Anti-Corrosion Methods and Materials

CORROSION TESTING OF AEROSOL PRODUCTS

M.J. Root M.J. Maury
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To cite this document:
M.J. Root M.J. Maury, (1960),"CORROSION TESTING OF AEROSOL PRODUCTS", Anti-Corrosion Methods and Materials,
Vol. 7 Iss 3 pp. 85 - 87
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 CORROSION TESTING OF AEROSOL PRODUCTS
Since the advent of cosmetic aerosols in metal cans, corrosion has taken
its place as a major problem in the formulation of these products. Much
corrosion information can be gathered by electrochemical measurement
that cannot be obtained in any other way. This article, which deals with
these modern systems, is an abridged version of a paper presented to the
Society of Comestic Chemists, May 1959, in New York.
THE classic method of evaluating
corrosion in metal containers has been
the test pack. The product is placed
in the container, sealed and allowed
to stand at various temperatures for
a specified period and then opened
and inspected. Although temperature
is an important factor in shelf-life
tests, it is still no substitute for time,
as elevated temperatures are not
always a guarantee of accelerated cor-
rosion, and the need for a less-time-
consuming method is obvious.
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Ten-week analysis
In 19551 we reported on a method
of analysing aerosol products for
metallic contamination due to corro-
sion at various periods up to 10 weeks.
From this analysis it was possible to
gain an insight into the electrolytic
behaviour of the container metal.
Thus it was possible to demonstrate
from the greater iron contamination
in an alkyl sulphate shampoo that the
iron in the container was anodic to the
tin. This method has proven extremely
useful for detecting the metallic con-
tamination level at which product dis-
coloration or perfume oil deterioration
sometimes takes place.
It has been noted that, in certain
instances, product discoloration can
occur with as little as 5 p.p.m. of iron
or tin in the product from corrosion
processes. Corrosion at this level
would not be apparent by container
examination. Perfume deterioration
has been detected with as little as 20
p.p.m. of tin in the product from
corrosive action on the tin plate.
E.M.F. measurement
In 1954, G. Barr & Co.2 set up a
fellowship to study the possibility of
using electrodes prepared from tin
foil and mild-steel base stock for
measuring the electromotive force
existing across a tin-steel electrode
system in various products, such as
shaving cream, hair sprays, shampoos
*G. Barr & Co., Chicago 9, Illinois.
March 1960 CORROSION TECHNOLOGY
By M. J. Roof and M. J. Maury*
and other cosmetics. It was found
in this work that, in the formulations
studied, the tin was anodic to the steel.
It was also shown that steel corrodes
more rapidly when insulated from tin
than when in electrical contact. This
indicates the furnishing of cathodic
protection to the steel by the tin.
In 1955, Continental Can Co.3 in
collaboration with the Armour Re-
search Foundation developed their
'corrosivity tester' which they used
for prediction of shelf life for car-
bonated beverages in tin cans. With
this technique it was possible to plot
perforation data from controlled test
packs plotted against a curve based
on calculated perforation times of cans
with 0.0012 sq. in. area of exposed
iron. The correlation between the
two plots was good. Agreement was
also good between microampere read-
ings and actual iron content (p.p.m.)
of controlled test packs plotted with
the theoretical curve based on Fara-
day's law of electrolysis.
In some recent work,4 Johnson and
Daly have shown by the use of their
'corrosivity tester' that anti-oxidants
such as ascorbic acid and glucose
oxidase-catalase enzyme systems were
effective in reducing iron pick-up and
can perforation in soft drinks. Re-
moval of air in the head space also
produced a more satisfactory shelf life
of canned soft drinks.
In a paper5 presented by these same
authors along with Koehler and Fran-
cis of the Armour Research Foun-
dation before the National Association
of Corrosion Engineers in March 1959,
they pursued the corrosion processes
in carbonated beverage further with
the use of the 'corrosivity tester.'
Practical electrode
. Perhaps the most significant part of
the work was the development of a
practical test metal electrode. Tin
wire, solder, steel black plate, or any
other metal, is mounted in an epoxy
resin. Wire leads extending from the
tin and steel are coupled externally
through a device of sufficient sensiti-
vity and sufficiently low resistance to
measure the galvanic currents pro-
duced. Electrodes of this type have
the following advantages:
(1) Size of cathode and anode metals
can be accurately controlled.
(2) Proximity of electrodes can be con-
trolled within limits.
(3) Fresh electrode areas can be ex-
posed by grinding.
(4) Electrodes can be made of iden-
tical metal found in container
under question.
Except for proximities of the elec-
trodes and relative sizes of the anode
and cathode, this electrode simulates
what is occurring in a metal container
where two or more dissimilar con-
ductors in contact with an electrolyte
(product) convert energy liberated by
a spontaneous chemical reaction
directly into electrical energy.
85
 Test cell and procedure
The test cell which we used con-
sisted of this electrode, a saturated
calomel reference electrode and a gas
flushing tube, held in place in a 1-pt.
Mason jar with a large rubber stopper.
This assembly and construction of the
electrodes has been described.6
With non-aqueous aerosol products,
the container was first chilled, then
opened and emptied into the test cell.
Measurements of current and poten-
tial were made when the product was
at room temperature (70 to 75°F.).
Second readings were taken after 24
hr. During all time intervals the
electrodes were in external contact
with each other. With foam products,
the foam was expelled directly into
the test cell, and with compressed gas
products similarly, the product was
dispensed directly into the test cell
for measurements. In these tests no
special efforts were made to control
the atmosphere above the solution.
With the liquid propellant products,
there no doubt remained a trichloro-
fluoromethane vapour above the solu-
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tion in all measurements.
Shellac hair spray
Fig. 1 shows a current-voltage plot
of a typical shellac-type hair spray.
The potentials of the couple and each
of the metals present in a seamed can
against the calomel reference cell is
shown at the bottom right, and the
galvanic current flow between the
electrodes is shown at the left. The
solder and the tin are anodic to the
iron. Since the current flow between
the anode (solder) and the iron
(cathode) is the same, 1.30 microamp.,
we can say that corrosion is under
both anodic and cathodic control.
Solder corrosion could be expected,
but, because of the low current values,
it would not be of considerable con-
sequence except where the solution of
small amounts of lead would be dele-
terious to the product.
Fig. 2 is a shellac-type hair spray in
which the shellac has been partially
esterified. The relative potentials
have not changed but the current
values are about one-half of the pre-
vious product. Corrosion would there-
fore be reduced to about one-half with
an esterified shellac. Here, again,
corrosion is under both anodic and
cathodic control.
As indicated by a current-voltage
plot of a PVP-type hair spray, the same
potential relationships still hold, that
is, the tin and solder are anodic to the
iron; however, the current values are
extremely low, indicating very little
corrosion would take place with this
86
particular formulation. This is not to
be taken as indicative of all PVP hair
spray formulations, since minor quan-
tities of additives can cause a very
large change in the corrosion picture.
With these hair spray products, shelf
life of at least two years has been
obtained. A continuous current flow
of 0.04 microamp. in a can for one
year will raise the iron content of a
12-oz. can by only 1 p.p.m. To cause
a can perforation through 0.010-in.
plate in a year's time, a current flow
of 0.2 microamp. concentrated at an
assumed pit size of 1 sq. mm. would
be required.
Shampoos
Fig. 3 illustrated very graphically
the reason that sodium lauryl sulphate
shampoos, which were packaged in
aerosol cans, would perforate. The
iron is anodic to the tin and solder.
Also, the high current value, 6.60
microamp., between the iron and the
FRANCAIS
Essais de Corrosion des P r o d u i t s
Aerosol
Des procédés d'analyse de produits aerosols
destinés à déceler la contamination métallique
se manifestant à bref délai out permis de
clarifier le comportement electrolytique du
métal de base du contenant. De cette façon,
on a pu démontrer, à partir de la contamina-
tion ferreuse plus importante qui existe dans
une émulsion alkaline sulfatée, que le fer du
contenant réagit anodiquement sur l'étain.
On a pu démontrer, à l'aide d'un disposilif
à mesurer la corrosion, que les produits
antioxidants, tels que l'acide ascorbique et
les systèmes glucose-oxidase-catalase-enzyme
étaient efficaces à réduire la corrosion ferreuse
et l'usure qui se produisent avec les fers-
blancs pour boissons non-alcooliques. On a
démontré que les données courant/tension
peuvent beaucoup aider à étudier l'effet sur
ces valeurs par: reformulation; émulseur;
suppression de la soudure étain-plomb;
preventifs de corrosion; polarisateurs;
oxygène.
DEUTSCH
Prüfung von Aerosolprodukten auf
Aggressivität
Methoden, mit denen sich schon nach
kurzer Zeit ein etwaiger Melallgehalt in
Aerosolprodukten feststellen lässt, haben
einen Einblick in das elektrolytische Ver-
halten des Behältermaterials ermöglicht. So
konnte aus der Tatsache, dass in einem
Shampoo auf Alkyhulfatgrundlage beson-
ders Eisen als Verunreinigung auftrat, der
Schluss gezogen werden, dass das Eisen im
Behältermaterial gegenüber dem Zinn ano-
disch war. Mit Hilfe eines 'Aggressitivitäts
prüfers' kounte gezeigt werden, dass oxy-
dationsverhütende Stoffe wie Ascorbinsäure
oder das Enzymsystem OxydasejKatalase
bei Glucose die Aufnahme von Eisen und die
Durchlöcherung von Büchsen für alkohol-
freie Getränke verringert. Der Einfluss von
Anderungen in der Zusammensetzung, Zusatz
von Emulgatoren, Inhibitoren, Polarisatoren
oder Sauerstoff, sowie die Folgen des Ver-
zichts auf Blei/Zinn-Lote lässt sich an
Hand der StromlPotential-Kurven gut
verfolgen.
tin-solder indicates accelerated cor-
rosion and, since this corrosion is
taking place at relatively small areas
(baseplate pinholes), perforation can
be expected. A coating would not
help this particular situation, since the
coating would be even more strongly
cathodic than the tin and, therefore,
accelerate corrosion.
Fig. 4 shows the same conditions
existing with a triethanolamine lauryl
sulphate shampoo: high current flow
between the iron and tin-solder elec-
trodes with the iron anodic. It was
felt at one time that the substitution of
TEA lauryl sulphate for the sodium
lauryl sulphate would solve perfora-
tion problems, but from this graph
we can see this change would make
little difference.
We have known for some time that
emulsion products (oil/water) are quite
corrosive to the tin plate cans; how-
ever, the characteristic has been
attributed to the emulsifier used.
W a x and resin emulsions
Fig. 5 is a current e.m.f. plot of
a wax emulsion product which has a
soap emulsifier. Corrosion currents
are very low and the tin and solder
are anodic to the steel. Shelf-life tests
have verified the non-corrosive nature
of this product.
An experimental shelf pack of a resin
emulsion showed very high perforation
after as short a period as three weeks.
Fig. 6 is a current e.m.f. plot of this
product. As can be seen, the iron is
anodic and the current value between
the iron and the tin-solder is 5.5 micro-
amp. The low current value of the tin
cathode indicates that corrosion was
under cathodic control. Perforation,
as would be expected, took place at the
liquid/vapour line where oxygen was
present to effect depolarisation of the
tin (cathode). The use of a coated
drawn can with nitrogen flushing of
the head space resulted in a commer-
cially feasible package. A drawn can
increased the anode area and, there-
fore, decreased the intensity of the
corrosion.
Current-potential data can be ex-
tremely useful for corrosion reduction
by studying the effect of these values
by the following:
(1) Reformulation.
(2) Emulsifier.
(3) Elimination of lead-tin solder.
(4) Inhibitors.
(5) Polarisers.
(6) Oxygen.
There are limitations to this tech-
nique such as inability to determine
CORROSION TECHNOLOGY March 1960

vapour-phase corrosion and also in-
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ability to determine product damage
such as discoloration and perfume de-
generation. Care must be exercised in
interpreting these data, since the anode
and cathode are separated by a much
Book Review
Metals v. Chemicals
Corrosion of Chemical Apparatus, by
G. L. Shvartz and M. M. Kristal.
Translated from the Russian by Con-
sultants Bureau Inc., New York. Chap-
man & Hall Ltd., London, 1959. Pp.
250, illus. £3.
It can be fairly said that this book
presents its subject with a complete-
ness rarely found in works of a similar
nature dealing with the subject of
corrosion. It is written by research
engineers for designers and application
engineers, discussing not only the
theory of intercrystalline and stress
corrosion of stainless steel, carbon
steel, alloyed steel and non-ferrous
metals, but also makes recommenda-
tions for the prevention of corrosion
and protection from the effects of
stress corrosion. Much of the material
presented is the result of the authors'
own investigations and is amplified by
references to Russian and other publi-
cations.
Ferrous materials take up 150 pages
and non-ferrous metals 30 pages.
Amongst the latter are the following,
and their alloys: Aluminium, copper,
nickel, magnesium, lead, titanium,
tantalum, and zirconium. The text is
March 1960 CORROSION TECHNOLOGY
also cause an error in the interpretation
of the results. It is for these reasons
that, in order to get as much infor-
mation as possible, the methods men-
tioned earlier will continue to be used
along with this new method for the
interpretation of corrosion data.
This article is published here by kind
permission of the Journal and Society of
Cosmetic Chemists.
REFERENCES
1
M. J. Root, 'Corrosion of Aerosol Metal
Containers,' Chem. Specialties Mfrs.
Assoc. Proc. 42nd Ann. Meeting,
2
Dec. 1955.
D. A. Brooks, 'A Study of the Corrosion
Processes in Tin-plated containers
Used for Packaging Aqueous Aero-
sols,' thesis for degree of Master of
Science, Michigan State University,
3
1955.
H. T. Johnson, A. W. McAlphin and
A. M. Schenck, Food Technol., 1955,
4
9 (12), 643.
H. T. Johnson and J. J. Daly, Jr., Proc.
5
Soc. Soft Drink Technol., April 1957.
E. H. Koehler, J. J. Daly, Jr., H. F.
Francis and H. Johnson, 'Corrosion
Processes in Carbonated Beverage
greater distance than in the container; Cans,'15th Ann. Meeting, N.A.C.E.,
hence resistance of solution and the 6
March 1959.
unnatural formation of corrosion pro- J. J. Daly, Jr., 'Corrosivity Tester,
ducts are sources of error. Variation Theory, Equipment, Test Methods,'
confidential report, Continental Can
of anode/cathode areas from what is Co. Inc., metal division, research and
actually the case in the container can development department.
ing and publishing it in the States, the
information presented is up to date.
'Corrosion of Chemical Apparatus '
accompanied by 140 illustrations. is bound to fill a lacuna on every
Whereas the line drawings are clear— scientist's and engineer's bookshelf.
as they have obviously been redrawn—
the few halftones there are look
anaemic, very much like second-rate
unretouched photographs of illus-
Analyser Resists Corrosion
trations reproduced straight from the
Russian book. Almost every detail The first Canadian order for the
has been lost, which is a pity. The Titromatic analyser, manufactured by
typesetting is not all what might be Electronic Instruments Ltd., Rich-
expected of it. Sectional headings mond, Surrey, valued at over $ 10,000,
are set in the same type as the text, has been received from the Canadian
but are underlined, which is not Aluminium Co. Ltd. Because of the
standard practice here. Editing could corrosive nature of the reagents re-
have avoided some minor, but irritat- quired in the assay of the aluminium
ing, grammatical faults or collo- content of the ore, special arrange-
quialisms (if that sounds less harsh). ments were made for flushing and
So, for instance, the term ' highly- mechanically brushing the electrodes
alloyed' is found on page 66 (correct, after each titration.
except for the hyphen), but on page 25 The analyser is intended to assay
' low-alloyed ' steels are mentioned. the aluminium content and the free
Nevertheless, the book can be highly alkali offiveseparate ore plant streams.
recommended to engineers, physicists, To perform this it automatically carries
chemists and technologists working in out a double end-point titration with
metals. The reviewer is not aware of two added reagents on each of the five
another recent publication containing streams. The ore liquid is highly
in one volume the wide range of new corrosive and all taps, vessels and
and useful data as does this book. In piping in contact with it are PTFE-
spite of the inevitable time delay lined. To avoid scale formation, the
involved in writing and publishing complete sampling system is flushed
the book in Russia, and then translat- frequently with water and acid.
87