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Article No : a27_049

Tin, Tin Alloys, and Tin Compounds


GÜNTER G. GRAF, Freiberg, Federal Republic of Germany

1. History . . . . . . . . . . . . . . . . . . . . . . . . . 1 5.1.3. Removal of Arsenic. . . . . . . . . . . . . . . . . . 20


2. Properties . . . . . . . . . . . . . . . . . . . . . . . . 2 5.1.4. Removal of Lead. . . . . . . . . . . . . . . . . . . . 20
3. Occurrence; Ore Extraction and 5.1.5. Removal of Bismuth . . . . . . . . . . . . . . . . . 21
Beneficiation . . . . . . . . . . . . . . . . . . . . . . 4 5.2. Electrorefining . . . . . . . . . . . . . . . . . . . . . 21
3.1. Minerals. . . . . . . . . . . . . . . . . . . . . . . . . . 4 5.2.1. Electrorefining in Acid Medium . . . . . . . . . 21
3.2. Deposits . . . . . . . . . . . . . . . . . . . . . . . . . . 4 5.2.2. Electrorefining in an Alkaline Medium . . . . 22
3.3. Mining . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 5.2.3. Other Methods of Electrorefining . . . . . . . . 22
3.4. Ore Beneficiation . . . . . . . . . . . . . . . . . . 6 6. Recovery of Tin from Scrap Materials and
4. Smelting. . . . . . . . . . . . . . . . . . . . . . . . . . 7 Residues . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.1. Fundamental Theory of Smelting . . . . . . 7 7. Analysis . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.2. Special Aspects of the Winning of Tin from 7.1. Analysis of Ores and Concentrates . . . . . 23
its Ores . . . . . . . . . . . . . . . . . . . . . . . . . . 9 7.2. Analysis of Metallic Tin . . . . . . . . . . . . . . 24
4.3. Production of Crude Tin . . . . . . . . . . . . . 10 8. Economic Aspects . . . . . . . . . . . . . . . . . . 24
4.3.1. General Aspects . . . . . . . . . . . . . . . . . . . . 10 9. Tin Alloys and Coatings . . . . . . . . . . . . . 25
4.3.2. Ore Preparation prior to Reduction . . . . . . . 10 10. Inorganic Tin Compounds . . . . . . . . . . . . 27
4.3.2.1. Pyrometallurgical Enrichment of Low-Grade 10.1. Tin(II) Compounds . . . . . . . . . . . . . . . . . 27
Concentrates . . . . . . . . . . . . . . . . . . . . . . 10 10.2. Tin(IV) Compounds. . . . . . . . . . . . . . . . . 28
4.3.2.2. Roasting . . . . . . . . . . . . . . . . . . . . . . . . . 11 11. Organic Compounds of Tin . . . . . . . . . . 29
4.3.2.3. Leaching . . . . . . . . . . . . . . . . . . . . . . . . . 12 11.1. Properties of Organotin Compounds . . . . 29
4.3.3. Reduction . . . . . . . . . . . . . . . . . . . . . . . . . 13 11.2. Production of Organotin Compounds . . . 30
4.3.3.1. Reduction in a Shaft Kiln . . . . . . . . . . . . . 13 11.3. Industrially Important Compounds . . . . . 31
4.3.3.2. Reduction in a Reverberatory Furnace . . . . 13 11.4. Analysis of Organotin Compounds . . . . . 32
4.3.3.3. Reduction in Rotary Kilns . . . . . . . . . . . . . 15 11.5. Storage and Shipping of Organotin
4.3.3.4. Reduction in an Electric Furnace . . . . . . . . 15 Compounds . . . . . . . . . . . . . . . . . . . . . . . 32
4.3.3.5. Other Reduction Processes . . . . . . . . . . . . 16 11.6. Pattern of Production and Consumption . 32
4.3.4. Slag Processing . . . . . . . . . . . . . . . . . . . . 17 12. Toxicology . . . . . . . . . . . . . . . . . . . . . . . . 32
5. Refining . . . . . . . . . . . . . . . . . . . . . . . . . 19 References . . . . . . . . . . . . . . . . . . . . . . . . 33
5.1. Pyrometallurgical Refining . . . . . . . . . . . 19
5.1.1. Removal of Iron . . . . . . . . . . . . . . . . . . . . 19
5.1.2. Removal of Copper . . . . . . . . . . . . . . . . . . 20

1. History [1–4], [6], [11], [15] tombs dating from the end of the 4th millenni-
um B.C.
Because of its luster and softness, tin was Pure tin was first produced in China and Japan
usually assigned to the planet Jupiter, more around 1800 B.C. Around 600 B.C., the ancient
rarely to Venus. The name of the element is Egyptians occasionally placed pure tin artifacts
derived from the Old High German zin and the in mummies’ tombs. Tin is not only an essential
Norse tin. The symbol Sn from the Latin constituent of tin bronze, but is also a constituent
stannum was proposed by BERZELIUS. Histori- of lead alloys for solders and tin plating. Tin and
cally tin is of major cultural importance, being especially its alloys have shaped the develop-
an essential component of the copper alloy ment of many geographical regions, e.g., China,
bronze which gave its name to the Bronze Age. Indochina, Indonesia, India, the Near East, North
The first bronze objects appeared in Egyptian Africa, and Europe.

 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


DOI: 10.1002/14356007.a27_049
2 Tin, Tin Alloys, and Tin Compounds Vol. 37
b-Sn (white tin) tetragonal (A5)
The cultural and historical importance of tin Transformation temperature 286.2 K
from the Middle Ages to early modern times lay a-Sn $ b-Sn
in its use for sacred objects, articles of daily use, Enthalpy of transformation 1966 J/mol
and jewelry. Lattice constants at 25  C
a-Sn a ¼ 648.92 pm
There is no historical evidence concerning the b-Sn a ¼ 583.16 pm
oldest methods of tin extraction. It is fairly c ¼ 318.13 pm
certain that in 100 B.C. in Cornwall, England, tin Density of b-tin
was smelted from very pure ore over wood fires 20  C 7.286 g/cm3
100  C 7.32 g/cm3
in pits and later in small furnaces. Up to the 230  C 7.40 g/cm3
1200s, Cornwall provided most of Europe’s tin. Density of a-tin 5.765 g/cm3
Today, these deposits are virtually exhausted. Density of liquid tin
Tin was probably produced in Bohemia around 240  C 6.992 g/cm3
400  C 6.879 g/cm3
1150. Also, the first tin mines were opened in 800  C 6.611 g/cm3
Saxony at this time, and these supplied European 1000  C 6.484 g/cm3
requirements until they were destroyed in the Molar heat capacity of b-tin
Thirty Years War. Then, as these various deposits 25  C 27.0 J mol1 K1
230  C 30.7 J mol1 K1
gradually became exhausted and as ocean trans- Liquid 28.5 J mol1 K1
port developed, tin from overseas became Melting point 505.06 K
dominant. Enthalpy of fusion 7029 J/mol
The largest tin mines are in Asia, the most Boiling point 2876 K
Enthalpy of vaporization 295 763 J/mol
important ore-supplying countries in the world Vapor pressure
being Malaysia and Indonesia, followed by Chi- 1000 K 9.8104 Pa
na. The second largest tin-producing region in- 1800 K 750 Pa
cludes Brazil and Bolivia. The countries export- 2100 K 8390 Pa
2400 K 51 200 Pa
ing the largest quantities of tin ores also produce Cubic coefficient of expansion
the most tin metal. a-tin at 130  C to þ10  C 14.1106 K1
World annual production has developed as to 4.7106 K1
follows: b-tin at 0  C 59.8106 K1
b-tin at 50  C 69.2106 K1
b-tin at 100  C 71.4106 K1
b-tin at 150  C 80.2106 K1
ca. 1800 9 100 t Molten tin at 700  C 105.0106 K1
ca. 1850 19 000 t Coefficient of thermal conductivity 0.63 W cm1 K1
ca. 1900 91 900 t of b-tin at 0  C
ca. 1950 172 100 t Surface tension
1980 243 600 t 232  C 0.53 – 0.62 N/m
1990 225 600 t 400  C 0.52 – 0.59 N/m
800  C 0.51 – 0.52 N/m
The principal consumer countries are the 1000  C 0.49 N/m
Dynamic viscosity
United States, Japan, China, and Russia. 232  C 2.71103 Pa  s
400  C 1.32103 Pa  s
1000  C 0.80103 Pa  s
2. Properties Specific electrical resistivity
a-tin at 0  C 5106 Wm
b-tin at 25  C 11.15106 Wm
Physical Properties [1], [2], [4], [16–19], Transition temperature for 3.70 K
[20]. Tin, Sn, exists in two crystalline modifica- superconductivity
tions, the a- and b-forms. A third modification Magnetic susceptibility of b-Sn 2.61011 m3/kg

may also exist. Some physical properties of a-


and b-tin are listed in the following: In the periodic table, tin lies on the boundary
between metals and nonmetals. The transforma-
tion of the a- to the b-modification is accompanied
Natural isotopes 10
Relative atomic mass 118.69
by a complete change of lattice structure, affecting
Crystal structure the physical, chemical, and mechanical properties.
a-Sn (gray tin) fcc (A4) diamond type Also, at 170  C there is a secondorder transforma-
Vol. 37 Tin, Tin Alloys, and Tin Compounds 3

tion accompanied by a discontinuous change in the exponentially increasing rate. Typical impurities
lattice parameters and thermomechanical proper- present after metallurgical production (e.g., Sb,
ties. A tetragonal highpressure modification of tin, Tl, Bi, and Fe) promote oxidation. Treatment
stable between 3500 and 11 000 MPa, is described with carbonate or chromate solutions leads to
in the literature, the lattice constants being a passivation.
381 pm and b ¼348 pm. Molten tin at temperatures up to ca. 500  C
The transformation of b-tin (white tin) into a- picks up oxygen from the air at a rate that obeys a
tin (gray tin) is of practical importance, as it parabolic law, a result of the compact layer of
involves a volume increase of 21 %. The trans- oxide formed.
formation process requires a high energy of Gaseous water and nitrogen do not dissolve in
activation, and can be very strongly hindered. solid tin. Dissolution in molten tin only occurs at
White b-tin can therefore exist for many years at high temperatures (ca. > 1000  C). Under the
30  C. The presence of a-tin seed crystals is conditions of electrochemical reduction in hy-
important for the transformation process, and drochloric acid solutions, atomic hydrogen forms
these are formed by repeated phase transitions. SnH4, and elemental nitrogen forms Sn3N4.
Foreign ‘‘elements’’ also affect the transforma- Tin is stable towards fluorine at room temper-
tion temperature and rate. These can consist of ature, but SnF2 or SnF4 are formed at higher
impurities and deformations. The effect of im- temperatures.
purities on transformation behavior is described Rapid and vigorous reactions occur with chlo-
in [21]. Tin vapor consists of Sn2 molecules. rine, bromine, and iodine, these reactions being
accelerated by moisture and elevated tempera-
Mechanical Properties [1], [2], [4], tures. The reaction products are SnCl4, SnBr4,
[20–23]. Mechanical properties are not of great SnI2, and SnI4.
relevance to most applications of pure tin. The Sulfur reacts rapidly with molten tin at > 600
most important are listed in the following: C to form the sulfides SnS, Sn2S3, and SnS2. The
reaction rate is lower above 900  C, and only SnS
Yield strength at 25  C 2.55 N/mm2
is formed.
Ultimate tensile strength Reaction with hydrogen sulfide is slow and only
120  C 87.6 N/mm2 occurs in the presence of oxygen and moisture.
15  C 14.5 N/mm2 Sulfur dioxide reacts with molten tin to form SnO2
200  C 4.5 N/mm2
Brinell hardness (10 mm, 3000 N, 10 s)
and S, and a molten solution of tin in copper reacts
0 C 4.12 with SO2 to form SnO2 and Cu2S (an important
100  C 2.26 reaction in pyrometallurgy). Tin is stable towards
200  C 0.88 pure hot water, steam, and dry ammonia. Nitrogen
Modulus of elasticity E
170  C 65 000 N/mm2
oxides only react with molten tin.
20  C 50 000 N/mm2 Tin is amphoteric, reacting with both strong
0 C 52 000 N/mm2 bases and strong acids with evolution of hydro-
40  C 49 300 N/mm2 gen. Having a normal electrode potential of
100  C N/mm2
200 C
44
26
700
000 N/mm2
0.136 V, tin lies between nickel and lead in
the electrochemical series.
With sodium hydroxide solution, tin forms
Na2[Sn(OH)6], and with potassium hydroxide
Chemical Properties [1], [2], [4], [20]. Tin solution K2[Sn(OH)6].
has the atomic number 50 and is a member of Tin reacts slowly with acids in the absence of
group 14 of the periodic table. The electronic oxygen. The high hydrogen overvoltage is
configuration is 1s22s2p63s2p6d104s2p4d10 5s2p2. caused by a layer of atomic hydrogen at the metal
Tin can be di- or tetravalent. It is stable in dry air, surface preventing further attack. Vigorous reac-
but is considerably more rapidly oxidized at a tions occur with nitric acid, the rate depending on
relative humidity of 80 %. Bright metallic tin the acid concentration. The reactions are very
becomes dull within 100 d even in indoor atmo- vigorous with 35 % acid, but complete passiv-
spheres. Oxygen is rapidly and irreversibly che- ation can occur at concentrations > 80 %. Tin
misorbed, and the oxide layer formed grows at an is stable towards fuming nitric acid. While
4 Tin, Tin Alloys, and Tin Compounds Vol. 37

hydrogen fluoride does not attack tin, hydrochlo- fine grained aggregates of cassiterite. Cassiterite
ric acid reacts even at a concentration of 0.05 % is an oxidic mineral and is chemically very
and temperatures below 0  C. Tin is not attacked resistant, in particular towards weathering.
by sulfurous acid or by < 80 % sulfuric acid. Stannite (bell metal ore), Cu2(Fe,Zn)SnS4,
The most important use of tin and tin-plated forms tetragonal crystals, has a Mohs hardness
materials is in the preserved food industry. For of 4, a density of 4.4 g/cm3, and a tin content of
this reason, the possibility of reactions of tin with up to 27.6 %. Its color is steel gray with an olive
certain organic acids is important. Lactic, malic, green tinge. It is chemically less resistant than
citric, tartaric, and acetic acids either do not react cassiterite, seldom occurs in hydrothermal de-
at all at normal temperatures or do so to a posits, and is of little economic importance.
negligible extent, especially in the absence of Hydrocassiterite (varlamoffite), H2SnO3, is a
atmospheric oxygen. This is also true of alcohols tetragonal gel-like stannic acid. It occurs in
and hydrocarbons. Bolivia, usually accompanying cassiterite.
Other tin minerals include teallite, (Sn,Sb)S;
herzenbergite, SnS; franckeite, Pb5Sn3Sb2S14; cy-
3. Occurrence; Ore Extraction and lindrite, Pb3Sn4Sb2S14; thoreaulite, SnTa2O7; hul-
Beneficiation site, (iron tin borate); and stokesite, CaSn(Si3O9)
 2 H2O. None are of economic importance.
The average concentration of tin in the earth’s
crust is estimated to be 2 – 3 ppm, comparable to
cerium and yttrium. Owing to the high atomic 3.2. Deposits
mass of tin and the high density of its important
minerals, its volume concentration is very low. The economically important tin deposits are close-
However, it occurs in only a small number of ly associated with acidic to intermediate magmatic
locations, where consequently its relative abun- rocks which were formed in the orogenic phases of
dance is high. In general, 1000-fold enrichment is the earth’s history. Tin, a volatile metal, was
necessary to give workable tin deposits, i.e., with deposited primarily during the pegmatitic, pneu-
a tin content of at least 0.2 %. The question of matolytic, or hydrothermal phase in the region of
whether a deposit can be economically extracted, the exo- or endocontact of the intrusive bodies. The
for a given world market price level, depends on economically much more important secondary tin
the mining conditions. For example, there are deposits exist as eluvial, alluvial, or marine placer
deposits in Bolivia containing 1 % Sn which deposits which can be near to or remote from these
cannot be economically extracted, whereas in acidic magmatic rock complexes. An overview of
South East Asia placer deposits containing the ore reserves and of the amounts extracted in
0.02 % Sn are successfully mined. 1990 is given in Table 1.
Table 1. Tin ore reserves and mine outputs for various countries in
1990
3.1. Minerals
Country Ore reserves Output
Native tin occurs only very rarely and has only (t metal content) (t metal content)
been identified with certainty in Canada. Malaysia 1 200 000 28 500
Cassiterite, SnO2, is the most economically Thailand 1 200 000 14 600
important tin mineral. It forms tetragonal crys- Indonesia 1 550 000 31 700
Bolivia 980 000 17 300
tals, has a Mohs hardness of 6 – 7, a density of Russia 1 000 000 13 000
6.8 – 7.1 g/cm3, and a tin content of up to 79 %. China 1 500 000 35 800
The color is usually brown to brownish black. Australia 330 000 7 400
The presence of Ti, Fe, Nb, Ta, or Mn can lead to Brazil 400 000 35 100
Zaire 200 000 1 600
colors varying from gray to white. Contact de- United Kingdom 260 000 3 200
posits of cassiterite can be combined with, e.g., South Africa 50 000 1 100
magnetite, arsenical iron pyrites, or zinc blende. Nigeria 280 000 200
Placer deposits of cassiterite are of major impor- Others 765 000 17 000
World total 9 715 000 210 700
tance. ‘‘Wood tin’’ consists of gel-like or very
Vol. 37 Tin, Tin Alloys, and Tin Compounds 5

Primary deposits originate from the pegmatit- by gravitational enrichment due to landslips and
ic formation of cassiterite in contact with granites eluviation at the bottom of mountainsides.
or their secondary rocks. Cassiterite occurs there Alluvial or fluviatile placers are formed by the
in idiomorphic pyramidal crystals of > 2 mm transport of weathered tin-bearing rocks by flow-
diameter. These tin-bearing granites and pegma- ing water derived from atmospheric precipita-
tites typically include the minerals quartz, albite, tion. The softer and lighter components of the
potassium feldspar, muscovite, and cassiterite. rock are more extensively size reduced and
Columbite is an important accompanying mine- therefore transported further than the hard, resis-
ral. Deposits of this type are found in central and tant cassiterite minerals, which sink due to their
southern Africa, Brazil, and Russia (Siberia). high density and are deposited at points where
They account for < 5 % of world production. flow rates are low. The most important alluvial
Cassiterite quartzes of the pneumatolytic cat- placer deposits are in central Africa (Zaire, Ruan-
athermal phase were formed in vein fissures of da), western Africa (Nigeria, Niger), and Brazil.
granites and their secondary rocks. Individual veins Marine placers are formed where primary tin-
or lodes can have a tin content of up to 3 %. They bearing rock complexes have been directly trans-
can be 0.2 – 1 m thick and up to 200 m deep. ported by surf, or where rivers have carried the
There are various types of paragenesis of the cassiterite-containing sediment into the sea,
granites, leading to the greisen type (mica – feld- where it is then deposited in coastal strips. These
spar – quartz formed by pneumatolysis with fluor- are the most important deposits, and represent ca.
spar, lepidolite, and tourmaline), the topaz – quartz 60 % of the world’s workable reserves. The
type, the feldspar – quartz type, and the quartz largest of these deposits are in south-east Asia,
type. Such deposits contain ca. 20 % of the world’s the coast of Thailand, the Thai Island of Phuket,
tin reserves, and are found in Malaysia, Russia in Malaysia, and on the Indonesian Islands of
(Siberia), and Germany (Erzgebirge in Saxony). Bangka and Billiton.
Cassiterite – sulfide deposits of the hydro- Secondary deposits usually have tin contents
thermal phase are formed as vein ores associated of 0.05 – 0.5 %, reaching 3 % in some cases.
with intrusions of granodioritic rocks, or are Marine placers have tin contents of 0.01 –
formed by remigration of the metal content of 0.03 %. At present, deposits containing 0.1 % Sn
older pegmatitic tin deposits caused by younger are workable by the open-pit method. For under-
acidic subvolcanoes. Characteristic of these ground mining, deposits should contain 0.3 % Sn.
types of deposit is the paragenesis of cassiterite
with stannite, iron pyrites, arsenical iron pyrites,
galena, zinc blende, magnetic iron pyrites, and 3.3. Mining
copper sulfides. These deposits, which can be
very large, are mined in Bolivia, Russia, southern Primary tin ores are extracted by underground
China, Thailand, Burma, Australia, South Africa, mining. Depths can reach 1000 m in exceptional
and also England. They constitute ca. 15 % of the cases. Most of the technologies used in nonfer-
world’s tin reserves. rous metal mining are used, the method in a given
Because cassiterite is resistant to weathering situation being determined by the thickness,
and is hard and dense, the weathering of the shape, and orientation of the ore body, and
primary tin-bearing rocks enables it to become geological factors.
concentrated as it is transported to form secondary In secondary deposits, the loosely packed
deposits, i.e., eluvial, deluvial, or marine placers. weathered hard mineral rock which contains the
Eluvial placers are formed by intense weath- cassiterite together with associated deposits of
ering and breakdown of cassiterite-containing sand and gravel is extracted by high-production
granites or granodiorites, especially under tropi- loading techniques which also perform prelimi-
cal climate conditions. The lighter minerals are nary classification. General local conditions, in-
washed out or carried away by wind, while the cluding the state of economic development in the
cassiterite and other heavy minerals remain be- region, have a great influence on the mining con-
hind and can become concentrated in deposits of ditions. For example, in Zaire, surface eluvial
considerable thickness, as in Malaysia and Zaire. deposits (weathered pegmatites) with tin contents
Very coarse and deluvial placers are also formed of up to 0.15 % are extracted by conventional
6 Tin, Tin Alloys, and Tin Compounds Vol. 37

open-pit methods. In Thailand, Malaysia, and In- has now become the preferred method for treat-
donesia, loose alluvial and marine deposits in river ing the most finely intergrown, complex tin ores.
valleys and in the undersea regions just off the Flotation of cassiterite with particle sizes be-
coast are extracted by dredging shovels, dragline tween 40 and 10 mm is mainly carried out with
excavators, chain and bucket excavators, and sim- arsonic acids.
ilar equipment specially designed for local condi- The flow diagram (Fig. 1) shows the flotation
tions. The initial separation of gangue and other of primary tin concentrates to remove sulfides of
foreign materials (e.g., wood) is performed by this
equipment. Cassiterite in thick deposits of loose
sediments and coarse detritus in Southern China
and Thailand is treated with powerful water jets
operating at pressures of up to 1.5 MPa. These
generate a mixture of water and heavy sand which
is then fed to the treatment plant.
Off the coasts of Indonesia, Thailand, and
Malaysia, chain and bucket excavators are used
to extract cassiterite from alluvial deposits under
water at depths of up to 40 m. This also gives a
preliminary beneficiation.

3.4. Ore Beneficiation [11], [24–28]

The beneficiation of primary tin ores is difficult.


The principal mineral, cassiterite, is nonmag-
netic and is not suitable for flotation, so that
mainly gravimetric sorting processes must be
used. Furthermore, cassiterite is often strongly
intergrown, and the accompanying minerals be-
have similarly to cassiterite during processing.
Current technologies are characterized by
controlled multistage size reduction of the ores
and separation of the cassiterite released after
each size reduction stage using sorting methods
based on density. Screen jigs and shaking tables
of various designs are used. However, very small
particles (< 30 mm) cannot be processed to give
satisfactory yields and production rates. If the
degree of intergrowth of the ores requires finer
grinding, as is increasingly the case with ores
from Russia, the United Kingdom, Bolivia,
South Africa, and Portugal, the flotation method
for sorting particles < 100 mm is sometimes
used. This technique was also used for the tin
ore from the Altenberg region of Saxony, whose
mines were closed in 1990. The following stages
of beneficiation of primary tin ores are used:
Ores with an average degree of intergrowth
are concentrated mainly by processes based on
density. Flotation is increasingly used to sort
fine-grained material and ground middlings ob-
tained by the density-based sorting process, and Figure 1. Flotation of primary tin ores
Vol. 37 Tin, Tin Alloys, and Tin Compounds 7

similar paragenesis, followed by flotation of


cassiterite from the preconcentrate, and magnetic
separation of paramagnetic minerals from the
flotation product.
Composition ranges for complex tin concen-
trates are:

Sn 5.6 – 60 wt %
S 1.0 – 15 wt %
As 0.1 – 3 wt %
Sb 0.1 – 2 wt %
Bi 0.1 – 0.5 wt %
Cu 0.1 – 0.7 wt %
Pb 0.1 – 3 wt %
Zn 0.1 – 4 wt %
Ag up to 500 ppm
W 0.1 – 5 wt % WO3
Nb/Ta 1 – 3 wt % Nb2O3 þ Ta2O3

The ores from placer deposits are thoroughly


broken down by natural weathering processes
which separate the material roughly according
to the rate at which it settles out of suspension.
The fine-grained cassiterite is mixed with coarser
sand or gravel. On board the floating dredges,
which operate in artificial dredging ponds or
natural surface waters, there is ore beneficiation
equipment which produces a preconcentrate for
further processing on shore (Fig. 2). The ore
passes through a drum screen which removes
coarse gravel (10 – 20 mm), wood, and other
foreign bodies. The material passing through the
Figure 2. Preparation of secondary tin ores (placer deposits)
screen is desludged in a hydrocyclone, and treat- on floating dredgers
ment on a three-stage screen jig then produces
heavy metal concentrate for further processing on
shore.
The ore obtained from placer deposits on land 4. Smelting
using water cannons or from the seabed using
special ships with suction pumps is processed 4.1. Fundamental Theory of Smelting
using conventional ore beneficiation methods [1–3], [5], [29–34]
such as screen jigs or screen troughs.
Concentrates from placer deposits are rela- Because the most important tin-bearing mineral
tively pure; a typical analysis follows: in tin ore is cassiterite (SnO2), the carbothermic
reaction
Sn 70 wt % Ni 0.01 wt % SnO2 þ2 CO
Snþ2 CO2
As 0.1 wt % Ta2O5 0.2 wt %
Sb 0.05 wt % Nb2O5 0.1 wt % is of fundamental importance.
Pb 0.008 wt % WO3 0.05 wt % A theoretical consideration of tin smelting
Cu 0.005 wt % SiO2 5.0 wt %
must include the temperature dependence of this
Zn 0.01 wt % CaO 0.1 wt %
Bi 0.015 wt % TiO2 0.1 wt % equilibrium and the behavior of the important
Fe 0.3 wt % Al2O3 1.0 wt % reactants (Sn, O, and C) and accompanying ele-
ments and impurities in the concentrate, e.g., Fe,
8 Tin, Tin Alloys, and Tin Compounds Vol. 37

Cu, Sb, Bi, Pb, Ag, Si, Ca, Al, Mg, Nb, Ta, etc., of
which Fe is the most important. The equilibrium
diagrams for Sn – O – C and Fe – O – C are of
crucial importance in the reduction of tin. At
temperatures above 1100  C, not only the Sn but
also the Fe present in the oxidic precursors is
reduced, so that selective winning from indus-
trial tin-containing raw materials, which always
also contain iron, is impossible. Furthermore, in
this temperature range, up to 20 % tin dissolves in
iron, and iron – tin compounds (known as hard
head) are formed at lower temperatures, so that
iron-free tin cannot be obtained under these
conditions. This restricts the advantage of using
a high process temperature to give a faster reac- Figure 3. Calculated Fe/Sn ratios in the metal and slag at
tion rate in carbothermic cassiterite reduction. equilibrium as a function of temperature
Also, the technique of stably binding iron in
fayalite, to enable tin reduction to be carried out 0.5 % iron in the tin), there will be high losses of
selectively, though realized on a laboratory scale tin in the slag, whose tin content can be 10 –
by WRIGHT [29], could not be scaled up to pro- 25 %. These slags are starting materials for a
duction conditions. second process stage.
The elements involved in tin reduction can be The reactions in the slag phase are of major
divided into the following groups: importance for selective reduction, whereby
SnO is an important component. Experiments
1. Elements more noble than tin are reduced at on pure substances have shown that although
lower temperatures than tin, and dissolve in SnO melts at 980  C it is unstable below
molten tin (e.g., Cu, Pb, and Sb) 1100  C, decomposing into SnO2 and Sn. The
2. Elements that are much less noble than tin and activity of SnO in SnO – SiO2 melts obeys
which are not reduced under the reduction Raoult’s Law between 1000 and 1250  C. The
conditions, but which act as important slag negative free energies of mixing SiO2 with FeO,
formers, such as Ca, Al, and Si in the form of ZnO, PbO, MnO, and MgO increase in this
their oxides order, and increase the SnO activities in the
3. Iron, the most important accompanying ele- silicate melts. The position of the metal – slag
ment, which behaves similarly to tin equilibrium in the reaction
4. Gaseous compounds produced in the reduc- FeþSnO
SnþFeO
tion process
5. Sulfur, which has an important role in the is expressed by the distribution coefficient
reduction and volatilization process of pyro-    
Sn Fe
metallurgical tin production K¼ 
Fe metal Sn slag

Both the iron and the slag formers must be


removed in a liquid slag; this determines the K should be as large as possible, and at the usual
minimum process temperature. The iron content reaction temperature of 1000 – 1100  C used in
of the metal product depends on the Fe/Sn ratio in tin metallurgy, should be ca. 300 to give an iron
the slag. This relationship, represented in Fig- content of ca. 1 % in the tin.
ure 3, illustrates the principal problem of tin Binary and ternary slag systems containing
production from oxidic raw materials. If a high tin oxides have been thoroughly investigated
tin yield is to be obtained, i.e., small losses of tin [33] and give useful guidance for carrying out
in the slag (e.g., < 10 %), high reduction tem- the tin reduction. However, practical results
peratures must be used, giving an iron content in depend very much on the viscosity of the
the tin of > 8 %, so that subsequent refining is molten products, the density differences, the
more difficult. If a purer metal is desired (e.g., surface tension, and colloidal dispersion and
Vol. 37 Tin, Tin Alloys, and Tin Compounds 9

chemisorption of the slags. Thus, under pro- 4.2. Special Aspects of the Winning of
duction conditions stronger bases displace Tin from its Ores
SnO bound in silicate, and FeO increases the
fluidity of the slags. Problems in ore beneficiation often lead to con-
The difference between the kinetics of tin centrates with low tin contents, as unacceptably
oxide reduction and iron oxide reduction affects high losses of material would occur if ore con-
the selectivity of the reduction process and centrates with higher tin contents were produced.
hence the iron content of the tin and the perfor- Therefore, a pyrometallurgical ‘‘thermal ore ben-
mance parameters of the furnace systems. Other eficiation’’ stage is necessary prior to the actual
important parameters are the pore structure and reduction process. This is a volatilization process
particle size of the raw materials, the partial that exploits the fact that the iron compounds and
pressures of the reduction gases, removal of the other slag formers have low vapor pressures at
reaction gases, formation of seed crystals and 1000 – 1500  C, while SnO and SnS volatilize
coatings, and heat transfer. Thus, from the point very readily. This technique can also be used to
of view of reaction rate, the reverberatory fur- treat tin-containing slags.
nace is not the best equipment for carrying out The vapor pressure of SnS is considerably
reduction as it contains a large slow moving higher than that of SnO. Therefore, in practice,
mass of material with a large bed thickness SnS is vaporized and then oxidized to SnO and
where heat is supplied only from above. The SO2. Pyrites (FeS2) added as sulfur source
poor heat transfer leads to an extremely low causes problems in later stages of the process,
smelting capacity, i.e., < 0.7 t metal per m3 as the FeO formed must be slagged, and the SO2
furnace volume per day. Because slag formation evolved makes waste-gas cleaning necessary.
is very slow, some of the tin reduced at the start However, this is outweighed by the advantages
of the process can be tapped off as a relatively of a high yield of tin at relatively low process
pure, low-iron product before the entire charge temperatures.
is smelted. Economic advantages can be achieved by
In contrast, highly turbulent reaction systems using cheap sulfur-containing grades of heating
lead to process rates orders of magnitude higher. oil as fuel in the roasting process.
Under practical reaction conditions above The naturally occurring ore beneficiation pro-
900  C, the reaction cess that takes place in cassiterite deposits in
SnO2 þ2 CO
Snþ2 CO2
surface waters and the increasing use of ore
concentration processes with finely intergrown
is rapid, and the reaction ores lead to extremely fine grained materials.
Processes of agglomeration or compaction would
CþCO2
2 CO
be very costly. For this reason, these types of raw
becomes rate determining. This is why oxygen material are usually treated in an ore reverbera-
has to be added to the mixture of solid charge and tory furnace.
reducing carbon in the furnace. The main problem in pyrometallurgical tin
World production of tin is two-thirds from production processes is separating tin from iron.
oxidic and one-third from sulfidic raw materials. Under production conditions, simultaneous re-
The main problem in treating sulfidic tin con- duction of SnO and FeO cannot be prevented.
centrates is their complex composition. As many Molten tin can dissolve large amounts of iron,
impurities as possible are vaporized in an initial and intermetallic compounds, which are very
roasting stage. difficult to separate, can be formed on solidifica-
Arsenic requires special treatment, as it is tion. To minimize this problem, tin production is
oxidized to As2O3 and As2O5, which combines carried out in two stages. In the first stage, under
with Fe2O3, formed by roasting, to give nonvol- mild reduction conditions, a relatively pure tin
atile iron(III) arsenate. In practical operation, a and a rich slag are produced. The latter is treated
somewhat reducing atmosphere is therefore pro- under strongly reducing conditions in the second
duced by adding charcoal to the charge. Another stage, giving a discardable slag and a very impure
possibility is to vaporize heavy metal chlorides tin – iron compound. The metallic phase is
by adding NaCl. returned to the first stage, where the iron is
10 Tin, Tin Alloys, and Tin Compounds Vol. 37

reoxidized. The two-stage process must be car- Optimum results are only obtained if the
ried out such that the iron initially in the concen- reaction of the sulfide with oxygen takes place
trate is eventually removed from the process in exclusively in the gas phase; therefore, reducing
the waste slags. conditions must be maintained in the furnace.
Although gaseous sulfur is the best sulfiding
agent from a thermodynamic viewpoint, pyrites
4.3. Production of Crude Tin is used almost exclusively under production con-
ditions. If calcium sulfate is used, the disadvan-
4.3.1. General Aspects tage that energy is required for its dissociation
must be balanced against the advantage that the
The choice of a crude-tin production process CaO produced is a useful slag former.
involves consideration of factors associated with Although the vaporization of tin as SnS is used
both raw materials and location, and the follow- in all production plants, there is no generally
ing questions must be posed: accepted model of the reactions that take place.
However, it is probable that in view of the S/Sn
1. Whether the raw materials are highly enriched ratios required, the available polysulfidic sulfur
concentrates with low levels of impurities in the pyrites does not take part in the formation
2. Whether the raw materials used are low-grade of tin sulfide. Furthermore, it can be deduced
concentrates whose principal impurities are from the importance of the added carbon to the
slag components reaction product obtained and from the CO con-
3. Whether complex raw materials containing at tent or oxygen demand of the reaction gases that
least one other valuable element (e.g., W, Nb, SnO2 is reduced first to SnO in an intermediate
or Ta) are used stage and SnS is then formed by the reaction of
SnO with FeS. This is supported by the fact that
Other important factors include the availabil- the pyrites or the FeS formed therefrom forms
ity of raw materials, energy costs, environmental SnS more readily than does sulfur vapor, contrary
considerations, and personnel costs. to what would be expected from thermodynamic
considerations.
These results, especially when supported by
4.3.2. Ore Preparation prior to Reduction practical experience, show that the overall equa-
tion and the individual reactions are probably as
As a result of the problems described in Sec- follows [28]:
tion 3.4 and also of the efforts to recover as much
SnO2 þFeS2 þ1=2 SiO2 þCþ3=2 O2
SnSþ1=2ð2 FeOSiO2 Þ
of the tin from the ore as possible, the tin content
of the ore concentrate can range from 8 to 60 %. þSO2 þCO2
Hence in most cases, pretreatment is necessary,
e.g., pyrometallurgical enrichment of low-grade FeS2
FeSþS
raw materials, a roasting stage (sometimes with
addition of fluxes), or a leaching operation. SþO2
SO2

4.3.2.1. Pyrometallurgical Enrichment of Cþ1=2 O2


CO
Low-Grade Concentrates [1–5], [28–30],
[34–41] SnO2 þCO
SnOþCO2

Low-grade tin concentrates are subjected to SnOþFeS


SnSþFeO
pyrometallurgical enrichment. The tin is vapor-
ized as sulfide, and then oxidized in the gas phase 2 FeOþSiO2
2 FeOSiO2
by atmospheric oxygen to form SnO2. The non-
volatile components of the raw material are
selectively removed, and with careful process Pyrometallurgical enrichment of low-grade
control, 90 – 95 % of the tin can be recovered as tin concentrates can be carried out in various
an oxidized product containing 40 – 60 % Sn. types of furnace.
Vol. 37 Tin, Tin Alloys, and Tin Compounds 11

Initially, rotary and shaft kilns were used for mixture with uniform distribution of the fuel
the vaporization process. Although the operation and air to the individual jets. Heating oil and
of both types of equipment was technically so- natural gas are preferred because they are more
phisticated, there were considerable disadvan- easily metered than solid fuels. If pyrites is used
tages, which eventually led to their abandon- as the sulfiding agent, an S/Sn ratio of 0.8 is
ment. Apart from the high energy and fuel re- necessary, which places high demands on the
quirements typical of both systems, the shaft kiln equipment for removing sulfur dioxide. When
process led to a relatively low direct yield of tin in pyrites is used, only FeS is effective in the slag
the flue dust, mainly due to the production of phase, so that only 50 % of the sulfur is used for
matte, which required separate processing. The sulfiding. If pyrrhotite (magnetic pyrites) or
rotary kiln method led to a low tin concentration calcium sulfide is used, the S/Sn ratio need only
in the flue dust, and, for raw material of high iron be 0.4, and the emission of sulfur dioxide de-
content, to the formation of matte, and hence to a creases by 50 %.
drum clinker, which had then to be processed in a The good metallurgical results of the slag
shaft kiln. blowing process, in which flue dusts containing
High-capacity thermal concentration proces- 65 – 70 % Sn and final slags containing 0.1 % Sn
ses, already established on a large scale in the are obtained, must be balanced against the dis-
nonferrous metal industry, were therefore advantage of a batch process. This leads to
adapted to tin enrichment. The fluidized bed and nonuniform loading of the downstream plant,
the cyclone smelting processes were not used. e.g., the waste heat recovery and gas cleaning
Also, the flash smelting (levitation smelting) equipment.
process has severe limitations because of the raw
materials used. Good results could be obtained 4.3.2.2. Roasting [1], [2], [4], [5], [11], [17],
with concentrates in which most of the material [32], [42–50]
had a particle size of 200 – 300 mm. Using such
concentrates containing 10 – 12 % Sn, dis- The roasting process, not only converts sulfides
cardable slags containing 0.2 – 0.4 % Sn and flue to oxides, but also volatilizes major oxidic im-
dusts containing 50 – 60 % Sn could be obtained. purities (e.g., arsenic). Roasting can be an inde-
On using low-grade concentrates that had not pendent process, or a pretreatment prior to hy-
been desludged and which contained significant drometallurgical leaching. It is significant that
amounts of material with a particle size of 50 – the level of impurities As, Sb, Pb, and Bi in tin
60 mm, the amount of primary flue dust increases concentrates has increased in spite of great ef-
significantly, and the tin concentration in the flue forts to improve ore beneficiation technology. If
dust sometimes decreases to < 40 %. Also, the the levels of As and Pb are > 0.1 %, and of Bi and
tin content of the slags is unacceptably high (1 – Sb > 0.03 %, a roasting process, sometimes with
2 %). the addition of a leaching stage, is both useful and
The main disadvantage of the flash smelting necessary for the benefit of the final tin reduction
process is that it imposes strict requirements on and refining processes.
the physical form of the concentrate. The important reactions in the roasting pro-
The slag blowing process, originally used for cess are as follows (M ¼ metallic impurity):
detinning the slags from the reduction process,
has been increasingly used for enrichment of tin 1. DissociationFeS2
FeS þ 1/2 S24 FeAsS
in low-grade concentrates and exploitable gang-
4 FeS þ As4
ue from ore processing. These products were at 2. Roasting reactionsMS þ 3/2 O2
MO þ SO2
first added to the initial smelting process, but they 3. OxidationMO þ 1/2 O2
MO2
were later added in solid form directly to the
blowing furnace. Smelting and blowing can be Although the roasting reactions and especially
carried out in a single furnace, so that it is not the oxidation reactions are exothermic, addition
necessary to build a special smelting plant. This of fuel is necessary in industrial-scale roasting
enables capital and operating costs to be reduced. processes. The pore structure of the material must
An important part of the practical operation be maintained to enable the gaseous metallic and
is the maintenance of the correct fuel – air nonmetallic impurities to be vaporized. The
12 Tin, Tin Alloys, and Tin Compounds Vol. 37

upper temperature limit for the roasting process separation of tin from iron. In a reducing atmo-
is imposed by the melting point of the low- sphere, i.e., in the presence of C or CO, only
melting sulfide eutectic. However, the tempera- SnCl2 is formed.
ture should be kept as high as possible to prevent In the Warren Spring process [50], CaCl2 is
the formation of sulfates, e.g., lead and calcium used as chloridizing agent, and the CaO formed is
sulfate. used in the reductive smelting by adding lime-
A mildly reducing atmosphere is necessary to stone in accordance with the following equa-
suppress sulfate formation and also prevent for- tions:
mation of higher nonvolatile oxides of the impu-
SnO2 þCaCl2 þC
SnCl2 þCaOþCO
rities (e.g., As2O5).
The roasting processes are carried out in
SnCl2 þCaCO3 þC
SnþCaCl2 þCOþCO2
multideck or rotary kilns. The use of fluidized-
bed furnaces with carefully controlled operating
parameters has been reported [48]. The industrial-scale reaction is difficult to
Chloridizing roasting is also suitable for the carry out, as moisture resulting from the hy-
pretreatment of tin concentrates, owing to the groscopic properties of the tin chloride and the
high affinity of the main impurities for chlorine. quicklime must be avoided. The corrosive
However, problems can be caused by chlorida- properties of the reaction gases make very
tion of tin, which itself then volatilizes as SnCl4 high demands on the construction materials
and SnCl2. used.
Chloridizing roasting of tin concentrates in A special form of roasting is the heating of
rotary kilns is carried out in Thailand. The con- high-tungsten tin concentrates with NaOH or
tents of lead and bismuth are lowered from 2.0 % Na2CO3 to give soluble Na2WO4, which can be
to 0.04 %, and from 0.1 % to 0.02 %, respective- leached out.
ly. The flue dust contains 10 % As, 3 % Sn, 20 %
Pb, and 4 % Bi. Treatment of this product pre- 4.3.2.3. Leaching [1–4], [32], [47], [51–55]
sents serious problems [2].
The processes for removing impurities by In tin metallurgy, the main use of leaching pro-
chloridation differ fundamentally from those for cesses is to remove typical impurities from the
the volatilization of tin from concentrates, being concentrate. Tin, which is nearly always present
based on the fact that a large phase field exists in in the raw materials as SnO2, can only be brought
the phase diagrams Sn – HCl – H2 and Fe – into aqueous solution if the SnO2 is reduced to
HCl – H2 between 900 and 1000  C in which SnO in a precisely controlled CO/CO2 atmo-
selective chloridation and volatilization of tin is sphere. It can then be extracted in acid or alkaline
possible without chloridizing iron. media. This procedure has not yet been operated
The overall reactions are as follows (M ¼ on an industrial scale.
Mg, Ca, or Na): Only hydrochloric acid is used on an in-
dustrial scale to remove impurities by leach-
SnO2 þMCl2 þCO
SnCl2 þMOþCO2 ing, the typical impurities in the concentrate,
Fe, Pb, Cu, Sb, or As, going into solution in
SnO2 þCl2 þC
SnCl2 þCO2 the form of their chlorides. Best results are
obtained using > 20 % hydrochloric acid at
SnO2 þ2 HClþCO
SnCl2 þH2 OþCO2 100 – 110  C. Suitable reaction vessels are
high-pressure, acid-resistant spherical boilers
The presence of iron oxide increases yield and with a capacity of 20 t. This batch process
reaction rate, which can only be explained by must sometimes be repeated several times. The
intermediate formation of FeCl2: solids are removed by thickeners and vacuum
filters, and the dissolved impurities are pre-
4 SnO2 þ6 FeCl2
2 Fe3 O4 þ2 SnCl2 þ2 SnCl4
cipitated from the liquor by cementation on
scrap iron.
Here, the instability of iron chloride in the The high costs of these special reactors, the
presence of tin oxide is the reason for the good batch mode of operation, and the expense of the
Vol. 37 Tin, Tin Alloys, and Tin Compounds 13

process for recovering the hydrochloric acid have 4.3.3. Reduction


restricted the use of hydrochloric acid leaching to
some special cases. As explained in Section 4.1, it is not possible to
It is preferable to carry out chloridizing roast- obtain high yield and high metal purity at the
ing before leaching out the impurities. This then same time. Reduction is therefore carried out in
only requires a dilute acid solution. two stages, the first stage giving a relatively pure
Leaching of tungsten-containing tin concen- metal (up to 97 % Sn) and a rich slag (8 – 35 %
trates to recover tungsten is important. After Sn). This slag is treated in a second stage, and
digesting the ore with sodium carbonate in spher- sometimes in a third. Slag treatment processes
ical boilers, the tungsten is converted to its are described in Section 4.3.4.
hexavalent form, which is soluble in hot water. Various types of furnace are used for reduc-
It is then precipitated from the neutral solution tion. Very low grade ore in lump form can be
with CaCl2: treated in a shaft kiln. However, as most con-
centrates obtained in ore beneficiation are very
Na2 WO4 þCaCl2
CaWO4 þ2 NaCl2
finely divided, and agglomeration, e.g., by sinter-
An easily filtered precipitate containing up to ing, is impossible, other types of furnace must be
60 wt % WO3 (on dry basis) is obtained. used in this case. Reverberatory or rotary air
Tungsten can also be extracted from tin con- furnaces are often used for reduction, and electric
centrates by leaching with an aqueous solution of furnaces are also employed. Each furnace type
ammonia: has its own advantages and disadvantages.
H2 WO4 þ2 NH4 OH
ðNH4 Þ2 WO4 þ2 H2 O 4.3.3.1. Reduction in a Shaft Kiln [1–3], [5],
The concentration of WO3 in the filtrate can [30], [56], [57]
reach 50 g/L, and this can be precipitated as
artificial scheelite (Ca[WO4]). The tungsten con- Shaft kilns are historically the oldest type used
tent of the tin concentrate can be reduced to for tin reduction. They have their origin in the old
0.5 %. Chinese natural draught furnaces made of
Most of the tin can be leached from a tin rammed clay held together with wooden posts
concentrate containing 2 wt % bismuth with and operated on mountainsides. The hearth was
5 % hydrochloric acid at 80  C [46]. usually sloped so that the molten product ran off
Treatment with sulfuric acid is used to remove continuously. Modern shaft kilns are water-
iron present as carbonate in Australian tin con- jacketed, and have a melting capacity of 5.5 –
centrates. By removing gangue material in this 8 t m2 d1. The good heat transfer and the
way, the tin content of the concentrate is in- continuous method of operation give a higher
creased from 37.2 % to 47.1 %. melting capacity than is obtained in comparable
A process for the removal of arsenic from tin reverberatory furnaces. The air flow rate must be
concentrates by bacterial leaching with Thioba- low to prevent volatilization. Shaft kilns require
cillus ferrooxidans has been tested in Russian raw material in lump form. The iron content must
research institutes [54]. be as low as possible in order to limit the forma-
The tin can be leached out of ores that are tion of hard head in the reducing atmosphere.
difficult to treat if these are first reductively
smelted with CuCl2 and HCl, in accordance with 4.3.3.2. Reduction in a Reverberatory
the following series of reactions [42]: Furnace [1–3], [5], [30], [32], [58–61]
SnþCuCl2
CuþSnCl2 The necessity for treating fine-grained concen-
trates from ore beneficiation has led to the re-
CuþCuCl2
Cu2 Cl2 placement of the shaft furnace by the reverbera-
tory furnace, and this is today the most important
Cu2 Cl2 þHCl
2 CuCl2 þH2 type of reduction equipment used in tin metal-
lurgy. Modern reverberatory furnaces have inter-
Tin is precipitated from solution by adding nal dimensions of 3 – 4 m width, 10 – 13 m
zinc, and copper by adding iron. length, and 1 – 1.5 m height. In a freshly lined
14 Tin, Tin Alloys, and Tin Compounds Vol. 37

hearth the height available for the molten charge Table 2. Typical compositions of products from a reverberatory
furnace (in wt %)
is no more than 0.5 m. This increases with
increasing wear of the furnace bottom. The bath Component Crude tin Slag Flue dust
volume of modern tin ore reverberatory furnaces
Sn 97 – 99 8 – 25 40 – 70
is 20 – 50 m3. As the tin is very fluid at the Fe 0.02 – 2.0 15 – 40 0.8 – 4.0
reaction temperatures (up to 1400  C), high As 0.01 – 2.0 0.1 – 0.7
pressures can be produced at the bottom of the Pb 0.01 – 0.1 0.1 – 0.5 0.2 – 1.6
hearth. To prevent this, either holes must be Bi 0.003 – 0.02 0.01 – 0.1
Sb 0.005 – 0.2 0.01 – 0.02 0.1 – 0.4
provided in the steel sheet bottom to allow the Cu 0.001 – 0.1 0.02 – 0.05
tin to drip into a lower chamber where it can Al2O3 7 – 12 1.0
solidify in stalactite form, or the reverberatory SiO2 10 – 30 2.0
furnace must have a water-cooled bottom so that CaO 4 – 14 0.6
MgO 1 – 4 0.6
the tin solidifies in the gaps between the bricks. S 0.01 – 0.05 1.0
The refractory bricks and mortar used to line the
furnace must be made of high-grade chrome-mag-
nesite. This must be very pure because of possible tent is therefore considerably higher than that in
reactions of SnO or Sn with iron oxides or silica. the charge material.
Chamotte can only be used above the slag zone. To Compositions of products obtained when a
avoid disturbance of the brickwork in the melting relatively pure concentrate (> 70 % Sn) is trea-
zone, charging is carried out through the roof. ted in a reverberatory furnace are listed in Ta-
The burners, which use heavy fuel oil, are ble 2. The amount of slag is relatively small
situated on the narrow sides of the furnace. The (14 wt % of the charge), but the slag must under-
furnaces operate discontinuously using the re- go a further stage of processing because of its
generative principle, the duration of a heat being high tin content.
16 – 20 h. Specific melting capacities are in the A simplified flow diagram for the treatment of
range 1.2 – 2.0 t m2 d1. Charge batches con- high-grade concentrates is shown in Figure 4.
sisting of concentrate, carbon, and fluxes weigh The process flow diagram for low-grade, im-
between 40 and 70 t. Optimum results can only pure, and complex concentrates is considerably
be achieved by extremely careful operation. more complex. With high-grade concentrates, a
Thus, at the start of a new heat, the amount of tin yield, including that obtained from slag treat-
material charged to the furnace should be limited, ment, of 99.6 % can be achieved, as actual losses
e.g., by adding the charge in two portions, to of tin can only occur in the waste slag and by loss
prevent a large drop in temperature. The amount of airborne dust. In the treatment of low-grade
of carbon added in the form of coke, coal, petro- concentrates, the yields of tin may only be 95 %,
leum coke, or charcoal is determined by the tin and and in exceptional cases 92 %, because of the
iron contents and also by the incidence of hard head. numerous tin-containing waste products.
The carbon addition is adjusted so that coreduction Control of the CO partial pressure, which
of the iron is prevented as far as possible. determines the reduction potential, is more diffi-
The furnace draught must be kept low to cult in a stationary reverberatory furnace, which
prevent entry of cold air and to maintain the contains a slow-moving mass of charge, than in a
oxygen content in the waste gas below 5 vol %, shaft furnace, in which the coke and air move in
thereby minimizing oxidation of the tin. countercurrent flow. This is also the reason for
The first tin can be tapped off after 4 – 5 h of a the poor heat transfer and hence the low rates of
24 h cycle. As this is comparatively pure, it is reduction and melting in a reverberatory furnace.
preferable to treat it separately. The material Under operating conditions, care must be
tapped off later separates into metal and slag in taken that the slag formers do not melt too
a settler outside the smelting furnace. Some rapidly, as this impairs the contact between the
furnaces have facilities for tapping off the metal furnace atmosphere and the unmelted charge. At
and the slag separately. the same time, the melting temperature of the
Up to 6 % of the weight of charge material is slag must be as low as possible, so that the use of
converted to flue dust, which consists of en- such slag formers as CaO and SiO2 should be
trained charge, SnO, and some SnS. Its tin con- limited. Added lime is of special significance,
Vol. 37 Tin, Tin Alloys, and Tin Compounds 15

Figure 4. Process for treating high grade concentrates (simplified)

because it displaces tin from silicate, can lead to The furnace availability (300 d/a) is superior
calcium stannate formation if present in excess, to that of reverberatory furnaces (260 d/a). Also,
and increases the melting point of the slag. there is less requirement for mixing operations or
The effect of the slag constituents, especially agitation of the melt by stirring (rabbling). The
on melting point and viscosity, is described in metallurgical results of both types of furnace are
detail in [3]. In a process optimization/cost min- very similar. However, the considerably poorer
imization exercise, it is always necessary to stability of the refractory lining, the higher ener-
include the effect on costs of the amount of tin gy requirement, and the significantly larger quan-
tied up in materials being recycled [59]. tities of flue dust are all disadvantages. Separa-
tion of the tin from the slag has to be carried out
4.3.3.3. Reduction in Rotary Kilns [1–3], [5], outside the furnace in a settler.
[30], [32], [57–62] Tin concentrate can also be reduced in short
drum kilns in which the ratio of the length to the
Rotary kilns (rotary air kilns) are horizontal cross-section is 1. The metallurgical function is
smelting units that operate batchwise. They have basically similar to that of the rotary kilns.
a higher melting capacity than stationary rever- The compositions of the smelting products in
beratory furnaces, but lead to considerably more an Indonesian tin smelting works in which high-
severe stress on the refractory lining. Operating grade concentrates are reduced in a rotary kiln are
procedures in two tin smelting works in Indone- given in Table 3.
sia and Bolivia in which the reduction process is
based on the rotary kiln principle are reported in 4.3.3.4. Reduction in an Electric Furnace
the specialist literature [63]. The furnaces have a [1–3], [5], [30], [32], [58], [64–68]
length of 8 m, a diameter of 3.6 m, a surface area
of reacting material of ca. 22 m2, and a specific Electric resistance and arc furnaces used in met-
melting capacity of 1.36 – 1.5 t m2 d1. allurgy are characterized by high reaction
16 Tin, Tin Alloys, and Tin Compounds Vol. 37

Table 3. Typical compositions of products from a rotary kiln at Both stationary and tilting furnaces are used.
Mentok, Bangka (in wt %)
Linings of carbon bricks give a service life of up
Component Crude tin Slag Flue dust to three years. Electric currents of 6 – 20 kA at
50 – 150 V are used. Depending on the charac-
Sn 99.78 – 99.83 14 – 25 60 – 72
Fe 0.089 – 0.144 15 – 26 1–4 teristics of the raw materials, energy consump-
Pb 0.010 – 0.031 tion is 750 – 1400 kW  h/t concentrate (1300 –
As 0.010 – 0.188 1860 kW  h/t tin). Precise control of the elec-
Sb 0.005 – 0.010 trode immersion depth is essential for good
Bi 0.0025 – 0.003
Cu 0.002 – 0.025 control of the process.
SiO2 8 – 24 0.2 – 2.0 Electric furnace technology enables a wide
CaO 2 – 10 1 – 1.2 range of process parameters to be used. For
MgO 2–4 example, when low-iron concentrates are trea-
S 0.2
ted, a tin quality suitable for normal refining can
be produced. The high-tin slags produced (up to
temperatures and low waste-gas volumes. Dis- 30 % tin) are treated in a second stage to recover
advantages are the necessity for thorough pre- the tin. If the iron contents are much greater than
mixing of the raw materials and the batch opera- 3 %, the tin obtained has a high iron content (3 –
tion. Tin smelting is often carried out in regions 10 %).
where electrical energy is less readily available It is also possible to operate at ca. 1400  C by
than energy from other sources such as gas, coal, using strongly reducing conditions. A tin-con-
or oil. Wherever electric furnaces are used in tin taining slag is then obtained together with hard
metallurgy, the object is to utilize their advan- head containing ca. 40 % tin and 50 % iron. The
tages of high reaction temperature and the pro- iron can be removed by smelting with ferrosili-
duction of heat by the Joule effect directly in the con in a second pass, and a crude tin containing
smelting bath. ca. 1 % iron is obtained.
Because their reducing action is so effective, Great efforts have been made to overcome the
electric furnaces are particularly suitable for disadvantage of batch operation of the electric
extracting tin from slag (see Section 4.3.4). In furnace. For example, a continuously operated
concentrates whose iron content is significantly lengthened double chamber electric furnace has
less than 5 %, it is even possible to produce crude been reported in Russia. Each chamber has a
tin in a single stage, with tin levels in the slag of hearth area of 1 m2 and two electrodes. The
< 0.7 %. reduced tin flows out of the first chamber over
Electric furnaces are used in many tin smelt- an air-cooled overflow, and the tin is extracted
ing works for primary tin production from con- from the high-tin slag in a second chamber [68].
centrates. These concentrates are often imported, The process is still at the pilot stage. The furnace
e.g., in Germany, France, Italy, Canada, and capacity is reported to be less than 10 t/d.
Japan, although tin concentrate producing coun-
tries, e.g., Brazil, Zaire, South Africa, Russia, 4.3.3.5. Other Reduction Processes [1–3], [5],
Thailand, and China also use electric furnaces. [30], [58], [60], [69]
The raw materials for the electric furnace process
must be intensively mixed. Very fine-grained All the processes described above have disad-
materials such as flue dust are pelletized. A vantages, and many other methods and types of
moisture content of ca. 2 % must not be equipment have therefore been suggested for the
exceeded. reductive treatment of tin concentrates, but few
Typically, circular furnace vessels with an of these proposals have led to an industrial plant.
outside diameter of up to 4.5 m and a height of One of the few methods tested at full scale is
1.5 – 3 m are used, or oval furnace vessels with the top blown rotary converter (TBRC) devel-
dimensions 2.51.81.8 m. Heating is carried oped in the United States and based on the
out with three-phase electric arcs using graphite ‘‘Kaldo’’ converter used in ferrous metallurgy.
electrodes. In single-phase furnaces, the furnace Oxygen is blown onto the top of charge as the
bottom acts as the counterelectrode for the im- converter rotates about its axis, which is set at an
mersed graphite electrodes. angle. The volume of waste gas is very low as
Vol. 37 Tin, Tin Alloys, and Tin Compounds 17

there is no ballast nitrogen. The favorable heat Table 4. Tin and iron balance for two-stage smelting of a concentrate
containing 73 % Sn and 0.7 % Fe based on 1000 kg concentrate treated
transfer to the charge leads to a high reaction rate.
Disadvantages include batch operation, a high kg Sn kg Fe
rate of wear of the refractory lining, and the
Smelting of concentrate
complexity of the system for controlling the Charge :
oxygen lance. 1000 kg concentrate 730 7
After completion of the reduction process, the 95 kg hard head 38 42
tin is tapped off. The tin in the remaining slag is 220 kg coke/coal 2
40 kg flue dust 18
vaporized as chloride by adding calcium chlo- 11 kg recycled material 6 3
ride, and a discardable slag is thereby produced. Total 792 54
The tin chloride is scrubbed out of the waste Product :
gases and then precipitated as SnO2 by adding 733 kg crude tin 730 2
200 kg primary slag 47 51
CaO, regenerating CaCl2. 30 kg flue dust 15 1
The potential for transferring proven process- Total 792 54
es used in nonferrous metallurgy to tin metallur- Smelting of slag
gy is discussed in detail in [69]. Charge :
200 kg primary slag 47 51
Apparently no completely new processes for 40 kg coke/coal
reducing tin concentrates have become established Total 47 51
in the industry because of the high capital invest- Product :
ment required and the hidden risks involved. 100 kg secondary slag 1 8
95 kg hard head 38 42
10 kg flue dust 5
2 kg Fe alloy 1
4.3.4. Slag Processing [1], [2], [5], [32], Total 44 51
[38], [47], [62], [63], [70–79]

The slags produced during the reduction of high- The balance shows that the iron introduced
tin concentrates can contain 5 – 10 % of the tin. into the concentrate smelting process with the
This can increase to 20 % in the case of low-grade concentrate and reducing agent (7 þ 2 kg) must
and complex ores. One- or two-stage treatment of be removed from the slag smelting process in the
the slag is then necessary. It is in principle possi- secondary slag and iron – tin alloy (8 þ 1 kg).
ble to use strongly reductive smelting (e.g., in a Of the tin in the concentrate, 6 % is in circulation
reverberatory or rotary furnace) or blowing pro- in the primary slag (47 kg out of 730 kg).
cesses to volatilize the zinc from the slag. However, the concentrates treated usually
On reductive smelting, the tin and iron form contain considerably more iron, so that a larger
an alloy, the so-called hard head, which is re- amount of primary slag and hard head are pro-
cycled to the primary tin production process. The duced, and the amount of tin contained therein
secondary slag has such a low tin content that it can rise to 20 % of the raw material used.
can be removed from the process. In practical slag smelting, the SnO in silica-
In the blowing process, the tin is converted rich slags is mainly present as 2 SnO  SiO2, and
into a flue dust, which is recycled to the primary the high activity of the SnO in silica- and lime-
smelting process. The slag, which usually has a containing slags decreases with increasing FeO
high iron content, can be discarded. contents, so that in practice simultaneous reduc-
Under production conditions, the intermedi- tion of tin and iron occurs. Theoretically, it is
ate products, e.g., the tin-containing secondary only possible to produce crude tin and low-tin
slag, the hard head, and the flue dusts, contain slag if the FeO activities are extremely low.
considerable quantities of tin. These are impor- However, the processes would proceed at high
tant for the economic operation of the process temperatures with large additions of reducing
because of the amount of capital tied up if they carbon.
are not immediately treated. The tin and iron The binary Fe – Sn phase diagram shows a
balances in the treatment of a concentrate with a miscibility gap at > 1100  C between 20 and
very high tin content and a low iron content are 50 wt % Fe. On cooling to room temperature,
shown in simplified form in Table 4. separation of a-iron first takes place, followed by
18 Tin, Tin Alloys, and Tin Compounds Vol. 37

formation of FeSn and FeSn2. At room tempera- necessary intense reducing effect is achieved by
ture, the region of the composition of the hard adding 10 – 20 % reduction carbon and by oper-
head is always in the a-iron/FeSn two-phase ating at temperatures up to 1500  C. In the
region. electric furnace process, energy consumptions
Wright has found by calculation of the distri- are 500 – 1000 kW  h/t, and 1 – 10 kg elec-
bution constant K at equilibrium trode is consumed per tonne of slag. The reaction
    products, i.e., the final slag and the hard head
Fe Sn
K¼  alloy, are separated in settlers and then granu-
Sn slag Fe metal
lated in water.
that the balance of the process is improved as the As highly turbulent conditions are favorable
ratio in the first quotient increases, i.e., as the to the process, reductive detinning can be carried
amount of iron removed in the slag increases. out with a lance (‘‘submerged combustion’’),
However, there must then be a higher iron con- which produces a high reaction rate by agitation
centration in the tin. If the tin in the primary slag of the bath. Methane or natural gas have been
is present as 2 SnO  SiO2, the reaction mecha- used as reducing gas, and experiments have also
nism is as follows: been carried out using hydrogen, carbon monox-
ide, and powdered solid fuels. Heat is produced
CþSnO
COþSn by partial combustion of the injected gases and
transferred to the molten slag. However, because
COþSnO
CO2 þSn SnO is volatile, 20 % of the tin goes into airborne
dust, a further undesired tin-containing reaction
COþFeO
CO2 þFe product in addition to the hard head.
An effective method of detinning primary tin
COþFe2 O3
CO2 þ2 FeO reduction slags is by the blowing process, which
can be carried out in reverberatory furnaces or
3 FeO
FeþFe2 O3 true blowing furnaces. Gypsum or pyrites can be
used as the sulfur source. The gypsum is first
FeþSnO
FeOþSn reduced to CaS, and then reacts with SnO to form
SnS and CaO. If pyrites is used, impurities such as
2 FeOþSnO
Fe2 O3 þSn Pb, Zn, or As are introduced into the metallurgical
process, adding to the difficulties of treating the
Thus the reaction first occurs only at the tin-containing flue dusts. Blasting technology is
surface of the carbon, and then via the iron oxides also often used as the third stage of slag detinning.
as intermediate phases. A high relative rate of In the second stage, a thermal reduction, Sn
reaction of carbon, slag, and reaction gas is contents of 2 – 5 % and FeO contents of ca.
therefore important for the reaction kinetics. 30 % are obtained. The tin content of the molten
The reactions that occur in the detinning of slag in the furnace is reduced to ca. 0.5 % by
slag are described in Section 4.3.2.1 (pyrometal- addition of sulfur sources. The addition of pyrites
lurgical enrichment of low-grade concentrates), can be up to 400 % of the theoretical amount
but here they start from SnO. As a matte phase calculated for the formation of SnS. Since smaller
must be present, the reaction will be: additions are possible in the case of acid slags,
CaS is probably formed in basic slags. The treat-
SnOþFeS
SnSþFeO ment of primary slags in true blowing furnaces
consists of blowing the pyrites into the molten
As the slag is saturated with FeS, the amount slag. However, the process is discontinuous. The
of SnS formed is proportional to the activity of SnS vapor is oxidized in the furnace atmosphere,
SnO in the slag, but indirectly proportional to the and recovered as SnO dust by filtration.
activity of FeO. The slag blowing process can be carried out in
Reverberatory or electric furnaces are usually furnaces of various designs, e.g., in a type of shaft
used in the reductive smelting process for the kiln with a floor area of 0.5 – 6 m2 and a water-
extraction of tin from primary reduction slags, cooled shaft 7 m in height. The charge of primary
though shaft kilns are occasionally used. The slag can be 5 – 20 t. Cyclone and short drum
Vol. 37 Tin, Tin Alloys, and Tin Compounds 19

kilns are also used. Process parameters, e.g., Only Sb, Cd, Bi, Zn, and Pb are significantly
ratios of sulfur source to oxygen, fuel to atmo- soluble in tin at room temperature. This is the
spheric oxygen, and tin to sulfur must be care- basis for the removal of insoluble impurity ele-
fully controlled to obtain optimum results. ments by liquation. However, the liquation pro-
Other proposed methods of detinning primary ducts have high tin contents, making costly re-
tin slags, such as vacuum-assisted volatilization covery processes necessary.
of SnO (which has a considerably lower vapor In pyrometallurgical tin refining, the individ-
pressure than SnS), have not been used on an ual impurities are removed stepwise in batch
industrial scale [29]. processes. The use of the time-consuming opera-
tions is justified by their high selectivity.
Proposed continuous processes have not been
5. Refining [1–3], [5], [32], [46], [47], operated on an industrial scale.
[80–84]
The crude tin obtained by the reduction process is 5.1. Pyrometallurgical Refining
insufficiently pure for most applications.
Most national standards specify maximum 5.1.1. Removal of Iron
contents of typical impurities. However, nonme-
tallic impurities such as oxygen and sulfur and The process for removing iron is based on the
less common impurities such as noble metals are temperature dependence of the solubility of iron
neglected, and the tin content is simply deter- or Sn – Fe mixed crystals in tin. Accurate ex-
mined by subtracting the total amount of analyti- periments have shown that the solubility of iron
cally determined impurities from 100. in tin at 250  C is 0.0058 wt % [81]. In industrial
The following three standard grades are ac- practice, even lower figures are achieved, which
cepted internationally: Sn 99.0 %, Sn 99.75 %, can only be explained by other impurities, such as
and Sn 99.9 %. Cu, As, or Sb, causing deviations from ideal
There are some variations in these standards solubility behavior. On cooling molten crude tin,
from country to country; the German standard is a-Fe, g-Fe, FeSn, and FeSn2 precipitate succes-
DIN 1704. sively. The density of the precipitated com-
The level of impurities in the crude tin deter- pounds is almost the same as that of the molten
mines the extent of the refining operation. Treat- tin. In practice, ‘‘poling’’, i.e., passing steam or
ment of very pure concentrates can give a tin air into the melt, is used to coagulate the precipi-
content of up to 99.0 % in the crude metal. The tated particles, which rise to the surface of the
main impurity is iron (0.8 %), the sum of all the bath and are removed from the molten tin by
other impurities being only 0.2 %. In the case of filtration through graphite, slag wool, or a slab
low-grade and complex concentrates, the situa- made of silica and limestone chippings. This
tion is very different, the tin content of the crude should be carried out just above the melting point
tin obtained sometimes being only 92 %. of tin, or in practice at a temperature not less than
The impurities Fe, As, Sb, Cu, Ni, Pb, Bi, and 260  C. The process is sometimes carried out in
the noble metals affect the amount of work in- two stages. Iron contents of 0.003 –0.01 wt %
volved in the refining process. The metals Zn, Cd, can be achieved.
Mg, Si, Ca, Te, Se, and also sulfur and oxygen do As Ni, Co, Cu, As, and Sb form intermetallic
not require special treatment, as they are present compounds with each other as well as with Fe,
in the crude metal in only small concentrations, these impurities are also removed to some extent.
and are removed together with the other impuri- The treatment of the recovered intermetallic
ties during the various stages of purification. compounds is very complex, as these are in the
The phase diagrams for tin and its typical form of a slurry with large amounts of adhering
impurities lead to the following conclusions: molten tin. The iron content is only a few per
In the temperature range between 1000 and cent, i.e., considerably less than that of the inter-
1300  C used in pyrometallurgical reduction, the metallic compound FeSn2.
impurities are completely soluble with the ex- The metal slurry is treated in small liquation
ception of Fe and Cr. furnaces. A controlled temperature increase over
20 Tin, Tin Alloys, and Tin Compounds Vol. 37

the range 230 – 300  C enables pure tin to be Any aluminum remaining in the molten tin
removed, and a residue containing ca. 15 % Fe can be removed by adding sodium, sodium hy-
suitable for use in the primary smelting stage to droxide, chlorine, or steam, and residual sodium
be obtained. by adding sulfur.
In high-capacity tin smelting works, high- The storage, transport, and treatment of the
temperature centrifuges are used. These enable Al – As product presents problems. Contact with
a solid residue containing up to 25 % Fe to be water must be avoided as this leads to the forma-
obtained [83]. tion of highly toxic arsine and stibine. The mate-
rial is stored in closed vessels and is converted
into a safe product as soon as possible by oxida-
5.1.2. Removal of Copper tive roasting or by treating with alkali solution
and collecting and burning the liberated arsine to
After iron has been removed by liquation, the form As2O3 and H2O. The residues obtained both
copper content is up to 0.01 %. Elemental sulfur from the roasting and the leaching processes can
(2 – 5 kg/t) is stirred in at 250 – 300  C, en- be recycled to the process.
abling copper contents as low as 0.001 % to be The large differences in vapor pressure bet-
attained. The resulting copper dross can be re- ween the impurities (arsenic, antimony, bismuth,
moved from the process after several stages of and lead) and tin enable selective evaporation at
enrichment. reduced pressure to be used. However, numerous
proposed processes have resulted in only two
industrial applications.
5.1.3. Removal of Arsenic In a system tested in Russia, the impure tin
flows from the top of a vertical reactor under a
After removal of iron by liquation, the arsenic vacuum of 1 Pa into heated evaporating dishes.
content is ca. 0.1 %, significantly higher than The evaporated impurities are collected in a
permitted levels. For example, the commonly separate chamber. Barometric valves are used
used Sn 99.75 grade should contain < 0.05 % to remove the purified tin and the condensate.
As according to DIN 1704. In the Bergs€oe – Redlac system, a cylinder,
Arsenic can be removed from the melts along cooled on the inside, rotates in a horizontal
with some Cu, Ni, and residual Fe by forming vacuum chamber above the melt, and the vapor-
intermetallic compounds with aluminum. For ized impurities are deposited on this in solid
this, the aluminum must be present as an ideal form. In the next stage of the process, they are
solution in the tin. For this reason, the melt must scraped off and removed. The results of the
be heated to a temperature close to the melting vacuum distillation process depend on the reac-
point of aluminum before the aluminum is added. tion temperature and time. The high energy
Special precautions are necessary, e.g., operation requirement for heating and for producing the
in a closed vessel so that the aluminum does not vacuum, 400 – 700 kW  h/t tin, is a disadvan-
burn on the surface of the bath. The amount tage. Moreover, significant quantities of tin are
added must be approximately three times the vaporized. The use of selective evaporation of
stoichiometric amount. The use of Al – Sn mas- typical impurities in crude tin always involves a
ter alloys enables the operation to be carried out compromise between the purity and tin yield.
at a lower temperature. Intense agitation if fol- Practical experiments are described in [85].
lowed by a settling process with cooling to 350 –
400  C, and the Al – As mixed crystals can then
be removed. Separation of the Al mixed crystals 5.1.4. Removal of Lead
is assisted by poling.
With correct operation, As contents of If the lead content is still not low enough after the
< 0.02 % can be achieved, i.e., below the per- first stages of the refining process, the lead can be
mitted level for Sn 99.90 %. This process enables converted into its dichloride by treatment with
Sb contents of 0.005 %, Cu contents of 0.02 %, chlorine, tin dichloride, or tin tetrachloride:
and Ni contents of 0.005 % to be attained, and any
SnCl2 þPb
PbCl2 þSn
remaining Fe to be removed.
Vol. 37 Tin, Tin Alloys, and Tin Compounds 21

The equilibrium is shifted to the right at low operated at low current densities, leading to low
temperatures, so that the process must be carried process rates and inefficient utilization of energy
out at a temperature only a little above the (e.g., low current yields). Also, the presence of
melting point of tin. The process also removes large amounts of expensive metal tied up in the
any remaining zinc and aluminum. process is undesirable economically.
The best results are obtained by using two- These negative aspects mean that electrore-
stage operation, i.e., the product of the second fining is only worthwhile if the tin contains high
stage, with a reduced lead content, is returned to concentrations of noble metals.
the first stage. Precise control of the operation can Electrorefining can be carried out in acid or
lead to final lead contents of 0.008 wt %. alkaline medium.

5.1.5. Removal of Bismuth 5.2.1. Electrorefining in Acid Medium

In analogy to the thermal refining of lead, bis- When sulfate electrolytes are used, additions of
muth can be precipitated as an intermetallic chloride, fluoride, crude cresol, glue, nicotine
compound by adding calcium or magnesium. sulfide, a- and b-naphthol, diphenylamine, phe-
The molar ratio Ca/Mg should be ca. 2 to obtain nol, and/or cresolsulfonic acid are made. The
the best results [46]. A ternary compound is sulfate ions cause the anodically dissolved lead
probably formed at this ratio. Under production to go into the anode slime in the form of lead
conditions, scrap magnesium is used, as this is the sulfate. Also, sulfides such as nicotine sulfide can
most economic material. lead to the formation of lead sulfide, which is
Final bismuth contents of 0.06 – 0.003 wt % deposited in the anode slime. The organic sul-
have been reported for full-scale plant. In ana- fonic acids prevent the formation of basic tin salts
logy to a technique used when removing arsenic on the anodes.
from aluminum, the calcium and magnesium In spite of these precautions, the formation of
remaining in the tin can be converted to their coatings on the anode is the main problem in the
chlorides and removed, e.g., by treatment with electrolytic refining of tin in an acid medium. The
ammonium chloride. main cause of coating formation is the lead
content of the anodes, which must be removed
mechanically when the bath voltage increases.
5.2. Electrorefining The following operational data are quoted:

The theoretical conditions for the electrorefining


Anode mass: 100 – 200 kg
of tin are favorable. The position of tin in the Anode thickness: 30 mm
electrochemical series of the elements in aqueous Cell dimensions: 3.0 – 4.5 m long, 1.0 – 1.2 m
solution show that Au, Ag, Cu, Bi, As, and Sb do wide, 1.0 – 1.5 m deep
Cell construction: wooden cells with lead cladding
not go into solution under electrorefining condi-
or concrete
tions, but will appear in the anode slime. The Cathode replacement: after 6 d
elements Ni, Fe, Zn, and Al can be largely Anode replacement: after 10 – 12 d
removed by a preliminary pyrometallurgical re- Anode composition: 94 – 96 % Sn
0.01 – 0.03 % Fe
fining operation. Only lead lies close to tin in the
0.3 – 1.3 % Pb
electrochemical series. The high electrochemical 0.1 – 0.6 % Cu
equivalent weight of tin also favors the use of an 0.1 – 3.5 % Bi
electrometallurgical refining process. However, 0.02 – 0.35 % As
0.1 – 0.25 % Sb
there are considerable problems in the practical
100 – 300 g/t Ag
realization of the process. 0.3 – 0.7 g/t Au
Simple and cheap electrolytes such as solu- Cathodes: starter sheets of pure tin
tions of sulfate or chloride lead to spongy or
needle-like deposits, and these effects are only
slightly moderated by extremely large additions The current yield is largely determined by the
of colloidal materials. The process can only be rate of removal of anode passivation. The energy
22 Tin, Tin Alloys, and Tin Compounds Vol. 37

consumption is 150 – 200 kW  h/t tin. Because in the neighborhood of metal smelting works
iron accumulates in the electrolyte, regeneration there are often small scrap metal operations
of the electrolyte is necessary. which sort, separate, refine and blend with pri-
mary metals to produce a primary metal that
corresponds to the standard specification of an
5.2.2. Electrorefining in an Alkaline original metal [87].
Medium The recovery of tin from tinplate is becoming
increasingly difficult, as the change to electro-
In alkaline medium, i.e., in NaOH or Na2S lytic methods of tinning is leading to very thin
electrolytes, less pure anodes (75 % Sn) can be coatings which sometimes diffuse into the steel
used than are used in an acid medium. A smooth sheet. The recycling of this material will continue
deposit can be obtained without addition of to be a technically and economically difficult
colloids. However, current densities are very task. Two processes are used for recovering tin
low, and the process must be carried out at 90  C. from tinplate: the alkaline electrolytic method
Detailed information about the possibilities and the alkaline chemical method.
and limitations of electrorefining, deposition be- In the alkaline electrolytic detinning of tin-
havior, deposition mechanism, and effects of plate, baskets of cleaned scrap are immersed in
additives to the electrolyte, pH, and impurities hot 5 – 10 % sodium hydroxide solution. The
are given in [4]. baskets form the anodes, and the tinned steel
sheet forms the cathodes. The tin is deposited in
the form of a sponge. As contact with atmospher-
5.2.3. Other Methods of Electrorefining ic carbon dioxide cannot be prevented, sodium
carbonate is formed, and the electrolyte bath
Many attempts have been made to use molten salt must be frequently regenerated. The lacquer
electrorefining to overcome the disadvantages of coating on the scrap tinplate is removed by
electrorefining in aqueous solutions. The elec- adding solvents to the bath or by a special
trolyte was molten CaCl2 – KCl –NaCl. Various pretreatment process. The bath is operated at a
grades of crude tin were used. The electrodes temperature of 65 – 75  C, a voltage of 1.5 V,
consisted of graphite crucibles and graphite rods. and a cathode current density of 300 A/m2.
The operating temperature was ca. 650  C, and In the alkaline chemical detinning of tinplate,
the current density 50 –200 A/dm2. Arsenic was the scrap material in perforated containers is
effectively removed (reduced from 1.5 wt % to immersed in sodium hydroxide solution. Hydrat-
0.005 wt %), and the antimony content was re- ed sodium stannate is formed according to the
duced from 0.32 wt % to 0.01 wt %. It proved equation
impossible to scale up from pilot scale to full
scale operation, mainly because of problems in Snþ2 NaOHþ4 H2 O!Na2 SnO3 3 H2 Oþ2 H2
the control of the high-temperature process [77].
The hydrogen liberated must be reacted with
an oxidizing agent; sodium nitrate is suitable.
6. Recovery of Tin from Scrap The dissolution process is accelerated by motion
Materials and Residues [1–3], [5], [11], of the container in the liquor. The detinning time
[86], [87] is 2 – 4 h, depending on the concentration and
the temperature. If sodium nitrite is used instead
Scrap materials and residues which are produced of sodium nitrate, the tin goes into solution, the
during the processing of metals to give semifin- foreign metals, e.g., lead, iron, and antimony, can
ished and finished products are usually known as be precipitated, e.g., by hydrogen sulfide, and the
‘‘new scrap,’’ while the returned old material tin can then be recovered by electrowinning.
from industry, trade, building construction, fac- Processing tin-containing alloys is easier than
tories, and consumption is known as ‘‘old scrap.’’ recovering tin from scrap tinplate. However, the
The use of old and new scrap supplements pri- tin content of many alloys has decreased over
mary production. It is collected by scrap mer- recent years, and alloys have in some cases
chants who work directly with the smelters. Also, been replaced by cheaper materials. Both these
Vol. 37 Tin, Tin Alloys, and Tin Compounds 23

developments have tended to limit the potential with hydrochloric acid and partially evaporated
for recovering secondary tin, and also explain to drive off arsenic. The antimony is then pre-
why the amount of recovered tin in Europe has cipitated with iron powder (cementation). The tin
decreased from 15 800 t in 1980 to 13 300 t in in the filtrate can then be ‘‘cemented’’ by adding
1990. In the United States, the amounts of recov- aluminum powder, and determined by iodo-
ered tin have remained almost constant at metric titration.
16 900 t in 1980 and 17 100 t in 1990 [9].
The quantification of tin recovery from sec- Tungsten-Containing Ores and Concen-
ondary raw materials is difficult because most of trates. The tungsten can be precipitated from
it is obtained from scrap alloy. the acidified solution by adding cinchonine. The
In addition to the tin concentrates treated in excess of this reagent in the filtrate is decomposed
the primary smelting process, there are also other by fuming with sulfuric acid. The solution is then
materials that must be treated, including the slags taken up in hydrochloric acid and treated as in the
(see Section 4.3.4), oxidic flue dusts, ash, and determination of tin in tungsten-free ores.
sweepings containing very variable amounts of
tin. Tin-containing processing scrap is also pro- Silicate-Containing Ores and Concen-
duced during casting, metal forming and cutting, trates. The material is boiled to dryness with
tinning, and alloying. Considerable amounts of nitric acid, and the residue is then strongly heat-
recycled scrap also come from the manufacture ed, fumed with HF/H2SO4, and fused with sodi-
of cans, tinplate, tubes, foil, pure tin articles, and um peroxide. The tin determination can then be
alloys such as solders, antifriction and bearing carried out as for tungsten-free materials.
metals, type metal, etc.
In recycling it is essential to sort tin-contain- Determination of Other Elements. The
ing materials into standard grades with exact determination of tungsten is carried out by pre-
analytical specifications so that the metallurgical cipitating with cinchonine after the fusion stage.
process can be optimized. The precipitate is strongly heated (ca. 750  C) to
Short drum furnaces are suitable for proces- form WO3, and tungsten is then determined
sing oxidic materials, although shaft kilns and gravimetrically.
reverberatory furnaces are also used. The reduc- Arsenic is determined by distilling it out of the
tion is performed by coke/coal, with added sodi- acidified solution of fused product and then
um carbonate or fluorspar as flux. The process is carrying out a bromatometric titration on the
operated in one or two stages, depending on the distillate.
material. Scrap alloys containing high propor- Antimony is determined by adding iron pow-
tions of lead, antimony, or copper are remelted to der to the acidified fusion product to precipitate
form alloys. Scrap babbitt (bearing metal) con- antimony sponge. This is dissolved in Br2/HCl,
tains zinc, which is either removed in the slag or and any arsenic still present is driven off by
selectively volatilized. Scrap solder alloys are evaporating with HCl. The antimony is purified
refined like crude tin. by reprecipitation, and determined by bromato-
metric titration.
For the determination of other elements such
7. Analysis [88] as cadmium, iron, nickel, copper, bismuth, lead,
zinc, and the noble metals, it is best to remove
7.1. Analysis of Ores and Concentrates zinc, arsenic, and antimony from the dissolved
product of a sodium peroxide fusion (acidified
Determination of Sn. In the determination with HCl) by evaporating with Br2/HBr. The
of tin in ore concentrates, the choice of method elements can be determined in the solution by
depends on the presence or absence of typical atomic absorption spectrometry.
impurities. To determine sulfur, the sample is heated in a
stream of oxygen, the SO2 formed is collected in
Tungsten-Free Ores and Concentrates. a dilute solution of H2O2, and the H2SO4 formed
After fusion with sodium peroxide and dissolu- is determined by titration. The sulfur content of
tion in water, the solution obtained is acidified the tin is calculated from this.
24 Tin, Tin Alloys, and Tin Compounds Vol. 37

7.2. Analysis of Metallic Tin and international standards for the analysis of
water, wastewater, and sewage sludge.
The preferred methods of analysis of pure and After dissolution of the tin in a mixture of Br2,
commercial-grade tin are detailed in DIN 1704 HBr, and HClO4, the accompanying antimony,
[88]. arsenic, bismuth, copper, iron, lead, aluminum,
Arsenic is determined by dissolving the metal cadmium, and zinc can be determined with a high
in a strongly acidic solution of FeCl3. The AsCl3 degree of accuracy in the presence of each other,
formed is distilled off, and can be determined without first separating them, by means of AAS
photometrically by the molybdenum blue and ICP-AES. In the determination of arsenic and
method. antimony, other dissolution processes must first
Antimony is determined by dissolving the be performed. The analysis of metallic tin and tin
metal in concentrated sulfuric acid. After adding alloys is often carried out by spectral analysis
hydrochloric acid, the antimony is oxidized with with spark or arc excitation, and the analysis of
cerium(IV) to antimony(V). This is then ex- tin slags and concentrates by X-ray fluorescence
tracted with isopropyl ether and can be deter- analysis.
mined photometrically as yellow potassium
tetraiodoantimonate.
Lead is determined by dissolving the metal in 8. Economic Aspects [2], [9], [11]
a mixture of Br2, HBr, and HClO4, fuming this to
volatilize the zinc, removing any Tl that might The amounts of tin mined, smelted, and con-
still be present by extraction with isopropyl ether, sumed in the years 1980 – 1990 are given in
and determining the lead by polarography. Table 5.
In the determination of copper, the initial Even in 1938, smelting production amounted
dissolution is similar to that used in the deter- to 171 200 t [3], and this had increased by only
mination of lead. The copper in the solution then 66 500 t or 38.8 % in 1990. This is an average
is determined photometrically as the diethyl- increase of 9.75 % per annum.
dithiocarbamate complex after extraction with Typically in the production and consumption
CCl4. of tin, the production processes of mining and
The determination of zinc also requires a smelting are geographically remote from the
dissolution process similar to that for lead. The places where the metal is consumed.
solution is acidified with hydrochloric acid, and The main producers, i.e., Brazil, Indonesia,
heavy metals still present are precipitated as Malaysia, Bolivia, and to some extent China,
sulfides. The zinc in the filtrate obtained can be consume very little tin themselves (see Table 6).
determined by polarography. On the other hand, the United States, Japan,
Iron is determined by first carrying out the Germany, and the United Kingdom produce little
dissolution and precipitation of heavy metals as or no primary tin themselves and are the main tin
for zinc determination. The iron in the filtrate can consumers. In the CIS, production and consump-
be determined photometrically as the sulfosa- tion are approximately equal.
licylic acid complex. The continuous fall in the price of tin
The determination of aluminum also requires (> 30 000 DM/t in 1985, ca. 10 000 DM/t in
dissolution and removal of heavy metals by 1990) has led to many casualties worldwide. The
precipitation of their sulfides as for iron determi- worst effects have been in Malaysia, where over
nation. The aluminum in the filtrate can be deter- 80 suppliers have been closed down. In 1980,
mined photometrically as the eriochrome cya- Malaysia was the main producer of tin, with a
nine complex. mine output of 61 000 t. This fell to 28 500 t in
As well as the analytical methods recom-
mended in DIN 1704, rapid and efficient meth- Table 5. World production and consumption of tin (in 103 t)
ods such as atomic absorption spectrometry
(AAS) and atomic emission spectrometry with Year Mining output Smelting output Consumption

inductively coupled plasma excitation (ICP- 1980 235.5 243.6 221.4


AES) are also being used to an increasing extent 1985 185.3 216.2 214.3
1990 210.7 225.6 232.7
[89]. These methods are specified in the German
Vol. 37 Tin, Tin Alloys, and Tin Compounds 25

Table 6. Mining output and consumption of tin in various countries casting. The casting methods are sometimes
1990 [9]
automated, whereby the low casting tempera-
Country Mining output Consumption tures make small demands on the material used
for the shells and molds.
in 103 t as % in 103 t as % As very thin-walled cast tin cannot always be
Brazil 39.1 18.6 6.1 2.6 produced, pressure forming methods are now
Indonesia 37.1 15.1 1.4 0.6 also widely used. For example, a circular sheet
Malaysia 28.5 14.3 3.3 1.4 can be spun over a former. This method is
Bolivia 17.3 8.2 0.4 0.2
China 35.8 17.0 18.0 7.7 especially suitable for simple rotationally sym-
Russia (CIS) 13.0 6.1 20.0 8.5 metrical items without asymmetrical surface
United States 0.1 0.04 37.3 16.0 effects.
Japan 33.8 14.5 Owing to the good forming properties of tin,
Germany 19.3 8.2
United Kingdom 3.4 1.6 10.4 4.3 other methods can also be used. For example,
stamping and extrusion present no special prob-
lems, and individual items can be produced by
forging and hammering processes.
1990, and Malaysia now produces less tin than The composition of the metal used to produce
Brazil, China, or Indonesia. Even the well-known tin articles is specified in DIN 17 810 and the
tin smelter Capper Pass in the United Kingdom materials regulation RAL-RG 683. The DIN
has ceased production, as have the tin mines in 17 810 specification is as follows:
the Altenberg region of Saxony.

Grade Sn 90–10
Material no. 2.3710
9. Tin Alloys and Coatings [1], [2], Tin min. 90 %
[11] Antimony  7%
Copper  3%
Silver  4%
Tin is one of the most important constituents of Lead max. 0.5 %
low-melting nonferrous alloys. The following Sum of others 0.3 %
important properties of the metal are exploited

1. Low melting point The lead limit of 0.5 % is imposed merely


2. Low hardness because this is technically feasible. It has been
3. Good wetting properties shown that a lead content of 2 % leads to insig-
4. Effective incorporation of foreign particles nificant releases of lead even after utensils have
5. Good compatibility with foodstuffs been kept at unusually high temperatures and for
unusually long periods of time.
Tin Utensils have been produced for over
5000 years, and well-preserved examples exist Solders. Most solders are based on the tin –
from the various epochs. lead binary system (! Lead Alloys), which has a
Tin utensils are always made of tin alloys, as eutectic at ca. 63 % tin and 183  C. The solid
the pure metal is too soft. The most important solubility of 1 – 2 % lead in tin and 13 % tin in
alloying elements are antimony, copper, and lead is not relevant to production conditions.
lead. The tin is usually melted first, and it then In solder applications, it is of great importance
readily forms alloys with pure metals, which to know what percentage of impurities can cause
have good solubility properties. To minimize problems, and, conversely, whether alloying ele-
burning, especially of antimony, master alloys ments can have a detrimental effect on soldered
are usually used. joints under certain conditions. This question is
As tin has good flow and casting properties, extremely important in the electronics industry
casting is the most important method of produc- because of the small amounts of solder used in a
ing tin articles. All the processes used in a soldered joint, and the small distances between
modern foundry are suitable. Those most often the soldered joints. The state of knowledge is as
used are sand, shell, centrifugal, and pressure die follows [11Chap. 5.8]:
26 Tin, Tin Alloys, and Tin Compounds Vol. 37
G-Cu Sn 7 Zn Pb 83 % Cu, 7 % Sn, 4 % Zn, 6 % Pb
Zinc: Visible impairment of the surface of the solder Leaded bronze
by oxide formation at 0.005 %. Recommended G-Cu Pb 5 Sn 85 % Cu, 5 % Pb, 10 % Sn
limit: 0.001 %. G-Cu Pb 15 Sn 77 % Cu, 15 % Pb, 8 % Sn
Aluminum: Impairment of adhesive bond, hot brittleness, G-Cu Pb 22 Sn 76 % Cu, 22 % Pb, 2 % Sn
and dull appearance at 0.005 %. Recommended Wrought alloys
limit: 0.001 %. Cu Sn 2 98 % Cu, 2 % Sn
Phosphorus: Increased oxidation at 0.001 %. Lower Cu Sn 6 94 % Cu, 6 % Sn
concentrations reduce oxidation in unstirred baths. Cu Sn 6 Zn 88 % Cu, 6 % Sn, 6 % Zn

It is known that other elements, such as arsenic Although the copper – tin alloys are some of
and sulfur, can have detrimental effects, but precise the oldest materials used by humans, their devel-
quantitative experimental results are not available. opment is not yet exhausted even today.
The most important development aims are
Low Friction Materials and Bronzes have improvement of mechanical properties and cor-
the following useful properties: rosion resistance, and reduction of the tin
content.
1. High mechanical strength with good electrical
conductivity Sintering Metallurgy of Bronzes. An inter-
2. Good soldering properties esting new use for tin is as an addition in powder
3. Extremely good properties as a bearing (anti- form when sintering bronze. Especially when this
friction) metal is for use as a bearing metal, economic advantages
4. Good machinability at room temperature are obtained by the addition of 4 % tin to the copper
5. Good general corrosion resistance towards powder with or without lead addition.
the atmosphere and seawater, and, in the case
of zinc-free alloys, towards stress corrosion Low-Melting Alloys are of great importance
in several technical applications. Their melting
Apart from cast articles, the most important points usually lie significantly below 150  C.
forms are wire, rolled profile, sheet, and strip. Bismuth is always an essential alloy constituent.
The material is also used in bearings and in the Their most important application areas are in
chemical industry. Its use in domestic items, e.g., mold making, safety systems for the prevention
fittings and mountings, is also considerable. The of fire and overheating, and stepwise soldering.
alloys are classified as casting alloys and wrought Melting points, compositions, and areas of use
alloys, the latter having lower tin contents. Some of typical low-melting alloys are listed in
important copper – tin alloys, as specified in Table 7.
DIN 1705/1716, are listed in the following:
Amalgams. Tin has been used for dental
fillings since the Middle Ages, and amalgams
Gunmetal since the 1800s. Subsequent developments have
G-Cu Sn 12 88 % Cu, 12 % Sn
G-Cu Sn 12 Ni 86 % Cu, 12 % Sn, 2 % Ni
led to the silver – tin amalgams used today (!
G-Cu Sn 12 Pb 86 % Cu, 12 % Sn, 2 % Pb Dental Materials, Section 2.3.2.). A typical amal-
Red bronze gam has the following composition: 52 % Hg,
G-Cu Sn 10 Zn 88 % Cu, 10 % Sn, 2 % Zn 33 % Ag, 12.5 % Sn, 2 % Cu, 0.5 % Zn.

Table 7. Melting points, compositions, and applications of typical low-melting alloys


Melting point, C Typical composition, wt % Applications

Bi Sn Pb In Cd

47 44.7 8.3 22.6 19.1 5.3 test castings, fixing lenses


58 49.0 12.0 18.0 21.0 fixing components
70 49.4 12.9 27.7 10.0 supporting components
70 – 73 50.0 13.3 26.7 10.0 tube bending, radiation protection, fixing components
96 52.0 16.0 32.0 temperature fuses
138 – 170 40.0 60.0 accurate molds, cores, gravity die casting
Vol. 37 Tin, Tin Alloys, and Tin Compounds 27

When the mixture of metals is ground toge- purposes have a strong tendency to change into
ther, the following hardening reaction takes place: tin(IV) compounds and are therefore strongly
reducing. For example, SnCl2 precipitates gold
AgSn3 þ4 Hg!Ag2 Hg3 þSn78 HgþAg3 Sn
and silver in metallic form from their salt
solutions.
The metallographic structure of a dental amal- The salts in both valency states hydrolyze in
gam consists of islands of solid undissolved aqueous solution to form insoluble salts. In alka-
particles of alloy (Ag3Sn) in a soft matrix of line media, stannites (divalent) and stannates
silver and tin amalgams. (tetravalent) are formed.

Alloy Coatings. Tin alloys are important in


the production of coatings by electroplating and 10.1. Tin(II) Compounds
hot tinning. The most important of these are
tin – zinc, tin – nickel, tin – cobalt, and tin – Tin(II) Chloride, SnCl2, is the most impor-
copper. tant inorganic tin(II) compound. It is produced on
Tin – lead coatings are mainly used for cor- an industrial scale by reducing tin(IV) chloride
rosion protection and as a preparation for solder- with molten tin, or by direct chlorination of tin.
ing. Electrolytically applied coatings must be Solutions of tin(II) chloride are obtained by
treated with hot palm oil or by infrared heating. dissolving metallic tin in hydrochloric acid, or by
This melts the coating and can prevent the for- reducing a solution of SnCl4 with metallic tin.
mation of whiskers. The anhydrous substance is white, has a
Tin – zinc coatings are increasingly replacing greasy luster, and dissolves readily in water,
the toxic cadmium coatings. alcohol, ethyl acetate, acetone, and ether. The
Tin – nickel and tin – cobalt coatings are clear, nondeliquescent, monoclinic dihydrate,
mainly used in electrical installations, e.g., to SnCl2  2 H2O, crystallizes from aqueous solu-
produce electrical connectors. tion and is the commercial product.
On dilution, the aqueous solution becomes
Additions to Alloys. Tin is increasingly cloudy as hydrolysis causes precipitation of the
used as an alloy addition in the steel industry. basic salt:
The addition of 0.1 – 0.5 % tin causes cast iron to
SnCl2 þH2 O
SnðOHÞClþHCl
solidify with a pure pearlitic structure, making it
uniformly hard and wear-resistant. The cloudiness can be prevented by small
additions of hydrochloric acid, tartaric acid, or
Sinter Metallurgy. In the sinter metallurgy ammonium chloride. Because of its strong ten-
of iron, addition of 2.5 – 5 % of a tin – copper dency to hydrolyze, the dihydrate can only be
alloy (2 : 3) gives reduced sintering temperatures dehydrated over concentrated sulfuric acid or by
and times, and in particular improves the dimen- heating in a stream of hydrogen chloride.
sional accuracy of the sintered components. Tin(II) chloride is an important industrial
reducing agent, being used to reduce aromatic
nitro compounds to amines, aliphatic nitro com-
10. Inorganic Tin Compounds pounds to oximes and hydroxylamines, and ni-
triles to aldehydes.
Consumption of inorganic tin compounds is Tin electroplating can be carried out in a fused
lower than that of organic tin compounds, but eutectic salt mixture of 20 % SnCl2 and 80 % KCl
they are often the starting materials used to at 200 – 400  C [90], [91].
produce the organic tin compounds.
In minerals, tin is nearly always tetravalent Tin(II) Oxide Hydrate and Tin(II) Oxide.
and bonded to oxygen or sulfur. The only excep- If aqueous solutions of SnCl2 or other tin(II) salts
tion is herzenbergite, SnS, in which it is divalent. are reacted with alkali metal carbonate or am-
In industry, tin(II) and tin(IV) compounds are monia, an amorphous white precipitate of tin(II)
produced from metallic tin. Many tin(II) com- oxide hydrate, 5 SnO  2 H2O, is obtained [92].
pounds which are sufficiently stable for practical Sn(OH)2 does not exist. Tin(II) oxide hydrate is
28 Tin, Tin Alloys, and Tin Compounds Vol. 37

amphoteric. Dehydration in a stream of carbon acid:


dioxide gives tin(II) oxide. Tin(II) oxide hydrate
SnCl4 þ2 H2 O!SnO2 þ4 HCl
and tin(II) oxide are starting materials for the
production of other tin(II) compounds.
In moist air, the pentahydrate, SnCl4  5 H2O,
Other Tin(II) Compounds. is formed, the so-called butter of tin, a white
deliquescent crystalline mass with a melting
Tin(II) Fluoride, SnF2, is formed from tin(II) point of 60  C. In industry, SnCl4 is produced
oxide hydrate and hydrofluoric acid, and is added by the reaction of chlorine with tin. The anhy-
to toothpastes as an anticaries agent. drous product is obtained if the metal is covered
with SnCl4. Anhydrous tin(IV) chloride is an
Tin(II) Fluoroborate Hydrate, Sn(BF4)2  n important starting material for the production of
H2O, is formed by dissolving the oxide hydrate or organic tin compounds (see Sections 11.2 and
the oxide in aqueous fluoroboric acid. Sulfuric 11.3).
acid reacts with the oxide hydrate or the oxide to Tin(IV) bromide, SnBr4, and tin(IV) iodide,
form tin(II) sulfate. Both tin(II) sulfate and tin(II) SnI4, are also obtained by the reaction of metallic
fluoroborate are important in the production of tin with the halogens. Tin(IV) fluoride is pro-
metallic tin coatings by electroplating. duced by the reaction of tin(IV) chloride with
anhydrous hydrogen fluoride:
Tin(II) Bromide, SnBr2, and tin(II) iodide, SnCl4 þ4 HF!SnF4 þ4 HCl
SnI2, are produced by reacting metallic tin with
the appropriate hydrogen halide.
Tin(IV) halides react readily with metal ha-
Tin(II) Cyanide, which is produced from bis- lides to form the halostannates(IV), the coordina-
(cyclopentadienyl)tin(II) and hydrogen cyanide, tion number of the tin increasing from four to six.
is the only known compound of tin with inorganic The reaction proceeds as follows (X ¼ halogen):
carbon:
SnX4 þ2 MX
M2 SnX6
ðC2 H5 Þ2 Snþ2 HCN!SnðCNÞ2 þ2 C2 H6
One of the best known compounds of this type
is ammonium hexachlorostannate, (NH4)2SnCl6,
The tin(II) salt of ethylhexanoic acid is an the so-called pink salt.
effective catalyst in polyurethane production. Hexachlorostannic acid, H2SnCl6  6 H2O, is
formed by passing HCl into a concentrated solu-
tion of SnCl4.
10.2. Tin(IV) Compounds
Tin(IV) Oxide, Tin(IV) Oxide Hydrate,
Tin(IV) Hydride. The toxic, colorless, and Stannates(IV). Tin(IV) oxide decomposes
flammable gas, tin(IV) hydride, is formed by the above 1500  C without melting to form tin(II)
reduction of tin(IV) chloride by LiAlH4 in diethyl oxide:
ether at 30  C. It is stable for several days at
2 SnO2 !2 SnOþO2
room temperature, and decomposes into its ele-
ments at 150  C in the absence of air, forming a
tin mirror. Pure tin(IV) oxide can be obtained by the
combustion of powdered tin or sprayed molten
Tin(IV) Halides and Halostannates(IV). tin in a hot stream of air. It is insoluble in acids
Anhydrous tin(IV) chloride is a colorless liquid and alkalis. Specially prepared tin(IV) oxide has
which fumes strongly in air. It is a good solvent many uses, total world consumption of this ma-
for sulfur, phosphorus, and iodine, and is misci- terial being > 4000 t/a. It is used in combination
ble in all proportions with carbon disulfide, al- with other pigments to produce ceramic color-
cohol, benzene, and other organic solvents. It ants. It has a rutile structure, and hence can
hydrolyzes in water, evolving much heat and absorb the colored ions of transition metals. The
forming colloidal tin(IV) oxide and hydrochloric products obtained form the basis of ceramic
Vol. 37 Tin, Tin Alloys, and Tin Compounds 29

colors, and include tin vanadium yellow, tin 11. Organic Compounds of Tin [3],
antimony gray, and chrome tin pink. The thermal [95], [96]
stability of the tin colors enables them to be used
both in and under the glaze. The organic chemistry of tin has attracted major
Electrodes made of SnO2 are used in the interest since 1945. The first organotin com-
production of lead glass [93]. They are resistant pounds were prepared in 1849 by FRANKLAND
to corrosion by molten glass, and have good and in 1852 by L€oWIG [97]. In the first technical
electrical conductivity when hot. application in 1936, the discovery of the stabi-
Coatings of tin(IV) oxide treated with indium lizing effect of these compounds on poly(vinyl
oxide (<100 mm thick) give good transparency chloride) was utilized. The biocidal properties of
properties to aircraft window systems, increase other organotin compounds have been known
their strength, and give protection from icing. since ca. 1950.
If tin(IV) oxide is reacted with a solution of Only the organic compounds of tetravalent tin
alkali, or a solution of stannate is reacted with are used in industry.
acid, a white, gel-like precipitate of tin(IV) oxide Most organotin molecules contain a single tin
hydrates is formed which are very soluble in atom with 4 substituents. They are classified
alkalis and acids. This precipitate was formerly according to the number of direct tin-carbon
known as ‘‘a-stannic acid’’, and the aged product, bonds: R4Sn, R3SnX, R2SnX2, RSnX3.
which is sparingly soluble, as ‘‘b-stannic acid’’ Here, R denotes any hydrocarbon group and X
(metastannic acid). Today, this product is re- denotes a group such as a halide, OH, OR, SR,
garded as tin(IV) oxide hydrate with the formula acid group, etc. Most of these compounds are
SnO2  n H2O, where n decreases with aging. colorless liquids at room temperature or slightly
The reaction of powdered or granulated tin above. They are very soluble in organic solvents
with concentrated nitric acid leads to the forma- but sparingly soluble in water.
tion of the reactive b-tin(IV) oxide hydrate. This Organotin compounds have a very wide range
can be used as a catalyst for aromatics. of applications, depending on their type, includ-
The b-tin oxide hydrate gels precipitated from ing the stabilization of PVC, catalysis, crop
SnCl4 by ammonia and then dried are stable protection, and wood preservation. Also, for
towards nuclear radiation, and can be used in some time, various organotin compounds have
chromatographic columns for separating radio- been increasingly used as laboratory chemicals,
active isotopes [94]. especially organotin alkoxides and hydrides.
Fusion of tin(IV) oxide with alkali metal These are used as synthesis auxiliaries and as
hydroxides leads to formation of alkali metal mild and selective reducing agents.
hexahydroxystannates according to the follow- Organotin compounds do not occur in nature.
ing reaction scheme (M ¼ alkali metal):

SnO2 þ2 MOHþ2 H2 !M2 ½SnðOHÞ6 


11.1. Properties of Organotin
The sodium and potassium complexes are Compounds
used as alkaline electrolytes in electrolytic tin
plating. Under the influence of light, atmospheric oxy-
Tin(IV) sulfide, SnS2, is formed as golden gen, or certain microorganisms, organotin com-
yellow flakes with a hexagonal crystal structure pounds are degraded in a relatively short time,
by passing hydrogen sulfide through a weakly the hydrocarbon groups being split off to leave
acidic solution of a tin(IV) salt. On heating, the behind nontoxic inorganic products. Although
crystals become dark red to almost black, revert- both the tin – carbon bond (average dissociation
ing to yellow on cooling. energy 209 kJ/mol) and the tin –oxygen bond
The tin disulfide known as ‘‘mosaic gold’’ is (average dissociation energy 318 kJ/mol) are
produced industrially by heating tin amalgam reactive, they are sufficiently stable for general
with sulfur and ammonium chloride. It is used handling purposes.
for gilding picture frames, and in painting to The symmetrical tetraalkyltin compounds
produce deep yellow to bronze color shades. have a very slight odor. They are colorless, form
30 Tin, Tin Alloys, and Tin Compounds Vol. 37

monomolecular solutions, are fairly stable to- sponding organotin chlorides are obtained:
wards water and air, and can be distilled without
decomposition at < 200  C. Their solubilities SnR4 þ1=3 SnCl4
4=3 R3 SnCl
and boiling points are similar to those of the
branched chain paraffins with similar molecular SnR4 þSnCl4
2 R2 SnCl2
mass; the higher homologues are waxy sub-
stances. SnR4 þ3 SnCl4
4 RSnCl3
The symmetrical tetraaryltin compounds
are stable towards air and water and are also
The production of triorganotin chlorides and
colorless. They melt at temperatures above
diorganotin dichlorides proceeds smoothly ac-
150  C.
cording to this reaction. Monoorganotin trichlor-
The organotin hydrides, with the exception
ides can only be obtained in a few cases where
of some aryl tin hydrides which are solid at
R ¼ acryl or vinyl and in special solvents or with
room temperature, are colorless, nonassociated
catalysts.
liquids which are rapidly attacked by oxygen
and therefore can only be prepared and stored
under inert gas. They are important reducing Direct Synthesis of Organotin Chlorides from
agents. Tin. Organotin chlorides can be obtained by di-
The organotin fluorides, the diorganotin rect reaction of tin with unsaturated organic com-
dihalides, and the aromatic organotin mono- pounds and hydrogen halides (ester tin process) or
halides are solids at room temperature, while from organic halides (catalytic direct process).
the aliphatic organotin monohalides and triha-
lides are liquids. The higher triorganotin deri- Ester Tin Process for the Production of Tin
vatives have a broad biocidal effect on micro- Carboxylic Acid Derivatives from Tin. Unsatu-
organisms such as fungi, bacteria, and harmful rated organic compounds, such as esters of
waterborne organisms such as algae, tube substituted or unsubstituted acrylic acid, acrylo-
worms, shellfish, etc. The most active com- nitrile, or vinylphosphoric diesters, react with
pounds are the tributyl-, trichlorohexyl-, and metallic tin and hydrogen chloride in a polar
triphenyltin compounds. medium (ethanol, concentrated hydrochloric ac-
The di- and monoorganotin derivatives in id, or diethyl ether) to form the so-called ester tin
which methyl, butyl, and octyl groups are bonded compounds, e.g., bis(2-methoxycarbonylethyl)
to the tin stabilize polymers sensitive to light and tin dichloride [98].
temperature such as PVC if the tin is bonded via
oxygen or sulfur to certain other groups. Catalytic Production of Organotin Halides
from Tin. Organotin halides can be produced
discontinuously or continuously from metallic
11.2. Production of Organotin tin and organic halides with the aid of catalysts at
Compounds elevated temperatures. The most effective of
these catalysts are the tetraalkylammonium ha-
Tetraorganotin Compounds from Tin Tetra- lides, tetraalkylphosphonium halides, and other
chloride and Organometallic Compounds. Tin derivatives of N, P, As, or Sb.
tetrachloride is the key substance for the produc-
tion of organotin(IV) compounds. In industry, Production of Organotin Trichlorides by Ad-
the tin tetrachloride is first alkylated with organic dition of Tin Dichloride and Hydrogen Chlo-
compounds of magnesium, aluminum, or sodium ride. The unsaturated starting compounds suit-
to form tetraorganotin compounds. The process able for the ester tin process, when reacted with
is usually continuous. tin(II) chloride and hydrogen chloride, form the
corresponding organotin trichlorides, e.g., (2-
Organotin Chlorides from Tetraorganotin methoxycarbonylethyl)tin trichloride [99].
Compounds and Tin Tetrachloride. If tetraor-
ganotin compounds are reacted with stoichio- Production of Unsymmetrical Organotin
metric amounts of tin tetrachloride, the corre- Compounds by Addition of Organotin Hydrides
Vol. 37 Tin, Tin Alloys, and Tin Compounds 31

(Hydrostannation). Unsymmetrical tetraorga-


(CH3)2Sn[SCH2COOC5H10CH(CH3)2]2 75 %
notin compounds that may contain functional or
CH3Sn[SCH2COOC5H10CH(CH3)2]3 25 %
unsaturated groups in the alkyl groups can be
synthesized by addition of organotin hydrides to
alkenes and alkynes. The reaction is favored by
radical formers and UV light. Butyl Compounds. Tetrabutyltin, (C4H9)4Sn,
can be converted to tributyltin chloride,
Conversion of Organotin Chlorides to other (C4H9)3SnCl, and this can be converted to bis
Halides or Derivatives with Heteroatoms via (tributyltin) oxide, (C4H9)3SnOSn(C4H9)3, by
Organotin Oxides. The organotin chlorides are treatment with NaOH. This product, which is
quantitatively converted into organotin oxides in insoluble in water and miscible with industrial
alkaline medium: solvents, is moderately toxic. It is an active
biocide with many uses. For example, it is used
2 R3 SnCl!ðR3 SnÞ2 O as an antifouling paint for ships, for the preven-
tion of slimes in industrial recirculating water
R2 SnCl2 !1=nðR2 SnOÞn systems, for combating freshwater snails that
cause bilharzia, as a wood and textile preserva-
RSnCl3 !1=nðRSnO1:5 Þn tive, and as a disinfectant.
The readily interconvertible compounds di-
In acid media, many organotin compounds, butyltin chloride (C4H9)2SnCl2 and dibutyltin
e.g., fluorides, bromides, iodides, pseudohalides, oxide [(C4H9)2SnO]n (a polymeric powder) are
carboxylates, thiolates, etc., are obtained from the starting substances for the production of the
the organotin compounds: most common PVC stabilizers, i.e., the liquid
dibutyltin dilaurate (C4H9)2Sn(OCOC11H23)2,
ðR3 SnÞ2 !2 R3 SnX the polymeric solid dibutyltin maleate
[(C4H9)2SnOCOCH¼CHCOO]n, the liquid di-
1=nðR2 SnOÞn !R2 SnX2 butyltin bis(isooctylmaleate) (C4H9)2Sn
[OCOCH ¼CHCOOC5H10CH(CH)3]2, and the
1=nðRSnO1:5 Þn !RSnX3 liquid dibutyltin bis(thioacetic acid isooctyl es-
ter) (C4H9)2Sn[SCH2COOC5H10CH(CH3)2]2.
X ¼ halogen or other functional group
Octyl Compounds. The stabilizers used in
These transformation reactions are of indus- the production of PVC film for the foodstuffs
trial importance, as they enable the sensitive industry, i.e., the liquid octyltin(thio)acetic acid
organotin compounds to be converted into orga- isooctyl esters with the formulas (n-C8H17)2Sn
notin oxides that are insoluble in water, stable to [SCH2COOC5H10CH(CH3)2]2 and n-C8H17Sn
air, easily transported, and storable for long [SCH2COOC5H10CH(CH3)2]3 are produced
periods. These can then be used to produce either from isooctyl mercaptoacetate and dioctyltin
the original organotin oxides or other organotin dichloride (C8H17)2SnCl2 or octyltin trichloride
compounds when required. C8H17SnCl3, respectively.

Cyclohexyl Compounds. Tricyclohexyltin


11.3. Industrially Important hydroxide (cyclo-C6H11)3SnOH is obtained by
Compounds alkaline hydrolysis of tricyclohexyltin chloride
(cyclo-C6H11)3SnCl. It is a colorless, crystalline
A few typical examples of the many applications substance, insoluble in water, and has a very
of organotin compounds are described here. marked acaricidal action, attacking many mites
and acarides, thereby protecting plants and use-
Methyl Compounds. A legally permitted ful insects. It is the main component of the
stabilizer for PVC used with foodstuffs is pro- commercial product Plictran (Dow Chemical),
duced from dimethyltin dichloride and methyltin which is used in fruit growing, viticulture, and
trichloride. It consists of: greenhouses.
32 Tin, Tin Alloys, and Tin Compounds Vol. 37

Phenyl Compounds. The phenyl deriva- 12. Toxicology


tives of tin are used as fungicides, e.g., for the
treatment of potato rot and leaf spot in root Metallic tin is generally considered to be non-
tubers. Typical compounds are triphenyltin hy- toxic. As early as the Middle Ages, it was used in
droxide, (C6H5)3SnOH (Du Ter, Philips- the form of plates, jugs, and drinking vessels.
Duphar), and triphenyltin acetate, (C6H5)3SnO- Even large amounts of tin salts in the digestive
COCH3 (Brestan, Hoechst). system cause negligible harm. Apparently, tin
can migrate only very slowly through the intesti-
nal walls into the blood. Orally ingested tin is
11.4. Analysis of Organotin
poorly resorbed by animals and humans. The
Compounds half-life in the kidneys and liver is 10 – 20 d,
and in the bones 40 – 100 d. Cases of poisoning
The analysis of organotin compounds is a complex are almost unknown. Massive inhalation of tin or
field. Methods used are described in detail in [100]. tin oxide dust by exposed industrial workers can
In the determination of individual organotin lead to irritation of the respiratory tract. In ex-
compounds by gas chromatography, it is first treme cases, metal fume fever with similar symp-
necessary to convert the organotin halides or toms to those of ‘‘zinc fever’’ or ‘‘brass fever’’
oxides into unsymmetrical tetraorganotin com- also occurs. As the peroral ingestion of tin and its
pounds by methylation or butylation with inorganic compounds is comparatively harmless
Grignard reagents [100]. because of the relatively low resorption, the limit
value for the prevention of sickness and diarrhea
11.5. Storage and Shipping of for fruit conserves is ca. 250 – 500 mg/kg, and
Organotin Compounds for fruit juices 500 – 1000 mg/kg. In current
industrial practice, the tin cans are additionally
Organotin compounds are stored and transported lacquered, and the tin concentrations in preserved
in drums and vessels of steel sheet coated on the fruit and vegetables are < 250 ppm. The MAK
inside with a special paint. In the case of solids, the value, calculated as tin and measured in total dust,
emission of hazardous dust can be prevented by has been 2 mg/m3 for many years [101], [102].
incorporating these products in paste formulations. Hydrochloric acid formed by the hydrolysis of
tin chloride can cause acid burns. Tin hydride is
very toxic, having a similar effect on the human
11.6. Pattern of Production and organism to arsine [103].
Consumption Organotin compounds are very toxic; the
MAK value is 0.1 mg/m3 [102]. These com-
World production of organotin compounds was pounds can differ widely in their effects, and
ca. 50 t/a in 1950, 35 000 t/a in 1981, and can also be slowly converted to other compounds
40 000 t/a in the mid-1990s. The tin content of in the organism, so that toxic symptoms can
these materials is ca. 25 %. change during the induction time. The toxicity
In the main producing and consuming areas – of alkyl and aryl tin compounds decreases in the
United States, Western Europe, and Japan – 76 % series: trialkyl > dialkyl > tetraalkyl > mono-
of the organotin compounds are used as stabili- alkyl compounds. Whereas tributyl- and triphe-
zers for PVC, 10 % as antifouling biocides, 8 % nyltin compounds are almost as toxic as HCN,
as agricultural biocides, and 5 % as catalysts for the monoalkyl compounds have a toxicity similar
the production of polyurethanes and silicones. to that of the inorganic tin compounds.
The main producers of organotin compounds The resorption of tin alkyl and tin aryl com-
are: pounds can have harmful effects on the CNS,
such as edema of the brain and spinal cord and
United States: M & T Chemicals, Thiokol-Charstal, and damage to the respiratory center. The volatile
Interstab (Akzo) organotin compounds cause persistent head-
Japan Hokko Chemical Industries, Yoshitomi aches, epileptiform convulsions, narcosis, and
Pharmaceutical Industries, Nitto Kasei, and respiratory paralysis.
Somkyo Organic Chemicals
Europe Schering, Akzo Chemie, and Ciba-Geigy Dibutyltin dichloride, tributyltin chloride, and
analogous alkyl tin halides, after a latent period,
Vol. 37 Tin, Tin Alloys, and Tin Compounds 33

cause irritation and burning of the skin and espe- 25 H. Breuer, Gl€ uckauf Forschungsh. 42 (1981) 213.
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86 Winnacker-K€ uchler, 3rd ed., 6. M. N. Gitlitz, M. K. Moran: ‘‘Tin Compounds’’, Kirk Othmer
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