3 Corrosion Principles

CORROSION ENGINEERING
CHAPTER 3
CORROSION PRINCIPLES
Department of Mechanical & Manufacturing Engineering, MIT, Manipal

Introduction
• To view the corrosion engineering from its proper

perspective, it is necessary to remember that the choice of a
material depends on many factors, including its corrosion
behaviour.
• Following diagram shows some of the important factors that

determine the choice of an engineering material.
Department of Mechanical & Manufacturing Engineering, MIT, Manipal 2 of 65

Introduction

Introduction
• The engineering aspect of corrosion resistance cannot be

over emphasized.
• Complete corrosion resistance almost in all media can be

achieved by the use of either platinum or glass. But these
materials are not practical in most cases.
• Corrosion resistance depends on many factors. These are

shown in the following diagram.

Introduction

Introduction
• Thermodynamics and electrochemistry are of great

importance in understanding and controlling corrosion.
• Thermodynamic studies and calculations indicate the

spontaneous direction of a chemical reaction. It is used to
determine whether or not corrosion is theoretically possible.
• While thermodynamics can predict whether a corrosion

reaction will take place or not, it does not provide an
indication of the rate of corrosion reactions

Introduction
• Metallurgical factors frequently have a pronounced influence

on corrosion resistance.
• In many cases, the metallurgical structure of the alloy (grain

structure) may be modified to reduce the corrosive attack.
• Physics/chemistry and its various disciplines are most useful

for studying the mechanisms of corrosion reactions, the
surface conditions of metals due to corrosion, and other
basic properties.

Corrosion Rate Measurements
• Measurement of corrosion is essential for the purpose of

material selection.
• The compatibility of a metal with its environment is a prime

requirement for its reliable performance.

Corrosion rate measurement is necessary for
• the evaluation and selection of materials for a specific

environment,
• for a given definite application,
• for the evaluation of a new or old metal or alloy to

determine the environments in which they are suitable.

• Often, the corrosive environment is suitably treated to make

it less aggressive, and corrosion rate measurements of a
specific material in untreated and treated environments will
reflect the efficacy of the treatment.
• In addition, corrosion rate measurement is also essential in

the study of the mechanisms of corrosion.

Corrosion Rate Expressions

• Corrosion involves dissolution of metal, as a result of which
the metallic part loses its mass (or weight) and becomes
thinner.
• Corrosion rate expressions are therefore based on either

weight loss or penetration into the metal.
• Corrosion rates have been expressed in a variety of ways in

the literature; such as percent weight loss, milligrams per
sq. cm. per day, gram per sq. inch per hour (weight loss
only).
• These do not express corrosion resistance in terms of

penetration.
• The most widely used weight expression, based on weight

loss, is mg/dm2/day (mdd) and the rate expression on
penetration is inch of penetration/year (ipy) and mils of
penetration/year (mpy).
1 mil = (1/1000)th of an inch.


• From the engineering view point, the rate of penetration, or
the thinning of a structural piece, can be used to predict the
life of a given component.
• The expression mils per year (mpy) is the most desirable

way of expressing corrosion rates. The most commonly
used expression is,
𝐶𝑅(𝑚𝑝𝑦) = 534𝑊 / 𝐷𝐴𝑇
Where, W= Weight loss, mg, D= Density of specimen, g/cm3, A=
Exposed area of the specimen, sq.in , T= Exposure time, h.

• One mil is one thousandth of an inch. Thus, 0.002 ipy is

simply expressed as 2 mpy.
• A good corrosion rate expression should involve
• Familiar units
• Easy calculation with minimum opportunity for error
• Ready conversion to life in years
• Whole numbers without cumbersome decimals.

Conversion from other units to obtain mils per year (mpy)

Electrochemical Nature of Corrosion

Atoms:
• All matter is made of atoms composed of protons, neutrons,
and electrons.
• The centre, or nucleus, of the atom is composed of

positively charged protons and neutral neutrons.
• The outside of the atom has negatively charged electrons in

various orbits.
• All atoms have the same number of protons (positively

charged) and electrons (negatively charged).
Atoms:
• Therefore all atoms have a neutral charge (the positive and
negative charges cancel each other).
• Most atoms have approximately the same number of

neutrons as they do protons or electrons, although this is
not necessary.

Atoms:
• The number of protons (atomic number) in an atom
determines the kind of atom we have.
• The atomic mass (weight) of the atom is determined by the

number of protons and neutrons in the nucleus (the
electrons are so small as to be almost weightless).

Ions:
• Ions are formed when atoms, or groups of atoms, lose or
gain electrons. Metals loose some of their electrons to form
positively charged ions.
e.g. Fe2+, Al3+, Cu2+, etc.
• Nonmetals gain electrons and form negatively charged ions.
e.g. Cl-, O2-, S2-, etc.

Molecules:
• A molecule is formed when two or more atoms join together
chemically.
• A compound is a molecule that contains at least two

different elements.
• All compounds are molecules but not all molecules are

compounds.

Molecules:
• Most of us are familiar with the formula H2O, which indicates
that each water molecule is made of two hydrogen atoms
and one oxygen atom.
• Many molecules are formed by sharing electrons between

adjacent atoms.
• A water molecule has adjacent hydrogen and oxygen atoms

sharing some of their electrons.

Acids and Bases:

• Water is the most common chemical on the face of the
earth.
• It is made of three different constituents, hydrogen ions,

hydroxide ions, and covalently bonded (shared electron)
water molecules.
• Most of water is composed of water molecules, but it also

has low concentrations of H+ ions and OH- ions.

Acids and Bases:

• Neutral water has an equal number of H+ ions and OH- ions.
• When water has an excess of H+ ions, we call the resultant

liquid an acid.
• If water has more OH- ions, then we call it a base.

Oxidation and Reduction:

• Metals are elements that tend to lose electrons when they
are involved in chemical reactions, and non-metals are
those elements that tend to gain electrons.
• Sometimes these elements form ions, charged elements or

groups of elements.
• Metallic ions, because they are formed from atoms that

have lost electrons, are positively charged (the nucleus is
unchanged).

• When an atom or ion loses electrons it is said to have been
oxidized.
• A common oxidation reaction in corrosion is the oxidation of

neutral iron atoms to positively charged iron ions:
Fe » Fe2+ + 2e-


4H+ + O2 + 4e- » 2H2O
or
2H+ +2e- » H2
• While other reduction reactions are possible, the reduction of
oxygen is involved in well over 90% of all corrosion reactions.
• Thus the amount of oxygen present in an environment, and its

ability to absorb electrons, is an important factor in determining
the amount of oxidation, or corrosion, of metal that occurs.

Electrochemical Theory and Reactions
• Corrosion is an electro-chemical process involving an

anode, a cathode and an electrolyte.
• In the case of steel, when favourable condition for corrosion

occurs/ exists, the ferrous ions go into solution from anodic
areas.
• Electrons are then released from the anode and move

through the cathode where they combine with water and
oxygen to form hydroxyl ions.

• These react with the ferrous ions from anode to produce

hydrated ferrous oxide, which further gets oxidised into ferric
oxide, which is known as the ‘red rust’.
Anodic Reaction:
• Iron is oxidized to ferrous ions (Fe2+ ions) by the removal of
electrons.
• Ferrous ions combine with hydroxide ions to form ferrous

hydroxide by atmosphere.

• Finally ferric hydroxide decomposes to form ferric oxide,

which is nothing, but red rust.
Fe → Fe 2+ + 2e-
Fe2+ + 2OH- → Fe(OH)2
Fe(OH)2 → Fe(OH)3
Fe(OH)3 → Fe2O3 + H2O

• The electrons released at the anode are absorbed at the

cathode to form either hydrogen or water or hydroxide ion
depending on the nature of the atmosphere.
• This completes the formation of the cell, which favours

rusting of iron.

Cathodic Reaction
• Depending on the nature of the atmosphere the following

reactions take place at the cathode.
• When the atmosphere is acidic and contains no oxygen,

hydrogen will be given out.
2H+ + 2e- → H2
• When the atmosphere is acidic and contains more oxygen

water will be given out.

2H+ + [O] + 2e- → H2O
• When the atmosphere is basic or neutral and contains no

oxygen, OH- and H2 will be given out.
2H2O+ 2e- → H2 + 2OH-
• When the atmosphere is basic or neutral and contains more

oxygen, OH- will be given out.
2H2O + O2 + 4e- → 4OH-

• From the above discussion, it is clear, that the main interest of the
designers is to prevent the formation of the “corrosion batteries”.
• For example, if we can wipe out the ‘drop of water’ from the
surface, the corrosion will not take place!
• Hence using the “eliminate the electrolyte” principle, wherever

possible we need to device detailing and protection to surfaces of
structural steel work to ensure that the combination of oxygen
and water are avoided and hence the corrosion batteries are
avoided.

• On the other hand, steel is anodic in the presence of

stainless steel or brass and cathodic in the presence of zinc
or aluminium and the second property can be used to
protect it from corrosion.


• The two metal strips shown below are exposed to the same
acid.
• Both metals undergo similar oxidation reactions:

Cu → Cu2+ + 2e-
and
Zn → Zn2+ + 2e-
• The electrons freed by the oxidation reactions are

consumed by reduction reactions.
• On the copper the reduction reaction is:
4H+ + O2 + 4e- → 2H2O

• The corrosion rate of the copper is limited by the amount of

dissolved oxygen in acid.
• On the zinc the reduction reaction is:
2H+ + 2e- → H2
• The hydrogen ions are converted to hydrogen gas

molecules and can actually be seen bubbling off from the
acid.

40 of 65
• If we now connect the two metal samples with a wire and

measure the electricity through the connecting wire, we find
that one of the electrodes becomes different in potential
than the other and that the corrosion rate of the copper
decreases while the corrosion rate of the zinc increases.
• By connecting the two metals, we have made the copper a

cathode in an electrochemical cell, and the zinc has become
an anode.

• The accelerated corrosion of the zinc may be so much that

all of the oxidation of the copper stops and it becomes
protected from corrosion.
• We call this method of corrosion control cathodic protection.
• Cathodic protection is a common means of corrosion control

Factors Affecting The Corrosion Rate
• Nature of metal
• Ratio of cathode to anode
• Nature of corrosion product
• pH of the medium
• Temperature
• Effect of oxygen
• Surface roughness
• Stress
Nature of metal:
• Metals with very high electrode potentials do not corrode

easily.
• They are noble metals like, gold, platinum, silver.
• Whereas metals with lower electrode potentials readily

undergo corrosion. e.g. metals like, zinc, magnesium,
aluminium.


Nature of metal:
• When two metals are in contact with each other, higher the
difference in electrode potentials greater is the corrosion.
• For eg., the potential difference between iron and copper is

0.78V which is more than that between iron and tin (0.3V).
• Therefore, iron corrodes faster when in contact with copper

than that with tin.

Nature of metal:
• Thus, the use of dissimilar metals should be avoided

wherever possible.
• For example, bolt and nut or screw and washer should

be made of the same metal (or alloy) to avoid
galvanic/two metal corrosion.

Cathodic to Anodic ratio:
• The rate of corrosion is influenced by relative size of

cathodic to anodic area. If the metal has small anode
and large cathodic region, corrosion rate is very high.
• As the ratio increases corrosion rate also increases.

• At anode electrons are liberated, which are consumed at

cathodic region.
• If cathodic region is larger the liberated electrons are

rapidly consumed at cathode.
• This further enhances, the anodic reaction (oxidation)

leading to increase in overall rate of corrosion.

• When two dissimilar metals are in contact, Corrosion is

more rapid and severe, if the anodic area is small and
cathodic area is large (e.g., a small steel pipe fitted in a
large copper tank).
• If during plating of tin on iron, some areas are not

covered or some pin holes are left, there results a small
anode and large cathode, leading to severe corrosion.

Nature of corrosion product:

• The corrosion product formed like metal oxide may act
as protective film, if it is stable, insoluble, and non
porous.
• If it acts as a protective film, it prevents further corrosion

by acting as barrier between metal surface and corrosive
medium.


• On the other hand, if corrosion product is unstable,
porous, and soluble it further enhances corrosion.
• For example, in oxidizing environments, metals like

aluminium, chromium, titanium, etc., are highly passive
as their oxides as corrosion products form protective
films on the metal surface, preventing further corrosion.


• Metals such as iron, zinc, magnesium etc., do not form
any protective film and are highly susceptible for
continuous corrosion, when exposed to oxidizing
environments.

pH of the medium :
• In general, rate of corrosion is higher in acidic pH (<7)

than in neutral and alkaline pH (>=7).
• In case of iron, at very high pH protective coating of iron

oxide (Fe2O3) is formed which prevents corrosion.
• Whereas, at low pH severe corrosion takes place. But for

metals like Aluminium, corrosion rate is high even at high
pH.


Temperature:
• Corrosion rate increases with increase in temperature.
• This is due to the increase in conductance of the

medium with increase in temperature and hence an
increase in the ion diffusion rate.
• As a consequence, corrosion progresses faster at higher

temperatures. In some cases, rise in temperature
decreases passivity, which again leads to an increase in
the corrosion rate.
Effect of oxygen:
• Oxygen acts as an important corroding medium. If the

metal is exposed to different concentration of oxygen,
differential aeration corrosion takes place.
• The region which is less exposed to oxygen acts as

anode hence undergoes corrosion and region exposed
to high oxygen concentration acts as cathode hence
doesn’t undergo corrosion.


Surface Roughness:
• The surface finish of the component also has an impact on

the mode and severity of the corrosion that can occur.
• Rough surfaces or crevices can facilitate the formation of

concentration cells.
• Surface cleanliness can also be an issue, with deposits or

non-uniform films acting as initiation sites.
• Biological growths can behave as deposits or change the

underlying surface chemistry to promote corrosion.
Stress:
• Stresses, either residual or applied, impact the mode of

corrosion and lower the energy needed for corrosion to
initiate.
• Stress is a requirement for stress corrosion cracking

(SCC) or corrosion fatigue, but can also influence the
rate of general corrosion.

Other Variations:
• Other variations within the metal surface on a

microscopic level influence the corrosion process.
• Microstructural differences such as

secondary/intermediate phases, grain size, grain shape
or grain orientation will also affect the way corrosion
manifests itself.

Other Variations:
• For corrosive environments where grain boundaries are

attacked, the grain size of the material plays a significant
role in how rapidly the material’s properties deteriorate.
• Chemistry variations in the matrix of weld deposits (Base

metal & the weld pool) are also a factor.

Time:
• Finally, time is a factor in determining the severity of

corrosion.
• Corrosion rates are expressed using a time dimension.
• Some corrosion processes are violent and rapid while

most are so slow as to be imperceptible on a day-to-day
basis.

Time:
• Equipment is planned to provide a useful service life.
• A chief goal in understanding corrosion is the proper

selection of materials, equipment, processes, or controls
to optimize our natural and financial resources.

3 Corrosion Principles

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CORROSION ENGINEERING

Department of Mechanical & Manufacturing Engineering, MIT, Manipal

• To view the corrosion engineering from its proper

• Following diagram shows some of the important factors that

Department of Mechanical & Manufacturing Engineering, MIT, Manipal 2 of 65

Department of Mechanical & Manufacturing Engineering, MIT, Manipal 3 of 65

• The engineering aspect of corrosion resistance cannot be

• Complete corrosion resistance almost in all media can be

• Corrosion resistance depends on many factors. These are

Department of Mechanical & Manufacturing Engineering, MIT, Manipal 4 of 65

Department of Mechanical & Manufacturing Engineering, MIT, Manipal 5 of 65

• Thermodynamics and electrochemistry are of great

• Thermodynamic studies and calculations indicate the

• While thermodynamics can predict whether a corrosion

Department of Mechanical & Manufacturing Engineering, MIT, Manipal 6 of 65

• Metallurgical factors frequently have a pronounced influence

• In many cases, the metallurgical structure of the alloy (grain

• Physics/chemistry and its various disciplines are most useful

Department of Mechanical & Manufacturing Engineering, MIT, Manipal 7 of 65

Corrosion Rate Measurements

• Measurement of corrosion is essential for the purpose of

• The compatibility of a metal with its environment is a prime

Department of Mechanical & Manufacturing Engineering, MIT, Manipal 8 of 65

Corrosion Rate Measurements

Corrosion rate measurement is necessary for

• the evaluation and selection of materials for a specific

• for a given definite application,

• for the evaluation of a new or old metal or alloy to

Department of Mechanical & Manufacturing Engineering, MIT, Manipal 9 of 65

Corrosion Rate Measurements

• Often, the corrosive environment is suitably treated to make

• In addition, corrosion rate measurement is also essential in

Department of Mechanical & Manufacturing Engineering, MIT, Manipal 10 of 65

Corrosion Rate Expressions

• Corrosion rate expressions are therefore based on either

• Corrosion rates have been expressed in a variety of ways in

Corrosion Rate Expressions

• These do not express corrosion resistance in terms of

• The most widely used weight expression, based on weight

1 mil = (1/1000)th of an inch.

Department of Mechanical & Manufacturing Engineering, MIT, Manipal 12 of 65

Corrosion Rate Expressions

• The expression mils per year (mpy) is the most desirable

Exposed area of the specimen, sq.in , T= Exposure time, h.

Department of Mechanical & Manufacturing Engineering, MIT, Manipal 13 of 65

Corrosion Rate Expressions

• One mil is one thousandth of an inch. Thus, 0.002 ipy is

• A good corrosion rate expression should involve

• Easy calculation with minimum opportunity for error

• Ready conversion to life in years

• Whole numbers without cumbersome decimals.

Department of Mechanical & Manufacturing Engineering, MIT, Manipal 14 of 65

Corrosion Rate Expressions

Conversion from other units to obtain mils per year (mpy)

Department of Mechanical & Manufacturing Engineering, MIT, Manipal 15 of 65

Electrochemical Nature of Corrosion

• The centre, or nucleus, of the atom is composed of

• The outside of the atom has negatively charged electrons in

• All atoms have the same number of protons (positively

Electrochemical Nature of Corrosion

• Most atoms have approximately the same number of

Department of Mechanical & Manufacturing Engineering, MIT, Manipal 17 of 65