Engineering/Applied Chemistry

CODE NO: 07A1BS07/04

I B.TECH
MECHNICAL/CIVIL ENGINEERING
Unit No: III
Nos. of slides: 122
 Engineering/Applied Chemistry
CORROSION SCIENCE
Term: 2008-09

Unit-III Power Point Presentations

Text Books:
 A text book of Engineering Chemistry by
Jain & Jain,
 Chemistry of Engineering Materials by C.P.
Murthy, C.V. Agarwal and A. Naidu
L1-
 INDEX
UNIT-III PPTS
Srl. Module as per Lecture PPT
No. Session Planner No. Slide No.
-------------------------------------------------------------------------------------------------
• Introduction , Definition, Examples L-1 L1-1 to L1-19
2. Types of Corrosion L-2 L2-1 to L2-28
3. Principles of Corrosion L-3 L3-1 to L3-18
4. Mechanism of Wet Corrosion L-4 L4-1 to L4-18
5. Factors Influencing Corrosion. Control of Corrosion L-5 L5-1 to L5-19

L1-
 It may be defined as

“The destruction of a
metallic material by
chemical, electrochemical,
or metallurgical interaction
between the environment
and the material”.

L1-1
 It may be defined as

 The term corrosion does not cover the

destruction of non-metallic materials like
plastic.
 Wood, ceramics etc., by the environment.
It is distinct from erosion which is the
physical wearing away of metals by the
surroundings.
 Rusting of Iron based on Electrochemical
Theory of corrosion
L1-2
L1-3
L1-4
L1-5
L1-6
L1-7
L1-8
L1-9
L1-10
• Metals have a natural tendency to
revert back to combined states.
During this process mostly, oxides
are formed though in some cases
sulphides, carbonates, subparts
etc.m may result due to presence of
impurities. Any process of
deterioration and loss of solid
metallic material by chemical or
electrochemical attack by its
environment is called corrosion.
Corrosion is the reverse process of
L1-11
 Corrosion (Oxidation)
Metal Metallic compound + energy
Metallurgy (Reduction)
e.g., rusting of iron when exposed to
atmospheric conditions. Rust is
hydrated oxide (Fe2O3.xH2O).

L1-12
 TYPES OF CORROSION
Several types of Corrosion occur:
• Dry (or) Chemical Corrosion
• This type of Corrosion occurs mainly
through the direct chemical action of
atmospheric gasses (O2, halogen,
H2S.SO2.N2.or anhydrous inorganic
liquid) with metal surpasses in
immediate proximity.

L2-
Oxidation Corrosion:
This is carried out by the direct
action of oxygen low or high
temperatures on metals in absence
of moisture at ordinary temperature
metals or very slightly attacked. The
Exceptions are Alkali metals and
Alkaline earth metals. At high
temperature all metals are oxidized.
The exception is Ag, Au and Pt.

L2-
 2Mn 2Mn++2ne-
(De- electro nation)
(Metal ion)
nO2+2ne- 2nO2-
(Electronation)
(Oxide ion)
2M+ nO2 2Mn+ +
2nO2-
(Metal oxide)

L2-
 Mechanism:
• At the surface of metal oxidation occurs
and the resulting metal oxide scale forms a
barrier which restricts further oxidation.
• For oxidation to continue either the metal
must diffused out wards through the scale to
the surface or the oxygen must defuse in
wards through the scale to the underlying
metal.
• Both the cases are possible.
• But the out word diffusion of metal is
generally more rapid than inward diffusion of
oxygen since metal ion is appreciably smaller
than the oxygen ion and hence more mobile.
L2-
Metal + Oxygen Metal oxide
When oxidation starts, a thin layer of oxide
is formed on the metal surface and the
nature of this film decides further action.
If the film is,
stable, it behaves has a protective coating in
nature e.g., the oxide films on Al,Pb,Cu,Pt
etc., are stable and therefore further
oxidation correction of prohibited.
Unstable that is the oxide layer formed
decomposes back into metal and oxygen.
So, oxidation Corrosion is not possible.
Metal oxide Metal + Oxygen
e.g., Ag, Au and Pt do not undergo oxidation
Corrosion.
L2-
• Volatile that is oxide layer volatilizes after
formation and as such leaves the
underlying metal surface exposed further
attack.
• This causes continuous which is
excessive.e.g. Molybdenum oxide (MoO3)
• Porous that is the oxide layer formed
having pores or cracks.
• In this case the atmospheric oxygen passes
through the pores or cracks of the
underlying metal surface.
• This causes continuous corrosion till
complete conversion of metal into its oxide.
L2-
• Wet or Electrochemical Corrosion.-
• This type of Corrosion occurs
• Where a conducting liquid is in contact
with the metal or
• When two dissimilar metals or alloys are
dipped partially in a solution.
• 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.
• L2-
Hence corrosion always occurs at anodic
At Anode: M Mn+ + ne-
Mn+ dissolution
Formation of compound

L2-
• At cathodic part, reduction reaction
(electro nation) occurs.
• It does not affect the cathode, since
most metals cannot be further
reduced.
• At cathodic part, the dissolved
constituents in the conducting
medium accepts the electrons
forming ions (OH-, O2-).
• The metallic ions formed at anodic
part and the ions formed at cathodic
part diffuse towards each other
through conducting medium and form
L2-
 Red-brown
flaky rust

L2-
Black
magnetite
L2-
 Blue/green
unstable
L2-
rust
Mechanism:

• Electrochemical corrosion involves

flow of electrons between anode and
cathode.
• The anodic reaction involves
dissolution of metal liberating free
electrons.

L2-
•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.

L2-
L2-
i) Evolution of hydrogen
• This type of corrosion occurs in acidic
medium e.g., considering the metal Fe,
anodic reaction is dissolution of iron as
ferrous ions with liberation of electrons.
• Fe Fe2+ + 2e- ( Oxidation)
• The electrons released flow through the
metal from anode to cathode, whereas
H+ions of acidic solution are eliminated as
hydrogen gas.

L2-
• 2H++2e‑ H2
• The overall reaction is
•
Fe+ H++ Fe2+ + H2
• This type of corrosion causes displacement
of hydrogen ions from the solution by
metal ions.
• All metals above hydrogen in
electrochemical series have a tendency to
get dissolved in acidic solution with
simultaneous evolution of H2 gas.
• The anodes are large areas, whereas
cathodes are small areas.
L2-
 ii) Absorption of oxygen
• For example, rusting of iron in neutral
aqueous solution of electrolytes in presence
of atmospheric oxygen. Usually the surface
of iron is coated with a thin film of iron oxide.
If the film develops cracks, anodic areas are
created on the surface. While the metal parts
act as cathodes. It shows that anodes are
small areas, while the rest metallic part
forms large cathodes.
• At anode: Fe Fe2+ + 2e-
(Oxidation)
L2-
At cathode:
The released electrons flow from anode to cathode
through iron metal.
½ O2 + H2O + 2e- 2OH- (Reduction)

Fe2+ + 2OH- Fe(OH)2

If oxygen is in excess, ferrous hydroxide is easily
oxidised to ferric hydroxide.
4Fe2+ (OH)2 + O2 + 2H2O 4Fe (OH)3
The product called yellow rust corresponds to Fe2O3.
xH2O.

If apply of oxygen is limited, the corrosion product may

be black anhydrous magnetite (Fe3O4).

L2-
 Concentration Cell
Corrosion
•This type of corrosion is due to electrochemical attack
on the metal surface exposed to an electrolyte of
varying concentrations or of varying aeration.
•The most common type of concentration cell corrosion
is the differential aeration corrosion which occurs when
one part of metal is exposed to different air
concentration from other part.
• This causes a difference in potential between the
differently aerated areas. Experimentally it has been
observed that poor oxygenated parts are anodic.
• Differential aeration of metal causes a flow of current
called the differential current.

L3-
L3-
•If a metal e.g., Zn is partially immersed in a
dilute solution of a neutral salt e.g., NaCl and
the solution is not agitated properly,
•then the parts above and adjacent to the
waterline are strongly aerated and hence
become cathodic.
•Whereas parts immersed show a smaller
oxygen concentration and become anodic.
•so there is a difference of potential which
causes flow of current between two
differentially aerated areas of same metal.
• Zinc will dissolve at anodic areas and
oxygen will take up electrons at the cathodic
areas
L3-
forming hydroxyl ions.
 Zn Zn2+ + 2e- (Oxidation)

½ O2 + H2O + 2e- 2OH-

(Reduction)

L3-
 Following are the facts about
differential aeration corrosion:
• Less oxygenated part is the anode.
Therefore cracks serve as foci for corrosion.
• Corrosion is accelerated under
accumulation of dirt, scale or other
contaminations.
• This restricts the access of oxygen resulting
an anode to promise greater accumulation.
• The result is localized corrosion.
• Metals exposed to aqueous media corrode
under blocks of wood or glass which
restricts the access of oxygen.
L3-
 Galvanic
Corrosion

L3-
• When two dissimilar metals are
electrically connected and exposed
to an electrolyte, the metal higher in
electrochemical series undergoes
corrosion.
• This type of corrosion is called
Galvanic corrosion.
• e.g, Zinc (higher in electrochemical
series) forms the anode and is
attacked and gets dissolved; whereas
copper (lower in electrochemical
series) acts as cathode.
L3-
Mechanism
• If the solution is acidic then corrosion
occurs by hydrogen evolution
process and if the solution is neutral
or slightly alkaline in nature then
corrosion occurs by oxygen
absorption process.
• The electrons flow from the anodic
metal to the cathodic metal.
• Zn Zn2+ + 2e- (Oxidation

L3-
• Thus the corrosion is a localized
accelerated attack resulting in the
formation of pits, holes or cavities.

• Pitting corrosion therefore results in

the formation of pinholes, pits and
cavities in the metal.

L3-
The pitting corrosion may be due to
following reasons:
• Metal surface are not homogeneous.
• External environment is not
homogeneous.
• Films are not perfectly uniform.
• Crystallography directions are not
equal in the reactivity.
• Environment is not uniform with
respect to concentration.
L3-
• Pitting is usually the result of the
breakdown or cracking of the
protective film on a metal at specific
points.
• This gives rise to the formation of
small anodic and large cathodic
areas.
• In process of correct environment
this produces corrosion current.

L3-
L3-
L3-
L3-
L3-
• e.g., Stainless steel and aluminum show
characteristic pitting on chloride solution.
• Pitting is caused by the presence of sand,
dust scale and other extraneous impurities
present on the metal surfaces.
• Because of differential amount of oxygen
in contact with the metal , the small part
(underneath the impurity) become the
anodic areas and the surrounding large
parts become the cathodic areas.
• Intense corrosion takes place in the anodic
areas underneath the impurity.
• Once a small pit is generated, the rate of
corrosion will be increased
L3-
 Waterline Corrosion
• This s also known as differential oxygen
concentration corrosion.
• In general, when water is stored in a steel tank, it is
observed that the maximum amount of corrosion
takes place along a line just beneath the level of the
water meniscus.
• The area above the waterline (highly oxygenated)
acts as cathodic and is not affected by corrosion.
• However, if the water is relatively free from acidity,
little corrosion occurs.
• The problem of waterline corrosion is a matter of
concern for marine engineers.
• This type of corrosion is prevented to a great extent
by painting the sides of the ships by antifouling
paints.
L3-
 Erosion Corrosion
Erosion Corrosion results by the combined effect of the
abrading action of vapours, gases and liquids and
the mechanical rubbing action of solids over the
surface of metals.
• This type of corrosion is caused by the breakdown of
a protective film at the spot of impingement and its
subsequent inability to repair itself under existing
abrading action removes protective films from
localized spots on the metal surface, thereby
resulting in the formation of differential cell at such
areas and localized corrosion at anodic points of the
cells.
• Erosion corrosion is most common in agitators,
piping, condensers, tubes and vessels in which
steams of liquids or gases emerge from an opening
and strike the side walls with high velocities.
L3-
 Pitting corrosion:
• Pitting corrosion is a localized accelerated
attack, resulting in the formation of cavities
around which the metal is relatively
unattacked.
• Thus pitting corrosion results in the
formation of pinholes, pits and cavities in
the metal.
• Pitting is usually the result of the
breakdown or cracking of the protective film
on a metal at specific points.
• This gives rise to the formation of small
anodic and large cathodic areas. In the
L4-
Pitting corrosion:
• The presence of the extraneous impurities
(like sand, dust, scale etc.), embedded on the
surface of the metals, also lead to pitting
once a small pit is formed, the rate of
corrosion will be increased.
• If the presence of some extraneous
impurities like sand, dust and scale is
checked, pitting can be reduced.
• If the concentration of oxygen is uniform,
then also pitting is reduced.
• Otherwise differential aeration corrosion
takes place leading to pitting.

L4-
Fe2+ + 2OH-  Fe(OH)2
Corrosion product
More oxygenated cathode More oxygenated cathode
H2O + ½ O2 + 2 e- 2 OH- H2O + ½ O2 + 2 e- 2 OH-

L4-
 Stress corrosion:
stress corrosion is the combined effect of static
tensile stresses and the corrosive environment on
the metal.
It is characterized by a highly localized attack
occurring, when overall corrosion is negligible.
For stress corrosion to occur:
4.Presence of tensile stress, and
5.2. a specific corrosive environment are necessary.
The corrosive agents are highly specific and selective
such are
a. Caustic alkalis and strong nitrate solution for mild
steel.
b. Traces of ammonia for brass,
c.
L4- acid chloride solution for stainless steel.
L4-
Stress corrosion:
This type of corrosion is seen in fabricated
articles of certain alloys like high-zinc
brasses and nickel brasses due to the
presence of stresses caused by heavy
working like rolling, drawing or insufficient
annealing.
• However, pure metals are relatively
immune to stress corrosion.
• Stress corrosion involves in a localized
electrochemical corrosion, occurring along
narrow paths, forming anodic areas with
respect to the more cathodic areas at the
L4-
metal surface.
Stress corrosion:
Presence of stress produces strains,
which result in localized zones of
higher electrode potential.
• These become so chemically-active
that they are attacked, even by a mild
corrosive environment, resulting in
the formation of attack, which grows
and propagates in a plant, until failure
occurs or it may stop, after
progressing a finite distance.
L4-
ELE CT ROCH EM ICA
L C OR ROS ION

L5-1
 Electrochemical corrosion is a
process is a resulting in part or all
of the metal being transformed from
the metallic to the ionic state. This
corrosion mostly occurs under wet
or moist conditions through the
formation of short-circuited
galvanic cells. It is a fast process
which involves the setting up of a
large number of galvanic cells.
L5-2
 It involves separate anodic and cathodic parts
between which current flows through the
conducting medium.
 Since, oxidation reaction takes place at anodic
areas, corrosion destroying the metal by either
dissolving or assuming combined state.
 M  M+n + ne- (oxidation)
 M+n  dissolves in solution
 Therefore, reduction reaction takes place at
cathodic areas which do not affect the cathode,
since most metals cannot be further reduced. At
cathodic area
 M+ + ne-  (Reduction)
L5-3
 Stainless steel is resistant to
corrosion and its surface remains
bright because, while in contact
with the atmosphere or with
oxidizing solutions, a passive film of
Cr2O3 is formed on the surface
which protects the underlying
metal. The most common steel of
this class is known as 18-8 stainless
steel and is widely used for making
household utensils.
L5-4
 Compared to Fe, stainless steel
is able to withstand the
corrosive action of the
atmosphere due to the
protective action o the oxide
film on the surface. Therefore
stainless steel is resistant to
atmospheric conversion.
L5-5
L5-6
 Iron or steel is anodic with respect to copper.
When iron in contact with copper is exposed to
atmosphere, galvanic corrosion starts and the
anodic metal (iron) starts corroding.
 more over, it causes rapid and intense corrosion
(or destruction).
 Hence, iron in contact with copper corrodes more
readily structure of the oxide has affinity or oxygen
than the host metal the structure of the oxide and
the metal match so well that the oxide layer is
coherent.

L5-7
GALVANIC
CORROSION

L5-8
 Galvanic corrosion may occur two
different metals are in contact and jointly
exposed to corrosion atmosphere.
 Zinc and copper, zinc and silver, iron and
copper constitute galvanic couples.
 In zinc and copper galvanic cell, zinc
behaves as anode where oxidation and
corrosion occurs and copper behaves as
cathode and is protected.

L5-9
 The difference in electrical potential
between the two metals provides as the
driving force to pass through the
corrodent and results in corrosion of the
anodic metal close to the junction of the
two metals.
 The larger the potential difference
between the two metals, the greater may
be the galvanic corrosion.

L5-10
Hence, t his ca n be
mi ni mi zed b y

1. Avoiding galvanic couple

2.Providing an insulating material between
the two metals.

L5-11
DIFFERENTIAL
AERATION
CORROSION

L5-12
 it occurs when a metallic surface is
partially immersed in an electrolyte and
partially exposed to air as shown in the
figure below.
 Poorly oxygenated metallic part becomes
anodic and undergoes oxidation.
 Zn  Zn +2 + 2e-

L5-13
 Well oxygenated part
becomes cathodic. At the
cathode, O2 takes up
electrons to form OH- ions.
The Zn+2 and Oh- ions
interact to give Zn(OH)2.
Thus the corrosion occurs at
anode.
L5-14
 An Iron rod partly immersed in water
undergoes corrosion near waterline because
of differential aeration.
 The rod above and closely adjacent to the
waterline is more strongly aerated and hence
becomes cathodic, while the lower part of rod
immersed in water is less-oxygenated and
hence becomes anodic.

L5-15
 So, a difference of potential is created
and electrochemical corrosion takes
place.
 This causes corrosion of the anodic part.
 Hence, iron rod starts corroding at the
bottom i.e., near waterline.

L5-16
 Corrosion inhibitors are those substances
which when added in a small quantity to
the corrosive environment, effectively
reduces the corrosion rate.

L5-17
 ANO DI C IN HI BI TORS:
 Anodic inhibitors are those which prevent the
corrosive reaction occurring at anode by reacting
with the ions of the anode and forming insoluble
precipitates.
 The precipitate thus absorbed on the surface of the
metal and forms a protective coating resulting in
reducing the corrosion rate.
 If insufficient inhibitors are used, it results in certain
area unprotected leading to severe local attack.
 The anodic inhibitors used are phosphates,
chromates, molybdates, alkalis, tungstates etc.
L5-18
CA THOD IC INH IBI TORS:
 The cathodic reaction occurs in acidic
solution is the evolution of hydrogen given as
2 H+ + 2e-  H2
 The diffusion of hydrogen ions in the acidic
solution can be slowed by using organic
inhibitors like a mines, mercaptanes, and
heterocyclic nitrogen compounds etc. This
organic inhibitor is absorbed at the metal
surface and reduces the corrosion rate.
 The cathodic reaction occurs at the neutral
solution is H2O
L5-19
FACTORS
INFLUENCING
CORROSION

L6,7-1
 The rate and extent of
corrosion depends on the
nature of the metal and
nature of corroding
environment.
L6,7-2
 NATURE OF METAL:

 Position in galvanic series: when 2

metals or alloys are in electrical
contact in presence of an electrolyte
the more active metal having higher
position in the galvanic series
undergoes corrosion. The greater is
the difference in position, the faster is
the corrosion
L6,7-3
  Mg
 Mg alloys
 Zn
 Al
 Cd
 Al alloys
 Mild steel
 Cast Iron
 high Ni cast Iron
 Pb-Sn solder
 Pb
 Sn
 Iconel
 Ni-Mo-Fe alloys
 Brass
 Monel
 Silver solder
 Cu
 Ni
 Cr stainless steel
 18-8 stainless steel
 18-8 Mo stainless steel
 Ag
 Ti
 Graphite
 Au
 Pt
L6,7-4
 Mg
Mg alloys
Zn
Al
Cd
Al alloys

L6,7-5
 Pb-Sn solder
Pb
Sn
Iconel
L6,7-6
Ni-Mo-Fe alloys
Brass
Monel
Silver solder
Cu
Ni

L6,7-7
 Cr stainless steel
18-8 stainless steel
18-8 Mo stainless
steel
Ag
Ti
Graphite
Au
Pt
L6,7-8
 Electrochemical
seriesGalvanic series
 This series consists of metals and
non-metals
 The position of a metal in this series
is permanently fixed.
 It predicts the relative displacement
tendencies.
 Electrode potentials are measured by
dipping pure metals in their salt
solution of 1M concentration.
L6,7-9
 This series consist of metals
and alloys.
Position of pure metal and
when present in the form of
alloy is different.
It predicts the relative
corrosion tendencies.
Corrosion of metals and alloys
is studied in unpolluted sea
water.
L6,7-10
 Over voltage:
 reduction in overvoltage of the
corroding metal accelerates the
corrosion rate. E.g. Zn in 1N H2SO4
undergoes corrosion slowly because
of high overvoltage of zinc metal (0.7
V) which reduces the effective
potential to a small value. In
presence of CuSO4 the corrosion rate
of zinc is accelerated.
L6,7-11
 Relative areas of anodic
and cathodic parts:
 When 2 dissimilar metals are in
contact, the corrosion of the anodic
part is directly proportional to the
ratio of areas of cathodic part and
the anodic part. Corrosion is rapid
and localized if anodic area is small,
because the current density at a
smaller anodic area is greater.
L6,7-12
 Purity of Metal:
 Impurities in a metal generally cause
heterogeneous state forming minute
electrochemical cells resulting
corrosion of anodic part. E.g. Zinc
metal with impurities Pb or Fe.
Corrosion resistance of a metal may
be improved by increasing its purity.

L6,7-13
 Physical state of Metal:
 The rate of corrosion is influenced by
physical state of the metal such as
grain size, stress; orientation of
crystals etc., The smaller the grain
size of even in pure metal becomes
the anode undergoing corrosion.

L6,7-14
 Nature of surface film:
 In aerated atmosphere, all metals get
covered with a thin surface film of
metal oxides. The ratio of the
volumes of metal oxides to the metal
is known as specific volume ratio.
Greater is this value lesser is the
oxidation corrosion rate.

L6,7-15
 Passivity of Metal:
 Passive metals are resistant to
corrosion due to the formation of
highly protective but very thin film
on the metal or alloy surface E.g.
Corrosion resistance of stainless steel
is due to passivity character of
Chromium present in it.

L6,7-16
 Solubility of corrosion
products:
 In electrochemical corrosion if the
corrosion product is soluble in the
corroding medium then corrosion is
rapid. If the corrosion product is
insoluble, then acts as barrier
thereby suppressing further
corrosion.

L6,7-17
 Volatility of corrosion
products:
If the corrosion product is
volatile, then the underlying
surface is exposed for further
attack. This causes rapid and
continuous corrosion. E.g.
MoO3 is volatile.

L6,7-18
 Nature of corroding
environment:
Temperature: As the temperature of
environment is increased the reaction rate
is increased thereby accelerating
corrosion.

 Humidity of air: critical humidity is

defined as the relative humidity above
which the atmosphere corrosion rate of
metal increases sharply. The value of
critical humidity depends on nature of
metal and corrosion products.
L6,7-19
 Corrosion of a metal is furnish in humid
atmosphere because gases (CO2, O2) and
vapours present in atmosphere furnish
water to the electrolyte essential to
establish an electrochemical corrosion cell.
The oxide film on the metal surface has
the property to absorb moisture. In
presence of this absorbed moisture,
corrosion rate is enhanced. Rain water
may also wash away the oxide film from
the metal surface. This leads to enhanced
atmospheric attack. The exceptions are Cr,
Al.
L6,7-20
 ANODIC INHIBITORS
 Anodic inhibitors are those which prevent
the corrosive reaction occurring at anode
by reacting with the ions of the anode and
forming insoluble precipitates. The
precipitate thus absorbed on the surface of
the metal and forms a protective coating
resulting in reducing the corrosion rate. If
insufficient inhibitors are used, it results in
certain area unprotected leading to severe
local attack. The anodic inhibitors used are
phosphates, chromates, molybdates,
alkalis, tungstates etc.
L6,7-21
 CATHODIC INHIBITORS:
 The cathodic reaction occurs in acidic
solution is the evolution of hydrogen given
as 2 H+ + 2e-  H2
 The diffusion of hydrogen ions in the acidic
solution can be slowed by using organic
inhibitors like a mines, mercaptanes, and
heterocyclic nitrogen compounds etc. This
organic inhibitor is absorbed at the metal
surface and reduces the corrosion rate.

L6,7-22
 The cathodic reaction occurs at the neutral
solution is H2O + ½ O2 + 2e-  2OH-
 In this, the corrosion reaction rate can be
controlled by reducing the diffusion of
oxygen to the cathodic area or by removing
oxygen from the corroding medium. For this,
Na2SO3 is used to eliminate O2 and Mg, Zn
or Ni salts are used to reduce the diffusion
of O2 to the corroding area.
 These inhibitors react with OH- ions at the
cathode forming a layer of insoluble
hydroxides which are impermeable and
hence reduce the diffusion of oxygen to
L6,7-23
 VAPOUR PHASE INHIBITORS:
 These are organic inhibitors which
readily sublime and form a protective
layer on the surface of the metal.
 Example: Diclohexyammonium nitrite
is used for the protection of
machineries and sophisticated
equipments.

L6,7-24
 CATHODIC PROTECTION
 The cathodic protection of metals is
used to control corrosion metals
where it is impractible to alter the
nature of the corrosion medium. The
principle involved in this method is to
protect metals and alloys from
corrosion by making them
completely cathodic. Since there will
not be any anodic area on the metal,
therefore corrosion does not occurs.
L6,7-25
 The following are 2 types of
cathodic protections.

 Sacrificialanodic protection
 Impressed current cathodic
protection

L6,7-26
 Sacrificial anodic protection:
 In this method, the metal structure can be
protected from corrosion by connecting it with
wire to a more anodic metal.
 As this more active metal is sacrificed in the
process of saving metal from corrosion, it is
known as sacrificial anode.
 The metals which are commonly used as
sacrificial anodes are Mg, Zn, Al and their
alloys. The important applications of this
method are
 Protection of underground cables and
pipelines from soil corrosion.
 Protection of ships and boat hulls from marine
corrosion.
 Prevention of rusty water by inserting Mg
sheets or rods into domestic water boilers or
tanks.
L6,7-27
Impressed current cathodic
protection:
 As the name implies, an impressed current
is applied to convert the corroding metal
from anode to cathode. The applied
current is in opposite direction since to
nullify the corrosion current. This can be
accomplished by applying sufficient
amount of direct current source like
battery or rectifier to an anode like
graphite, high silica iron, stainless steel or
platinum buried in the soil or immersed in
the corrosion medium. And connected to
the corroding metal structure which is to
be protected as shown in the diagram
below..
L6,7-28
 In impressed current cathodic
protection, electrons are supplied
from an external cell, so that the
object itself becomes cathodic and
not oxidized. This type of cathodic
protect ion has been applied to
buried structures such as tanks and
pipelines, transmission line-towers,
marine piers, laid-up ships etc. since,
their operating and maintenance
costs are less, they are well suited
for large structures and long term
L6,7-29
 CORROSION CONTROL
METHODS:

L8,9-1
The corrosion methods are as
follows

 1. Proper Designing
 2. Using Pure metal
 Using Metal alloys
 Cathodic Protection
 Modifying the Environment
 Use of Inhibitors
 Application of Protective coatings

L8,9-2
 Proper Designing
 The design of the material should be such
that, even if the corrosion occurs, corrosion is
uniform and doesn’t result in intense and
localized corrosion. Important design
principles are,
 Avoid the contact of dissimilar metals in the
presence of a corroding solution.
 When 2 dissimilar metals are to be in contact,
the anode metal should have as large area as
possible, whereas the cathode metal should
have as much smaller area as possible.
 If 2 dissimilar metals in contact have to be
used, they should be as close as possible to
each other in the electrochemical series.
L8,9-3
 Whenever the direct joining of dissimilar
metals, is unavoidable, an insulating
fitting may be applied in-between them
to avoid direct metal electrical contact.
 The anode metal should not be painted
or coated, when in contact with a
dissimilar cathodic metal, because any
break in coating would lead to rapid
localized corrosion.
 Prevent the occurrence of in
homogenitics, both in the metal and in
the corrosive environment.
L8,9-4
 Itis desirable that the design allows
for adequate clearing and flushing of
the critical parts i.e., susceptible to
dirt, deposition, etc. for the
equipment.
 Whenever possible, the equipment
should be supported on legs to allow
free circulation of air and prevent the
formation of stagnant pools or damp
areas.

L8,9-5
 Uniform flow of corrosion liquid is
desirable, since both stagnant areas
and highly turbulent flow and high
velocities can cause accelerated
corrosion. So, highly impingement
conditions of flowing liquid should be
avoided as much as practically
possible.
 A proper design should prevent
condition subjecting some areas of
structure to stress (cold-worked part).
L8,9-6
 USING PURE METAL:
 Impurities in a metal cause heterogeneity,
which decreases corrosion-resistance of the
metal.
 Thus, the corrosion-resistance of a given
metal may be improved by increasing its
purity.
 Purification of metals like Al, Mg, etc.,
provides a coherent and impervious
protective oxide film on their surface, when
ex[posed to environment.
 However, corrosion-resistance of a purified
L8,9-7
 USING METAL ALLOYS:
 Noble, but precious metals such as
platinum and gold are corrosion-
reistant. Corrosion-resistance of most
metals is best increased by alloying
them with suitable elements.
 But for maximum corrosion-
resistance, alloy should completely
homogeneous.
 Chromium is the best suitable
alloying metal for iron or steel.
L8,9-8
 CATHODIC PROTECTION:
The principle involved in this
method is to force the metal
to be protected to behave
like a cathode.
There by corrosion does not
occur. There are 2 types of
cathodic protections.
L8,9-9
 Sacrificial Anodic
Protection Method:
 Inthis protection method, the metallic
structure is connected by a wire to a
more anodic metal, so that all the
corrosion is concentrated at this more
anodic metal.
 The more anodic metal itself gets
corroded slowly, while the parent
structure is protected.

L8,9-
 Impressed Current
Cathodic Protection:
In this method, an impressed
current is applied in
opposite direction to nullify
the corrosion current, and
convert the corroding metal
from anode to cathode.

L8,9-
 MODIFYING THE
ENVIRONMENT:
 The corrosive nature of the
environment can be reduced either,
 a. by the removal of harmful
constituents, or
 b. by the addition of substances,
which neutralize the effect of
corrosive constituents of the
environment.
L8,9-
 USE OF INHIBITORS:
A corrosion inhibitor is “a
substance which when added
in small quanties to the
aqueous corrosive
environment effectively
decreases the corrosion of a
metal”.

L8,9-
 Inhibitors are mainly 2 types

1. Anodic Inhibitors
2. Cathodic Inhibitors

L8,9-
 Inhibitors are mainly 2 types
Anodic Inhibitors: Such as
chromates, phosphates, tungstates
or other ions of transition elements
with high oxygen content are those
that stifle the corrosion reaction
occurring at the anode, by forming a
sparingly soluble compound with a
newly produced metal ion.

L8,9-
 Inhibitors are mainly 2 types
Cathodic Inhibitors: In acidic solutions,
the main cathodic reaction is evolution
of hydrogen.
 2H+ (aq) + 2e-  H2 (g)
 Consequently, corrosion may be
reduced either by slowing down the
diffusion of hydrated H+ ions to the
cathode, and by increasing the over
voltage of hydrogen evolution.
L8,9-
 APPLICAION OF PROTECTI|VE COATINGS:

Protecting the surface of an object

by the application of coating is
probably the oldest of the common
procedures for corrosion
prevention. A coated-surface
isolates the underlying metal from
the corroding environment.

L8,9-
 Assignment work
 What is meant by cathodic and
anodic inhibitors ?
 Describe the cathodic protection of
corrosion control.
 Write about various factors
influencing the corrosion.
 Write in brief an account of corrosion
control methods.
L8,9-