4.
0 Copper and Its Alloys
4.1. Introduction
The most important property of pure copper is its good electrical conductivity -- being second
only to that of silver. The conductivity is at its best in the pure annealed metal and is greatly
affected (reduced) by impurities. Impurities has an effect on conductivity and the most profound
effect is caused by phosphorous and silicon. However, cadmium reduces the conductivity only
nominally and is usually added to copper for telephone wires to improve the strength.
Nearly all alloying elements increase the strength of copper. The only exceptions are bismuth
and antimony. These are insoluble in copper and collect at the grain boundaries causing
brittleness.
Copper and copper-based alloys, possessing a desirable combination of physical properties, have
been used in quite a variety of applications since antiquity. Unalloyed copper is so soft and
ductile that it is difficult to machine; also, it has an almost unlimited capacity to be cold worked.
Furthermore, it is highly resistant to corrosion in diverse environments including the ambient
atmosphere, seawater, and some industrial chemicals. The mechanical and corrosion-resistance
properties of copper may be improved by alloying. Most copper alloys cannot be hardened or
strengthened by heat-treating procedures; consequently, cold working and/or solid-solution
alloying must be used to improve these mechanical properties.
4.2 Sources of materials
Refined copper is produced from primary and secondary raw materials by a relatively small
number of copper refineries; their product is copper cathode. This is melted, alloyed and further
processed to produce rods, profiles, wires, sheets, strips, tubes, etc. This step may be integrated
with the refinery but is frequently carried out at another site.
Important copper mine production can be found in with 512,000 tonnes copper extracted in 2005.
Other sizeable EU mining countries are Spain with a capacity of 72 000 tonnes in 2009, Portugal,
Sweden and Bulgaria
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4.3 Processes to produce copper and its alloys from primary and secondary raw materials
Primary copper can be produced by pyrometallurgical or hydrometallurgical processes.
Approximately 10 % of the primary copper is produced by the direct leaching of ores
(hydrometallurgical route). Nowadays; concentrates (15 - 45 % Cu) are the most important raw
materials for the pyrometallurgical primary copper route, with a share of more than 85 %. To a
small extent, oxidic/sulphidic mixed ores and, more seldom, bituminous ores are processed. The
sulphidic concentrates consist of complex copper/iron sulphides; they are derived from ores that
contain 0.5 - 2 % copper by flotation. Further inputs used for primary copper production are
fluxes (silicate, lime, sands, etc.), additives/reactants (iron, carbon, etc.) and recycled materials
(scrap, dross, lime sludges, used abrasive materials, slags, dusts, etc.) The generic processes are
discussed below.
4.3.1 Extraction of copper from ores
1. Copper ores are normally associated with sulphur in which copper can be extracted from
chalcocite Cu2S, chalcopyrite CuFeS2 and cuprite Cu2O.
Extraction processes:
(a) Pyrometallurgical- for copper sulphide based ores.
(b) Hydrometallurgical- for oxide or carbonate ores.
2. Copper sulphide concentrates are produced through different ore dressing processes
(crushing, Washing, screening, roasting).
3. The concentrates are smelted in a reverberatory furnace to produce matte (mixture of copper
& iron sulphides, and slag (waste).
4. Matte is then converted into blister copper (elemental copper with impurities) by blowing air
through the matte in a copper converter.
Note: Iron sulphide is oxidized and slagged of while some copper is also oxidized.
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4.3.2 Refining of blister copper
1. Blister copper is later fire-refined in the process called poling to produce tough pitch
copper, which can be used for some applications other than electrical applications.
2. Most impurities are oxidized and slagged off.
3. The remained copper oxide Cu2O is reduced using coke or charcoal and green tree trunks
until the copper oxide content is about 0.5% then stop.
Electrolytic refining of tough pitch copper
Further refining of copper to about 99.95% is for electronics applications.
(a) Electrolytic refining converts fire-refined copper at anode into high-purity copper at
cathode.
(b) Electrolyte used is CuSO4 + H2SO4
(c) This high-purity copper is subsequently melted and cast into shapes.
4.4 Main properties of copper:
(a) High electrical and thermal conductivity
(b) Good corrosion resistance, Machinability, strength
(c) Ease of fabrication
(d) Non magnetic
(e) Has a pleasing colour
(f) Can be welded, brazed, and soldered
(g) Easily finished by plating and lacquering
Electrical conductors- 99.9% Cu and identified as Electrolytic Tough Pitch (ETP) copper or
Oxygen Free High Conductivity (OFHC) copper.
Arsenical copper - ≈ 0.3% Arsenic – improved resistance to special corrosive conditions
Free cutting copper - ≈ 0.6% Tellurium – excellent machining properties
Silver bearing copper – 7 to 30 oz/ton silver – Silver raises the recrytallization of copper
4.5 Copper alloys
Copper forms two commercially important series of alloys -- brasses and bronzes which are the
most important general purpose industrial materials after cast iron and steel.
4.5.1 Brasses
Brasses are principally alloys of copper and zinc with up to 45% Zn. They are important due to
the following properties:
a) Wide range of mechanical properties,
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b) They are soft and easy to work,
c) Have a pleasant appearance
d) Largely resistant to corrosion.
The most common copper alloys are the brasses, for which zinc, as a substitutional impurity, is
the predominant alloying element. In the copper– zinc phase diagram, the α phase is stable for
concentrations up to approximately 38 wt% Zn. This phase has an FCC crystal structure, and α-
brasses are relatively soft, ductile, and easily cold worked. Brass alloys having higher zinc
content contain both α and β` phases at room temperature. The β` phase has an ordered BCC
crystal structure and is harder and stronger than the α phase; consequently, α + β` alloys are
generally hot worked.
Brasses can be divided into two major groups: a brasses (alpha) and a-b (alpha-beta) brasses. α
brasses contain up to 38% zinc and consist of a single phase a (a solution of copper in zinc) at
room temperature. α-brasses, being a solid solution, is soft and ductile. The highest ductility
(approximately 69%) occurs at about 30% Zn. α-brasses are therefore suitable for cold working
and are cold rolled into sheets, rods, tubes and wires.
Some of the common brasses are yellow, naval, and cartridge brass; muntz metal; and gilding
metal. The compositions, properties, and typical uses of several of these alloys are listed in Table
4.1. Some of the common uses for brass alloys include costume jewellery, cartridge casings,
automotive radiators, musical instruments, electronic packaging, and coins.
Other commercially available brasses include: leaden brass or free machining brass. This is brass
to which 1.5 - 3.5% lead has been added to improve the machinability (lead is insoluble in
copper and collects at grain boundaries making it easier for chips to break during machining);
high tensile brass - α-β brass to which one or more of the following elements has been added to
improve the strength: iron, aluminium, manganese, tin, nickel. High tensile brass can have
ultimate tensile strengths up to 740 MN/m2.
4.5.2 Bronze
The bronzes are alloys of copper and several other elements, including tin, aluminum, silicon,
and nickel. These alloys are somewhat stronger than the brasses, yet they still have a high degree
of corrosion resistance. Table 4.1 lists several of the bronze alloys and their compositions,
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properties, and applications. Generally they are used when, in addition to corrosion resistance,
good tensile properties are required.
The alloy most often referred to as bronze is tin--bronze. The diffusion is so slow that the
structure remains a (solution of Sn in Cu) at room temperature. This alloy is tough and ductile
and hence is cold workable. Tin bronze, which is the most abundant bronze commercially,
contains about 7% Sn and is supplied as rolled sheets or rods.
Tin bronzes are also supplied as cast alloys with about 18% Sn. These alloys however have a
problem of coring which may make the brittle phase appear at phase boundaries. To be useful,
these cast alloys need prolonged annealing at about 700°C to form a which is then cold worked.
The unannealed cast alloys are used for bearings due to their high wear and shock resistance.
There are four other commercially available bronzes containing elements other than (or in
addition to) tin:
(i) Phosphor bronze
These contain 0.1 - 1.0% phosphorous in addition to copper and tin. Phosphorus increases the
strength and improves the corrosion resistance. They may be supplied wrought (as wires or rods)
or cast. They are used for bearings requiring high strength due to their low coefficient of friction.
(ii) Bronzes containing zinc
Contain about 3% Sn together with approximately 2.5% Zn. The alloy is used making "copper”
coins. When cast (10% Sn; 2% Zn), zinc bronzes are used for corrosion resistant castings and
for military decoration "gunmetal".
(iii) Leaden bronzes
These are tin bronzes containing about 2% lead which improves their machinability. The
bronzes have good thermal conductivity and are used in high speed bearings e.g., aircraft and
automobile crankshaft bearings.
(iv) Aluminium bronze
These are alloys of copper and aluminium. The relevant part of the equilibrium diagram is the
eutectoid reaction at 565°C (11.8% Al). Due to this eutectoid reaction, heat treatment
(hardening), similar to formation of martensite in steels, is possible. A 10% Al alloy for
example consists of β at 900°C. This can be water quenched to produce an alloy which is hard
and brittle.
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In addition to their capability to undergo heat treatment, aluminium bronzes have the following
useful properties:
i) They retain their strength at high temperatures.
ii) They have good resistance to corrosion which is retained at high temperatures.
iii) They have good wear resistance.
iv) They have a pleasant gold like appearance and are hence used in imitation jewellery.
As in the case of brasses, there are two series of alloys:
1) Alloys - usually contain 4 to 7% Al with the microstructure consisting of the single phase
(solution of Al in Cu). They are used in manufacture of condenser tubing and for imitation
jewellery. Being single phase, they are cold workable, have moderate strength and good
corrosion resistance.
2) Alloys: contain 7 to 12% Al and consist of two phase at room temperature (under equilibrium
conditions). Like steels, they can be hot worked (forged/hot rolled) after heating to the single
phase. They are used in chemical engineering plants especially those exposed to high
temperatures. This is mainly due to their corrosion resistance at high temperatures.
Aluminium bronzes can also be cast (9 to 12% Al) and the cast alloys used in marine
applications (pump rods, propellors, etc.), auto engines (valve seats, spark plug bodies), for
manufacture of heavy duty bearings and in manufacture of gears.
4.5.3 Cu-Ni alloys
In presence of tin, copper nickel alloys have a silvery appearance and are used in the
manufacture of "silver" coins. They are also used as electrical resistors and for high strength
springs. They can attain strengths up to 900 MN/m2.
Copper and nickel show complete solubility in the solid state and hence from a whole series of
alloys termed "cupro-nickels". These are used for condenser tubes and, with iron, as
thermocouples.
The most common heat-treatable copper alloys are the beryllium coppers. They possess a
remarkable combination of properties: tensile strengths as high as 1400 MPa (200,000 psi),
excellent electrical and corrosion properties, and wear resistance when properly lubricated; they
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may be cast, hot worked, or cold worked. High strengths are attained by precipitation-hardening
heat treatments. These alloys are costly because of the beryllium additions, which range between
1.0 and 2.5 wt%. Applications include jet aircraft landing gear bearings and bushings, springs,
and surgical and dental instruments. One of these alloys (C17200) is included in Table 4.1.
Table 4.1 Compositions, Mechanical Properties, and Typical Applications for Eight Copper
Alloys
a
The balance of the composition is copper.
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