Handbook of Extractive Metallurgy Copper: Per and of The Corresponding Words in Most
Handbook of Extractive Metallurgy Copper: Per and of The Corresponding Words in Most
492
8.1 Introduction
Copper, the red metal, apart from gold the
only metallic element with a color different
from a gray tone, has been known since the
early days of the human race. It has always
been one of the significant materials, and today it is the most frequently used heavy nonferrous metal. The utility of pure copper is
based on its physical and chemical properties,
above all, its electrical and thermal conductivity
(exceeded only by silver), its outstanding
ductility and thus excellent workability, and
its corrosion resistance (a chemical behavior
making it a half-noble metal).
Its common alloys, particularly brass and
bronze, are of great practical importance. Copper compounds ores are distinguished by
bright coloration, especially reds, greens, and
blues. Copper in soil is an essential trace element for most creatures, including humans.
Etymology. According to mythology, the goddess Venus (or Aphrodite) was born on the
Mediterranean island of Cyprus, formerly
Kurrpoc (Greek), where copper was exploited
millennia before Christ. Therefore, in early
times the Romans named it cyprium, later
called cuprum. This name is the origin of copper and of the corresponding words in most
Romance and Germanic languages, e.g., cobre
(Spanish and Portuguese), cuivre (French),
Kupfer (German), koper (Dutch), and koppar
(Swedish).
A "cross with handle", from the Egyptian
epoch, was called the mirror of Venus. In the
alchemistic period, this sign meant the metal
copper. Even now in astronomy it designates
the planet Venus and in biology stands for "female".
History [21-24]. The first metals found by
Neolithic man were gold and copper, later silver and meteoric iron. The earliest findings of
copper are presumed to be nearly nine millennia old and came from the region near Konya
in southern Anatolia (Turkey). Until recently
the six-millennia-old copper implements
from Iran (Tele Siallc) were presumed to be the
Anatolia
Egypt, Mesopotamia, Palestine, Iran, and
Turkestan
Aegean, India
Cyprus
Iberia, Transcaucasis, and China
Central Europe
British Isles
Scandinavia
Copper
493
Table 8.1: World mine production of copper (approximate, from several sources).
Production,
Production,
Year
Year
1700
1800
1850
1900
1950
1955
103 t 9
1
7 57
450
2500
3100
1960
1965
1970
1975
1980
1984
103 t
4200
5000
6400
7300
7900
8100
494
nine
syntheti
c
radioact
ive
isotopes
with
atomic
masses
between
59 and
68,
of
which
67
Cu has
the
longest
half-life,
ca. 58.5
h.
Crystal
Structur
e.
At
moderat
e
pressure
s,
copper
crystalli
zes from
low
temperat
ures up
to
its
melting
point in
a cubicclosestpacked
(ccp)
lattice,
type Al
(also F1
or
Cu)
with the
coordina
tion
number
12.
Xray
structure
analysi s
y
iL
a
M
i
A
t
A
t
D
T
hC
o
C
aC
a
T
hT
h
t,
solid copper 20
600
900
1083
liquid copper 1083
1200
q heating
u causes
T
a the
embrittl
ement.
Howeve
r, such
an effect
can be
desirable
when
free
cutting
is
P required
.
At
subzero
temperat
ures,
copper
is
a
highstrength
material
without
cold
brittleness.
The
changes
in
typical
mechani
cal
properties such
as
tensile
strength,
elongati
on, and
hardness
by heat
treatmen
t result
from
recrystalli7atio
n [25].
The
depende
Copper
495
nce of
recrystal
lization
temper
ature
and
grain
size on
the
duratio
n
of
heating
the
amount
of
previou
s cold
deforma
tion and
the
degree
of
purity
of
copper
can be
determi
ned
from
diagram
s. The
recrysta
llization
tempera
ture is
ca. 140
C for
highpurity
copper
and is
200300 C
for
commo
n types
of
copper.
A low
recrysta
llization
tempera
ture is
usually
advanta
g
e
c 1 bar)
o 2731273 K
T
a (0-1000
C) at
100 kPa
M
eV Coefficient
of linear
a thermal
S expansio
p n
a 273n 373 K
a (0n
d 100C)
273-673
K
(01 400 C)
0 between
0 273 and
1173 K
k (0-900
P C)
a
Thermal
A conductivit
v
y
e
r at 293 K
a (20 C)
g
e
s
p
e
c
i
f
i
c
h
e
a
t
2
7
3
5
7
3
K
(
0
3
0
0
C
)
a
t
1
0
0
k
P
a
(
Unit
K
K
J/g
J/g
Pa
Jg
Value
1356 (1083 C)
(2595 C)
2868 210
4810
0.073
0.385
0.494
0.411
0.437
J g-11C-1
Electri
cal
proper
ties. In
practice
,
the
most
importa
nt
propert
y
of
copper
is
its
high
electrical
conduct
ivity;
among
all
metals
only
silver
is
a
better
conduc
tor.
Both
electri
cal
conduc
tivity
and
therma
16.9 x 10-6
17.9 x 10-6
19.8 x 10-6
Wm-IK-1
394
l
conduc
tivity
are
connec
ted
with
the
Wiede
mannFranz
relation
and
show
strong
depend
ence
on
temper
ature
(Table
8.4).
The
old
Americ
an
standar
d,
100%
IACS
(Intern
ational
Anneal
ed
Copper
Standa
rd),
corres
ponds
to
58.0
MS/m
at 20
C, and
it
is
still
widely
used in
the
United
States.
The
corresp
o
n
d
i
n
g
e
l
e
c
t
r
i
c
a
l
r
e
s
i
s
t
i
v
i
t
y
(
p
)
i
s
1
.
7
2
4
1
x
1
0
4
5
2
c
m
,
a
n
d
t
h
e
l
e
s
s
u
s
u
a
l
r
e
s
i
s
t
i
v
i
t
y
b
a
s
e
d
o
n
w
e
i
g
h
t
(densit
y
of
8.89
g/cm 3,
IEC) is
0.1533
Wgm 1
. The
correspondi
ng
temper
ature
coeffici
ents
are
0.0068
x 10-8
Sim K-1
(dp/dT)
and
0.00393
K-1 (p-1
dp/dT).
The
theoreti
cal
conduc
tivity
at 20
C is
nearly
60.0
MS/m
or
103.4%
IACS,
and today
comme
rcial
oxygen
-free
copper
(e.g.
C1020
0
or
CuOF)
has a
conduc
tivity
of
101%
IACS.
The
factors
that
increas
e the
strengt
h decrease
electri
cal
conduc
tivity:
cold
workin
g and
elemen
ts that
form
solid
solutio
ns.
Ele
m
e
O
T
hT
h
T
a Temperature
K
17
73
113
173
273
293
373
473
573
973
-256
-200
-160
-100
8
.
3
C
h
e
m
i
c
a
l
P
r
o
p
e
r
t
i
e
s
I
n
20
100
200
300
700
nd
t subgrou
113
h p
(togethe
e
r with
silver
p and
e gold);
r therefor
i e,
it
o behaves
d as
a
i typical
c transitio
n metal.
t It
a appears
b in
l oxidatio
e n states
, +1
to
+4, its
c compou
o nds are
p colored,
it
p and
e tends to
r form
complex
ions.
i
At
s relativel
y
low
p tempera
l ture,
a copper(I
c I) is the
e most
d stable
state,
i but
n above
800 C,
copp
per(I)
e
predomi
nates,
r
which is
i
significa
o
nt
for
d
pyromet
allurgic
4 al
process
a es;
oxidatio
states
496
Coordination
Radius, tun
Cuu
cu2
0.128
0.096
V
Cu
0337 V
These
values
[31],
or
thermochemical
data
[32],
in
comparison with those of other elements, establish copper as a relatively
noble metal.
Behavior in Air. Copper in dry air at
room temperature slowly develops a
thin protective film of copper(1) oxide.
On heating to a high temperature in the
presence of oxygen, copper orms first
copper(I) oxide, then copper(II) oxide,
both of which cover the metal as a loose
scale.
In the atmosphere, the surface of
copper oxidizes in the course of years
to a mixture of green basic salts, the
It
patina, which consists chiefly of the
basic sulfate, with some basic arbonate.
(In a marine atmosphere, there is also
some basic chloride.) Such covering
layers protect the metal.
ehavior versus Diverse Substances.
While many substances scarcely react
Passivity
1.0 Corrosion
Cu2*
05.6H'4e"c2H2O
Copper
',A -0.5
-1.0
CuO
CuOV
Cup
._s\
Immunity
4
12
6
8
10
14
pH-.
Figure 8.1: Pourbaix diagram for copper in
highly dilute aqueous solution at normal
temperature [35].
Corrosion [33-34]. M. J. N.
Pourbaix has developed potential pH equilibrium
diagrams for
metals in dilute aqueous solutions
[35]. Such
497
steam:
Cu20 + 211 2Cu + H 2 0 (0
8.4 Occurrence
In the upper part of the earth's crust
(16 km deep), the average copper
content is ca. 50 ppm. Older
estimates were nearly 100 ppm,
while recent spectral analysis
values are 3040 ppm. Copper is
26th in order of abundance of the
elements in the accessible sphere of
the earth. Table 8.5 shows average
copper contents in natural materials.
498
Table 8.6: The most important copper minerals.
Mineral
Native copper
Chalcocite
Digenite
Covellite
Chalcopyrite
Bomite
Tennantite
Tetraedrite
Enargite
Boumonite
Cuprite
Tenorite
Malachite
Azurite
Chrysocolla
Dioptase
Brochantite
Antlerite
Chalcanthite
Atacamite
Formula
Cu
Cu2S
Cu9S5
CuS
CuFeS2
CU5FeS4/CU3FeS3
Cu 12A54S 13
CU 2$134S 13
Cu3AsS4
CuPbSbS3
Cu20
CuO
CuCO3- Cu(01-1)2
2CuCO3Cu(01-1)2
Cu SiO3. nH2O
Cu6[Si60:31 61420
Cu SO4- 3Cu(011)2
Cu SO4- 2Cu(011)2
CuSO4.5H20
Cu C12- 3Cu(OH)2
Copper
599.92
79.9
78.0
66.5
34.6
55.5-69.7
42-52
30-45
48.4
13.0
88.8
79.9
57.5
55.3
30-36
40.3
56.2
53.8
253
59.5
Crystal system
cubic
orthorhombic
cubic
hexagonal
tetragonal
tetragonal
cubic
cubic
orthorhombic
orthorhombic
cubic
monoclinic
monoclinic
monoclinic
(amorphous)
rhombohedral
monoclinic
orthorhombic
triclinic
orthorhombic
Density, g/cm3
8.9
5.5-5.8
5.6
4.7
4 1-4.3
4.9-5.3
4.4-4.8
4.6-5.1
4.4-4.5
5.7-5.9
615
6.4
4.0
3.8
1.9-2.3
3.3
4.0
3.9
2.2-2.3
3.75
Copper
499
in the Western world. There are many examples of different types of hydrothermal deposits. Examples: Butte, Montana (gangue
deposit); Tsumeb. Namibia (metasomatic
deposit); Bingham Canyon, Utah; Chu quicamata, Chile; Toquepala, Peru; Bougainville, Solomon Islands (impregnation
deposits). Impregnation deposits are also
called disseminated copper ores or porphyry
copper ores (or simply porphyries) because
of their fine particle size.
F,xhalative sedimentary ore deposits originate from submarine volcanic exhalations
and thermal springs that enter into seawater,
and constitute a transitional type to sedimentary deposits. These ores are third in
economic importance in the Western world.
The actual formation of such sulfidic precipitations can be observed, for example,
the marine ore slimes in the Red Sea. Examples: Mount Isa, Queensland; Rio Tmto,
Spain; Kammelsberg (Harz), Germany.
Ore reserves,
6
>: 10
t
99.6
Percentage of
963
30.6
30.3
29.6
27.4
23.1
16.1
12.7
11.9
10.8
10.0
world21.1
reserves
203
6.5
6.4
6.3
5.8
4.9
3.4
2.7
2.5
2.3
2.1
398.6
84.5