Conservation and restoration of copper-based objects
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The conservation and restoration of copper and copper-alloy objects is the preservation and protection of objects of historical and personal value made from
copper Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pink ...
or
copper alloy Copper alloys are metal alloys that have copper as their principal component. They have high resistance against corrosion. The best known traditional types are bronze, where tin is a significant addition, and brass, using zinc instead. Both of t ...
. When applied to items of
cultural heritage Cultural heritage is the heritage of tangible and intangible heritage assets of a group or society that is inherited from past generations. Not all heritages of past generations are "heritage"; rather, heritage is a product of selection by soc ...
, this activity is generally undertaken by a conservator-restorer. Historically, objects made from copper or copper alloy were created for religious, artistic, technical, military, and domestic uses. The act of conservation and restoration strives to prevent and slow the deterioration of the object as well as protecting the object for future use. The prevention and removal of surface dirt and corrosion products are the primary concerns of conservator-restorers when dealing with copper or copper-alloy objects.


History


Copper Age

Copper occurs naturally as
native copper Native copper is an uncombined form of copper that occurs as a natural mineral. Copper is one of the few metallic elements to occur in native form, although it most commonly occurs in oxidized states and mixed with other elements. Native coppe ...
and was known to some of the oldest civilizations on record. It has a history of use that is at least 10,000 years old, and estimates of its discovery place it at 9000 BC in the Middle East; a copper pendant was found in northern Iraq that dates to 8700 BC. There is evidence that gold and
meteoric iron Meteoric iron, sometimes meteoritic iron, is a native metal and early-universe protoplanetary-disk remnant found in meteorites and made from the elements iron and nickel, mainly in the form of the mineral phases kamacite and taenite. Meteoric ir ...
(but not iron smelting) were the only metals used by humans before copper. The history of copper metallurgy is thought to have followed the following sequence: 1)
cold working In metallurgy, cold forming or cold working is any metalworking process in which metal is shaped below its recrystallization temperature, usually at the ambient temperature. Such processes are contrasted with hot working techniques like hot r ...
of
native copper Native copper is an uncombined form of copper that occurs as a natural mineral. Copper is one of the few metallic elements to occur in native form, although it most commonly occurs in oxidized states and mixed with other elements. Native coppe ...
, 2) annealing, 3)
smelting Smelting is a process of applying heat to ore, to extract a base metal. It is a form of extractive metallurgy. It is used to extract many metals from their ores, including silver, iron, copper, and other base metals. Smelting uses heat and a c ...
, and 4) the lost wax method. In southeastern Anatolia, all four of these metallurgical techniques appears more or less simultaneously at the beginning of the Neolithic c. 7500 BC. However, just as agriculture was independently invented in several parts of the world (including Pakistan, China, and the Americas) copper smelting was invented locally in several different places. It was probably discovered independently in China before 2800 BC, in Central America perhaps around 600 AD, and in West Africa about the 9th or 10th century AD.
Investment casting Investment casting is an industrial process based on lost-wax casting, one of the oldest known metal-forming techniques. The term "lost-wax casting" can also refer to modern investment casting processes. Investment casting has been used in vari ...
was invented in 4500–4000 BC in Southeast Asia and
carbon dating Radiocarbon dating (also referred to as carbon dating or carbon-14 dating) is a method for determining the age of an object containing organic material by using the properties of radiocarbon, a radioactive isotope of carbon. The method was de ...
has established mining at
Alderley Edge Alderley Edge is a village and civil parish in Cheshire, England. In 2011, it had a population of 4,780. Alderley Edge is northwest of Macclesfield and south of Manchester, at the base of a steep and thickly wooded sandstone escarpment, Alder ...
in
Cheshire Cheshire ( ) is a ceremonial and historic county in North West England, bordered by Wales to the west, Merseyside and Greater Manchester to the north, Derbyshire to the east, and Staffordshire and Shropshire to the south. Cheshire's county tow ...
, UK at 2280 to 1890 BC. Ötzi the Iceman, a male dated from 3300–3200 BC, was found with an axe with a copper head 99.7% pure; high levels of
arsenic Arsenic is a chemical element with the symbol As and atomic number 33. Arsenic occurs in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. Arsenic is a metalloid. It has various allotropes, b ...
in his hair suggest his involvement in copper smelting. Experience with copper has assisted the development of other metals; in particular, copper smelting led to the discovery of iron smelting. Production in the Old Copper Complex in
Michigan Michigan () is a state in the Great Lakes region of the upper Midwestern United States. With a population of nearly 10.12 million and an area of nearly , Michigan is the 10th-largest state by population, the 11th-largest by area, and t ...
and
Wisconsin Wisconsin () is a state in the upper Midwestern United States. Wisconsin is the 25th-largest state by total area and the 20th-most populous. It is bordered by Minnesota to the west, Iowa to the southwest, Illinois to the south, Lake M ...
is dated between 6000 and 3000 BC.Pleger, Thomas C. "A Brief Introduction to the Old Copper Complex of the Western Great Lakes: 4000–1000 BC",
Proceedings of the Twenty-Seventh Annual Meeting of the Forest History Association of Wisconsin
', Oconto, Wisconsin, October 5, 2002, pp. 10–18.
Natural bronze, a type of copper made from ores rich in silicon, arsenic, and (rarely) tin, came into general use in the Balkans around 5500 BC. Previously the only tool made of copper had been the awl, used for punching holes in leather and gouging out peg-holes for wood joining. However, the introduction of a more robust form of copper led to the widespread use, and large-scale production of heavy metal tools, including axes,
adze An adze (; alternative spelling: adz) is an ancient and versatile cutting tool similar to an axe but with the cutting edge perpendicular to the handle rather than parallel. Adzes have been used since the Stone Age. They are used for smoothing ...
s, and axe-adzes.


Bronze Age

Alloying copper with tin to make bronze was first practiced about 4000 years after the discovery of copper smelting, and about 2000 years after "natural bronze" had come into general use. Bronze artifacts from
Sumer Sumer () is the earliest known civilization in the historical region of southern Mesopotamia (south-central Iraq), emerging during the Chalcolithic and early Bronze Ages between the sixth and fifth millennium BC. It is one of the cradles of ...
ian cities and Egyptian artifacts of copper and bronze alloys date to 3000 BC. The
Bronze Age The Bronze Age is a historic period, lasting approximately from 3300 BC to 1200 BC, characterized by the use of bronze, the presence of writing in some areas, and other early features of urban civilization. The Bronze Age is the second pri ...
began in Southeastern Europe around 3700 - 3300 BC, in Northwestern Europe about 2500 BC. It ended with the beginning of the Iron Age, 2000-1000 BC in the Near East, 600 BC in Northern Europe. The transition between the
Neolithic The Neolithic period, or New Stone Age, is an Old World archaeological period and the final division of the Stone Age. It saw the Neolithic Revolution, a wide-ranging set of developments that appear to have arisen independently in several pa ...
period and the Bronze Age was formerly termed the
Chalcolithic The Copper Age, also called the Chalcolithic (; from grc-gre, χαλκός ''khalkós'', "copper" and  ''líthos'', "Rock (geology), stone") or (A)eneolithic (from Latin ''wikt:aeneus, aeneus'' "of copper"), is an list of archaeologi ...
period (copper-stone), with copper tools being used with stone tools. This term has gradually fallen out of favor because in some parts of the world the Calcholithic and Neolithic are coterminous at both ends. Brass, an alloy of copper and zinc, is of much more recent origin. It was known to the Greeks, but became a significant supplement to bronze during the Roman Empire.


Antiquity and Middle Ages

In Greece, copper was known by the name ' (χαλκός). It was an important resource for the Romans, Greeks and other ancient peoples. In Roman times, it was known as ''aes Cyprium'', ''aes'' being the generic Latin term for copper alloys and ''Cyprium'' from
Cyprus Cyprus ; tr, Kıbrıs (), officially the Republic of Cyprus,, , lit: Republic of Cyprus is an island country located south of the Anatolian Peninsula in the eastern Mediterranean Sea. Its continental position is disputed; while it is ...
, where much copper was mined. The phrase was simplified to ''cuprum'', hence the English ''copper''.
Aphrodite Aphrodite ( ; grc-gre, Ἀφροδίτη, Aphrodítē; , , ) is an ancient Greek goddess associated with love, lust, beauty, pleasure, passion, and procreation. She was syncretized with the Roman goddess . Aphrodite's major symbols incl ...
and
Venus Venus is the second planet from the Sun. It is sometimes called Earth's "sister" or "twin" planet as it is almost as large and has a similar composition. As an interior planet to Earth, Venus (like Mercury) appears in Earth's sky never f ...
represented copper in mythology and alchemy, because of its lustrous beauty, its ancient use in producing mirrors, and its association with Cyprus, which was sacred to the goddess. The seven heavenly bodies known to the ancients were associated with the seven metals known in antiquity, and Venus was assigned to copper. Britain's first use of brass occurred around the 3rd–2nd century BC. In North America, copper mining began with marginal workings by Native Americans. Native copper is known to have been extracted from sites on Isle Royale with primitive stone tools between 800 and 1600. Copper metallurgy was flourishing in South America, particularly in Peru around 1000 AD; it proceeded at a much slower rate on other continents. Copper burial ornamentals from the 15th century have been uncovered, but the metal's commercial production did not start until the early 20th century. The cultural role of copper has been important, particularly in currency. Romans in the 6th through 3rd centuries BC used copper lumps as money. At first, the copper itself was valued, but gradually the shape and look of the copper became more important.
Julius Caesar Gaius Julius Caesar (; ; 12 July 100 BC – 15 March 44 BC), was a Roman general and statesman. A member of the First Triumvirate, Caesar led the Roman armies in the Gallic Wars before defeating his political rival Pompey in a civil war, an ...
had his own coins made from brass, while Octavianus Augustus Caesar's coins were made from Cu-Pb-Sn alloys. With an estimated annual output of around 15,000 t, Roman copper mining and smelting activities reached a scale unsurpassed until the time of the
Industrial Revolution The Industrial Revolution was the transition to new manufacturing processes in Great Britain, continental Europe, and the United States, that occurred during the period from around 1760 to about 1820–1840. This transition included going f ...
; the
provinces A province is almost always an administrative division within a country or state. The term derives from the ancient Roman '' provincia'', which was the major territorial and administrative unit of the Roman Empire's territorial possessions ou ...
most intensely mined were those of
Hispania Hispania ( la, Hispānia , ; nearly identically pronounced in Spanish, Portuguese, Catalan, and Italian) was the Roman name for the Iberian Peninsula and its provinces. Under the Roman Republic, Hispania was divided into two provinces: Hi ...
,
Cyprus Cyprus ; tr, Kıbrıs (), officially the Republic of Cyprus,, , lit: Republic of Cyprus is an island country located south of the Anatolian Peninsula in the eastern Mediterranean Sea. Its continental position is disputed; while it is ...
and in Central Europe. The gates of the
Temple of Jerusalem The Temple in Jerusalem, or alternatively the Holy Temple (; , ), refers to the two now-destroyed religious structures that served as the central places of worship for Israelites and Jews on the modern-day Temple Mount in the Old City of Jerusa ...
used Corinthian bronze made by depletion gilding. It was most prevalent in Alexandria, where alchemy is thought to have begun. In ancient India, copper was used in the holistic medical science
Ayurveda Ayurveda () is an alternative medicine system with historical roots in the Indian subcontinent. The theory and practice of Ayurveda is pseudoscientific. Ayurveda is heavily practiced in India and Nepal, where around 80% of the population rep ...
for surgical instruments and other medical equipment. Ancient Egyptians (~2400 BC) used copper for sterilizing wounds and drinking water, and later on for headaches, burns, and itching. The Baghdad Battery, with copper cylinders soldered to lead, dates back to 248 BC to AD 226 and resembles a galvanic cell, leading people to believe this was the first battery; the claim has not been verified.


Modern period

The Great Copper Mountain was a mine in Falun, Sweden, that operated from the 10th century to 1992. It produced two thirds of Europe's copper demand in the 17th century and helped fund many of Sweden's wars during that time. It was referred to as the nation's treasury; Sweden had a copper backed currency. The uses of copper in art were not limited to currency: it was used by
Renaissance The Renaissance ( , ) , from , with the same meanings. is a period in European history marking the transition from the Middle Ages to modernity and covering the 15th and 16th centuries, characterized by an effort to revive and surpass ide ...
sculptors, in photographic technology known as the
daguerreotype Daguerreotype (; french: daguerréotype) was the first publicly available photographic process; it was widely used during the 1840s and 1850s. "Daguerreotype" also refers to an image created through this process. Invented by Louis Daguerre a ...
, and the
Statue of Liberty The Statue of Liberty (''Liberty Enlightening the World''; French: ''La Liberté éclairant le monde'') is a colossal neoclassical sculpture on Liberty Island in New York Harbor in New York City, in the United States. The copper statue, ...
. Copper plating and
copper sheathing Copper sheathing is the practice of protecting the under-water hull of a ship or boat from the corrosive effects of salt water and biofouling through the use of copper plates affixed to the outside of the hull. It was pioneered and developed b ...
for ships' hulls was widespread; the ships of Christopher Columbus were among the earliest to have this feature. The
Norddeutsche Affinerie Aurubis AG (formerly Norddeutsche Affinerie AG) is listed on the stock exchange and is the largest copper producer in Europe (the second largest in the world) and the largest copper recycler worldwide. Its headquarters is in Hamburg, German ...
in Hamburg was the first modern
electroplating Electroplating, also known as electrochemical deposition or electrodeposition, is a process for producing a metal coating on a solid substrate through the reduction of cations of that metal by means of a direct electric current. The part to be ...
plant starting its production in 1876. The German scientist
Gottfried Osann Gottfried Wilhelm Osann (26 October 1796, Weimar – 10 August 1866, Würzburg) was a German chemist and physicist. He is known for his work on the chemistry of platinum metals. He studied natural sciences and became a ''privatdozent'' in physic ...
invented powder metallurgy in 1830 while determining the metal's atomic mass; around then it was discovered that the amount and type of alloying element (e.g., tin) to copper would affect bell tones. Flash smelting was developed by Outokumpu in Finland and first applied at
Harjavalta Harjavalta () is a town and municipality in Finland. It is located in the province of Western Finland and is part of the Satakunta region, southeast of Pori. The town has a population of () and covers an area of of which is water. The p ...
in 1949; the energy-efficient process accounts for 50% of the world's primary copper production. The Intergovernmental Council of Copper Exporting Countries, formed in 1967 with Chile, Peru, Zaire and Zambia, played a similar role for copper as
OPEC The Organization of the Petroleum Exporting Countries (OPEC, ) is a cartel of countries. Founded on 14 September 1960 in Baghdad by the first five members (Iran, Iraq, Kuwait, Saudi Arabia, and Venezuela), it has, since 1965, been headqua ...
does for oil. It never achieved the same influence, particularly because the second-largest producer, the United States, was never a member; it was dissolved in 1988.


Metallurgy


Corrosion


Conservation


Historical objects


Documentation

Systematic and well-managed documentation is today an essential prerequisite for quality executed conservation and restoration treatments, including documentation of the state of objects before, during and after treatment. Identification of materials and procedures used to produce object and the results of any scientific research must be part of documentation too. Last but not least, an integral part of the documentation must be a recommendation for further care of object.


Research

*identification of metals, alloys and metallic coatings *identification of other organic/inorganic materials *identification of corrosion products and processes *identification of technology used to produce object


Decision making

In preparing the strategy of the metals conservation project interdisciplinary approach to the same is essential. It implies the participation of as many experts as is possible, as a minimum, we can take curator (archaeologist, historian, art historian), scientists specialized for corrosion of metallic objects of cultural heritage and the conservator - restorer


Cleaning


Consolidation


Stabilization

*
benzotriazole Benzotriazole (BTA) is a heterocyclic compound with the chemical formula C6H5N3. Its five-membered ring contains three consecutive nitrogen atoms. This bicyclic compound may be viewed as fused rings of the aromatic compounds benzene and triazole. ...


Protective coatings

*clearcoats - Paraloid B-72 - Incralac - Ormocer - Everbrite Coating - Pantarol A *waxes -
Renaissance Wax Renaissance Wax is a brand of microcrystalline wax polish used in antique restoration and museum conservation around the world. Commonly used to polish and conserve metal objects, it is also used on gemstones and such organic materials as wood, ...
- Cosmolloid 80 H - Dinitrol 4010 - Poligen ES 91 009 *combinations - Paraloid B-72 + topcoat Renaissance Wax etc.


Archaeology objects


Documentation


Research


Decision making


Cleaning

*mechanical -Microsandblasting -Dry ice blasting -Scalpel or scraper High speed micromotor -Steel or ceramic burs and cutters -Abrasive wheels -Wire brushes -Glass fibre brushes and pens -Setting hammer


Consolidation


Stabilization

*chloride removal *corrosion inhibitors -
benzotriazole Benzotriazole (BTA) is a heterocyclic compound with the chemical formula C6H5N3. Its five-membered ring contains three consecutive nitrogen atoms. This bicyclic compound may be viewed as fused rings of the aromatic compounds benzene and triazole. ...
. -4 methyl imidazole -
tannin Tannins (or tannoids) are a class of astringent, polyphenolic biomolecules that bind to and precipitate proteins and various other organic compounds including amino acids and alkaloids. The term ''tannin'' (from Anglo-Norman ''tanner'' ...
-ammonium sulphideBelkin A.P.,Nackiy M.V. Metod obrabotki ochagov "bronzovoi bolezni" mednih splavov sulfidami amoniya//Restavracija pamjatnikov istorii i kulturi/GEL,Informkultura/Ekspres-informacija.Moscow,1987.Bp. 3. -S.6-8


Protective coatings

*clearcoats - Paraloid B-72 - Incralac - Ormocer - Everbrite Coating - Pantarol A *waxes -
Renaissance Wax Renaissance Wax is a brand of microcrystalline wax polish used in antique restoration and museum conservation around the world. Commonly used to polish and conserve metal objects, it is also used on gemstones and such organic materials as wood, ...
- Cosmolloid 80 H - Dinitrol 4010 - Poligen ES 91 009 *combinations - Paraloid B-72 + topcoat Renaissance Wax etc.


Preventive conservation

The items should be stored in rooms that are protected from polluted air, dust, ultraviolet radiation, and excessive relative humidity - ideal values are temperature of 16-20 °C and up to 40%(35-55% according to recent Canadian Conservation Institute recommendations) relative humidity, noting that if metal is combined with organic materials, relative humidity should not be below 45%. Archaeological objects must be stored in rooms (or plastic boxes) with very low relative humidity, or in the case of particularly valuable items in the chambers with nitrogen or argon. Copper or copper alloy objects with active corrosion up to 35% RH. Shelves in the storerooms must be of stainless steel or chlorine and acetate free plastic or powder coated steel. Wood and wood based products (particle board, plywood) must be avoided. Also do not use rubber, felt or wool. When you are handling metal objects, always wear clean cotton gloves . Lighting levels must be kept below 300 lux (up to 150 lux in case of lacquered or painted objects, up to 50 lux in case of objects with light sensitive materials).


See also

* Conservation and restoration of metals * Conservation and restoration of ferrous objects * Conservation and restoration of glass objects * Conservation and restoration of ivory objects * Conservation and restoration of ceramic objects * Conservation and restoration of silver objects


References


Further reading


Books

*Selwyn, L. ''Metals and Corrosion - A Handbook for the Conservation Professional,'' Ottawa 2004. *Scott, D.A. ''Metallography and Microstructure of Ancient and Historic Metals,'' Santa Monica 199
(online)
*Scott, D.A. ''Ancient and Historic Metals - Conservation and Scientific Research,'' Santa Monica 199

*Scott, D.A. ''Copper and Bronze in Art - Corrosion, Colorants, Conservation,'' Los Angeles 200
(online)
*Cronyn, J.M. ''The Elements of Archaeological Conservation,'' London 1990. *Rodgers, B. ''The Archaeologist Manual for Conservation - A Guide to Non-toxic, Minimal Intervention Artifact Stabilization,'' New York 2004. *La Niece,S. and Craddock,P. ''Metal Plating and Patination: Cultural, Technical and Historical Developments,'' Boston 1993. {{Cultural Conservation-Restoration , state=expanded Copper Conservation and restoration of cultural heritage