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 or copper alloy. When applied to items of cultural heritage, 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.
Copper occurs naturally as native copper 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; [1] a copper pendant was found in northern Iraq that dates to 8700 BC. [2] There is evidence that gold and meteoric iron (but not iron smelting) were the only metals used by humans before copper. [3] The history of copper metallurgy is thought to have followed the following sequence: 1) cold working of native copper, 2) annealing, 3) smelting, 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. [4] 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. [5] Investment casting was invented in 4500–4000 BC in Southeast Asia [1] and carbon dating has established mining at Alderley Edge in Cheshire, UK, at 2280 to 1890 BC. [6] Ötzi the Iceman, a male dated from 3300 to 3200 BC, was found with an axe with a copper head 99.7% pure; high levels of arsenic in his hair suggest his involvement in copper smelting. [7] Experience with copper has assisted the development of other metals; in particular, copper smelting led to the discovery of iron smelting. [7] Production in the Old Copper Complex in Michigan and Wisconsin is dated between 6000 and 3000 BC. [8] [9] 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, adzes, and axe-adzes.[ citation needed ]
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 Sumerian cities and Egyptian artifacts of copper and bronze alloys date to 3000 BC. [10] The Bronze Age 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 period and the Bronze Age was formerly termed the Chalcolithic 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. [10]
In Greece, copper was known by the name chalkos (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, where much copper was mined. The phrase was simplified to cuprum, hence the English copper. Aphrodite and Venus 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. [11]
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. [12] 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 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 provinces most intensely mined were those of Hispania, Cyprus and in Central Europe. [13] [14]
The gates of the Temple of Jerusalem used Corinthian bronze made by depletion gilding. It was most prevalent in Alexandria, where alchemy is thought to have begun. [15] In ancient India, copper was used in the holistic medical science Ayurveda 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. [16]
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. [17] It was referred to as the nation's treasury; Sweden had a copper backed currency. [18]
The uses of copper in art were not limited to currency: it was used by Renaissance sculptors, in photographic technology known as the daguerreotype, and the Statue of Liberty. Copper electroplating and copper sheathing for ships' hulls was widespread; the ships of Christopher Columbus were among the earliest to have this feature. [19] The Norddeutsche Affinerie in Hamburg was the first modern electroplating plant starting its production in 1876. [20] The German scientist Gottfried Osann 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 in 1949; the energy-efficient process accounts for 50% of the world's primary copper production. [21]
The Intergovernmental Council of Copper Exporting Countries, formed in 1967 with Chile, Peru, Zaire and Zambia, played a similar role for copper as OPEC 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. [22]
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.
Chemical | Electrochemical | Mechanical | Ultrasonic | Laser | Plasma |
---|---|---|---|---|---|
Ammonium citrate 5% / pH 9 [23] Citric acid 20% + 4% thiourea [24] Phosphoric acid 10–20% + 1% thiourea [24] EDTA 4% pH 10 [24] Potassium sodium tartarate 25% NaOH 120 g/40 g glycerol/1 L water [24] Polymethacrylic acid 10–15% pH 4.5–5.5 [25] | NaOH 2–5%, stainless steel anodes + Ecorr measurement! | Precipitated chalk/water mixture scalpel micromotor and steel/or bristle brushes microsanblasting unit dry ice blasting | 4-6 g sodium carbonate /6–8 g sodium phosphate 10-12 g sodium metasilicate 1 L distilled water 2–5 minutes, then rinse well and repeat if needs | Can be used [26] | Can be used [29] [30] |
-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
-4 methyl imidazole [32]
-ammonium sulphide [34]
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).
An alloy is a mixture of chemical elements of which in most cases at least one is a metallic element, although it is also sometimes used for mixtures of elements; herein only metallic alloys are described. Most alloys are metallic and show good electrical conductivity, ductility, opacity, and luster, and may have properties that differ from those of the pure elements such as increased strength or hardness. In some cases, an alloy may reduce the overall cost of the material while preserving important properties. In other cases, the mixture imparts synergistic properties such as corrosion resistance or mechanical strength.
Brass is an alloy of copper and zinc, in proportions which can be varied to achieve different colours and mechanical, electrical, acoustic and chemical properties, but copper typically has the larger proportion, generally 66% copper and 34% zinc. In use since prehistoric times, it is a substitutional alloy: atoms of the two constituents may replace each other within the same crystal structure.
Bronze is an alloy consisting primarily of copper, commonly with about 12–12.5% tin and often with the addition of other metals and sometimes non-metals, such as phosphorus, or metalloids, such as arsenic or silicon. These additions produce a range of alloys that may be harder than copper alone, or have other useful properties, such as strength, ductility, or machinability.
The Bronze Age was a historical period lasting from approximately 3300 to 1200 BC. It was characterized by the use of bronze, the use of writing in some areas, and other features of early urban civilization. The Bronze Age is the middle principal period of the three-age system, between the Stone and Iron Ages. Worldwide, the Bronze Age generally followed the Neolithic period, with the Chalcolithic serving as a transition. The Bronze Age may have included a widespread societal collapse between c. 1200 and 1150 BC, known as the Late Bronze Age collapse, although the extent of this is debated.
The Iron Age is the final epoch of the three historical Metal Ages, after the Chalcolithic and Bronze Age. It has also been considered as the final Age of the three-age division starting with prehistory and progressing to protohistory. In this usage, it is preceded by the Stone Age and Bronze Age. These concepts originated for describing Iron Age Europe and the Ancient Near East. The indigenous cultures of the New World did not develop an iron economy before 1500.
Metallurgy is a domain of materials science and engineering that studies the physical and chemical behavior of metallic elements, their inter-metallic compounds, and their mixtures, which are known as alloys.
Smelting is a process of applying heat and a chemical reducing agent to an ore to extract a desired base metal product. It is a form of extractive metallurgy that is used to obtain many metals such as iron, copper, silver, tin, lead and zinc. Smelting uses heat and a chemical reducing agent to decompose the ore, driving off other elements as gases or slag and leaving the metal behind. The reducing agent is commonly a fossil-fuel source of carbon, such as carbon monoxide from incomplete combustion of coke—or, in earlier times, of charcoal. The oxygen in the ore binds to carbon at high temperatures, as the chemical potential energy of the bonds in carbon dioxide is lower than that of the bonds in the ore.
Copper is a chemical element; it has symbol Cu 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 pinkish-orange color. Copper is used as a conductor of heat and electricity, as a building material, and as a constituent of various metal alloys, such as sterling silver used in jewelry, cupronickel used to make marine hardware and coins, and constantan used in strain gauges and thermocouples for temperature measurement.
A crucible is a container in which metals or other substances may be melted or subjected to very high temperatures. Although crucibles have historically tended to be made out of clay, they can be made from any material that withstands temperatures high enough to melt or otherwise alter its contents.
Arsenical bronze is an alloy in which arsenic, as opposed to or in addition to tin or other constituent metals, is combined with copper to make bronze. The use of arsenic with copper, either as the secondary constituent or with another component such as tin, results in a stronger final product and better casting behavior.
Archaeometallurgy is the study of the past use and production of metals by humans. It is a sub-discipline of archaeology and archaeological science.
Ferrous metallurgy is the metallurgy of iron and its alloys. The earliest surviving prehistoric iron artifacts, from the 4th millennium BC in Egypt, were made from meteoritic iron-nickel. It is not known when or where the smelting of iron from ores began, but by the end of the 2nd millennium BC iron was being produced from iron ores in the region from Greece to India, The use of wrought iron was known by the 1st millennium BC, and its spread defined the Iron Age. During the medieval period, smiths in Europe found a way of producing wrought iron from cast iron, in this context known as pig iron, using finery forges. All these processes required charcoal as fuel.
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, ivory, and tortoiseshell. The product is sometimes used by reenactors to protect armor and weapons. Waxes are more protective and longer-lasting than oil, especially for swords and helmets that are frequently touched by human hands. It has recently been introduced in the world of guitar building, as a finish that protects and gives colour to the wood.
The metals of antiquity are the seven metals which humans had identified and found use for in prehistoric times in Africa, Europe and throughout Asia: gold, silver, copper, tin, lead, iron, and mercury.
Metallurgy in pre-Columbian America is the extraction, purification and alloying of metals and metal crafting by Indigenous peoples of the Americas prior to European contact in the late 15th century. Indigenous Americans had been using native metals from ancient times, with recent finds of gold artifacts in the Andean region dated to 2155–1936 BC, and North American copper finds being dated to approximately 5000 BC. The metal would have been found in nature without the need for smelting, and shaped into the desired form using hot and cold hammering without chemical alteration or alloying. To date "no one has found evidence that points to the use of melting, smelting and casting in prehistoric eastern North America."
Metals and metal working had been known to the people of modern Italy since the Bronze Age. By 53 BC, Rome had expanded to control an immense expanse of the Mediterranean. This included Italy and its islands, Spain, Macedonia, Africa, Asia Minor, Syria and Greece; by the end of the Emperor Trajan's reign, the Roman Empire had grown further to encompass parts of Britain, Egypt, all of modern Germany west of the Rhine, Dacia, Noricum, Judea, Armenia, Illyria, and Thrace. As the empire grew, so did its need for metals.
Conservation and restoration of metals is the activity devoted to the protection and preservation of historical and archaeological objects made partly or entirely of metal. In it are included all activities aimed at preventing or slowing deterioration of items, as well as improving accessibility and readability of the objects of cultural heritage. Despite the fact that metals are generally considered as relatively permanent and stable materials, in contact with the environment they deteriorate gradually, some faster and some much slower. This applies especially to archaeological finds.
Iron, steel, and ferrous metals constitute a large portion of collections in museums. The conservation and restoration of iron and steel objects is an activity dedicated to the preservation and protection of objects of historical and personal value made from iron or steel. When applied to cultural heritage this activity is generally undertaken by a conservator-restorer. Historically, objects made from iron or steel were created for religious, artistic, technical, military and domestic uses. Though it is generally not possible to completely halt deterioration of any object, 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. One of the first steps in caring for iron is to examine them and determine their state, determine if they are corroding, and consider options for treatment.
Non-ferrous extractive metallurgy is one of the two branches of extractive metallurgy which pertains to the processes of reducing valuable, non-iron metals from ores or raw material. Metals like zinc, copper, lead, aluminium as well as rare and noble metals are of particular interest in this field, while the more common metal, iron, is considered a major impurity. Like ferrous extraction, non-ferrous extraction primarily focuses on the economic optimization of extraction processes in separating qualitatively and quantitatively marketable metals from its impurities (gangue).
The conservation and restoration of outdoor bronze artworks is an activity dedicated to the preservation, protection, and maintenance of bronze objects and artworks that are on view outside. When applied to cultural heritage this activity is generally undertaken by a conservator-restorer.
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