Unit iii part A

CORROSION & its control

CHEMISTRY CH132P/232P
 One of the most significant problems faced by advanced industrial society.
 30-40% iron and steel produced annually to replace the rusted materials.

 Touches everything – appliances used inside or outside home, on road, in sea, in

plants and in aerospace vehicles.
 Total cost of floods, hurricanes, fires, lightening and earthquakes are less than the
costs due to corrosion.
 Word corrosion derived from Latin word corrodere – means to gnaw
away.
 Metals undergo corrosion when exposed to air, water or other substances.
Example:- Rusting of iron, rusting weakens bridges, car bodies, etc.
Corrosion:- Defined as the destruction of the metals or alloys by the
surrounding environment through chemical or electrochemical changes.
 Pure metals have the natural tendency to revert back to their combined
states. Corrosion of a metal is the reversal of extraction.
Extractio
n

Metal ore Metal

Corrosio
n

 Erosion:- wearing away of nonmetallic coating materials such as

plastics, wood and ceramics by environment.
> Corrosion is continuous process and it is visible till it attains advance stage. In

metals the problems due to corrosion are

o Damage to the plants (chemical) and equipments.

o Wastage of raw materials which leads to the contamination of the

products

 Atmospheric air and water are the main factors which initiate corrosion.
 TYPES OF CORROSION

Dry corrosion: Corrosion occurs in a dry environment.

• By direct attack of dry gases through chemical reactions. Ex. Attack of dry oxygen or
air on metals.
• Dry corrosion, sometimes also called chemical corrosion, is a type of corrosion that
occurs without moisture or water, which are the main drivers of the conventional types
of corrosion.
• Here, metal oxidizes with only the atmosphere, in a process sensitive to temperature.
• Dry corrosion, therefore, refers to an oxidation process sustained by oxygen in the air
without a liquid solution.
• Dry corrosion is not as severe as wet corrosion in most cases
Wet corrosion:
• Corrosion occurs in an aqueous environment. The metal undergoes an
electrochemical reaction with the moisture and oxygen present in the atmosphere:
Ex: Rusting of iron.
• Wet corrosion of metals occurs through electron transfer, involving two
processes, oxidation and reduction.
• In oxidation, the metal atoms lose electrons. The surrounding environment then
gains the electrons in reduction. The metal, where electrons are lost, is called the
anode.
• The other metal, liquid or gas which gains the electrons is called the cathode.
 Dry corrosion Wet corrosion
The corrosion occurs in dry condition is The corrosion occurs in wet condition is
known as dry corrosion. known as wet corrosion.

Dry corrosion explain the absorption Wet corrosion explains the electrochemical
mechanism. mechanism.

The corrosion takes place in the dry The corrosion takes place in the wet
condition is uniform. condition is not uniform.

Dry corrosion is very slow process. Wet corrosion is a fast process.

Dry absorption occurs on the Wet corrosion occurs on heterogeneous

heterogeneous and homogeneous surfaces. surfaces only.
Dry corrosion takes place when there is Wet corrosion takes place when there is
direct attack of chemical substance in the electrochemical attack occurs in the presence
absence of the moisture. of the moisture or an conducting medium.
The product after the wet corrosion
The product after the corrosion
accumulates at the cathode while the
accumulate at the place where the
reaction is carried out at the anode that
corrosion actually occurred.
means at the opposite poles.
 Characteristics of Ideal Protective Layer
The oxide layer formed over the surface of certain metals acts as protective layer and they
have the following characteristics.

 Stoichiometric
 Highly insoluble
 Nonporous
 Low ionic and electronic conductivity.
 Low permeability
 Natural Formation
 Good corrosion stability
 Water resistance
 Chemical resistant
 Abrasion resistant
Alumina layer forms almost instantaneously, creating a thin, yet highly protective barrier over
the aluminum surface. The reaction is self-limiting, meaning that once the surface is covered
with alumina, further reaction is minimized because the layer is impermeable to oxygen.
Generally, Oxides of metals such as TiO2 , ZnO, CrO3, Al2O3 etc.. are more stable than metal
chlorides, bromides.
 Electrochemical theory of CORROSION
 When a metal like iron exposes to air, following electrochemical changes occurs,

(i) Formation of Galvanic cell:- Anodic and cathodic areas are formed resulting in
minute Galvanic cells.

(ii) Anodic reaction:- Oxidation takes place by release of two electrons, results in
corrosion of iron.

Fe → Fe2+ + 2 e-

(iii) Cathodic reaction:- Reduction occurs by the flow of electrons from anode to
cathode.
 Reduction can takes place in 3 different ways,

(i) If solution is aerated and almost neutral, oxygen reduced in the presence of H 2O
to OH-
O2 + 2H2O + 4e → 4 OH-
 If the solution is deaerated and neutral, water reduced to H 2 and OH-.

2H2O → 2H+ + 2 OH-

2H+ + 2e-→ H2

2H2O + 2e-→ H2 + 2 OH-

 If the solution is deaerated and acidic, the H+ ions are reduced to H2.
2H+ + 2e-→ H2

 Metal ions formed at the anode combines with OH- ions to form the metal
hydroxide and finally the hydrated metal oxide (rust).
2Fe2+ + 4OH-→ Fe(OH)2

2 Fe(OH)2 + O2 + (n-2) H2O→ Fe2O3. nH2O

 Diagrammatic representation of
Electrochemical theory of CORROSION

AI R
Water film /
moisture

Anodic area Cathodic Area

Anodic reaction : Fe → Fe2+ + 2 e-

Cathodic reaction : O2 + 2H2O + 4e → 4 OH-

 Rate of CORROSION

Rate of corrosion = icorr / nF grams per second

icorr = corrosion current

n = charge of the ion

F = Faraday constant

The total current due to the cathodic and anodic

reaction must be equal but opposite in sign

( icorr) = -Σia = Σic

 Reason behind the formation of galvanic cell /
corrosion
 Due to the presence of heterogeneities at the interface of metal and
environment.
 The heterogeneities may develop due to several reasons,

 Difference in concentration of air or oxygen (area in contact with

more air or oxygen act as cathode, while area in contact with less air or
oxygen acts as anode).

 Contact of two different metals (Example:- copper and iron –

copper acts as cathode and iron acts as anode).

 Stress in the metal (area under strain acts as the anode).

 Types of corrosion

 Differential metal corrosion

 Differential aeration corrosion

 Stress corrosion

 Grain boundary corrosion

 1. Differential metal corrosion
> A potential difference is developed if two different metals are in contact with

each other. Metal acts as the anode undergoes corrosion and the metal act as the

cathode is unaffected.

 Metals higher in electrochemical series act as anode to the metal below to it.

Example:- Fe is anodic to Cu, Ni and Sn

but, Fe is cathodic to Zn and Mg.

Therefore, Fe corrodes in contact with Cu, Ni and Sn. Whereas , Zn and Mg corrodes

in presence of iron.

 Anode: Highly electropositive/ metallic/ lower electrode potential/ lower position

in electrochemical series.
 The rate of corrosion depends on the amount of current passes from anode to

cathode.

 Higher the potential difference, higher the corrosion.

Example: Iron / copper : Iron undergoes corrosion

e-

Fe Zn
Fe Cu

e-

Example: Iron and Zinc : zinc undergoes

corrosion and iron is unaffected
 2. Differential aeration corrosion
 Occurs due to the difference in the concentrations of air over the surface of
the metal.
 A strip of pure iron partially immersed in an aerated solution of sodium
chloride.
 Concentration of oxygen is high at the surface than inside the solution.
 Area near the water line (above the surface of the water) acts as cathodic area.

 Lower concentration of
oxygen at the bottom part makes
it anodic area.
 Electrons pass from bottom
portion to top portion and
corrosion products forms at the
junction.
 Examples for differential aeration corrosion,

(i) water-line corrosion and (ii) pitting corrosion

(i) Water-line corrosion:-

 Observed mainly in steel water tanks.

 Metal just below the water-line is more anodic (less oxygenated).

 The meniscus (creep) which is immediately above the water-line is more

oxygenated, acts as the cathode and is unaffected.
  This type of corrosion commonly observed in ships floating in seawater for
long periods of time.

(ii) Pitting corrosion:-

 Caused by the deposition of dust particles on metal surface.

 The portion covered by dust particles will be less aerated compared to the
exposed surface.
 The exposed portion becomes cathodic and the covered portion becomes
anodic.

 In the presence of electrolytes and moisture,

corrosion starts beneath the dust resulting in a
pit.
 The formation of small anodic area and the
presence of large exposed cathodic area
accelerates the rate of corrosion.
 3. Stress corrosion
 Two samples of steel, one of which is under stress, are placed in a corrosive
environment, stressed specimen corrodes at a faster rate.
 Stress can be due to ,

Poor design, Riveting, Cold working, Welding, Bending, Pressing,

Quenching.
 Stressed portion becomes anode with respect to the unstressed portion under
corrosive environment.
 Presence of both stress and specific environment are necessary for stress
corrosionceases
 Cracking to occur.
when either
the corrosive environment or
the tensile stress is
eliminated.
 Reason behind STRESS CORROSION ?

 The atoms are displaced slightly due to stress which results in the
formation of the anodic zone of higher potential.
 The stress produces strains which results in localized zones of high
energy.
 These high energy zones are easily attacked even by the mild
corrosive agents.

Example, Crack progress in a plane perpendicular to the stress.

Stress is a force that can cause a change in a physical body

Strain is the change in shape or form of an object when stress is applied

 What type of corrosive environment
required for a stress corrosion ?

Corrosive Metal / Alloy Corrosive environment

Mild steel Sodium hydroxide
Low carbon steel Nitrates (Ca(NO3)2, NaNO3)
Stainless steel Metal chlorides (MgCl2, ZnCl2, LiCl, NaCl )
Brackish / sea water
Solution of NaOH and H2O2
Nickel Strong solution of alkalis (NaOH or KOH)
Brass Vapours of NH3 and Ammoniacal solution
 Example for stress corrosion - Intercrystalline Corrosion or Caustic
Embrittlement in boilers.
CAUSTIC EMBRITTLEMENT
 Fine cracks are formed at the stressed portion of the mild boilers.
 The alkaline impurities present in the water penetrate through the fine cracks
by capillary action.
 During heating water evaporates and caustic soda settles in the cracks.
 An electrochemical cell is set up between the iron under stress (ANODE) and
the iron in the main body which is free from stress (CATHODE).
 Iron surrounded by dilute NaOH is the cathode and the iron under stress acts
as the anode and gets corroded resulting in boiler failure.
Iron Concentrate Dilute
Iron
under d NaOH NaOH (in
(main
stress (in the boiled
body)
(anode) cracks) water)
 a. Factors affecting rate of corrosion

Primary factors (Due to Metal ) Secondary factors (Due to Environment)

Electrode potential pH

Anodic and cathodic areas Temperature

Nature of surface of the metal Conductance of the medium

Surface protective film Humidity

Polarization of the electrode Presence of the impurities in the

surface environment

Hydrogen over voltage Acid fumes

Surface state of the metal Hydrogen sulphide

 1. Potential difference

 The potential difference between the anodic and cathodic area is known as the
corrosion potential.
 The larger the potential difference higher is the rate of corrosion.

 Potential difference between iron and copper is 0.78 V, which is more than Fe
and Sn (0.3 V). Therefore, Fe corrodes faster in contact with Cu than in contact
with Sn.
 Farther the positions of the metals in electrochemical series, greater the intensity
of corrosion of the anodic metal.
 Use of dissimilar metals avoided to minimize this type of corrosion.

 But the actual rate of corrosion is determined by the polarization of the electrode
areas.
 2. Anodic & cathodic areas

 Corrosion occurs fast if ANODE is small and CATHODE area is large.

Example:- Coating of zinc on iron protects iron ; iron acts as cathode and

zinc acts as anode.

 3. Nature of corrosion product
 The product of corrosion is a thin oxide layer over the surface of the metal.

 This layer determines the further corrosion rate of the material.

 The oxide layer acts as protective layer if the layer composition is

stoichiometric, highly insoluble and nonporous with low ionic and electronic

conductivity.

 The layer prevents further corrosion.

 Example:- Al, Ti and Cr develops such layers. Stainless steel (18% Cr and 8% Ni)

builds a thin films (20 Ao), but a highly protective film of Cr2O3.

 Ta, Zr and Mo forms a protective layer and this layer is capable of self repairing

oxide layer when it is damaged.

 4. Polarization of electrode surface

 Corrosion is due to the flow of electrons from anodic area to cathodic area.

 Magnitude of current depends on the extent of polarization of the electrodes.

 There is an irreversible tendency around the electrodes which tend to oppose

the direction of current flow. This is called polarization of electrodes.

 Polarization: The deviation of the potential of an electrode from the open circuit

potential due to irreversible reactions around the electrode.

 This tendency makes anode to become more cathodic and vice versa.

 Therefore, as a result of polarization effect, potential difference between the

electrodes decreases steadily and hence the current flowing from anode to

cathode which in turn reduces the corrosion.

 When corrosion begins the concentration of electrolyte around the electrode
surface and the bulk of the electrolyte changes.
 For corrosion to progress, species must be supplied or removed from medium
by diffusion.
 Diffusion is low in non-conducting medium, at low temperature and at low
concentration.
 Under these conditions electrodes gets polarized and rate of corrosion
decreases.
 The deviation in potential finally reaches equilibrium (steady state) at which
the rate of oxidation at anode is equal to the reduction at cathode.
 The potential at steady state is called corrosion potential E corr . The current

corresponding to this steady state is called corrosion current (i corr);

where, icorr = ia = ic
 Greater the polarization of the electrodes on anode or cathode smaller is

the corrosion current and smaller the corrosion, this is applicable even if the

potential difference between the electrodes is high.

Anodic polarization: If the anode alone undergoes polarization the rate of

corrosion is controlled by the potential of the anode alone known as anodic

polarization.

Cathodic polarization: If the cathode alone undergoes polarization the rate

of corrosion is controlled by the potential of the cathode alone known as

cathodic polarization.

Mixed control: If both the electrode undergoes polarization.

 5. Hydrogen Overvoltage

 Applicable to metals undergoing corrosion in acid environment.

 In deaerated conditions, cathodic reaction is the release of H 2.

 Evolution of H2 gas in the cathode determines the extent of corrosion in

deaerated conditions or non-oxidizing acidic environment.

 This is measured in terms of Hydrogen Overvoltage.

 Hydrogen overvoltage is difference in potential between the cathode at which

hydrogen is evolved and that of hydrogen electrode at equilibrium in the same

solution.

H2 overvoltage =  measured – 0.0591 log[H+]

=  measured + 0.0591 pH

Where  is the potential of cathode at which hydrogen evolution takes place.

 How Hydrogen over voltage affects ?

 The release of H+ ions increases with increase in rate of cathodic reaction.

 The accumulation of H+ ions increases the rate of corrosion due to acidic

environment.

 The conversion of H+ ions into hydrogen molecules reduces the acidic

concentration which in turn indirectly reduces the corrosion.

 The increase of hydrogen over voltage, slower the rate of corrosion in acidic

environment.
Factors affecting Hydrogen over voltage:-

 Increase in temperature decreases hydrogen voltage.

 Roughening the surface of metals decreases hydrogen voltage.

 Presence of P or As decreases the formations of hydrogen molecules which

reduces the rate of corrosion.

6. Surface state of a metal

 The rate of corrosion is high.

If surface of metal is rough and uneven.

Presence of cracks and bends.

Presence of acid environment.

 Secondary factors

a. pH

 Rate of corrosion increases with decrease in pH.

 At pH greater than 10 corrosion ceases due to a protective coating of

hydrous oxide is formed.

 At pH between 3-10 the presence of oxygen is essential for corrosion.

 At pH less than 3 corrosion happens even in absence of air due to

evolution of hydrogen from cathodic areas.

 b. Temperature

 Rate of corrosion increases with increase in temperature due to,

• Increase in conductance of aqueous medium

• Increase in rate of diffusion

• Decreases passivity which increases rate of corrosion again.

 c. Humidity

 The rate of corrosion increases with humidity.

 Above a certain relative humidity known as critical humidity corrosion

takes place at rapid rate.

Less than 60% of relative humidity iron rusts very slowly beyond this value

it undergoes rusting much faster rate, due to porous capillary structure.

 The capillaries get filled at relative humidity and at critical humidity the

pores are filled.

 An increase beyond critical humidity will allow water to penetrate the

surface results in severe rusting of iron.

 D. Presence of impurities in atmosphere

 0.01% of SO2 and relative humidity of 50% after 60 days negligible corrosion.

 0.01% of SO2 and relative humidity of 90% exhibits severe corrosion in one day.

 Rate of corrosion decreases in presence of CO2 due to two reasons :

1. CO2 modifies gel structure of rust becomes less permeable.

2. CO2 forms insoluble basic carbonate on the surface which offers protection to metal.

 High levels of H2S reduces corrosion in steels, this is due to

Formation of metal sulphide at temperature above 60 0C accompanied by liberation of

hydrogen .
 E. Acid fumes

 HCl and H2SO4 are used in industry.

 These alloys are used to protect the metals from H 2SO4

(i) Cast iron with 14.5% Si – Duriron

(ii) Lead alloys

Chemical lead - (0.06% copper)

Hard lead – (4-15% Sb)

Zn, Cd, Ni, Fe are not resistant to H2SO4 fumes.

 Why HCl is More Corrosive Than H2SO4

 Higher solubility of chlorides.

 Higher mobility of chloride ions.

 These alloys are resistant to HCl fumes,

1. High silicon iron alloy containing molybdenum – DURICHLOR

2. A nickel alloy with high molybdenum content – CHLORIMENT

 GALVANIC SERIES Mg
Zn
 The galvanic series determines the electrochemical potential Al
Cd
and nobility of metals and metal alloys.
Mild
steel
 The series in which the metals are arranged in an increasing
Cast iron
order of their electrode potential values. Pb
Sn
 This table is made by studying the corrosion of metals in the Brass
Ni
environment without the removal of oxide film.
Stainless
 A metal higher in the series is more anodic and undergoes steel
Ag
corrosion faster compared to metals present below. Ti
Au
• When two metals are submerged in an electrolyte, while also
electrically connected by a metallic conductor, the less noble will
experience galvanic corrosion.
• The less noble metals becomes the anode and corrodes faster than it
would all by itself, while the other becomes the cathode and corrodes
slower than it would alone.
Corrosion control
 Corrosion can be controlled by the preventing the formation of galvanic cells.

This can be done in different ways,

1. Design and selection of materials

2. Protective coatings
(I) Inorganic coating
(A) Metal coatings:- Anodic and Cathodic
(B) Surface conversion coatings:- Anodizing and Phosphating
(II) Organic Coatings
Example:- paints and enamels
3. Cathodic protection
4. Anodic protection
5. Corrosion inhibitors
 1. Design and selection of materials

1. Avoid use of dissimilar metal, choose materials having closer potential values.

2. Cathode must be small anode must be of large surface area

3. Anode should not be painted when in contact with cathode this decreases

anodic area.

4. Bolt, nut, rivets must be made up of materials which can act as cathode.

5. An insulator is needed to avoid contact between two dissimilar metals.

6. Porous materials like asbestos, wood and magnesia should not be used as

insulators since they hold liquids and they act as electrolytic conductors.

7. Gaps must be avoided since some liquids can trap which results in differential

, , aeration corrosion.
8. Welded joints are preferred than nuts, bolts and rivets in low pressure boilers and

chemical plants.

9. Stress corrosion can be avoided by annealing.

10. Prior designing of the equipment includes,

a. Supported legs instead of large blocks to facilitate air circulation and prevention of

stagnant pool and damp areas.

b. Smooth edges which can avoid dust accumulation which prevents pitting corrosion

and differential aeration corrosion.

 2. Protective Coatings

 Corrosion can be controlled by covering the substrate or base metal by another

metal, known as metal coating.

(I) Inorganic coating

(A) Metal coatings:- Anodic and Cathodic
 There are two types of inorganic metal coating,
i) Anodic metal coating
ii) Cathodic metal coating
i) Anodic metal coating

 The metal / equipment to be protected are coated using metals which are

highly anodic. Example:- Hot dipping, galvanizing, etc.

 The anodic coating if peels off undergoes corrosion slowly due to the large

anodic area and small cathodic areas.

 Hot Dipping
 Dipping the base metal (metal to be protected) into molten anodic metal.
 The coating metal is melted at a relatively low temperature.
 The base metal must with stand this temperature without undesirable changes in its
physical and chemical properties.
 Process of Coating zinc on iron by hot dipping is called Galvanizing.
 Galvanization of iron includes following steps,
(i) Degreasing of iron with organic solvents.
(ii) Pickling sheet is washed with sulphuric acid and later rinsed with water.
(iii) The sheet is treated with aqueous solution of ZnCl2 and NH4Cl and dried.
(iv) The sheet is dried and dipped in molten zinc (430-470 0C).
(v) Excess zinc over the iron surface is removed by rolling wiping or passing
trough blast air.
ii) Cathodic Metal Coatings

 Cathodic metal coatings are coating with metals which are catodic to the specimen.

Example:- Coating of copper , Nickel and chromium on iron.

 They should cover the surface of the specimen without leaving a pin hole.

 Otherwise, rapid corrosion of the base metal takes place due to large cathodic and

small anodic area.

 The process of coating tin on iron is called Tinning.

 Tinning is the process of thinly coating sheets of wrought iron or steel with tin,

and the resulting product is known as tinplate.

 Involves following steps,

(i) Degreasing of iron with organic solvents.

 (ii) Pickling sheet is washed with sulphuric acid and later rinsed with water.

(iii) The sheet is treated with aqueous solution of ZnCl2 and NH4Cl and dried.

(iv) The sheet is dried and dipped in molten tin

(v) Excess tin over the iron surface is removed by rolling.

(vi) The coated tin is dipped in palm oil to avoid oxidation.

Cathodic Metal Coatings - Advantages of Tinning

 Tin is non toxic.

 Tinning gives a fine film which completely covers the surface and avoid
corrosion.
 Tinning is economical than electroplating.
 (B) Surface conversion coatings:- anodizing and phosphating

i) Anodising
 Al as cathode, allows electrons to pass through.
 Aluminium is made as anode by connecting it to a metal which can act as
cathode.
 Anode ceases to conducts electricity when it is made anode in aqueous solution
of chromic acid and sulphuric acid due to anodic passivity known as anodising
or anodic oxidation.
 The passivity of Al is due to the formation of thin layer of Aluminium oxide
over Al.
 Mg, Ti, Ta, V and Zn also forms anodic films but not found any commercial
applications.
 Gives attractive finish and environmental safety makes anodised Al as one of the most

widely used industrial, commercial and domestic material.

 Anodizing involves following steps,

1. The anode is degreased, polished and connected to the anode.

2. The electrolyte – 5-10% chromic acid, The temperature of bath is 35 0C.

3. Potential applied - 0-40 V during first 10 minutes.

4. An opaque oxide layer of 2-8 m thickness is obtained.

5. The article is dipped in dye at 50-60 0C and finally dipped in nickel acetate

followed by boiling water.

 ii) Phosphating
 Process of depositing a coating of metal phosphate over metal surfaces known as

phosphating.

 The metal to be coated treated with solutions contain a mixture of free phosphoric acid,

a metal phosphate and an accelerator.

 Accelerator speed up reaction and reduce the crystal size, normally nitrates are used as

accelerators.

 pH = 1.8 - 3.2, temperature – 35 0C

 The process of phosphating involves

a. Dissolution of metal as metal ions

b. Reaction of metal ions with the phosphate ions to form metal phosphates

c. Deposition of metal phosphates on the surface of the metal .

 II. Organic coatings
 Metallic surfaces can be coated with paints or enamels with the capacity to inhibit corrosive
attack. The term organic coating is used when the layer thickness is less than 0.4 mm.
 Coatings thicker than 0.4 mm are referred to as mastics or linings.
 Coating of meal surface with organic coating involves two stages.

Preparation of metal surfaces (I stage)

1. Removal of rust by mechanical brushing followed by pickling in dilute sulphuric acid
2. Treating with wash primer (consists of phosphoric acid). This converts residual rust into
insoluble adherent phosphate coating.
3. Coating with priming paint containing corrosion inhibitive pigment such as zinc chromate
red lead or heavy metal benzoate.
Zinc rich paint-consisting of epoxies, chlorinated
hydrocarbons, and other polymers; or inorganic
based on organic alkyl silicates
Multi coat of paint (II stage)
4. The undercoat of pigment is given to decrease the permeation of
water, finally the surface is provided with multicoat of paint.
 3. Cathodic Protection

 Electrons flow from anode to cathode ; cathode is unaffected.

 A method to protect a specimen or material from corrosion by providing

electrons from an external source is known as cathodic protection.

 Cathodic protection is based on reversing the flow of electrons.

 Two important method of cathodic protections,

(i) Sacrificial anode method:

 Converting anodes to cathode by using metals
which is more anodic than material to be protected.
 The anodic metal which undergoes corrosion is
known as sacrificial anodes.
 (ii) Impressed voltage method:
 The electrons are supplied from an external source of direct current, the material to be

protected is connected to the negative terminal of the source.

 The cathode is material to be protected and the anode is resin bonded graphite rod, high

silicon – iron alloy or platinized Ti or Ta connected to positive terminal.

Schematic diagram showing the set-up of Impressed Current

Cathodic Protection (ICCP) System
 4. Anodic Protection

 Metals like Ti and alloys like stainless steel readily gets passive and

cannot be offered cathodic protection.

 Anodic protection involves deposition of an oxide film on a metal

surface by applying anodic current in an oxidising environment.

 Minimum potential required to protect the metal can be obtained from

potential-current curve.
 Y

 Initially current increases along AB,

Passive
C
shows the dissolution (corrosion) of --------------------------------------------

Potential
the metal. ---------------------------------
B
Ep
Active
 When current reaches Icri, oxide layer
A
(passivation) starts forming.
Ip Current Icri X

 Potential at Icri is called passivating potential (Ep).

 Above Ep (along BC) current flow decreases to very low value – passivating current I p.

 Ip is the minimum protective current density to maintain passivation.

 At this stage, an increase in potential will not corrode the metal as the metal is in a highly

passive state.
 Anodic protection is used for carbon steel storage tanks containing extreme pH
environments including concentrated sulfuric acid and 50 percent caustic soda where
cathodic protection is not suitable due to very high current requirements
 Advantage:- (i) Requires only a very small amount of current.
 Disadvantages:-
(i) Cannot be applied to metals which do not passivate.
(ii) Corrosion rate cannot be reduced to zero.
 Finds application mainly in the transportation of concentrated acids using steel containers.
Potentiostat

 A schematic arrangement for anodic protection In

Out
device consists of
ΔE
•Generator cable of producing high current density
•An auxiliary platinum electrode
Reference electrode
•A reference calomel electrode
-----------------------------
•A potentiostat to maintain constant potential ----
Pt
•A specimen kept in oxidizing atmosphere as anode. Oxidizing medium
Metal
 Working,

(i) The potential is first increased to (Ep) for initial corrosion to occur.

(ii) Then potential is slightly increased to (Ef ) flade potential where current

decreases to small value.

(iii) Potential is kept constant to Ep and current is maintained at ip.

5. Corrosion Inhibitors

 Chemicals which slow down anodic or cathodic reactions by forming a

film over anode or cathode.

 Two types,

(i) Anodic Inhibitors

(ii) Cathodic Inhibitors

 (i) Anodic inhibitors

 Oxidising agents; chromates, molybdates, tungstates, nitrites, etc.

 Oxidizes the surface of the anode forming a thin protective layer of oxide or

chromate, thus decreases the rate of anode reaction.

 Chromates and nitrites maintain the protective layer even in the absence of

oxygen.

 Chromates used as inhibitors in the IC engines, rectifiers and cooling towers.

 To achieve inhibition concentration of the inhibitors should exceed a minimum

value, if it is below that concentration, they increases the corrosion rate.

 Critical concentration for chromates and nitrites are in the range of 10 -3 to 10-4 M.
(ii) Cathodic inhibitors

 Inhibits cathodic reactions like liberation of H2 and OH- .

 Organic cathodic inhibitors are,

amines, mercaptans thioureas and sulphoxides – effective towards acidic

medium.

 Forms a protective layer on cathode and prevents corrosion.

 Inorganic cathodic inhibitors are,

 sulphates of Mg, Mn, Ni and Zn in neutral or alkaline medium.

 React with OH- liberated at cathode forming insoluble hydroxides which

form a protective film over cathodic area.

 Neutral hydroxide layer does not conduct electrons and hence no corrosion.
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