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Cupronickel or copper-nickel (CuNi) is an alloy of copper that contains nickel and strengthening elements, such as iron and manganese. The copper contents typically varies from 60 to 90 percent. (Monel metal is a nickel-copper alloy that contains a minimum of 52 percent nickel.)

Despite its high copper content, cupronickel is silver in colour.

Another common modern use of cupronickel is silver-coloured coins. For this use, the typical alloy has 3:1 copper to nickel ratio, with very small amounts of manganese. In the past, true silver coins were debased with cupronickel.

Name


Aside from the terms cupronickel and copper-nickel, several other terms have been used to describe the material: the tradenames Alpaka or Alpacca, Argentan Minargent, and the French term cuivre blanc ("white copper") are still registered; cupronickel is also occasionally referred to as hotel silver, plata alemana (Spanish for "German silver"), German silver, and Chinese silver.[2]

Applications


Cupronickel alloys are used for marine applications[3] due to their resistance to seawater corrosion, good fabricability, and their effectiveness in lowering macrofouling levels. Alloys ranging in composition from 90% Cu–10% Ni to 70% Cu–30% Ni are commonly specified in heat exchanger or condenser tubes in a wide variety of marine applications.[4]

Important marine applications for cupronickel include:

  • Shipbuilding and repair: Cupronickel alloys are used in seawater cooling, bilge and ballast, sanitary, fire fighting, inert gas, hydraulic and pneumatic chiller systems.[5]
  • Desalination plants: Cupronickel alloys are used in brine heaters, heat rejection and recovery, and in evaporator tubing.[6]
  • Offshore oil and gas platforms and processing and FPSO vessels: Cupronickel alloys are used in systems and splash zone sheathings.[7]
  • Power generation: Cupronickel alloys are used in steam turbine condensers, oil coolers, auxiliary cooling systems and high pressure pre-heaters at nuclear and fossil fuel power plants.[8]
  • Seawater system design: Cupronickel alloys are used in tubular heat exchangers and condensers, piping and high pressure systems.[9]
  • Seawater system components: Cupronickel alloys are used in condenser and heat exchanger tubes, tubesheets, piping, fittings, pumps, and water boxes.[10]
  • Hulls of boats and ships[11]

The successful use of cupronickel in coinage is due to its corrosion resistance, electrical conductivity, durability, malleability, low allergy risk, ease of stamping, antimicrobial properties and recyclability.[12]

In Europe, Switzerland pioneered the nickel billon coinage in 1850, with the addition of silver. In 1968, Switzerland adopted the far cheaper 75:25 copper to nickel ratio then being used in Belgium, the United States, and Germany. From 1947 to 2012, all "silver" coinage in the UK was made from cupronickel, but from 2012 onwards the two smallest cupronickel denominations were replaced with lower-cost nickel-plated steel coins.

In part due to silver hoarding in the Civil War, the United States Mint first used cupronickel for circulating coinage in three-cent pieces starting in 1865, and then for five-cent pieces starting in 1866. Prior to these dates, both denominations had been made only in silver in the United States. Cupronickel is the cladding on either side of United States half-dollars (50¢) since 1971, and all quarters (25¢) and dimes (10¢) made after 1964. Currently, some circulating coins, such as the United States Jefferson nickel (5¢),[13] the Swiss franc, and the South Korean 500 and 100 won are made of solid cupronickel (75/25 ratio).[14]

Single-core thermocouple cables use a single conductor pair of thermocouple conductors such as iron-constantan, copper constantan or nickel-chromium/nickel-aluminium.

Cupronickel is used in cryogenic applications. Its combination of good ductility retention and thermal conductivity at very low temperatures is advantageous for low-temperature processing and storage equipment as well as for heat exchangers at cryogenic plants.[16][17][18]

Beginning around the turn of the 20th century, bullet jackets were commonly made from this material. It was soon replaced with gilding metal to reduce metal fouling in the bore.

Currently, cupronickel and nickel silver remain the basic material for silver-plated cutlery. It is commonly used for mechanical and electrical equipment, medical equipment, zippers, jewelry items, and both for strings for instruments in the violin family, and for guitar frets. Fender Musical Instruments used "CuNiFe" magnets in their "Wide Range Humbucker" pickup for various Telecaster and Starcaster guitars during the 1970s.

For high-quality cylinder locks and locking systems, cylinder cores are made from wear-resistant cupronickel.

Cupronickel has been used as an alternative to traditional steel brake lines, as it does not rust.

Properties


The loss of the coppercolor due to nickel's high electronegativity causing copper's d-shell electron loss.

Important properties of cupronickel alloys include corrosion resistance, inherent resistance to macrofouling, good tensile strength, excellent ductility when annealed, thermal conductivity and expansion characteristics amenable for heat exchangers and condensers, good thermal conductivity and ductility at cryogenic temperatures and beneficial antimicrobial touch surface properties.[19]

The alloys are:

  • These values may vary in other standards

Subtle differences in corrosion resistance and strength determine which alloy is selected. Descending the table, the maximum allowable flow rate in piping increases, as does the tensile strength.

In seawater, the alloys have excellent corrosion rates which remain low as long as the maximum design flow velocity is not exceeded. This velocity depends on geometry and pipe diameter. They have high resistance to crevice corrosion, stress corrosion cracking and hydrogen embrittlement that can be troublesome to other alloy systems. Copper-nickels naturally form a thin protective surface layer over the first several weeks of exposure to seawater and this provides its ongoing resistance. Additionally, they have a high inherent biofouling resistance to attachment by macrofoulers (e.g. seagrasses and molluscs) living in the seawater. To use this property to its full potential, the alloy needs to be free of the effects of, or insulated from, any form of cathodic protection.

However, Cu–Ni alloys can show high corrosion rates in polluted or stagnant seawater when sulfides or ammonia are present. It is important, therefore, to avoid exposure to such conditions, particularly during commissioning and refit while the surface films are maturing. Ferrous sulfate dosing to sea water systems can provide improved resistance.

As copper and nickel alloy with each other easily and have simple structures, the alloys are ductile and readily fabricated.

Applications for Cu–Ni alloys have withstood the test of time, as they are still widely used and range from seawater system piping, condensers and heat exchangers in naval vessels, commercial shipping, multiple-stage flash desalination and power stations. They have also been used as splash zone cladding on offshore structures and protective cladding on boat hulls, as well as for solid hulls themselves.

Fabrication


Due to its ductility, cupronickel alloys can be readily fabricated in a wide variety of product forms[21] and fittings. Cupronickel tubing can be readily expanded into tube sheets for the manufacturing of shell and tube heat exchangers.

Details of fabrication procedures, including general handling, cutting and machining, forming, heat treatment, preparing for welding, weld preparations, tack welding, welding consumables, welding processes, paintina, mechanical properties of welds, and tube and pipe bending are available.[22]

Standards


ASTM, EN, and ISO standards exist for ordering wrought and cast forms of cupronickel.[23]

Thermocouples and resistors whose resistance is stable across changes in temperature contain alloy constantan, which consists of 55% copper and 45% nickel.

History


Cupronickel alloys were known as "white copper" to the Chinese since about the third century BC. Some weapons made during the Warring States period were made with Cu-Ni alloys.[24] The theory of Chinese origins of Bactrian cupronickel was suggested in 1868 by Flight, who found that the coins considered the oldest cupronickel coins yet discovered were of a very similar alloy to Chinese paktong.[25]

The author-scholar, Ho Wei, precisely described the process of making cupronickel in about 1095 AD.

The late Ming and Qing literature have very little information about paktong. However, it is first mentioned specifically by name in the Thien Kung Khai Wu of circa 1637:

Ko Hung stated in 300 AD: "The Tanyang copper was created by throwing a mercuric elixir into Tanyang copper and heated- gold will be formed."

Joseph Needham et al. argue that cupronickel was at least known as a unique alloy by the Chinese during the reign of Liu An in 120 BC in Yunnan. Moreover, the Yunnanese State of Tien was founded in 334 BC as a colony of the Chu. Most likely, modern paktong was unknown to Chinese of the day – but the naturally occurring Yunnan ore cupronickel alloy was likely a valuable internal trade commodity.[25]

In 1868, W. Flight discovered a Greco-Bactrian coin comprising 20% nickel that dated from 180 to 170 BCE with the bust of Euthydemus II on the obverse. Coins of a similar alloy with busts of his younger brothers, Pantaleon and Agathocles, were minted around 170 BCE. The composition of the coins was later verified using the traditional wet method and X-ray fluorescence spectrometry.[25] Cunningham in 1873 proposed the "Bactrian nickel theory," which suggested that the coins must have been the result of overland trade from China through India to Greece. Cunningham's theory was supported by scholars such as W. W. Tarn, Sir John Marshall, and J. Newton Friend, but was criticized by E. R. Caley and S. van R. Cammann.[25]

In 1973, Cheng and Schwitter in their new analyses suggested that the Bactrian alloys (copper, lead, iron, nickel and cobalt) were closely similar to the Chinese paktong, and of nine known Asian nickel deposits, only those in China could provide the identical chemical compositions.[25] Cammann criticized Cheng and Schwitter's paper, arguing that the decline of cupronickel currency should not have coincided with the opening of the Silk Road. If the Bactrian nickel theory were true, according to Cammann, the Silk Road would have increased the supply of cupronickel. However, the end of Greco-Bactrian cupronickel currency could be attributed to other factors such as the end of the House of Euthydemus.[25]

The alloy seems to have been rediscovered by the West during alchemy experiments. Notably, Andreas Libavius, in his Alchemia of 1597, mentions a surface-whitened copper aes album by mercury or silver. But in De Natura Metallorum in Singalarum Part 1, published in 1599, the same term was applied to "tin" from the East Indies (modern-day Indonesia and the Philippines) and given the Spanish name, tintinaso.[25]

Richard Watson of Cambridge appears to be the first to discover that cupronickel was an alloy of three metals. In attempting to rediscover the secret of white-copper, Watson critiqued Jean-Baptiste Du Halde's History of China (1688) as confusing the term smelted readily available unprocessed ore:

During the peak European importation of Chinese white-copper from 1750 to 1800, increased attention was made to its discovering its constituents.

Another trial by Andrew Fyfe estimated the nickel content at 31.6%. Guesswork ended when James Dinwiddie of the Macartney Embassy brought back in 1793, at considerable personal risk (smuggling of paktong ore was a capital crime by the Chinese Emperor), some of the ore from which paktong was made.[26] Cupronickel became widely understood, as published by E. Thomason, in 1823, in a submission, later rejected for not being new knowledge, to the Royal Society of Arts.

Efforts in Europe to exactly duplicate the Chinese paktong failed due to a general lack of requisite complex cobalt-nickel-arsenic naturally occurring ore. However, the Schneeberg district of Germany, where the famous Blaufarbenwerke made cobalt blue and other pigments, solely held the requisite complex cobalt-nickel-arsenic ores in Europe.

At the same time, the Prussian Verein zur Beförderung des Gewerbefleißes (Society for the Improvement of Business Diligence/Industriousness) offered a prize for the mastery of the process. Unsurprisingly, Dr E.A. Geitner and J.R. von Gersdoff of Schneeberg won the prize and launched their "German silver" brand under the trade names Argentan and Neusilber (new silver).[26]

In 1829, Percival Norton Johnston persuaded Dr. Geitner to establish a foundry in Bow Common behind Regents' Park Canal in London, and obtained ingots of nickel-silver with the composition 18% Ni, 55% Cu and 27% Zn.[26] Between 1829 and 1833, Percival Norton Johnson was the first person to refine cupronickel on the British Isles.

Johnsons' most serious competitors, Charles Askin and Brok Evans, under the brilliant chemist Dr. EW Benson, devised greatly improved methods of cobalt and nickel suspension and marketed their own brand of nickel-silver, called "British Plate".[26]

By the 1920s, a 70–30 copper-nickel grade was developed for naval condensers.

See also


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