API RP 571: Damage Mechanisms Affecting Fixed

Equipment in the Refining Industry

PART-3

INTRODUCTION TO CORROSION
 CHAPTER-3
INTRODUCTION TO CORROSION

Corrosion is a major problem worldwide in all industrial sectors. It impacts on Safety, Health
and Environmental (SHE) issues with significant financial implications for operating
companies. The end result of corrosion may be thinning of the wall of a pressure
vessel or a hole in the wall of a flow line or tank, or a rough pitted underground
pipe, etc. Since the corrosion is the reactions of these metallic components with
surrounding, if these reactions can be understood, ways and means to prevent
future failures can be analyzed.

What is corrosion?

The most widely accepted definition of corrosion describes it as "the

deterioration of a material, usually a metal, by reaction with its environment." This
sounds simple enough. What is being described is an action, or more properly, a
reaction between at least two things, for example, a piece of metal and whatever
the metal is exposed to. In this study we will deal primarily with the corrosive
situations normally encountered in petroleum production.

In this first chapter, we will explore the basic mechanisms of corrosion

process. In addition to understanding of the principles of corrosion and the influence of
environments on engineering materials, we must, in practice, also consider the Engineering
Applications. Various mechanical loads, forces or stresses on equipment and plant items,
fluid flow conditions and, in the case of boilers, reactors and heat transfer equipment,
changes in wall temperatures. The discussion is designed to provide a foundation of
understanding for the corrosion types and prevention and control procedures of
corrosion covered in more details in the subsequent chapters. Technical terms are
defined and explained as they are encountered.

Why metals corrode?

Iron and similar metals exist in nature in the combined form such as oxides,
carbonates or sulfides. The ores are quite stable and are insoluble in ordinary water.
To change the ore form to purer and more useful refined metals requires energy addition like
heating in Blast furnace, or Open hearth furnace or in Bessemer converter or electrolytic
methods. Therefore, refined metals are at a higher energy level or an unnatural state as
compared to native ores. Thus, there is a normal tendency for refined metal to revert back to
its original form as it occurred in nature. This occurs through reaction with Oxygen, moisture,
carbon dioxide, hydrogen sulfide, and other components commonly found in the
atmosphere, soil, water, and process streams. This cycle is illustrated by Figure below.

The various metals have inherently different tendencies to revert to their stable,
combined forms. These differences are used both in predicting corrosion and in controlling it.
Later we will take a closer look at the chemical reactivity of various metals and learn to
organize the differences in a useful way.

As mentioned earlier in most metals are produced from natural compounds called ores.
These ores contain metals that are combined with oxygen or sulfur.

Figure below shows one more refining and corrosion cycle for a common iron ore called
hematite, Fe2O3. Hematite changes to iron when chemical energy is added during the
refining process.

Corrosion Cycle
Steel mills add carbon during the alloying process to change the iron to steel. The steel
releases the stored energy when it changes to rust, Fe2O3, during the corrosion process.
Notice that hematite and rust have the same composition. The noble metals - gold, silver
and platinum contain insufficient energy to react (corrode) in natural environments and are
therefore relatively inert.

Corrosion of metallic materials is an electrochemical process. This requires the presence of

an electrolyte (water) at low or ambient temperatures. At high temperatures, as found
with the flame side of boilers, gas turbines and many refinery processes the metal
undergoes direct oxidation (conversion to oxides and sulfides) by the hot gaseous
atmospheres.

Principles of Electrochemical Cells:

Electrochemical reactions cause corrosion in the petroleum industry. Electrochemical

eactions involve the transfer of electrons. Electrons and ions produced during the corrosion
process form part of the corrosion cell. The transfer of electrons is directly associated with
the creation of an electrical circuit. This electrical circuit and its associated chemical
reactions are called an electrochemical corrosion cell.
 corrosion "cell"

For any cell to exist, it must contain all of the following four components:
(i) an anode where oxidation occurs (in a corrosion cell there is metal dissolution and
production of electrons)
(ii) a cathode where electrons are consumed and a reduction reaction occurs
(iii) a metal path through which electrons move from the anode to the cathode
(iv) an electrolyte through which ionic current flows and in which the products of the
oxidation and reduction reactions are formed
A definition of an anode and cathode is:
anode - where oxidation reactions take place (electrons appear)
cathode - where simultaneous reduction occurs (electrons consumed)

As seen earlier, Corrosion may be defined as the deterioration of a metal resulting from a
reaction with its environment. Corrosion of steel structures is an electrochemical process.
For the corrosion process to occur, areas with different electrical potentials must exist on the
metal surface. These areas must be electrically connected and in contact with an electrolyte

The role anode and Cathode in the corrosion cell is as follows:

a. At the anode, the base metal goes into solution (corrodes) by releasing electrons and
forming positive metal ions. This happens initially because the relatively pure iron is at
a high energy level and has a measurable solution potential or tendency to
dissolve. For steel, the anodic reaction is:

b. At the cathode, chemical reactions take place using electrons released at the anode. No
corrosion takes place at the cathode. One common cathodic reaction is:

c. The metallic path provides a way for electrons released at the anode to flow to the
cathode.
d. The electrolyte contains ions and conducts current from the anode to the cathode by ionic
movement. The electrolyte contains both negatively charged ions called anions and
positively charged ions called cations that are attracted to the anode and cathode,

Typical corrodants (species that cause corrosion) are atmospheric oxygen, dissolved in sea
water and cooling waters, and hydrogen ions, in produced fluids/acid solutions.
Metal dissolution in aqueous environments produces metal ions, electrons and corrosion
products. However, the metal is often protected by the corrosion product film (oxide or
sulfide).The driving force for the corrosion reaction is the energy (potential/voltage)
contained in the metal/corrodant combination.
Effect of Coating on the Corrosion Cell

Effect of Corrosion inhibitor on Corrosion Cell

Much of the corrosion protection comes from the protective oxide and sulfide corrosion
product films that form on engineering metals and alloys. In some environments these
films can break or rupture which gives rise to an intense localized pitting attack .Corrosion of
engineering metals is inevitable. Corrosion can be slowed or temporarily stopped by means
of coatings, cathodic protection and inhibitors

Other most common method to control corrosion is use of corrosion resistant alloys.
Corrosion control methods aim to slow down the rate of release of the stored chemical
energy by making use of the protective corrosion product films or by using corrosion
inhibitors that adsorb on the metal surface.

The two most common corrosions are:

1. General Corrosion (Uniform Corrosion):
2. . Localized Corrosion

General Corrosion (Uniform Corrosion):

General corrosion is attack over the entire exposed surface, or a large area, of a metal. The
corrosion mechanism involves microscopic corrosion cells that comprise anodic areas of
high metal content (for example, ferrite) and small associated cathodic areas (for example,
iron carbide/cementite),

General or uniform corrosion

The metal loss is distributed uniformly across the exposed surface. In general corrosion,
thousands of microscopic corrosion cells occur on an area of the metal surface resulting in
relatively uniform metal loss

The term “uniform” implies that corrosion is perfectly even along the entire metal surface.
Since some irregularity in the corrosion almost always occurs, many people prefer to use the
term “general corrosion” to describe this form of attack.
Examples of general corrosion, atmospheric corrosion, Sulphidation, corrosion in water and
natural environments. The assumption that uniform attack will occur is the basis of many
designs that employ C-steel fabrications, the designer uses the concept of a “corrosion
allowance”.
Corrosion allowance is the additional thickness above that required to retain the operational
pressure. The aim is to provide some additional thickness which may be lost due to
corrosion. It assumes a gradual and controlled metal loss (See Figure below).

For example, If a thickness of 12 mm is required to contain the pressure in the vessel, then
the wall thickness would have to be increased to 16 mm to provide a minimum corrosion
allowance of 4 mm. In principle, general corrosion should be the easiest to deal with in terms
of risk to an operation. General corrosion can be measured by loss of thickness of the
metallic wall.

Corrosion Allowance Concept

The corrosion units are listed either as µpy (microns per year - a micron is one thousandth
part of a millimeter) or mpy (mils pert year-mil is thousandth part of inch). Generally average
corrosion rates of 50 – 150 µpy (2-6mpy) are considered acceptable.(Note that 1 mpy=25
µpy.)

Higher pit penetration rates may be tolerated compared to the general corrosion rate. The
concept is that pitting has to penetrate the full wall thickness to cause leakage, whereas
general corrosion/metal loss over a relative large area could under high internal pressures
result in local plastic deformation of the ductile steel and possible fracture/rupture

Localized Corrosion:
Galvanic corrosion occurs when two metals with different compositions (thus, different
electrolytic potentials) are connected in an electrolyte . Current will flow from the more active
metal (anode) to the less active metal (cathode) with accelerated attack at the anodic metal.
Galvanic corrosion is the corrosion that occurs when two dissimilar metals are electrically
connected and exposed to a conductive corrosive environment. The two metals are called a
galvanic couple. In a galvanic couple, the more active metal becomes the anode and
corrodes faster. The metal with the higher corrosion potential becomes the cathode (the
more noble metal) and is protected.
Since current takes the path of least resistance, the most severe corrosion attack will occur
in the area on the area immediately adjacent to the cathodic metal. The extent of such a
problem is dependent on several factors.

G
al v
a ni
c

corrosion
The most significant factors are:

a. the relative surface areas of the cathode and anode,

b. the relative potential difference between the two materials as determined by their position
in the galvanic series, and

Corrosion tends to be more severe when the anodic area is small with respect to the
cathode surface and the two metals are far apart in the galvanic series.
 Area principal for
galvanic corrosion