CHAPTER TWO

METHODS TO CONTROL CORROSION

Corrosion can be prevented by having a good understanding of the conditions that

contribute to corrosion. Making the right decision in the kind of metal to use could also
lead to a significant reduction in terms of corrosion. Proper observation and eradication of
defenseless surface conditions can be crucial in protecting metals from the deteriorating
effects of corrosion.( Pierre R. Roberge et al 2008)
Techniques for corrosion prevention can be categorized into five basic groups:

1.1. Material selection

1.1.1.Selection of the right material of construction

The right material of construction should have the following properties:

1- high mechanical strength,
2- high corrosion resistance,
3- low cost.

1.1.2.The material selection is carried out through the following steps:

1. Preliminary selection : Based on experience, availability and safety aspects.

2. Laboratory testing : Reevaluation of apparently suitable materials under process
conditions
3. Interpretation of laboratory results and other data Effect of possible impurities,
excess temperature, excess pressure, agitation, and presence of air in equipment.
4. Economic comparison of apparently suitable materials Material and maintenance
cost, probable life, cost of product degradation, and liability to special hazards.
5. Final selection.
1.2. Coating

There are two types of surface coating:

Figure 2.1 : Types of surface coating

1.2.1.Metallic coating

The structure is coated with a layer of other metal which may be more noble than
the structure or less noble than it e.g. steel structures can be coated with copper which is
more noble than steel or zinc which is less noble. In case of coating the structure with a
more noble metal care should be taken that the coat is free from pores or cracks to avoid
the formation of dissimilar metal corrosion cells which would lead to corrosion of the
structure. Factors that must be considered in selection of a coating metal:

1. The coating should be able to resist direct attack of the environment.

2. The coating should be nonporous and continuous (no cracks) to a void acceleration of
corrosion especially in case of a more noble metal (ex: coating of Fe by Cu).
3. The coating should be hard.( TalbottD., J. Talbott, 2009)

In case of coating the structure with a less noble metal the presence of pores and cracks in
the coat is not dangerous because in this case the less noble metal will corrode by the
formation of dissimilar metal cells while the structure will remain protected.
1.2.2.Non-metallic coating

There are two types of nonmetallic coating :

1.Organic Coatings. The primary function of organic coatings in corrosion protection is to
isolate the metal from the corrosive environment. In addition to forming a barrier layer
to stifle corrosion, the organic coating can contain corrosion inhibitors. Many organic
coating formulations exist, as do a variety of application processes to choose from for a
given product or service condition.

2.Inorganic coatings include porcelain enamels, chemical-setting silicate cement linings,

glass coatings and linings, and other corrosion resistant ceramics. Like organic coatings,
inorganic coatings for corrosion applications serve as barrier coatings. Some ceramic
coatings, such as carbides and silicides, are used for wear-resistant and heat resistant
applications, respectively.

1.3. Inhibitors

Corrosion inhibitors are substances that are added in small amount (e.g 0.1%) to the
corrosive medium stop or slow down electrochemical corrosion reactions on a metal
surface. (Wiley & Sons et al 2011)

1.3.1. Mechanism of Inhibitors

Corrosion inhibitors work by one or more of the following mechanisms.

1. They adsorb on metal surfaces to form protective films.
2. They combine with corrosion product films to protect metal surfaces.
3. They form precipitates, which visibly coat and protect metal surfaces.

1.3.2.Types of inhibitors :

Inhibitors can be divided into two main categories :

1. Inorganic inhibitors: are used mainly in boilers, cooling towers, and

fractionation units.

2. Organic inhibitors: are used mainly in oil field systems.

As shown in the Figure 2.2: Inorganic inhibitors are further divided into anodic and
cathodic classifications. These classifications describe the part of the electrochemical
process that is interrupted by the inhibitor . Organic film-forming inhibitors interrupt both
the anodic and cathodic processes.

Figure 2.2: Schematic of classification of inhibitors

1.4. Design

The application of rational design principles can eliminate many corrosion problems
and greatly reduce the time and cost associated with corrosion maintenance and repair.
Corrosion often occurs in dead spaces or crevices where the corrosive medium becomes
more corrosive. These areas can be eliminated or minimized in the design process. Where
stress-corrosion cracking is possible, the components can be designed to operate at stress
levels below the threshold stress for cracking. (William H. Hartt et al 2007)

Where corrosion damage is anticipated, design can provide for maximum

interchangeability of critical components and standardization of components.
Interchangeability and part standardization reduce the inventory of parts required.
Maintenance and repair can be anticipated, and easy access can be provided. Furthermore,
for the large items that are critical to the entire operation, such as primary pumps or large
fans, redundant equipment is installed to permit maintenance on one unit while the other is
operating. These practices are a sampling of rational design principles.
1.5. Cathodic Protection

2.5.1 Background

The first application of CP dates back to 1824, long before its theoretical foundation
was established, and is credited to Sir Humphrey Davy. Davy cathodically protected
copper sheeting used for cladding the hulls of naval vessels in seawater with iron , zinc or
tin In the USA by 1945 the use of CP was commonly applied to the rapidly expanding oil
and natural gas industry . In the UK CP was applied from the 1950s onwards and Cathodic
Protection Company Limited was established in this period , pioneering it’s use in the UK.
CP is now well established on a large variety of immersed and buried metallic structures as
well as reinforced concrete structures , and provides effective corrosion control.( Dr. Jafer
T. Al-Haidary et al )

2.5.2 The Principles of Cathodic Protection

Metal that has been extracted from its primary ore (metal oxides or other free radicals)
has a natural tendency to revert to that state under the action of oxygen and water. This
action is called corrosion and the most common example is the rusting of steel. Corrosion
is an electro-chemical process that involves the passage of electrical currents on a micro or
macro scale. The change from the metallic to the combined form occurs by an “anodic”
reaction involving the oxidation of the metal to its ions :

A common example is :
++ ¿→ Fe¿

2 e−¿+Fe ¿

This reaction produces free electrons, which pass within the metal to another site on the
metal surface (the cathode), where it is consumed by the cathodic reaction. In acid
solutions the cathodic reaction is :
In alkaline solutions, where hydrogen ions are rare, the reduction of water will occur to
yield alkali and hydrogen :

In neutral solutions the cathodic reaction involves the consumption of oxygen dissolved in
the solution :

Corrosion thus occurs at the anode but not at the cathode (unless the metal of the cathode is
attacked by alkali).

Figure 2.3 : Corrosion cell / Bimetallic corrosion

The anode and cathode in a corrosion process may be on two different metals connected
together forming a bimetallic couple, or, as with rusting of steel, they may be close
together on the same metal surface.

2.5.3 Methods of Cathodic Protection for Corrosion Control

 Cathodic protection is a widely accepted method of corrosion control. Corrosion
of above ground steel storage tank bottoms may be reduced or eliminated with proper
application of cathodic protection. Cathodic protection is a technique for preventing
corrosion by making the entire surface of the metal to be protected act as the cathode of
an electrochemical cell. There are two systems of cathodic protection.

2.5.3.1Galvanic systems

Galvanic systems use a metal more active than the structure to be protected to
supply the current required to stop corrosion (see Table 1 for a partial galvanic series).
The more active metal is called an anode, commonly referred to as a galvanic anode or
a sacrificial anode. The anode is electrically connected to the structure to be protected
and buried in the soil. A galvanic corrosion cell develops and the active metal anode
corrodes (is sacrificed) while the metal structure (cathode) is protected. As the
protective current enters the structure, it prevents the flow of corrosion current from
the metal surface. Current then returns to the galvanic anode through a metallic
conductor (see Figure. 2.5). Metals commonly used as galvanic anodes in soil are
magnesium and zinc in either cast or ribbon form. The anodes are usually distributed
around the perimeter of the tank or buried beneath the tank bottom. Galvanic systems
are normally applied. (Pierre R. et al 2008)

Figure 2.4 : Galvanic Cathodic Protection With Sacrificial Anodes

Advantages and disadvantages of Galvanic Systems :

There are several advantages of galvanic systems
1. No external power supply is required.
2. Installation is relatively easy.
3. Capital investment is low for small-diameter tanks.
4. Maintenance costs are minimal.
5. Interference problems (stray currents) are rare.
6. Less frequent monitoring is required.

There are several disadvantages of galvanic systems

1. Driving potential is limited.
2. Current output is low
3. Method is limited to use in low-resistivity soils.
4. Method is not practical for protection of large bare structures
2.5.3.2 Impressed current system

The second method of applying cathodic protection to an aboveground

storage tank bottom is to use impressed current from an external source. Impressed
current systems use direct current usually provided by a rectifier attached to an AC
power source. The rectifier converts alternating current to direct current. Direct current
from the rectifier flows to the buried impressed current anode, from the anode through
the soil electrolyte, and onto the tank bottom as shown in Fig. 3.6 .

Figure 2.5 : Impressed Current Cathodic Protection

Advantages and disadvantages of Impressed Current Systems

The advantages of impressed current systems include

1. Availability of large driving potential.
2. High current output capable of protecting large structures.
3. Capability of variable current output.
4. Applicability to almost any soil resistivity.

The disadvantages of impressed current systems include

1. Possible interference problems (stray currents) on foreign structures.
2. Loss of AC power causes loss of protection.
3. Higher maintenance and operating costs.
4. Higher capital cost for small installations.
5. Safety aspects of rectifier location.
6. Safety aspects of negative lead connection.
7. More frequent monitoring.

2.5.4 Components of Impressed Cathodic Protection System and Design

Information

2.5.4.1 Structure

Physical dimensions of structure to be protected one important element in

designing a cathodic protection system is the structure's physical dimensions drawing
of structure to be protected, Corrosion history of structures in the area. The most
common uses for carbon steel are for structures, Oil country tubular goods (OCTGs),
and piping and process equipment. The term “carbon steel” is applied to any alloy
consisting of iron plus carbon. Other elements may be added for deoxidation or
machinability purposes. The term “killed steel” is applied to steels where the dissolved
gases have been removed by the addition of either silicon or aluminum. It is common
to have minimum residual content requirements for these elements to insure that most
of the dissolved gases have been removed. Most carbon steels used in the oil field are
killed (El-Haidary, et al ) .
2.5.4.2 Anode groundbed

The term groundbed usually refers to a group of anodes interconnected and

operated as a unit. They are two types of groundbed remote groundbed, close
groundbed (represented by distributed anode system). The terms, close and remote, are
related to the area of influence in the electrolyte around the anode. In the case of
remote anode groundbed surrounding the pipe, the pipeline is negative with respect to
the remote earth as opposed to the close groundbed system, where the local earth is
made positive with respect to the pipe. Groundbed consists of a carbonaceous extender
generally coke breeze and graphite, silicon-iron scrap steel, platinized titanium or
niobium anodes. Identified the following desirable properties of an “ideal” impressed
current anode material: .( Al-Haidary. et al 2003).

1. Low consumption rate, irrespective of environment and reaction products

2. Low polarization levels, irrespective of the different anode reactions
3. High electrical conductivity and low resistance at the anode-electrolyte interface.
The lowest grounding resistance practically possible should be designed for in
order to keep down the electric power and therefore the operating costs .
4. High reliability
5. High mechanical integrity to minimize mechanical damage during installation,
maintenance, and service use
6. High resistance to abrasion and erosion
7. Ease of fabrication into different forms
8. Low cost, relative to the overall corrosion protection scheme.

2.5.4.3 Test Station

Test points are the best means of electrically examining a buried pipeline to
determine whether or not it is cathodically protected as well as to make other tests
associated with corrosion control work.. .( Al-Haidary. et al 2003)

2.5.4.4 Reference Electrode

 It is used primarily in field measurements where the electrode must be
resistant to shock and where its usual large size minimizes polarization errors .

2.6 Factors Affecting Cathodic Protection System

2.6.1 Soil

There are over 50 general types of soil that have been characterized for corrosion
properties. Each soil has specific resistivity. Soil resistivity is the lowest and the
electrical potential difference is the greatest. Examples of corrosive soils are Merced
(alkali) silt loam, Montezuma (alkali) clay adobe, Muck, and Fargo clay loam.
Pipelines or tanks that are exposed to an electrolyte that is not homogeneous exhibit
different electrical potentials in the different components of the soil. The area(s) with
the higher potential becomes the anode in this electrochemical corrosion cell. In
general buried steel pipelines suffer from soil corrosion because one or more of the
following conditions.( Al-Haidary. et al 2003)

1. Moisture Content in soil, if a pipe is buried in two types of soil having different
moisture contents, the area of the pipe in contact with wet soil (high moisture)
would corrode, whereas the pipe in contact with the dry soil would not corrode. The
area of the pipe in contact with the dry soil becomes the cathode and the area in
contact with the wet soil, the anode (TalbottD., J. Talbott 1998).

2. pH value, the pH of the soil or water electrolyte in an electrochemical corrosion

cell affects the rate of the corrosion by speeding or slowing the chemical reactions
at the anode and/or the cathode. The pH of an electrolyte is basically referred to the
concentration of hydrogen ions. A corrosion rate of mild steel increases for pH
below 4, and it will be increases tremendously at pH of 3 . The generation of
OHions raises the pH of the electrolyte at the metal surface, producing some
important incidental effects. The rise in alkalinity is protective to the metal because
it tends to passivate the steel and also promotes precipitation of a protective
carbonate scale on the metal surface . Iron in air free soils at pH of 9.0 has a
 negligible corrosion rate at a potential of 13 -0.78 V versus KCl electrode this
equivalent to -0.85 V measured against a Cu/CuSO4 (L.L. Shreir et al 1996) .

3. Soil Resistivity, the resistivity essentially represents the electrical resistance of a

standardized cube of material . Resistivity variations in the electrolyte between the
anode and cathode also have a strong influence on the current distribution. Areas of
low resistivity will “attract” a higher current density, with current flowing
preferentially along the path of least resistance. The lower the soil resistivity, the
more current will flow from the anodic areas to the cathodic areas, and resulting
corrosion rate will be higher. If the soil resistivity varies from higher to lower
values in a short distance localized accelerated corrosion can occurred . The
resistivity is inversely proportional to current, and therefore to corrosion, if it is
double and all other factors remain the same the amount of corrosion is reduced to
half. (Basham, et al 2003)

4. Degree of aeration, a pipeline is buried in a completely uniform soil and that some
areas of the line have a free supply of oxygen and other areas have a restricted
supply. The part of the pipe buried in the soil with free supply of oxygen (high
oxygen content) would form the cathode and the part with a less supply of oxygen
or poorly aerated forms that anode this is commonly called a differential aeration
cell.

5. Presence chlorides, sulfates microorganisms .

2.6.2 Interference:

The following is a summary of preventive methods which could be used to

minimize the interference: (Anderson H. H et al 1951 )
 The current output of the main rectifier may be reduced.
 The ground bed may be re-sited, if necessary. This is applicable if a foreign
pipeline passes close to the ground bed.
 Installation of a crossing bond between the pipes. A bond between the two points of
crossing is installed and the amount of current flow is controlled by a resistor.
 Installation of magnesium anodes on the corroding structure.
  Isolation of the anodic section of the structures and installation of continuity bonds
across the anodic section.
 Coating the metal/ electrolyte interface, or the contact surfaces. In cases of foreign
line, the foreign line must be coated.

2.6.3 Stray Currents

In a cathodic protection system, the conventional current, for example Zn++

ions, flows from the ground bed through the earth towards the metallic structure. If a
current encounters a metallic structure on its way it is picked up by the metallic
structure, transmitted to other parts of the structure and finally discharged from the
structure through the earth and retunes to the cathode. The point at which the 15
current is discharged from the metallic structure to the ground becomes the anode and,
therefore, corrodes (forming Fe++ ions). The undesired currents which enter the
metallic structure on its way to the cathode is called stray currents and the corrosion
caused by stray current is called stray current corrosion.( Evert D.D et al 2018)
There are two main categories of stray currents
 Static type, cathodic protection rectifier, railroad signal batteries.
 Dynamic type, DC Equipment in mines, electric railway generating equipment.

If the catholically protect metallic object is buried near the path of the stray current,
the current may “jump-on” the protected structure because it offers a lower resistance
path for the current to flow. The affected structure will be cathodic where the stray
current enters but will be highly anodic where the stray current returns to the earth. At
the point where the current discharges, rapid corrosion of the structure intended to be
protected will occur. If unsteady readings are observed on the protected structure and
you have determined that it is not because of a bad electrical connection, you should
suspect that stray current is affecting the protected structure (Baeckmann et al 1997).

1. Influence:
It is the inherent tendency of a cathodic protection installation to produce stray
currents; it depends on the amount of current used, the location of the anodes or
groundbeds, their configuration and resistance to earth, and the type of structure being
protected. For any fixed anode arrangement, and type of structure, and soil resistivity,
the influence is directly proportional to the current . (Anderson H. H et al 1951 )

2. Susceptivness:
It is the inherent ability of an unprotected structure to pick up stray current and
discharge it in manner likely to cause corrosion, the most susceptive structure is an
uncoated one, and the least susceptive is a structure with a highly insulated coating a
pipe line with poor coating

3. Coupling:
It is the change in potential of a particular unprotected structure when protective
current is applied to a nearby structure. Assuming a constant influence and
susceptiveness, the tendency of a cathodically protected structure and its anode to cause
the flow of current in a nearby structure depends upon the earth resistivity and the
physical separation between the structures .

4. Telluric Currents:
Disturbances in the earth’s magnetic field sometimes cause induced current in
metallic structures. Where this current leaves the structure to enter into the earth,
corrosion occurs . (Anderson H. H et al 1951 )

2.6.4 Anode/Cathode Ratio:

The relative area between the anode and cathode of a corrosion cell greatly
affects the rate at which the anode corrodes. If the anodic area is small in relation to
that of cathode for example a steel rivet in a copper plate, the anode (steel rivet) will
corrode rapidly. This is because the corrosion current is concentrated in a small 17
area (large current density). Also, the large cathode may not polarize easily, thus
maintaining a high rate of corrosion. When a small cathode is connected to a large
anode (copper rivet in a steel plate), the corrosion current density on the anode (steel)
is much less than in the opposite case discussed above, and the anode corrodes more
 slowly. Polarization may play an important role here, too. The small cathode may
polarize rapidly, reducing the rate of corrosion current flow.

2.7 Uses of Cathodic Protection :

Structures that are commonly protected by cathodic protection are the exterior
surfaces of:

1. Pipelines.
2. Storage tank bases.
3. Ships’ hulls.
4. Jetties and harbour structures.
5. Steel sheet, tubular and foundation pilings.
6. Offshore platforms, floating and subsea structures.
7. Cathodic protection is also used to protect the internal surfaces of:
8. Large diameter pipelines.
9. Ship’s tanks (product and ballast).
10. Storage tanks (oil and water).
11. Water-circulating systems.

However, since an internal anode will seldom spread the protection for a distance of more
than two to five pipe-diameters, the method is not usually practical, or suitable, for the
protection of small-bore pipework. Cathodic protection may be applied to control the
corrosion of steel embedded in reinforced concrete structures (bridges, buildings, port and
harbour structures, etc.) – See Guide in Corrosion Control, Corrosion and Protection of
Steel in Concrete and it’s Monitoring.( Revie, R. W. and H 2008)