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ATMOSPHERIC CORRQSION OF

TIN A N D TIN ALLOY§

bY

M. E. Warwick

INTERNATIONALTIN RESEARCH INSTITUTE


Fraser Road, Perivale, Greenford, Middlesex
Tel: 01-997 4254
(I .TA. 1. Publication No.602)
CONTENTS Page

Introduction 3

1 TIN
1.? Allotropic transformation
1.2 Tin whiskers
1.3 Oxidation of tin
1.4 Reaction of tin with other gases
1.5 Atmospheric corrosion of tin
1.6 Long-term atmospheric corrosion of tin
1.7 Surface treatments for tin

2 PEWTER 7

3 TIN-LEAD ALLOYS 7

4 TIN-COPPER ALLOYS 8
4.1 Oxidation of tin-copper alloys 8
4.2 Atmospheric corroSion of tin-copper alloys 9
4.3 Long-term atmospheric corrosion of tin-copper
alloys 10

5 TIN-ZINC ALLOYS 10

6 TIN-CADMIUM ALLOYS 11

7 TIN-NICKEL ALLOYS 11
7.1 Passivation of tin-nickel alloy 12
7.2 Atmospheric corrosion of tin-nickel alloys 12

8 TIN-COBALT ALLOYS 12

9 TIN-SILVER ALLOYS 13

Acknowledgements 13

References 13
Introduction
Tin has found an extremely wide range of applications of which
the two most important are tinplate, steel with a thin coating of
tin, and soft solder which is most commonly an alloy with lead.
There are also a large number of other uses for which the
atmospheric corrosion resistance of tin and tin alloys plays an
important role. These range from pewter, an alloy with a very
high tin content, to bronzes and include tin and alloy coatings of
both ferrous and non-ferrous substrates. The general corrosion
properties of tin and tin alloys have been summarised in two
recent publications. '-*
This review will concentrate on those alloys of tin where
atmospheric corrosion is relevant to the normal use of the
material and where tin is present at a significant level. Thus,
white metal bearings are not included as they are not exposed
to the atmosphere but to an oil film while aluminium-tin
bearings, zircalloys, titanium alloys, dental amalgams and
superconducting nobium-tin alloy will not be considered, as tin
forms the minor constituent.

1 TIN
The comments applied t o the corrosion of bulk tin can usually
be equally directed to tin when used as a coating if one
overlooks any local corrosion at pore sites in the coating.
Indeed some of the data referred t o below were derived from
studies of tin coatings. In all cases given, the information will be
Fig. 1
concerned with performance of P-tin, which is the normal Gray tin formation on pun, tin. Both samples were stored at -20% but
allotropic state in which the metal is used. However, since the the top sample was bent at this tempemtun, end the other was left
corrosion of tin in the atmosphere is occasionally confused with undistul6ed.
the allotropic transition to cc-tin or with the growth of whiskers,
some reference to factors governing the appearance of these
phenomena are given first.

1.lAllotropic Transformation
It must be emphasised that genuine cases of failure because of
The transition temperature for the oc-p transformation of tin is
an allotropic transformation appear t o be rare and the results of
13.2OC but, in practice, the p form is found to be stable even
atmospheric corrosion or other forms of attack have been
below O°C unless specific factors trigger the change. A incorrectly described as tin pest.
prerequisite for the transition to occur is that the tin is of
exceptional p ~ r i t yIt. ~can be induced by inoculation of a cooled
specimen with crystals of oc-tin or by recrystallisation occurring 1.2 Tin Whiskers
at low temperature following deformation. Small quantities of The phenomenon of whisker growth on pure tin coatings is only
impurity elements, such as those present in grades of mentioned insofar as it could be mistaken for atmospheric
commercial purity tin are sufficient to prevent a spontaneous corrosion in the true sense of the word. Like a number of
allotropic transition OF to delay an induced change. Deliberate metals, tin can undergo a recrystallisation at room temperature
additions to either bulk or electroplated coatings of elements which manifests itself as the growth of single crystal filaments
such as bismuth (0.1%) or antimony (0.3%)can be made t o or whiskers, from the surface of tin coatings. The growths
prevent the transformation. The effects on the transformation appear t o occur t o relieve stresses in the coating including
temperature of crystal orientation and impurities were studied those induced by excessive codeposition of plating bath
by Tammann and Dreyer! additives,' migration through the coating of atoms from the
Tin coatings produced by hot-dipping seem t o be virtually substrate (e.g. zinc) and externally applied pressures.' A number
immune from allotropic change, probably as a result of of studies have been carried out into the mechanism of the
impurities present in the tin or because it is completely stress- process. 9-10
free. The same is true of most electrodeposited coatings The potential problem of whisker growth need never materialize
although in the case of tin plated from an alkaline bath, since a number of steps can be taken to give virtual immunity of
codeposition of other materials may be negligible and thicker coatings against their appearance. Thermal stress-relief is an
coatings may be susceptible t o change. effective process and alloying, particularly with lead, is widely
The transformation of p-tin tocc-tin is accompanied by volume used in the electronics industry where the problem could have
change since the densities of the t w o forms are 7.29g cm-' and the most serious consequences?
5.779 cm-3 re~pectively.~ The cc-tin forms in isolated areas as In those cases where whisker growth does occur, it can vary in
blue-grey "warts" on the white, metallic Etin and it crumbles appearance from long (up to 1 cm) thin filaments t o a mass of
away as a coarse grey powder when disturbed. The damaged very small filaments. It is in this second form that a superficial
specimen then appears as in Figure 1 and it can be readily seen examination of the material may suggest the presence of a
how the name "tin-pest" arose from this form of metal loss. surface corrosion product but observation under a low power
The mechanism and kinetics of the process were studied by viewing lens quickly reveals the true nature of the surface
Burgers and Groen.6 change.

3
1.3 Oxidation of Tin

Under most atmospheric exposure conditions, the corrosion of


tin depends on the formation and stability of an oxide film and
so it is pertinent to refer to laboratory studies of its production
and chemistry.
The most complete study of the interaction between tin and
oxygen was reported by Boggs et. al. in a series of papers.
They followed the oxidation of tin using a vacuum microbalance 10 20 30 40
a t temperatures in the range 1 5 0 - 2 2 0 ° C and a t oxygen Time, days
pressures between 10-3mmto 500 mm Hg. Below an oxygen
pressure of 1 mm Hg, dendritic a-SnO crystallites grew at a Fig 2
continuously increasing rate over the duration of the The effect of relative humidity on the rate of oxidation of tin. ( 0 )
Samples stored in a cupboard. (0)Samples stored in a desiccator.
experiment with the rate-determining step apparently being the
dissociation of oxygen. Above an oxygen pressure of 1 mm Hg,
the oxide growth curves had a characteristic sigmoid shape.
The initial stages of growth corresponded to the lateral spread
of oxide from numerous nuclei to form platelets of a-SnO.
Subsequent growth followed a logarithmic law and was
consistent with control by the diffusion of tin through an oxide
film under a parabolic or cubic law while the formation of Other laboratory studies of the oxidation of tin have been
cavities in the oxide film progressively reduced the area through concerned with the metal in contact with air. Kutzelnigg 17-18
which diffusion ,could take place. Finally, for long oxidation demonstrated the formation of an oxide film in air and
times, the thick oxide film was subject to random fracture, Macnaughton and Hedgesi9 produced weight-increment
giving rise to erratic results. Similar work was carried out by curves. Kenworthy” followed the weight gain of tin during
Luner l5 at about the same time, using tin contaminated with indoor exposure and decided that growth of the oxide film was
0.17% Pb and 0.024% Sb over the temperature range 168 - linear after the first few days and it was of the non-protective
21 1.5OC. His results could be described by a logarithmic rate type. Britton and Bright2’, then Britton and Sherlock,22studied
law and were in broad agreement with those of Boggs et. al. the oxidation of tin and tinplate and followed the growth of
films by coulometric and X-ray analysis. They decided that the
A more systematic study of the effect of impurities on the rate
growth of the oxide film followed a logarithmic rate law up to
of oxidation of tin was again carried out by Boggs et. using
13O0C, but above that temperature, growth tended to be
a vacuum microbalance under similar conditions of pressure
parabolic. It was not possible unequivocally to identify the oxide
and temperature as their previous studies. Their results are
species present but the results could be explained on the basis
summarised in Table 1 and can be rationalised as follows. If the
that a t room temperature an amorphous film is formed, while at
oxide of the alloying element is less thermodynamically stable
higher temperatures it is apparently crystalline aSnO, possibly
than tin (11) oxide, the oxidation rate of the alloy remains
with some SnO,.
unchanged for additions whose ions have the same valency as
the tin. However, in those cases where the formal ionic charge J e n k i n ~ ,found
~ t h a t SnO films were formed on tin just above
of the addition element is greater (Sb, Bi, Fe, TI) then the rate of its melting point but that SnO, was formed at higher
oxidation of tin increases. Those alloying elements forming on temperatures. Hart24demonstrated the effect by spot-heating a
oxide more stable than tin (11) oxide undergo preferential piece of foil. He found SnO, at the centre surrounded by SnO
oxidation at the surface, thus inhibiting the oxidation of tin. which in turn was surrounded by amorphous oxide. In fact, SnO
Included in this group are alloying additions of zinc, indium, is unstable with respect to SnO, but Platteeuw and MeyerZ5
phosphorus and germanium. have demonstrated that the disproportionation of SnO to tin
and SnO, is a slow process even a t 3OOOC. Again, a recent
E.S.C.A. study has shown 26 that tin exposed to oxygen a t
100°C produces an oxide film of both SnO and SnO,. Close
interpretation and comparison of results achieved in the study
Table 1 of the oxidation of tin in the laboratory should not be
overemphasised since it has been found that the surface
The effect of alloying additions (0.1 atomic %) on the rate of
oxidation of tin at 190°C and 10 torr oxygen pressure
preparation of tin plays an important role in determining
(Data abstracted from ref. 16). oxidation rates. Davis and Shah” showed that cathodic
cleaning reduced the subsequent rate of oxidation of tin. In
addition, the same authors demonstrated that the relative
Increase in weight humidity under which experiments are carried out can have a
Alloying element after 1000 minutes profound effect on oxidation rates as shown in Fig. 2. Other
pg cm-2
workers showed that minor impurities could affect the rate of
Manganese 2.7 reaction of tin exposed to air. Britton and Bright2’ confirmed the
Antimony 2.5
2.1 results of Boggs et. al., whose data were collected in a closed
Thallium
Bismuth 1.7 system, when they found that small amounts of indium,
Iron 1.6 phosphorus or zinc slowed down the oxidation of tin. However,
Lead 1.3 0.1% aluminium or 0.1% magnesium have been shown to
No alloying addition 1 .o
reduce the resistance to attack of tin in moist conditions.
Cadmium 1 .o
0.3 Rawdon2* found that traces of aluminium can cause
Phosphorus (0.5%)
Zinc 0.2 embiittlement as a result of intercrystalline attack. This effect
lndiurn 0.1 may, however, be counteracted by an addition of antimony.

4
1.4 Reaction of Tin with other Gases More recently, Speddin very briefly reported4I the results of a
MantellZ9carried out a comprehensive survey of the interaction ten-year exposure test for tin in industrial, marine and rural
between tin and H,S and SO,. Under normal atmospheric atmospheres. The added costs as a result of SO, pollution of
conditions, both have little effect but above 100°C, SnS is atmospheres were estimated for a number of metals.
formed. High concentrations do however produce darkening or Clarke and Longhurst4, have carried out atmospheric exposure
tarnish, while a t low temperatures, Cooke30found that liquid or tests on tin in a variety of tropical environments over a period of
gaseous SO, produced a crystalline solid with tin. Skorchelletti 2 years. Test samples 15 x 10cm were exposed in open or
and Tukachinskii3' monitored the thickness of adsorbed sheltered conditions in three sites in Nigeria. The first w a s hot-
moisture films on tin a t relative humidities below 100% using a damp inland, the second hot-damp town and the third hot-
torsion microbalance. They found that SO, at different levels damp sea coast. The specimens for full exposure were mounted
had little influence on their results. 30° to the horizontal, approximately 1.2m above ground and
The halogens attack tin readily at room temperature except for facing south. The sheltered exposure samples were supported
fluorine which only reacts a t a significant rate above 100°C. by insulated slots vertically inside a ventilated box. The results
Similarly, fumes from concentrated acids attack tin. of both tests are summarised in Table 3.
Tin resists corrosion by the vapours of organic acids and other
organic compounds such as might be emitted from wood or
other packing materials. Rance and C ~ l and,
e ~ more
~ recently, Table 3
Donovan and Stringer33 have been among those who have
Corrosion of coatings of tin, 80%tin/20??zinc and zinc (alI25-pm
studied this aspect of tin corrosion. thick) on steel at three tropical sites. Full exposure weight loss
was measured after removing the corrosion products
cathodically (Data abstracted from ref. 42).
1.5 Atmospheric Corrosion of Tin
This subject has been studied by a number of workers using a
range of exposure sites and with either tin or tin coatings under
test. Coatings 25pm thick on steel
Test I i t e
WhittakeP4 surveyed available data in 1924 but K e n ~ o r t h y ~ ~
was the first to carry out a comprehensive test on tin. He Tin 80%Sn/2W/obn Zn
showed that in normal indoor environments, tin remains bright
indefinitely, especially if regularly washed with soap and water. Material loss, Jungle 0.1 8 0.46 0.53
In outdoor exposure, without exceptional pollution, tin does not pmlyear
after 2 year Town 1.02 1.35 1.45
tarnish but gradually becomes dull with the eventual formation
full exposure
of some white corrosion product when the surface is sheltered Coast 3.02 2.87 2.90
from the rain.
The most comprehensive study of the atmospheric corrosion of Weight loss, Jungle 1.6 9.3 16.5
bulk tin was reported over a period of 20 years by mg/dm2
after 2 year Town 11.3 15.5 10.7
subcommittee VI of the ASTM Committee B-3 on Corrosion of sheltered
Non-Ferrous Metals and alloy^.^^-^^ Commercial tin of exposure Coast 40 23 18.1
99.85+% purity was exposed as 9 x 12in. (23/30cm) sheets
and corrosion rates were determined from weight loss
measurements. In addition, tensile properties and surface
appearance were recorded. The tests were conducted at seven Tin does not have great structural strength and so it finds most
sites in the U.S.A. and included industrial, sea coast and rural application as a coating for both ferrous and non-ferrous
atmospheres and results were reported after 1, 3, 5, 1 0 and 20 substrates. Use is made of the corrosion resistance, soldering
years exposure. The most valuable data are probably those characteristics or ability to prevent galvanic corrosion effects
based on weight loss measurements and these are summarised between other metals. During atmospheric exposure, the
in Table 2. The change in strength of some of the test samples presence of a substrate, exposed through pores in the coating,
was due to inadequate support during exposure while the has little effect on the corrosion of tin.
majority probably experienced normal self-annealing and the Tin on steel is widely used as a packaging material and for the
effect measured did not result from corrosion. fabrication of processing and storage equipment, particularly in
the field of food handling although other materials such as
stainless steel are increasingly favoured for these applications.
Table 2 Under atmospheric exposure conditions, tin offers no galvanic
Average weight loss of tin exposed to different environments protection to the underlying steel and so rusting at pores in the
over a period of 10 and 2 0 years (Data abstracted from ref. 40). coating is the form of attack always found. The presence of
exposed steel seems to have little or no effect on the
atmospheric corrosion of tin. Despite these apparent limita-
tions to the protection afforded to steel by tin coatings, a
Corrosion Rate, mg dm-* day-'
Site Description number of studies have been carried out. C ~ m p t o nbriefly ~~
commented on the performance of bin coatings on steel but a
1Oy test 20y test more complete study was reported for the Protective Coatings
Heavy Industrial - 0.34 (Corrosion) Sub-Committee of the Corrosion Committee of the
Marine Heavy Industrial - 0.26 British Iron and Steel Research Association. In that work
Marine (New Jersey) 0.38 -
0.46 - Hudson et. al. r e p ~ r t e d on
~ ~exposure
-~~ tests carried out for up
Marine (Florida)
0.57 to twelve years in an industrial atmosphere (Sheffield), or
Marine (California) -
Semi-arid __ 0.088 marine atmosphere (Calshot and Congella, S.Africa) and a rural
Rural 0.097 - atmosphere with heavy rainfall. The production of protective

5
corrosion residues in the pores of the coating was cited in corrosion products which adversely affect its solderability and
explanation of the superior performance of samples in the contact resistance and increase the susceptibility of the tin to
industrial atmosphere. Britton46 has made similar comments whisker growthg. The problem is easily overcome by ensuring
about his own results. Dettner4' carried out a similar that a barrier metal is deposited between the coating and
programme using accelerated corrosion tests and outdoor substrate and 2.5ym of copper or nickel have been found to be
exposure in the urban atmosphere of Berlin. Testing was only effective materiak8
carried out for one year but a number of conclusions were The specifications for tin coatings on non-ferrous substrates
drawn from the work. Reflowing (fusion) of tin coatings was with the exception of brass are similar to those for steel. IS0
claimed to improve their corrosion resistance except to a salt 2093-1973 suggests 30pm of tin for applications in which
spray test and deposits from an acid electrolyte were said to be substrate exposure cannot be tolerated and 15pm for severe
better than those from a stannate bath. Again, in a similar srudy service. Moderate service environments require 8pm of tin
conducted at about the same time, Biestek r e p ~ r t e d results
~~-~~ while 4pm is sufficient for solderability purposes. Qther authors
for the exposure of tinned steel to urban, urban-industrial, recommend that to guarantee an acceptable shelf-life for
seacoast industrial, industrial and rural atmospheres. solderable materials, a coating thickness of 5pm should be
A separate trial was also organised by Biestek50in China during sed.^'-^^.
which tin plated steel was exposed to a tropical atmosphere.
Samples of plated mild steel were tested in two environments. 1.6 Long-Term Atmospheric Corrosion of Bin
In the first, they were mounted a t 45' in the open and facing
A number of studies of artefacts of archaeological interest have
south. In the second condition, the racks were placed in a
been carried out and although the exposure conditions cannot
matting shed so that solar radiation, wind and rain were kept
be accurately described, it is interesting that the corrosion
away from the samples. The test was continued for 5 8 months
products found are consistent with all of the preceding
but it was found that coatings of 25pm of matte tin should not
comments.
be exposed in either environment for mor-e than one year and
that similar coatings 32pm thick should not be exposed for two Bannisters6studied a mediaeval or Roman tin scabbard found in
or more years. a gutter in Roman Watling street in England. The article was
covered by an adherent layer 2.5mm thick with the
In general, the conclusion of all these studies was that the
composition shown in Table 4. The protected metai was 2mm
corrosion resistance of tin coatings, meaning their protection of
thick and contained 99.98% tin and a trace of copper. Several
steel, was not very high. This is reflected in the international blocks of tin have been discovered and the results of an analysis
standard covering tin coatings (IS0 2093-1 973) which
of rhe corrosion products present have been reported. Smythe"
requires 3 0 k m thick deposits for exceptionally severe
studied a 72kg biock of tin, dredged from Falmouth Harbour in
conditions, 20pm for severe service, 42pm for moderate
1823 among a number of other specimens. The data available
service and 4pm for mild service where the main requirement is
suggests that it was weathered for six years before being
for good soiderability of the material.
placed in a museum. The surface of the sample was covered in
Tin coatings are also widely used on non-ferrous substrates, a thick, light grey-brown scale and its composition was as
usually for one of four reasons. The solderability of materials shown in Table 5. A smaller block, found at Treireife in 1841,
can be improved and retained over a long period by the use of was covered in a brown scale which was found to be 44.7%
tin coatings. As with steel, food contact applications still make hydrated SnO.
use of tinned articles as does some non-food processing equip-
ment. Finally, tin coatings are used to prevent galvanic effects
between dissimilar metals and to provide low resistance
contacts in some electronic applications. In view of these
applications, it is not surprising to find that copper and copper
alloys are the most frequently tinned non-ferrous materials. Tin
tends to be anodic to copper and copper alloys and to the inter-
metallic compounds formed between tin and copper in most Table 4
aqueous environments and hence accelerated corrosion of the Analysis of the scale of corrosion product on an ancient tin
coating might be expected. This can show itself as the scabbard (Data abstracted from ref. 56).
appearance of "black spots" on a tin coating. These are a
manifestation of local corrosion of tin around discontinuities in
the coating and while normally associated with total aqueous
Compound Wt. % of total
immersion, their appearance can follow outdoor exposure
Hydrotis tin(ll)oxide 43.35
involving cyclic condensation. However, since tin and copper Tin(lV) oxide 54.68
both show good atmospheric corrosion resistance, references Copper oxide 0.8 1
in the literature to studies of their performance tend to be Sulphuric anhydride 0.85
related to changes relevant to specific end-uses. Iron oxide etc. 0.1 2
Lime 0.10
The deterioration of the solderability of tinned copper during
ageing has been the subject of many studies and accelerated
tests have been developed to simulate the e f f e ~ t . ~Similarly,
l-~~
changes in the contact resistance54of tin coatings have been Table 5
monitored and the increase found can be related to the growth Analysis of the scale of corrosion product on an ancient block
of the oxide film on tin. of tin (Data abstracted from ref. 57).
Compound Wt. %of total
Special mention should be made of the atmospheric corrosion
Tin(lV) oxide 84.93
of tin coatings on brass. It has been demonstrated that zinc can Hydrous tin(ll)oxide 2.61
rapidly diffuse through tin and that its appearance a t the Tin(ll) chloride dihydrate 5.03
surface of the coating is the cause of a number of problems.* Silica 1.67
The surface of the tin becomes covered with white zinc Water 5.89

6
Examples of ancient tin coins from Malaysia were examined by retained. Surfaces contaminated by particles of foreign matter,
Plenderleith and OrganJ8who found them to be covered by whether it is a fabrication residue or household dust, can
successive layers of brown and grey scale. Analysis showed the deteriorate as a result of local breakdown of the protective
scale to be principally SnO, with about 7% tin (11) compound, oxide film but regular simple washing ensures that the surface
probably the oxide. Sulphate and traces of silica and iron were remains in good conditi~n.’~-’~
found but significant levels of chloride ion were not detected. In the past, pewter alloys contained lead and this played a
LihEsyreported a study of seventeenth-eighteenth century tin significant role in the corrosion of the material, producing a dark
sarcophagi in Vienna in which tin pest had been suspected as patina during atmospheric exposure. Mention will be made of
the cause of the visible deterioration of the sample. However, this below in dealing with tin-lead alloys but it should be noted
he found that the casting was porous and that air and moisture that some modern pewter is chemically treated to reproduce
had produced oxide films within the casting. The resultant this patina. A number of proprietary processes exist including
volume change then caused sweiling, blistering and cracking. those based on immersion in iron chloride or sodium nitrate
As in the previously mentioned examples, the principal solutions or acidic solutions of copper and a r ~ e n i c . ’ ~Electro-
-~~
corrosion products were SnO and SnO, and in this case, some chemical treatments such as anodizing in phosphate solution
basic copper carbonate was also found. will also produce the patina.67 Once formed, the coloured
surface film on pewter appears to have the same stability
1.7 Surface Treatments for Tin against atmospheric corrosion as the normal oxide film on tin.
Surface treatments are not applied to tin for the majority of its The stability of pewter against tarnishing in the atmosphere has
applications although, as has been mentioned above, cathodic been reported by Kenworthy and W a l d r a n ~ ’ ~but further
cleaning in dilute sodium carbonate solution can reduce detailed studies do not appear t o have been carried out.
oxidation rates of the metai. This is presumably related to the
removal of residues which might otherwise help to break down 3 TIN-LEAD ALLOYS
the oxide and so prevent a continuous film from growing and
The second largest industrial use of tin is as a constituent of
stifling the reaction, The deliberate growth of tin oxide or mixed
soft solder where it is most commonly alloyed with lead. 1,
oxide films in both acid and alkaline solution has been
addition, both ferrous and non-ferrous substrates are coated
reviewed6’ recently and will not be discussed further here.
with tin-lead alloys to confer solderability on those materials.
The exception to the above is electrolytic tinplate which However, a coating of tin-lead is also used to give corrosion
receives a surface treatment during its production, which is resistance to some materials and the most important example
referred to loosely as “passivation”. The purpose of such treat- of this is the coated steel material called ternepiate. The name
ments is to produce a surface more amenable to can-making is applied to a range of products made from cold rolled mild
operations such as lacquering and soldering and more resistant steel coated with an alloy of 2-20% Sn balance Pb. The uses of
to sulphide staining by natural protein present in foodstuffs. this material have been recently reviewed by M a ~ k a y . ’ ~
These aims are achieved by modifying or removing the oxides
Even very small additions of lead t o tin cause tarnishing of the
produced on the surface of tinplate during manufacture and
depositing a stable protective film. The most common treat- material in full exposure to the atmosphere. Much longer times
ments involve either simple immersion or cathodic polarization or higher lead contents are required to produce the same effect
in sodium dichromate solution, although a number of in indoor environments. As the lead content increases, the
alternatives exist. surface of the alloy takes on an increasingly dull appearance but
destructive corrosion is rare. Occasionally, condensed water
A great deal of discussion surrounds the identification of the may extract lead from the alloy but the most common cause of
species produced on the surface of tinplate during passivation
failure in the atmosphere is contact with organic acid vapours.
and the consensus view is that a mixture of tin oxides and Unlike tin, lead does not resist attack by these and contact with
chromium oxides with various levels of hydration are present. In materials which are sources of formic and acetic acids, among
addition, the majority of workers consider that significant
others, should be avoided. In most atmospheric exposure
amounts of metallic chromium exist in the film produced conditions, tin-lead alloys become covered by corrosion
cathodically and they cite both electrochemical 61,62 and products, such as lead sulphate, which offer protection against
E.S.C.A.h’-h4 data as evidence. further metal loss. However, in marine environments or where
Despite the universal use of passivation films for tinplate, little residues, such as fluxes from a soldering operation, are present,
has been published concerning their effect on the atmospheric then this film may break down.
corrosion of the material. Those paper^"^-^^ which have Tompkins 7 7 has reported a study of the interaction of O,, SO,,
appeared show that rusting resistance is increased and this of NOz, H,S, Cl,, CO and NH, with a 50% Sn/50% Pb alloy and the
course probably results from the effect the treatment has on the changes found at different relative humidities. He found that
iron exposed through pores in the tin coating of tinplate. A high humidity enhanced the reactions with low concentrations
number of papers however, have been concerned with the of CI2 which produced PbCI, and SnCI,. On the other hand the
increased resistance to oxidation of the tin coating on tinplate
activity of low concentrations of NO, in producing Pb(NO,), was
as a result of the passivation treatment, but these largely relate
inhibited by high relative humidity. All of the other gases had
to elevated temperature treatments such as would be carried
some interaction with the alloy when they were present at high
out during the lacquering of the material.hx-7”
concentrations, except CO and NH,, but only CI, and NO, were
active below a concentration of 100 ppm.
Bird7nhas recently carried out an E.S.C.A. study of a tin-lead
alloy, the surface of which was exposed to a laboratory
2 PEWTER atmosphere for only a few minutes. He concluded that the tin
Modern pewter is an alloy of tin containing up to about 7.5% was markedly segregated at the surface of the alloy and that it
antimony and about 2.5% copper. The material behaves in promoted the formation of a form of lead, thought to be PbO,,
virtually the same way as pure tin and in indoor environments, more highly oxidised than that obtained on the surface of pure
to which it is normally exposed, a bright, white lustre is lead under the same conditions,

7
K e n ~ o r t h appears
y~~ to be the only researcher t o have carried Smith" compared the performance of a number of commercial
out a systematic atmospheric corrosion study of a bulk tin-lead terneplates in both accelerated corrosion tests, sulphur dioxide,
alloy and his work led him t o the conclusion that a 3% Sn/97% humidity and salt-spray, and in full outdoor exposure to either
Pb alloy had indoor corrosion resistance superior to that of pure an industrial or marine environment. Exposure was for 12
lead. Both the surface appearance and weight increment data months only and interpretation of the results was complicated
after 1 4 months testing supported this. In full outdoor by the fact that samples were not prepared to standard coating
exposure, there was little difference between the performance thicknesses. Assessment was on the basis of the degree of
of this alloy and pure lead. rusting of the substrate steel, little mention being made of any
In addition to a study of ancient tin blocks which was attack on the coating. However, it was noted that lead-tin
mentioned earlier, Smythe5' investigated the corrosion alloys showed greater resistance to chloride attack than lead-
products found on two tin-lead alloy blocks. The first was of antimony alloys. At the same time, it was said that coverage of
Roman origin and was found at Benwall in Northumberland. the steei increased with tin content of the alloy and that the
Analysis showed it to be a 96.7% Sn/2.73% Pb alloy and the resistance of the coating to attack in both chloride-rich and
humid conditions aiso appeared to increase.
~

scale had the composition given in Table 6. Also in that Table


are the results of the analysis of the hard and brittle off-white The use of tin-lead coatings on copper alloy substrates to
scale found on a block of 94.7% Sn/5.3% Pb alloy. This was maintain the solderability of such materials for the electronics
also Roman in origin and was found at Cambridge. industry has led a number of workers to comment on the
importance of surface changes on performance without
systematic studies of those changes having been carried out.
Examples of the effect of storage, in part related to atmospheric
Table 6 corrosion are summarised by Thwaitess5 and have been
Analysis of the scales of corrosion product on two Roman discussed briefly by T i ~ s i e r . *As
~ a result of the importance of
blocks of tin-lead alloy (Data abstracted from ref. 57). the degradation of solderability during storage, a number of
accelerated ageing techniques have been developed and
Ackroydsz has recently reviewed these procedures. Increasing
interest is now being shown in the use of tin-lead coatings as
Wt. % of total
Compound contact materials. One of the potential difficulties faced by tin-
lead materials as low energy contacts would be the formation
96.YO%Sd2.73%Pb 94.79Sd5.3%Pb of films of corrosion product which might lead to poor electrical
Tin (IV) oxide 68.8 57.3 conductivity ,for the system. A number of a ~ t h o r s have ~~-~~
Hydroustin(ll)oxide 27.9 34.1
Tin(ll)chloride - 4.4 commented on the atmospheric corrosion of these contact
Silica 0.5 - materials although systematic controlled studies have not really
Lead sulphate - 2.7 been carried out. One of the reasons for this appears to be that
Basic lead carbonate 2.7 - the films which are normally formed are readily mechanically
Iron carbonate - 1.5 disturbed when contacts are mated and hence their presence
Water 0.1 -
does not normally create a problem.86

4. %!RI-COPPER ALLOYS
Most outdoor atmospheric corrosion studies of tin-lead alloys
This group of materials, consisting mainly of bronze, gunmetal
have been carried out on coatings on steel. As with rin coatings,
and brass with tin additions, represent the first to be considered
deposition of the alloy can be electrolytic or by hot-dipping or
in this paper in which tin is not normally a major alloying
metal spraying. Generally speaking, the higher the tin content
addition although in exceptional cases it may be present at
of the coating on terneplate, the lower its porosity and hence
concentrations up to 25%. Thus the corrosion of bronze in the
the greater the protection afforded to the substrate. Again, like
atmosphere is really like that of copper and is usually
tin coatings, tin-lead does not offer any galvanic protection to
accompanied by the formation of a layer of green basic copper
steel in the atmosphere and hence protection against rusting
salts, mainly suiphate, on the surface. The layer is adherent and
largely depends on coating continuity and the formation of
protective and can have a pleasant appearance.
protective corrosion products in the pores that are present.
Hudson and 5anfield79studied tin-lead coatings on steel in an xidation 0f Tin-Copper Alleys
industrial atmosphere. They compared 12% Sn/88% Pb with Early studies of the effect of tin additions on the rate of
pure tin and lead and found that the lead-containing coatings oxidation of copper include those of J ~ r d i s , *who
~ sealed
developed a white film which they believed to be lead sulphate. samples into tubes with air or oxygen and then tleated them.
At about the same time, Durose" looked at the corrosion However, a more thorough study has been carried out by
protection afforded to steel by electrodeposited tin-lead Gesmundo er who investigated the weight gain of Cu-Sn
coatings, using a range of coating weights and different plating alloys containing up to 13% Sn in oxygen ( 1 atm.) in the
bath additives. He concluded that a 5.5% Sn/94.5% Pb alloy temperature range 550-800OC. They found that the oxidation
was superior to a pure lead coating and also coatings rate of a 3% Sn alloy was lower than pure copper at 5 5 0 and
containing 7, 10 or 15% tin. The 10 and 15% tinhead alloys SOOOC but higher above 60ODC. The rate of oxidation of more
were found to be comparable with pure tin coatings. This result concentrated alloys however was always lower than pure
was in part confirmed by Graham and Pinkerton" who reported copper. They argued that the formation of an SnO, layer at the
atmospheric exposure results at three sites for lead, 5% base of the scale, although thin and usually discontinuous,
Sn/95% Pb and 14% Sn/86% Pb electrolytic coatings on steel. slowed down the outward diffusion of copper. The highest tin
Protection of the panels at all the sites (severe industrial, rural concentration allowed by its high temperature solubility in
and marine) by the tin containing alloys was superior to that copper was not sufficient to produce a continuous thick healing
produced by the lead alloy, particularly on the backs of the test layer of SnO, at the alloy surface but nevertheless, it produced a
panels. pronounced decrease of the oxidation rate.

8
4.2 Atmospheric Corrosion of Tin-Copper Table 8
Alloys Loss of strength of a number of copper alloys after exposure to
four different environments for ten years (Data abstracted from
In 1929, Hudsons9 reported the results from atmospheric ref. 90).
corrosion tests carried out on a number of copper alloys.
Included i n t h e programme was a bronze w i r e
(6.3%Sn/O.O3%P/Cu) and sheet (6.3%Sn/0.08%P/0.5%Zn/Cu)
and exposure for one year in rural, suburban, urban, industrial Loss of Strength after 10 years, %
Exposure
and marine environments was monitored. Corrosion in both
sheltered and full exposure was measured by following weight Environment Copper 8%Tin 7o%Gopper 7WCopper
gain, electrical resistance and tensile strength changes. All of Bronze 30%Zinc 29% Zinc
the materials showed performance which varied with the level 1% Tin
of atmospheric pollution and the bronze samples were always Heavy Industrial 5.9 7.2 30.9 9.0
among the better specimens. This was attributed to the fact Marine Heavy
Industrial 6.3 8.0 28.2 7.9
trhat they appeared not to form deliquescent corrosion products 7.6 5.7 8.0 2.5
Severe Marine
when submitted to accelerated corrosion tests. Table 7 shows Rural 3.1 3.1 3.2 2.2
the loss of tensile strength (mean for all five locations) derived
from Hudson’s work and the superiority of the bronze to
brasses can easily be seen.

corrosion films were found t o be basic chlorides and sulphates


of copper although copper metal and cuprous oxide were also
found together with traces of the alloying elements. A similar
Table 7 comment concerning the ecomomic results of SO2 pollution on
Mean values for the loss of strength of a number of copper the corrosion of a number of materials, including an 8%Sn
alloys exposed at five different sites (Data abstracted from ref.80). bronze was recently made by Speddinn4’
A number of authors have been concerned w i t h the
performance of tin-copper alloys in tropical environments.
Loss of Strength after 1 year Ambler and 5aing3compared the corrosion resistance of some
Alloy % common metals, including a tin-containing brass, at more than
6% Tin bronze 1.21
2.40
2 0 sites in Nigeria. In another study, Southwell ’‘et. al.
H. C. Copper compared the performance of five stainless steels with
3.5% Aluminiilm bronze 2.10
3.24 phosphor bronze (4.38%Sn/O.358%P/Cu) and a low alloy steel
70 Nickel/3O Copper
60 Copper/40 Zinc 18.4 a t tropical inland and sea-coast sites over a period of eight
70 CopperJBOZinc 8.58 years. The marine atmosphere was more aggressive towards
the bronze and a t both sites the stainiess steels showed lower
weight losses while the low alloy steel was severely attacked.
However, the bronze did not suffer pitting attack or a loss in
tensile strength while this did occur for some of the stainless
In a major study extending over 20 years and conducted at 7 steels. In a subsequent gaper,95the same authors reported the
different sites, Tracygo reported the atmospheric corrosion results of 1 2, 4, 8 and 7 6 years tests on a number of copper
I

resistance of a number of copper alloys. The samples included based alloys. Two tropical sites, marine and inland semi-rural,
phosphor bronze (7.85%Sn/O.O3%P/Cu), Admiralty metal were used and the tin containing alloys were phosphor
(1.22% .Sn/29.01%2n/69.75% Cu) and a nickel tin bronze bronze (4.38%Sn/0.36%P/Cu) Naval brass
( 1.04%Sn/28,64%Ni/O.55%Zn/69.1 %CuL As with Hudson’s (0.84%Sn / 39.02%Zn / 60.08% CUI and manganese bronze
study, corrosion was monitored by following weight, electrical (0.65%Sn/l.o4%Fe/40.25%Zn/Cu). Generally, all of the copper
resistance and tensile strength changes and in agreement with alloys tested were resistant to the tropical atmospheres, again
his work, atmospheric pollution was a major factor In deciding corroding more a t the coastal site than inland. The tin-
the rate of corrosion. industrial atmospheres were more containing alloysawere as good as, or slightly superior to the
corrosive than marine which in turn were more aggressive than other alloys. More recently,96 the same group of workers has
rural environments. in general, the extent of pitting was found summarised their results and drawn together comparative data
to be negligible for all. of the alloys studied. Some from different programmes conducted at the same tropical
representative data from the study are shown in Table 8. The sites. Results for four cast bronzes, (5%Sn/5%&/5%Pb/Cu;
ability of tin additions to restrict dezincification of brass was 6 % S n/3%Zn/2% P b/ 1 %N i/Cu ; 9 % S n/3%i!n/ 1% N i/C u ;
also apparent. 3%Sn/2%Zn/6%Ni/Cu) were added to the previously reported
Another study was conducted in the U S A . by Quickv1 who data but the conclusions were broadly the same as before. The
exposed screen wire cloth at four different sites for up to nine most interesting additional data presented in this final paper in
years. He included brasses, aluminium bronze, nickel/copper the series was for the effect of coupling phosphor bronze to
and a 2% tin bronze. The brasses failed rapidly but the tin equal areas of a wide range of other metals. In this test it was
bronze showed the lowest percentage loss of strength at all the found that the coastal environment was 4-8 times more
sites. aggressive than the inland atmosphere.
Brittong2 confirmed the effects of pollution, particularly by Mention should also be made here of the generally superior
sulphur containing compounds and showed that in railway resistance of tin-copper alloys to corrosion fatigue. Gough and
tunnels used by steam locomotives the rate of corrosion of a Sopwithg7 compared a 4% tin phosphor bronze with other
number of copper alloys was about an order of magnitude copper alloys and stainless steels in a salt-spray and found it t o
faster than in the open air. Despite this, the projected lifetimes be superior to all the materials. The second best sample was a
for the materials, including a 2%Sn bronze wire, were good. The beryllium-copper alloy. The subject of stress corrosion cracking

9
is really best considered in the context of copper alloys but it is suggested a number of remedies to nullify the effect of CuCl or
generally agreed that phosphor bronzes show high resistance to to remove it completely.
this form of attack while Admiralty brass in common with Collins"' examined a number of Chinese bronzes which had
70/30 brass is not very resistant. been buried for 1,000 to 4,000 years. The alloys covered a
Occasional references have appeared in the literature to studies wide range of compositions and slight differences in their
carried out on the atmospheric corrosion of complex bronze corrosion films were found. On some of the bronzes, a layer of
alloys. A P%Sn/S%Ni/Cu alloy was developed by the Bell botryoidal malachite (CuCQ,.Cu(OH),) 1.2 cm thick was found.
Telephone Laboratories in collaboration with others and it was This was accompanied by crystals of cuprite (Cu,O) and thick
claimed to have tarnish resistance superior to that of other crusts of azurite (2CuC03.Cu(OH),). Leaded bronze
bronzes used in the electronics industry as connector materials. (21%Sn/4%Pb/Cu) was examined by Gettens"' after it had
Ward and Lovettg8 have summarised the principal properties probably been buried for about 2,500 years. He described the
claimed for the alloy, including the effect of atmospheric ageing surface as having an outer, completely mineralized zone and an
on solderability. This is an index of the amount and nature of inner partially mineralized region. This contained CuCl covered
the corrosion film on the alloy and it is clear that the alloy is by Cu,O interspersed with disconnected seams of SnO,.
superior in performance to both nickel-silver and an 8% tin Summarising the work of others, Mantel1112 lists those
phosphor bronze. A more general study of the Cu-Ni-Sn and compounds found in the patina of bronze as malachite
Cu-Ni-Zn-Sn systems was made by Mori and Nakojimag9but (CuCO,.Cu(OH),). atacamite (CuCl,.3Cu(OH),). and azurite
little reference was made to atmospheric corrosion except to (2CuCO,.Cu(OH),). These can be mixed with cupric chlorides
suggest that the zinc containing alloys were found to be more and salts of alloying elements such as tin oxide and lead
stable against oxidation. Habrakenlooet. al. studied some alloys chloride.
in the Cu-Sn-AI system and decided that those containing a t
least 5% each of tin and aluminium had promising tarnishing 5 TIN-ZINC ALLOYS
resistance. Alloys were exposed to rural, urban and industrial
atmospheres and the mosr promising material was found to be Alloys of tin and zinc, normally in the range of 15-30% Zn, find
5%Sn/7%AI/Cu. In a later paper, AhmadlO1 pointed out that limited applications as a corrosion protection coating for steel
such alloys could be brittle but that further additions of 1% Fe with good to moderate solderability characteristics. Over the
and 1% M n overcame this difficulty while the presence of tin years, spasmodic interest has been shown in such coatings as
still improved the corrosion properties of the alloy. substitutes for cadmium plating and it appears that for certain
applications they offer a viable alternative. The literature on the
Electrodeposited copper-tin alloy coatings find some industrial atmospheric corrosion of these alloys reflects this interest
applications. Bronze deposits containing 10-20% tin have been although Lashko and La~hko-Avakyan"~ reported the results of
used as undercoatings102for nickel-chromium or tin-nickel a study of tin-zinc alloys used as solder to join aluminium. They
deposits for decorative applications. They have also been used found that the corrosion resistance of the solder to a tropical
in their own right a t a thickness of 5 0 ~ m
on steel components atmosphere during up to 9 months exposure was a function of
of hydraulic mine equipment. This has been because of their the zinc content. The alloy 80%Sn/20%Zn was found to be the
superior hardness and slightly better corrosion resistance to most resistant to attack and to have the best strength retention.
marine atmospheres than copper. The alloy containing 42% tin
Tin-zinc alloy coatings behave as a simple mixture of the two
which at its correct composition is actually the intermetallic
compound Cu,Sn 103-104 was once used as a material for metals and may be deposited from a number of bath
formulations over virtually the entire composition range.114The
mirrors, hence the name speculum. When polished, a coating of
zinc in the coating can provide protection to any substrate steel
speculum has a similar appearance to silver and it shows a
exposed a t pores but in full inland exposure to polluted
good resistance to sulphur compounds and other tarnishing
atmospheres, the depletion of zinc is too rapid so that rust
agents. It normally remains bright indoors but rapidly turns dull
appears before it would on a zinc coating of comparable
and grey when exposed outdoors if it is not frequently cleaned.
thickness. However, in sea-spray or similar marine
Early work by Faust et. al.105describes some of the properties of environments, coatings containing 70-85%Sn can perform
bronze and speculum coatings and more recently, Laub106 has better than pure zinc because of the apparent formation of a
reported the corrosion resistance of tin-copper alloys plated protective corrosion product. The main uses of the coating have
onto steel in both industrial and marine environments. been in sheltered environments where its ease of solderability
and protection of steel exposed a t pores are an advantage.
4.3 Long-Term Atmospheric Corrosion of Tin- Under these conditions, it is less likely than zinc to produce
Copper Alloys loose corrosion product and it is also less affected by exposure
In view of the long history of the use of bronze, it is not to acid vapours from wood. It is also possible to improve the
surprising that a number of workers have been concerned with solderability and long-term cleanliness of the coating by
corrosion damage and repair of the material. Fink and depositing tin separately on top of a layer of zinc which is then
Eldridge'O' reported a method for reducing the basic salts still able to offer protection at pores in the duplex coating.
present in the crust of corrosion products on ancient bronzes by Angles and Kerr'" appear to have made the first systematic
electrolytic reduction in a 2% NaOH electrolyte. A series of study of tin-zinc coatings on steel. They examined the
electrolytic treatments were also used by Evans'O* to recover performance of alloys in the range 28-92% Sn and compared
artefacts which had suffered "bronze disease." This took the them with coatings of tin, zinc and cadmium. The conclusion
form of the production of soluble copper acetate beneath the from both accelerated tests and atmospheric exposure in an
porous original patina. Acetic acid was thought to have derived urban environment for one year was that coatings of
from the packing materials used to store the articles. The 80%Sn/20%Zn offered superior protection to steel and that the
acetate was converted to basic carbonate or sulphate, releasing appearance of white zinc corrosion product increased with the
the acetic acid for further attack on the bronze. zinc content of the alloy. A suggestion was also made that
Another case of bronze disease was investigated by Organlog chromate passivation treatments improved the overall
who suggested that the formation of unstable CuCl in the lower performance of the coating, making it less susceptible to
layers of the patina was the cause of the problem. He staining by finger or grease marks. This study was followed by a
number of authors who largely came to the same conclusions 6 TIN-CADMIUM ALLOYS
concerning the protection of steel against atmospheric
corrosion by ti n-zinc a Iloy coati ngs. 42,46,'I
The atmospheric corrosion studies carried out on these alloys
refer t o their performance as coatings for the protection of
One of the more complete studies, again by Angles119 but in steel. However, there has been little practical use made of them
collaboration with Britton, compared coatings in urban, although interest is occasionally renewed as a result of some of
suburban and marine environments. They decided that the the test results previously reported.
order of merit in urban exposure was zinc, 50%Sn/50%Zn, The range of tin-cadmium alloys may be electrodeposited or
80%Sn/20%Zn, then cadmium. i n marine exposure, mechanically plated and in appearance and behaviour they are
50%Sn/50%Zn was better than zinc and cadmium but like tin-zinc coatings. Since cadmium is less effective at
$O%Sn/20%Zn was inferior to zinc and no better than sacrifically protecting steel exposed at pores, the optimum
cadmium. These results have been summarised in Table 9. concentration in the coating is in the range 25-50%. As with
tin-zinc deposits, the merits of using a duplex coating of tin on
top of cadmium have been explored and have proved to be
valuable where exposure to organic vapour might be expected.
Bennett,Iz3 then Scott and Gray"4 developed the electrolytes
Table 9 for the deposition of tin-cadmium alloys and reported some
The reiative ability of different coatings to prevent the rusting work on the protection afforded to steel by the coatings. Britton
of steel in a marine atmosphere (Data abstracted from ref. 119). and de Vere S t a ~ p o o l e carried
'~~ out a thorough investigation of
the coatings, in particular suggesting that the alloys performed
better than cadmium alone in marine environments. This was
Months to the first appearance of rust followed by a study by CohenIz6who reinforced the point made
Coating Metal by Britton that the attack on the coating by organic vapours
was less than for pure cadmium. Burneri2' went further than
7.5pm 12.5~m 25wm
these authors in suggesting that tin-cadmium alloy coatings,
Zinc 18 33 36 particularly with a chromate surface treatment, performed
Passivated zinc 18 18 36
35 better than cadmium coatings of the same thickness.
50% tin/50% zinc 25 )48
Passivated Recently, two other papers have appeared which again came to
50% :in/50% zinc 29 35 )48 the same conclusions as those referred to above. Beck and
80% tin/20% zinc 9 18 36
Passivated 3anowsky"8 reported that the protection afforded to steel by
80% tin/20% zinc 13 21 36 alloy deposits was greater than that given by duplex coatings of
Cadmium 8 21 34 tin and cadmium. Cooke et. al.'29 showed that zinc or tin-zinc
Passivated coatings gave greater protection to steel in industrial
cadmium 13 21 25
environments than tin on cadmium or cadmium on tin but that
Tin 1 1 1
the order of their relative performance was reversed in a marine
atmosphere.

a TIN-NICKEL ALLOYS
The most recent contribution on the subject was published by As with tin-zinc and tin-cadmium alloys, the use of tin-nickei
Raub et. al.Izo who also included information concerning the alloys is restricted to that of a coating on both ferrous and non-
latest developments in the nature of the electroiyte used in ferrous substrates. Alloys in the range 18-25% nickel may be
depositing the alloys. deposited from a mixed cyanide-stannate bath as hard, bright
Britton and de Vere Stacpoole121investigated the properties of coatings with good resistance t o nitric acid. However, no
tin-zinc alloy coatings on steel nuts and screws exposed to interest has been shown in these finishes, mainly because of
suburban, industrial and marine atmospheres in contact with the brittleness of the product of this particular plating
aluminium plates. They found 80%Sn/20%Zn coatings to be process.i30 Similar work w i t h complex pyrophosphate
generally superior to zinc and cadmium when considering ail electrolyte was reported by Rama Char.'31 Application of tin-
the exposure conditions in that, while failure of the coating nickel alloy deposits has centred on the intermetallic compound
resulted in rusting of the steei more quickly than with zinc and NiSn which may be readily plated from mixed acid
cadmium in particular environments, it did not result in rapid chloride/fluoride e l e ~ t r o l y t e s . ' ~ ~ - ' ~ ~
attack of the aluminium. An additional advantage was the The deposit is metastable but does not transform to a mixture
absence of hvgroscopic corrosion products on the tin-zinc alloy of other intermetallic compounds unless thermally aged.'34 It is
so that a ring of moisture did not form around the nuts and hard, nearly bright and reasonably solderable, has remarkable
screws; this was a source of potential problems with the zinc resistance to attack by a wide range of solutions and displays
and cadmium finishes. good wear r e ~ i s t a n c e . 'Because
~~ of this, the coating has been
The resistance of tin-zinc alloy coatings to the production of used as a decorative corrosion resistant finish for balance
copious amounts of corrosion product when exposed to the weights, drawing instruments and pistons on automobile brake
atmosphere was illustrated in work by Phillips and Johnson.122 systems. It has recently gained popularity in food contact
They measured the contact resistance of a number of coatings applications, being specified as a finish in beer dispensing
on steel after exposure to a rural outdoor atmosphere. They equipment. Despite these applications, the full potential of the
found that tin-zinc and tin-cadmium alloy deposits maintained a coating does not seem to have been realised and this might be
lower contact resistance than did equal thickness of tin, tin-lead in part due to its limited d ~ c t i l i t y . ' ~ This
~ - l ~means
~ that impact
or tin-antimony alloys. The samples were exposed for 2 months damage could lead to damage of the substrate since this
under a constant mating load and while the contact resistance cannot receive any galvanic protection from the very noble
of a tin-lead alloy coating was IOW, it failed to give as good coating.
corrosion protection to the substrate during the test. Coating thicknesses for various duties are specified in I S 0
2179:1972 and this requires a deposit of 25pm for severe etching, tin could diffuse from the grain boundaries to cover the
service, 15pm for moderate environments and 8pm for mildly surface again. This explanation does not however seem to be
corrosive conditions. For coatings on steel intended for compatible with all of the observations made on the long-term
moderate or severe service, an undercoat of copper, tin or stability of this alloy.
bronze with a minimum thickness of 8ym is also specified and
porosity tests are required.
7.2 Atmospheric Corrosion of Tin-Nickel Alloys
Studies of the atmospheric corrosion of tin-nickel alloy electro-
7.1 Passivation of Tin-Nickel Alloy deposits can be separated into two clear phases. The early work
Renewed interest in the properties of the equiatomic alloy of tin was concerned with the potential use of these coatings in
and nickel as a contact material, on its own or with an over- decorative applications where corrosion resistance was also
plate of gold, has been partly responsible for a number of. required. Performance under these conditions was often
studies of the growth and composition of the air-formed compared with nickel-chromium systems and frequently
passivation film on the alloy. This film provides the basis for the encouraging results were obtained.
chemical stability of the alloy but a t the same time it produces In a series of paper^,'^^-'^^ Britton established that electro-
high and unpredictable electrical resistance which can inter- plated tin-nickel alloy is untarnished by atmospheres grossly
fere with its operation as a low voltage contact material. Antler polluted with SO, and H,S. Comparisons made with nickel-
has been very active in this field of studies and has recently chromium deposits by the same author showed that in
produced a comprehensive review of the subje~t.',~Early work positions sheltered from the rain, tin-nickel was better able to
was necessarily electrochemical in nature dnd led to the retain its brilliance. Chadwick15* then L ~ w e n h e i m " came
~ to
suggestion, supported by several worker^,'^*-'^^ that the similar conclusions, at the same time considering the composi-
passive film was environment sensitive but that it probably con- tion of undercoats used for both alloys on steel. Nickel-
tained oxides and hydroxides of tin and nickel in the same chromium deposits were found by Angles154to be superior to
proportion as the metals appeared in the bulk material. The tin-nickel plate in marine environments.
possibility of specific mixed nickel-tin oxides was also
More recent studies of the atmospheric corrosion of tin-nickel
post~lated.~~'-~~~
alloy electrodeposits have been concerned with the effect that
More recently, physical techniques such as Auger spectro- surface changes have on the electrical contact resistance of the
scopy and E.S.C.A. have been turned to the problem and a more material, either alone or with a thin cover of gold. Contact resis-
complicated picture emerges. Hoar et. al.143 suggested that tance is adequately low for moderate voltage (e.g. 5 0 V )
the air-formed film contained tin and nickel in the ratio 3:l with applications, but is too high for low voltage uses. This is largely
an oxygen to total metal ratio of 0.7. Tompkins and Bennett'44 as a result of the insulating passive film which forms and the
questioned some of these findings and from their own work high hardness of the material. Mills'55briefly summarised the
concluded that the surface of NiSn in air was rich in tin as an properties of NiSn as a contact material but more recently,
oxide film several atoms thick. The same authors followed this Antler has been much involved with such studies. He
work with another similar in which they also suggested reportedlS6or: the interaction of SO,, H,S, NH,, NO, sulphur
that the other intermetallic tin-nickel compounds (Ni,Sn,, vapour, salt-spray and synthetic dust with NiSn, Ni,Sn, and
Ni,Sn, and Ni,Sn) probably carried a comparable passive film. Ni,Sn,. The behaviour of all three phases was found to be
Other authors, most notably Thomas and Sharma, 146,147 have similar and stability against attack and comparatively small
recently produced a series of papers supporting the conclu- changes in contact resistance were found after exposure to
sions of Tompkins and Bennett and providing more quantitative each of the atmospheres. In a later study, Antler'57followed the
detail. Tompkins, Wertheim and Sharma'4xfollowed the growth change in contact resistance as a function of time in different
and composition of an air-formed passivation film over a period atmospheres. Changes were relatea to the growth of the
of up to 62 days. Some of the samples were aged straight from surface oxide film under different conditions of temperature and
the plating electrolyte while others were given a hydrochloric relative humidity. These results have since been r a t i ~ n a l i z e d " ~
acid etch before ageing. As-plated films of any age were by that author in the light of studies of the passivation film
composed of amorphous hydrous tin oxide n i t h an oxygen'tin cornposition which were discussed above.
ration of about 3. They were all about 2nm thick over the
ageing range of 2 minutes to 62 days but during that time, the
nickel:tin ratio of h e film increased f r o m 0 to 0.1 1. The
8 TI N-COBALT ALLOYS
crystallinity of the film was also seen to increase with time. The Interest has recently been aroused in electrodeposits of tin-
samples which had been etched before ageing showed a cobalt alloys which in many ways resemble those of tin-nickel.
different pattern of film growth. They increased in thickness Deposits of SnCo'5R-'59 or SnCo mixed with Sn,Co'60 have been
from 1.2 to 2nm over the period 2 minutes to 52 days and the obtained and proprietary systems have been patented. The
0xygen:tin ratio was much higher, changing from 5.5 to 6.5. deposits are bright and have a colour very similar to decorative
However, the nickel:tin ratio was comparable with that for chromium plate and advantages in the deposition process have
unetched samples, increasing from 0 to 0.13. In both the suggested their use in place of that element in nickel-chromium
etched and unetched samples, the nickel in the passive film systems. Most studies have therefore been concerned with the
was thought to be an hydroxide. performance of systems consisting of steel coated by nickel
with a very thin film of tin-cobalt alloy to provide a pleasing
It is generally agreed from the work described that tin concen- finish.
trates at the surface of tin-nickel alloy electroplates but no
adequate explanation of this phenomenon has yet been put Miyashita and Kurihara,I6' in reporting details of the electro-
forward. Antler'" reports that Lo has suggested in a private deposition of tin-cobalt alloys, commented on the resistance of
communication that the surface is actually composed of Ni,Sn, the coatings to salt-spray and CASS tests and exposure to
grains with tin concentrated a t the grain boundaries. Thus the ammonia. They found that the deposit resisted attack in all of
bulk analysis would still yield a composition corresponding to these and that furthermore. its ductility was higher than that of
NiSn but the explanation assumes that tin would be present on a tin-nickel deposit.
the surface of a deposit in the as-plated condition and that after The results of CASS tests and outdoor exposure tests on plated

12
systems consisting of nickel plus tin-cobalt alloy were reported 14. W. E. Boggs, R. H. Kachik, and G. E. Pellissier, J. Electrochem.
by Hyner'62and then Hemsley and R ~ p e r .They' ~ ~ each used a Soc., 111 (6).636 (1964).
15. C. Luner, Trans. Met. Soc. A.I.M.E., 218 (31,572 (1960).
different bath and minor differences in the deposits were 16. W. E. Boggs, R. H. Kachik, and G. E. Pallissier, J. Electrochem.
produced but their conclusions were very similar. The perfor- Soc., 110 (11, 4 (1963).
mance of the system was claimed to be comparable with that 17. A. Kutzelnigg, Z. Anorg. Chem., 202, 418 (1931).
of a nickel-chromium system in all but the more severe 18. A. Kutzelnigg, Z. Electrochem., 41, 450 (1935).
exposure conditions. 19. D. J. MacNaughton and E. S. Hedges, Proc., lnt, Congr. Mining,
Metallurgy and Appl. Geology, Paris, (1935).
As might be expected by comparison with tin-nickel alloy 20. L. Kenworthy, Trans. Faraday Soc., 31, 1331 (1935).
coatings, tin-cobalt owes its stability and corrosion resistance 21. S. C. Britton and K. Bright, Metallurgia, 56, 163 (1957).
to the formation of an adherent protective passive film. This 22. S. C. Britton and J. C. Sherlock, Br. Corros. J., 9, 96 (1974).
was demonstrated by Tsuji and I ~ h i k a w a for ' ~ ~a number of
23. R. D. Jenkins, Proc. Phys. Soc., 47, 107 (1935).
24. R. K. Hart, Proc. Phys. Soc., 658, 955 (1952).
electrolytes, then Thomas and S h a r r r ~ a carried
'~~ out an Auger 25. J. C. Platteuw and G. Meyer, Trans. Faraday Soc., 52, 1066
and an E.S.C.A. study of the alloy surface. They concluded that 11956).
plated coatings of 80%Sn/20%Co alloy exposed to oxygen 26. C. L. Lau and G. K. Wertheim, J. Vac. Sci. Technol., 15 (2),622
grow a film similar to that found on 65%Sn/35%Ni atby. That is (1978).
27. S. N. Shah and D. E. Davies, Firstlnt. Congr. on Metallic Corrosion,
to say, the surface layer which varies from 6.5-10.5 A consists
Butterworths, London, 1961,p.232.
primarily of hydrated tin(lV) oxide with some cobalt (11) oxide. 28. H. S. Rawdon, lnd. Eng. Chem., 19,613 (1927).
Similar results were found for layers of sputtered tin-cobalt 29. C. b. Mantell, Corrosion of Tin andlts Alloys, Amer. Inst. Min. Met.
alloy exposed to oxygen unless the partial pressure of that gas Eng., Tech. Publ. 171,3 (1929).
was low. Under those conditions, the film was primarily tin (11) 30. W. Cooke, Australian Chem. Inst. J. and Proc., 6, 58 11938).
31. V. V. Skorchelletti and S. E. Tukachinskii, J. Appl. Chem.
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34. H. F. Whittaker, Research lnforaation Surveys on Corrosion of
9 TIN-SILVER Metals, Tin, National Research Cohncil Publication, Washington D.
C., 1924.
Some years ago, tin-silver alloys were examined as potential 35. L. Kenworthy, The Atmospheric Corrosion and Tarnishing of Tin,
replacements for sterling silver in decorative applications. Price B.N.F.M.R.A. Research Reports No. 231,236,237,254,270and
and Thomas166compared the corrosion resistance of silver with 293, London, 1934.
the 7.5%Sn/92.5%Ag alloy and found i t t o have a number of 36. W. Finkeldy, A . S. T.M. Symp. on Outdoor Weathering of Metals,
advantages. Duckett, Robins and BrittonI6' followed this with a A.S.T.M., Philadelphia, 1934,p 69-87.
37. Report of Committee 83, Proc. A.S.T.M., 34 (I), 221 (1934).
study of the binary system between tin and silver for alloys
38. Report of Committee 83. Proc. A. S. T.M., 35 (1 ), 1 (1 935).
containing up t o 10% tin. The tarnishing of alloys in hydrogen 39. G. 0.Hiers, A.S.T.M. Symp. on Outdoor Weathering of Metals,
sulphide, sulphur dioxide and indoor atmospheres was followed A.S.T.M., Philadelphia, 1946.
and the resistance to oxidation on heating in air and to salt was 40. G. 0. Hiers and E. Minarcik, A.S. T.M, Spec. Tech. Publ. No. 775,
compared with that of sterling silver. The tin containing alloys 135 (1956).
41. P. L. Speddin, Australian Corros. Engng., 15 (8),27 (1971).
were found to be at least as good as the copper containing 42. S. C. Clarke and E. Longhurst, First lnt. Congr. on Metallic
alloys and in some cases they were even better. In particular Corrosion, Butterworths, London, 1961,p 70.
the resistance to chloride attack was considerably better and 43. K. G. Compton, Corrosion, 4, 112 (1948).
discolouration during heating in air was less. The pre-oxidation 44. J. C. Hudson and T. H. Banfield, J. Iron Steel Inst., 154, 229
of tin-silver alloys was found to improve their resistance to (1946).
45. J. C. Hudson and J. F. Stanners, J. Iron Steel Inst., 175, 381
attack by sulphur-containing atmospheres. (1 953).
46. S. C. Britton, Metallurgia ltaliana, 46, 89 (1954).
AC KNO W L EDG ME NTS 47. M. Dettner, Plating, 46 (5).469 (1959).
The assistance of Mr. G. O'Boyle in assembling many of the 48. T. Biestek, Prace. Inst. Mech., 7 126).89 (1959).
49. T. Biestek, Prac. Inst. Mech., 11, 1 1 (1'963).
references contained herein and the permission of the Inter- 50. T. Biestek, Met. Fin., Oct, 39-41 and 61 (1974).
national Tin Research Council to publish the paper are 51. W. D. Bader and R. G. Baker, Plating, March, 242 (1973).
gratefully acknowledged. 52. M. L. Akroyd, A Survey of Accelerated Ageing Techniques for
Solderable Substrates, International Tin Research Institute
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