3.

12 Corrosion of Tin and its Alloys

S. B. Lyon
Corrosion and Protection Centre, School of Materials, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK

This article is a revision of the Third Edition article 4.6 by S. C. Britton, volume 1, pp 4:157–4:167,
ß 2010 Elsevier B.V.

3.12.1 Introduction 2068

3.12.1.1 Physical Properties 2068
3.12.1.2 Applications 2069
3.12.2 Electrochemistry 2070
3.12.2.1 Thermodynamics 2070
3.12.2.2 Dissolution 2071
3.12.2.3 Passivation 2071
3.12.3 Corrosion and Oxidation 2072
3.12.3.1 Atmospheric Corrosion 2072
3.12.3.1.1 Oxidation in dry air 2072
3.12.3.1.2 Corrosion in humid air 2072
3.12.3.1.3 Atmospheric corrosion products 2072
3.12.3.2 Corrosion in Acid 2073
3.12.3.2.1 Mineral acids 2073
3.12.3.2.2 Organic acids 2073
3.12.3.3 Corrosion in Near-neutral Conditions 2073
3.12.3.4 Corrosion by Alkalis 2073
3.12.3.5 Corrosion in Foodstuffs 2074
3.12.3.6 Galvanic Corrosion 2074
3.12.4 Applications 2074
3.12.4.1 Tin Coatings 2074
3.12.4.2 Solders 2075
3.12.4.3 Tin Interconnections 2076
3.12.4.4 Bearing Metals 2076
References 2077

Glossary Abbreviations
Allotropy The existence of two or more different AES Auger electron spectroscopy
forms (allotropes) of the same element that SHE Standard hydrogen electrode
are bonded in a different manner; allotropes XPS X-ray photoelectron spectroscopy
are thus different structural modifications of
an element.
Gray tin The low-temperature allotrope of tin
having a cubic structure that is stable below 3.12.1 Introduction
13  C. Note that the transformation from 3.12.1.1 Physical Properties
white tin to gray tin is sluggish and generally
does not proceed significantly until the The element tin is located in Group VI of the
temperature is well below 0  C. periodic table, lying above lead, with which it shares
White tin The high temperature allotrope of tin many properties. Tin, like lead, is one of the metals
having a body centered tetragonal structure known from antiquity and highly prized for its abi-
that is stable above 13  C. lity to harden copper, forming bronze. There is evi-
dence that tin was mined in the United Kingdom in

2068
 Corrosion of Tin and its Alloys 2069

Cornwall from the early bronze age (2100–1500 BC). Given increasing health and safety concerns that
Certainly, by Roman times, tin from the western edge lay severe limits on the use of lead in materials, there
of Europe (mainly Cornwall and Spain) was traded has been, for some time, a legislative driver for the
widely throughout the known world. Tin ore development of essentially lead-free tin alloys. This
resources are not widely distributed and production has reintroduced problems relating to the formation of
is mainly from two forms: (1) hard rock, typified by gray tin (at lower temperatures) and tin whiskers that
the Cornish deposits and similar ore bodies in Bolivia were generally absent in lead-containing materials. For
and Queensland; and (2) alluvial (placer) deposits, example, in the electronic industry, where tin-based
typified by the southeast Asian ore field stretching solders are now widely used, whisker growth, in par-
from Indonesia and Malaysia to Thailand. ticular, can cause problems such as short-circuiting.7
Tin is allotropic with the normal, metallic (b)
form being body-centered tetragonal above the
3.12.1.2 Applications
transformation temperature, that is, 13.2  C.1 The
lower temperature allotrope, a or ‘gray’ tin, is cubic The industrial use of tin is limited by its low strength
and forms with a significant volume change that and very limited solubility for most elements at room
tends to result in the disintegration of the material. temperature. However, tin is essential in a number of
However, the transformation is kinetically sluggish, alloys where it is a minor constituent (e.g., in copper–
although it can be encouraged by mechanical defor- tin bronzes) and also where it is the major component
mation and delayed, or effectively suppressed to (e.g., in pewter). The most important forms in which
lower temperatures, by impurities such as antimony, tin is used are
lead, and bismuth.2 Gray tin normally appears as
1. tin of more than 99% purity for specialist
nodules of a friable material on the surface of the
applications;
metallic form and resembles a corrosion product.
2. tin hardened by additions of 1–2% Cu or Sb;
Thus, the transformation is often not readily distin-
3. pewter with 90–95% Sn, 4–8% Sb, and 1–2% Cu;
guishable from corrosion.3 The transformation mecha-
4. coatings for other metals, which may be pure tin or
nism has been studied by high-resolution electron
tin plus a codeposited species;
microscopy in order to obtain the lattice orientation
5. soft solders with tin and lead in all proportions;
relationship between the two allotropes.4 Thus, the
6. lead-free soft solders with >90% Sn and additions
(011) plane of gray tin is parallel to the (001) plane
of silver, copper, bismuth, indium, or zinc;
of white tin, and the [211] direction of gray tin is nearly
7. bearing metals ‘high tin’ and ‘head lead’ with a
parallel to the [010] direction of white tin. This evi-
wide range of proportions of tin, antimony, copper,
dence supports a model for the a-to-b transformation
and lead, or with tin (5–30%) in aluminum;
that is partly martensitic and partly diffusional.
8. diecasting alloys containing 70–80% Sn with anti-
The use of unalloyed tin is restricted by its low
mony, copper, and lead, either one of them or a
melting point (232  C) and by its low tensile strength
combination.
(15 MPa). On the other hand, its melting point, and
its ability to ‘wet’ other metals (often by the forma- The corrosion behavior of tin and tin alloys, what-
tion of intermetallic compounds), facilitates its use as ever their form, is basically similar, except in the case of
solder (for metal joining) and as a coating (for corro- solders and bearing metals where the wide composition
sion protection), while its softness and high ductility range and special duties of the materials give particular
make it suitable for cold working and for bearing issues. The impurities likely to be present in nominally
applications. Given its relatively low melting point, pure tin are unlikely to affect its corrosion resistance,
tin recrystallizes readily at room temperatures, and except for minor effects on the rate of oxidation in air.
therefore, the effects of mechanical working are slight Low aluminum contents, however, may result in a
and arise from the differences in grain size and not severe intergranular attack by water; the addition of
from the effects of work hardening. The formation of antimony counteracts this effect. Although 0.1% mag-
tin whiskers is also thought to be a consequence of its nesium appears to be tolerable, larger amounts pro-
low melting point, which results in the growth of fine duce effects similar to those of aluminum.8
threadlike structures, typically 1–2 mm in diameter, Apart from the special uses in solders and bearings
with growth rates of up to millimeters per month metal already referred to, and as coatings, tin and its
under appropriate conditions.5,6 alloys find employment where we can take advantage
2070 Non-Ferrous Metals and Alloys

of their physical properties and their fair resistance to because of the stability of tin (IV) oxide, SnO2, which
tarnish and corrosion in near-neutral environments. is stable at a lower pH than is PbO. However, tin will
Tin has traditionally been used in many food-grade dissolve as Sn2+ ions at pH < 2 and as the cor-
applications, although such applications nowadays responding (II)- or (IV)-valent oxy-anion species at
increasingly use cheaper materials, such as stainless pH > 11. Note, however, that in regions where, as
steels and polymers. Tin pipe can be used to con- shown in the diagram, the dissolution of tin is possible,
dense steam for high-purity distilled water, as a the rate of corrosion may be very low. This is because
conveyor of beer and soft drinks, especially in coils the overpotential for hydrogen evolution on tin is
through cooling media, and, in a larger size, as organ high, particularly in acid solution. Thus, in a range
pipes. Some pharmaceutical and food products are of concentrations of H2SO4,9 the exchange current for
packed in collapsible tin tubes, and tinfoil coverings the hydrogen evolution reaction was found to
are used on cork wads for jar and bottle closures. The be 10 11 A cm 2 with a Tafel slope of 0.118 mV per
tin alloy pewter is most valued for the decorative decade current, indicating that a one-electron transfer
forms into which it is easily worked or cast, but it is reaction was rate controlling. In KOH solutions,10 the
also used for making drinking vessels and dishes. exchange current was higher, 3  10 6 A cm 2, while
the Tafel slope was similar to that in acid, 0.120 mV
per decade current. Consequently, in alkaline or
3.12.2 Electrochemistry moderately acid solutions free from oxygen or oxidiz-
ing agents, the corrosion of pure tin may be barely
3.12.2.1 Thermodynamics
detectable unless the tin is in contact with another
The Pourbaix diagram for tin, Figure 1, refers only metal that has a lower overpotential (higher exchange
to solutions in which the formation of soluble tin current density) for hydrogen evolution.
complexes (e.g., with citric acid) does not occur. Tin The passivity of tin in the middle pH range (i.e.,
is a slightly active metal with its domain of stability between 3 and 10), its solubility in acids or alkalis
below that of the hydrogen equilibrium; in theory, it (modified by the high hydrogen overpotential), and
will corrode in acid, evolving hydrogen gas. It is more the formation of complex ions (especially with
noble than iron and nickel, but slightly less noble organic acids) are the bases of its general corrosion
than lead, although in practice, passivity will alter behavior. Other properties that have influenced
this sequence. Tin shows a wide range of passivity the selection of tin for particular purposes are the

Sn–H2O system at 25 ⬚C
2.0

1.5

1.0 SnO2

Sn(OH)6(–2a)
0.5
Eh (V)

0.0
Sn(+2a)
–0.5

Sn(OH)3(–a)
–1.0

–1.5 Sn

–2.0
0 2 4 6 8 10 12 14
pH
5
Figure 1 Pourbaix (E–pH) diagram for tin in water at a dissolved concentration of 10 M tin species. Reproduced from
HSC: Chemistry, version 6.12, Outotec Research Oy, Finland, 2007.
 Corrosion of Tin and its Alloys 2071

low toxicity of tin salts (that permit the use of tin in the formation of SnO2 as a passive film is one of the
food-grade applications) and the absence of catalytic reasons for the excellent corrosion resistance of tin in
promotion of oxidation processes that may cause noncomplexing aqueous environments.
changes in oils or other neutral media affecting In 4–8 M sulfuric acid, passivity is consistent with
their quality or producing corrosive acids. thin films of stannous oxide (SnO); SnO2 only formed
at significantly more positive potentials.12 Passive
films on tin corroded at the open circuit potentials
3.12.2.2 Dissolution
in 6.7 M nitric acid, 5.7 M hydrochloric acid, and
The electrochemistry of tin was extensively reviewed 9 M sulfuric acid were analyzed using Mössbauer
by Stirrup and Hampson in 1977.11 As can be seen spectroscopy and found to consist of hydrated SnO2,
from the Pourbaix diagram, tin shows passivity by Sn4(OH)6Cl2, and SnSO4, respectively.14
virtue of the formation of Sn(IV) oxide (SnO2), over Passive films on tin were studied using infrared
an extended pH range from about 3 to above 10. Also, and surface-enhanced Raman spectroscopy.15 In 0.1 M
as previously indicated, the dissolution kinetics are NaOH solution, Sn(OH)4 was found to dominate, and
slow, especially in acid, by virtue of a low exchange further exposure to dry air was found to dehydrate the
current density for hydrogen evolution. film to SnO2, with the evidence of only a small amount
At potentials just above its reversible value, tin of SnO. The passive film on 0.15 M NaCl solution
dissolves under anodic polarization in acids initially (near-neutral) was found to consist only of Sn(OH)4.
as stannous ion (Sn2+). In 4–8 M sulfuric acid, this However, angle-resolved X-ray photoelectron spec-
reaction has a Tafel slope of close to 40 mV per troscopy (XPS) was used to develop a model for the
decade current, indicating a two-electron transfer passive film on tin in 0.1 M KOH, and it was found that
reaction with a probable bisulfate ion intermediate.12 tin hydroxide was present only in the outer layers of the
The stannous ion is unstable in water at most values film. The inner layer consisted of SnO2, with the evi-
of pH (except in acid concentrations typically >1 M), dence of SnO adjacent to the metal–oxide interface.16
and at low concentrations, is hydrolyzed giving This appears to be consistent with results from phos-
a number of species, depending on pH: SnOH+, phate buffer solutions (pH 4.3) where Sn(OH)4 was
Sn(OH)2, Sn(OH)3 , etc.; at higher tin concentra- found along with a reduced species, either Sn(OH)2
tions, the complex species Sn2(OH)2+ 2 and Sn(OH)4
2+
or SnO, at the metal–oxide interface.15 An electro-
13
are prevalent. The hydroxide complexes are well chemical study of the anodic oxidation of tin was per-
known to react with halides to give a number of formed in carbonate–bicarbonate buffer solution at pH
Sn(II) hydroxy–halide complexes; however, these 8.9. From 0.1 to 1.2 V (SCE), tin exhibited an essen-
are only present in solution when the halide con- tially potential-independent, steady-state, passive cur-
centration is >10 3 M and at pH values <4. In alka- rent, which was found to be independent of flow
line conditions, tin initially dissolves as stannite ion, conditions.17 The results indicate that the anodic film
Sn(OH)3 , which is subject to the same speciation as a grows according to the Mott–Cabrera model and is an
function of pH, as indicated earlier. oxygen ion conductor. Finally, the electrochemical
At higher potentials, Sn(II) is universally oxidized passivation of tin was studied in citric acid buffer at
to Sn(IV) species. There are very little experimental pH 6.18 Prepassivation was found to occur along with
data on this reaction; however, Sn(II) to Sn(IV) oxi- Sn(II) and Sn(IV) species, while full passivation was
dation was studied in strong sulfuric acid and found associated with Sn(IV) species only. The results indi-
to have first-order kinetics with respect to the dis- cated that, although the initial film formed coincided
solved species; an increase in H+ ion concentration mainly with Sn(OH)4, this transformed at longer peri-
decreased the reaction rate, while an increase in ods of time to the more thermodynamically stable SnO2
SO24 had the opposite effect. species.
In summary, tin is found to passivate in aqueous
environments from below pH 1 to above pH 12,
3.12.2.3 Passivation
forming an oxide film that consists of Sn(OH)4 or
Over the majority of the pH range, the passive film is SnO2. The latter oxide, which is more stable, may
generally assumed to consist of Sn(OH)4 or SnO2; form either initially or transform gradually with
however, in view of its very low solubility, data for time from the hydroxide. It is likely that a thin layer
the speciation of tin (IV) oxides and hydroxides of Sn(II) species is stable at the interface between the
in aqueous environments are very sparse. Indeed, passive film and the metal, although films consisting
2072 Non-Ferrous Metals and Alloys

predominantly of Sn(II) species are not observed 6 weeks, and although the use of soap was necessary
except in high concentrations of the reducing acid. thereafter, almost a complete preservation of reflectiv-
ity was achieved.
The impurities ordinarily present in the atmo-
3.12.3 Corrosion and Oxidation sphere do not appreciably affect the character of
corrosion. No tarnishing effect is exerted by hydrogen
3.12.3.1 Atmospheric Corrosion
sulfide, sulfur dioxide, and other acids in low concen-
3.12.3.1.1 Oxidation in dry air trations, including formic, acetic, and other organic
Oxidation of tin in dry air is slow; the metal remains acids, which, when evolved from wood or insulating
bright and interference colors are not developed materials, are very often destructive to metals other
below 180  C. On a rolled tin surface heated in than tin, in the confined spaces of electrical equipment
air,19,20 the thickness of the oxide grew according to or of packages. Chlorides accelerate corrosion and
the logarithmic law at temperatures of up to 160  C tend to form a white corrosion product containing
and according to the parabolic law at higher tem- oxychloride. The presence of some impurities, notably
peratures, for which the oxide was identified as SnO. zinc, in the metal may cause tarnishing and a loss
For electropolished tin heated in oxygen at pressures of brightness in atmospheres containing SO2.29 The
of 130 N m 2 and above, three stages of oxidation corrosion rate of electroplated tin on nickel in the
were observed at temperatures of up to 220  C:21–24 presence of sub-ppm amounts of either SO2 or NOx
did not increase. However, a synergetic effect was
1. an initial sigmoid growth curve during nucleation;
found with both pollutants where the corrosion rate
2. a logarithmic growth curve when cavities acted as
was increased significantly.
diffusion barriers;
The atmospheric pollution prevailing in special
3. erratic behavior caused by random film rupture.
industrial or laboratory locations may induce more
The oxide formed was identified as SnO at tem- severe corrosion, for example, the vapors from con-
peratures down to 75  C. However, a mixture of SnO centrated hydrochloric or acetic acid will etch tin,
and SnO2 is formed in dry air at lower temperatures, and moist sulfur dioxide will produce a sulfide tar-
and in humid air, at temperatures of at least 100  C.25 nish, as will hydrogen sulfide at temperatures of
The electrochemical reduction analysis on tin oxidized above 100  C, and halogens attack tin readily.
in dry air at 125 and 150  C confirmed the presence of When tin is fully exposed out of doors, corrosion is
SnO with a thin surface layer of SnO2.26,27 Small addi- uniform, and the rate falls only slightly with time.
tions, for example, 0.1%, of indium, zinc, or phospho- The metal becomes dull and accumulates a compact
rus reduce the rate of oxidation, and the addition of layer of pale gray product, mainly stannous oxide.
antimony, thallium, or bismuth accelerates it.24 Rates observed during exposures in the United States
for periods of up to 20 years were 1.3–1.8 mm year 1
3.12.3.1.2 Corrosion in humid air in industrial atmospheres (i.e., mainly polluted with
In the absence of polluting gases or dusts, increasing sulfur dioxide), 1.8–2.8 mm year 1 in marine atmo-
relative humidity tends to increase the rate of oxida- spheres (i.e., mainly polluted with sea-salt), and less
tion28 and may cause the development of interference than 0.5 mm year 1 in rural atmospheres (i.e., rela-
colors. In an ordinary atmosphere, some corrosion tively unpolluted).30
product may be formed over time. However, tin pro-
ducts are not hygroscopic, and tin is not attacked at 3.12.3.1.3 Atmospheric corrosion products
relative humidities of below 100% unless the dust The corrosion of tin in various humid atmospheres
falling on the surface is hygroscopic, or impurities in has been examined using a number of surface analyt-
the metal are able to form a hygroscopic product. ical techniques, including XPS and Auger electron
Indoors, in an unpolluted laboratory atmosphere, a spectroscopy (AES).25,31,32 While it is difficult to
gray film, increasing in weight linearly with time (4 mg resolve the peaks of the oxide from those of the
m 2 day 1), is formed, while in sheltered exposure (no hydroxide, and hence, to establish their degree of
rain) outdoors, the corrosion rate declined with time. surface hydration, there is a general agreement that
The reflectivity of the surface is slowly lost if it is left both SnO and SnO2 may be present depending on the
untouched, but may be preserved by regular washing; temperature of exposure.
in one experiment, when the surface was washed at In atmospheres polluted with >100 ppm nitrogen
intervals of 3 weeks, a water wash was adequate for dioxide, tin nitrate was reported to form at 30–35%
 Corrosion of Tin and its Alloys 2073

RH.33 In a mixed atmosphere containing more rep- 3.12.3.3 Corrosion in Near-neutral

resentative atmospheric conditions (40 ppb H2S, Conditions
350 ppb SO2, 500 ppb NO2, and 3 ppb Cl2) at 81%
Pure tin is completely resistant to distilled water, hot
RH, only tin oxides were found.34 An XPS study on
or cold. Local corrosion occurs in salt solutions that do
the films formed in SO2 and NOx found only oxide
not form insoluble compounds with stannous ions (e.g.,
species in SO2, but a mixture of oxides and nitrates
chloride, bromide, sulfate, nitrate), but is unlikely in
with NOx. No synergy was noted between at-ppm
solutions giving stable precipitates (e.g., borate, mono-
concentrations of SO2 and NOx at 85% RH.35
hydrogen phosphate, bicarbonate, iodide).40 In all
solutions, oxide film growth occurs and the potential
3.12.3.2 Corrosion in Acid of the metal rises. Any local dissolution may not begin
for several days, but once it has begun, it will continue,
3.12.3.2.1 Mineral acids
its presence being manifested at first by small black
As the high overvoltage restricts hydrogen evolution,
spots and later by small pits. The movement of the
corrosion in organic acids or dilute nonoxidizing
solution tends to prevent pitting; stagnation, especially
mineral acids is generally controlled by the rate
in crevices where the tin touches another solid surface,
of supply of oxygen.2,3 In solutions of acid open
favors its progress. Contact with a more noble metal
to air, with specimens of size 50  20 mm com-
such as copper or nickel increases the number and
pletely immersed, corrosion rates were, in a range
intensity of pits; contact with metals such as aluminum
of 0.1 M organic acids, 400–500 g m 2 day 1, and in
and zinc gives cathodic protection.
0.1 M hydrochloric or sulfuric acids, 600 g m 2 day 1.
As indicated earlier, the bicarbonate ion inhibits
In the absence of oxygen, the rates in the two mineral
the process, which does not occur, therefore, in many
acids were 100–150 g m 2 day 1, while they were neg-
supply waters; attack is most likely in waters that, by
ligible in the organic acids. Phosphoric acid forms a
nature or as a result of treatment, have a low bicar-
protective layer, and even in the presence of air, the
bonate content and relatively high chloride, sulfate,
corrosion rate is only 20 g m 2 day 1. Nitric acid
or nitrate content. The number of points of attack
corrodes tin freely even in the absence of oxygen;
increases with the concentration of aggressive anions,
however, chromic acid forms a protective film. This
and ultimately, slow general corrosion may occur.
film, which contains chromic oxide and tin oxides, will,
During the exposure of 99.75% tin to seawater for
after withdrawal from the acid, give some degree of
4 years, a corrosion rate of 0.0023 mm year 1 was
protection against mildly corrosive conditions. Thus,
observed.41 Corrosion in soil usually produces slow
hot solutions of chromic acid, alone or mixed with
general corrosion with the production of crusts of
phosphoric acid, may be used as passivating media.
oxides and basic salts. For example, the production
of the significant quantities of the metastable corro-
3.12.3.2.2 Organic acids
sion product romarchite (SnO) is commonly seen
Tin forms complex ions with many organic acids,
when studying pewter corrosion products from
including those commonly found in fruits (citric,
marine archaeological sites,42 but is never seen,
oxalic, malic). This action has important effects on
except transiently or as a thin interfacial phase, in
the galvanic behavior of tin. The normal electrode
passive films and atmospheric corrosion products.
potential of tin is 0.136 V, but the reduction of
stannous ion activity resulting from the formation of
complexes may depress the corrosion potential to
3.12.3.4 Corrosion by Alkalis
make tin anodic to iron.36
The attack of tin by oxalic, citric, and tartaric acids The Pourbaix diagram indicates the possibility of
was found to be under the anodic control of the Sn2+ attack by solutions of pH values above 10.5, but
salts in solution in oxygen-free conditions.37 In a the position of this limit is influenced by tempera-
study of tin contaminated by up to 1200 ppm Sb, it ture, by the constitution of the solution, and by the
was demonstrated38 that the modified surface chem- surface condition of the metal. Corrosion will ensue if
istry catalyzed the hydrogen evolution reaction in the surface oxide is significantly soluble, which will
deaerated citric acid solution. Tin was found to cor- occur increasingly beyond pH 12.
rode more rapidly in tartaric acid because of the Once corrosion begins, its rate is governed by the
reduction in the hydrogen overpotential; passivation oxygen supply and temperature and is not greatly
was caused by a film of tin hydroxide or oxide.39 affected by the character of the alkali. Rates of attack
2074 Non-Ferrous Metals and Alloys

for specimens completely immersed in still solu- Table 1 Standard reduction potentials and galvanic
tions open to air are 600 g m 2 day 1 at 30  C and series compared with tin
1000 g m 2 day 1 at 70  C. In intermittent immersion Standard reduction Practical galvanic series in
such as is experienced in the cleaning of tinned ware potentials (vs. SHE) sea water
by alkaline detergents, however, the rate of corrosion
Cu2+ + 2e = > Cu: +0.34 V Graphite
is affected by the nature and concentration of the Pb2+ + 2e = > Pb: 0.12 V Passive stainless steels
solution, as these affect the time required for the Sn2+ + 2e = > Sn: 0.14 V Copper alloys
removal of the oxide film at each fresh immersion.43 Ni2+ + 2e = > Ni: 0.25 V Tin (and tin-rich solders)
Saturated ammonia solutions do not attack tin, possi- Fe2+ + 2e = > Fe: 0.44 V Lead (and lead–tin solders)
bly because of the negligible oxygen content, but Zn2+ + 2e = > Zn: 0.76 V Steel and cast iron
Al3+ + 3e = > Al: 1.67 V Aluminum
more dilute solutions behave like those of other alka- Mg2+ + 2e = > Mg: 2.37 V Zinc
lis of comparable pH. In aerated alkaline conditions, Magnesium
0.01–1 M NaOH, corrosion of tin was confirmed to be
under cathodic control, and additions of other spe-
cies, apart from chromate, were found to make little
difference to the corrosion rate.44
3.12.3.6 Galvanic Corrosion
The removal of oxygen from an alkaline solution,
as by the addition of sodium sulfite, can prevent As indicated from the galvanic series, tin is less noble
corrosion unless the tin is in contact with another than copper and stainless steels, but more noble than
metal, such as steel, from which hydrogen can be most other elements in common use (Table 1). How-
evolved. Additions of oxidizing agents in small amounts ever, tin is usually ineffective as a sacrificial anode
stimulate corrosion, but sufficiently large additions because of its very low self-corrosion rate, and gen-
produce passivity. Alkaline chromate solutions in the erally, may be safely used in contact with most mate-
passivating range produce a film containing chromium rials.46 However, in the presence of species such as
oxide, which has some protective value.19,45 citric acid, which can form complex ions, tin will
activate with its equilibrium potential moving to
more negative values. This effect is important in the
3.12.3.5 Corrosion in Foodstuffs
corrosion protection of steel cans with tinplate.
Sulfide solutions, sulfurous acid, and some foodstuffs
containing organic sulfur compounds produce stains
of sulfide, but the rate of loss of metal is low.2,3 Milk 3.12.4 Applications
and milk products are usually without action,
3.12.4.1 Tin Coatings
although local corrosion has been known to occur
in dairy equipment. Beer initially dissolves a trace Interested readers are directed to the dedicated sec-
of tin and this may be sufficient to cause a haze in the tion on tin coatings elsewhere in this volume; only
liquor, but any corrosion usually slows to an insignif- brief comments are provided here. Tin coatings
icant rate after some time. may be applied either by hot-dipping from molten
In general, near-neutral aqueous products are metal or by electroplating from either acid or alka-
without action except for possible sulfide staining, line solutions2,3 or by metal spraying.47 Also, tin may
or when there are dissolved salts present, some local be codeposited during electroplating with a range of
corrosion. The slight acidity, which may develop other elements such as nickel, cobalt, copper, and
in solutions of some organic compounds such as zinc, each of which gives rise to a particular property.
formaldehyde or alcohols can be tolerated. Many Tin-plated steel is extremely widely used in the
organic liquids, including oils (essential, animal, food and beverage canning industry as a container
vegetable, or mineral), alcohols, fatty acids, chlori- and relies on both the low corrosion rate of tin (can
nated hydrocarbons, and aliphatic esters, are without exterior) and the common potential reversal to steel
action. The absence of any catalytic action of tin in the presence of natural complexing agents (can
on oxidative changes is helpful in this respect. interior). In practice, because of the high cost of tin,
When, however, mineral acidity can arise, as with it is essential to use as thin a layer as possible. Thus,
the chlorinated hydrocarbons containing water, there the corrosion protection afforded by the tin is usually
may be some corrosion, especially at elevated supported by internal and external lacquering
temperature. (organic coating) of the can, and it is therefore, the
 Corrosion of Tin and its Alloys 2075

organically coated tin that provides the full corrosion hence, careful selection of the flux material is neces-
protection system for the steel substrate. sary. Otherwise, corrosion in service will be pro-
The thinnest tin coatings are most efficiently moted locally.50 It is, however, possible to select
applied by electroplating; where this is likely to give fluxes that are active when hot, but give noncorrosive
pinholes, surface melt reflowing may be used to residues when cold, for example, solid organic acids.
improve the performance. Where thicker coatings If it is necessary to use more vigorous materials, such
are required, usually for specialist applications, for as zinc chloride, any residues must be fully removed.
example, hot dipping or metal spraying can be used. By the nature of their use as a jointing material,
For example, traditional copper cooking utensils are solders are usually presented to a corrosive environ-
frequently internally coated with tin to several tens ment as a small area within a much larger area of
of microns in thickness to prevent the interaction of another metal. Thus, if the solder is anodic to the
copper with foods that can lead to the development metal it joins, and if the corroding medium has good
of taints. The advantage of this process is that when the electrical conductivity, damaging corrosion is possi-
tin wears off, it can be easily replaced by redipping. ble due to the unfavorable (small anode versus large
Hot-dipped (and sprayed) coatings take advantage of cathode) anode-to-cathode area ratio.
the formation of tin–iron or tin–copper intermetallic Traditional lead–tin solders are anodic to copper,
species for excellent adhesion of the coating. but soldered joints in copper pipes have been widely
used without trouble for cold supply waters; possibly,
corrosion is restricted by the deposition of cathodic
3.12.4.2 Solders
carbonate scales and the formation of insoluble lead
Alloys of tin with lead and/or a number of other compounds. Hot supply waters tend to be more aggres-
elements comprise a class of jointing materials sive, but are likely to still give satisfactory service.
known as solders. Solders are used for cost-effective However, electrolytes of sufficiently high conductivity,
and efficient jointing of many materials, most com- such as seawater, will cause corrosion of soldered joints
monly for copper alloys (e.g., heat exchangers) and in copper and copper alloys. In automotive radiators,
steels (e.g., cans). Solders are generally characterized antifreeze solutions have been alleged to cause corro-
by their ability to flow across or ‘wet’ the metal to be sion, possibly because materials such as ethylene glycol
jointed; such wetting is usually accomplished by the sometimes detach protective deposits. Sodium nitrite,
formation of intermetallic compounds between the valuable as a corrosion inhibitor for other metals in a
solder and the substrate. Thus, tin forms Cu6Sn5 and radiator, tends to attack solders, but sodium benzoate is
Cu3Sn with copper alloys48 and FeSn, Fe3Sn, and safe, and in addition, protects the soldered joint against
FeSn2 with steel.49 The mechanical properties of the action of nitrites.51
these intermetallic species are critical; thus, they In environments in which tin is less readily corroded
provide a metallurgical bonding between the jointed than lead, corrosion resistance of the alloy decreases as
materials, but must not form brittle phases. Many the lead content increases; the decrease may, in some
types of tin-based solders are available, for example, circumstances, be sharp at a particular composition. In
Sn–Pb (traditional solders with compositions from the more corrosive media, a sharp increase of corrosion
60/40, 50/50, 40/60 depending on use), Sn–Zn (for rate is observed as the lead content increases beyond
jointing aluminum), and Sn–Ag (lead-free solder for 30%. However, in waters with low contents of dissolved
general use). In particular, for health reasons, there is salts, the corrosion rate increases slowly with lead
an increasing use of low-lead, or lead-free solders, content up to 70% and then rises more steeply.
especially for joints in water supply systems and in Selective dissolution of tin has been reported to occur
food canning. These environmental concerns are now in prolonged contact of solders with solutions of
making the electronics industry also move to lead- anionic surface active agents.52
free formulations. In view of the known tendency for lead to be
Effective soldering requires a clean surface, free of released in supply waters from conventional soldered
contamination such as greases, oils, and water and the joints,53 there is an accelerating trend away from the use
removal of the normal air-formed oxide on the mate- of lead-containing solders in contact with potable
rial that is to be jointed. Typically, this is carried out water, which is also being driven by legislation.54 The
initially by mechanical abrasion or solvent cleaning effects of galvanic corrosion of one of the substitute
with the final removal of the tenacious surface oxide alloys (Sn–3Ag) in contact with a number of other
via a ‘flux’. A flux is, by its nature, corrosive, and metals, including copper, have therefore been studied.55
2076 Non-Ferrous Metals and Alloys

3.12.4.3 Tin Interconnections failure by short-circuit. Tin whisker formation has

been known for many years and was originally thought
Tin-based jointing alloys (solders) are the materials of
to be driven primarily by electromigration between
choice for connections and interconnections in the
two contacts or conductive tracks.58,59 More recently,
electronics industry. Traditionally, a eutectic tin–lead
however, it has become clear that most whisker growth
(67Sn–33Pb) alloy has been used, but the legislative
is a process driven by relief of stresses60 (i.e., from
driver for the removal of lead has also affected this
plating or from contact forces), although electromi-
sector, which has now effectively moved to encompass
gration may play a role in more extreme conditions.61
the use of lead-free solders. The performance charac-
teristics of electronic connectors is dominated by
(1) local galvanic corrosion between different metals, 3.12.4.4 Bearing Metals
either in contact or as a coating and influenced by
There are several classes of tin-containing bearing
applied direct currents; (2) the corrosion of the solder-
alloys for use in lubricating conditions: high-tin alloys
ing alloy, which is controlled largely by the presence of
(substantially lead-free), bearing alloys containing
residues from various manufacturing and assembly
increasing amounts of lead, and aluminum tin alloys;
operations; (3) fretting forms of corrosion damage
each class may have minor elements (e.g., antimony,
induced by repeated making and breaking of electrical
indium) added to promote, for example, intermetallic
contacts; and (4) the formation of metal whiskers of tin
formation. The corrosion of tin-rich white metal bear-
that tend to be produced as a result of applied stress
ings is rare, and consequently, detailed studies of the
and voltage. All of these phenomena can lead to either
phenomenon are not extensive in the literature. High-
a reduction of performance or an outright failure via a
tin alloys are relatively resistant to corrosion in the
variety of mechanisms,55 the most important of which
organic acids that tend to be formed during the deg-
are increases in the contact resistance with time and
radation of lubricating fluids and the tin salts that
short-circuit current paths between contacts because
form have antioxidant capability. Where corrosion of
of corrosion products, soldering residues (i.e., fluxes),
tin-rich bearings has occurred, it is invariably asso-
and whiskers of tin.
ciated with water ingress.62 For example, 500 ppm
Many lead-free solders are based on Sn–Ag–Cu
water has been shown to be sufficient to cause corro-
formulations, with Sn–3.5Ag, Sn–0.7Cu, and Sn–
sion, especially in conjunction with chlorine-based
3.8Ag–0.7Cu widely in use because of their good
high-pressure additives in the oil.63
mechanical and wetting properties. In 3.5% sodium
When free access of salt water to a bearing is
chloride solution, lead-free solders show an improved
possible, the tin–lead ‘Babbitt’ alloys are not suitable,
corrosion resistance compared with Sn–Pb solder
since they are cathodic to steel shafts. For underwater
because of lower active currents and lower passive
bearings, alloys with 70% Sn, 1.5% Cu, and the
current densities and that the Sn–Ag material was
balance Zn, are traditionally used; the possible disso-
the most resistant.56 The contact resistance and fret-
lution of zinc gives cathodic protection to the shaft,
ting corrosion resistance of lead-free solders were
although the more easily replaced bearing suffers
measured as a function of time.57 In this case, the con-
some corrosion.
tact resistance of the conventional eutectic solder fell
more quickly than the lead-free solder; however, the
fretting corrosion resistance of Sn–Ag materials was
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