copper carbonates below the gold plating can mobile but react with the silver to form highly
create bubbles of carbon dioxide that may lift insoluble AgCl:
and detach the thin gilded surface. In the past,
2CuCl + Ag2O " Cu2O + 2AgCl
chemical stripping of corrosion using organic
acid solutions – formic, citric, tartaric or oxalic However, exposure to ultraviolet light can
acids has been used in the cleaning of copper reduce the AgCl to metallic silver, in a reaction
alloys, especially the bulk cleaning of many analogous to the exposure of a photographic
objects such as in coin hoards, etc. Certain alkali emulsion, and release the chlorides again. As
salts have also been used – 15% NaKTartarate an alternative treatment, the copper object can
/ 5% NaOH (pH 13), NaOH/Glycerol (pH 13) or be exposed to ammonia vapour that complexes
Na2EDTA at pH 8. However this runs the risk of with copper chloride by forming a strong
removing or radically altering the patina and ligand. The object is then put in a saturated
de-zincifies or de-stannifies the metal below. acetone vapour leading via a condensation
Simple electrolytic stripping of archaeological reaction to triacetone amine that encloses
bronzes has been used by wrapping Cu wire the AgCl. However, once again there is the
around bronzes and immersing them in NaOH danger of colour changes in the patina and any
and a closely related method is electrochemical cyclic copper acetylene compounds formed are
stripping using zinc granules and warm NaOH. intrinsically unstable.
Here the method relies upon the generation of
Most conservators now use treatment with
bubbles above the remaining metal to disrupt
benzotriazole (C6H5N3) to stabilize all but the
and weaken the external corrosion. However,
most unstable bronzes and copper alloys.
there is a danger that zinc metal may plate
Benzotriazole is commonly referred to as
out onto the objects being cleaned. Sodium
BTA and can act as either an electron donor
sesquicarbonate washing in 5% aqueous
or electron acceptor - having three lone pair
solution has also been used in the past in an
electrons that can form coordinate bonds with
attempt to reduce the chloride content of the
copper. It is thought to form three different BTA
corrosion crusts. The reaction targets cupper I
compounds with copper to give a thin film over
chloride:
the whole metal surface – although it remains
2CuCl + H2O Cu2O + 2HCl unclear to what extent it binds to copper within
the corrosion layer. This film is less than 500
The HCl created is neutralized by the carbonate nanometres thick and therefore quite fragile.
to give off carbon dioxide, thus driving the In practice, objects are degreased in acetone
reaction to the right and leading to the slow and then immersed under vacuum in a 3%
removal of CuCl from the object. However, very aqueous solution of BTA or 3% in ethanol. If
pure chemicals must be used and the treatment the object is too large to completely immerse
can cause colour changes in the patina. 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
5.4.3 Stabilisation of Copper vapour phase inhibitor – BTA being carried as a
vapour into the pore structure of the corrosion
Alloys where it undergoes reaction with copper
For any archaeological copper alloy it is
compounds. As an important health and safety
usually necessary to chemically stabilize the
note, BTA is a suspect carcinogen and should
corrosion products in the patina to prevent
be treated with the respect accorded to all
future corrosion (bronze disease). Problems
reagents in the conservation laboratory.
with post-excavation corrosion usually result
from chlorides closely bound to the metal To further protect copper alloy objects they
surface below the patina and most chemical 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.
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)
in zinc ribbon and placing it in a bath of alkali 0.02-0.05 Amp cm-2 to give a satisfactory
such as caustic soda (NaOH) or by the use of result. All residues of electrolytes should be
an applied external dc current. The stripped carefully removed by long rinsing in tap water
metal core was then treated with hot wax to and then distilled water and the objects dried
prevent future corrosion. in an oven at 60 oC.
grit or asphalt particles, soot and other oily the display case or by using fibre optic lights.
residues. Removal of this particulate matter For sensitive metals such as silver and lead
requires more care because the dust in this especial care must be taken to prevent
case may be sticky or may scratch the surface enclosing the objects for very long periods with
of objects if a simple cloth is used to rub over a source of pollution such as hydrogen sulphide,
the surface. Open display of silver objects is ammonia or organic acids. Materials used
more problematic and not only in terms of in the construction of museum cases should
security. Pollution in the form of hydrogen always be regularly tested to see if they are in
sulphide gas will lead to rapid tarnishing of a danger of releasing reactive gasses that may
polished silver surface and the silverware will damage metal. Potential sources of problem
slowly turn brown and then black. gasses include: woollen textiles that release
hydrogen sulphide from the decomposition of
Dust and other pollution is much reduced if the sulphur containing amino acid cysteine
the objects are displayed within a glass case present in keratin1; rubber seals for glass cases
because it is much easier to control a small, that contain sulphur and may also release
enclosed environment. Some glass cases can hydrogen sulphide; ammonia vapour evolved
be extremely sophisticated in design with from paints and silicone rubber sealants used
dry air piped into the airspace to maintain in cases; formic and acetic acids vapours given
an overpressure that prevents dust and other off by poor quality wood, particle boards and
pollutants from entering the display case. papers used in displays. All materials used in
These are useful for extremely valuable or the construction of storage and display cases
sensitive metal artefacts but in most instances should be tested for suitability, for example
a well sealed case will buffer displayed objects using the simple Oddy test of accelerated aging
from extremes in temperature and humidity. at elevated temperatures (Green and Thickett
In many museum cases cold sources of light 1995).
are used by having spotlights located outside
1
Human hair contains 5% cysteine by weight.
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.
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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