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Corrosion and Protection of Metals: II. Types of Corrosion and Protection

Methods

Article  in  Transactions of the Institute of Metal Finishing · August 1993

DOI: 10.1080/00202967.1993.11871002

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,J

APPLIED
TUTORIAL NOTE 1
Corrosion and Protection
(PART2) of Metals: II. Types of
Corrosion and Protection
Methods.

F. Walsh, G. Ottewill
and D. Barker
Applied Electrochemistry G ro up,
Chemistry Departmenc, University of
Portsmouth, Portsmowh POJ 2DT, UK.
SUMMARY- The term corrosion covers a wide variety of types of surface attack and mechanism.
Broadly, these may be subdivided into two categories, those associated mainly with the metal and
those with the environment. In this second paper, typical cases of localised corrosion are outlined
and are illustrated by examples, Available strategies for corrosion protection are reviewed and
methods of prevention are concisely considered.

TYPES OF CORROSION deep. It can occur where a small break

F. Walsh. G Ottewill and D. Barker.
Trans. Inst. Metal Finish .. 1993. 71(3). 117
Types of corrosion associated primarily
with the metal
Figure 1 depicts eight differe nt modes
of corrosive attack on metal:
1. Uniform or general auack involves an
even rate of corrosion over the entire
metal surface.
2. Pitting is a very localised form of
attack and may be very directional and
3. lntergranular attack may occur
Oxide film or noble metol
in a protective layer, a layer of noble
metal, for example , or an oxide film ,
renders the underlying metal prone to
a ttack. Prolonged or highly localised
forms of pitting can lead to perforation
of the metal. The depth of the pits is
generally large compared with their
diameter; a wide range of pit depths
are experienced, ranging from sub-
microscopic dimensions to over 1 mm.
wherein corrosion sets in along crys-
talline grain boundaries (as in the case

~"'"'' Metal \•:=3"' of weld decay in some stainless steels).

In the case of layer corrosion, a ttack
follows a structural layer pattern and a
common example is the exfoliation of
layers of oxide from corroding alu-
Uniform attack Pitting minium plates where rolling of the
metal during production leads to the
orientation of intermetallic phases
which allow corrosion cells to develop
~Groinboundory
in which the pure aluminium phase is
attack anodic.
Crystalline 4. Where the metal substrate is an alioy.
grains selective phase corrosion is possible at
small sites of one of the phases. For
Inte r g ra n ula r Layer example, in the case of brass, a 60%
copper - 40% zinc alloy may show
preferential dissolution of the zinc-rich
Porous Cu
(3-phase rather than the copper-rich a-

~~~~~;~:. \~ j;
""''''".~
of metal phase, resulting a porous alloy, the
effect often be ing referred to as dezin-
octrng os cification. A further example of
cathodes selective phase corrosion is graphitic
corrosion of grey cast iron where
Selective Phase Graphit i c
inclusions of graphite act as cathode
sites, leading to anodic loss of metal in
Lood Stress surrounding areas.
Crocks
5. Finally, corrosive processes may result

~l
Crocks ~11
w lw from mechanical stress. Stress cor-
rosion occurs due to the conjoin t
action of a load applied to the surface
and a corrosive environment which
Str ess Fati g ue leads to rapid crack growth from the
surface into the bulk metal. The cracks
Figure I. Types of corrosion associated mainly with the metal. (Af1er may propagate from the bottom of
Fontana and Greene). pits. Corrosion fatigue arises in circum-
 stances where oscillating mechanical
stresses combine with a corrosive envi-
ronment to allow cracks to open up
and grow rapidly.
It is clear that corrosion is by no means
a simple. single process in practice.
Moreover. most instances of metal cor-
rosion will involve simultaneous
occurrence of more than one of the indi-
vidual modes of attack described.
Types of Corrosion Associated with the
Environment
The specific environment in which a metal
is found may render it vulnerable to cor-
rosive attack of a particular kind. Figure 2
illustrates eight examples of this type of
corrosion.
1. A crevice. i.e. a narrow gap between
adjacent metal surfaces. permits
exposure of the enclosed surfaces to
moist air or allows seepage of liq uid
between the two surfaces.
2. Similarly. trace moisture trapped
between a metal surface and a film of
paint or as a deposir of debris creates
an environment suitable for corrosive
attack.
3. Filiform corrosion is the term applied
to the form of attack in which cor-
rosion products form a network
pattern beneath an oxide or paint
coating on the metal surface. The
pattern is due to the complex actions
of localised differences in concen-
tration. the forma tio n of directional
activity and the presence of self-ca t-
alytic corrosion products near the
corrosion front.
4. Metal surfaces partially immersed in
water are particularly vulnerable to
corrosion at the waterline. The high
oxygen content near the water surface
results in a cathodi c zone and promotes
more severe attack than that possible
in the bulk liquid where the dissolved
oxygen content remains much lower.
5. The same differential in the oxygen
concentration occurs in a drop lying
on the metal surface. The thin layer
of water around the circumference of
the drop has a high concentration of
dissolved oxygen rela tive to that in
the central thicker porti on of the
drop. Corrosive attack tends to be
most pronounced just inside the edges
of the drop where the greatest dif-
ference in dissolved oxygen
concentration occurs under the outer
rim of the drop.
6. Erosion of a metal, in which portions
of the metal are physically removed,
becomes possible where combinations
of dissolved air, inert particles of e.g.
silt, or dead sea shells move across the
surface causing a scouring effect.
7. Where turbulent flow of electrolyte
occurs next to a metal surface, loss of
metal may occur via surface disruption
caused by high speed impingement of
the electrolyte onto the surface. At
high flow velocities, the pressure drop
across air bubbles may become suffi-
ciently high to cause cavitarion, where
the bubbles collapse and implode -
118
Narrow
g op
./
crevice
Air
I
water Ii ne attack
- Flow
l~I
Physical remo• ol of metol
erosion
Turbulent U '\.) 0 ,.-. ,J
f ie .... u G v
I@ w ~
Loss o f m e tol vio surface d isruption
coused by collapse of gos bubble cavitat ion
turbulent flow
Figure 2. Types of corrosion associated mainly with th e en vironmenr.
(After Fontana and Greene).
releasing mechanical energy in the
process.
8. Fina ll y.fretting corrosive attack occurs
where two metal surfaces are sub-
jected to very small but frequent
relative mo\'ement in the presence of
an aggressive e nvironment.
CORROSION PREVENTION AND
CONTROL
The Strategy for Corrosion Prevention
T he prevention of e lectrochemical cor-
rosion depends on disruption of the
corrosion cell (see Part I) by one of the
following strategies:
(i) The anode, anode-electrolyte
interfa ce or anode reaction.
(ii) The cathode, cathode-electrolyte
interface or cathode reaction.
(iii) The electrolyte.
(iv) The cathodic reactant, e.g., H +, o~
(v) The electrical connection between
anodic and cathodic sites.
It is important to recognise that, in a
real corrosion situation, the corrosion cell
and nie electrochemical reaction will not
always be readily identified or isolated.
Protective methods are broadly sub-
divided into four categories:
(i) Materials and design.
(ii) Modification of the electrolyte
(iii) Change in the electrode potential
(iv) Surface coating
PROTECTIVE METHODS
Materials Selection and Design
Due consideration to the suitability of a
material coupled with care in design
(Figure 3) can alleviate many corrosio n
problems. Amongst the most important
factors to be borne in mind are:
Point f ilm or d ebris
~
deposi t
Corrosion products form
o network under o coating
I
filiform
drop
Ver y small, frequen t movement
0 ~
I ,~
!?!?illlil~Wll/l??~il?i?/1111
fretting
(i) Materials (metals, alloys, non-
metallic materials) - which sho uld
be chosen to take into account,
cost. availability and suitability to
the environment in which the item
is to be placed. It is important to
appreciate that rates of corrosion
are strongly dependent for
example. on conditions of flow
and aeratio n.
(ii) Contact between metals of dif-
fere nt stand ard electrode
potentials - designs should avoid
contact between dissimilar metals
where the kinetics of attack on
o ne metal surface are enhanced
by the presence of the second.
(iii) Geometry - localised attack can
be minimised by the avoidance of
areas particularly susceptible to
erosion or cavitation.
(iv) Mechanical factors - excessive
stress, internal or externally
applied, should be avoided espe-
cially in metals known to be
vulnerable to stress-corrosion
cracking. This will reduce the
instances of corrosion fa tigue or
fretting corrosion.
(v) Surface conditions - surface con-
ditions that enhance susceptibility
to localised attack should be
avoided, e.g. roughened surfaces,
broken films of metal or oxide and
weld spatter.
(vi) Electrochemical protection -
where possible, designs should
include provision for cathodic or
anodic protection or for the appli-
cation of protective coatings.
(vii) Alloying speciality alloys
 1~~~~::
e- Electrical connection
lncompleteL (providing a galvanic e-
. drornoge coupling)
Cre111ce Cathode :
corrosion-..... ·"''- _:;:'~ object to be
Soluble anode
protected (ship's
() h()Air leg. Al, Mg or Znl
'---+----' hull, buried tonk
Corrosion or pipt!line,
Access for pointing
offshore structure
(a) and inspection etc)
(a)

Cathod<>: Inert or.ode,

object to be e.g. C, platinized - Ti,
protected Pb, Fe-Si,
Fe 3 0 4
(b)

Figure 4. Methods of applying cathodic protection to a metal. (a) sacrificial

anodes (b) impressed current
Rusr

~ Tock welding Continuous welding construction of a galvanic cell between the

ength w eld metal substrate and the introduced anodes
ag free) which are made of a different metal. To
operate successfully a sacrificial anode
Steel plate
must dissolve at a uniform rate at a
potential negative with respect to the cor-
rosion potential of the metal it protects. It
(c)
will then provide a consistent. protective
Poor practice Good practice current of sufficient magnitude.
Dissolution of the second metal results in
Figure 3. The influence of some design factors on corrosion. (a) storage a negative shift of the electrode potential
tanks should be fabricated to allow complete drainage and access to the
external surface for painting and maintenance. (b) the insulation of cool of the protected metal. As long as the two
pipe supports may prevent condensation of an electrolyte film on internal metals have approximately equal
or external surfaces. (c) full-length, continuous welds are preferred to inter- potentials the second will act as the anode
mittent, tack ones; slag and surfaces oxides must be removed prior to and the protected surface as the cathode.
surface coating in order to achieve good adhesion of the coating. Thus, while the overall rate of loss of
metal is increased, it is the auxiliary metal
provide an excellent means of cor- into an aqueous solution in contact with that dissolves. This anode is, therefore.
rosion prevention for certain the metal surface. Several different mech- 'sacrificed' in order to protect the cathode.
applications. In tidal zones, for anisms exist for the inhibition. Zinc, magnesium and certain alu-
example, the use of Ni-Cu alloys Inhibitors may act by adsorption on the minium alloys are commonly used as
in the construction of jetties and surface of the metal. Adsorption occurs sacrificial anodes in the protection of
offshore oil platforms has proved around the corrosion potential and steel. A steel ship's hull is often fitted
effective against corrosive attack reduces the rate of either the anodic or with zinc blocks, for example, which are
by seawater. cathodic reaction. Various sulphur, simply removed and replaced when nec-
arsenic or phosphorus compounds act in essary.
Modification of the Electrolyte this way. ~In impressed curre nt cathodic pro-
Electrolyte modification may adopt one of An alternative mechanism for inhi- tection, a power supply is employed to
three tactics: bition involves the formation of the drive current to the protected metal
(a) Removal of the aggressive species precipitate on the metal surface or which serves as a cathode with respect to
or catalysis of a passivating reaction. an auxiliary anode. The cathode
(b) Addition of corrosion inhibitors. Phosphonate, polyphosphate or hydrogen potential is maintained within the
(c) Removal of aggressive species. carbonate salts belong to this category of required limits by current or cell voltage
Six possible strategies may be identified, inhibitor. regulation in a case such as a pipeline or
summarised as follows: A third group of inhibitors comprises by a large scale potentiostat (controlled
1. Elimination of dissolved oxygen redox reagents which act by shifting the potential power supply) for an offshore
usually by evacuation, nitrogen satu- surface potential to a region where construction. The cost of maintaining a n
ration or by means of oxygen cathodic or anodic protection occurs. The electrical current must. of course, be
scavengers such as hydrazine. dichromate ion (Cr20 / -) acts by this type taken into account.
2. Elimination of acidity by neutrali- of mechanism. Sacrificial anodes and impressed
sation, by addition of lime, for current protection each offer advantages
example. Change of Electrode Potential and disadvantages. The advantages of a
3. Elimination of dissolved salts by It is, theoretically, possible to raise the sacrificial anode include:
means of reverse osmosis or ion e lectrode potential away from the cor- l. Operation that is indepe ndent of an
exchange, for example. rosion potential to a value where a stable external power supply
4: Reduction of humidity by means of passive state is attained, i.e., the surface is 2. Installation is relatively straight-
desiccants such as silica gel. anodically protected. Conversely, the forward
5. Reduction of local humidity by potential may be lowered, removing it 3. Additional anodes can be fitted
means of a localised temperature away from the cor rosion potential and where protection proves inadequate
increase of around 5°C. into a stable zone, i.e., the surface is 4. Incorrect polarity connection is not
6. E limination of solid particles in cathodically protected. possible.
order to prevent deposit corrosion. (a) Cathodic protection 5. No regulation of power supply is
Cathodic protection may be achieved by needed.
(b) Addition of corrosion inhibitors means of a sacrificial anode (Figure 4(a)) 6. Overprotection is easily avoided.
A corrosion inhibitor is an inorganic or or by the use of impressed current (Figure 7. A uniform electrode potential is
organic species that retards corrosion 4(b). easily achieved.
when introduced, in low concentration, Use of a sacrificial anode involves the T he main disadvantage is that its appli-

119
 cation 1s limited, by the low value ot the
potei;tia-1 difference to cond uctive envi-
ronments with small anode-cathode
separation
Impressed current protection offers the
following advantages:
1. A wide range of potential difference
is attainable
2. The potential difference may be
adjusted to meet the requirements of
changing conditions.
3. Large areas can be protected. even
those with large anode-cathode sepa-
rations and those located in a highly
resistive environment.
4. Few anodes are necessary.
The most serious disadvantages are:
1. The requirement of a reliable power
supply
2. The risk of overprotection
3. Incorrect polarity connections are
possible
4. A uniform electrode potential over
the metal surface is not easily
achieved.
(b) Anodic protection
The principle of anodic protection
depends on maintaining a stable passi-
vating layer on the metal surface.
Addition of elements such as palladium or
copper as low concentration components
in alloy steel produces galvanic anodic
protection of the steel.
Impressed current anodic protection is
used to a much lesser extent than its
cathodic counterpart, although examples
include protection of chemical storage
tanks (Figure 5) and heat exchangers. On
commissioning. the impressed current must
exceed the critical value necessary to pas-
sivate the surface. Thereafter, a reduction
in current occurs such that th e impressed
current maintains the passive film. Current
is then minimal. Stainless steel and
titanium alloys, for example, may be pro-
tected in an acidic electrolyte by means of
impressed current anodic protection.
Surface Coatings
A diverse range of surface coatings may
be applied to protect a metal surface.
Due consideration must be paid to the
avoidance of localised damage that could
render areas of the surface vulnerable to
corrosion. Examples of surface coating
protection layers include:
1. Paint or a polymer cladding.
2. Metal oxides, as in the anodising of
aluminium.
3. Metal coating, eg., steel sheet elec-
troplated with zinc or hot-dipped
galvanised iron.
Solution
Zinc
Steel
(a)
Figure 6. Corrosion of a subs1rme al damaged or defeel sites in coolings: (a) zinc-p/a1ed steel where 1he zinc is anodic with respect to the underlying steel
and the zinc corrodes pref erenlially: (b) a tin coaling is ca1hodic wilh res peel 10 1he underlying s1eel and rapid, localised corrosion of the subsirate takes
place: this is lhe adverse case of a small anode area and a large caihode area: (c) localised corrosion of a me/al subs1ra1e can take place al a damaged site
on a paini coa1i11g. (It is assumed in all cases that oxygen red11c1ion is 1he ca1hode process).
120
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To porenriosror
2. U. Wranglen, 'An Introduction to
Counrer-
Corrosion and Protection of Metals'
electrode Chapman and Hall, London, 1985. '
- a broad coverage of the principles.
3. J.M. West, ' Basic Corrosion and
Cornode Oxidation', Ellis Horwood
Chichester. 1980. '
-an excellent treatment of the funda-
mental thermodynamics and kinetics.
Reference electrode probe
4. E. Mattson, 'Basic Corrosion Tech-
nology for Scientists and Engineers'
Ellis Horwood, Chichester, 1989. '
Figure 5. Anodic protec1ion of a s1ee/ 1ank by 1he -a useful low-level introduction with
applica1ion of an impressed currenl. The many case study examples.
po1ential of 1he 1ank surface is maimained a1 a 5. D.Pletcher, ' A First Course in
prede1ermined value (wilh respecl 10 a reference Electrode Processes', The Electro-
elecirode) using a specialised power supply chemical Consultancy, Romsey, 1991.
known as a po1en1ios1at.
-a simplified electrochemical approach
to electrochemistry techniques.
In all cases of protective coatings, the 6. D.Pletcher and F.C.Walsh, 'Industrial
consequences of defects in the coating Electrochemistry', 2nd Edn.,
(possibly due to surface preparation) or Chapman and Hall, London, 1990'.
damage of the coating (perhaps during -the fundamental and technological
installation or in service) for corrosion aspects of corrosion are placed in per-
must be taken into account. Examples are spective within the f ramework of other
shown in Figure 6 where galvanic cor- types of electrochemical processes.
rosion can result at pore sites or damaged 7. M.G.Fontana, 'Corrosion En-
sites in metal coatings (Figures 6(a) and gineering', 3rd Edn., McGraw-Hill
(b)) and atmospheric corrosion may result Int. Edns., New York, 1987.
at a damaged zone in a paint coating on a -a specialised text with an extensive
metal (Figure 6(c)). coverage of principles and practice.
8. U.R.Evans, 'An Introduction to
CONCLUSIONS Metallic Corrosion', 3rd Edn, Arnold,
The large variety of different types of cor- London, 1981.
rosion can occur according to the specific -one of the classical text books on the
circumstances of the metal surface. A principles of corrosion and protection.
number of these are dependent on the 9. P.Neufeld (Ed.), 'A Working Party
metal itself while the remaining are asso- Report on Practical Corrosion
ciated with its environment. A wide range Principles' European Federation of
of preventative methods are available for Corrosion Publications No.2, The
the control of corrosion; all of these depend Institute of Metals, London, 1989.
upon removing the components in a cor- - a useful summary of the principles
rosion cell or (more commonly) on with a description of simple exper-
lowering the rate of the electrode processes. iments.
10. F.C. Walsh, 'Electrode Reactions in
ACKNOWLEDGEMENTS Metal Finishing· and E lectrochemical
The material contained in this tutorial Cell Reactions in Metal Finishing,
note is used in corrosion lectures to first Trans. Inst. Metal Finish., 69(3),
year BSc Applied Chemistry, BSc (1991), 107-116.
Applied Environmental Science and -the first two parts of a tutorial series
BTEC HNC/HND undergraduate courses in metal finishing.
and has been addressed to delegates on 11. M.G. Fontana and N.D. Greene,
industrial short courses at the Universities 'Corrosion Engineering', McGraw-
of Southampton and Sheffield. The Hill, New York, 1967.
authors are grateful for feedback from - a classical text book on the principles
their many students. of corrosion engineering and pro-
tection.
FURTHER READING 12. F.C. Walsh and B.D. Barker, 'The
1. K.R. Trethewey and J. Chamberlain, Overall Rates of E lectrode
'Corrosion for Students of Science Reactions; Faraday's Laws of
and Engineering', Longman Harlow, Electrolysis', Trans. Inst. Metal
1988. Finish., 69(4), (1991) 155-162.
-a useful low-level introduction aimed -the third and fourth papers in this
at a wide readership. tutorial series.
Woter +low cone. electrolytes
Solution (from co., so,, Noell
Point
Tin
Steel (c)
Metal
(b)