CHAPTER XIII

CORROSION
13.1 Introduction

• Corrosion is the deterioration of a substance or its properties because of a reaction

with its environment.
• Metals in general are relatively unstable with respect to most environments and have
a natural tendency to return to their original state, or corrode.
• Millions of dollars are lost each year because of corrosion. Much of this loss is due to
the corrosion of iron and steel, although many other metals may corrode as well.
• The problem with iron as well as many other metals is that the oxide formed by
oxidation does not firmly adhere to the surface of the metal and flakes off easily
causing "pitting".
• Extensive pitting eventually causes structural weakness and disintegration of the
metal. (It should be noted, however, that certain metals such as aluminum, form a
very tough oxide coating which strongly bonds to the surface of the metal preventing
the surface from further exposure to oxygen and corrosion).

13.2 Corrosion as an Electrochemical Process

Corrosion occurs in the presence of moisture. For example when iron is exposed to moist
air, it reacts with oxygen to form rust,

The amount of water complexed with the iron (III) oxide (ferric oxide) varies as indicated
by the letter "X". The amount of water present also determines the color of rust, which
may vary from black to yellow to orange brown. The formation of rust is a very complex
process which is thought to begin with the oxidation of iron to ferrous (iron "+2") ions.
 Fe -------> Fe+2 + 2 e-

Both water and oxygen are required for the next sequence of reactions. The iron (+2) ions
are further oxidized to form ferric ions (iron "+3") ions.

Fe+2 ------------> Fe+3 + 1 e-

Tthe electrons provided from both oxidation steps are used to reduce oxygen as shown.

O2 (g) + 2 H2O + 4e- ------> 4 OH-

The ferric ions then combine with oxygen to form ferric oxide [iron (III) oxide] which is
then hydrated with varying amounts of water. The overall equation for the rust formation
may be written as :

The formation of rust can occur at some distance away from the actual pitting or erosion
of iron as illustrated below. This is possible because the electrons produced via the initial
oxidation of iron can be conducted through the metal and the iron ions can diffuse
through the water layer to another point on the metal surface where oxygen is available.
This process results in an electrochemical cell in which iron serves as the anode, oxygen
gas as the cathode, and the aqueous solution of ions serving as a "salt bridge" as shown
below.
The involvement of water accounts for the fact that rusting occurs much more rapidly in
moist conditions as compared to a dry environment such as a desert. Many other factors
affect the rate of corrosion. For example the presence of salt greatly enhances the rusting
of metals. This is due to the fact that the dissolved salt increases the conductivity of the
aqueous solution formed at the surface of the metal and enhances the rate of
electrochemical corrosion. This is one reason why iron or steel tend to corrode much
more quickly when exposed to salt (such as that used to melt snow or ice on roads) or
moist salty air near the ocean.

A piece of bare iron left outside where it is exposed to moisture will rust quickly. It will
do so even more quickly if the moisture is salt water. The corrosion rate is enhanced by
an electrochemical process in which a water droplet becomes a voltaic cell in contact
with the metal, oxidizing the iron.

The rusting of unprotected iron in the presence of air and water is then inevitable because
it is driven by an electrochemical process. However, other electrochemical processes can
offer some protection against corrosion. For magnesium rods can be used to protect
underground steel pipes by a process called cathodic protection.
13.3 Electrochemical aspects of corrosion

• In oilfield situations we are generally faced with corrosion attacks in aqueous

environments
• Basically all attacks in aqueous solutions are electrochemical in nature.
• Besides the chemical reaction there will also be a flow of electrons, resulting in a
flow of current.
• The current flows from a higher potential to a lower one.

Cathodic Protection against Corrosion

Underground steel pipes offer the strength to transport fluids at high pressures, but they
are vulnerable to corrosion driven by electrochemical processes. A measure of protection
can be offered by driving a magnesium rod into the ground near the pipe and providing
an electrical connection to the pipe. Since the magnesium has a standard potential of -
2.38 volts compared to -.41 volts for iron, it can act as a anode of a voltaic cell with the
steel pipe acting as the cathode. With damp soil serving as the electrolyte, a small current
can flow in the wire connected to the pipe. The magnesium rod will be eventually
consumed by the reaction

Mg(s) -> + Mg2+(aq) + 2e-

while the steel pipe as the cathode will be protected by the rea

Polarisation
• An electrochemical reaction is said to be polarized or retarded when it is limited
by various physical and chemical factors.
• The reduction in potential difference in volts due to net current flow between the
two electrodes of the corrosion cell is termed polarization.
• The overall reaction is controlled by the slowest reaction, anodic or cathodic.

• If the slower reaction is anodic or the polarization occurs mostly at the anode the
corrosion reaction is said to be “anodically controlled”
• When the slower reaction is cathodic and polarization occurs mostly at the
cathode, the corrosion rate is “cathodically controlled”
• Polarization can be divided into
• Activation polarization
• Concentrationpolarization
• Activation polarization is an electrochemical reaction that is controlled by the
reaction occurring on the metal-electrolyte interface
• Concentration polarization is an electrochemical process controlled by the
diffusion within the electrolyte.

Passivity
Passivity is the loss of chemical reactivity of certain metals and alloys under specific
environmental conditions.
Oxide film theory
 • States that the passive film is a diffusion-barrier layer of reaction products(i.e.,
metal oxides or other compounds).
• The barriers separate the metal from the hostile environment and thereby slow the
rate of reaction.

Adsorption theory of passivity

• This states that the film is simply adsorbed gas that forms a barrier to diffusion of
metal ions from the substrata.
• Metals that exhibit passivity can be used in moderately to strongly oxidizing
environments.
• In highly oxidizing environments they will lose their corrosion-resistant
properties and, therefore,cannot be used.

13.4 Forms of corrosion attack

Uniform Corrosion
• All homogeneous metals without differences in potential between any points on
their surfaces are subject to this type of general attack under some conditions.
• Uniform corrosion is usually characterized by a chemical or electrochemical
attack over the entire exposed surface
• Metal corrodes in an even and regular manner becoming thinner, and
consequently leads to failure due to reduction of the material's load-carrying
capabilities
• The rate of penetration or the thinning of a structural member can be used directly
to predict the service life of a given component.
• The expression mils penetration per year (mpy) is used to express corrosion
resistance directly in terms of penetration.
Galvanic Corrosion

• Galvanic corrosion occurs when two different metals electrically contact each
other and are immersed in an electrolyte.
• In order for galvanic corrosion to occur, an electrically conductive path and an
ionically conductive path are necessary. This effects a galvanic couple where the
more active metal corrodes at an accelerated rate and the more noble metal
corrodes at a retarded rate.
• When immersed, neither metal would normally corrode as quickly without the
electrically conductive connection (usually via a wire or direct contact). Galvanic
corrosion is often utilised in sacrificial anodes.
• What type of metal(s) to use is readily determined by following the galvanic
series. For example, zinc is often used as a sacrificial anode for steel structures,
such as pipelines or docked naval ships.
• Galvanic corrosion is of major interest to the marine industry and also anywhere
water can contact pipes or metal structures.

Factors such as relative size of anode (smaller is generally less desirable), types of metal,
and operating conditions (temperature, humidity, salinity, etc.) will affect galvanic
corrosion. The surface area ratio of the anode and cathode will directly affect the
corrosion rates of the materials

To prevent or reduce galvanic corrosion we can employ several techniques:

• If a metal or alloy combination is to be selected, choose combination of metals as
close together in the galvanic series as possible.
• Choose the metal or alloy so that the anode area is larger than the cathode area.
• If any dissimilar metals are in contact with each other, isolate them electrically so
that no electricity flows between them.
• Apply proper coatings with caution, and keep the coatings in good repair.
• Add proper inhibitors with appropriate practices.
 • Avoid threaded joints for materials that are far apart in galvanic series.
• Anodic parts should be designed so that they are easily replaceable. They may
also be designed thicker than what is required to extend their service life

Pitting corrosion

Certain conditions, such as low concentrations of oxygen or high concentrations of

species such as chloride which compete as anions, can interfere with a given alloy's
ability to re-form a passivating film. In the worst case, almost all of the surface will
remain protected, but tiny local fluctuations will degrade the oxide film in a few critical
points. Corrosion at these points will be greatly amplified, and can cause corrosion pits of
several types, depending upon conditions. While the corrosion pits only nucleate under
fairly extreme circumstances, they can continue to grow even when conditions return to
normal, since the interior of a pit is naturally deprived of oxygen and locally the pH
decreases to very low values and the corrosion rate increases due to an auto-catalytic
process. In extreme cases, the sharp tips of extremely long and narrow can cause stress
concentration to the point that otherwise tough alloys can shatter, or a thin film pierced
by an invisibly small hole can hide a thumb sized pit from view. These problems are
especially dangerous because they are difficult to detect before a part or structure fails.
Pitting remains among the most common and damaging forms of corrosion in passivated
alloys, but it can be prevented by control of the alloy's environment, which often includes
ensuring that the material is exposed to oxygen uniformly (i.e., eliminating crevices).

Microbial corrosion

Microbial corrosion, or bacterial corrosion, is a corrosion caused or promoted by

microorganisms, usually chemoautotrophs. It can apply to both metals and non-metallic
materials, in both the presence and lack of oxygen. Sulfate-reducing bacteria are common
in lack of oxygen; they produce hydrogen sulfide, causing sulfide stress cracking. In
presence of oxygen, some bacteria directly oxidize iron to iron oxides and hydroxides,
other bacteria oxidize sulfur and produce sulfuric acid causing biogenic sulfide corrosion.
Concentration cells can form in the deposits of corrosion products, causing and
enhancing galvanic corrosion.

Inter-Grannular Corrosion

• Inter-granular corrosion is a localized type of attack at the grain boundaries, with

relatively little corrosion of the grains.
• The metal or the alloys lose their strength, ductility and eventually disintegrate
• Relatively small areas of grain-boundary material act as anodes, and are in contact
with larger areas of grain material, the cathodes.
• The attack can be caused by impurities at the grain boundaries, enrichment of one
of the alloying elements, or depletion of one of these elements in the grain-
boundary areas. Inter-granular corrosion can be prevented or minimized by the
following

considerations:

• Choose proper treatment for the environmental conditions of service.

• Use properly heat-treated metals and alloys.
• Use materials that contain strong carbide-formers, the stabilizers.
• Use low-carbon grade materials.
• Avoid high-strength aluminum alloys

Cavitation Corrosion

• Cavitation is a special form of erosion corrosion results from formation and

collapse of vapour bubbles in a liquid near a metal surface
 • Collapsing bubbles destroy the protective surface film, thereby exposing the metal
to increased corrosion attack.
• Cavitation damage is often seen in high-velocity, turbulent, liquid-flow areas such
as drilling-mud pumps.
• Titanium and corrosion-resistant, cobalt-base alloys appear to be suitable for a
wide range of environments causing cavitation erosion.

Erosion Corrosion

• Most metals and their alloys are susceptible to erosion corrosion

• Erosion corrosion occurs when the protective films or deposits are removed by
mechanical wear effects of abrasion.
• Once the protective surface is damaged, accelerated corrosive attack occurs at the
fresh metal surface.
• The damage done by this form of corrosion appears as grooves, gullies, waves,
rounded holes, pits and valleys, and generally, exhibits a directional pattern

There are basically five ways to reduce or prevent erosion corrosion:

• Choose materials with a high resistance to erosion and wear.

• Keep erosion corrosion in mind while designing the equipment.
• Use proper coatings.
• Alter environment-add inhibitors, remove abrasives as soon as possible.
• Use cathodic protection wherever possible. This does not affect the erosion part of
the attack, but it may reduce the corrosive attack.

Hydrogen Damage

• In general corrosion, hydrogen ions (H) are reduced to atomic hydrogen (HO)
• These hydrogen atoms combine with each other and form molecular hydrogen
• 2H. + 2e- -> 2H0 ->H2
• Sulphide ions, phosphorus and arsenic compounds reduce the rate at which
hydrogen combines to form molecules.
• Atomic hydrogen can diffuse through metal matrix and cause mechanical damage
Therefore, hydrogen damage is a mechanical damage of metal caused by the
presence of atomic hydrogen
• Some of the forms of hydrogen damage are as follows:
• Hydrogen Blistering
• Penetration of hydrogen in low-strength steel with any discontinuities in the steel
such as laminations, inclusions or voids may result in hydrogen blistering
• Hydrogen produced on the surface of the metal evolves in part as gas bubbles and
the rest diffuses through the metal.
• The different hydrogen atoms collect in the void, and combine to form hydrogen
gas molecules
• Hydrogen gas molecules are too large to diffuse back through the metal.
• The gas pressure increases to sufficient levels to burst out to the metal surface.

Sress Corrosion

• Stress-corrosion cracking occurs when a metal is under constant tensile stress and
exposed simultaneously to a corrosive environment.
• The source of this stress can be external (caused by slip or tong notch, etc., on
drill pipes, collars and tool joints, and the weight of the drill stem) or it can be
residual in the metal from heat treatment or cold working.
• The area damaged by the slips becomes stressed and undergoes accelerated
corrosion as it becomes anodic to the rest of the unstressed area of the pipe.
• The area damaged by the slips becomes stressed and undergoes accelerated
corrosion as it becomes anodic to the rest of the unstressed area of the pipe.
• The appearance of damage is of a brittle mechanical fracture, but it results from
local corrosion attack
• The cracks are inter-granular or trans-granular depending on the metal structure
and the corrosive environment.
• Cracks generally develop perpendicular to the applied stresses.
• They are randomly oriented and can vary in degree of branching depending on the
metal structure and composition, the nature of stress and the corrosive
environment.
• Cracks vary from being totally branchless to extremely branched like the “river
delta.”
• As the stress increases, the time before failure decreases.
• The minimum stress may vary from 10% of the yield stress to 70% of the yield
stress.
• As stress corrosion proceeds, the cross-sectional area is reduced, resulting in a
cracking failure due to mechanical action.
• At first, the crack propagation rate is roughly constant; but as cracking progresses,
the cross-sectional area decreases.
13.5 Factors Influencing Corrosion Rate

1) PH

• pH = -log[H+]
• The time to failure increases as the pH rises
• Below pH 7, failure occurs in less than an hour in the presence of hydrogen
sulfide
• As the pH rises above 7, time to failure rapidly increases.
• Both carbon dioxide and hydrogen sulphide lower the pH level to acidic regions
and , consequently, increase the corrosion rate.
• The corrosion rate is dependent upon the diffusion rate of oxygen through the
protective layer to the metal surface
• The corrosion rate increases with increasing oxygen concentration and with
erosion of the protective layer in the presence of high-velocity turbulent flow,
which is often imposed on the drill-string

2) Temperature

• The effect of temperature on corrosion rate is influenced by the following:

• 1. Increase in temperature increases the redox reaction.
• 2. Solubility of gases in water decreases with increasing temperature.
• 3. Change in viscosity may affect the circulation, diffusion and other properties
pertinent to the corrosion process.
• 4. Solubility of some reaction products can be affected by temperature variation.
• When corrosion is due to the presence of mineral acids dissolved in water,
resulting in hydrogen evolution, the corrosion rate generally increases with
increasing temperatures
• If the corrosion is due to dissolved oxygen in water, the rate decreases with
increased temperature. This is due to the increased solubility of oxygen with rise
in temperature
 • In a closed system, where oxygen coming out of solution cannot escape, the rate
of corrosion increases with increase in temperature

3) Velocity

• The velocity of fluids over the metal surface has an effect on the corrosion rate
through influencing other factors responsible for corrosion
• High velocity may increase erosion corrosion by either washing away the
protective film or by mechanically agitating the metal surface
• On the other hand, stagnant systems where the fluid velocity is zero may
experience deposition of sludge and other suspended solids
• This deposition may create