0% found this document useful (0 votes)
21 views70 pages

Corrosion Unit IV

Uploaded by

Lakshay Arya
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
0% found this document useful (0 votes)
21 views70 pages

Corrosion Unit IV

Uploaded by

Lakshay Arya
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 70

UNIT - IV CORROSION & ITS CONTROL

• Causes, effects & consequences;


• Chemical/Dry corrosion & its mechanism
(Pilling-Bedworth Rule)
• Electrochemial/Wet Corrosion & Its mechanism,
• Rusting of Iron
• Passivity,
• Galvanic series,
• Galvanic Corrosion,
• Soil Corrosion
• Pitting Corrosion,
• Concentration Cell/Differential Aeration Corrosion,
• Stress Corrosion.
• Factors Influencing Corrosion:
Nature of metal and nature of corroding
environment;
• Protective measures:
Galvanization,
Tinning
Cathodic Protection,
Sacrificial Anodic protection,
Electroplating,
Electroless plating,
Prevention of Corrosion by Material selection &
Design.
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.
Eg. Iron undergoes corrosion to form reddish brown
colour 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. 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., 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.
Theories of corrosion –
1. Dry corrosion or Chemical corrosion
This type of Corrosion occurs mainly
through the direct chemical action of
atmospheric gasses like O2, halogens, H2S,
SO2, N2 or anhydrous inorganic liquid with the
metal surface. There are three types of
chemical Corrosion:
(1.) Oxidation corrosion
(2.) Corrosion due to other gases
(3.) Liquid metal corrosion
(1.) Oxidation Corrosion:
This is carried out by the direct action
of oxygen low or high temperatures on
metals in absence of moisture. Alkali
metals and Alkaline earth metals are
rapidly oxidized at low temperatures. At
high temperature all metals are oxidized
(except Ag, Au, Pt).
• M M2+ + 2e- (Oxidation)
• O2 + 2e- 2O2- (Reduction)
• M + O2 M2+ + 2O2- (Metal oxide)
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 nature of metal
oxide.
(a) If the metal oxide is stable, it behaves as
a protective layer which prevents further
corrosion.
Eg. 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.
(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. Eg: Alkali and
alkaline earth metals (Li, Na, K, Mg etc.)
(2.) Corrosion due to other gases:
This type of corrosion is due to
gases like SO2, CO2, Cl2, H2S, 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 Bedworth
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. Eg. 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.
Eg. Coolant (sodium metal) leads to
corrosion of cadmium in nuclear reactors.
2. 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 M+n + ne-
• The cathodic reaction consumes electrons
with either evolution of hydrogen or
absorption of oxygen which depends on the
nature of corrosive environment.
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.
Anode: 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.
Cathode: 2H+ + 2e- H2 (Reduction)
• The overall reaction is: Fe + 2H+ 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.
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. The released electrons flow
from anode to cathode through iron metal.
At anode: Fe Fe2+ + 2e- (Oxidation)
At cathod: ½ O2 + H2O + 2e- 2OH-(Reduction)
Overall reaction: Fe2+ + 2OH- Fe (OH)2
If oxygen is in excess, ferrous
hydroxide is easily oxidized to ferric
hydroxide.
4Fe (OH)2 + O2 + 2H2O → 4Fe(OH)3
The product called yellow rust
corresponds to Fe2O3. 3H2O.
Types of corrosion
1. 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.
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.
• 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
3. Pitting corrosion
A cavity, pinholes and cracks on the
protective film developed on the metal
surface creates the formation of small
anodic areas in the less oxygenataed parts
and large cathodic areas in well oxygenated
parts. The flow of electrons is from anode to
cathode and ions move through
atmospheric moisture medium.
4. Carry over
The boiler water concentrated with
dissolved salts is carried along a steam or in
the form of droplets of water which gets
deposited on the turbine plates. The metal
under the drop becomes anodic due to high
concentration of the dissolve salts and gets
corroded. The remaining large areas of
turbine plate becomes cathodic.
5. Caustic embrittlement
Boiler feed water contains certain
amount of Na2CO3 which decomposes to
NaOH under the high pressure of the boilers.
Na2CO3 + H2O 2NaOH + CO2
NaOH gets deposited in the
cracks/pits of the boiler plate creating a
concentration cell. The metal deposited with
NaOH becomes anodic while the metal
surround through drop becomes cathodic.
6. Underground corrosion (Soil erosion) -
Underground corrosion is due to the
corrosiveness of the soil. As the acidity of
the soil increases, the rate of corrosion
increases.
7. Stress corrosion –
Stress corrosion is due to the
combines effect of the stratic tensile stresses
and the corrosive environment of the metal.
The tensile stress is usually observed in
fabricated articles like alloys of Zn and Ni.
8. Inter granular corrosion –
This corrosion occurs along grain
boundaries. The grain boundary where the
metal is sensitive undergoes corrosive
attack. The grain boundary contains a
material which shows more anoidic
potential. The metal at the grain boundary
decays as it becomes anodic and the centre
of the grain becomes cathodic which is
protected.
9. Erosion corrosion –
Erosion Corrosion results by the combined
effect 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 abrasion.
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.
Factors effecting corrosion –
The rate and extent of corrosion depends
upon various factors due to nature of metal
and nature of corroding environment.
Factors due to nature of metal
1. Purity of the metal:
Heterogeneity of the metal is due to the
presence of impurities which form tiny
electrochemical cells at the exposed parts.
The anodic parts get corroded.
2. Electrode potentials:
Metals with higher reduction potentials do
not corrode easily. They are noble metals
like gold, platinum and silver. Whereas the
metals with lower reduction potentials
readily undergo corrosión (eg. Zn, Mg, Al
etc.).
3. Position of metal in Galvanic series:
Metals which possess low reduction
potentials and occupy higher end of galvanic
series undergo corrosion easily.
Metals which possess high reduction
potentials and occupy lower end of galvanic
series do not undergo corrosion and they
get protected. When two metals are in
electrical contact in presence of an
electrolyte, then the metal which is more
active undergoes corrosion. The rate of
corrosion depends on the difference in
their position in Galvanic series. Greater the
difference more will be the extent of
corrosion at anode.
4. Relative areas of anodic and cathodic
cells:
The relative areas o of corrosion is
influenced by cathodic to anodic cells. If the
metal has small anodic and large cathodic
area, the rate of corrosion is very high. This is
because the electrons are liberated at anode
which is consumed at cathode. If the cathodic
area is larger, the liberated electrons are
rapidly consumed at cathode.
This further enhances the anodic reaction
leading to increase the rate of corrosion.
5. Hydrogen over voltage:
When a cathode reaction is
hydrogen evolution type, the metal with
lower hydrogen over voltage on its surface
is more susceptible for corrosion, since the
liberation of hydrogen gas is easy at this
condition. Hence the cathodic reaction is
very fast which in turn makes anodic
reaction fast. Hence the rate of corrosion
increases. Higher the over voltage, lesser is
the corrosion.
6. Physical state of metal:
Metals with small grain size have more
tendencies to undergo corrosion. Metal with
more stress/strain also undergoes corrosion
easily.
7. Nature of surface film:
If the corrosion product formed is more
stable, insoluble and nonporous, 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).
Factors due to nature corrosive environment
1. Temperature:
The rate of corrosion reactions
increases with increase in temperature.
2. Humidity in air:
The moisture or humidity present in
atmosphere furnishes water to the
electrolyte which is essential for setting up of
an electrochemical cell. The oxide film
formed has the tendency to absorb moisture
which creates another electrochemical cell.
3. 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.
4. pH value:
pH value of the medium has the
greater effect on corrosion. Acidic pH
increases the rate of 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.
Corrosion control methods
I. Cathodic protection
The method of protecting the base metal by
making it to behave like a cathode is called as
cathodic protection. There are two types of
cathodic protection
(a) Sacrificial anode method
(b) Impressed current method.
a. Sacrificial anode method –
In this protection method, the metallic
structure to be protected (base metal) 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
(cathodic) is protected. The more active
metal so employed is called sacrificial
anode. The corroded sacrificial anode is
replaced by a fresh one, when consumed
completely. Metals commonly employed as
sacrificial anode are Mg, Zn, Al and their
alloys which possess low reduction potential
and occupies higher end in electrochemical
series.
Eg. A ship-hull which is made up of
steel is connected to sacrificial anode (Zn-
blocks) which undergoes corrosion leaving
the base metal protected.
Eg. The underground water pipelines
and water tanks are also protected by
sacrificial anode method. By referring to the
electrochemical series, the metal with low
reduction potential is connected to the
base metal which acts as anode.
Sacrificial anode method:
ship hull and underground water pipeline
b. Impressed current method
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. The impressed
current is slightly higher than the corrosion
current. Thus the anodic corroding metal
becomes cathodic and protected from
corrosion. The impressed current is taken from
a battery or rectified on A.C. line. The impressed
current protection method is used for water
tanks, water & oil pipe lines, transmission line
towers etc.
II. Surface coatings
The application of surface coating is
the common method to protect the surface
of the metal from the corroding
environment. These surface coatings exhibit
chemical inertness to corrosive
environment, adhesive properties and
impermeable.
a. Organic surface coatings
Organic surface coatings are applied
over the metallic surfaces to prevent from
the corrosion.
Properties of Organic surface coatings –
1. Chemical inertness to the corrosive
environment
2. Good surface adhesion
3. Impermeability to water, gases and salts
Eg. Paints
Paint is a mechanical dispersion
mixture of several constituents in a vehicle
oil or drying oil. The following are the
constituents of paints and their functions.
1. Pigment –
• It is a major constituent of the paint.
• Provides desired colour to the paint.
• It protects the paint by reflecting harmful
U.V radiation.
• Gives strength and increases weather
resistance of the film.
E.g. White lead, ZnO , Red lead, Ferric
oxide
2. Vegetable oil –
• Drying oil & forms the film forming constituent of the
paint.
• It acts as medium for the dispersion of various
constituents.
• It gives durability , adhesion and water proofness to
the paint.
E.g. Sunflower oil, Mustard oil, Soyabean oil.
3. Thinners -
• Reduces the viscosity and increases the elasticity of
the paint film.
• Enhances the dissolving the additives in vehicle
medium. E.g. Turpentine, Kerosene, Naphtha.
4. Driers –
• Driers are oxygen carrying catalysts.
• They accelerate the drying of the paint film
through oxidation, polymerization and
condensation.
E.g. Tunstates and nahthalates of Pb, Zn
and Co.
5. Extenders/Fillers –
• Low refractive indices materials.
• They reduce the cost and cracking nature of the
paint film. E.g. BaSO4, gypsum, talc, china clay.
6. Plasticizers –
• They provide elasticity to the film and
minimize cracking.
E.g. Tributylphosphate,
triphenylphosphate
7. Anti skinning agents –
• They prevent the gelling nature og the
paint film.
E.g. Polyhydroxy phenols
b. Metallic coatings –
The surface of the base metal is coated
with another metal (coating metal). Metallic
coatings are broadly classified into anodic and
cathodic coatings.
1. Anodic coating:
The metal used for the surface coating
is more anodic than the base metal which is
to be protected. For example, coating of Al,
Cd and Zn on steel surface are anodic becoz
their electrode potentials are lower than that
of the base metal iron.
Therefore, anodic coatings
protect the underlying base metal
sacrificially. The formation of pores and
cracks over the metallic coating exposes
the base metal and a galvanic cell is
formed between the base metal and
coating metal. The coating metal
dissolves anodically and the base metal is
protected.
2. Cathodic coating:
Cathodic coatings are obtained by coating
a more noble metal (i.e. metals having higher
electrode potential like Sn, Au, Ag, Pt etc.) than the
base metal. They protect the base metal as they
have higher corrosion resistance than the base
metal due to cathodic nature. Cathodic coating
protect the base metal only when the coating is
uniform and free from pores. The formation of
pores over the cathodic coating exposes the base
metal (anode) to environment and a galvanic cell is
set up. This causes more damage to the base
metal.
Methods of application of metallic coatings –
1. Hot dipping-
Hot dipping process is applicable to the
metals having higher melting point than the
coating metal. It is carried out by immersing
a well cleaned base metal in a bath
containing molten coating metal and a flux
layer. The flux cleans the surface of the base
metal and prevents the oxidation of the
molten coating metal. Eg. Coating of Zn,
Pb, Al on iron and steel surfaces.
The most widely used hot dipping processes
are (a) Galvanizing & (b) Tinning.
a. Galvanizing
Galvanizing is a process in which the iron
article is protected from corrosion by
coating it with a thin layer of zinc. It is the
anodic protection offered by the zinc. In this
process, at first iron or steel is cleaned by
pickling with dilute sulphuric acid solution
at a temperature range of 60-90oC for 15 to
20 minutes.
Therefore, it removes scale, rust and
other impurities present and then washed
well in a water bath and dried. Then after
dipped in the bath containing molten zinc
which is at 425-450oC. To prevent it from
oxide formation, the surface of bath is
covered with a ammonium chloride flux.
When the iron sheet is taken out it is coated
with a thin layer of zinc. To remove excess
zinc, it is passed through a pair of hot rollers
and then it is annealed at a temperature of
450oC followed by cooling.
Galvanizing is widely used for protecting iron
exposed to the atmosphere (roofs, wire fences,
pipes etc.) Galvanized metallic sheets are not used
for keeping eatables because of the solubility of Zn.
b. Tinning –
The process of coating tin over the iron or
steel articles to protect them from undergoing
corrosion is known as tinning. Tin is a noble
metal and therefore it possess more resistance
to chemical attack. It is the cathodic protection
offered by the tin. In this process, iron sheet is
treated in dilute sulphuric acid (pickling) to
remove any oxide film, if present. A cleaned
iron sheet is passed through a bath ZnCl2
molten flux followed by molten tin and finally
through a suitable vegetable oil.
2. Metal cladding
The surface of the base metal to be
protected is sandwiched between two thin
layers of coat metal and pressed between
rollers. Coating of a thin homogeneous layer
of a coating metal on a base metal such that
it strongly binds permanently either on one
side or on both sides under heat and
pressure. The finished product may be
welded at the edges. The coat metal has to
be anodic to the base metal and only plain
surfaces can be cladded.
This method is used for coating Al, Cr, Ni,
Duralumin, etc. All corrosion-resistant metals like
Ni, Cu, Ag, Au & Pt and alloys like steel/nickel
alloys can be used as cladding materials.
Duralumin is very light metal alloys used in
aircrafts industry which is cladded with aluminum
to get Alclad.

Cladding of Duralumin
3. Electroplating –
• Electroplating is the process of coating
metals and protect them from corrosion,
wear and chemical attack. Electroplating is
the method of electro-deposition of metal by
means electrolysis over surface of metals and
alloys. The base metal is first subjected to
acid pickling to remove any scales, oxides etc.
The base metal is made as cathode of the
electrolytic cell and the coating metal is made
as anode. The two electrolytes are dipped in
the electrolyte solution which contains the
metal ions to be deposited on the base metal.
When a direct current is passed from an external
source, the coating metal ions migrate towards
cathode and get deposited over the surface of base
metal in the form of a thin layer. Low temperature,
medium current density, low metal ion concntration
conditions are maintained for better electro-plating.

You might also like