Chapter –II

Principles of Corrosion
Objectives:
Understand about principles of corrosion.
 Understand about specific forms of corrosion.
 Understand about different types of corrosion.
 Understand about high temperature corrosion.

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2.1 Introduction
Corrosion
 The surface of almost all the metals begin to decay more or less
rapidly when exposed to atmospheric gases, water or other
reactive liquid medium.
 The process of decay metal by environmental attack is known as
corrosion.
 Metals undergo corrosion and convert to their oxides, hydroxides,
carbonates, sulphides etc.
E.g. Iron undergoes corrosion to form reddish brown color rust
[Fe2O3. 3H2O]. Copper undergoes corrosion to form a green film
of basic carbonate [CuCO3+ Cu (OH)2].
Causes of corrosion
 The metals exist in nature in the form of their minerals or ores, in
the stable combined forms as oxides, chlorides, silicates,
carbonates, sulphides etc.
 During the extraction of metals, these ores are reduced to metallic
state by supplying considerable amounts of energy. 2
 Cont’d
 Hence the isolated pure metals are regarded as excited states than their
corresponding ores.
 So metals have natural tendency to go back to their combined state
(minerals/ores).
 When metal is exposed to atmospheric gases, moisture, liquids etc.,and
the metal surface reacts and forms more thermodynamically stabled
compounds.

Effects of corrosion
 Wastage of metal in the form of its compounds.
The valuable metallic properties like conductivity, malleability, ductility etc. are
lost due to corrosion.
 Life span and efficiency of metallic parts of machinery and fabrications is
reduced.
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CLASSIFICATION OR THEORIES OF CORROSION

 Based on the environment, corrosion is classified into

(i) Dry or Chemical Corrosion
(ii) Wet or Electrochemical Corrosion
DRY or CHEMICAL CORROSION:
 This type of corrosion is due to the direct chemical attack of
metal surfaces by the atmospheric gases such as oxygen,
halogen, hydrogen sulphide, sulphur dioxide, nitrogen or
anhydrous inorganic liquid, etc.
 The chemical corrosion is defined as the direct chemical attack
of metals by the atmospheric gases present in the environment.
Example:
(i) Silver materials undergo chemical corrosion by Atmospheric
H2S gas.
(ii) Iron metal undergo chemical corrosion by HCl gas. 4
 Cont’d
TYPES OF DRY or CHEMICAL CORROSION:
1.Corrosion by Oxygen or Oxidation corrosion
2.Corrosion by Hydrogen
3.Liquid Metal Corrosion
1. CORROSION BY OXYGEN or OXIDATION CORROSION:
 Oxidation Corrosion is brought about by the direct attack of oxygen at
low or high temperature on metal surfaces in the absence of moisture.
 Alkali metals (Li, Na, K etc.,) and alkaline earth metals (Mg, Ca, Sn,
etc.,) are rapidly oxidized at low temperature. At high temperature, almost
all metals (except Ag, Au and Pt) are oxidized. The reactions of
oxidation corrosion are as follows:

5
 Cont’d
Mechanism:
 Initially the surface of metal undergoes oxidation and the resulting metal oxide
scale forms a barrier which restricts further oxidation.
 The extent of corrosion depends upon the nature of metal oxide.
(a) If the metal oxide is stable
 It behaves has a protective layer which prevents further corrosion.
E.g., The oxide films of Al, Sn, Pb, Cu, Cr, W etc. are stable and therefore further
corrosion is prohibited.

(b) If the metal oxide unstable, the oxide layer formed decomposes back into
metal and oxygen. So, oxidation corrosion is not possible.
E.g., Ag, Au and Pt do not undergo oxidation corrosion.

6
 Cont’d
(c) If the metal oxide layer is volatile, then the oxide layer volatilizes after
formation and leaves the underlying metal surface exposed for further
attack. This causes continuous corrosion which is excessive in
molybdenum oxide (MoO3).

(d) If the metal oxide layer is porous, the oxide layer formed has pores or
cracks. In this case the atmospheric oxygen penetrates through the pores or
cracks and corrode the underlying metal surface. This cause continuous corrosion
till conversion of metal into its oxide is completed. Ex: Alkali and alkaline
earth metals (Li, Na, K, Mg etc.)

7
 Cont’d
Pilling Bed worth rule:
 According to it “an oxide is protective or non porous, if the volume of
the oxide is at least as great as the volume of the metal from which it is
formed”. On the other hand, “if the volume of the oxide is less than the
volume of metal, the oxide layer is porous (or non-continuous) and
hence, non-protective, because it cannot prevent the access of oxygen to
the fresh metal surface below”.
 Thus, alkali and alkaline earth metals (like Li, K, Na, Mg) form oxides
of volume less than the volume of metals. Consequently, the oxide layer
faces stress and strains, thereby developing cracks and pores in its
structure.
Corrosion due to other gases:
 This type of corrosion is due to gases like H2 ,SO2, CO2, Cl2, H2S, and
F2 etc. In this corrosion, the extent of corrosive effect depends mainly on the
chemical affinity between the metal and the gas involved. The degree of
attack depends on the formation of protective or non protective films on the
metal surface which is explained on the basis of Pilling Bed worth rule.
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2.Corrosion by hydrogen gases
Hydrogen Embrittlement:
 Loss in ductility of a material in the presence of hydrogen is known
as hydrogen embrittlement.

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 Cont’d
According to Pilling Bed Worth rule,
i) If the volume of the corrosion film formed is more than the
underlying metal, it is strongly adherent; non-porous does not allow
the penetration of corrosive gases.
Ag + Cl2 2AgCl (protective film)
(ii) If the volume of the corrosion film formed is less than the underlying
metal, it forms pores/cracks and allow the penetration of corrosive
gases leading to corrosion of the underlying metal.
Ex. In petroleum industry, H2S gas at high temperature reacts with steel
forming a FeS scale.
Fe (steel) + H2S FeS (porous)
(3.) Liquid metal corrosion:
 This corrosion is due to chemical action of flowing liquid metal at
high temperatures on solid metal or alloy. The corrosion reaction
involves either dissolution of a solid metal by a liquid metal or
internal penetration of the liquid metal into the solid metal.
E.g. Coolant (sodium metal) leads to corrosion of cadmium in nuclear
reactors. 10
 Cont’d
Wet corrosion or electrochemical corrosion
 This type of Corrosion occurs where a conducting liquid is in contact
with the metal. This corrosion occurs due to the existence of separate
anodic and Cathodic parts, between which current flows through the
conducting solution. At anodic area, oxidation reaction occurs thereby
destroying the anodic metal either by dissolution or formation of
compounds. Hence corrosion always occurs at anodic parts.
Mechanism:
 Electrochemical corrosion involves flow of electrons between anode and
cathode.
 The anodic reaction involves dissolution of metal liberating free
electrons.
M Mn++ ne-
 The Cathodic reaction consumes electrons with either evolution of hydrogen or
absorption of oxygen which depends on the nature of corrosive environment.

11
Cont’d

12
Cont’d

13
 Cont’d
Difference between (dry) chemical and (wet) electrochemical corrosion

14
 Cont’d
 The electrochemical corrosion is classified into the following
two types:
(i) Galvanic (or Bimetallic) Corrosion
(ii) Differential aeration or concentration cell corrosion.
Galvanic Corrosion:
 When two dissimilar metals are electrically connected and exposed
to an electrolyte, the metal higher in electrochemical series (low
reduction potential) undergoes corrosion and the metal lower in
electrochemical series (high reduction potential) is protected. This
type of corrosion is called Galvanic corrosion.
E.g. When Zn an Cu are connected and exposed to corroding
environment, Zinc (higher in electrochemical series) forms the
anode; undergoes oxidation and gets corroded. Cu (lower in
electrochemical series) acts as cathode; undergoes reduction and
protected as the electrons released by Zn flow towards Zn. 15
 Cont’d
The figure below shows galvanic corrosion.

2.Concentration cell corrosion

This type of corrosion occurs due to electrochemical attack of the metal
surface exposed to electrolyte of varying concentrations or varying
aeration. This type of corrosion is due to
(i) Difference in concentration of metal ions.
(ii) Difference in the exposure to air/oxygen (Differential aeration
corrosion).
(iii) Difference in temperature.
16
 Cont’d
 Differential aeration corrosion is the most common type of
concentration cell corrosion. When a metal is exposed to different air
concentrations, it has been found to be poorly oxygenated of the metal
becomes anodic and well oxygenated part becomes Cathodic.
 The potential difference is created which causes the flow of electrons
from anode (metallic part immersed in NaCl solution) to cathode
(exposed to atmosphere).
Eg. Zn rod immersed deep in NaCl solution: Anode
Zn rod above NaCl solution: Cathode

17
 Cont’d
 Corrosion is a problem common to most metals used for structural
purposes.
 The basic process comprises a reaction between the metal, oxygen
and water to produce a soluble form of the metal or one of its
oxides.
 Within the oil and gas industries our main concern is the corrosion
of steel and in particular buried pipelines.
WHY METALS CORRODE
 The force that makes metals corrode is a natural consequence of
their temporary existence in the metallic form.
 To attain the metallic state from their natural form as various
chemical compounds, it is necessary to expend varying amounts of
energy from external sources, this process normally being carried
out in a furnace.
18
 Cont’d
 The more reactive a metal is with its environment, the more energy is
required to bring about the change from its natural state to the metallic form.
 It is relatively high for metals such as magnesium, aluminum and iron and
relatively low for metals such as copper, silver and gold.
 Table 1 shows materials arranged in order of the diminishing amounts of
energy required to convert them from their natural states.
Most Energy Required Potassium
Magnesium
Beryllium
Aluminum
Zinc
Chromium
Iron
Nickel
Tin
Copper
Silver
Least Energy Required Platinum
Least Energy Required TABLE 1 19
Gold
 Cont’d
 The most common example, for our purposes, is the conversion of
iron ore, hematite to metallic iron for alloying to steel. As an oxide
(Fe203) in its natural state, iron ore has the same composition as
rust.
 The energy required to convert iron ore to metallic iron is returned
slowly as the material corrodes and in so doing produces iron oxide
or rust.
 The only difference between conversion of oxide to metallic iron
and metallic iron to oxide is the rate at which the energy is
expended.
 The relative difficulty of extracting metals from their ores, in terms
of energy required and the tendency to release that energy during
the corrosion process, is reflected by the positions of pure metals in
a list where the energy involved determines its position on the list,
and is known as the Electromotive series, the more common
elements of which are shown on Table 2.

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 Cont’d
METAL ION FORMED POTENTIAL
Potassium K+ -2.92

Magnesium Mg++ -2.40

Aluminum Al+++ -1.70

Zinc Zn++ -0.76

Chromium Cr++ -0.56

Iron Fe++ -0.44

Nickel Ni++ -0.23

Tin Sn++ -0.14

Hydrogen H+ 0.00

Copper Cu++ +0.47

Silver Ag+ +0.80

Gold Au+ +1.50

TABLE 2 21
2.3 THE CORROSION REACTION
 Corrosion may be defined as: “The destruction of a metal or its
properties by chemical or electro-chemical reaction with its
environment”. The dissolution of the metal is electro-chemical in
nature. That is, it is basically a chemical reaction accompanied by
the passage of an electric current.
For corrosion to occur, all of the following conditions must be present:
(1) There must be an anode and a cathode.
(2) There must be a potential difference between the anode and the
cathode.
(3) There must be a metallic path connecting the anode and the
cathode.
(4) There must be a conducting electrolyte surrounding both the anode
and the cathode.
 The anode is the area at which oxidation or corrosion occurs where
the current leaves the metal to enter the electrolyte.
 The cathode is the area at which reduction or negligible corrosion
occurs where the current leaves the electrolyte to enter the metal.22
 Cont’d
 The electrolyte is a solution in which the conduction of electric current
occurs by the passage of dissolved ions.
 When the above conditions are met an electric current will flow and
metal will be consumed at the anode, i.e. the anode corrodes. See Fig. 1.
a. Corrosion occurs by an electrochemical process.
 The phenomenon is similar to that which takes place when a carbon-zinc
“dry” cell generates a direct current. Basically, an anode (negative
electrode), a cathode (positive electrode), an electrolyte (environment),
and a circuit connecting the anode and the cathode are required for
corrosion to occur (see Figure 1).

23
 Cont’d
 Dissolution of metal occurs at the anode where the corrosion current enters
the electrolyte and flows to the cathode. The general reaction (reactions, if
an alloy is involved) that occurs at the anode is the dissolution of metal as
ions:
M → M n+ + e n- ……. (Eq 1)
Where
M = metal involved
n = valence of the corroding metal species
e = electrons
Examination of this basic reaction reveals that a loss of electrons, or oxidation,
occurs at the anode. Electrons lost at the anode flow through the metallic
circuit to the cathode and permit a Cathodic reaction (or reactions) to occur.
In alkaline and neutral aerated solutions, the predominant Cathodic reaction
is
O2 + H2O + 4e- → 4(OH) ……….Eq (2)
The Cathodic reaction that usually occurs in deaerated acids is
2H+ + 2e- → H2……………. Eq(3)
In aerated acids, the Cathodic reaction could be
O2 + 4H+ + 4e- → 2H2O …………. Eq (4)
 All of these reactions involve a gain of electrons and a reduction process…24
 Cont’d
Galvanic series:
 In the electrochemical series, a metal high in the series is more
anodic and undergoes corrosion faster than the metal below it.
 For example, Li corrodes faster than Mg; Zn corrodes faster than
Fe; Fe corrodes faster than Sn; Cu corrodes faster than Ag and so
on.
 However, some exceptions to this generalization are known. For
example, Ti (above Ag in the electrochemical series) is less
reactive than Ag. In Zn-Al couple, Zn (below Al in the
electrochemical series) is corroded; while Al acts Cathodic and is
protected.
 From the above, it is clear that electrochemical series does not
account for the corrosion of all metals and consequently, a more
practical series, called galvanic series have been prepared by
studying the corrosion of metals and alloys in a given environment.
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 Cont’d
 The figure below shows the galvanic series of metals and alloys.

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 Factors which influence the rate of corrosion
 Factors influencing corrosion:
i) Nature of metals
ii) Nature of the corroding environment
I. Nature of metals:
1) Position in galvanic series:-The metal higher in series is more active and suffers
corrosion. The rate and extent of corrosion is directly proportional to electrode
potential difference between them.
2) Over voltage: - when a metal, which occupies a high position in galvanic series
(say Zinc), is placed in H2SO4, it undergoes corrosion forming a film and
hydrogen gas.
The initial rate of reaction is quite slow, because of high over voltage (0.70V) of the
zinc metal, which reduces the effective electrode potential to a small value.
However, if few drops of copper sulphate (CuSO4) are added, the corrosion rate
of zinc is accelerated, because some copper gets deposited on the zinc metal
forming minute cathodes, where the hydrogen over voltage is only 0.33V, thus,
reduction in over voltage of the corroding metal/ alloy accelerates the corrosion
rate. Zn has over hydrogen voltage due to which the rate of corrosion of Zn is
very slow (Zn rod dipped in ZnSO4). (Over voltage of zinc metal is 0.73) 27
 Cont’d
3) Purity of metal:-Impurity of a metal generally causes heterogeneity
and form minute electrochemical cells and the anodic part gets
corroded. For e.g.: Zn metal containing impurity such as Pb ( or) Fe
undergoes corrosion.
 The rate and extent of corrosion increases with extent of impurities.
4) Passivity of metal: Metals like Ti, Al, Cr and Ni are passive they
exhibit much higher corrosion resistance, due to the formation of
highly protective on the metal. Moreover the film is self healing
nature. Thus corrosion resistance of stainless steel is due to passive
character of Cr.
5. Physical state of metal:
 The rate of corrosion is influenced by physical state of the metal.
The smaller the grain-size of the metal or alloy, the greater will be
its solubility and hence, greater will be its corrosion.
28
 Cont’d
6. Nature of surface film:
 If the corrosion product formed is more stable, insoluble and non-
porous, it acts as protective layer and prevents further corrosion (Eg.
Ti, Al and Cr). If the corrosion product is porous, volatile and soluble, it
further enhances the corrosion (Fe, Zn and Mg).
II Nature of the corroding environment:-
1) Temperature: With increase of temperature, the corrosion rate also
increases because the reaction as well as diffusion rate of ions in the
corrosion medium increases.
2) Humidity: The higher the humidity of the atmosphere the greater is rate
and extent of corrosion because the moisture acts as medium for O2 in air
and behaves as an electrolyte.
For e.g. Atmospheric corrosion of iron is slow in dry air compound to moist
air. Iron combines with O2 and water to form ferrous hydroxide which
combines with atmospheric CO2 to form ferrous bicarbonate.
2Fe +O2+2H2O–-------> 2Fe (OH)2
Fe (OH)2+ CO2–------>Fe (HCO3)2
3) PH value: PH value of the medium has the greater effect on corrosion.
Generally Acidic media (i.e., pH <7) are more corrosive than alkaline
and neutral media. 29
 Cont’d
4) Presence of impurities:
 Atmosphere is contaminated with gases like CO2, SO2, H2S; fumes of H2SO4,
HCl etc. and other suspended particles in the vicinity of industrial areas. They
are responsible for electrical conductivity, thereby increasing corrosion.
5) Amount of oxygen in atmosphere:
 As the percentage of oxygen in atmosphere increases, the rate of corrosion also
increases due to the formation of oxygen concentration cell. The decay of metal
occurs at the anodic part and the Cathodic part of the metal is protected.

30
 Cont’d

THE END!!!

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