Module : Cathodic Protection Principles

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Corrosion is a natural process that by some estimates costs as much as 3% of a
country s gross national product. A properly designed, installed and maintained,
cathodic protection system will minimize such corrosion effects and hence the
costs associated with it. Cathodic protection systems are one of the main means to
achieve this in certain industrial applications
Enter Module Learning Outcome below this line
Upon successful completion of this unit the student will be able to demonstrate a
knowledge of the principles of cathodic protection systems and their installation
and maintenance requirements.
Enter Module Prerequisite(s) below this line
II-313-02
Enter Module Performance Evaluation below this line
Module assignments must be completed and handed in for evaluation.
When included attempt the Self-Test questions in the Module and check your
answers with the Self-Test Answer Guide to ensure you have understood the
Module material.
Enter Module Introduction below this line
In previous modules it was stated that corrosion is an electrochemical process in
which a current leaves a structure at an anode site, passes through an electrolyte,
and reenters the structure at a cathode site.
Cathodic protection is a long established and proven technique to inhibit (reduce)
metals from corrosion by minimizing the potential difference between identified
anode and cathode sites. As such it is unique amongst the various methods of
corrosion control in that if required it is able to stop corrosion completely, but it
remains the choice of the operator to accept a lesser, quantifiable, level of
protection and therefore it is an important and versatile technique.
In principle, cathodic protection can be applied to any so-called engineering
metals, although in practice, it is most commonly used to protect ferrous-materials
and predominantly carbon steel on structures such as buried pipelines, ships, piers
and jetties, oil production platforms and liquid storage tanks.
It is possible to apply cathodic protection in most aqueous corrosive
environments, although its use is largely restricted to natural near-neutral
environments (soils, sands and waters, each with air access).
Cathodic protection would appear to be restricted in its scope of application
despite its apparent versatility. However within the limits of this restricted scope
the number and criticality of the structures to which cathodic protection can be
applied is extremely high (e.g.: pipelines, underground storage tanks, and ship
hulls.)
There are two common methods of applying cathodic protection, using an
impressed current or a sacrificial anode, the former requires a source of can D.C.
power, and the latter operates independently of a source of D.C. power. The
relative advantages of the two methods largely derive from these basic
differences.
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1. Define the purpose of any cathodic protection system.
2. Name the two common types of cathodic protection systems.
3. What are the four recognized methods of minimizing corrosion in structures?
4. List the four classifications of cathodic measurement instruments.
5. What two basic criteria must be met in order for a cathodic protection system
to operate properly?
Enter Module Self Test Answers below this line
1. The purpose of any cathodic protection system is the reduction of corrosion.
2. The two common types of cathodic protection systems are:
a. Impressed Current
b. Sacrificial Anode.
3. The four recognized methods of minimizing corrosion effects in structures
are:
Cathodic / Anodic Protection.
Protective Coatings or linings.
Chemical Inhibitors
Material Design and Selection
4. Cathodic-protection instruments are classified as:
Potential-measuring
Current-measuring
Resistance/conductance-measuring
Multi-combination and Recording Instruments.
5. The two basic criteria that must be met in order for a cathodic protection
system to operate properly are that the structure to be protected and the anode
used to provide the protection have to be in both metallic and electrolytic
contact with each other.
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1. What is the basic difference between cathodic and anodic protection.
2. List typical structures that would require cathodic protection.
3. Explain in your own words the difference between sacrificial anode and
impressed current systems of cathodic protection.
4. Explain why cathodic protection cannot be employed to control atmospheric
corrosion?
5. What are the fundamental requirements of any commercial sacrificial anode?
Enter Module References below this line
Enter Module Appendix below this line
Technical Glossary
Adsorption: Taking up one substance at the surface of another; tendency of all
solids to condense on their surfaces a layer of any gas or solute that contacts such
solids.
Aeration cell (oxygen cell): Electrolytic cell in which a difference in oxygen
concentration at the electrodes exists, producing corrosion.
Amphoterics: Materials subject to attack by both acid and alkaline environments;
include aluminum, zinc, and lead (commonly used in construction).
Anaerobic - free of air or uncombined oxygen; anaerobic bacteria are those that
do not use oxygen in their life cycle.
Anion: A negatively charged ion that migrates toward the anode under influence
of a potential gradient.
Anode: Electrode at which oxidation of its surface or some component of the
solution is occurring (opposite: cathode).
Bell hole: Excavation to expose a buried structure.
Cathode: Electrode at which reduction of its surface or some component of the
solution is occurring (opposite: anode).
Cathodic Corrosion: Corrosion resulting from a structure's cathodic condition,
usually caused by the reaction of alkaline products of electrolysis with an
amphoteric metal.
Cathodic Protection: Technique to prevent metal surface corrosion by making
that surface the cathode of an electrochemical cell.
Cation: Positively charged ion of an electrolyte that migrates toward the cathode
under the influence of a potential gradient.
Concentration Cell: Electrolytic cell in which a difference in electrolyte
concentration exists between anode and cathode, producing corrosion.
Continuity Bond: Metallic connection that provides electrical continuity.
Corrosion: Deterioration of a material, usually a metal, because of a reaction with
its environment.
Current Density: Current per unit area.
Electrical Isolation: Condition of being electrically separated from other metallic
structures or the environment.
Electrosmotic Effect: Passage of a charged particle through a membrane under
the influence of a voltage; soil can act as the membrane.
Electrode Potential: Potential of an electrode as measured against a reference
electrode. The electrode potential includes no loss of potential in the solution due
to current passing to or from the electrodes (that is, it represents the reversible
work required to move a unit charged from the electrode surface through the
solution to the reference electrode).
Electrolyte: Chemical substance or mixture, usually liquid, containing ions that
migrate in an electric field; examples are soil and seawater.
Electromotive Force Series (EMF series): List of elements arranged according
to their standard electrode potentials; the sign is positive for elements with
potentials cathodic to hydrogen and negative for those elements with potentials
anodic to hydrogen.
Foreign structure: Any structure not intended to be part of the system of interest.
Galvanic Anode: Metal that, because of its relative position in the galvanic
series, provides sacrificial protection in the galvanic series when coupled in an
electrolyte. These anodes are the current source in one type of cathodic protection.
Galvanic Cell: Corrosion cell in which anode and cathode are dissimilar
conductors, producing corrosion because of their innate difference in potential.
Galvanic Series: List of metals and alloys arranged according to their relative
potentials in a given environment.
Holiday: Coating discontinuity that exposes the metal surface to the environment.
Hydrogen Overvoltage: Voltage characteristic for each metal-environmental
combination above which hydrogen gas is liberated.
Impressed Current: Direct current supplied by a power source external to the
electrode system.
Insulating Coating System: All components that comprise the protective
coating, the sum of which provides effective electrical insulation of the coated
structure.
Interference Bond: Metallic connection designed to control electrical
interchange between metallic systems.
Ion: Electrically charged atom or molecule.
IR drop: Voltage across a resistance according to Ohm's Law.
Line Current: Direct current flowing on a pipeline.
Local action: Corrosion caused by local cells on a metal surface.
Mill Scale: Heavy oxide layer formed during hot fabrication or heat-treatment of
metals. Applied chiefly to iron and steel.
Molality: Concentration of a solution expressed as the number of gram molecules
of the dissolved substance per 1000 grams of solvent.
PH: Measure of hydrogen ion activity defined by pH log 10 (1/aH+), where aH+
= hydrogen ion activity = molal concentration of hydrogen ions multiplied by ion
activity coefficient (a = 1 for simplified calculations).
Polarization: Deviation from the open circuit potential of an electrode resulting
from the passage of current.
Reference Electrode: Device for which the open circuit potential is constant
under similar conditions of measurement.
Reverse-current Switch: Device that prevents the reversal of direct current
through a metallic conductor.
Stray Current: Current flowing through paths other than the intended circuit.
Stray Current Corrosion: Corrosion resulting from direct current flow through
paths other than the intended circuit.
Structure-to-Electrolyte Voltage (also Structure-to-Soil Potential or Pipe-to-
Soil potential): Voltage difference between a buried metallic structure and the
electrolyte, measured with a reference electrode in contact with the electrolyte.
Structure-to-Structure Voltage (also Structure-to-Structure Potential):
Difference in voltage between metallic structures in a common electrolyte.
Voltage: Electromotive force, or a difference in electrode potentials, expressed in
volts.
Enter Module Acknowledgements below this line
The material in this module was developed in line with and based on the
apprenticeship course outlines for the relevant trades training programs in place in
North America (Canada).
The original coursework was introduced as Revision 0 during the initial course
development for Pt Inco Indonesia in 2005.
Future modifications will be incrementally revised and noted hereafter.
Objective:0

Define the basic principles, methods and

Enter Objective Learning Activity below this line.
Discuss the use and operating principles of sacrificial anodes in cathodic
protection.
Describe, with sketches, the impressed current cathodic protection system.
Discuss the importance of correctly connecting the cathodic protection
system.
Define the basic difference between anodic and cathodic protection systems.
List the applications for cathodic protection systems.
Enter Objective Learning Material below this line.
PRINCIPLES OF CATHODIC PROTECTION
Corrosion (review)
Corrosion is an electrochemical process in which a current leaves a structure at
the anode site, passes through an electrolyte, and reenters the structure at the
cathode site (see fig 1).
The metal loss (pit corrosion) occurs during the corrosion process only at the
anodic areas of the structure, where current is leaving the steel, flowing through
the electrolyte to the cathodic areas.

Fig 1: Corrosion in a pipe due to localized anode and cathode site generation
With reference to figure 1, because the steel pipe is in a soil with low resistivity
compared to the rest of the line. Current would leave the pipeline at that anode
site, pass through the soil, and reenter the pipeline at a cathode site.
Current flows because of a potential difference between the anode and cathode
(the anode potential is more negative than the cathode potential, and this
difference is the driving force for the corrosion current.
This total system comprising of ; anode, cathode, electrolyte, and metallic
connection between the anode and cathode is termed a corrosion cell.
There are four recognized methods of minimizing corrosion effects:
Cathodic / Anodic Protection.
Protective Coatings or linings.
Chemical Inhibitors
Material Design and Selection
All or some may be used in any given situation.

Cathodic Protection Principles

Cathodic protection is a method to reduce corrosion by minimizing the difference
in potential between anode and cathode sites. This is achieved by applying a
direct current to the structure to be protected (such as a pipeline) from some
external source to oppose the discharge of corrosion current from the anodic areas
of the metal structure.
When enough current is applied, the whole metal structure will convert into a
cathode by collecting current from the surrounding electrolyte. This is
accomplished by forcing sufficient current to flow to the structure being protected
from the electrolyte so that there is no net flow of current from any point on the
metal surface to the electrolyte. When external current is applied to a corroding
surface, part of the current goes to the anodic areas and part of it goes to the
cathodic areas.
The basic principle of effective cathodic protection is therefore to apply sufficient
current to the structure being protected to cancel out the natural corrosion current
by the introduction of additional electrons at the metal surface If additional
electrons are introduced in this way the cathodic reaction would speed up (to
consume the electrons) and the anodic reaction would be inhibited (metal
dissolution would be slowed down).
If corrosion is to be stopped, there must be no current leaving the surface of the
structure being protected. However it should be realized that cathodic protection
does not stop corrosion; instead it transfers the corrosion from the structure under
protection to another known location where the current discharging anode(s) can
be designed for long life and simple replacement.
Cathodic protection can only be applied to the surface of the metal exposed to the
same electrolyte as the anode.
For example: cathodic protection for the exterior bottom of a storage tank has no
effect on internal corrosion of the tank from corrosive water.

Methods of Applying Cathodic Protection

There are two principal methods of applying cathodic protection, these are known
as:
Impressed Current Systems
Galvanic Anode Systems (Sacrificial Anodes)
The main differences in these methods of application are that the impressed
current systems includes the structure as part of a driven electrochemical cell and
the sacrificial anodes includes the structure as part of a spontaneous galvanic cell.

Fig 2: (a) Galvanic Anode System (b) Impressed Current System

Note that both types have:
Anodes (from which current flows into the electrolyte)
A continuous electrolyte from the anode to the protected structure
(cathode)
An external metallic connection (wire).
These items are requirements, essential for all cathodic protection systems.

Galvanic (Sacrificial) Anode Systems

A galvanic cathodic protection system makes use of the corrosive potentials for
different metals. Without cathodic protection, one area of the structure exists at a
more negative potential than another, and corrosion results. If, however, a much
less inert object (that is, with much more negative potential, such as a magnesium
anode) is placed adjacent to the structure to be protected, such as a pipeline, and a
metallic connection (insulated wire) is installed between the object and the
structure, the object will become the anode and the entire structure will become
the cathode.
That is, the new object corrodes sacrificially to protect the structure as shown in
figure 3, thus the galvanic cathodic protection system is more generally referred
to as a sacrificial anode - cathodic protection system because the anode
corrodes sacrificially to protect the structure.
Galvanic anodes are usually made of magnesium, zinc or aluminium because of
these metals higher potential compared to steel structures (see figure 3)

Figure 3: Basic Galvanic System Magnesium Anode.

When galvanic anodes are buried in the soil, they are usually surrounded with a
special backfill material that provides a uniform environment around the anode,
which in turn promotes uniform anode consumption. The backfill also isolates the
anode from direct contact with the soil, preventing the possibility of formation of
passive films on the anode surface due to reaction with chemicals in the soil.
These special backfill materials have low electrical resistance, which results in
greater current output. A typical backfill material for magnesium anodes is a
mixture of 75% hydrated gypsum, 20% bentonite clay, and 5% sodium sulphate.

Anode Requirements
The fundamental requirements of a sacrificial anode are to impart sufficient
cathodic protection to a structure economically and predictably over a defined
period, and to eliminate, or reduce to an acceptable level, corrosion that would
otherwise take place.
In view of these criteria, the following properties are pre-requisites for
commercial sacrificial anodes:
The anode material must provide a driving voltage sufficiently large to
drive adequate current to enable effective cathodic polarization of the
structure. This requirement implies that the anode must have an operating
potential that is more negative than the structure material to be protected.
The anode material must have a more or less constant operating potential
over a range of current outputs. Consequently the anode must resist
polarization when current flows; the polarization characteristics must also
be predictable.
An anode material must have a high, reproducible and available capacity,
i.e. whilst acting as an anode, it must be capable of delivering consistently
and on demand a large number of ampere hours per kilogram of material
spent. The ideal anode material will corrode uniformly thus avoiding
mechanical fragmentation (hence wastage), and will approach its
theoretical capacity.
The production of large quantities of alloy material in anode form, and
possessing the desired mechanical properties, must obviously be
practicable and economic. Thus secondary processing such as heat
treatment is undesirable.

Sacrificial Anode Materials

In a sacrificial anode - cathodic protection system the anode must be more
electronegative than the structure being protected. This tends to limit the range of
suitable materials available to protect the structure. The range is further restricted
by the fact that the most electronegative metals (Li, Na and K) tend to corrode
extremely rapidly in aqueous environments.
In practical terms only magnesium, aluminium and zinc are useable so these
metals form the basis of the three commercially available (generic) types of
sacrificial anode.
In practice, with one minor exception (pure zinc), the pure metals are unsuitable
as sacrificial anode materials because they fail to meet one or more of the pre-
requisites outlined above. Therefore alloying elements are added to the pure
metals to ensure more acceptable properties are obtained (see table below).
 Figure 1: Anode Potentials of commercial sacrificial anode types
From the table it should be clear that there are major differences in performance
between one generic type and another and the magnesium alloys, which have
more negative operating potentials are therefore able to provide a large driving
voltage for cathodic protection than zinc and aluminium alloys.
Aluminium alloys, by contrast, provide a greater current capacity, more than
twice that available from zinc or magnesium alloys.
Whilst it might appear that this implies that if the driving voltage is the most
important feature in a given cathodic protection system then magnesium alloys
are to be preferred, but if a high capacity is required aluminium alloys would be
better. However in practice, selection is significantly more complicated and
detailed knowledge of the factors influencing the operation of sacrificial anodes
and design parameters is essential in order to select an anode that will achieve
optimum performance. This is beyond the scope of this introduction.

Applications of Sacrificial Anodes

Examples of the more common application of sacrificial anodes include the
following:
Hot spot (small areas of high corrosion) protection on bare buried pipelines.
Protection of short, well-coated buried pipelines.
Internal protection of vessels which are partly filled with water, such as tanks,
separators, treaters, and filters.
Ships Hulls
Offshore oil and gas drilling rigs, production platforms/semi submersibles and
support facilities.
Underwater pipelines.
However there are many other uses, including a large range of industrial
equipment where the surfaces are in contact with corrosive electrolytes, e.g. heat
exchangers, pump impellers and vessel internals.
However in cases where sufficient dc current cannot be obtained from galvanic
anodes, impressed current systems are required.
Impressed Current Systems
Impressed current cathodic protection systems use the same basic elements as the
galvanic protection system; only the structure is protected by applying a current to
it from an anode. The anode and the structure are connected by an insulated wire,
as for the galvanic system. Current flows from the anode through the electrolyte
onto the structure, just as in the galvanic system.
The main difference between galvanic and impressed current systems is that the
galvanic system relies on the difference in potential between the anode and
structure, whereas the impressed current system uses an external power source to
drive the current, as figure 4 shows.
The power supply is usually a transformer/rectifier combination that converts a.c.
power to d.c. Typically the d.c. output will be in the range 15-100 Volts capable
of generating 5-200Amps. These are fairly substantial driving voltages and
currents. Where mains power may not be available, diesel or gas engines, solar
panels or thermoelectric generators have all been used to provide a suitable d.c.
source.
It will be seen that the impressed current electrode discharges positive current, i.e.
it acts as an anode in the cell. There are three generic types of anode used in
cathodic protection, consumable, non-consumable and semi-consumable. The
consumable electrodes undergo an anodic reaction that involves their
consumption.
Anodes used in impressed current systems are usually made of materials that will
not corrode or deteriorate appreciably such as graphite or high-silicon cast iron
(common choices for soil work) or lead alloys and platinized titanium (used in
salt water service).

Figure 4: Impressed Current System

Anodes used in soils are normally installed as a groundbed. Each anode is again
surrounded by low resistance backfill, in the case of impressed current systems
however metallurgical coke is normally used.
Figure 4 is a typical impressed current cathodic protection system that utilizes a
groundbed made up of many anodes connected together. Notice that the positive
side of the rectifier is connected to the anodes in the groundbed and the negative
side is brazed to the pipe (brazed connections are superior to mechanical
connections, which could corrode in a very short time).
Note:
The negative terminal of the rectifier must always be connected to the
structure which is to be protected, and the positive terminal must be
connected to the groundbed. If the terminals are inadvertently reversed,
severe corrosion of the structure will result.

CATHODIC PROTECTION: INSTRUMENTS

Several measurement parameters (principally electrical) are necessary in order to
ensure that the cathodic-protection system is correctly designed to provide full
protection to the system and to determine the effect of such a system on other
structures.
All instruments used in cathodic-protection work must be:
Accurate
Reliable
Easy to maintain.
Most instruments used in cathodic-protection work are essentially field
instruments, and must therefore be portable and sufficiently robustly constructed
to withstand rough handling and to be capable of operating reliably under a wide
range of climatic conditions. They should be so constructed that repairs or
replacements can be made quickly, with standard, readily obtainable components
used. Instruments are normally calibrated to an accuracy of 0-5% or less of full-
scale deflection and scales are selected that the majority of the readings taken fall
within the upper half of the scale, where the least error will occur.
The application of cathodic protection generally involves the use of direct current
(dc) and therefore the movement in nearly all instruments used in cathodic
protection tends to be of the moving-coil permanent-magnet type, which gives
coil deflection (and thus pointer deflection) proportional to the current in the coil.
The main advantages of this type of instrument are;
Uniformity of scale
High torque to weight ratio
Low power consumption.
Additionally with the use of suitable shunts and/or resistances it is possible to use
one instrument to measure both current and voltage over a wide range.

Instrument Types
Cathodic-protection instruments may be classified as:
Potential-measuring
Current-measuring
Resistance/conductance-measuring
Multi-combination and Recording Instruments.
The various types are dealt with in some detail below.

POTENTIAL MEASURING DEVICES

Reference Electrodes
The generally accepted criterion for the effectiveness of a cathodic-protection
system is the structure/electrolyte potential In order to determine this potential it
is necessary to make a contact on the structure itself and a contact with the
electrolyte (soil or water). The problem of connection to the structure normally
presents no difficulties, but contact with the electrolyte must be made with some
form of reference electrode .
If an ordinary steel probe were used as a reference electrode, then inaccuracies
would result for two main reasons:
Electrochemical action between the probe and the soil
Polarization of the probe owing to current flow through the measuring
circuit.
Figure 5 shows two basic types of copper / copper sulphate (Cu / CuSO4) half-
cells commonly used as reference electrodes. These show the general features of
the many different types commercially available.

Fig 5: Copper/copper sulphates Cell

The copper / copper sulphate half-cell is universally used for the measurement of
structure/electrolyte potentials on buried structures. Its main advantages being that
it is cheap, simple to construct and the materials are easily obtainable and
therefore it can be assembled quickly.
Another type, the silver / silver chloride (Ag/AgCl) half-cell uses a chloridised
silver electrode which is generally immersed in either a saturated potassium
chloride(KCL) solution and is normally used for measurement of
structure/electrolyte potentials of immersed structures.
One further type of reference electrode is the zinc half-cell which consists merely
of a high-purity zinc rod. Such an electrode will maintain a constant potential
after a short 'settling down' period following installation (particularly
in sea-water). The main advantages of a zinc reference electrode are that it
requires no special preparation and no subsequent remaking during its life making
it ideal for use as a permanent reference electrode installed on a cathodic
protection system where inspection is infrequent and access to the structure while
it is operating is impossible. Generally the zinc electrode is used where the
electrolyte surrounding the protected structure is water, as this ensures good
contact with the electrode.

Voltmeters and Potentiometers

These instruments may also be generally referred to as corrosion voltmeters. As
mentioned previously, the current flowing through any potential-measurement
circuit must be small to avoid errors due to polarization. Moreover, if the current
flow is too large, errors will be introduced owing to the voltage drop caused by
the contact resistance between the reference electrode and the electrolyte. It is
thus clear that the prime requirement of a potential measurement circuit is high
resistance.
For a direct-reading instrument, sensitivity should be at least of the order of 50 k-
ohm/V, and instruments are commercially available with sensitivities of up to and
exceeding 1 Megohm/V. Direct-reading meters are usually made to show several
ranges, which are obtained by the use of suitable resistances placed in series with
the indicating instrument.

Figure 6: Basic Potentiometer / Voltmeter Circuit

In this type of instrument the voltage to be measured is balanced against an
external applied voltage (usually from batteries within the instrument). At
balance, no current flows through the external circuit and thus errors due to
contact resistance are eliminated.
The technique adopted in measuring structure/electrolyte potential is illustrated in
Fig. 7.

Figure 7: Structure / Electrolyte Potential Measurement

CURRENT MEASURING INSTRUEMNTS

These devices are generally classified depending on whether they are used to:
Measure current delivered or drained by the structure under protection.
Measure current flowing within the structure itself.
By the use of suitable shunts, a basic moving-coil movement can be adapted to
measure an almost unlimited range of currents.
Figure [Link] a direct-indicating instrument with a current shunt designed to
measure current up to 5 A d.c. To ensure that the resistance of the circuit is not
materially altered by the insertion of an ammeter, it is usual to install either a
shunt or the meter itself (usually a moving-coil meter with internal shunt)
permanently into the circuit.
Ammeter shunts are normally of the four-terminal type, to avoid contact
resistance errors, i.e. two current terminals and two potential terminals, as shown.
 Figure 8: Direct indicating instrument
In the case of making measurements of current flowing within a structure, it is
extremely important that additional resistance (for example a shunt) is not
introduced into the circuit, otherwise erroneous measurement will result.
One of the more accurate methods and one that can be applied to all structures, is
the zero-resistance ammeter or, as it is sometimes called, the zero-current
ammeter. The basic circuit of such an instrument is shown in Fig. 9.

Figure 9: Zero-Resistance Ammeter

From this circuit it should be evident that if Ib is adjusted until there is zero
voltage indicated on the voltmeter, then Is = Ib.
Where measurements of current in massive structures with extremely low
longitudinal resistances are required a refinement of the zero-resistance ammeter
Application is employed using a high-sensitivity D'Arsonval galvanometer (with a
center scale) instead of a voltmeter. The connections remain essentially the same
except that a reversing switch is incorporated so that the current /b can be applied
first in one direction and then in the other. The zero-resistance ammeter is seldom
employed for routine maintenance testing however.

RESISTIVITY / CONDUCTIVITY INSTRUMENTS

This category of measuring instruments is used for the measurement of electrolyte
resistivity, resistance, and insulation (i.e. protective-wrap) conductivity.

Resistivity Measurement
The most common method of measuring soil resistivity is by the four-electrode
'Wenner' method. Figure 10.48 indicates the basic circuit.
The mean resistivity RM is given by
RM = 2a(E/I)
Where:
I = the current applied between the current electrodes C1 and C2.
E = is the potential developed between the potential electrodes P1 and P2.
The value given by this method is the average resistivity of the soil to a depth a
equal to the spacing of the electrodes. It is most important to note that for accurate
and consistent results, the electrodes must be equidistant from one another and
placed in a straight line.
This relatively simple set-up however suffers from inaccuracies arising from
polarization of the potential electrodes and effects of possible stray currents
in the soil.
To minimize these, the electrodes used for measuring potential P1, P2 should be
Cu / CuSO4 (copper / copper-sulphate) half-cells, and reverse polarity readings
should be taken. One source of inaccuracy that cannot be overcome with this
method is that due to the contact resistance of the potential electrodes P1 and P2
to earth.

Fig. 10: 'Wenner' method of soil resistivity measurement.

To avoid the errors of polarization and stray currents, special resistivity
/conductivity meters are employed that generate an alternating current source by
applying an alternating (DC) potential between the potential electrodes.
Nowadays these meters tend to be solid-state battery-powered versions employing
digital circuitry and the measuring circuit utilizes only two-electrodes in a single
measuring rod.
The single rod has a calibration constant, determined by the area of the positive
electrode. At balance the resistivity is given by the resistance multiplied by the
rod constant. This instrument is portable and simple to operate, but it cannot be
recommended when very accurate results are required.

Figure 11: Single-rod Resistivity Probe

Resistivity of an electrolyte (solution) can also be measured by passing a known
current through a known length and cross-section of the electrolyte, and
measuring accurately the voltage drop across the length.
Again it is preferable to use alternating current to avoid polarization effects.
Special (conductivity) cells exist for use with resistivity meters, which are so
constructed and calibrated that resistivity, can either be read directly from the
instrument or simply calculated from the product of the measured resistance and
known cell constant.

Measurement of conductivity
The measurement of electrolyte conductivity (the reciprocal of the resistivity) is
calculated from the resistivity as measured by some of the methods described
above. Often it is necessary in designing a cathodic-protection system to know the
conductivity of a protective coating (e.g. bitumen enamel) on a structure.
This measurement is usually carried out by finding the resistance between an
electrode of known area placed in contact with the coating and the structure itself.
The resistance between the pad and the metal is measured by means of a
resistivity meter, as previously described.

Measurement of resistance
The measurement of resistance to remote earth of a metallic structure is normally
carried out with a four-electrode instrument. The connections are shown in Fig 12.
A current I is passed between the structure and a remote electrode. The potential
difference V is then measured between the structure and a second remote
electrode. In this way the ohmmeter records the resistance of the structure to
earth, i.e. V/I.
The spacing of the electrode from the structure is important and must be such that
the remote potential electrode lies on the horizontal part of the resistance/distance
curve, as shown in the figure below.
Generally speaking, a minimum distance of 15 m from the structure is necessary
for the potential electrode to lie on the flat part of the curve, with the current
electrode usually at least twice the distance of the potential electrode.

Fig. 12: Measurement of resistance of a structure to remote earth

Multi-combination and Recording Instruments

These instruments are capable of carrying out a variety of measurements, e.g.
structure/electrolyte potentials, current, resistivity and voltage. Most instruments
of this type contain two meters in one case, one being a low-resistance
millivolt/voltmeter and milliamp/ammeter, and the second a high-resistance
voltmeter.
The advantages of this type of instrument are:
Only one instrument is required for all necessary measurements
It is portable and thus particularly suitable for field work.
The main disadvantage is that should a fault occur in one circuit of the instrument
the complete instrument is often rendered inoperative.
The advent of the multiprocessor and electronic miniaturization of electronic
components has enabled the construction of compact, portable, battery-operated
digital recorders allowing for the measurement and storage of pipe/soil potential
fluctuations (data) over extended periods of time.

CATHODIC PROTECTION: APPLICATIONS

Whilst cathodic protection systems all rely on very basic electro-chemical
principles, the application can be complex due to the variety of techniques
available and the systems requiring protection. The applicable method is
determined by several factors not the least of which may be economical.
In principle however cathodic protection can be utilized in any application where
a metal is immersed in an aqueous electrolyte solution ranging from pure water to
soils and dilute acid solutions, as long as the structure to be protected and the
anode used to provide the protection are in both metallic and electrolytic contact.
Hence for example cathodic protection cannot be employed to control
atmospheric corrosion. However in general application can be found in the control
of:
General corrosion.
Pitting corrosion.
Stress corrosion.
Bacterial corrosion
Corrosion fatigue
Cavitation corrosion

ANODIC PROTECTION
Anodic protection may be described as a method of reducing the corrosion rate of
immersed metals and alloys by controlled anodic polarization (which induces
passivity)
It can only be applied to those metals (and alloys) that when in contact with an
appropriate electrolyte indicate passivity. This decrease in corrosion not only
increases the life of components and physical plant but also reduces
contamination of the liquid; hence it is particularly beneficial in the manufacture,
storage and transport of chemicals (acids in particular). The first feasible
industrial application of anodic protection was demonstrated and tested on small-
scale stainless-steel boilers used for sulphuric acid solutions

Principles
Before considering the principles of this method, it is useful to distinguish
between anodic protection and cathodic protection (when the latter is produced by
an external emf.).
Both techniques depend upon electrochemical mechanisms that result from
changing the potential of a metal. This tends to reduce the corrosion of the metal
in contact with the electrolyte solution.
The appropriate potential-pH diagram for the Fe-H2O system (see figure below)
indicates the magnitude and direction of the changes in the potential of iron
immersed in water (pH about 7) necessary to make it either passive or immune;
In the former case the stability of the metal depends on the formation of a
protective film of metal oxide (passivation).
In the latter the metal itself is thermodynamically stable and egress of
metal ions from the lattice into the solution is thus prevented.

Fig 13: Equilibrium potential-pH diagram for an Fe-H2O system.

Another difference is that in anodic protection the corrosion rate (passivation
current density) will always be finite, whereas ideally a completely cathodically
protected metal should not corrode at all.
Raising the potential of an anodically protected metal may actually increase the
corrosion rate if the metal exhibits transpassivity, whereas depressing the
potential of a metal far below the protective potential will not affect the corrosion
rate although it will be wasteful in terms of power consumption and a too negative
potential can be detrimental in certain cases.
Hence over- or under-protection can cause catastrophic increases in the corrosion
rates, suggesting that 'passivation is tricky'.
In anodic protection the article to be protected is made the anode in an
electrochemical circuit with an appropriate cathode such as mild steel, stainless
steel or oxidized graphite. The potential of the anode is maintained in the passive
region by a potentiostat using a suitable reference electrode.
It is sufficient to note that in order to produce passivation:
The critical current density must be exceeded.
The potential must then be maintained in the passive region and not
allowed to fall into the active region or rise into the transpassive region.
It follows that although a high current density may be required to cause
passivation only a small current density is required to maintain it, and that in the
passive region the corrosion rate corresponds to the passive current density.

Applications and Limitations

The majority of the applications of anodic protection involve the manufacture,
storage and transport of sulphuric acid (which happens to be the most produced
chemical in the world).
The corrosion rate of steel in sulphuric acid (of 77-100% concentration) is 5-10
times greater at 10O0C than at 240C which indicates the necessity for additional
protection at temperature.
Anodic protection can be applied to metals and alloys in mild electrolytes
as well as in very corrosive environments, including strong acids and alkalis, in
which cathodic protection is not normally suitable.
Corrosion of unprotected steel in sulphuric acid can give an iron concentration of
5-20 ppm per day, making it almost impossible to produce electrolytic grade
sulphuric acid in bare or unprotected steel, because this grade should not contain
more than 50 ppm iron.
One consequence of reducing the rate of corrosion of steel in an acid is that it also
decreases the formation of hydrogen, which causes blisters at inclusions in the
metal surface and also grooving on vertical surfaces. Anodic protection, which
has been found to reduce the formation of hydrogen by 97%, can therefore
prevent these effects.
The limitations of anodic protection arise from the inability to form a stable,
continuous, protective, passive film on the metal to be protected. Metals and
alloys which don t form passive films and non-conducting solutions cannot be
used.
Common applications of anodic-protection systems tend to be for reasons of
chemical purity and corrosion control in acid storage vessels.
Economically the installation of anodic protection is often very good. The
advantages include a reduction in capital investment, lower maintenance and
replacement costs and an improvement in the product quantity and value.
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