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Protection Parameters
CHAPTER 3
Metal Potentials
Measurements
The measurement of the potential of a metal immersed in an electrolyte is, in practice, the measurement of the potential of a cell which consists
of the metal and solution as one electrode system and a half cell as the other,
the two being joined by an electrolyte bridge. In theoretical electrochemistry, it is usual to refer to the hydrogen electrode as the standard half cell.
This is not a convenient instrument for use in the field and other, more rugged, electrodes are used.
The use of the half cell introduces a large resistance into the circuit and
potential readings must be made using a high impedance instrument. The
voltage measured usually has a value of betwee; M V and 1 W V and an
accuracy of 2 mV, or exceptionally 1 mV, is required. The total circuit
resistance varies from below 20 ohms in low resistivity environments to
more than 50,000 ohms in high resistivity soils. Moving-coil instruments
are available with resistances of 100,000ohm per volt and these are suitable
for low resistance circuits. In high resistance circuits electronic solid state
voltmeters or potentiometers are employed, one is shown in Figure 11.
Fig. 12 shows a typical potential measurement being made. Generally
the metal will be connected to the negative of the meter and the half cell to
the positive. Thus a reading of 600 mV between steel and a copper sulfate
reference cell would mean that the copper half cell was 600 mV positive to
the metal-soil half cell. In cathodic protection work it is general practice to
refer to the potential of the metal-soil electrode system relative to the half
cell, that is the metal has a potential of - 600 mV to the copper sulfate half
cell. This convention, being universally adopted, will be used throughout
the remainder o f the text.
27
28
Structure
Voltmeter
Half-Cell
Electrolyte
has a high resistivity, especially if the current flux o r density is high. The
changes that occur on varying the current are those due both to polarization
of the metal interface and the changed voltage drop through the ohmic
resistance of the soil. The opposite of the above effects would occur if the
metal were acting as a cathode; moving the half cell away would cause a
more negative metal potential and bringing the half-cell nearer would cause
the metal to display a less negative potential. Increasing the current flow
towards the metal which is acting as a cathode wduld make it display a more
negative potential, while decreasing the current will make the metal potential more positive.
These effects can be illustrated by considering an insulated box of electrolyte divided by a block of metal as in Fig. 13a with a direct current flowing from left to right through the electrolyte and metal. The metal potential
relative to various half cell positions is shown in Fig. 13b for several values
of the current.
If the current flowing into and out of a vertical cylinder of metal buried
in the ground (or suspended in a liquid electrolyte) is considered, then the
curves shown in Fig. 14 give the potential that the metal will display relative to a half cell at various positions. The left-hand side of the graph shows
the relationship when the metal is a cathode and the right-hand side when
the metal is an anode. The shape and magnitude of these curves will vary
with the metal shape and the resistivity of the electrolyte. Changes in the
current density will affect the curve both by the change in polarization at
the metal interface and the ohmic voltage in the electrolyte.
29
Current
Potential Relative
to Half-Cell
FIGURE 13 Potential variations close to electrodes at various currents into and out of metal
plate lying in electrolyte trough.
Electrodes
In the discussion on the equivalent circuit for a simple cell in Chapter
1 it was shown that the potential of the anode in the cell would be more
negative than that of the cathode. In a practical corrosion cell the potential
of the anodic area will be more negative to a half cell adjacent to it than is
displayed by the cathodic area to a similar half cell placed close to it. This is
illustrated in Fig. 15a.
If the current flowing through the cell is controlled by inserting a
resistor in the electrical circuit (as opposed to the electrolytic circuit) then
the potential of the anode and cathode relative to points x and y is shown in
Fig. 15b. The difference between the curves relative to x and y being the
voltage loss in the electrical circuit by virture of the introduced resistor.
It is possible to determine the anodic and cathodic areas on a structure
30
Rod acts as
cathode
Rod acts as
anode
Half-cell position
Current
31
& to Distant
Half-Cell
Ea to Distant
Half-Cell
Half-Cell Position
Ea
Ec to Cathode
Metal Connection
Ec Relative to
Anode Metal
a Relative to
Cathode Metal
Ea to Anode
Metal Connection
Half-Cell Position
Polenlkl
lo
33
MetaUsolution
Metal
Potential
Volts
-0.85
-0.80
-0.76
-0.78
+0.25
more negative than the copper, will become polarized; this polarization will
make the steel display a more positive potential than it normally would. If
this same piece of steel is corroding by its surface having anodic and
cathodic areas, then the anodic areas will display a more negative potential
and this, despite some polarization, will be more negative than the potential
that the steel plate would display to a remote electrode.
Half Cells
A practical half cell consists of a piece of metal, usually a rod, surrounded by a standard solution of one of its salts, connected to the corroding electrolyte via a salt bridge. In practice the bridge consists of a
porous plug of wood, sintered glass or ceramid, soaked in the cell electrolyte. In the majority of half cells the bridge ends with a cross-sectional area
of a few square centimeters and for most field purposes this acts as a point
contact. For laboratory work it is general practice to make the bridge tip as
small as possible in order to achieve a reading at a precise point, often by
the use of an extension salt bridge.
The most common half cells used in corrosion practice and in cathodic
protection are listed in Table 111. Opposite each cell is indicated the potential that would be measured if they replaced each other in a particular
measurement of steel at its protection potential. The copper sulfate electrode is used generally for non-marine work and the zinc and silver chloride
cells for marine work. The calomel electrode finds limited research use in
both fields.
34
35
FIGURE 17
36
The methods have tended to run into the techniques used for determining the ohmic volts drop around the structure by the use of a superimposed alternating current. The greatest application is in the protection of
buried pipelines and these are discussed later in that chapter later in the
book.
Lead
Extensive cathodic protection installations have been made to lead
cable sheaths, either buried in the ground or when they rest in ducts. The
potential of a lead cable sheath to earth depends upon the earth conditions
and can vary from -0.55 V to -0.65 V to a copper sulfate electrode.
This electrode is not always used and a piece of cable sheath alloy,
usually an antimony alloy, or a lead/lead chloride half cell is employed. The
lead alloy is either placed in a filled duct or at the bottom of a manhole and
used as a zero reference. That is, when the lead sheath is receiving no protection it and the reference length of lead alloy display the same potential.
The lead chloride half cell, usually lead 3 per cent antimony alloy in normal
lead chloride (or sometimes saturated lead chloride) displays a potential of
-0.58 V to - 0.59 V t o a copper sulfate half cell and so is generally about
the potential of the lead cable sheath.
37
Aluminum
Aluminum is finding increasing use as a sheathing material for cables
and considerable lengths of it are buried in the ground and in various
waters. Similar developments are taking place in piping and-using
modern welding techniques-aluminum pipe lines are being installed. A
great weight of aluminum is being fabricated into chemical plants and
many storage vessels are now made of it. Small ships and boats are being
built with aluminum hulls and these techniques are being extended to light
warships.
All these uses of aluminum involve its contact with bulk electrolytes.
Coatings on aluminum have been tried with some success, but inevitably
38
even the best coatings suffer damage and pitting corrosion occurs. Cathodic
protection has been used successfully in a great number of applications and
with a large number of aluminum alloys. In soils it has been found that a
negative swing of 100 to 200 mV protects the aluminum and this makes its
potential about - 0.80 V to - 0.85 V to a copper sulfate half cell. 99.5 per
cent pure aluminum and some of the structural alloys have been protected
in sea water and in various brackish waters at potentials of - 0.85 V. The
aluminum alloys used to clad the structural alloys often initially display
potentials more negative than this in sea water. For cathodic protection in
sea water a potential swing of - 100 mV to - 200 mV has been adopted.
Where aluminum is used in chemical plant the cathodic protection criterion
is best established in the particular electrolyte.
Aluminum suffers cathodic corrosion as the result of an excessive accumulation of alkali. In many soils potentials as negative as - 1.3 V to copper sulfate can be tolerated and in moving sea water it is difficult to cause a
cathodic attack. The presence of a second metal, such as steel, can cause
alkali to accumulate by the cathodic reaction on the steel which will attack
the aluminum at potentials more positive than those generally considered
safe. Because of the diverse electrolytes and alloys that are found with
aluminum careful use of swing potential criteria and site experiments will
allow the successful use of cathodic protection.
Galvanizing
Zinc is rarely used structurally but there is widespread use of it in hot
dip galvanizing and other similar processes. Steel that has been galvanized
can be successfully cathodically protected: this should be achieved by the
zinc which forms a sacrificial coating, but in practice this coating acts for a
few days and then becomes passive. Galvanized tanks, pipes, ships hulls,
etc., can be protected and the potential required for protection seems to be
about - 1.O V to copper sulfate. While the protection of the old galvanizing, or rather the underlying steel, can be achieved at less negative potentials than this, it is difficult to avoid potentials more negative than - 1.O V
with new galvanizing when a swing criterion of 100 mV can be adopted.
Zinc dust in an inorganic binder used to coat steel in sea water can be
protected at normal steel potentials. It is suggested that if the steel is protected by a further 100 mV, that is to about - 0.95 V to - 1.80 V to copper
sulfate, then the coating will remain intact and the zinc not corrode or leach
out. The coating integrity is retained but this may be caused by oxidation
of the outer layer of zinc which then seals the surface.
Zinc metal coating, if it is in electrical contact with thc steel, will act as
a potential barrier which will display seemingly very high cathodic
resistance at moderate potential swings.
It is suggested that zinc coatings on steel can be polarized for short
39
periods and then in the absence of cathodic protection will continue to prevent corrosion. Proposals involving periods of about one minute application of current and one hour continuation of protection have been suggested.
Cathodic corrosion could conceivably occur with a galvanized structure, but since the corrosion of the galvanizing would reveal only steel
which would be adequately protected, there is little information on this
point.
Stainless Steel
Stainless steel relies for its corrosion resistance upon a film of oxide
which passivates or protects the metal. T o maintain this film it is essential
that there is a supply of oxygen to the surface. This condition is achieved
under anodic, not cathodic, conditions and there is considerable experience
of successful anodic protection of stainless steel. Under cathodic conditions
the supply of oxygen to the cathode is diminished. Small cathodic changes
of 100 mV can destroy the oxide film on stainless steels and render them
liable to corrosion. A further potential change, while destroying the natural
protection of the oxide film, protects the steel by the normal cathodic protection processes.
Anodic protection of stainless steel and other passivating metals is
achieved by holding the potential within the band at which the minimum
corrosion occurs. This means that a miniscule anodic current is flowing and
causing the continuous re-passivation of the surface. The corrosion rate
under these conditions is the minimum and the system is designed to
tolerate this.
40
Current
Electrolyte
Anode
cathode
Electrolytk
Electrical
Potential Plot of Clrcult
. alloys used
41
R , at the anolyte and R, at the catholyte, so that the value of the cell current
will be
The rate of corrosion per unit area will be proportional to the current density at the anode and this figure is of greater practical significance than the
actual cell current. If the anode area is A, then the rate of loss of metal per
unit area will be proportional to
Electrode Size
If the dimension of the cell is increased by a factor m, then the resistances at the anode and cathode will decrease by this amount and the anode
area will increase by its square, m2.The cell current will increase because of
the reduction in circuit resistance and the current density will be less
because of the greater increase in area. The decrease in current density will
mean there will be less polarization so the value E, - Ec will increase. Had
there been no polarization the current density, and hence the rate of corrosion per unit area would be smaller by the factor m, the increase in dimensions of the cell. Where the electrodes polarize the decrease will not be as
marked because the polarization will tend to maintain a constant current
density.
If the metal rods are made unequal in size by increasing the size of only one, then the current will increase and the current density on the rod that
remains the same size will be greater while the current density on the one
that has increased in size will be less. The cathode will not be affected, but
the anode will probably corrode more rapidly if its current density increases.
In a large corrosion cell the current density is smaller a n d polarization
will have less effect, while in a small cell with high current density polarization will become important and can assume complete control. In a cell with
electrodes of unequal size, the control-that is the factor that has the major
influence on the cell current-may rest either with the cell resistance or the
polarization of the electrodes. The rate of corrosion will almost invariably
depend upon the size of the anode. As well as the influence of the size of the
electrodes, considerable control can be exercised by the amount of electrolyte present. The current flowing in a cell formed by two flat metal elec-
42
trodes lying on the bed of shallow water will be influenced by the depth of
water over them until this depth exceeds the plate dimensions.
FIGURE 19 Current/potentialrtlationshiparound
a cylindrical electrode.
43
6V
I
2*r
-13,p
An&
cathode
FIGURE 20
44
-0.0 v
- 0.2 v
Anode
A'
Cathode
0.7 v
0.9 v
45
Addltlonal
Cathode
Polarlzatlon
Anode
Al
Cathode
0.9 v
Effect of
Anode Slze
Half-Cell Should
Be On This Equlpotentlal
46
the metal surface. At this position the polarization of the cathode will include all the acceptable catholyte resistance potential drop. Placing the half
cell remote from the structure would lead to a loss of protection as a potential drop caused by the resistance of the electrolyte would be included in the
measured voltage. Equally, were corrosion caused by two different soil
types over the length of a long pipeline, then applying protection relative to
a half cell placed very close to the pipeline would demand more cathodic
protection current than was necessary.
Half-Cell
FIGURE 23
protection.
47
FIGURE 24
relative to a half cell at position 2, that is, over the pipe at the soil surface,
will prevent corrosion from short and long line currents and reduce local
cell corrosion. Protection relative to a half cell at position 1, within an inch
of the pipe metal, will prevent all three forms of corrosion.
Perhaps it would be useful to study a plot of potential along the pipe
surface, assuming all three types of corrosion to be taking effect. Fig. 24
shows such a plot. In the curve, two features are important: the frequency
of the change along the length of the pipeline, and the amplitude of these
changes. A small ripple on the long line corrosion pattern will be suppressed by long line protection, but local cell corrosion with low frequency
modulation of its amplitude will not be controlled by long line protection.
The second example illustrated in Fig. 25 shows a water storage tank
being protected by a single anode. The tank base is covered with a layer of
sediment from the water and a large differential aeration cell exists between
this and the tank walls. The walls, though cathodic to the base, themselves
suffer corrosion of an intense pitting character. The base-to-wall cell may
be likened to the long line current corrosion and if protection potential is
achieved relative to a half cell at position 1 this corrosion will cease and the
pitting attack on the walls will be reduced. To control the pitting, or local
cell action, at the walls, the protection potential must be achieved relative to
a half cell within $4 inch of the wall.
The third example concerns the position of the half cell relative to a
protected structure such as an H girder. This is illustrated in Figure 26.
The half cell at position 1 will deal with corrosion from top to bottom of the
girder that may occur with stratified sea water, river water and mud or by a
temperature differential in an otherwise homogeneous liquid. The corrosion between the steel weld metal and the steel will be reduced, but in order
that this is eliminated then the protective potential must be reached within
the girder recess.
48
Tank
Wall
FIGURE 25
49
FIGURE 26
50
ture. Either of these quantities may be the larger, though generally the
mean current density will be greater as it will include any overprotection of
the system. Where one sector of the structure is subject to a depolarizing influence or perhaps part of its surface has a low coating resistance, the local
absolute current density may exceed the mean current density. An efficiency figure could be calculated based on the ratio of the absolute current density to the mean current density, though this will have little meaning economically as the low efficiency in current density may be offset by a high efficiency in current generation.
It is usual to refer to the superficial area when the area of the
cathode is being considered. A corroded or weathered surface will be rough
and this roughness may increase the true surface area by 25% or more.
Similarly, most metal surfaces will be covered by a layer of corrosion product which may be quite thin. Bright metal that has been freshly scraped will
have a significantly different current demand from metal surfaces found in
practice where both surface roughness and corrosion films will be present.
The following considerations will include only the normally corroded and
roughened surfaces of the metal. Mechanical and pneumatic erosion of the
surface will be considered as it affects the normal current requirements.
Temperature variations and other phenomena, such as relative movement
of the metal and the electrolyte, will be considered where relevant.
51
- 1.4
- 1.1
- 0.8
- 0.5
io
20
30
50
40
&tlfcerl
c.
g 10
100
300
200
4bo
500
52
a,
= q5(1
7-15
-)
255
Present day practice in pipe laying is to use a highly insulating coating such
as tapes or coal tar enamel. There are, however, many millions of square
feet of bare steel buried in the ground. In aerobic soils this requires 1 to 3
mA/sq ft at which polarization occurs and reduces the on-going current
density.
Under anaerobic conditions 0.5 to 3 mA/sq ft may be required depending upon the presence of sulfate-reducing bacteria. Excessive currents
may be required to achieve the enhanced potential criterion in their
presence but generally three to six months at 3 mA/sq ft will bring about
polarization and the protective potential will be achieved. This delay seems
to depend upon the bacterial activity and the total charge passed per sq ft of
surface area. High current density, while causing the pipe to exhibit protective potentials, will not cause immediate sustained polarization. Steel will
require a slightly higher current density in a low resistivity soil than in a
high resistivity soil. Coatings on steel may reduce the required current density to 0.01 mA/sq ft and polythene tape, plastic extrusions and powder fusion coatings to even lower values. At about these values of coating
resistance handling damage becomes significant and without the care comparable with that found in the laboratory lower current densities are not attainable.
Reinforcing bars in concrete are usually bare steel often with a keying
indentation. Where the concrete is in good condition its alkalinity
passivates the steel and corrosion is not a problem. In many areas carbonates and chlorides either naturally or by use of de-icing salt degrade the
concrete and the steel rebar corrodes. Cathodic protection will prevent this
corrosion and where the concrete is buried or immersed the current density
is similar to that found with polarized steel. Where the structure is free
standing the concrete is the electrolyte and can be treated as an extension of
protection in soil. Both these applications are discussed as special cases in
the appropriate chapters, together with the effects of coating and galvanizing the rebar.
Galvanizing and aluminizing reduce the required current density to
53
about one third that of bare steel and polarization to more negative values
is easier.
Non-ferrous Metals
Aluminum can be protected at current densities of 0.2 to 3 mA per sq
ft, with the environment and the particular alloy influencing these figures.
Heavily anodized aluminum requires 0.002 rnA per sq ft to 0.01 mA per sq
ft and from the results of limited tests this current density does not appear
to destroy the anodic film.
With lead it is similarly difficult to predict the current density required, but between 0.5 and 5 mA per sq ft are usually required for protection. Lead cables are perhaps the main field for this type of work and here
the current density often depends on the duct conditions.
Swing Tests
Many structures exhibit an almost ohmic relationship between the applied current and the potential. This is either because of a particular
polarization characteristic or because the potential is controlled by an
ohmic coating. Where the current required to protect such a structure is
low, below about 10 Amps, then a reliable estimate of this current can be
made using a four terminal resistivity meter. In this type of instrument a
current is caused to flow in the circuit connected to terminals C, and C, and
54
Four-Terminal
Resistance Meter
55
'
0.1
l:o
Protection
Current
impressed Current-Amps
io
Piotection
Current
ParallelSided
Elastic
Enclosure
Electrodes
Voltmeter to
Measure Potential
and Potential Gradient
Structure Surface
57
necessarily be the same, even if they indicate the same current requirement, as these potentials may be measured relative to differently placed
electrodes.
Accepting this revised interpretation of the graph, the method has a
great deal to commend it and doubtless is a powerful tool when new or different circumstances suggest a modified protection criterion. In the field
the method suffers from two defects: firstly the large number of skilled
measurements that have to be taken even to make the determination at a
single point; and secondly, the method only works where a section of the
structure receiving a current from a single source can be isolated. Thus, on
a pipeline the point most remote from the cathodic protection should be
subject to this type of test, but where this point falls between two installations the tests would have to be arranged by varying the current from both
stations in the anticipated ratio that they will ideally have in practice.
Fig. 29 shows typical plots of installation close to and remote from the
anode and how they will appear in practice. As can be seen, the interpretation of the break in the curve is comparatively easy, whereas the determination of the point where the practical curve deviates from a straight line is
more difficult, particularly as the current, the factor that is to be determined, is on a log scale.
The introduction of electronic simple computing will revive interest in
this technique, though it will still require considerable elegance and experience in the field in selecting the sites for the cathodic protection tests
and in placing the reference electrodes.
A number of different types of enclosures can be used in sea water to
determine the E v Log i curve break at any particular point. The ideal
method seems to be one in which a sector of the electrolyte is shielded so
that both the surface potential and the current density, by a measurement of
the potential gradient, are determined. Such a unit is shown in Fig. 30 and it
has the advantage of an open structure so that the electrolyte can flow freely
next to the cathode. In using this technique the curve that results will either
be the one obtained before polarization or it can be used where the structure is believed to be close to the protection potential and then the results
will indicate the current density required after that period of operation.
The second series of methods of determining the minimum current required for cathodic protection is based on attempts to measure the net flow
of current on to or off the metal surface. In a long pipeline, for example,
it would be possible to determine that the current flowing in the pipe
(towards the cathode return) is always increasing, showing that at all points
there is a net gain of current and the pipe is cathodic. This might be difficult to interpret where the cause of corrosion is current flowing between
top and bottom of the pipe. It is a most useful tool in surveying deep well
protection.
58
Experimental Techniques
The current density and potential criterion and the eficacy of the cathodic
protection of a metal in a particular environment can be determined by
laboratory experiment. Small samples of the metal can be placed in the
electrolyte and the minimum current density required for protection can be
determined. These results can be transposed to the field, though this has to
be done with due regard to the change in dimensions.
In field trials, as opposed to the laboratory, the structure itself can be
used and various parts of it subject to different degrees of protection. This
can be done by techniques which cause different areas of the structure to
receive different degrees of protection. For example, areas close to the
anode may have a much larger potential swing than areas further away.
Similarly, plastic insulating sheets can be used in certain electrolytes to
cause a variation of potential in the electrolyte. The results of inspection
will give the correct potential criteria in the field.
Alternatively metal coupons can be attached to the structure placed in
close contact with and electrically bonded to the structure, either directly or
through a zero potential measuring circuit. The coupons themselves can be
accurately and rapidly monitored and they can be used to assess both the
current density and the potential criteria. Care has to be taken that the
coupon exactly matches the main cathode conditions, not receiving
preferential or diminished protection. From these coupon tests the cathodic
protection current density can be determined. This type of work has been
carried out continuously for many years and in most environments the
criteria are well known or a sensible interpolation can be made from the
literature. In other cases, particularly where there is a bad history of corrosion, the application of cathodic protection-be it adequate or not-will
reduce the rate of corrosion and from this practical application the best or
sufficient criterion will be determined. There will be a reluctance to reduce
the protection below the level that has been found to be adequate and so the
criterion may be one which has shown itself to be sufficient though not
necessarily the minimum.
Partial Protection
Sometimes it is found that rapid corrosion is taking place over a few
limited zones. This is particularly true of structures that are exposed to a
59
Protective Coatings
As the criterion of cathodic protection is a potential change, then the
current density required to achieve this will depend upon the resistive state
of the metal/electrolyte interface. This resistance can be greatly increased
by coating the surface with an insulating coating such as a paint.
In a typical soil a pipeline may require 2 mA per sq ft to protect it,
whereas a similar pipe, coated by modern techniques, would require only
20 micro amps per sq ft or 1 per cent of the bare steel value. This leads to a
tremendous reduction in the cathodic protection components required, and
in the case of a pipeline, greatly simplifies the engineering.
The current density that is required by a pipe covered with a modern
coating will be the sum of two components, firstly that required to overcome the purely ohmic drop through the coating substance, and secondly,
that required to polarize any pin holes, flaws or damaged areas. If no
cathodic protection were applied the areas of damage would become the
anodes and the coated areas the cathodes. The overall corrosion of the
metal structure would be less, but the concentration of the corrosion current at the anodes would lead to deep pits and, where this is critical, corrosion failure. As a protective measure, this type of coating can cause more
rapid failure than would occur in its absence. On the other hand, using
such a coating will greatly reduce the cathodic protection costs. The total
cost of the combined coating and cathodic protection may be more or less
than that of the cathodic protection alone, according to the difficulty and
60
cost of coating the structure. In most cases the minimum cost will be found
where cathodic protection is applied as a complement to, not the substitute
for, a coating.
The electrochemical reactions that take place at the cathode surface
and the electrical circuit control of the cathodic protection scheme suggests
a series of properties which a successful coating must possess. There will be
an accumulation of alkali close to the cathode, so it is essential that the
coating is not attacked by alkalies. When protection is just achieved a pH of
about 9 will be found at the cathode but where some over-protection is inevitable and higher values of 10, 11 or 12 are possible.
The electrical potential which is established across the coating is
capable of transmitting moisture by electro-osmosis. This phenomenon occurs in a variety of substances and the water generally travels in the same
direction as the conventional current. The use of unsuitable fillers can
greatly increase the rate of electro-osmotic penetration, particularly if the
fillers are not well dispersed and some areas are over-filled. Water that
travels through the coating can form bubbles behind the coating with
breakdown of the coating to metal adhesion. Corrosion will occur and the
cathodic protection from the outside will be of no effect in preventing it. A
good coating to metal bond is essential, with coatings that are susceptible to
electro-osmosis.
Electrically, it is essential that the coating maintains its high insulating
property, otherwise constant adjustments of the electric generator and frequent detailed inspections must be made. Water absorption, whether by
the influence of alkali, by electro-osmosis or purely as a property of the
material, will reduce its electrical resistance.
The majority of coatings used on structures that are buried or immersed in water are organic and many of these are hot applied or tested for
pin holes by high voltage breakdown. These techniques, unless carefully
controlled, can burn the coating, causing the formation of a coke. As this
will be in contact with the metal the cell so formed, metal-electrolyte-coke,
can be very aggressive. This condition cannot be successfully be suppressed
by normal cathodic protection techniques.
Pipe Coatings
The pipeline engineer has to use a coating that will stand up to soil
stress found in the ground and one which will not be destroyed by contact
with and movement through the earth. Most coatings rely on bulk for this
type of protection, often with an outer shield wrap in bad conditions.
The earliest types of protectives were greases; these and petroleum
based jellies and wases are still used though now reinforced with wrappers
and tapes which often hold inhibitors. The electrical resistance of these is
not high and about five per cent of the bare-steel current is required. Some
61
FIGURE 31
of them have a tendency to absorb moisture and their resistance drops with
time.
O n long pipelines for site application over the trenches, asphalt, a
product of the petroleum industry, coal tar enamels and plastic tapes are
used. Asphalt is often filled with an inert powder and wrapped in an outer
shield which protects it from damage. The coating may vary from 1/32
minimum to a half inch or more. Asphalt has a high water absorption, 6 to
7 g per sq ft in 100 days, while a well formulated asphaltic enamel might absorb 2 g per sq ft in the same time. With this type of coating its water absorption can be considerably increased by electro-osmosis.
Coal-tar enamels provide a superior coating to the asphalts. Carefully
applied, and this is essential, the right enamel reinforced with woven or
felted glass fibers will have a high electrical resistance that will remain nearly constant with time. At low voltages, less than 1 volt negative swing on
most practical coatings, osmosis is negligible, and even at higher swings of
up to 2 V it is low. The current density required to provide protection to a
metal surface covered with a well applied coal-tar enamel is shown in Fig.
31. Coal-tar enamel however, tends to have a very narrow working
temperature range, softening above it and embrittling below it. Additions
to the enamel to widen this range can be made with resins which do not
significantly reduce its electrical properties.
Plastic tapes have been developed to a point where they provide excellent electrical properties, low water absorption, and only a small tendency to electro-osmosis. Their use is increasing and the early difficulties with
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Under-Water Paints
Paints used to protect marine structures have to stand the same electrical conditions as do coatings. The other properties required are slightly
different. The coating used on submarine pipes will be similar to that used
on land-based installations except that the pipe coating will be overlaid with
a weight coating. This is usually one or two inches of concrete reinforced
with a wire mesh. The pipeline will be constructed on a barge or on the
shoreline by welding together short lengths of pipe. These may be single
pipe lengths or two, three or four lengths previously welded together. Each
individual length will have been coated, both with the anti-corrosive composition and with the concrete weight coat. The welded joint then has to be
protected both against corrosion and mechanically. Where the pipe is constructed onshore and towed out to sea there will be time to make this joint
by the same techniques that are used on the general length of pipe or even
to set up a pipe mill and continuously coat the pipe before long lengths are
floated out to sea. O n the lay barge there will be very little time to make the
joint, coat it and protect it. A number of techniques have been developed.
The earliest was the use of an overfilled asphaltic mastic which was hotapplied to the joint to be flush with the concrete weight coating surface. The
mastic provided only a low degree of corrosion control and principally
reduced the amount of cathodic protection required at the joint by reducing
the rate of arrival of oxygen at the pipe surface and preventing the dispersion of the inhibiting catholyte.
More recently the joint has been coated beneath the asphalt mastic,
usually with a plastic tape. Coaltar enamels have been applied to the joint
and mechanically protected by concrete or by resin/ballast mixes.
When a ships hull is cathodically protected the paint will be required
to stand higher potential variations in the comparatively small area close to
impressed current anodes. The hull paint must remain smooth under the
influence of cathodic protection and particularly not be roughened by bubbling. There will be an increase in the current required when the ship is
underway. The increase in the cathode reaction will be compensated by the
action of the moving water washing away any alkali which might otherwise
accumulate. There is evidence that cathodic protection has adversely af-
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fected paint adhesion over certain primers. This technology is now well
understood and the latest marine paints are capable of maintaining a
smooth, pristine finish in the presence of cathodic protection over a wide
range of potentials. Thick, self-polishing coatings restore hull smoothness
when applied over microrough surfaces and retain this on a fully protected
steel hull.
In many seawater applications the cathodic protection will have to supply massive amounts of current for long periods of time to protect a bare
structure. There will also be problems with the distribution of this current
within complex structures. Under these circumstances a coating-whether
over the whole of the structure or only over part of it-that reduces the
overall current requirement by a factor or two or three may be suficient to
make considerable difference to the cathodic protection engineering. A simple coating technique that could economically be applied to this type of
structure and cause a reduction in current requirement would find a great
deal of use on large sea-water structures.
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