Anti-Corrosion Methods and Materials

CORROSION OF METAL CONTAINERS

R.K. Sanders
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R.K. Sanders, (1955),"CORROSION OF METAL CONTAINERS", Anti-Corrosion Methods and Materials, Vol. 2 Iss 8 pp. 238
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 CORROSION OF METAL CONTAINERS
By R. K. Sanders, M.A.
(Head of Research Division, The Metal Box Co., Ltd.)

The corrosivity of the materials used for the fabrication of metal containers has always been an
important consideration in the choice of these materials and the use to which they can be put. As far
as this country is concerned, at any rate, tinplate is the material most commonly used for metal
containers which are used for literally hundreds of different products, for each of which the tinplate/
product complex must be studied for possible harmful corrosive effects. In this article the author
considers tinplate, 'blackplate' and aluminium in their roles as structural metals for containers,
outlining their corrosion characteristics under varying conditions and reviewing the present state of
knowledge of this important subject of metal container corrosion.

FOR the purposes of this paper, I pro- troversial one and, up to now, really lytic plate decreases from 16 to 4 oz.,
pose to consider only three structural definitive work has been precluded by the porosity generally increases.
metals — tinplate, 'blackplate' and the absence of a reproducible measure It follows from this that, as, for the
aluminium. Of these, in this country of porosity under conditions satis- sake of economy, more electrolytic
at any rate, and almost universally, factorily similar to those multifarious plate of lower and lower coating
tinplate is by far the most important. ones pertaining during the shelf lives weights is used, more care has to be
of commercial containers. Current exercised in the fabrication, handling
Tinplate thought seems to be that, under the and storage of the containers made
Tinplate is mild-steel sheet coated acidic and anaerobic conditions pre- from it. It would appear, however,
on both sides with a thin layer of vailing in cans of fruits and vegetables, that, at least as far as protection against
Anti-Corrosion Meth & Material 1955.2:238-242.

almost pure tin. This coating is now porosity in itself is not of major con- external rusting is concerned, the most
applied by two different processes, the sequence; but that field has been economical course is to use low tin-
products of which differ quite mar- dealt with in recent articles in this coating weights and a coat of lacquer,
kedly from the point of view of cor- journal and is not under discussion in which is more effective than the use of
rosion. In the older process, the tin is this one. higher tincoating weights unlacquered.1
applied by passing the steel in sheets It can be said, however, (a) that the (iii) If the tincoating is removed from
through baths of molten tin (hot- porosity of tinplate has an important electrolytic tinplate by an acid
dipped tinplate), while in the newer bearing on its rust resistance, (b) that solution of antimony trichloride
process the steel is passed in con- the greater the initial porosity the and the steel is then placed in
tinuous strip form through electrolytic greater will be the added amount of concentrated hydrochloric acid,
plating baths and heated momentarily steel exposure as a result of deforma- there is usually a lag period before
(by induction or by resistance) to the tion by bending or stamping and (c) hydrogen is freely evolved. The
melting point of tin to produce a bright that, as the coating weight of electro- existence and magnitude of this
finish (electrolytic tinplate).
These two products differ in many
ways, but in a survey of corrosion of
metal containers we may perhaps
confine ourselves to the following:
(i) It has never been possible by the
old hot-dipping process to apply
uniform coatings of tin of less
than about 14 oz. per basis box,*
whereas serviceable coatings as
light as 4 oz. can be and are
applied electrolytically.
(ii) The 'porosities' of the coatings
applied by the two methods are
different in degree, and perhaps
even in kind also.
The question of the significance of
porosity in the corrosion resistance of
tinplate has always been a highly con-
*A basis box is the equivalent in area of
both faces of 112 sheets each 20 x 14 in.
(i.e. 31,360 sq. in. of coated surface). The
practice of specifying tincoating by weight
per basis box is universal, and in this
country it is usually expressed as C4, C8,
C16, etc.

238 CORROSION TECHNOLOGY August 1955

 lag period (which is never ex-
hibited by the steel from hot-
dipped tinplate) are known to be
associated with the conditions
under which the steel has been
annealed and pickled before tin-
ning,2 and it is also known that
the shelf life of some canned
fruits is inversely correlated with
the lag period of the plate from
which the cans were made. To
what extent this phenomenon may
have a bearing on corrosion under
other than acidic and anaerobic
conditions is not yet known.
(iv) The rate of solubility of the tin-
coating itself in various corroding
media unquestionably differs
according to whether the coating
has been hot dipped or applied
electrolytically. Whether this is
directly due to physical or other
difference between the two coat-
ing structures, or whether it is
due to cathodic differences be- Many factors enter into the external Vapour-phase inhibitors are now well
tween the underlying steels in the rusting of tinplate containers, and a known and widely recommended, but
two types of tinplate, is still a few random notes about the more our experience, particularly in the
matter of some controversy, but important of them may be of value. exporting of flattened can cylinders
the fact is undisputed and does where raw cut edges of steel are in
have a bearing on the replacement Generally speaking, tinplate will not
contact with board, has been that
Anti-Corrosion Meth & Material 1955.2:238-242.

of hot-dipped by electrolytic rust in the absence of water in the

liquid phase, but, even under con- vapour-phase inhibitors are ineffective
tinplate. if tinplate is in contact with damp
ditions where actual condensation does
not occur, the presence of hygroscopic board of high chloride content, and
(v) Finally, the surface of hot-dipped unnecessary if it is not.
tinplate carries a film, however material in the atmospheric dust (as
thin and discontinuous, of an in- -in seaside and most urban atmo- In the canning industry, the pre-
determinate mixture of palm oil spheres) will promote rusting of tin- sence of chloride and sulphate ions in
and zinc, tin and sodium salts of plate containers exposed to the settle- the cooking or cooling water can pro-
palm oil fatty acids. The final ment of such dust, while others pro- mote serious rusting, and an instance
processes in the manufacture of tected from it will remain clean. has been observed in which intense
electrolytic tinplate, on the other The mention of hygroscopic mat- rusting underneath the lacquer on
hand, cover its surface with a erials introduces the fact that, par- externally lacquered can ends could
more or less controlled film of ticularly if electrolytic tinplate is used, be seen taking place within seconds
tin oxide, followed by a closely or if containers are destined for export of removal of the cans from the retort,
controlled film of pure cottonseed to climates of high humidity, either due to excessively high chloride and
oil. As will be seen when we the fluxes used in any soldering opera- sulphate content in the cooling water.
discuss corrosion of milk cans, tion must be free from hygroscopic The addition of rusting inhibitors,
these surface differences are sig- and corrosive compounds like zinc most notably dichromates, to cooling
nificant, and it may well be that chloride, or the containers must be waters has been practised in the United
further study of them may lead washed free of flux residues after States3 and the well-known Protectatin
to modification of the treatments soldering. If this is done, it is usually process developed by the Tin Research
that would significantly improve as well to follow washing by treatment Institute4 confers definitely increased
some aspects—notably the rust with some dewetting compound and, rust-resisting properties on tinplate
resistance—of the corrosion in any case, to ensure that the con- components that have not had their
characteristics of electrolytic tainers are thoroughly dry before tincoating severely mutilated by manu-
tinplate. stacking them or placing them in facturing operations. Such damage
cartons. obviously impairs the rust resistance
Rusting—external of tinplate, particularly electrolytic,
The rusting of tinplate is markedly and it is normally advisable that deeply
For most civilian purposes it can accelerated by the presence of chloride stamped or drawn components be
safely be said that, as far as external and sulphate ions, and the practical made from lacquered plate.
rusting is concerned, hot-dipped tin- effects of this are quite widespread.
plate carrying not more than 16 oz. Label papers and labelling adhesives The special treatment involving pro-
of tin per basis box has got 'what it should be substantially free from cessing in steam or water at tempera-
takes.' In circumstances in which such chloride ions and, if transport or tures up to 260°F. and subsequent
plate requires care in treatment or storage conditions are liable to bring cooling in water that tinplate con-
storage, C. 8 electrolytic plate requires cartons of cans into contact with liquid tainers receive in the canning industry
even greater care and C. 4 plate water, the chloride content of the subjects them to considerable hazard
usually requires lacquering. carton board should also be controlled. of rusting if these processes are not

August 1955 CORROSION TECHNOLOGY 239

 properly executed. Several excellent tomato) sauces which corrode tinplate
accounts of what constitutes good with the production of gaseous hydro-
practice in this respect have already gen. Even these packs do not normally
been published.5 form hydrogen swells even after very
A more recent development being long periods of storage if hot-dipped
explored in our laboratories is the tinplate is used, but it is advisable not
addition of very small quantities of to use electrolytic tinplate. The second
volatile oil to each retort load of cans category of fish packs includes all those
immediately before processing. Dur- in oil or brine which may attack either
ing the processing an extremely thin the tin or the steel in varying degrees,
film of oil is deposited on every can, but without the formulation of gaseous
thin enough not to interfere with label- hydrogen. The mechanism of this
ling or to attract dust but conferring type of attack by marine products is
considerable resistance to rusting. not fully understood, but the impor-
tant part played by trimethylamine
Rusting—internal oxide, normally present in sea fish,
in reacting directly with metallic tin
Rusting of tinplate is arrested in an has been extensively studied in Nor-
atmosphere in which the ratio of con- way, and an excellent account of this
centration of CO 2 to oxygen exceeds work and the whole field of corrosion
1.6 In the headspace atmosphere pre- of tinplate cans by fish products is
vailing in processed food cans after given by Jakobsen and Mathiesen.7
processing this ratio is normally ex- area of the cans during their manu-
ceeded. In one or two special in- facture—whether they are lacquered Milk. For the most part canned
stances, however, e.g. fruit salad made or not. The exact composition of these milk presents no corrosion problems,
by repacking already once-canned brown, blue or black stains on the but one aspect of the canning of
fruit, the headspace gas has the normal tin surface and of the jet-black com- evaporated milk in vent-hole cans
atmospheric CO2/O2 ratio and rusting pounds formed by the attack on the made of electrolytic tinplate is perhaps
occurs. The unsightly effect of this is steel is not known, but it is customary of some theoretical interest.
overcome by storing the cans upright and convenient to refer to them Electrolytic tinplate is normally
respectively as tin and iron sulphide.
Anti-Corrosion Meth & Material 1955.2:238-242.

for a few days, after which, all the finished by oxidising the surface either
oxygen having been consumed in rust- The sulphide staining on the tin, by a chemical (chromic acid) dip or
ing the top end, the cans may be since it forms a very firmly adherent by electrochemical (anodic) treatment.
inverted so that the rust on the top film, is of no consequence beyond its During manufacture of the cans this
(now bottom) end is dissolved in the unsightliness. It can be prevented by oxide film is damaged, by scratching
acid fruit juice, the new top end the use of suitable lacquers; the Pro- and in bands where the three seams
remaining free from rust. tectatin process has also been shown have been soldered. Where the film
In what are known as general-line to be very effective in preventing it, is damaged the tin surface becomes
containers—those miscellaneous boxes and it does not occur in canned meats anodic to that of the undamaged areas
and tins used for all products other that have been subjected to a high and suffers a discolouring etching by
than processed foods—rusting prob- sodium nitrite cure. Iron sulphide the milk during processing and sub-
lems are varied and not susceptible to staining, however, is a different matter, sequent storage. If, however, cans are
systematic treatment. In general, how- since this intensely black compound made from plate whose final treatment
ever, if the pH of the contents is such does not adhere to the surface of the has been cathodic and so does not
as to permit of the formation of actual metal, but usually comes away with carry any oxide film anywhere, the
rust at all, the practical solution usually the product, giving a very unsightly entire inside surface remains quite free
devolves on whether or not the product and quite unacceptable out-turn. from attack.
will soften or otherwise impair a The use of lacquers pigmented with
lacquer coating. If it does not, lacquer- zinc oxide, which actually removes General-line containers
ing of the tinplate in the flat sheet is most of the sulphur compounds before
usually effective; if it does, a solution they attack the steel, is of some value Broadly speaking, internal corrosion
involving addition of volatile inhibitors in preventing this form of corrosion, (apart from rusting) in general-line
to the product has to be sought. though non-reactive lacquers and tin- tinplate containers may be considered
filming treatments like Protectatin may under two headings:
only aggravate matters by protecting (a) Solution of iron due to the exis-
Processed foods the tin surface and thus leaving the tence of conditions in which iron
From the point of view of corrosion, whole of the sulphur-bearing com- occupies its ' classical,' anodic
processed foods, other than fruits and pounds produced during processing relation to tin as opposed to the
vegetables, may be considered under available for attack on the steel. strictly anaerobic condition pre-
three headings: meat products, fish The nature of this attack on the vailing inside processed fruit
products and milk. steel is not fully understood, but it cans in which the tin is the
Meat products. Chemical action has been realised for many years now anodic metal. In some cases,
inside meat cans consists of the com- that the fresher the meat at the time e.g. french polish and beer, this
bined attack by the meat acids and the of packing the less likelihood there is attack on the steel may be rela-
volatile sulphur-bearing compounds of iron sulphide staining developing. tively slight and superficial and
given off during the cooking process Fish products. From the corrosion undesirable only because of its
on the surface of the tin (in un- point of view, canned fish products deleterious effect on the product.
lacquered cans) and on the steel fall into two categories. The first con- In others, e.g. distempers in
exposed in the end- and side-seam sists of those in acid (vinegar or which phenolic mould inhibitors

240 CORROSION TECHNOLOGY August 1955

 have been used and PVA-type
emulsion paints to which stabi-
lisers to prevent the gradual for-
mation of acetic acid have not
been added, the attack usually
goes even further, eventually
perforating the walls of the
container.
In either case the alternative
defences are:
(i) elaborate systems of apply-
ing protective coatings of
lacquers or waxes as late as
possible in the manufac-
turing of the containers so
as to reduce to a minimum
the amount of metal ex-
posed by the manufactur-
ing operation. The out-
standing example of the tively rare occasions, however, Blackplate is very readily corrodible
use of this procedure is in general-line products may con- and only solderable after pickling and
the manufacture of cans tain compounds, notably alkalis fluxing processes much more complex
for beer where the second and strong oxidising agents that than those required for tinplate. Con-
alternative is impracticable, will cause rapid stripping of thesequently, while blackplate is widely
or tin. This can usually be over- used for big drums that will stand the
(ii)the addition of corrosion come by lacquering, otherwise cost of welding and of individual
inhibitors to the product. reformulation of the product is lacquering, it is not popular with
The classic example of this necessary. makers of small containers outside the
recourse is french polish, United States where special considera-
in which small amounts of Blackplate tions lead to the practice of maximum
Anti-Corrosion Meth & Material 1955.2:238-242.

iron dissolved from the This product—mild-steel sheet un- economy in the use of tin. Obviously,
container render the pro- coated with any other metal—was, blackplate differs from tinplate in that
duct useless when it is until recently, only available with the mild-steel sheet, so vulnerable to
applied to wood, with the more or less heavy layers of blue or rusting conditions and to attack by all
tannin in which the iron dark-brown oxides on its surface, and acid media, has neither the purely
reacts to form a black pro- so was not grossly misnamed black- physical covering nor the electro-
duct which prohibitively plate. Modern practice, however, chemical protection that the film of
darkens the wood. permits of the cooling stage of the tin gives to tinplate. By the use of
(b) As has been said, tin is normally annealing cycle being carried out in multiple coats of the most scratchproof
cathodic to mild steel in aerobic a reducing atmosphere and modern and flexible lacquers and by lacquering
conditions, though in general cold-reduced blackplate (now better the more sharply deformed com-
nothing but superficial and quite called untinned tinplate base) has a ponents after fabrication, blackplate
unexceptionable etching of the surface almost as clean in appearance containers can be made for almost any
tin surface occurs. On compara- as stainless steel. product for which tinplate is suitable.
The lengths in this direction to which
the total absence of tin drove German
can-makers during the last war and
the surprising success they achieved
are fully described in the C.I.O. report
on the subject.8 Since the war the
Germans have even succeeded in
marketing beer cans made entirely of
blackplate, but the extreme sensitivity
of this product to exposed steel and
the long-term permeability of lacquers
to ionic iron has limited the shelf life
of such cans to periods shorter than
those achievable with tinplate.
During the last war much blackplate
was used in this country for general-
line containers and for the ends of
processed food cans. One of the prin-
cipal difficulties met with at that time
was the phenomenon of underfilm or
filiform corrosion. This was the for-
mation, under any rust-promoting con-
ditions, of red or brown ferrous cor-
rosion products in the form of net-

August 1955 CORROSION TECHNOLOGY 241

 works of straggling threads on the surfaces is somewhat unpredictable.
surface of the steel and underneath Much work has been done in this
any film of lacquer or decoration that country in an attempt to improve this
had been applied. The reaction never adhesion by chemical (phosphate and
penetrated beyond the surface of the chromate) treatments less costly than
steel and could be masked with pass- anodising, but significant improve-
able success by the use of opaque ments were obtained only with films
coatings, but was effectively inhibited sufficiently thick to produce a pro-
only by the practice in the United hibitively unsightly appearance.
States of bonderising the steel surface In conclusion, it may be of interest
before lacquering it. This pheno- to mention experiences in our own
menon has since been observed on laboratories when, in an attempt to
metals other than steel, both with and conserve tinplate by a usage that would
without protective lacquers, and a good involve no soldering problem and in
account of its general nature is given which mechanical weakness would be
by van Loo, Laiderman and Bruhn.9 of minor significance, test packs of
several processed foods were put up
Aluminium in cans having tinplate bodies and
aluminium (NS3) ends. As had been
When tinplate is freely available, feared, in spite of lacquering, the small
commercially pure aluminium, S1C amounts of the two metals exposed
(B.S. 1470), and its 1.25% manganese during the fabrication of the cans had,
alloy, NS3 (B.S. 1470), find only spheric corrosion. This, coupled with
the fact that most aluminium com- where they were in contact in the end
specialised applications in the rigid seam regions, set up powerful couples
container industry on account of their pounds are either colourless or white,
renders aluminium containers gener- in which the acidic conditions at the
price, their relative mechanical weak- anode (aluminium) caused perforation
ness and the extreme difficulty of ally free from any of the hazards of
external disfigurement by atmospheric and the alkaline conditions arising at
soldering them at high speeds. How- the cathode (tinplate) were sufficiently
ever, aluminium lends itself admirably corrosion to which tinplate is some-
times vulnerable. An exception to this intense to cause extensive stripping of
to deep drawing and to impact extru- the lacquer.
sion, and shortage of tinplate in various general truth is that boiling in some
Anti-Corrosion Meth & Material 1955.2:238-242.

countries has led in the past to waters produces unsightly blotchy REFERENCES
widespread use of aluminium. black stains on aluminium, and this 1
W. J. Mutschler, Canning Trade, 75 (34),
has caused considerable trouble when 29.
From the corrosion point of view aluminium has been used for processed 2
E. L. Koehler, Trans. Amer. Soc. for
aluminium and its alloys differ from food cans. In most instances this 3
Metals, 1952, 44, 1076-1096.
tinplate in three important respects. C. L. Smith, The Conner, 90 (12),
attack can be prevented by the Part 2, 65.
(1) Since aluminium carries no sacri- addition of sodium silicate to the 4
Tin Research Institute, 'Anti-rust and
ficial metallic coating, attack on it is water, but the most effective safeguard Anti-staining Treatment of Tinplate,'
more prone to lead to perforation than against it is to anodise the aluminium. March 1950.
5
Can Manufacturers Inst., Washington,
is usually the case with tinplate. This As has been stated, aluminium is D.C., ' H o w to Obtain Best Service
is most spectacularly illustrated by a reactive metal much susceptible to from Food Cans.'
6
experience with fingertip dispensers the pitting and therefore perforating G. Horner, Ann. Rept. Fruit & Veg.
having bodies made by impact extru- type of corrosion. This fact, together Preservn. Res. Stn., Campden, 1932-
33, p. 43.
sion of aluminium. Formulations with price and the difficulty of solder- 7
F. Jakobsen and E. Mathiesen, ' C o r r o -
which incorporate highly reactive com- ing, has discouraged the use of sion of Containers for Canned Foods,'
pounds, such as cosmetic products, aluminium at all widely for processed 8
Jacob Dybwad, Oslo, 1946.
tend to be very corrosive, primarily food containers except in Norway Combined Intelligence Objectives Sub-
due to the use of water or alcohol. where tinplate has been in extremely Committee report, 'A Survey of the
German Can Industry During the
The propellant system itself is non- short supply, aluminium has been Second World War,' File No. X X X -
corrosive, but, where Arcton 9 is used cheap and the can-making industry 9
85, 1946.
in the presence of water, the hydro- has been geared to the production of M. van Loo, D . D . Laiderman and R. R.
chloric acid produced attacks the solid-drawn containers. Even in Nor- Bruhn, Corrosion, 9 (8), 277.
10
aluminium surface. Even small way, where much research has gone D. Nickelsen, 'Continuous Surface
Treatment of Aluminium Strip for the
amounts of water present may cause into the protection of aluminium from Container Industry,' British Packer,
decomposition of a component of the corrosion, it has not been found 1952, 14 (1), 26.
pack, e.g. DDT, with subsequent cor- possible to use aluminium containers
rosion. In addition, alcoholysis of the for highly acid products, but the Rotodip and Granodine
aluminium can occur. The three development by the Aluminium Co. of
reactions described above may take the continuous anodising of aluminium We have been asked to point out
place singly or simultaneously and re- strip, followed immediately by 'filling' that the word ROTODIP referred to
sult in pitting and often in perforation the oxide film with a coat of a phenolic on page 140 of our May issue is the
of the aluminium. resin lacquer also applied in the strip,10 Registered Trade Mark of the Carrier
made it possible to use aluminium for Engineering Co. Ltd.
(2) Aluminium is corroded by alkalis a wide range of vegetables and marine GRANODINE is the Registered
as well as by acids, whereas tinplate is products. The adhesion of the lacquer Trade Mark of Imperial Chemical
stable under mildly alkaline conditions. to the aluminium achieved by this pro- Industries Ltd. Thus the photograph
(3) Aluminium is naturally covered cess is extremely high, but the adhesion described as showing car bodies en-
with a thin oxide film which gives it of lacquers to normal aluminium-sheet tering 'Rotodip Granodine ' plant
powerful protection against atmo- referred to two separate trade names.

242 CORROSION TECHNOLOGY August 1955