Corrosion Control by Anodic

Protection
By

c. Edeleanu, M.A., Ph.D.

Tube Investments Research Laboratories, Cambridge

It is well known that corrosion can somctimes be controlled by cathodic currents and,
even with an elementary knowledge of electrochemistry, it is easy to appreciate why this
should be so. Corrosion involves the oxidation of the metal and it is reasonable to expect
that cathodic polarisation, which discourages
oxidation and favours reductions at the metal
surface, should tend to cause protection. In
fact, the position is somewhat more complicated and, in many cases, other factors
override this apparently simple one.
It is not so well known that corrosion can
also be prevented in suitable cases by anodic
polarisation, and it is certainly very much
more difficult to understand why this should
be so from the somewhat oversimplified
theory of corrosion which the non-specialist
is bound to have. It is probably because of
this that this method, which is extremely
powerful and is often applicable just when
cathodic protection is not possible, has not
been easily accepted as a practical proposition and is still regarded as only a laboratory
curiosity. There is, it seems, a feeling, perhaps unconscious, that the method is basically
unsound, and the purpose of the present paper
is to explain, in as simple a way as possible,
why anodic protection is possible, and when
it may be expected to be useful.

the driving force available for corrosion to a

minimum, and the other is to ensure that the
corrosion product itself stifles the reaction
by forming a suitably protective film.
Using the terminology devised by Pourbaix
(I), we say that we make use of immunity in
the first case while in the second we depend
on passivity.
In practice we can achieve immunity by
doing one or more of the following:
(I) Using a suitably noble metal
(2)Removing

unnecessary oxidising
agents (e.g. air)

(3) Adding a cathodic inhibitor (lessening

the effectiveness of the oxidising agents)

General Principles
in Corrosion Control

(4) Applying cathodic protection

In chemical plant it is often not economic

to use noble metals, and if the solutions are
highly oxidising the other methods are inapplicable.

If the brute force methods of corrosion

control such as plastic, glass or other coatings
are neglected, there are two basic methods of
corrosion control available. One is to reduce

Platinum Metals Rev., 1960, 4, (3), 86-91

The technique of cathodic protection is

well known and has been widely applied
to a number of corrosion problems. It
is not so well known that corrosion can
also be prevented in suitable cases by
anodic protection, using a platinum
electrode system. The author shows that,
with adequate laboratory work beforehand and proper instrumentation, the
use of anodic protection can make an
efectiue contribution to the life of a
chemical plant.

86

Passivity is achieved by:

(I)

1.6

Using a metal having an oxide (or other

similar corrosion product) which is
virtually insoluble in the medium

1.2

0.8

(2)

Ensuring that sufficient oxidising agent

is always present for the oxide to be
formed

0.4
J

-4

(3) Applying anodic polarisation to maintain the oxide in constant repair

2
w

2- 0 . 4

In principle therefore anodic protection

has much in common with the practice of
adding oxidising substances such as chromates
or nitrites as inhibitors. Cathodic protection
on the other hand is, in some ways, related
to practices such as de-aeration.
The similarity can be taken further. In a
metal,/solution system in which corrosion is
low because of immunity, corrosion is generally enhanced by either the addition of
oxidising agents or by anodic polarisation,
while in a case depending on passivity it is
dangerous either to de-aerate or to apply
cathodic currents.

- 0.8

-I-2

IMMUNITY

Fig. 1 Pourbaix diagram .for iron in

aqueous

solutions

Protection of Ferrous Materials

in Acid Solutions
Anodic protection will probably prove most
useful with iron-based alloys in acid solutions
and for this reason this case has been selected
as an example. Fig. I shows the Pourbaix
diagram (I) for iron; the conditions for
passivity and immunity are indicated. From
this it will be seen that, in acid solutions,
there is a considerable gap of potentials over
which neither of these conditions is established and which should lead to heavy corrosion.
Lines A and B in this diagram refer to the
lower and upper limits of stability of water.
Above A water is oxidised to oxygen and
below A it is reduced to hydrogen.
If we place iron in a strong acid solution
we can in theory protect it cathodically by
lowering its potential to the region of immunity. However, since water is not stable
at such low potentials, continuous and rapid
hydrogen evolution will occur. This is not a

Platinum Metals Rev., 1960, 4, ( 3 )

87

practical way of avoiding corrosion both

because of the very heavy current requirement and because there is little point in
preventing corrosion if to do so we have to
decompose the solution.
Raising the potential of iron by anodic
polarisation or by the addition of a suitable
oxidising agent to sufficiently high values for
passivity does, on the other hand, seem to
be a more promising way of avoiding corrosion. This is particularly so since the area
of passivity for iron, and especially for some
of the iron-chromium alloys, is considerably
larger than indicated by Fig. I which was
obtained by calculation after making certain
assumptions.
The actual relation between potential and
corrosion rate at a given pH is shown diagrammatically in a somewhat simplified
manner in Fig. 2 . This is an experimentally
determinable curve for any given solution and
alloy by using the potentiostatic techniques
which are becoming widely used in corrosion
studies (2). From Fig. 2, which is typical
of many cases, it can be seen that once the
potential is raised sufficiently to establish

passivity the corrosion rate falls to really

negligible values. For example with iron
in normal sulphuric acid the rate falls to
approximately 0.I mgj cm2day and the current density necessary to maintain passivity
is 5 pA,lcm2. The rate of corrosion of passive
iron in this acid is therefore negligible and iron
could be a very satisfactory container material.
It is important to appreciate at this stage
that the rate of corrosion of a metal in a given
acid solution is an accurately determinable
property provided the potential is specified.
The highly scattered and apparently meaningless results often obtainable on conventional
corrosion test specimens are entirely due to
the potential wandering in an uncontrolled
manner, but once results such as those in
Fig. 2 have been obtained for a given metal
solution system we can fully depend on them
in practice, again provided we also ensure that
the potential of the plant relative to the solution is kept at the correct value. Alternatively
we can monitor accurately the rate of corrosion by measuring the potential and referring
to Fig. 2.

From the above it must have become

obvious that anodic protection is simply a
way of ensuring that the potential of the
metal is kept sufficiently high for passivity
to be stable.

Instrumentation
If the potential of iron is raised appreciably
above line A in Fig. I , oxygen evolution takes
place (i.e. the solution starts being decomposed and current is wasted) so that this
imposes an upper limit to the desirable
potential. With the stainless steels oxygen is
not generally evolved, but the corrosion rate
increases above a certain potential so that
again there is an upper limit for the potential,
With titanium (3), and some other metals
which form non-conductive films, there is
generally much greater latitude and it is
often possible to raise the potential by some
tens of volts, but in these cases too the protection can break down if the potential is
raised sufficiently.
The important fact is that there is an
upper, as well as a lower, limit to the range of
potentials which give satisfactory results.
This means that the instrument required for
anodic protection is a potentiostat but the
exact nature of the instrument depends
greatly on the system.
If the range of satisfactory potentials is
large, as with titanium, a very simple constant
voltage device such as an accumulator or
even a dry cell will meet the requirements.
I n such a case it can safely be assumed that
the potential of the inert cathode will not
wander by more than a few hundreds of
millivolts no matter what the current may be,
and if the potential between the cathode and
the plant is kept sufficiently great there will
be no danger that the potential of the plant
will fall to the breakdown point. Cotton has
in point of fact found this system completely
satisfactory for titanium in hydrochloric acid.
This simple method should also be applicable in certain cases for ferrous alloys, even
though the useful potential range is only a
few hundreds of millivolts but, in general, it

CORROSION R A T E

Fig.2 Relation between potential and corrosion

rate for iron i n sulphuric acid

Platinum Metals Rev., 1960, 4, ( 3 )

88

would be safer to use a true potentiostat.

This instrument measures the potential of
the plant against a standard electrode, and
maintains it at the desired value by passing a
polarising current through an inert auxiliary
electrode.
There are numerous potentiostat circuits
available and the laboratory types are fully
electronic and can control potentials very
accurately but have a rather low current output. For industrial use output is the main
requirement, and a servo-operated instrument
would be more satisfactory.
The cost of equipment for anodic protection should not be high even if a true potentiostatic system is called for but, if the method is
to be used to best advantage, it is worth
installing, at the same time, a monitoring
system to provide a record of the performance
of the plant from the corrosion point of
view (4). This could also provide a warning
should anything unforeseen occur.
The position is exactly analogous to the
use of a temperature controller on, for instance, a furnace, which will protect the
furnace from overheating, but, without a
temperature recorder or at least an indicator,
the system is incomplete.

Dangers and Limitations in the

Application of Anodic Protection
The method is particularly suitable for
application in the heavy chemical field, but
the solutions handled in chemical plant differ
so greatly that each case has to be studied on
a laboratory scale before anodic protection
can be safely applied.
This preliminary work must include a
metallographic study, since there are various
types of corrosion such as intercrystalline
corrosion and selective attack that can limit
the use of alloys to a smaller range of potential than might be appreciated (5).
The greatest danger comes, however, from
the shape of the curve sketched in Fig. 2.
In this it can be seen that at potentials just
below those at which protection establishes

Platinum Metals Rev., 1960, 4, ( 3 )

itself, the rate of corrosion is very high. In

some cases this rate can be many orders of
magnitude greater than that of the passive
metal. If a vessel were to go active, in order
to re-establish passivity the protective device
would have to be able to supply a current
equivalent to the highest possible rate of
corrosion. This means that the potentiostat
must be able to provide a current many
orders of magnitude above that necessary for
protection, and if it cannot it may lose control.
This is the reason why monitoring is thought
to be advisable. This danger may be one
reason why the method has not found much
support up to now. Serious as it is, it has
certainly been overstated possibly because, in
an effort PO demonstrate the spectacular
possibilities of the method, the solution used
in the first pilot plant experiments was one
of the most difficult to handle (6). In that
case the potentiostat available was highly inadequate for the purpose (having been constructed for laboratory studies on small
specimens) and could supply a current great
enough for protection, but there was little in
hand to allow for even small local accidents.
Nevertheless the plant ran successfully for
many hundreds of hours. More recent
American work (7, 8, 9) has shown that the
risk is not unduly great, and with suitable
instrumentation it should be possible to
overcome this difficulty entirely.
It is not possible to enumerate all the
limitations of the method but it is just worth
pointing out that not all metals show an
adequate range of passivity, and that with
any given metal passivity will not be stable in
all solutions. The method depends on an
electrolytic current arriving at the metal so
that it is inapplicable above the wash line
in a vessel or in similar places.

Applications of Anodic Protection

Although there have been some reports in
the technical press (9, 10)of the use of anodic
protection, and there have been a few other
trials, the method has as yet hardly been
tried in practice.

89

From a corrosion point of view all chemical

plant tends to be grossly over-designed, since
it is like a furnace without a temperature controller or recorder. The scope for the use of
protection and/or monitoring is therefore
enormous. With stainless steel plant, for
instance, it is usual to maintain acid strength,
temperatures, pressures or other such variables below values which give trouble. Since
there is generally no means of telling how
near the plant is to losing passivity the
materials are not used to their limit. Another
way of saying the above is that unnecessarily
expensive grades of material are usually
selected for chemical plant in order to
provide some degree of safety.
It seems that it is possible to make a distinction between two uses of anodic protection. In the first instance it should be possible
to employ it in order to allow existing plant
and materials to be used to their limit, with
anodic protection and/or monitoring only as
a safety device. With courage however there
seems no reason why plant should not be
specially designed from inferior materials
which would depend for survival entirely on
anodic protection. In this case, of course,
the anodic protection system may have to be
expensive but the economics could turn out
to be attractive if there were a substantial
saving on construction material, or if the plant
could be run under conditions much beyond
anything that could be visualised without
protection.

Plant and Electrode Design

There seems to be only one plant design
feature to take into account. An electrolytic
current must flow to the plant for protection.
The current necessary is generally lower than
IopA/cm2, and it is relatively easy to calculate how far it will throw if the conductivity
of the solution is known and if the available
voltage range has been established. In
practice it is found that the throwing power
is enormous, as has been demonstrated by
recent American work (9), and reasonably
long tubes can be protected easily provided

Platinum Metals Rev., 1960, 4, ( 3 )

the solution is a good conductor. Naturally,

it is somewhat morc difficult to deal with an
accidental breakdown at the end of a tube
than inside a vessel, but it is relatively easy to
assess the risks involved.
It is not possible to protect above the wash
line in a vessel where corrosion may be due to
spray. Some parts of valves and pumps are
also difficult, but there is no reason why
materials which are naturally resistant should
not be used at the danger points in conjunction with inferior materials elsewhere. Provided the materials are suitably selected there
should be no complications with stray
currents.
In so far as electrodes are concerned the
standard, if used, could be similar to that
which would be used for pH measurements
in the same medium. Bearing in mind however that the accuracy required of the standard
for this application is not great, very simple
and robust standards could be used instead.
For example, a platinum wire responding to
the natural redox potential of the solution
would be adequate if this were reasonably
stable.
As far as the cathode is concerned there is
again considerable latitude, but it is worth
remembering one point. If a potentiostatic
system is used there may be short periods
when the polarity of the current is reversed
so that the cathode becomes an anode. For
this reason if this electrode is made from, say,
copper or nickel, in the hope that it will be
protected cathodically, it may well vanish
during these reversals of polarity and, for
this reason, it is felt that noble metals are
more convenient. Platinum is a natural choice
because of its good electrical conductivity,
low hydrogen overvoltage, good sealing to
glass and not least the ease of cleaning were a
deposit to be formed as a result of the passage
of a current.

Summary and Conclusions

From a corrosion point of view anodic
protection is, to a chemical plant, what a
temperature controller is to a furnace. With-

90

point of fact there is nothing more strange in

protection by an anodic current than there is
in protection by oxidising agents such as
chromates, which are universally accepted.
There are of course dangers and limitations
but, with adequate laboratory work and suitable instrumentations these do not amount to
a serious objection to the technique.

out anodic protection chemical plant has to

be overdesigned and best use is not made of
materials.
The method has hardly been used in practice although it is simple to apply. This is
probably partly due to an inadequate understanding of how the method works and a
feeling that it is a laboratory curiosity. In

References
I

M. Pourbaix

V. Cihal and M. IPrazak

C. Edeleanu . .
..
..
..
3 J. B. Cotton
..
..
4 C. Edeleanu
..
..
5 C. Edeleanu
..
,.
6 C . Edeleanu
J.
D.
Sudbury,
0.
L.
Riggs,
7
2

..

..

..
..

..

..

..

..

..

..
..

..

and D. A.
Shock
8 D. A. Shock, 0. L. Riggs, and J. D.

Sudbury
9 0. L. Riggs, M. 13utchison, and N. L.
I0

Conger
W. Mueller

..

..

..

..

Thermodynamics of Dilute Aqueous Solutions,

Arnold, London, 1949
J . Iron & Steel Znst., 1959, 193, 360
J. Iron & Steel Inst., 1958, 188, 122
Chem. and Znd., 1958, p. 68; 1958, p. 492
Corrosion Technology, 1955, 2, 204
J. Iron & Steel Inst., 1957, 185,482
Metallurgia, 1954, 50, 113
Corrosion, 1960, 16, 91

Corrosion, 1960, 16,99

Corrosion, 1960, 16,102
Canadian J. of Technology, 1956, 34, 162

Properties of Platinum Metals and Alloys

AN ANNOTATED BIBLIOGRAPHY
The literature dealing with the properties
of platinum and the platinum group metals is,
on the whole, sparse and widely scattered. On
this account a recent publication, called a
technical phasc report, prepared by R. W.
Douglass, F. C. Holden and R. I. JafTee, of
Battelle Memorial Institute for the U.S.
Office of Naval Research, is particularly
welcome. This was written with the special
intention that it should serve as a guide to
planning experimental work on the platinum
group metals, revealing, as the authors put
it, areas where concentrated study is needed
and preventing duplication of previous work
and was produced as the first part of a study
at Battelle of the metallurgical properties of
the refractory platinum group metals.
As it is presented, this report provides a
very careful survey of the literature of the
past fifty years on the properties of the
metals and on the constitution of their
binary alloys, listing 281 references.

Platinum Metals Rev., 1960, 4, ( 3 )

The review of this mass of literature extends to 105 pages and is reasonably comprehensive. The publication as a whole is likely
to prove an invaluable source book to anyone
interested in the literature of the platinum
metals, but it is rather less valuable as a
critical survey. The brief introductory notes
on extraction and benefication are, for
instance, misleading as far as modem conditions are concerned, for today South Africa
is undoubtedly the most significant world
source of the platinum metals. A few of the
figures quoted for the physical and mechanical
properties are certainly in error-at least as
far as the pure metals are concerned-and
need to be treated with much more reserve
than is accorded them by the authors. However, if this is treated as a first-class annotated
bibliography-which
it primarily is-the
report will be found a most useful work of
reference by all interested in the platinum
metals.
J. C. C.

91