Cathodic Protection and Prevention: Principles, Applications and Monitoring

Marco Ormellese and Andrea Brenna, Politecnico di Milano, Milano, Italy

© 2017 Elsevier Inc. All rights reserved.

Introduction 1
Effects of Cathodic Protection 2
Thermodynamic Effects 2
Kinetic Effects 2
Chemical Effects 3
Side Effects 3
Amphoteric attack 3
Overprotection 3
Cathodic Protection by Immunity 4
Cathodic Protection by Passivity 4
Protection Current Density 5
Cathodic Protection Systems 6
Cathodic Protection by Galvanic Anodes 6
Cathodic Protection by Impressed Current System 7
Monitoring of CP 8
Potential Monitoring 8
Techniques to Eliminate the Ohmic Drop 8
Local reference electrode 9
Potential probe 9
ON-OFF technique 9
CP Effectiveness According to Standard 10
Reference Standards 10
References 11

Glossary
Anode The electrode at which oxidation proceeds or the current is leaving the metal surface.
Backfill A substance used to reduce anode-to-soil resistance.
Cathode The electrode at which a reduction reaction proceeds or the current is entering the metal surface.
Cathodic prevention Electrochemical technique to prevent passive metal corrosion consisting in applying a cathodic current
since the beginning when steel is passive.
Cathodic protection Electrochemical technique used to control corrosion of a metal structure by lowering its potential by
means of a direct cathodic current.
Galvanic anode Metals and alloys used to obtain cathodic protection of more noble metals.
Immunity A metal’s state of corrosion resistance that corresponds to an electrode potential more negative than the equilibrium
potential.
Passivity Kinetic condition in which the corrosion rate of a metal is practically negligible, due to the presence of a stable
compact passive layer on its surface.

Introduction

Cathodic protection (CP) has a long story. Alessandro Volta firstly made an indirect mention few years after his pile’s invention. In a
paper to the editors of the Swiss magazine, «Bibliothècque Britannique», dated 1802, he wrote “[. . .] oxidation decreases if the current
passes from the solution to the metal even to the point of extinction where hydrogen is evolved. [. . .]”,1 which is the description of the effects of
CP. A few years later, Humphrey Davy in 1806 mentioned the same effects as Volta did, and definitely in 1824 described its
application to the hull of ships of Royal Navy.2 CP officially was born. That experience was considered unhappy so remained
dormant for a century. Only after World War II, CP application started and spread largely in industry.
Despite the Davy’s experience, CP has proved in last 70 years that it works in a variety of applications, from soil and seawater, to
concrete, on either active and passive metals. Nevertheless, how it really works is still under debate whether protection is a matter of
thermodynamics or kinetics.

Reference Module in Chemistry, Molecular Sciences and Chemical Engineering https://doi.org/10.1016/B978-0-12-409547-2.14281-7 1

2 Cathodic Protection and Prevention: Principles, Applications and Monitoring

Effects of Cathodic Protection

CP is an electrochemical technique of corrosion prevention and protection, which can be applied to metals exposed to a conductive
environment.3 It consists in forcing a net direct current to flow from the electrolyte to the metal surface, in the same way as Volta and
Davy did, promoting the metal potential reduction. The metal supplying current is called “anode”, whereas the structure absorbing
current is the “cathode”.
As illustrated in Fig. 1, the circulating current can be obtained either by galvanic anodes (also called sacrificial anodes) or by
impressed current, thus defining the two types of CP systems.3 In the case of galvanic anodes, CP is achieved through galvanic
coupling with a less noble metal (Fig. 1A). For example, aluminium and zinc are used for the protection of steel in seawater while
magnesium is employed for the protection of steel in soil and fresh water; pure iron is usually utilized for the protection of stainless
steel and copper alloys. Impressed current systems make use of a DC feeder (Fig. 1B), with the positive pole connected to an anode,
generally made of insoluble metal, for example silicon cast iron, graphite or activated titanium, and the negative pole connected to
the structure.
On the metal surface reduction reactions would occur in accordance with thermodynamic conditions. Since CP is conveniently
applied practically only to soil, waters and concrete, which are “aerated” environments characterized by neutral or alkaline pH,
reduction reactions are oxygen reduction first, followed by water reduction to give hydrogen evolution3:

O2 þ 2H2 O þ 4e ! 4OH (1)

 
2H2 O þ 2e ! H2 þ 2OH (2)

In the following, these two reactions are simply indicated as cathodic processes.

Thermodynamic Effects
Starting from the free corrosion potential, Ecorr, the cathodic current provokes a potential drop toward to the equilibrium potential,
Eeq. If a potential more negative than equilibrium potential is reached, the so-called thermodynamic immunity is achieved: the
dissolution process of the metal stops, as clearly depicted by the Pourbaix diagram (Fig. 2 schematically shows the iron diagram).4 It
should be noted that immunity conditions are not settled for amphoteric metals, as lead and aluminium, because the dissolution
reaction is governed by chemical kinetics rather than electrochemical one.
When potential is lowered in between the free corrosion potential and the equilibrium potential, the corrosion rate is reduced
but not halted. This is the typical CP level in many practical applications; the so-called quasi-immunity conditions are established.
Indeed, this condition could appear to be kinetic rather than thermodynamic since a residual, but acceptable corrosion rate still
applies.

Kinetic Effects
On passive metals, such as stainless steel in waters or carbon steel in concrete, the potential lowering determines a kinetic effect,
which brings the metal to work in passive state or strengthens the passive film, hence increasing the anodic reaction resistance. In
these cases, the protection condition is referred to as CP by passivity. To reach this condition, it is not fundamental to reach the
equilibrium potential, but it is sufficient, and much more convenient, to set up a low cathodic polarization, no >200 mV. Such an
effect is used in field to protect stainless steel structures (tank, pipes,. . .) in seawater and carbon steel rebar in concrete to prevent or
stop chloride-induced corrosion.

Fig. 1 Cathodic protection systems: (A) galvanic anode: (B) impressed current. From Lazzari, L.; Pedeferri, P. Cathodic Protection, 1st ed., Polipress, Milan, 2005
with permission.
 Cathodic Protection and Prevention: Principles, Applications and Monitoring 3

Fig. 2 Pourbaix’s diagram for iron. Line a is the equilibrium potential of hydrogen evolution. Line b is the equilibrium potential of oxygen reduction. Blue area is
immunity; red area is corrosion; slight blue area is passivation. From Lazzari, L.; Pedeferri, P. Cathodic Protection, 1st ed., Polipress, Milan, 2005 with permission.

Chemical Effects
When a cathodic current is absorbed by a structure, a surface modification occurs due to some chemical effects occurring at the
metal-to-electrolyte interface, because of the cathodic reactions involved (see Eqs. 1 and 2):

• Oxygen consumption
• Production of alkalinity, that is the alkalization of the electrolyte in close proximity of the metal;
• Formation of metal oxides or hydroxides, as predicted by Pourbaix diagrams.4

These effects lead for examples carbon steel to work in passive condition (Fig. 2).
Only for seawater applications, CP causes on the protected metallic structure the build-up of a mixture of calcium carbonate and
magnesium hydroxide scale, commonly known as calcareous deposit. It is particularly beneficial because it reduces the protection
current by one order of magnitude by acting as a physical barrier that limits oxygen diffusion and maintains alkalinity at the metal
surface. The quality of the deposit depends especially on seawater composition, current density and mechanical action (abrasion
and vibration) all of which determine the thickness, porosity and adherence of the scale. Once protection is interrupted, the
calcareous deposit starts to dissolve and vanishes following the inverse sequence of its formation.

Side Effects
The application of CP may lead to some side effects, primarily related to the changes of surface conditions enhanced by the cathodic
current.

Amphoteric attack
CP applied to amphoteric metals, as lead, aluminium and zinc can lead to an amphoteric dissolution, instead of protection, when
CP produces enough alkalinity (high protection current density or slow ionic diffusion). The mechanism of the amphoteric
dissolution is a pure chemical dissolution occurring regardless the electrochemical conditions: the high cathodic current causes
an increase of pH up to 13–14, leading the metal surface to work in very alkaline condition. Amphoteric dissolution is a pure
chemical reaction, not governed by the electrochemical conditions. The direct proof is the evidence that regardless the potential
which causes a supply of electrons, metal dissolution takes place and the cathodic process (i.e., hydrogen evolution) is the sum of
available electrons.

Overprotection
When cathodic current density exceeds the oxygen limiting current density, the prevailing cathodic reaction is hydrogen evolution.
In this conditions, pH at the metal interface can exceed 13, hence favoring passivity set up on carbon steel. This CP conditions are
called “overprotection” and are always disadvantageous, since they causes a waste of current (i.e., energy) and dangerous side effects,
such as hydrogen embrittlement on susceptible metals and cathodic disbonding on coated structures. For carbon steel structure the
potential threshold is 1.2 V CSE (Copper Sulfate Electrode).
4 Cathodic Protection and Prevention: Principles, Applications and Monitoring

Cathodic Protection by Immunity

Thermodynamic immunity is achieved by bringing the potential to a value equal to or less than the equilibrium potential. Consider,
for example, the anodic reaction of iron dissolution:

Fe ! Fe2þ þ 2e (3)

The equilibrium potential is defined by Nernst’s equation:

RT
Eeq ¼ Eo þ 2:3 log aFe2þ ¼ Eo þ 0:03 log aFe2þ (4)
2F
where the constant 0.03 is calculated at 25 C, E is standard potential, R is universal gas constant, T is absolute temperature, F is
Faraday’s constant and a2þ
Fe is iron ion concentration in the solution in contact with the surface. For an active metal, when immunity
is achieved, corrosion stops regardless the operating conditions.
Theoretically, by applying Nernst’s law, it is possible to work out the values of immunity protection potential for every metal,
once established metal concentration in contact with the metal surface. Pourbaix4 suggested to use an ion concentration in solution
equal to 106 mol/L. Table 1 summarizes the protection potentials by immunity for most common metals. The protection
potentials used in practical applications is also reported, when quasi-immunity condition applies, where corrosion is not
completely arrested but proceeds at a reduced rate of about 10 mm/y, according to International Standards.

Cathodic Protection by Passivity

When setting up protection by passivity on metals exhibiting passive behavior, protection conditions should be named as based on
kinetics since the passive film is rebuilt (traditional CP on a corroding pit) or strengthened when Cathodic Prevention is adopted
before any corrosion attack had not yet taken place.
Passive metals, such as stainless steels, are subject to localized corrosion (pitting and crevice), when chloride concentration
exceeds a threshold value and a cathodic process, typically oxygen reduction, is available. For these metals, CP is applied for
preventing rather than stopping a corrosion attack. For this reason, it is called Cathodic Prevention, as Pietro Pedeferri proposed in the
90s.5,6
As Pietro Pedeferri stated, aims, operating conditions, throwing power, and effects (particularly those regarding hydrogen
embrittlement) of cathodic prevention, as well as many of the engineering and economic aspects of the design, construction,
monitoring and maintenance of cathodic prevention are different from those of normal cathodic protection.
Specifically, cathodic prevention should be regarded as different from classical CP for two reasons:

• protection conditions are not obtained by immunity

• passive film is strengthened to resist the chloride concentration, instead of repairing a film previously damaged.

To understand how cathodic prevention works in practice, it is convenient to refer to the Pedeferri’s diagram illustrated in Fig. 3. It
shows the variation of the potential, E, of a stainless steel (or steel reinforcement in concrete as Pedeferri studied originally) as a
function of chloride content, delimiting the zones of pitting occurrence (the upper), imperfect and perfect passivity (as named by
Pourbaix) and immunity zone. Pedeferri’s diagram shows that to setup cathodic prevention, it is sufficient to bring the metal in the
“imperfect passivity” zone. If a pit is started, the protection condition is different. In this case, cathodic prevention is ineffective
because for stopping pitting, perfect passivity has to be reached. It is worth noting that CP by immunity, and even by passivity,
requires a higher protection current density than cathodic prevention for which setting up imperfect passivity is sufficient.

Table 1 Immunity potential and protection potentials used in soil and seawater3

Immunity potential Protection potential

Metal [V CSE a] [V CSE a]

Copper and its alloys 0.26 0.45/0.60

Lead 0.60 0.50/0.65
Stainless steel 0.90 0.40
Carbon and low alloy steel
-normal conditions 0.92 0.85
-anaerobic conditions 0.92 0.95
-in concrete 1.12 0.75
Zinc 1.10 1.00
Aluminium 1.90 0.80
a
CSE, copper sulfate electrode (þ0.318 V vs SHE).
 Cathodic Protection and Prevention: Principles, Applications and Monitoring 5

Fig. 3 Pedeferri’s diagram for carbon steel in concrete: pitting potential as a function of chloride content. From Lazzari, L.; Pedeferri, P. Cathodic Protection, 1st
ed., Polipress, Milan, 2005 with permission.

Protection Current Density

In order to bring the potential of the structure to the protection condition, a direct cathodic current should be applied. Electrons are
supplied as required by the cathodic process (primarily the oxygen reduction), preventing the metal to supply theirs, then avoiding
the metal corrosion. Accordingly, protection current density is simply the sum of current densities of the cathodic processes
occurring at the operating protection potential.
In industrial applications, the prevailing cathodic process is oxygen reduction (CP in soil, waters and concrete) and rarely
associated to hydrogen evolution when potential drops below the equilibrium potential of the hydrogen.
Relatively to the potential, three regions can be distinguished (Fig. 4): noble potentials where oxygen reduction takes place under
activation control; an intermediate range where oxygen reduction occurs in diffusion regime; and negative potentials below the
equilibrium potential of the hydrogen evolution, where the latter adds to oxygen reduction.
Protection current density is different for each region:

• noble potentials: protection current density is less than oxygen limiting current density and it depends on metal. For instance, at
potentials close to the equilibrium of copper, as rule of thumb, protection current density is about 100 mA/m2 on copper,
10 mA/m2 on passive iron and about 1 mA/m2 on passive stainless steel;
• oxygen reduction under diffusion control: protection current density is independent from metal and follows Fick’s Law of diffusion
(see after)
• hydrogen evolution: protection current density increases from oxygen limiting current density by one order of magnitude every
120 mV potential lowering, in practice regardless the metal.
Concerning the second condition, when potential drops in the interval 0.2 to 0.95 V CSE (þ0.1 to 0.65 V SHE, standard
hydrogen electrode) protection current density, iprot (mA m2) is given by3,7:

Fig. 4 Cathodic curve of oxygen reduction and hydrogen evolution.

6 Cathodic Protection and Prevention: Principles, Applications and Monitoring

Table 2 Protection current densities in industrial applications, based on real working parameters

[O2] v T Typical range Notes

[mg L1] [m s1] [ C] [mA m2]

Soil 0.1–5 0 1–50 Max for hot pipelines

Fresh water <12–15 <4 <80 C 50–200 In tanks and boilers
Seawater (open sea; circuits) <10 <4 <40 C 100–250 Typically in heat exchangers
Concrete <3–5 0 25–40 C 2–20 Min. for prevention
Max for protection

T25  pffiffiffi
iprot ¼ 12½O2 2 25  1þ v (5)

where [O2] (mg L1) is oxygen content in water, T ( C) is temperature and v (m s1) is water velocity.
Parameters for calculation of protection current density are reported in Table 2. For passive stainless steels, when cathodic
prevention is adopted to prevent pitting, there is a second option: protection potential is fixed at 0.1 V below pitting potential,
hence protection current density is approximately one order of magnitude lower than values reported in Table 2. In the case of
crevice, the protection criterion of macrocell should be adopted for which the potential of the cathode has to be more negative or
close to the one of the anode inside crevice; accordingly, protection current density is as minimum the limiting current density
taking place on the cathodic surface outside the crevice.

Cathodic Protection Systems

CP is commonly applied to structures exposed to natural environments by means of two systems:

• Galvanic anodes systems: typically used in high conductivity environments, such as in seawater, and when a low current is
required, even in environments with a low conductivity (soil and concrete).
• Impressed current CP systems (ICCP): used in high resistivity environments, typically soil and concrete, and preferred when
extensive structures must be protected. A remarkable advantage of ICCP is its high flexibility during operation, because the
protection current can be easily regulated.

Cathodic Protection by Galvanic Anodes

CP by galvanic anodes is obtained with any metal, provided its working potential is less noble than the protection potential of the
metal to protect (Fig. 1A). To protect carbon steel structures, in accordance with the electrochemical series of the elements, a good
number of less noble materials may be used. Nevertheless, only aluminium, magnesium and zinc alloys are employed for practical
applications.
Two parameters determine CP performance:

• working potential: used to define the anode driving voltage and the anode current output and therefore the minimum anode
number necessary to reach protection;
• current capacity: is the charge per unit mass, and it defines the anode’s consumption and therefore determines the weight
necessary to ensure the duration of protection.
Table 3 summarizes main features of the three most used anodic materials.

Table 3 Physical and electrochemical properties of zinc, aluminium and magnesium alloys

Parameters Zn Al Mg

Atomic mass 65.38 26.97 24.32

Specific mass at 20 C [g cm3] 7.14 2.70 1.74
Equivalent mass 32.69 8.99 12.16
Theoretical consumption
-[kg A1 a1] 10.69 2.94 3.98
-[dm3 A1 a1] 1.5 1.1 2.3
Theoretical capacity [A h kg1] 820 2980 2200
Working potential [V vs CSE] 1.0 V 1.05/1.1 V 1.5/1.7 V
Anode efficiency 90%–95% 90%–95% 50%
 Cathodic Protection and Prevention: Principles, Applications and Monitoring 7

Table 4 Galvanic anodes for water and soil applications as a function of resistivity

Resistivity [O m]

Anode material Water Soil

Aluminium Up to 1.5 Not used

Zinc Up to 5.0 With backfill up to 15
Magnesium Over 5.0
-Standard (1.5 V CSE) with backfill Up to a 40
-High potential (1.7 V CSE) with backfill Up to 60

An anode is also characterize by the anode output, which is the current the anode is able to supply, simply obtained by using the
1st Ohm’s law:

I ¼ DE=R (6)

where DE is driving voltage (in V), and R is total resistance of the electrical circuit anode—electrolyte—cathode (in O). The driving
voltage is given by the difference between the anodic working potential and the protection potential. The driving voltage of steel
structures typically assumes a value of 250, 300 and 800 mV respectively for Zn, Al and Mg anodes. To maximize the current output,
the electrical resistance should be reduced to the minimum; accordingly, anodes are fabricated in suitable shapes or surrounded by a
suitable low resistivity backfill.
Anode type is chosen on the basis of environmental resistivity, as shown in Table 4. In soil, the environment surrounding the
anodes is changed by a suitable backfill to allow anodes a more stable potential by avoiding risk of their passivation. Typical backfill
is based on a mixture of clay, to guarantee high humidity and low resistivity, and gypsum, to maintain anode in active state. From an
economic point of view, aluminium alloys are the most convenient, since the relative cost of producing the same electrical charge is
1 for aluminium, 3 for zinc and 8 for magnesium.

Cathodic Protection by Impressed Current System

In ICCP systems, current is provided by a DC feeder through an anode which is able to supply current to the environment (Fig. 1B).
For soil applications, inert anodes such as iron–silicon alloy or activated titanium are typically used. Table 5 reports composi-
tions, consumption rates and working conditions of materials used for ICCP systems.
A backfill, typically calcinated carbon coke powders, is used to obtain a low anode resistance, generally <2 O, even in relation to
a maximum feeding voltage of 50 V, imposed by regulations for safety reasons. When high current output is required, a group of
multiple anodes is used.
The anodes supply current by means of an anodic reaction, which depends on the anodic material and the environment. For
example, in the case of scrap steel anodes, the anodic reaction is the dissolution of iron. For the so-called insoluble or inert anodes,
such as activated titanium or cast iron, the reactions are oxygen and chlorine evolution, depending on the environment (presence of
chlorides) and the current density.
Since a current feeder is used, the most important design parameter is the minimum feeding voltage necessary to supply the
protection current, given by the following relationship:

Vmin ¼ C þ Iprot Rtot (7)

Table 5 Anodic materials for ICCP

Applicationsa
Consumption
Material Description–composition [kg A1 y1] S FW SW C

Iron Scrap steel 10 ✓

Graphite Graphite impregnated with oil, resins, wax 1 ✓ ✓ ✓
Silicon Iron Cast Iron 14% Si, 0.75% Mn, 0.95C 1 ✓ ✓
Cast Iron 14% Si, 4.5% Cr, 0.75% Mn, 0.95C 0.5 ✓ ✓ ✓
Pt (on Ti) Platinized titanium 104 ✓ ✓ ✓
Pt (on Nb) Platinized niobium 104 ✓ ✓ ✓
MMO Titanium Titanium activated by mixed metal oxides (Ir, Rh) 104 ✓ ✓ ✓ ✓
a
S, soil; FW, fresh water, SW, sea water, C concrete.
8 Cathodic Protection and Prevention: Principles, Applications and Monitoring

where Iprot is the protection current required by design (obtained by the product of the protection current density and the surface
of the structure to be protected), Rtot is the circuit’s total resistance and C is the thermodynamic and kinetic contributions of
electrode reactions. For iron soluble anodes, C is negligible, but is 2–3 V in the case of inert anodes.

Monitoring of CP

CP monitoring includes all those operations that aim to verify the protection of a structure. Since the level of protection is related to
locally created conditions, rather than to global parameters, protection conditions are not related to the total protection current or to
the potential measured in a remote position. Instead, protection on a point of a structure is reached if the current density, at that
point, is equal to or greater than the protection value.

Potential Monitoring
The general criteria used to verify CP of a structure is based on potential measurement. According to the scheme in Fig. 5, this is done
through the use of a reference electrode placed in contact with the environment surrounding the structure (soil, fresh water,
seawater, concrete) and a high impedance voltmeter whose positive pole is connected to the structure and its negative one to the
reference electrode. This measurement technique is simple because it requires only a voltmeter and is of easy interpretation,
provided one takes into account that the potential reading may include errors that should be eliminated.
When measuring the potential by locating a reference electrode nearby the metal surface, there is an ohmic drop contribution, IR,
due to the flowing current in the electrolyte. This contribution alters the potential reading, hence has to be eliminated.
The measured value, EON, is the sum of two contributions:

EON ¼ EIRfree þ IR (8)

where EIR-free, often referred as “true potential” in the industrial practice, is the potential depurated by the ohmic drop.
The ohmic contribution is the spurious term that contaminates the measurement of potential. It depends on the position of the
reference electrode with respect the monitored structure, d, the resistivity of the electrolyte, r, and the flowing current density, i:

IR ¼ r  i  d (9)

It decreases when the reference electrode is placed close to the pipeline, therefore, the simplest technique to minimize it consists
in placing the reference electrode as close as possible to the structure. Of the three parameters determining ohmic drop, resistivity
plays the most important role. For example in seawater, where resistivity is low, even if current is high, the ohmic drop is often
negligible. On the contrary, in concrete and in soils, especially in the most resistive ones, the ohmic drop is not at all negligible, even
if small current circulates.
Therefore, for a correct measurement of potential, ohmic drop has to be evaluated or eliminated.

Techniques to Eliminate the Ohmic Drop

EN 13509 proposes several methods to eliminate the ohmic drop contribution from potential measurements. Based on Eq. (9) two
ways are possible:

• Reduction of the distance reference electrode—structure

• Elimination of circulating current

Fig. 5 Potential measurement for a buried pipeline and a submerged platform. From Lazzari, L.; Pedeferri, P. Cathodic Protection, 1st ed., Polipress, Milan, 2005
with permission.
 Cathodic Protection and Prevention: Principles, Applications and Monitoring 9

In the first case, local reference electrode or potential probes are used. The elimination of the circulating current is achieved by the
on-off method. Obvioulsly, resistivity can not be changed.

Local reference electrode

If the reference electrode is brought closer to the structure, the IR drop contribution is reduced or even eliminated. In practice, this is
done in seawater, for example on offshore platforms, where it is easy to place the reference electrode close to the jacket at the desired
point. For buried structures, it is necessary to make use of fixed reference electrodes, buried very close to the structure, up to a
maximum of 0.2 m.
While this method is efficient for bare structures, reducing the IR drop to tens of millivolts, it is questionable for coated
structures, since to know the true potential at a coating holiday, the reference electrode must be as close as possible to the defect. In
other words, by simply installing a reference electrode close to the coated structure, the potential measured is not representative of
the lower protection level established at holidays, unless the reference electrode is, by chance, close to the biggest one.

Potential probe
To overcome the previous problem, an artificial defect, or corrosion coupon, is used in association with a close reference electrode.
Coupon surface is in the range 1–10 cm2, according to ISO 15589-1. This device is the so-called potential probe, which consists of a
steel coupon embedded with an incorporated reference electrode, as schematically shown in Fig. 6. The reduction of the IR drop
depends on the geometry of the probe, ranging from total elimination, as in the case of Fig. 6, to a partial one for other geometries,
especially in high resistivity environments.8

ON-OFF technique
The ON-OFF technique is based on the experimental evidence that when the protection current is interrupted, the IR drop
disappears in a very short time, on the order of 106 s. Therefore, by recording the potential reading shortly after current
interruption, the IR drop is no longer included.
Obviously, by interrupting the current, overvoltages are also eliminated but over a much longer period than IR drop, ranging
from milliseconds for activation overvoltage to seconds or even days for concentration overvoltage. The latter is the prevailing one in
CP. Fig. 7 reports a typical potential recording obtained by means of a high frequency acquisition voltmeter (at least 10 Hz sampling
frequency) where the so-called OFF potential, EOFF, is the potential value recorded immediately after current interruption.
This technique is applied by locating the reference electrode close to the structure, typically in the case of a pipeline in the vertical
position.
To use the on-off technique correctly, some typical situations should be carefully considered.9

• Overprotection conditions. When measurement is taken on coated structures in overprotection conditions, that is with hydrogen
evolution, EOFF potential is difficult to define, since the activation overvoltage of hydrogen evolution disappears very rapidly, in
<1 ms. Therefore, by taking the OFF reading 0.1 to 1 s after current interruption, error can be as high as 200–300 mV. To reduce
this error, a high frequency acquisition datalogger voltmeter must be used.

Fig. 6 Potential probe with an embedded carbon steel coupon and reference electrode. From Lazzari, L.; Pedeferri, P. Cathodic Protection, 1st ed., Polipress,
Milan, 2005 with permission.
10 Cathodic Protection and Prevention: Principles, Applications and Monitoring

Fig. 7 Example of potential profile during an ON-OFF recording. From Lazzari, L.; Pedeferri, P. Cathodic Protection, 1st ed., Polipress, Milan, 2005 with permission.

• Coated structures. When coating holidays of various sizes are present, two problems arise. The first depends on the different
polarization level achieved by each defect according to its size: smaller defects are more polarized than larger ones. The resulting
EOFF reading is difficult to interpret and can not be associated to a single defect. The second problem is related to the fact that
once the protection current is interrupted, the more polarized holidays (the smaller ones) become anodes, releasing some
current to the less polarized holidays, acting as cathodes. The result is the circulation of a so-called equalizing current, which
makes an apparent lesser protection on the small holidays and an overestimated protection on the larger ones.
• Grounded structure. If the on-off technique is applied on grounded structure (for examples on a carbon steel pipeline with a
copper earthing), when current is OFF, galvanic corrosion between the two metals occurs and the measured potential is typically
the potential of wider surface, specifically the grounding system. For this reason, on-off technique can not be applied for
grounded structure.

CP Effectiveness According to Standard

ISO 15589-1 in Section 6 describe the principle of cathodic protection criteria to assure a residual corrosion rate <0.01 mm a1.
Same criteria were present in the past EN 12954.
The basic criterion is IR-free potential lower than protection potential. The protection potential of a metal depends on the
corrosive environment (soil) and on the type of metal used (carbon steel). The standard also states “application of potentials that
are too negative can result in cathodic over-protection leading to coating disbondment and blistering and hydrogen embrittlement
of some metals.” Therefore, the IR-free potential should not be more negative than a threshold value.
CP effectiveness is evaluated in two phases, according to ISO 15589-1:

• For a CP general assessment, ON potential should be measured at all test points, at a certain frequency; the structure is protected
if the ON potential is more negative than the free corrosion potential;
• For a detailed and comprehensive assessment of the CP, two alternatives are possible:
▪ OFF potential readings at all measuring points at least every 3 years;
▪ If OFF potential reading is not possible (for example in the presence of stray current), coupons or potential probes are
required.
Regarding the latter, it is important to underline that standard ISO 15589-1 reports, often confusing the reader, the terms “OFF
potential” and “IR-free potential”: in particular, IR-free potential is used in defining the protection criteria, except then use the term
OFF potential in the monitoring section. The confusion arises from the fact that OFF potential is not a synonymous of IR-free
potential, being the latter the potential measured with local reference electrode or potential probe.

Reference Standards
• ISO 15589-1—Petroleum, petrochemical and natural gas industries—Cathodic protection of pipeline systems—Part 1: On-land
pipelines.
• EN 12954—Cathodic protection of buried or immersed metallic structures—General principles and application for pipelines.
• EN 50162—Protection against corrosion by stray current from direct current systems.
• EN 13509—Cathodic protection measurement techniques.
 Cathodic Protection and Prevention: Principles, Applications and Monitoring 11

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