Corrosion Science PDF

Corrosion Science
Classified by Alfa Laval as: Business

Corrosion
Introduction
 Corrosion of metal is primary concern for all of us specially for the
engineers.
 It is the one of the most common phenomenon that we observe in our
daily lives.
 Disadvantages
 The process of corrosion is slow, occurs only at metal surfaces but
losses are enormous.
 Destruction of machines, building materials, different type of metallic
products.
 The valuable metallic properties like malleability, ductility etc. lost
due to corrosion.
 Life span of metallic parts of machineries is reduced as a result failure of machinery takes place.
 The corroded product must be replaced. The cost of replacement of materials and equipment lost
through corrosion is unlimited.
 Safety, health and environmental risks due to corrosion, especially in manufacturing plants.
 Preventive maintenance like metal coating or organic coating is required.
 Corrosion releases toxic products.

Examples
Rusting of iron objects due to formation of hydrated ferric
oxide (Fe2O3.3H2O)
Tarnishing of silver wares, utensils when are exposed to air,

they react with the sulphur gas present in the atmosphere, leads
to the formation of silver sulphide (Ag2S) which is black in
color.
Formation of green film of carbonate (CuCO3) on copper when

exposed to moist air containing Carbon dioxide.
The approximate estimate of loss of metal due to corrosion is 2

to 2.5 billions per annum all over the world .

What is corrosion?
Gradual destruction of materials (metals) by chemical
Oxygen
(O2)
or electrochemical reaction with the environment.
Water
(H2O)
It is natural process that cause the transformation of
pure metals into more stable form such as its oxide,
sulfides, hydroxides etc. by action environment.
It is spontaneous and irreversible process.
Adversely affect desirable properties of materials.

Why does corrosion occur?
 Except few metals like gold, silver, platinum, other metals found
How are metal
existing in in nature as their compounds such as oxides, hydroxides,
nature? carbonates, sulphates which are called as their ore.
 These compounds (ore) are stable and they are in low energy state.
How are we  Metals are thus obtained by extraction from their ore which are
getting metal
less stable and in higher energy state .
from nature?
 So metals has tendency to go back to their combined state (ore)
and thus prone to attacked by environment which leads to
Are we getting
Cu, Al etc. corrosion.
directly from ?
 Metals destruction starts at surface due to direct chemical attack or
nature?
electrochemical attack.

Minerals or Extraction Corrosion
Corrosion
Metal
ore product
(M)
(M n+) By reduction -ne (M n+)
+ne
Types of Corrosion
Corrosion
Wet or
Dry or Chemical
Electrochemical
Corrosion
Corrosion

Dry Corrosion
It involves direct chemical attack of atmospheric gases like CO2, O2, H2S, halogens and
inorganic acid vapours on metallic surface.
It occurs in the absence of aqueous environment.
Corrosion occurs uniformly on entire metallic surface.
Both oxidation and reduction occurs on metallic surface without formation of anodic and
cathodic area.
Extent of dry corrosion depends on nature of layer found on metallic surface and
attraction between gas and exposed metal.

Types of Dry Corrosion
Oxidation Corrosion by Liquid metal

Corrosion other gases corrosion
Oxidation Corrosion
 Oxygen present in atmosphere attacks the metal surface forming metal oxide layer (Direct chemical
reaction of O2 and metal)
 It involves process of adsorption of oxygen on metallic surface.
 It occurs in the absence of moisture or any electrolytic medium.
 Extend of oxidation corrosion depends on nature of oxide layer formed on metallic surface.

Mechanism of Oxidation Corrosion
On exposure of atmospheric oxygen (O2) metal get oxidized to form metal ions
2M 2 M n+ + 2 ne- (Oxidation)
2M 2 M n+ + 2 ne- (Oxidation)
M 2O n
Electrons lost by metal are taken by oxygen to form oxide ions
n/2 O2 + 2 ne- n O2- (Reduction)
Atm Metal
2 M n+ + n O2-
Overall reaction O2
2M + n/2 O2 2 M n+ + n O2- M2On

(Metal oxide)
n/2 O2 + 2 ne- n O2- (Reduction)
 When metal come in contact with atmospheric O2, metal undergo oxidation to form metal ions and oxygen
undergo reduction to form oxide ion.
 Metal ion and oxide ion get combined to form metal oxide.
 Metal under the oxide layer undergo the corrosion or not, this will be decided based on nature of metal oxide
layer. Classified by Alfa Laval as: Business
Nature of oxide layer
1. Stable metal oxide layer (Al, Sn, Pb, Cu etc)
 When the metal comes in contact with atm O2, it form metal oxide layer, this layer is firm
and densely packed, so we called this layer is stable layer or protective layer and does not
allow atm O2 to come in contact with metal and does not undergo corrosion.

2. Unstable metal oxide layer
 When the metal comes in contact with atm O2, it forms very unstable metal oxide layer
that it immediately return back to form metal and oxygen.
 This happens in case of Nobel metal such as gold, silver and platinum, that’s why we can
see even after 40-50 years, gold does not undergo corrosion.

3. Porous metal oxide layer (Na, K, Mg, Li)
 This is very interesting but very dangerous layer.
 When the metal comes in contact with atm O2, it forms metal oxide layer which is highly
porous in nature, easily form cracks, so atm O2 penetrate through these cracks.
 Metal present inside the metal oxide layer come in contact with oxygen and undergo
further corrosion.
 So over period of time, whole metal undergo corrosion .This happens in case of Na, K,
Mg, Li.

4. Volatile metal oxide layer (Mo)
 This is even more dangerous layer.
 When the metal like Mo comes in contact with atm O2, it forms metal oxide layer which is
volatile layer i.e it evaporates.
 When oxide layer evaporate, we have metal which is smaller than this size because this
upper part of metal oxide already escaped, then metal is freshly available to undergo
corrosion by reacting with atm O2.
 So this type of corrosion is very drastic and with in less time total metal undergo corrosion.
This can be very easily explain by Pilling- Bedworth rule

Why do some metals form protective layer and why do others form non-
protective layer?
Conditions to form stable protective coating of oxide on surface of metal:
1. The metal must be reactive enough to rapidly react with oxygen in atmosphere to form a layer of metal
oxide.
2. The metal oxide formed must be unreactive to moisture and other gases present in atmosphere, so that it will
stable.
3. Oxide layer must be insoluble in atmospheric moisture and water.
4. The crystal structures of metal and oxide formed must be compatible so that no expansion or contraction
occurs when oxide layer is formed.
5. Only few metal, like Al, Ni, Cr meet all above requirements and form protective coating. That is reason why
iron parts of automobiles electroplated with Cr, Ni

 The metals like sodium, potassium are highly reactive form reactive coating very rapidly. Oxide formed itself is
highly reactive and reacts with other components of atmosphere to form carbonates and hydroxides. In addition
to that oxides, carbonates, hydroxides are soluble in atmospheric moisture and quickly leeched off the surface
of metal, thus exposing fresh metal surface for corrosion.
 The crystal structures of metal and oxides in these case are not compatible. Expansion or contraction occurs
when oxide layer is formed. Thus oxide layer will develop pressure cracks and expose the fresh metal below
layer. The fresh metal surface again reacts with atmosphere to form oxide and process continues till all metal is
corroded.
 This is what happens in case of iron (Fe). Hydrated iron oxide rust have higher volume compared to iron from
which it is formed. Hence due to expansion cracks are formed. Through this cracks air and water enter and
cause further rusting. This continues till all Fe is changed to rust.
 Some metal oxides (Mo) has a very low melting point, they tends to form volatile layer.

Pilling – Bedworth Rule
It is the ratio of the volume of metal oxide to volume of metal consumed.
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑜𝑥𝑖𝑑𝑒 𝑓𝑜𝑟𝑚𝑒𝑑

𝑆𝑃𝑒𝑐𝑖𝑓𝑖𝑐 𝑣𝑜𝑙𝑢𝑚𝑒 𝑟𝑎𝑡𝑖𝑜 (𝑅𝑃𝐵) =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑚𝑒𝑡𝑎𝑙
Case 1. If the volume of metal oxide is more than the volume of metal from which it is formed, (RPB >1), then the metal
oxide layer is stable, nonporous and protective in nature, e.g. Al, Sn, Pb, Cu etc. CuO : Cu = 1.68
Case 2. If the volume of metal oxide is less than the volume of metal from which it is formed (RPB <1) then the metal oxide
layer is porous and non-protective in nature, e.g. Na, K, Mg, Li (Alkali and alkaline earth metals)

Corrosion by other gases
 In dry atmosphere these gases (Cl2, SO2, H2S, CO2 etc.) react with metal and form corrosion products which
may form protective or non-protective layer.
 The extent of corrosive effect depends mainly on the chemical affinity between metal and gas.
 The degree of attack depends on the formation of protective or non-protective films on the metal surfaces.

1. Halogen/chlorine
Chlorine attacks the metals to form metal chlorides which generally form porous film.
M + Cl2 MCl2
Mg + Cl2 MgCl2
2. Sulphur containing gases
Gases like SO2, SO3, H2S formed during combustion, attack on metal and corrode them.
Fe + H2S FeS + H2
3. Hydrogen
a) Decarburization
Process of removal of carbon from metal by the action of hydrogen. It decreases the mechanical strength of steel.
C + 4H CH4
b) H2 embrittlement
a) At high temperature, H2 penetrates within the gaps or voids of metal, leading to localized weakening of metal result into
fractures at weak point. This breaking of metal by hydrogen accumulation is known as hydrogen embrittlement.

4. CO and CO2
These gases produced in petroleum refining and during combustion of fuels, reacts with steel.
C + CO2 2CO
Fe + CO2 FeO + CO

Liquid-metal corrosion
 In several industries, molten metal passes through metallic pipes and causes corrosion due
to dissolution of solid metal by liquid metal or due to penetration of liquid metal into solid
metal. Both these modes of corrosion cause weakening of solid material.
 Ex. Liquid mercury dissolves most metals forming amalgams, thereby corroding them.

Wet corrosion (Electrochemical)

 Wet corrosion refers to the degradation and rust formation on a metal surface that occurs due to the
generation of a reactive electrochemical cell. Wet corrosion can damage metal structures and equipment,
including stainless steel.
It occurs;
1. When a metal in contact with moist air or any electrolyte or liquid medium.
2. When two different parts of metals are either immersed or partially dipped in a electrolyte solution.
3. When the two parts of a metal exposed to different concentration of oxygen.
4. Chemically non uniform surfaces of metals behave like electrochemical cells in the presence of water
containing dissolved O2 and CO2. It means that this corrosion is only possible on heterogeneous surfaces.
5. When metal is stressed at sharp corners, bends, pits, cervices, joint are exposed to a specific electrolyte
medium.
6. Corrosion occurs at anodic areas only while cathodic area is said to be protected.
7. Ex. Rusting of iron in moist atmosphere

 Mechanism
 Involves Oxidation-reduction reaction taking place separately at anode and cathode.
 Corrosion occurs through the mechanism of electrochemical reaction.
 It is fast process and occurs on heterogeneous metallic surface only.
 Electrons move from anode to cathode through the metal or through the corrosive medium
 At anodic area, oxidation reaction (i.e liberation of free electrons ) takes place so anodic metal is destroyed by either
dissolving or forming oxides. Hence corrosion always occurs at anodic area.
At anode,
M M n+ + ne -
M n+ Dissolves in solution or
Forms compound such as oxide
On the other hand, at cathodic area, reduction reaction (i.e gain of electron) takes place. Usually, cathodic reaction don't
affect cathode because here at cathode, dissolved constituents accepts the electron to form some ions.(like OH-)

Metallic ions at anodic area, and non metallic ions formed at cathodic part diffuse towards each other through
conducting medium and form corrosion product somewhere between anode and cathode . Thus, electrochemical
corrosion involves;
1. Formation of cathodic and anodic area in contact with each other
2. Presence of a conducting medium / electrolyte medium
3. Oxidation occurs at anode and reduction occurs at cathode
4. Only anodic area get corroded.
5. Formation of corrosion product somewhere between anodic and cathodic area.
6. Depending on the nature of corroding environment, electrons are consumed by cathode by two ways;
 H2 evolution
 O2 absorption

Wet or Electrochemical corrosion
H2 Evolution
O2 Absorption
Hydrogen Evolution
Mechanism:
 It generally occurs when a metal comes in contact with an acidic medium.
 Metallic part at anodic area undergo dissolution with the release of electrons.
 Electrons flow through the metal from anode to cathode, where H+ ions from acidic solution are
eliminated as H2.
 Such corrosion involves displacement of H+ ions from the acidic solution by the metal ions due to
which pH of the acidic solution increases.
 Hence, all the metals above the hydrogen in electrochemical series have a tendency to get dissolved
in acidic solution with evolution of hydrogen.
 In such type of corrosion, anode is usually large metallic area where as cathode is small metallic
areas.
Reactions involved
Ex. Iron metal in contact with HCl
Considering metal like Fe, the anodic reaction is dissolution of iron
as ferrous ion with the liberation of electrons.
Fe Fe2+ + 2e - (Oxidation)
These electrons flow through the metal, from anode to cathode where H+
ions (of acidic solution) are eliminated as hydrogen gas.
2H++ 2e- H2 (Reduction)
Overall reaction
Fe + 2H + Fe2+ + H2

Oxygen Absorption
Mechanism:
 Occurs when metal is exposed to neutral solution of electrolyte ( NaCl solution) in the presence of
oxygen. Ex. Rusting of iron in neutral aqueous environment ( NaCl solution)
 Due to presence of oxygen, surface of metal (like Fe) coated with thin film of oxide (FeO). If such
layer develops some cracks, anodic areas are created on the surface. In such type of corrosion,
anode is usually small metallic area where as cathode is large metal parts.

Reactions involved
Ex. Considering metal like Fe, the anodic reaction is dissolution of iron as ferrous ion with the liberation of electrons
Fe Fe2+ + 2e - (Oxidation)
These electrons flow through the metal, from anode to cathode where electrons accepted by dissolved oxygen and
water as;
½ O2 + H2O + 2e- 2 OH-
The Fe2+ ions at anode and OH- ions at cathode diffuse and when they meet, ferrous hydroxide is precipitated.
Fe2+ + 2 OH- Fe(OH)2
If enough oxygen is present, ferrous hydroxide is oxidized to ferric hydroxide
4Fe(OH)2 + O2 + 2H2O 4Fe(OH)3
This product is called yellow rust. If the supply of oxygen is limited, the corrosion product may be even anhydrous
magnetite Fe3O4 which is black in color.

Dry Vs Wet corrosion
Dry Corrosion Wet corrosion

Corrosion occurs in the absence of moisture Corrosion occurs in presence of conducting
medium
It involves direct attack of chemicals on the It involves formation of electrochemical cells
metal surface
The process is slow It is rapid process
Corrosion products are produced at the site of Corrosion occurs at anode but is deposited at
corrosion cathode
The process of corrosion is uniform It depends on the size of anodic part of metal

Types of corrosion
Types of corrosion
1. Stress corrosion
2. Waterline corrosion
3. Pitting corrosion
4. Crevice corrosion
5. Intergranular corrosion

Stress corrosion
It is combined effect of static tensile stresses and the corrosive environment on a metal
which resulting in a the formation of crack which propagates.
So necessary conditions are;
1. Presence of tensile stress
2. A specific corrosive environment
Highly
localized Formation of
Tensile
zones crack and
stress
(Chemically propagation
active)

Three key elements are essential for initiation and growth of the stress corrosion cracking: a sensitized material, a
specific environment, and adequate tensile stress. It is shown in figure;

Corrosive agents are highly specific and selective.
Susceptible metals Specific corrosive

environment
Mild steel Caustic alkalis and strong
nitrate solution
Brass/ copper alloys Traces of ammonia
Stainless steel Acid chloride solution

Causes of stress corrosion
This type of corrosion generally seen in fabricated articles of certain alloy due to presence of
stresses caused by heavy working like;
 Rolling
 Drawing
 Insufficient annealing
 Cold or hot bending
 Welding

Mechanism stress corrosion
 It involves localized electrochemical corrosion, occurring along narrow paths, forming anodic areas with respect to the
cathodic areas at metal surface
 Presence of stress produces strains which results in localized area of higher electrode potential.
 Localized zones become so chemically active that they are attacked even by mild corrosive environment resulting in the
crack which grows and propagates in plant until failure occurs or it may stop
Residual
compressive stress Residual
tensile stress

Examples of stress corrosion
Embrittlement
a) Caustic embrittlement
b) Hydrogen embrittlement
c) Seasonal Cracking

1. Caustic embrittlement
 It is a very dangerous form of stress corrosion which is common in high pressure boilers.
 Theses boilers are made from carbon and low alloy steel i.e mild steel undergo corrosion when exposed to
alkaline solution at high pressure.
 During softening process of water (in lime-soda process), free Na2CO3 is usually present in small proportion in
the softened water. In high pressure boilers, Na2CO3 decomposes to give sodium hydroxide and carbon
dioxide. This makes the boiler water caustic.
TECHNOLOGY Na2CO3 + H2O -------2NaOH + CO2
 The NaOH containing water flows into the minute hair-cracks, present in the inner side of boiler When water
evaporates and the dissolved caustic soda (NaOH) concentration increases progressively. This caustic soda
reacts with iron (which is base material of mild steel ) to form sodium ferroate in cracks where material is
stress and thus corrode the iron.

This sodium ferroate decomposes a short distance away from its
point of formation and sodium hydroxide is regenerated and
magnetite (Fe3O4) is precipitated, thereby enhancing further
corrosion.
3Na2FeO2 + 4H2O 6NaOH + Fe3O4 + H2
Prevention of caustic embrittlement

1. Addition of sodium sulphate instead of sodium carbonate to the boiler water
2. Use of tannin or lignin as additive to the boiler water
3. Both of these method prevent caustic embrittlement by blocking up the hair cracks and cervices, thereby
preventing the sodium hydroxide from infiltrating.

2. Hydrogen embrittlement
 Hydrogen is small molecule, easily diffused between metal atoms in crystal lattice. It fits into any gaps
between metal atoms, as the concentration of atomic hydrogen increases in voids/gaps, pressure develops in
cracks which further propagates.
 When hydrogen penetrates, its reacts with hydride forming elements to form metal hydride which are
extremely brittle and increases cracks.
 Atomic hydrogen is formed by two ways
1. Hydrogen ion reduction (when acidic environment is present, hydrogen ion consumes electron and forms
atomic hydrogen
2. Water reduction
Hydrogen get
attracted to Moves to Assists
regions of region of fracture of the
high tensile cracks metal
stress

3. Seasonal Cracking:
 Related to stress corrosion of copper alloys, mainly brass, occurs in rainy season.
 It occurs due to high residual stress caused by cold working in fabricated articles of brass in the presence of
ammonia or amines.
 As Cu alloys are more sensitive to ammonia, undergo intergranular corrosion.
 This attacks occurs along grain boundaries which become anode with respect to grain themselves. This
ammonia dissolves the brass forming stable complexes ions [Cu(NH3)]2, which initiate cracks in presence of
high tensile stress.
A grain boundary is the interface between two grains,

or crystallites, in a polycrystalline material. These are defects
in the crystal structure

Waterline corrosion
 When the water is stored in a steel tank, it is found that the maximum amount of corrosion occurs along a
line just beneath the level of the water meniscus. This is example of differential aeration corrosion.
 The area above the waterline is highly oxygenated /part of metal exposed to higher concentration of air
acts as cathode and completely unaffected by corrosion.
 The area below the waterline is poorly oxygenated /part of metal immersed inside the water exposed to
less concentration of air acts as anode and undergo corrosion.

 Electron flows from the anode to cathode through the metal and ions migrates to each other through the
electrolyte medium (water) producing the corrosion product
 At anode, dissolution of metal occurs due to corrosion.
 At cathode, absorption of oxygen type reduction reaction occurs producing hydroxide ions.
 Ex. In case of ships, waterline corrosion observed.

Differential aeration corrosion
Hydrogen evolution
Oxygen absorption

Pitting corrosion
 It is a localized attack in the metal resulting in the formation of pit, hole or cavity (confined to very small area)
 Pitting is usually, the result of the breakdown or cracking of protective film on the metal at specific point gives
rise to small anodic area and large cathodic area.
 At this point where cracking occurs, creates a weak point where water or corrosive solution attack on metal
and drastic corrosion occurs at anode to form a pit or hole.
 At cathode, reduction occurs by taking up electrons liberated at anode.
 As cathodic area is large, demand for electrons is too high. This can’t be satisfied by small anodic area . So
anode undergo drastic corrosion to meet this demand of cathode.
 Here area factor is important issue.
 Ex. 1st case- two copper plates are joined by iron rivet.
 2nd case- two iron plates are joined by brass (Cu- Zn alloy) rivet.

Fe Brass (Cu-Zn alloy)
Cu Fe
Cu Fe
• Fe rivet acts as anode and Cu plates act as cathode • Fe plates act as anode and brass rivet acts as cathode
• Large cathodic area and small anodic area • Large anodic area and small cathodic area
• Dissolution of iron rivet occurs quickly • Dissolution of iron take longer time, so loosing effect is
• Corrosion is aggressive hindered

Causes
1. When the anodic area is small and cathodic area is large
2. Damage or cracking of protective film on the metal surface
3. Surface roughness
4. Scratches/cut edges
5. Presence of impurities on metal surface
6. Chemical attack
Examples
Pitting corrosion occurs when a metal
is poorly maintained and exposed to
water droplets and dust particles

Crevice corrosion
 Crevice corrosion refers to the localized attack on metal surfaces (at crevice) by a stagnant solution
 Occurs under valve gaskets, rivets, bolts in alloy system like steel, titanium and copper alloys
 It occurs between be metal-metal or metal-nonmetal surfaces.
 This causes damage to the metallic part, which is initiated by the concentration gradient in chemicals.
 The most common form is oxygen differential cell corrosion. This occurs because portion below moisture
has a lower oxygen content when it lies in a crevice. The lower oxygen content portion in the crevice forms
an anode at the metal surface. The higher oxygen content portion forms cathode
 Mechanism of corrosion is similar to absorption of oxygen step of wet corrosion. As the solution is
stagnant, oxygen is used up and not replaced.
 When dust, sand and other corrosive substances are deposited on surfaces, they create an environment
where water will accumulate and corrode the part

.
.

Intense localized corrosion frequently occurs within crevice and other
shielded areas ( stagnancy) on metal surface exposed to corrosive environment
It can occur
1. Narrow space between metal-metal or metal-nonmetal contact areas
2. Near crack part
3. Deposition of dirt, mud

Intergranular corrosion
Grain and Grain boundaries
 Metals are made of atoms are assumed to be solid spheres.
 Atoms within a metallic crystal or grain are regularly arranged over great distances.
 The strength of metals suggest that these atoms are held together by strong bonds.
 To form the strongest metallic bonds metals are packed together as closely as possible. The outermost
electrons of the metals to be shared by all the surrounding atoms, resulting in positive ions (cations)
 Since electrons are attracted to many atoms, they have considerable mobility that allows for the good heat and
electrical conductivity seen in metals.

 Above their melting point, metals are liquids, and their atoms are randomly arranged and relatively free to
move. However, when cooled below their melting point, metals begin to pack together to form a crystal
lattice.
 Group of tiny atoms form tiny crystals. These tiny crystals increase in size by progressive addition of atoms.
 The resulting solid is not only one crystal but actually many smaller crystals called grains.
 In any one grain, all atoms are arranged with one particular orientation and one particular pattern The
juncture/interface between adjacent grains is called a "grain boundary." The grain boundary is a transition
region in which some atoms are not exactly aligned with either grain.
 The mismatch of the orientation of neighboring grains leads to a less efficient atomic packing within the grain
boundary. Hence the atoms in the boundary have a less ordered structure and a slightly higher internal energy
 The higher energies of grain boundary atoms make them slightly more reactive than grains.

Intergranular corrosion
 This type of corrosion occurs along grain boundaries and only where the material, especially sensitive to
corrosive attack and corrosive liquid posses a selective character of attacking only at the grain boundaries, but
leaving the grain interiors untouched or slightly attacked..
 Grain center act as cathode and grain boundary acts as anode
 This may be due to the precipitation of certain compounds at grain boundaries, thereby leaving the solid metal
solution just adjacent to grain boundary depleted in one constituent
 This depleted solid solution is anodic with respect to the grain centers as well as to the precipitated compound
so that it will be attacked preferentially by corrosive environment.

 This type of corrosion generally occurs in case of alloys
 Ex. During welding of stainless steel ( an alloy of Fe, C, Cr), chromium carbide is precipitated at grain
boundaries, thereby region just adjacent to grain boundaries become depleted in chromium composition and
is more anodic with respect to solid solution within grain which is richer in chromium. So it is anodic to the
particles of chromium carbide so precipitated
 Intergranular corrosion follows a path of grain boundaries and occurs on microscopic scale without any
external sign of intensive attack. Therefore sudden failure of material occurs without any re-warning .
 Prevention
 Proper heat treatment followed by rapid quenching to avoid heterogeneous precipitation that usually occurs
due to slow cooling.

Factors affecting corrosion

 More reactive metals have greater tendency to lose electrons and corrode or tarnish more readily. Ex. Fe is
more reactive than gold Au because it will readily give up electrons to oxygen while Au will not.
Meanwhile Copper (Cu) is more reactive than Au but less reactive than Fe. So ,Cu does not rust but it can
corrode in other oxidizing reactions. It turns a shade of blue-green as it corrodes.
 Due to more reactivity, Fe corrodes more quickly than most metals to form rust.
b) Relative areas of the anodic and cathodic parts
Corrosion is more rapid and severe, and highly localized, if the anodic area is small.
 Ex. A small steel pipe fitted in a large copper tank. Demand for electrons by the large cathode areas can
met by smaller anodic area only by undergoing drastic corrosion
The tendency of species to reduced by gaining electron is called reduction potential.

Reduction potential for hydrogen is zero and for metals above hydrogen is negative and for metals below
hydrogen is positive. Metals with –ve reduction potential has tendency to oxidize and silver with +ve reduction
potential has a maximum tendency to reduce.
2. Purity of metal
 Impurities in a metal, generally cause heterogeneity and form minute/tiny electrochemical cells at the exposed
parts, and the anodic parts get corroded. Ex. Zinc metal containing impurities such as Pb or Fe undergoes
corrosion of zinc due formation of electrochemical cells.
 The of corrosion increases with increasing exposure and extent of the impurities. Consequently, corrosion
resistance of metal may be improved by increasing purity.

3.Physical state of metal
 The rate of corrosion is influenced by physical state of metal ( such as grain size, orientation of crystal, stress
etc). The smaller the grain-size of metal or alloy, the greater will be its solubility and hence greater will be its
corrosion. Moreover, areas under stress, even in a pure metal, tend to be anodic and corrosion takes place at
these areas.
4. Nature of surface film
 In aerated atmosphere, practically all metals get covered with a thin surface film of metal oxide. The ratio of
the volumes of the metal oxide to the metal, is known as a “specific volume ratio”. Greater the specific volume
ratio, then metal oxide layer is protective, nonporous in nature and don’t allow metal for further corrosion. The
specific volume ratios of Ni, Cr and W are 1.6, 2.0 and 3.6 respectively. They form protective layer.

5.Solubility of corrosion products
 In electrochemical corrosion, if the corrosion product is soluble in the corroding medium, then corrosion
proceeds at faster rate. If the corrosion product is insoluble in the medium or it interacts with the medium to
form another insoluble product (ex. PbSO4 formation in case of Pb in H2SO4 medium), then the corrosion
product functions as physical barrier, thereby suppressing further corrosion.
6. Volatility of corrosion products
 If the corrosion product is volatile, it volatilize as soon as it is formed, thereby leaving the underlying metal
surface exposed for further attack. This cause rapid and continuous corrosion. Ex. Molybdenum oxide, the
oxidation corrosion product of molybdenum, is volatile.

Nature of corroding environment
1. Temperature
 Temperature affects corrosion. As the corrosion rates are determined by diffusion of ions and diffusion rates
are controlled by temperature.
 With increase of temperature of environment, the rate of reaction increases, thereby corrosion rate is generally
enhanced.
 As the temperature increases, the particles in metal move faster as they gain energy and collide more
frequently. Therefore, rate of corrosion proceeds faster in warmer environment than in cooler ones.
 Steel and other metals corrode at faster rates at higher temperatures than at lower temperatures.
 Essentially, every 10°C increase in the temperature can double corrosion activity

2. Influence of pH
 pH is a measure of the acidity or alkalinity on a scale of 1 to 14. pH 7 is neutral.
 In neutral sea water, the pH is around 7.5 which mean that the hydrogen ions (acid) and hydroxyl ions (alkali) are almost in balance.
Under such circumstances, the reaction that balances the iron dissolution is the reduction of dissolved oxygen to form hydroxyl ions.
 If however the environment becomes more acidic and the pH falls closer to 1, then there is a greater quantity of hydrogen ions than
hydroxyl ions present in the solution.
 The excess hydrogen ions can become involved in the balancing (cathodic) reaction which results in the evolution of hydrogen gas. As
both the hydrogen ions and the hydrogen gas can diffuse very rapidly, the steel can corrode faster.
 Under alkaline conditions, where there is an excess of hydroxyl ions and the pH levels tend towards 14, steel cannot corrode and remains
unaffected.
 Generally, acidic media pH<7 are more corrosive than alkaline and neutral media. However, metals like Al, Pb, etc dissolve in alkaline
solutions as complex ions.
 The corrosion rate of iron in oxygen free water is slow below pH 5 but the corrosion rate increases in the presence of oxygen.
 Corrosion of metals readily attacked by acid, can be reduced by increasing the pH of attacking environment.
 Ex. Zn rapidly corroded even in weakly acidic solution such as carbonic acid, suffers minimum corrosion at pH=11

3. Presence of suspended particles atmosphere
In case of atmospheric corrosion
1. If the suspended particles are chemically active in nature like NaCl , (NH4)2SO4, they absorbs moisture and acts as strong
electrolytes, thereby causing enhanced corrosion.
2. If the suspended particles are chemically inactive in nature (ex. Charcoal) they absorb both sulphur gases and moisture
and slowly enhance corrosion rate.
4. Conductivity of the medium

 For corrosion to occur there must be a conductive medium between the two parts of the corrosion reaction.
 Corrosion will not occur in distilled water.
 The rate of corrosion will increase as the conductivity increases due to the presence of more ions in the solution.
 Fresh water corrodes steel to a lesser extent than brackish or, with sea water usually being the most corrosive to steel

5. Nature of ions present
 Presence of anions like silicate in the medium leads to the formation of insoluble reaction products which inhibits further
corrosion.
 On the other hand, chloride ions, if present in the medium, destroy the protective surface film, thereby exposing metal
surface for fresh corrosion.
 Ex. Many metals, including iron, undergo corrosion rapidly, if the corroding medium contains ammonium salts.
 Presence of even traces of copper in mine water, rate of corrosion of the iron pipes carrying such water increases.
6. Formation of oxygen concentration cell

 With the increase in supply of oxygen to the moist metal surface, corrosion is promoted.
 Less oxygen concentration /less exposed part acts as anode while more oxygenated/ more exposed part acts as
cathode, thereby leading to the formation of oxygen concentration cell, in which anodic part suffers corrosion.
Thus oxygen concentration cell promotes corrosion and occurs where the oxygen concentration is lower.
 Ex. Waterline corrosion, crevice corrosion

Methods of corrosion control

Corrosion control methods
Cathodic Anodic Metallic Non-metallic

Protection protection Coating coating

Proper designing
The design of the material should be such that “corrosion, even if it occurs, is uniform and does not result in
intense and localized corrosion.
Important design principles are:
1. Avoid the contact of dissimilar metals in the presence of a corroding solution, if this principle is not
followed, then corrosion is localized on more active metal while less active metal is protected.
2. When two dissimilar metals are in contact, anodic metal should have large area as possible where as
cathodic metal should have smaller area as possible.
3. The anodic metal should not be painted when it in contact with the dissimilar cathodic material, because any
break in coating leads to rapid localized corrosion.
4. Prevent the occurrence of inhomogeneity, in the metal. Thus proper design should avoid the presence of
crevice between the adjacent parts of the structure, even in the same metal since crevice permits
concentration difference. Therefore bolts and rivets are replaced butt-weld.
5. It is desirable that design allows for adequate cleaning of critical parts which are susceptible to dirt, water
deposition etc.
6. Sharp corners should be avoided as the favor the formation stagnant area.
7. Whenever possible, the equipment should be supported on legs to allow circulation of air and prevent the
formation of stagnant condition

Protective metallic coating
Protective metallic coatings-

Hot dipping
Tinning
Cladding
Electroplating
Cementation

Hot Dipping
 Hot dipping: This technique is most widely used to control corrosion. It is process of coating the base
metal (metal with higher melting point ) by dipping into a bath containing molten coating metal. (metal
with low melting point) (Zn, Sn, Pb, Al)
 Ex. coating of low melting metals such as Zinc (419°C) or tin (232°C), etc. on metal like steels, copper,
brass, etc.
 The process in general consisting of immersed base metal in a bath of molten coating metal.
 Hot dipping is widely applied either by
 GALVANIZING
 TINNING

Galvanizing
 Coating of more active metal over less active metal. Ex. Coating of zinc over copper, iron, steel etc.
 It is the process in which iron or steel is protected from corrosion by coating with a thin layer of zinc
which alloys with the surface of base metal when immersing the metal in a bath of molten zinc at
temperature 425- 430 oC
 Process
1. Degreasing
Organic contaminants that are on the surface of steel must be removed prior to coating. Most common
contaminants are oil and dirt. A hot alkali solution is often used to remove organic contaminants.
2. Pickling
After the degreasing, pickling with dil. H2SO4 solution for 15-20 min at 60-90 oC. The steel is then washed
well and dried .This treatment removes any scale, rust (oxide film) and impurities.

3. Fluxing
After acid pickling, steel part are immersed in fluxing solution to remove oxide films and also prevent oxide
formation. Fluxing solution contains ZnCl2 and ammonium chloride (Zinc ammonium chloride flux)
4. Galvanizing
Prepared steel part is immersed in bath of molten zinc maintained at 425-430 oC. Here steel surface are coated
with zinc layer. At same time zinc-iron compounds are generated at the near regions.
 Then the metal sheet is passed through a pair of hot rollers which removes excess of Zinc and maintain
uniform thickness of Zinc on metal sheet.
 The sheet is subjected to quenching process and cooled slowly.

SURFACE PREPARATION

 When this sheet exposed to the atmosphere, the pure zinc (Zn) reacts with oxygen to form zinc oxide (ZnO),
which further reacts with carbon dioxide (CO2) to form zinc carbonate (ZnCO3), a usually dull grey, fairly
strong material that protects the steel underneath from further corrosion in many circumstances. Galvanized
steel is widely used in applications where corrosion resistance is needed is considered superior in terms of
cost and life-cycle
 Uses of Galvanization: It is used to protect Iron used for roofing sheets, wires, pipes, nails, bolts,
screws, buckets, and tubes.
 Defects :Galvanized utensils are not used for cooking because of zinc get dissolved in acidic food is
stored and poisons the food.

Tinning
 Tinning is the process of coating the base metal (metal with higher melting point) by dipping into a bath
containing molten tin (metal with low boiling point) over the Iron sheet or steel articles.
 Process
 Consists in first treating steel sheet ,with dil. H2SO4 solution to remove any oxide film, rust.
 After this it is passes through a bath of zinc chloride flux. Flux helps the molten metal to adhere to metal
steel.
 Then passes through a tank of molten tin and finally through a layer of palm oil which protect hot tin
coated surface against oxidation.
Uses: (1)It is widely used for coating of steel, copper, brass & bronze etc . It is used to store food stuff, ghee
oils, kerosene and used for refrigerators equipment.

Metal cladding
 It is the process of sandwiching the base metal between two
thin layers of coating metal by hot-rolling the composite to
produce a firm bonding.
 Cladding refers to the metallurgical process of coating
a metal onto another metal under high temperature and
pressure so as to protect the inner metal from corrosion.
 The coat metals are usually metals of least reactivity (Cu,
Ni, Ag, Ti)
 Coating is very thin and its thickness is only 5% of the total
composite metal.
 Copper-clad aluminum wires are extensively used in
electrical applications due to the cost advantage as well as
an improved electrical conductivity.

Cementation/Diffusion coating
 It is technique of coating metal with another metal by heating it with powdered metal which infuses into a
base metal and forms an alloy on the surface which acts as protective coating.
 In the cementation technique, coating metal diffuses into base metal and forming layer of alloy.
Uses
 Coating small articles line nuts, bolts, screws, spanners, screw drivers, tools furnace parts, and turbine blades.
 Applicable for base metal like steel.
 Strong coating and having good abrasion resistance.

Sherardizing

Electroplating
 Deposition of coating metal on the base metal by passing direct current through an
electrolytic solution which contain the soluble salts of the coating material.
 Electroplating is a process that uses an electric current to reduce dissolved metal cations so
that they form a thin coherent metal coating on an electrode.
Electrochemically coat metal is deposited on base metal.
This metal gives smooth, fine and uniform coating.

Applications of Electroplating
It is most important & frequently used technique in industries to produce metallic
coating
Both metals & non metals can be electroplated.
In metals the electroplating increases resistance to corrosion, chemical attack, hardness,
wear resistance and surface properties.
 In non metals electroplating increases strength and decorates the surface of non metal
like plastics, wood, glass.

Metallic coating
Differences between anodic coating and cathodic coating.
• Anodic coating • Cathodic coating

• If the coating metal is • If the coating metal is lower
higher placed in galvanic
series than the base placed in galvanic series than
metal, then the coating is the base metal, it is known as
called as anodic coating. cathodic coating.
• Anodic coating is mostly
preferred. • Cathodic coating is less
• Coating of Zn, Al, Cr on preferred.
steel • Coating of tin on steel, Ag or
• It is carried out by Au on brass
galvanizing process
• It is carried out by tinning
process.

Non-metallic coating
Non-Metallic Coatings
These coatings can be further classified as:
(a) Inorganic-coatings
(b) Organic-coatings
(a) Inorganic Coatings:
The main inorganic coatings on metals are
(i) Phosphate coatings are produced on steels by dipping them in suitable phosphate solutions.
(ii) Chromate coatings are used widely on magnesium alloys, and to a smaller extent on zinc. These thin coatings are
commonly obtained by dipping the metal in a chromate solution.

Phosphate coating
 Phosphate coating is the crystalline coating applied on the ferrous metals to inhibit corrosion.
 A phosphate coating is usually obtained by dipping the steel part in a dilute solution of phosphoric acid, possibly
with soluble zinc, or manganese salts.
 Immersion in a Zn salt bath containing phosphoric acid, causes growth of a crystalline zinc phosphate layer on the
surface of the base metal.
 Among these phosphates, manganese phosphate is more suitable for wear applications. Phosphate coating are usually
applied to carbon steel, low alloy steel.
 Typically thin coatings ~ 2.5 mm are obtained.
 Automobile bodies are given phosphalizing. This is used principally as an adherent base for the paint.

Chromate coating
 Chromate coatings are chemical or electrochemical treatments with mixtures of hexavalent chromium and
certain other compounds.
 It is type of coating which is used to passivate steel, aluminium, copper, magnesium.
 The coating serves as a corrosion inhibitor and as a primer to improve the adherence of paints and adhesives, as a
decorative finish, or to preserve electrical conductivity.
 It also provides some resistance to abrasion and chemical attack on soft metals.
 Chromate coatings are commonly applied to everyday items such as screws, hardware and tools. They usually
impart a greenish-yellow color to metals.
 The coating has a complex composition including chromium salts, and a complex structure.

Process
 Chromate coatings are usually applied by immersing the part in a chemical bath until a film of the
desired thickness has formed, then removing the part, rinsing it, and letting it dry.
 The process is usually carried out at room temperature, with a few minutes of immersion.
 The coating is soft and gelatinous when first applied, but hardens and becomes hydrophobic as it dries out,
typically in 24 hours or less.
 Curing can be accelerated by heating up to 700C but higher temperature will gradually damage the coating
on steel.
 The formulations typically contain hexavalent chromium compounds, such as chromates and dichromates.

Powder coating

 Why powder coat?
 Unlike conventional liquid paint which is delivered via an evaporating solvent, powder coating is typically
applied electrostatically and then cured under heat or with ultraviolet light.
 Elimination of volatile organic compounds (These VOCs escapes into air and contribute pollution outdoor
and inside our homes.
 Elimination of hazardous air pollutants and reduction in hazardous waste.
 Single component and solvent free material.
 Quick cure time.

Process
 A simple process generally used Spray gun to coat powder onto a metal surface. Typically the surface is steel,
aluminum or iron. Most of surfaces can be coated however, they must be able to withstand the high temperature
of the baking oven.
 Before coating the part, the surface must be cleaned. Often a sand blaster is used for this purpose. Parts must be
totally free of contaminants such as grease, rust, oil etc.
 As the powder leaves the gun, it is charged with static electricity. This charge then attracts the powder to the
surface that is being coated.
 After coating, parts are then baked in the oven about 200 oC for 10-45 minutes so that actual part will reach
these temperature to cure properly.
 While in oven, the powder melts and flows into smooth finish. Curing time is critical because under curing will
cause loss of adhesion and over curing will cause the decrease in strength of powder.
 The curing temperature of the powder can vary between different powders.

 The time needed in the oven, to reach the curing temperature of the powder, depends on the size and shape of
the substrate.
 Unlike painting, there are no runs or drips with powder coating, and due to the static charge, there is no need
of primers.
 If a mistake is made before baking, the powder can be simply blown off with air nozzle and reapplied. If the
mistake is realized after baking, the part must be sandblasted or coating may be burned off.

Powder types
 Thermoplastic
 Powder melts and flows to form a film.
 Continues to have the same chemical composition when it solidifies.
 Will re-melt when heated
 Examples:
1. Polyethylene
2. Polypropylene
3. PVC
 Thermoset
 Powder melt and flow which crosslink chemically to form products in the
form of film on the surface.
 Cured coatings have different chemical structure than the basic material
 Will not re-melt when reheated
 Can produce thin paint coating
 Ex. There are two main types of thermoset powders used for different applications which comes in many variety of
colors, textures and glosses
 Epoxy powder: Most indoor powders are made of epoxy. Epoxy is the most durable powder but it will become dull
from sun’s UV light
 Polyester powders (urethanes): They are not as durable as epoxy but since they are unaffected by UV light, used
mostly for outdoor applications.
Powder coating
Electrostatic Plasma
spraying Spraying

Electrostatic spraying
 For most of metal parts, coating material is applied via this method
 A process called electrostatic spray deposition (ESD) is typically used to achieve the application of the powder coating to
a metal substrate.
 The part to be coated grounded to release excess electric charge.
 By using a spray gun, which applies an electrostatic charge to the powder particles, which are then attracted to the
grounded part.
 After application of the powder coating, the parts enter a curing oven to cure the powder and form the film on metal part
 With the addition of heat, the coating chemically reacts to produce long molecular chains, resulting in high cross-link
density. These molecular chains are very resistant to breakdown.
 Powder coatings can also be applied to non-metallic substrates such as plastics and medium density fiberboard.

Plasma Spraying
 Plasma spraying is a coating process in which powders of the coating materials are fed into the plasma jet at
around 1500 0C, at which the coating materials melt and are sprayed over the substrate to be coated.
 Plasma spray coatings are applied using a high-temperature process where powdered coating material is injected into a
plasma jet. The material is rapidly heated and then accelerated toward the substrate.
 Once it reaches the surface, it begins to cool, forming a hard coating on the substrate and adding value to your final and
finished product, component, or assembly
 Plasma spray coatings creates a hard coating surface that protects substrates against wear, oxidation and corrosion
caused by environmental and operating conditions.
 The coatings are dense and strong, making plasma spray coating a favorable option for equipment protection.
 Used to produce a thin coating of 250-450 μm

Applications of Powder Coating
(i)Decoration of domestic appliances, heating and air conditioning equipments, computer, car accessories, etc.
(ii)Corrosion resistance of metals in outdoor and indoor applications like military, transportation, aerospace applications.
(iii)Dry film lubricants like graphite, MoS2, tungsten disulphide backed by binders like epoxy, phenolic resins, are applied
on metal surfaces for lubrication, by using powder coating method.

Advantages of powder coating
 It is environment friendly
 There is no solvent as in paints and thus no harmful air pollution
 There is absolutely no hazardous waste created with this process
 Overspray can be air vacuumed and reused, thus reducing the amount as waste produced as well as
saving cost.
Limitations
 Powder coating does not have the strength or hardness compare to other coatings such as zinc or
chromium coating
 Chipping is another main problem with powder coating. This often results because that part was not
baked long enough or not kept at proper cure temperature

Organic coatings
Organic coatings are inert organic barriers like paints, varnishes and enamels applied on metallic surfaces and other
constructional materials for both corrosion protection and decoration.
A good organic coating should process the following qualities.

i) Should be chemically inert to the corrosive environment.
ii) Should have good surface adhesion.
iii) Should be impermeable to water, salts and gases.
iv) Should possess good spreading capability

Why do we need paints?
Paints are surface coatings generally suitable for site use, marketed in liquid form.
They may be used for one or more of the following purposes

1. To protect the underlying surface from atmosphere, moisture.
2. To provide a decorative easily maintained surface.
3. To provide light- and heat-reflecting properties.
4. To give special effects

Paints:- Paint is a mechanical dispersion mixture of one or more pigments in a vehicle. Constituents of paints:-
Pigment: It is a solid substance which is an essential constituent of paint it provides

i) Capacity to paints ii) Strength to paint iii) desired color to paint iv) Esthetic appeal to the paint film. (v)
Protection to the paint film by reflecting harmful ultra violet light (vi) Resistance to paint film against
abrasion/wear (vii) impermeability of paint film to moisture (viii) increases the weather resistance of the film.
Important pigments used are i) whites – such as white lead, Zinc Oxide, litho phone, titanium oxide. Red
colored – red lead, ferric oxide, Venetian red, chrome red etc. Green colored: - Chromium Oxide Blue colored: -
Prussian blue Black colored: - Carbon black Brown colored: - Brown umber etc
Thinners:
i) Reduce the viscosity of the paint to suitable consistency, so that it can easily be handled and applied.
ii) Dissolves the vehicle and the additions increases the penetration power of the vehicle.
iii) Helps the drying of the paint film, as they evaporate. Common thinners are turpentine, benzene, dipentene,
naptha, kerosene etc

Oil Paints
•Well established and are the most widely used paints for general purposes including painting of wood
and metals.
•They were traditionally based on linseed oil but modern oil paints are manufactured.
•Once hardened, alkyd resin-based paints behave as thermosetting plastics, being resistant to solution in
oils from which they were formed.
•Unfortunately the hardening process continues slowly with time and these paints tend to become brittle
over a period of years, especially if exposed to sunlight. This leads to cracking.

Cathodic protection
In an electrochemical cell the reactions taking place at anode and cathode are :
e- e- e- e-
Liberation of H2
M Mn+ + ne- Metal surface Absorption of O2
e- e- e- e-
ANOdE CAThOdE
At anode dissolution of metal into metal ions At cathode e- are consumed and corrosion
Anode get
with the liberation of electrons corroded product formed

 Flow of electrons from anode to cathode generates some potential in metal surface and anode gets corrode.
 Total current discharged by anode is called local action current.
 If we stop the flow of electrons, then we can protect the metal from corrosion or we will reverse the direction
of flow of electrons.
 There are two methods by which we can protect the metal called as cathodic protection.
 Principle involved in this method is to force the metal to protected to behave like a cathode, thereby corrosion
does not occur.
Cathodic Protection
Impressed
Sacrificial anode
current

Sacrificial anode
 Metal which has to protected from corrosion is

Parent Metal
- connected by a wire to a more anodic metal, so that
all corrosion is concentrated at more active metal.
ANOdE  The most anodic (active) metals are at the
top and most cathodic (noble) at the bottom of
electrochemical series/reactivity series.
More active  The more active metal itself get corroded slowly
metal
and base/parent metal acts as cathode and it is
protected
 The more active metal so employed is called
“Sacrificial Anode”

Mg
Parent Metal Al
-
More active than Fe
CAThOdE
Zn
e-
e- Fe
Less active than Fe
e-
More active
metal
Sn
M Mn+ + ne- ANOdE
Pb
 At the more active metal (anode)l oxidation takes place by generation of
electrons and electrons will flow towards the parent metal which now acts as Cu
cathode.
 Thus we have protected parent metal and process is called cathodic protection
Application of sacrificial anode
 Underground iron metallic pipes are exposed corrosive environment in the soil. Hence corroded. But this pipe is connected
to more anodic metals like Mg i.e. the metal which is above to the iron in electrochemical series.
 The more anodic metal corrodes while iron pipeline behave as cathode hence protected. The electrons liberated from more
anodic metal magnesium travel towards iron pipeline.
 Thus, iron pipe becomes cathode and is protected while magnesium becomes anode and is corroded, thus protecting iron
pipe.
 Another applications include protection of underground cables, marine structures, water tanks etc.

Impressed current cathodic protection
 In this method, the parent metal is connected to -ve
Parent Metal -
terminal of external battery while +ve terminal
connected to auxiliary anode like graphite, high
CAThOdE - + silica iron, platinum

 The electron current is impressed in the opposite
e-
direction to corrosion current on the parent metal
 As consequence, the parent metal is converted to
Auxiliary
M Mn+ + ne- anode cathode and get protected
Insoluble anode like  An external battery is source of electron.
Graphite, high silica iron, platinum  As the current is impressed in the opposite direction
to corrosion current, hence method called as

impressed current cathodic protection.

In an electrochemical cell the reactions taking place at anode and cathode are :
e- e- e- e-
Liberation of H2
M Mn+ + ne- Metal surface Absorption of O2
e- e- e- e-
ANOdE CAThOdE
At anode dissolution of metal into metal ions Anode get At cathode e- are consumed and corrosion
with the liberation of electrons corroded product formed

 A corrosion current is the current produced in an electrochemical cell while corrosion is occurring. Electrochemical
corrosion involves the transfer of electrons from the anode to the cathode.
 The driving force for the flow of electrons is the difference in potential between the anode and the cathode. This process
is most evident in the corrosion between two dissimilar metals.
 When a metal is immersed in a liquid (electrolyte), it adopts an electrode potential (also known as corrosion potential).
The variance in potentials between the two metals results in a potential difference, which is responsible for the
movement of electrons from the anode to the cathode.
 The greater the potential difference, the greater the corrosion current generated, and therefore the more severe the rate
of corrosion at the anode.
 In this metal, an impressed current is applied in opposite direction to nullify corrosion current and convert parent metal
or corroding metal from anode to cathode.
 The impressed current is derived from direct current source like battery connected with insoluble anode like graphite,
high silica iron, platinum
 A sufficient current is applied to insoluble anode buried in soil or impressed in the corroding medium and connected to
metal to be protected
This type of cathodic protection has been applied to open water box coolers, water tanks, buried water pipes etc.

Anodic protection
 Principle: A metal is passivated by applying current in a direction that will make metal more anodic.
 It means that we are forcing metal to behave more and more anodic by applying anodic current in the
direction that will make metal more anodic.
 The growth of protective oxide film by the application of anodic current on metal surface in a suitable
corroding environment.
Anodic Protection
Potentiostatic Anodizing

Potentiostatic Anodic protection
 Using an electronic device called as potentiostat, we are forcing metal to undergo fast oxidation and form protective oxide
coating on exposed metal part as early as possible to protect beneath metal.
 The required potential for protecting the metal can be obtained from its potential-current curve.
 At an appropriate predetermined applied potential values, the changes in observed potential versus changes in the current
are plotted, thereby indicating corrosion/dissolution of metal at anode.

 When the current assumes a critical value I(crit), the development of
protective surface oxide film indicated
 The potential E(cirt)/E(pp) at critical value of current is known as
critical passivation potential for metal.
 Above Ecrit, the current drops a very small value, called passivation
current Ipass/Ip which may be defined as “The minimum protective
current density needed to maintain passivation in metal and
corresponding values of potential is called passivation potential Ep
 At this stage of Ep minimum corrosion of metal takes place because
the latter is already in fully passive state.
 Thus, only small current Ip if maintained is capable of keeping
metal in passive state and thereby reducing corrosion rate

 The metal to be protected is made as anode ( iron
Tank) in suitable oxidizing medium
 Tank is made anodic by using reference electrode Pt
and auxiliary electrode graphite
 Potentiostat (5) is used to apply desired potential
 Ammeter is used to watch corrosion current.
Minimum value of current indicates successful anodic
protection
 The potential of system is increased slightly to Ep
value to allow initial corrosion to take place
 Then the value of potential is slightly increased so
that current is always maintained at a very small value
Ip
 Thus by maintaining the values of both potential and
current Ip the metal remains in passivated state.
Anodizing
 Metals like Al, Ti, etc and their alloys form a thin oxide layer on their surface when exposed to air
 The oxide film is nonporous, uniform in nature thereby providing better corrosion resistance to base metal
 However, the thickness of naturally formed oxide layer is very small and it does not protect the base metal properly.
 To overcome this problem, the thickness of oxide film is increased by electrolysis.
 The anodized layer (oxide layer) also improves hardness, wear resistance etc.
In anodizing process
1. The component to be protected is connected as anode in electrolytic cell, contains strong electrolyte as conc. H2SO4
2. A small amount of current is passed which oxidizes the anode.
3. The thickness of oxide film formed is controlled by time and current density
4. The oxide layer then sealed by immersing the article in a bath of oil, wax, dye etc

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Corrosion Science

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

Tarnishing of silver wares, utensils when are exposed to air,

Formation of green film of carbonate (CuCO3) on copper when

The approximate estimate of loss of metal due to corrosion is 2

Classified by Alfa Laval as: Business

pure metals into more stable form such as its oxide,

sulfides, hydroxides etc. by action environment.

It is spontaneous and irreversible process.

Adversely affect desirable properties of materials.

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

It occurs in the absence of aqueous environment.

Corrosion occurs uniformly on entire metallic surface.

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Oxidation Corrosion by Liquid metal

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2M + n/2 O2 2 M n+ + n O2- M2On

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

This can be very easily explain by Pilling- Bedworth rule

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑜𝑥𝑖𝑑𝑒 𝑓𝑜𝑟𝑚𝑒𝑑

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

metal. Both these modes of corrosion cause weakening of solid material.

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

Dry Corrosion Wet corrosion

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

Susceptible metals Specific corrosive

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

Prevention of caustic embrittlement

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

A grain boundary is the interface between two grains,

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business

Classified by Alfa Laval as: Business