Cupronickel

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Cupronickel or copper-nickel is an alloy of copper that contains nickel and strengthening elements, such as iron and manganese. Cupronickel is highly resistant to corrosion in seawater, because its electrode potential is adjusted to be neutral with regard to seawater. Because of this, it is used for piping, heat exchangers and condensers in seawater systems, as well as marine hardware, and sometimes for the propellers, crankshafts and hulls of premium tugboats, fishing boats and other working boats.

A more familiar common use is in silver-coloured modern circulation coins. A typical mix is 75% copper, 25% nickel, and a trace amount of manganese. In the past, true silver coins were debased with cupronickel. Despite high copper content, cupronickel is silver in colour.

Thermocouples and resistors whose resistance is stable across changes in temperature contain the 55% copper-45% nickel alloy constantan.

Monel metal is a nickel-copper alloy, containing a minimum of 63% nickel.

Other names[edit]

Aside from cupronickel, many other terms exist which describe the same material. Still registered as tradenames are Alpaka or Alpacca' (registered trademark), Argentan Minargent, and the French term name Cuivre blanc. Occasionally, cupronickel is also referred to as "hotel silver", plata alemana (Spanish for "German silver"), "German silver" and "Chinese silver".[1]

History[edit]

Cupronickel was known to the Romans as an artificial "white" gold or silver termed claudianum and very possibly the molybdochalcum of the Alexandrians.

The cupronickel alloy was known by Chinese since about the third century BCE as "white copper" (some weapons from the Warring States period were in Cu-Ni alloy).[2]

The ancient Greeks were producing cupronickel and a lower-quality imitation of it in the Aegean Bronze Age and known as orichalcum. The Greco-Bactrian kings issued the first cupronickel coins, with Euthydemus II, dating from 180 to 170 BCE, and his younger brothers Pantaleon and Agathocles around 170 BCE.[3][4]

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.[4] Cunningham in 1873 argued the coins must have been the result of overland trade from China, through India to Greece – highly controversial at the time and much derided. In 1973, Cheng and Schwitter in their new analyses argued the Bactrian alloys (copper, lead, iron, nickel and cobalt) were closely similar to Chinese paktong, and of nine known Asian nickel deposits, only those in China could provide the identical chemical content ratios.[4] However, this hypothesis, although widely publicised, was later disproven by a perhaps overenthusiastic oversight of the well-known Persian arsenic-nickel mines much closer to Bactria and known to be exploited by the Greeks and Persians.[4]

Chinese history of cupronickel[edit]

The author-scholar Ho Wei described most exactly the process in about 1095 CE, which suggests the Chinese were unaware nickel was a metal in its own right. The paktong alloy was described as being made from adding small pills of naturally occurring yunnan ore to a bath of molten copper. When a crust of slag formed, saltpeter was added, the alloy stirred and the ingot immediately cast. Zinc is mentioned as an ingredient — but not detailed when exactly it was added. The ore used is noted as solely available from Yunnan, related from the story:

San Mao Chun were at Tanyang during a famine year when many people died, so taking certain chemicals, Ying projected them onto silver, turning it into gold, and he also transmuted iron into silver – thus enabling the lives of many to be saved [through purchasing grain through this fake silver and gold] Thereafter all those who prepared chemical powders by heating and transmuting copper by projection called their methods "Tanyang techniques".[4]

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

When lu kan shih (zinc carbonate, calamine) or wo chhein (zinc metal) is mixed and combined with chih thung (copper), one gets 'yellow bronze' (ordinary brass). When phi shang and other arsenic substances are heated with it, one gets 'white bronze' or white copper: pai thong. When alum and niter and other chemicals are mixed together one gets ching thung: green bronze.[4]

Ko Hung of 300 CE stated: "The Tanyang copper was created by throwing a mercuric elixir into Tanyang copper and heated- gold will be formed." However, the Pha Phu Tsu and the Shen I Ching describing a statue in the Western provinces as being of silver, tin, lead and Tanyang copper – which looked like gold, and could be forged for plating and inlaying vessels and swords.[4]

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 BCE in Yunnan. Moreover, the Yunnanese State of Tien was founded in 334 BCE 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.[4]

Western rediscovery[edit]

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, of 1599, the same term was applied to "tin" from the East Indies (modern-day Indonesia and the Philippines) and given the Spanish name: tintinaso.[4]

Richard Watson of Cambridge appears to be the first to discover 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 paktong, He noted the Chinese of his day did not form it as an alloy, but smelted readily available unprocessed ore:

appeared from a vast series of experiments made at Peking- that it occurred naturally as an ore mined at the region, the most extraordinary copper is pe-tong or white copper: it is white when dug out of the mine and even more white within than without. It appears, by a vast number of experiments made at Peking, that its colour is owing to no mixture; on the contrary, all mixtures diminish its beauty, for, when it is rightly managed it looks exactly like silver and were there not a necessity of mixing a little tutenag or such metal to soften it, it would be so much more the extraordinary as this sort of copper is found no where but in China and that only in the Province of Yunnan". Notwithstanding what is here said, of the colour of the copper being owing to no mixture, it is certain the Chinese white copper as brought to us, is a mixt [sic: mixed] metal; so that the ore from which it was extracted must consist of various metallic substances; and from such ore that the natural orichalcum if it ever existed, was made".[4]

During the peak European importation of Chinese white-copper from 1750 to 1800, increased attention was made to its discovering its constituents—Peat and Cookson found: "the darkest proved to contain 7.7% nickel and the lightest said to be indistinguishable from silver with a characteristic bell-like resonance when struck and considerable resistance to corrosion, 11.1%".

Another trial by Andrew Fyfe estimated the nickel content at 31.6%. Guesswork ended when James Dinwiddie of the Macartney Embassy of 1793 brought back, 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.[5] 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 to duplicate exactly the Chinese paktong failed in Europe due to a general lack of requisite complex cobalt-nickel-arsenic naturally occurring ore. However, the Schneeburg 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 and unsurprisingly, Dr E.A. Geitner and J.R. von Gersdoff of Schneeburg duly won the prize and launched their "German silver" under the trade names Argentan and Neusilber (new silver)[5]

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 of 18% Ni, 55% Cu and 27% Zn.[5] Between 1829 and 1833, Percival Norton Johnson was the first man to refine cupronickel on the British Isles; he became a wealthy man producing in excess of 16.5 tonnes per year, mainly made into cutlery by the Birmingham firm William Hutton and sold under the trade-name "Argentine". Johnsons' most serious competitor, 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: "British Plate"[5]

Coinage[edit]

Five Swiss francs

In Europe, Switzerland pioneered the nickel billon coinage in 1850, with the addition of silver. In 1879, Switzerland adopted the far cheaper 75:25 copper to nickel ratio then being used by the Belgians, 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¢),[6] the Swiss franc, and the South Korean 500 and 100 won are made of solid cupronickel (75/25 ratio).[7]

Marine engineering grades[edit]

By the 1920s, a 70–30 copper-nickel grade was developed for naval condensers. Soon afterwards, a 2% manganese and 2% iron alloy now known as alloy C71640 was introduced for a UK power station which needed better erosion resistance because the levels of entrained sand in the seawater. A 90–10 alloy first became available in the 1950s, initially for seawater piping, and is now the more widely used alloy.

The alloys are:

UNS standard compositions* of wrought alloys (in at%). Maximum or range.
Alloy UNS No. Common name European spec Ni Fe Mn Cu
C70600 90-10 CuNi10Fe 9-11 1-1.8 1 Remainder
C71500 70-30 CuNi30Fe 29–33 0.4–1.0 1 Remainder
C71640 66-30-2-2 29–32 1.7–2.3 1.5–2.5 Remainder
  • 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.

Properties of some Cu-Ni alloys[8]
Alloy Density
g/cm3
Thermal conductivity
W/(m·K)
TEC
µm/(m·K)
Electrical resistivity
µOhm·cm
Elastic modulus
GPa
Yield strength
MPa
Tensile strength
MPa
90-10 8.9 50 17 19 135 105 275
70-30 8.95 29 16 34 152 125 360
66-30-2-2 8.86 25 15.5 50 156 170 435

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.

Crack in 90-10 Cu-Ni metal plate due to stresses during silver brazing

As copper and nickel alloy with each other easily and have simple structures, the alloys are ductile and readily fabricated. Strength and hardness for each individual alloy is increased by cold working; they are not hardened by heat treatment. Joining of 90–10 (C70600) and 70-30 (C71500) is possible by both welding or brazing. They are both weldable by the majority of techniques, although autogenous (welding without weld consumables) or oxyacetylene methods are not recommended. The 70-30 rather than 90-10 weld consumables are normally preferred for both alloys and no after-welding heat treatment is required. They can also be welded directly to steel, providing a 65% nickel-copper weld consumable is used to avoid iron dilution effects. The C71640 alloy tends to be used as seamless tubing and expanded rather than welded into the tube plate. Brazing requires appropriate silver-base brazing alloys. However, great care must be taken to ensure that there are no stresses in the Cu-Ni being silver brazed, since any stress can cause intergranulary penetration of the brazing material, and severe stress cracking (see image). Thus, full annealing of any potential mechanical stress is necessary.

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.

Other usage[edit]

Copper nickels are commonly specified in heat exchanger or condenser tubes in evaporators of desalination plants, process industry plants, air cooling zones of thermal power plants, high-pressure feed water heaters, and sea water piping in ships.[9] The composition of the alloys can vary from 90% Cu–10% Ni to 70% Cu–30% Ni.

Single-core thermocouple cables use a single conductor pair of thermocouple conductors such as iron-constantan, copper constantan or nickel-chromium/nickel-aluminium. These have the heating element of constantan or nickel-chromium alloy within a sheath of copper, cupronickel or stainless steel.[10]

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 remains the basic material for silver-plated cutlery. It is commonly used for mechanical and electrical equipment, medical equipment, zippers, jewelry items, and as material for strings for string instruments.

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

See also[edit]

References[edit]

  1. ^ Deutsches Kupfer-Institut (Hrsg.): Kupfer-Nickel-Zink-Legierungen. Berlin 1980.
  2. ^ Ancient Chinese weapons and A halberd of copper-nickel alloy, from the Warring States Period.
  3. ^ Copper-Nickel coinage in Greco-Bactria.
  4. ^ a b c d e f g h i j Joseph Needham, Ling Wang, Gwei-Djen Lu, Tsuen-hsuin Tsien, Dieter Kuhn, Peter J Golas, Science and civilisation in China: Cambridge University Press: 1974, ISBN 0-521-08571-3, pp. 237–250
  5. ^ a b c d Mcneil I Staff, Ian McNeil Encyclopaedia of the History of Technology: Routledge: 2002: ISBN 0-203-19211-7: pp98
  6. ^ "The United States Mint: Coin Specifications". Retrieved 2008-06-11. 
  7. ^ "Currency in Circulation: Introduction to Coins". Archived from the original on 2010-09-27. Retrieved 2010-09-27. 
  8. ^ Information about Copper Nickels and their Properties
  9. ^ Kobelco: Copper alloy tubes for heat-exchanger; Shinko Metal Products, Japan; http://www.shinkometal.co.jp/catalog/copperalloy-en-sc.pdf
  10. ^ Robert Monro Black, The history of electric wires and cables Science Museum (Great Britain), IET: 1983 ISBN 0-86341-001-4: 290 p. 161

External links[edit]