Prepared by Mr.

Ali Abbas

Cathodic Protection (CP)

The science of cathodic protection (CP) was born in 1824, when Sir
Humphry Davy made a presentation to the Royal Society of London:
"The rapid decay of the copper sheeting on His Majesty's ships of war,
and the uncertainty of the time of its duration, have long attracted the
attention of those persons most concerned in the naval interest of the
count. ... I entered into an experimental investigation upon copper. In
pursuing this investigation, I have ascertained many facts ... to illustrate
some obscure parts of electrochemical science... seem to offer important
application." Davy succeeded in protecting copper against corrosion from
seawater by the use of iron anodes.

From that beginning, CP has grown to have many uses in marine and
underground structures, water storage tanks, gas pipelines, oil platform
supports, and many other facilities exposed to a corrosive environment
(see Corrosion Costs Study findings). Recently, it is proving to be an
effective method for protecting reinforcing steel from chloride-induced
corrosion. (reference)

History of Cathodic Protection

Cathodic protection has become a widely used method for controlling the
corrosion deterioration of metallic structures in contact with most forms
of electrolytically conducting environments, i.e. environments
containing enough ions to conduct electricity such as soils, seawater and
basically all natural waters. Cathodic protection basically reduces the
corrosion rate of a metallic structure by reducing its corrosion potential,
bringing the metal closer to an immune state. From a thermodynamics
point of view, the application of a CP current basically reduces the
corrosion rate of a metallic structure by reducing its corrosion potential
towards its immune state as shown here for iron and steel or here for
aluminum and its alloys.
Introduction to Cathodic Protection
Cathodic protection (CP) is : a technique to control the corrosion of a metal surface
by making it work as a cathode of an electrochemical cell.

Foreword

Corrosion or deterioration of metals has posed a problem to industry for many years.
Of all the various anti-corrosion systems used, Cathodic Protection is one of the most
efficient, being a positive and economical solution to the multiple corrosion problems
encountered either on shore or offshore (marine environments).

When dissimilar metals are in electrical or physical contact (the former through an
electrolyte), galvanic corrosion can take place. The process is akin to a simple DC
cell in which the more active metal becomes the anode and corrodes, where as the
less active metal becomes the cathode and is protected. The galvanic series shown
below in Table 1 can be used to predict the metal which will corrode in contact with
another metal, based on whether it is cathodic or anodic with respect to another. On
top of the table are the "Noble" or cathodic (protected) metals and at the bottom, the
more active or Anodic metals.

Table 1
Standard electromotive force series for selected metals

Potential at 25 oC (77 oF), V Metal-metal ion equilibrium (unit activity)

+0.80 Ag/Ag+
+0.34 Cu/Cu2+
(reference) 0 H2/H+
-0.44 Fe/Fe2+
-0.76 Zn/Zn2+
-1.66 Al/Al3+
-2.36 Mg/Mg2+

Cathodic Protection is an electrochemical means of corrosion control in which the

oxidation reaction in a galvanic cell is concentrated at the anode and suppresses
corrosion of the cathode in the same cell. Figure 1 shows a simple cathodic
protection system. The steel pipeline is cathodically protected by its connection to a
sacrificial magnesium anode buried in the same soil electrolyte.
 Figure1

Cathodic protection was first developed by Sir Humphrey Davy in 1824 as a means
of controlling corrosion on British naval ships. Virtually all modern pipelines are
coated with an organic protective coating that is supplemented by cathodic protection
systems sized to prevent corrosion at holidays (defects) in the protective coating.
This combination of protective coating and cathodic protection is used on virtually all
immersed or buried carbon steel structures, with the exception of offshore petroleum
production platforms and reinforced concrete structures.

Fundamentals of Cathodic Protection

Table1, shows the theoretical electrochemical potentials obtained by pure metals in 1
N solutions of their own ions. Figure2, shows two of these metals, iron and zinc,
separately immersed in a weak mineral acid (or sea water). The chemical reactions
that occur in Figure2 are:

Oxidation reaction Fe --> Fe2+ + 2e-

Reduction reaction 2H+ + 2e-
Net reaction 2H+ + Fe --> Fe2+ + H2
Oxidation reaction Zn --> Zn2+ + 2e-
Reduction reaction 2H+ + 2e- --> H2
Net reaction 2H+ + Zn --> Zn2+ + H2
 Figure2

Both metals corrode, and both corrosion (oxidation) reactions are balanced by an
equal reduction reaction, which in both cases involves the liberation of hydrogen gas
from the acid environments. The two corrosion reactions are independent of each
other and are determined by the corrosivity of hydrochloric acid on the two metals in
question.

If the two metals were immersed in the same acid and electrically connected
(Figure3), the reactions for zinc would then become:

Oxidation Zn --> Zn2+ + 2e-

Reduction 2H+ + 2e- --> H2
 Figure3

Almost all of the oxidation reaction (corrosion of zinc) has been concentrated at the
zinc electrode (anode) in Figure3, and almost all of the reduction reaction (hydrogen
liberation) has been concentrated at the iron electrode (cathode). The oxidation of
the zinc anode in Figure3, is much faster than that in Figure2. At the same time, most
of the corrosion of iron in Figure2, has stopped in Figure3. As shown schematically,
the zinc anode in Figure2, has been used to cathodically protect the iron cathode in
Figure3.
Of course, some corrosion of the iron may still occur; whether or not this happens
depends on the relative sizes of the zinc and iron electrodes. Some reduction of
hydrogen may still occur on the zinc anode. The anode is the electrode at which a
net oxidation reaction occurs, whereas cathodes are electrodes at which net
reduction reactions occur. All cathodic protection systems require an anode, a
cathode, an electric circuit between the anode and cathode, and an electrolyte. Thus,
cathodic protection will not work on structures exposed to air environments. The air is
a poor electrolyte, and it prevents current from flowing from the anode to the cathode.
Cathodic Protection can be accomplished by two widely used methods:

1. By coupling a given structure (say Fe) with a more active metal such as zinc or
magnesium. This produces a galvanic cell in which the active metal works as an
anode and provides a flux of electrons to the structure, which then becomes the
cathode. The cathode is protected and the anode progressively gets destroyed, and
is hence, called a sacrificial anode.

2. The second method involves impressing a direct current between an inert anode
and the structure to be protected. Since electrons flow to the structure, it is protected
from becoming the source of electrons (anode). In impressed current systems, the
anode is buried and a low voltage DC current is impressed between the anode and
the cathode.

Sacrificial anode systems are simpler. They require only a material anodic to the
protected steel in the environment of interest. Figure4, shows an impressed-current
system used to protect a pipeline. The buried anodes and the pipeline are both
connected to an electrical rectifier, which supplies direct current to the buried
electrodes (anodes and protected cathode) of the system. Unlike sacrificial anodes,
impressed-current anodes need not be naturally anodic to steel, and in fact, they
seldom are. Most impressed-current anodes are made from non-consumable
electrode materials that are naturally cathodic to steel. If these electrodes were wired
directly to a structure, they would act as cathodes and would cause accelerated
corrosion of the structure they are intended to protect. The direct current source
reverses the natural polarity and allows the materials to act like anodes. Instead of
corrosion of the anodes, some other oxidation reaction, that is, oxygen or chlorine
evolution, occurs at the anodes, and the anodes are not consumed.

Figure 4

Impressed-current systems are more complex than sacrificial anode systems. The
capital expenses necessary to supply direct current to the system are higher than for
a simple connection between an anode and a cathode. The voltage differences
between anode and cathode are limited in sacrificial anode systems to approximately
1 V or even less, depending on the anode material and the specific environment.
Impressed-current systems can use larger voltage differences. The larger voltages
available with impressed-currents allow remote anode locations, which produce more
efficient current distribution patterns along the protected cathode. These larger
voltages are also useful in low-conductivity environments, such as freshwater and
concrete, in which sacrificial anodes would have insufficient throwing power.
 Offshore Cathodic Protection 101
What it is, and how it works.

Richard Baxter, Jim Britton

How Does Steel Corrode in Water?

To understand cathodic protection one must first understand the corrosion mechanism. For corrosion to occur,
three conditions must be present.

1. Two dissimilar metals

2. An electrolyte (water with any type of salt or salts dissolved in it)
3. A metal (conducting) path between the dissimilar metals

The two dissimilar metals may be totally different alloys, such as steel and aluminum, but are more usually
microscopic or macroscopic metallurgical differences on the surface of a single piece of steel.

If the above conditions exist, at the more active metal surface (in this case we will consider freely corroding
steel which is non uniform), the following reaction takes place at the more active sites: (two iron ions plus four
free electrons)
2Fe => 2Fe++ + 4e-

The free electrons travel through the metal path to the less active sites where the following reaction takes place:
(oxygen gas converted to oxygen ion - by combining with the four free electrons - which combines with water to
form hydroxyl ions)
O2 + 4e- + 2H20 => 4 OH-

Recombinations of these ions at the active surface produce the following reaction, which yields the iron corrosion
product ferrous hydroxide: (iron combining with oxygen and water to form ferrous hydroxide)

2Fe + O2 + 2H2O => 2Fe (OH)2

This reaction is more commonly described as 'current flow through the water from the anode (more active site)
to the cathode (less active site).

How Does Cathodic Protection Stop Corrosion?

Cathodic protection prevents corrosion by converting all of the anodic (active) sites on the metal surface to
cathodic (passive) sites by supplying electrical current (or free electrons) from an alternate source.

Usually this takes the form of galvanic anodes, which are more active than steel. This practice is also referred to
as a sacrificial system, since the galvanic anodes sacrifice themselves to protect the structural steel or pipeline
from corrosion.

In the case of aluminum anodes, the reaction at the aluminum surface is: (four aluminum ions plus twelve free
electrons)
4Al => 4AL+++ + 12 e-

and at the steel surface, (oxygen gas converted to oxygen ions which combine with water to form hydroxyl ions)

3O2 + 12e- + 6H20 => 12OH-

As long as the current (free electrons) is arriving at the cathode (steel) faster than oxygen is arriving, no
corrosion will occur.
Figure 1: Sacrificial anode system in seawater

Basic Considerations When Designing Sacrificial Anode Systems

The electrical current which an anode discharges is controlled by Ohm's law; that is:

I=E/R

I= Current flow in amps

E= Difference in potential between the anode and cathode in volts
R= Total circuit resistance in ohms

Initially current will be high because the difference in potential between the anode and cathode are high, but as
the potential difference decreases due to the effect of the current flow onto the cathode, current gradually
decreases due to the polarization of the cathode. The circuit resistance includes both the water path and the
metal path, including any cable in the circuit. The dominant value here is the resistance of the anode to the
seawater.

For most applications the metal resistance is so small compared to the water resistance that it can be ignored.
(Not true for sleds, or long pipelines protected from both ends). In general, long thin anodes have lower
resistance than short fat anodes. They will discharge more current, but will not last as long.
Therefore a cathodic protection designer must size the anodes so that they have the right shape and surface
area to discharge enough current to protect the structure and enough weight to last the desired lifetime when
discharging this current. As a general rule of thumb:

Length of the anode determines how much current the anode can produce, and consequently how
many square feet of steel can be protected.

Cross Section (Weight) determines how long the anode can sustain this level of protection.

Impressed Current Cathodic Protection Systems

Due to the high currents involved in many seawater systems it is not uncommon to use impressed current
systems. Impressed current systems use anodes of a type that are not easily dissolved into metallic ions, but
rather sustain an alternative reaction, oxidization of the dissolved chloride ions.
2Cl- => Cl2 + 2e-
Power is supplied by an external DC power unit..

Figure 2: Impressed current cathodic protection system in seawater

How Do We Know When We Have Enough Cathodic Protection?
We know whether or not we have enough current by measuring the potential of the steel against a standard
reference electrode, usually silver silver/chloride (Ag/AgCl sw.), but sometimes zinc (sw.).

Current flow onto any metal shifts its normal potential in the negative direction. History has shown that if steel
receives enough current to shift the potential to (-) 0.800 V vs. silver / silver chloride (Ag / AgCl), the corrosion
is essentially stopped.

Due to the nature of the films which form, the minimum (-0.800 V) potential is rarely the optimum potential,
and designers try to achieve a potential between (-) 0.950 V and (-) 1.000 V vs. Ag/AgCl sw.

Figure 3: Protected vs Unprotected structures as verified by cathodic protection potential