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Cupronickel
Cupronickel (also known as coppernickel) is an alloy of copper that contains nickel and strengthening
elements, such as iron and manganese. Despite its high copper content, cupronickel is silver in colour.
Due to the specific properties of nickel and copper alloys, they are applied in various domains of industry e.g. mint
industry, armaments industry, desalination industry, marine engineering, extensively used in the chemical,
petrochemical and electrical industries. [1]
Cupronickel is highly resistant to corrosion in seawater. For this reason, it is used for piping, heat exchangers and
condensers in seawater systems, marine hardware, and sometimes for the propellers, crankshafts and hulls of
premium tugboats, fishing boats and other working boats.
Another common use of cupronickel is in silvercoloured moderncirculated 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.
Contents
Name
Applications
Marine engineering
Coinage
Other usage
Properties
Fabrication
Standards
History
Chinese history
GrecoBactrian coinage
European history
See also
References
External links
Name
Aside from the terms cupronickel and coppernickel, 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
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silver"), German silver, and Chinese silver. [2]
Applications
Marine engineering
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 preheaters 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]
Coinage
The successful use of cupronickel in coinage is due to its corrosion resistance,
electrical conductivity, durability, malleability, low allergy risk, ease of stamping
(metalworking), 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 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 Five Swiss francs
with lowercost nickelplated steel coins.
In part due to silver hoarding in the Civil War, the United States Mint first used cupronickel for circulating
coinage in threecent pieces starting in 1865, and then for fivecent 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 halfdollars (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]
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Other usage
Singlecore thermocouple cables use a single conductor pair of thermocouple conductors such as ironconstantan,
copper constantan or nickelchromium/nickelaluminium. These have the heating element of constantan or
nickelchromium alloy within a sheath of copper, cupronickel or stainless steel. [15]
Cupronickel is used in cryogenic applications. Its combination of good ductility retention and thermal
conductivity at very low temperatures is advantageous for lowtemperature 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 remains the basic material for silverplated cutlery. It is commonly used for mechanical
and electrical equipment, medical equipment, zippers, jewelry items, and as material for strings for string
instruments. Fender Musical Instruments used "CuNiFe" magnets in their "Wide Range Humbucker" pickup for
various Telecaster and Starcaster guitars during the 1970s.
For highquality cylinder locks and locking systems, cylinder cores are made from wearresistant cupronickel.
Properties
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]
Properties of some Cu–Ni alloys[20]
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
These values may vary in other standards
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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. Coppernickels 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. 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 Crack in 90–10 Cu–Ni metal plate
due to stresses during silver brazing
normally preferred for both alloys and no afterwelding heat treatment
is required. They can also be welded directly to steel, providing a 65%
nickelcopper 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 silverbase
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, multiplestage
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.
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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.
Monel metal is a nickel–copper alloy, containing a minimum of 63% nickel.
History
Chinese history
Cupronickel alloys were known as "white copper" to the Chinese since about the third century BCE. Some weapons
made during the Warring States period were made with CuNi 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 authorscholar, Ho Wei, precisely described the process of making cupronickel in about 1095 CE. The paktong
alloy was described as being made by 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 was stirred and the ingot was immediately
cast. Zinc is mentioned as an ingredient but there are no details about when it was added. The ore used is noted as
solely available from Yunnan, according to 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". [25]
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:
"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."[25]
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Ko Hung stated in 300 CE: "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. [25]
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 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. [25]
GrecoBactrian coinage
In 1868, W. Flight discovered a GrecoBactrian 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 Xray 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 GrecoBactrian cupronickel currency could be attributed to other factors such as
the end of the House of Euthydemus. [25]
European history
The alloy seems to have been rediscovered by the West during alchemy experiments. Notably, Andreas Libavius, in
his Alchemia of 1597, mentions a surfacewhitened 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
(modernday 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 whitecopper, Watson critiqued JeanBaptiste 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 rather
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 petong 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
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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."[25]
During the peak European importation of Chinese whitecopper from 1750 to 1800, increased attention was made
to its discovering its constituents. Peat and Cookson found that "the darkest proved to contain 7.7% nickel and
the lightest said to be indistinguishable from silver with a characteristic belllike 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 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
nickelarsenic naturally occurring ore. However, the Schneeberg district of Germany, where the famous
Blaufarbenwerke made cobalt blue and other pigments, solely held the requisite complex cobaltnickelarsenic
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 nickelsilver 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. He
became a wealthy man, producing in excess of 16.5 tonnes per year. The alloy was mainly made into cutlery by the
Birmingham firm William Hutton and sold under the tradename "Argentine".
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 nickelsilver,
called "British Plate". [26]
By the 1920s, a 70–30 coppernickel 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.
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See also
Brass (copper alloyed with zinc)
Bronze (copper alloyed with tin)
Copper alloys in aquaculture
Copper in heat exchangers
Nickel silver (another group of CuNi alloys)
References
1. Sakiewicz P.,Nowosielski R., Babilas R. Production aspects of inhomogeneous hot deformation in ascast
CuNi25 alloy, Indian Journal of Engineering & Materials Sciences, Vol. 22, August 2015, pp. 389398
2. Deutsches KupferInstitut (Hrsg.): KupferNickelZinkLegierungen. Berlin 1980.
3. Marine Applications for CopperNickel Alloys
http://www.copper.org/applications/marine/cuni/applications/#non_marine
4. Kobelco: Copper alloy tubes for heatexchanger; Shinko Metal Products, Japan;
http://www.shinkometal.co.jp/catalog/copperalloyensc.pdf
5. CopperNickel Alloys in Shipbuilding and Repair
http://www.copper.org/applications/marine/cuni/applications/shipbuilding_and_repair/
6. CopperNickel Alloys in Desalination Plants
http://www.copper.org/applications/marine/cuni/applications/desalination_plants/
7. CopperNickel Alloys in Offshore Oil and Gas Platforms and Processing
http://www.copper.org/applications/marine/cuni/applications/offshore_oil_and_gas/
8. CopperNickel Alloys in Power Generation
http://www.copper.org/applications/marine/cuni/applications/power_generation/
9. CopperNickel Alloys in Seawater System Design
http://www.copper.org/applications/marine/cuni/applications/seawater_system_design/
10. CopperNickel Alloys in Seawater System Components
http://www.copper.org/applications/marine/cuni/applications/seawater_system_components/
11. CopperNickel Alloys in Boat and Ship Hulls http://www.copper.org/applications/marine/cuni/applications/hulls/
12. CopperNickel in Coinage (http://www.copper.org/applications/marine/cuni/applications/coinage/)
13. "The United States Mint: Coin Specifications" (http://www.usmint.gov/about_the_mint/index.cfm?action=coi
n_specifications). Retrieved 20080611.
14. "Currency in Circulation: Introduction to Coins" (https://www.webcitation.org/5t41V6ltH?url=http://eng.bok.or.k
r/broadcast.action?menuNaviId=1708). Archived from the original (http://eng.bok.or.kr/broadcast.action?menuN
aviId=1708) on 20100927. Retrieved 20100927.
15. Robert Monro Black, The history of electric wires and cables Science Museum (Great Britain), IET, 1983,
ISBN 0863410014, p. 161
16. Cryogenic Properties of CopperNickel http://www.copper.org/applications/marine/cuni/properties/cryogenic/
17. LowTemperature Properties of Copper and Copper Alloys http://www.copper.org/publications/pub_list/pdf/104
5lowtemperatuare.pdf
18. Mechanical Properties of Copper and Copper Alloys at Low Temperatures
http://www.copper.org/resources/properties/144_8/
19. Properties of CopperNickel Alloys http://www.copper.org/applications/marine/cuni/properties/
20. Physical Properties of CopperNickel (http://www.copper.org/applications/marine/cuni/properties/physical)
21. CopperNickel Alloy Product Forms http://www.copper.org/applications/marine/cuni/forms/
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21. CopperNickel Alloy Product Forms http://www.copper.org/applications/marine/cuni/forms/
22. CopperNickel Alloy Fabrication http://www.copper.org/applications/marine/cuni/fabrication/
23. CopperNickel Standards http://www.copper.org/applications/marine/cuni/standards/
24. Ancient Chinese weapons (http://www.chinatoday.com.cn/English/e20026/sunzi1.htm) Archived (https://web.ar
chive.org/web/20050307083704/http://www.chinatoday.com.cn/English/e20026/sunzi1.htm) 20050307 at the
Wayback Machine. and A halberd of coppernickel alloy, from the Warring States Period. (http://www.chinatoda
y.com.cn/English/e20026/images/t20026/p581.jpg) Archived (https://archive.is/20120527042518/www.chinatod
ay.com.cn/English/e20026/images/t20026/p581.jpg) 20120527 at Archive.is
25. Joseph Needham, Ling Wang, GweiDjen Lu, Tsuenhsuin Tsien, Dieter Kuhn, Peter J Golas, Science and
civilisation in China (https://books.google.com/books?id=BYixSmXUCuMC&pg=PA237): Cambridge University
Press: 1974, ISBN 0521085713, pp. 237–250
26. Mcneil I Staff, Ian McNeil Encyclopaedia of the History of Technology: Routledge: 2002: ISBN 0203192117:
pp98
External links
CopperNickel Alloys (http://www.copper.org/applications/marine/cuni/)
CopperNickelAlloys: Properties, Processing, Applications (http://www.copper.org/applications/marine/cuni/pro
perties/DKI_booklet.html) (Source: German Copper Institute (DKI))]
CopperNickel Alloys for Seawater Corrosion Resistance and Antifouling A State of the Art Review (http://ww
w.copper.org/applications/marine/cuni/properties/corrosion/corrosion_resistance_and_antifouling.html) (C.A.
Powell and H.T. Michels; Corrosion 2000, NACE March 2000 (© NACE))
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