CORROSION

The word Corrosion is derived from Latin word CORRODERE, is defined as

“The destruction or deterioration and consequent loss of metals or alloys through chemical or electrochemical attack
by the surrounding environment”.

Metal Metal ore

The primary factors that initiate corrosion on metals are atmospheric air, water and conducting surface of the metal.
e.g., i) Rusting of iron (formation of hydrated ferric oxide (Fe2O3.nH2O), a reddish-brown scales),

ii) Green scales on copper vessels [It is due to the formation of basic cupric carbonates (CuCO3 + Cu (OH)2)]

Cause of Corrosion:

Metals exist in nature in the form of carbonates, sulphides and sulphates. These chemically combined states of metal
“known as ore” has a low energy and is thus thermodynamically stable state of metal. A considerable amount of
energy is required during metallurgy. The extracted metal has higher energy and thus it is thermodynamically
unstable state. Metals do this interacting chemically or electrochemically with its environment to form compound at
the surface and thus metal undergo corrosion.

Types of Corrosion

Corrosion of metal occurs either by direct chemical attacks or by electrochemical attack on the metal by the corrosive
environment.

1) Dry or Chemical Corrosion

2) Wet or Electrochemical Corrosion

1) Dry or Chemical Corrosion: If the corrosion takes place due to direct chemical attack (in the absence of moisture)
only in presence of atmospheric gases such as O2, N2, H2S, SO2 is known as dry corrosion. It is further of following
types:

a) Corrosion by O2 or oxidation corrosion.

b) Corrosion by other gases.

2) Wet or Electrochemical Corrosion: If the corrosion of metal takes place due to electrochemical attack in presence
of moisture or a conducting medium such corrosion is known as wet corrosion or electrochemical corrosion.

• When metals are exposed to air, moisture, soil etc. then they undergo corrosion through electrochemical
process.
• In this process a separate anode and cathode areas are form on the metal surface.
• Corrosion always occurs at the anodic areas of metal through oxidation reaction and release electron.
• The liberated electron from anode, move towards cathode, where reduction take place.

The overall theory is known as electrochemical theory of corrosion or Wet theory of corrosion because corrosion
takes place in presence of moisture.

The flow of free electrons in this corrosion takes place through following processes:

a) Hydrogen liberation
b) Absorption of Oxygen

a) Hydrogen Liberation

• Evolution of hydrogen occurs in acidic medium.

• Anode Area> Cathode Area
Let’s considering the metal Fe,

• Anodic reaction is dissolution of iron as ferrous ions with Liberation of electrons.

Anode: Fe Fe2+ + 2e- (Oxidation)

• The electrons released flow through the metal from anode to cathode, whereas H+ ions of acidic solution are
eliminated as hydrogen gas.

Cathode: 2H+ + 2e- H2 (Reduction)

• The overall reaction is:

Fe + 2H+ Fe2+ + H2

Mechanism of Hydrogen Liberation

b) Absorption of Oxygen

• The rusting of iron takes place in neutral aqueous solution of electrolytes (in presence of atmospheric oxygen).

• Cathode Area > Anode Area

If the metal surface develops cracks,

• Anodic areas are created on the surface whereas the metal parts act as cathodes.

At anode: Fe Fe2+ + 2e- (Oxidation)

• The released electrons flow from anode to cathode through iron metal.

At cathode: ½ O2 + H2O + 2e- 2 OH- (Reduction)

• Fe2+(at anode) and OH- ions (at cathode) reacts with each other and form ferrous hydroxide Fe(OH)2
precipitate

• The overall reaction is:

Fe2+ + 2 OH- Fe(OH)2

• [Fe(OH)2 is deposited near to cathode because Fe2+ (being smaller in size) diffuse faster than OH- (being larger
in size)]

• If oxygen is in excess, ferrous hydroxide is easily oxidized to ferric hydroxide.

4Fe (OH)2 + O2 + 2 H2O → 4 Fe(OH)3 (Yellow rust)

• Limited O2 results formation of black anhydrous magnetite Fe3O4

Comparison of Chemical Corrosion with Electrochemical Corrosion

Dry Corrosion Wet Corrosion

Occurs in absence of moisture Occurs in presence of conducting medium
Involves direct attack of chemicals on the metal
surface Involves formation of electrochemical cell
Slow process Rapid process
Corrosion products are produced at the site of Corrosion occurs at anode but rust is deposited at
corrosion cathode
Process of corrosion is uniform Depends on the size of the anodic part of the metal

Unit of Corrosion: It is measured in mils per year(mpy) and Millimeter per year(mmpy)

Types of Wet or Electrochemical Corrosion

1. Galvanic Corrosion / Bimetallic corrosion/ Differential metal corrosion

2. Concentration cell/Differential aeration corrosion
• Waterline Corrosion
• Pitting Corrosion
• Crevice Corrosion
3. Stress Corrosion
• Caustic Embrittlement

1. Galvanic Corrosion / Bimetallic corrosion/ Differential metal corrosion

• This occurs when two dissimilar metals are in contact with each other in a corrosive conductive medium. The
two metals differ in their tendencies to undergo corrosion. A potential difference is set up resulting in a
galvanic current.
• The metal with lower electrode potential (more active metal) acts as anode and the metal with higher
electrode potential acts as cathode.
• The potential difference between the two metals is the driving force for corrosion. Higher the difference
higher is the rate of corrosion.
• The anodic metal undergoes corrosion whereas cathodic metal remains unaffected.

E.g., when iron is in contact with copper, iron has lower electrode potential acts as anode and undergoes oxidation
as,

Fe → Fe2+ + 2e-
 2Fe2+ + 4OH- 2Fe (OH)2

In an oxidizing environment, the insoluble Fe (OH)2 oxidized to ferric oxide as following reaction

4Fe (OH) 2 + O2 + 2H2O 2(Fe2O3. 3H2O) yellow rust

Whereas copper which is having higher electrode potential acts as cathode remain unaffected.

The rate of galvanic corrosion depends upon

• potential difference between anodic and cathodic metals,

• ratio of anodic and cathodic area
• environmental factors and
• tendency of the metal to undergo passivity etc.

2. Concentration cell/Differential aeration corrosion

• Differential aeration corrosion occurs when metal surface is exposed to the differential air or oxygen
concentration, which develops galvanic cell and initiates the corrosion.
• The part of the metal exposed to lower oxygen concentration acts as anode and the part of the metal exposed
to higher concentration acts as cathode, so that poorly oxygenated region undergoes corrosion.

• At anode (less oxygen concentration) oxidation of metal takes place;

M Mn+ + ne-

• At cathode (more oxygen concentration) reduction of metal takes place;

O2 + 2H2O + 4e- 4OH-

• Examples:
1. Part of nail inside the wall, being exposed to lower concentration the exposed part, under goes corrosion.
2. Window rods inside the frame suffer corrosion but not the exposed region.
3. Paper pins inside the paper gets corrode and the exposed part is free from corrosion.
4. Metals under extraneous matter i.e., dirt, dust, sand or any other impurities undergo corrosion.
a) Water line corrosion

• This is a case of differential aeration corrosion commonly observed in steel water tanks, ocean going ships
etc. in which portion of the metal is always under water

• The part of the metal below the water line is exposed only to dissolved oxygen while the part above the
water is exposed to higher concentration of oxygen. Thus the metal part below the water line acts as anode
whereas above the waterline acts as cathode. Hence a difference in potential between the electrode is
created which causes a flow of current between the two differentially aerated areas of the same metal and
causes corrosion at anode.

b) Pitting Corrosion

• Pitting corrosion is generally initiated by the deposition of extraneous matter such as sand, water droplets,
dirt, dust etc., on a metal surface due to the breakdown of the protective film on the surface of a metal.

• The portion covered by the dust will not be well-aerated area compared to the exposed surface hence the
covered surface becomes anodic with respect to the surface exposed. In presence of conducting medium
(moisture) corrosion starts below the dust part and forming a pit. Once pit is formed the ratio of corrosion
increases, because of the formation of smaller anodic and larger cathodic area intense corrosion takes place.

• Pitting corrosion is a highly localized and accelerated corrosion and one of the most destructive forms of
corrosion.

• It causes equipment to fail because of perforation with only a small percent weight loss of the entire
structure. Because of the small sizes of the pits it is highly difficult to identify the pitting corrosion.
c) Crevice Corrosion

Crevice corrosion occurs between two joining surface which may be metal-metal or metal-nonmetal crevice. In
crevice corrosion, the joining surface area has low concentration of oxygen as compare to other area. The portion
with lower concentration of oxygen become anode and portion with higher concentration of oxygen becomes
cathode.

It is localized corrosion of metal or alloy surface.

3) STRESS CORROISON

• Stress corrosion of the metal formed by the combined effect of a tensile stress and a specific corrosive
environment. During stress corrosion, the metal or alloy is virtually unaffected over most of its surface, while
fine cracks progress through it normal to the direction of tensile stress

• The stress on the metal may be internal or external and stress is due to some mechanical (pressing,
hammering, bending etc.) or service conditions.

• The metal atoms under stress are always at higher energy level so acts as anode and stress-free parts of
metal acts as cathode as a result of this corrosion cell is formed.

• Example for stress corrosion is caustic embrittlement and season cracking.

a) Caustic embrittlement

• It is a form of stress corrosion taking place in boilers operating at high temperature and pressure. Caustic
embrittlement focus at stressed part of boilers such as cracks, rivets, bents, joints etc.

• Water used in boilers generally contain Na2CO3 (used for softening of hard water) which is hydrolysed at high
temperature to NaOH.

Na2CO3 + H2O 2NaOH + CO2

• The NaOH produced gets accumulated in stressed regions of boiler. When the concentration of NaOH
reaches sufficient level (> 10%) it attacks iron by developing cracks and makes the metal brittle by the
deposition of the product leading to corrosion and boiler failure.

2 NaOH + Fe Na2FeO2 + H2

3Na2FeO2 + 4H2O Fe3O4 + H2 + 6NaOH

➢ PASSIVITY OR PASSIVATION

Passivation is the phenomenon, by which a metal or alloy shows high corrosion resistance due to the formation of a
highly protective, very thin (0.0004 mm thick) and quite invisible surface film.

Passivation takes place only in certain environments, which tends to maintain the protective film on the surface.
Eg: Stainless steel alloy containing Cr exhibit corrosion resistance in presence of oxygen due to formation of thin
protective oxide film on the surface. On damage these films automatically repair in oxidizing environment, but in
reducing environment the passive metals get corroded.

Passivation makes effective electrode potentials of some metals more positive so they act cathodic and exhibit noble
behaviour which is opposite to that predicted by electrochemical series. Consequently, a more practical series called
galvanic series is prepared which gives information about corrosion of metals and alloys in a given environment

➢ Galvanic Series: is the relative hierarchy of metals arranged in order from Mg (Least noble) at the anodic
corroded end through platinum(most noble) at the cathodic, protected end.

The greater the difference in position between two metals or alloys, the greater the chances that corrosion will occur.

Difference between Galvanic and Electrochemical series:

Galvanic series predicts the corrosion tendencies of metals and nonmetals in actual environment. But
electrochemical series predicts the relative displacement tendencies of metals and nonmetals in electrolyte with
particular concentration of salts.

In Galvanic series electrode potential is measured by calomel electrode while in electrochemical series it is measured
using standard hydrogen electrode (SHE).

FACTORS INFLUENCING CORROSION

1. Nature of Metal d) Position in galvanic series

a) Purity of Metal e) Relative areas of anode and cathode
b) Physical state of metal f) Solubilities of the product of corrosion
c) Nature of oxide film g) Volatility of corrosion product

2. Nature of the Environment

a) Temperature e) Formation of oxygen concentration cell
b) Humidity f) Presence of suspended particles in
c) Effect of pH atmosphere
d) Nature of Electrolyte g) Presence of impurities in atmosphere

1. Nature of Metal

a) Purity of Metal: Impurities in a metal result in tiny electrochemical cells where anode part gets corroded.
Pure metals will not undergo any type of corrosion. Examples,
• Zn metal containing Pb or Fe
• Rate of corrosion of Al in HCl with increase in percentage of impurity is as given; For 99.99% purity
of Al relative rate of corrosion is 1, For 99.97% purity of Al relative rate of corrosion is 1000, For 99.2 % purity
of Al relative rate of corrosion is 30000
b) Physical state of metal: Metallic materials with unevenly distributed stresses (acts as anode) are easily
corroded. Also, metals with smaller grain size will have greater solubility and hence greater corrosion
c) Nature of Oxide Film:
Pilling–Bedworth Rule: The Pilling–Bedworth ratio (P–B ratio), in corrosion of metals, is the ratio of the
volume of the elementary cell of a metal oxide to the volume of the elementary cell of the corresponding
metal (from which the oxide is created).

Specific Volume ratio =Volume of oxide formed/volume of metal

• If Volume of Oxide < Volume of metal

Oxide film is porous and non-protective
Corrosion continues due to penetration of O2 through pores Eg. Metals such as Mg,Ca,Ba etc.
• If Volume of Oxide > Volume of metal
Oxide film is non-porous and protective
 No further Corrosion Eg. Metals such as Al,Cr,Ni etc.

d) Position in galvanic series

• Extent of corrosion depends upon the position of the metal in the galvanic series.
• Greater the oxidation potential, greater is the rate of corrosion.
• When two metals are in direct contact, the metal higher up in the galvanic series becomes anodic and
suffers corrosion.
• When two metals are in electrical contact, greater is the difference in their positions in galvanic series,
faster is the corrosion
• As Ag and Cu are below Fe in the galvanic series, so they do not undergo much corrosion like Fe in moist
atmosphere.
e) Relative areas of Anode and Cathode:
• Rate of corrosion is more if the size of cathodic area is large (demand of electrons is more)
• When 2 dissimilar metals are in contact, the corrosion of the anodic part is directly proportional to the ratio
of areas of the cathodic part and anodic part. Thus ,

𝐴 𝑐𝑎𝑡ℎ𝑜𝑑𝑒
• Rate of Corrosion α 𝐴 𝑎𝑛𝑜𝑑𝑒

f) Solubilities of the product of corrosion:

• Insoluble corrosion product function as physical barriers, thereby suppress the corrosion.
• But if they are soluble in corroding medium, corrosion will proceed faster
• Eg. Pb in H2SO4 medium forms PbSO4, (insoluble in H2SO4) hence corrosion rate is smaller
g) Volatility of corrosion product
• Excessive corrosion of metal takes place if corrosion product is volatile.
• This is due to the fact that as soon as corrosion product is formed it volatizes, thereby leaving behind the
underlying metal surface for further attack

2. Nature of the Environment

a) Temperature
b) Humidity
c) Effect of pH
d) Nature of Electrolyte
e) Formation of oxygen concentration cell
f) Presence of suspended particles in atmosphere
g) Presence of impurities in atmosphere

a) Temperature: Corrosion increases with temperature due to the increase in rate of diffusion of ions.

b) Humidity: Critical humidity is relative humidity above which the atmospheric corrosion rate of metal increases
sharply. In humid atmosphere, gases (CO2, O2) and vapor furnish water to the electrolyte and set up an
electrochemical corrosion cell.

E.g. Rusting of Iron increases when the moisture content increases from 60 to 80 %

c) Effect of pH: Rate of corrosion is maximum when the corrosive environment is acidic, but metals such as Al, Zn
dissolves in alkaline medium.
d) Nature of Electrolyte: If the conductance of electrolyte is high then, the corrosion current is easily conducted and
hence the rate of corrosion is increased.
• If the electrolyte consists of silicate ions, they form insoluble Silicates (acts as protective coating) and prevents
further corrosion.
• If the electrolyte consists of Chloride ions, they destroy the protective film and the surface is exposed for
further corrosion.
• Conductance of clayey and mineralized soils is more than that of dry sandy-soils, hence corrosion of
underground metallic structures is more in clayey and mineralized soils.
e) Formation of oxygen concentration cell: Due to differential aeration, "oxygen concentration cell" sets up and
anodic part having less oxygen concentration suffers corrosion. For example: Crevice corrosion and Waterline
corrosion occur due to the formation of differential-oxygen concentration cell.
f) Presence of suspended particles in atmosphere: Suspended active particles like NaCl, (NH4)₂SO4,etc. enhance
atmospheric corrosion because they absorb moisture and act as strong electrolytes. Inactive atmospheric
suspended particles like charcoal also slowly enhance corrosion rate because they can absorb moisture.
g) Presence of impurities in atmosphere: Corrosion of metals is more in areas near the industry and sea.
• This is due to the fact that corrosive gases (like H₂S, SO₂.CO₂) and fumes of H₂SO4, and HCl in industrial areas and
NaCl of sea water lead to increased conductivity of the liquid layer in contact with the metal surface, thereby
increasing the corrosion rate.

PROTECTION AGAINST CORROSION

1. Modification of the environment

2. Modification of metal properties
3. Protective coatings
4. Cathodic protection
5. Metal selection and design

1) Modification of the environment: Either by removal of corrosion stimulants or by use of inhibitors

a) Removal of corrosion stimulants: Substances which effectively increase the corrosion rate when added or present
in corrosive environment. Eg.
• Dissolved O2 from water is removed by physical or chemical means.
• Either deaeration is done or reducing substances like hydrazine (N2H4) and sodium sulphite (Na2 SO3) are added.
• Corrosion by acid is prevented by neutralization with lime
• Corrosion by salts is prevented by removing salts by ion exchange resins.
• Corrosion by moisture is prevented by removing moisture from air by dehumidification using silica gel.

b) Use of corrosion inhibitors: Substances (organic or inorganic) which effectively decrease the corrosion rate when
added in small quantities to corrosive environment. For selection of inhibitors Evan Polarization diagrams are
used. Types of corrosion inhibitors:

i. Anodic Inhibitors
ii. Cathodic Inhibitors
iii. Volatile inhibitors

i.Anodic Inhibitors: Like alkalis, molybdates, phosphates and chromates.

They react with the ions of the anode and produce insoluble precipitates, forming a protective film or barrier on
metal surface, thus reducing the corrosion rate.

This is not considered to be satisfactory, because for each inhibitor, there is a certain critical concentration of solution
above which inhibition may be expected.

ii.Cathodic Inhibitors: Like amines, mercaptans, heavy metal soaps, substituted ureas and thioureas.

In an acidic solution the cathodic reaction is: 2H+ + 2e- H₂(g)

the diffusion of H+ ions through the cathode can be slowed down by using organic inhibitors. They get absorb over
the cathodic metal surface and act as a protective layer.

iii.Volatile inhibitors: [vapour-phase inhibitors (VPI) or volatile corrosion inhibitors (VCI)] are organic inhibitors which
readily sublime and form a protective layer on the surface of metal.

For example, Dicyclohexylammonium nitrite(DCHAN) is used for the protection of machineries and sophisticated
equipment.

2) Modification of metal properties

Following methods are used to modify the properties of metals to decrease effect of corrosion

a) Alloying: The alloying for increasing corrosion resistance are ,

Passivating- Al, Cr, Tu Ni and Mo as protective oxide layers make steel less corrosive.
Inhibiting- As or Sb in brass prevents dezincification.
Neutralizing- Ta, Nb and Ti combine with carbon to form respective carbides and thus, make the stainless steel,
corrosion-resistant.
• Mn and Cu combine with S in steels.
• Provided the concentration of oxygen is low, alloy containing Ni, like monel metal (Ni= 67%, Cu-30%, Mn=
Fe= 1.2% rest C and Si) have good corrosion resistance in acid
b) Refining: It is done to lower the content of Sulphur and Phosphorus in steels and carbon in stainless steels.

c) Annealing: It is a heat treatment given to metals to remove the residual stresses.

3) PROTECTIVE COATINGS (SURFACE COATINGS): For protection against corrosion, the metal surface may be
coated with metallic or nonmetallic coatings.

Applications

(i) Surface coatings made up of (Zn, Sn, Ni, Cr, Al, Cu) metals (ie, metallic coatings) are used for protection of iron
from corrosion.

(ii)Manganese-iron phosphate coatings are used to reduce wear to friction in piston rings, cylinder lining of
automobiles and wire-drawing equipments.

(iii) Anodised oxide coatings are used for protection of Al, Zn, Mg and their alloys from corrosion.

(iv) Glass like protective and decorative vitreous or porcelain enamel coatings are applied to cast iron and steel
equipments mainly used in beverage, dairy, food, chemical and pharmaceutical industries. Enamelled steel is also
used in kitchen utensils, refrigerators, etc.

(v) Ceramic protective coatings are used in high temperature applications such as nozzles, thermocouple tubes and
electrical insulations.

(vi) Paints (i.e., organic coatings) are used on metals to impart decorative and aesthetic appeal and corrosion
protection.

(vii) Varnishes are used as a brightening coat to painted surface. It also provides protection against corrosion. They
also improve the appearance mainly of wooden furniture by intensifying the ornamental grains.

a) Metallic Coatings

Iron and steel are the most commonly used construction metals because of their low cost, easy availability and ease
of fabrication into desired structures. Iron and steel can be protected from corrosion by covering their surface with
metallic coatings. The metallic coatings often used are of zinc. tin, nickel, chromium, aluminum, copper etc. These
coatings separate the base metal from the corrosive environment and also function as an effective barrier for the
protection of base metals.

Types of Metallic Coatings: There are two types of metallic coatings:

i. Anodic coatings (Galvanization of iron)

ii. Cathodic coatings

Anodic coatings (Galvanization of iron): In these coatings, the metal used for coating is more "anodic" than the metal,
which is to be protected (ie, the base metal). Anodic coatings protect the underlying base metal sacrificially.

For example: In galvanized steel. Zn is coating metal and steel is base metal. Zn being anodic is attacked; leaving the
underlying cathodic (iron/steel) unattacked, even if it is exposed when pores, breaks or discontinuities occur in such
an anodic coating. Iron or steel is not corroded, till all the coating metal (Zn) is consumed.
 • Hydrogen evolved in acidic conditions
• Hydroxyl ions are formed on aerated neutral conditions
Application: Galvanized articles are mainly used in roofing sheets, fencing wire, buckets, bolts nuts, pipes and tubes
etc., but galvanized articles are not used for preparing and storing food stuffs as zinc dissolves in dil. acids and become
toxic.

Cathodic coatings: These coatings protect the underlying base metal because of their noble character and higher
corrosion resistance and gives effective protection only when they are completely continuous and free from pores,
breaks or discontinuities.

For example: Tin plated steel. In such coatings, if pores, breaks the corrosion of the base metal is speeded up. This is
due to the fact that exposed metal acts as anode and coating becomes the cathode. A galvanic cell is set up and an
intense localized attack at the small exposed part occurs. This results in severe pitting and perforation of the base
metal.

Application: used to protect numerous structures against corrosion, such as ships, offshore floaters, subsea
equipment, harbors, pipelines, tanks; basically all submerged or buried metal structures.

Difference between anodic and cathodic coatings

Anodic Coating Cathodic Coating

Protects the metal from corrosion sacrificially Protects the metal from corrosion due to its higher
corrosion resistance.

Base metal is not corroded, even if it is exposed till Corrosion of base metal is speeds up if coating
all the coating gets consumed breaks and metal gets exposed.

Eg: Coating Zn on Fe Eg: Coating Sn on Fe

Electrode Potential of Fe > Electrode Potential of Zn Electrode Potential of Sn > Electrode Potential of Fe

No problem provided some coating metal is Severe pitting and perforation if coating fails.
available

b) Inorganic Coatings (surface conversion coating) or chemical conversion coating

Here a surface layer of the metal is converted into a stable compound by chemical or electrochemical reactions,
which forms a barrier between the base metal and corrosion environment.

Eg. Anodizing, Phosphating

Anodizing is the process of formation of thin and compact layer of metal oxide over base metal through electrolysis.
It is used in satellite applications for their protection in space environment, used for decorative purpose

Phosphating is process in which phosphate coatings are generally obtained on steel surface by converting surface
metal atoms into their phosphates by chemical or electrochemical reaction. It is used as undercoating before painting
of automotive bodies, refrigerators, washing machines etc.

• These types of coating are different compared to that of metal coating because they are integral part
of the metal itself and in addition to corrosion resistance they also provide increased electrical insulation and
physical appearance of the metal.
c) Organic Coatings

Protection of a metal surface and other constructional materials from corrosion is done by using paints, varnishes,
enamels and lacquers. They collectively come under the category of organic coatings

The important functions of organic coatings are:(i) To impart decorative and aesthetic appeal and(ii) To protect the
metal from corrosion. In fact, organic coating is inert organic barrier.

4.CATHODIC PROTECTION (ELECTROCHEMICAL PROTECTION)

Let us consider the corrosion of a Metal (M) in an acidic environment. Metal (M) undergoes corrosion by its oxidation
(ie when metal behaves like an anode). This reaction is simultaneously accompanied by a reduction reaction viz,
evolution of hydrogen gas.

Anode : M Mn+ + ne-

Cathode: 2H+ +2e- H₂

As is clear from the above reactions, we can prevent the dissolution of metal (its corrosion) by forcing the metal to
behave like a cathode. This is the principle of cathodic protection.

Since there will not be any anodic area on the metal, corrosion does not occur.

Types of Cathodic Protection: There are following two types of cathodic protection:

i. Sacrificial Anodic Protection

ii. Impressed Current Cathodic Protection

Sacrificial Anodic Protection

• The metal structure can be saved from corrosion by connecting it with wire to a more active (ie, more
anodic) metal, so that all the corrosion is concentrated at the more active metal.
• As the more active metal is sacrificed in the process of saving metal from corrosion, hence, it is known
as sacrificial anode
• Metals commonly used as sacrificial anodes are Zn. Al Mg and their alloys.
• Zinc is used as sacrificial anode in good electrolytes such as sea water. Magnesium is used in high
resistivity electrolytes such as soils due to its most negative potential and it can provide highest current
output.
Applications: Protection of underground cables and pipelines from soil corrosion, ships and boat hulls from marine
corrosion, by attaching sacrificial Mg or Zn.

The formation of rusty water is prevented by the insertion of Mg sheets or rods into domestic water boilers or tanks.

b) Impressed Current Cathodic Protection

• In this method, current from an external source is impressed (applied in the opposite direction) to nullify the
corrosions current.
• This is done to convert corroding metal from anode to cathode. Once the metal becomes cathodic, it is
protected from corrosion.
• The anode may be either an inert material or one which deteriorates and will have to be replaced periodically.
• The commonly used anodic materials are graphite, carbon, stainless steel scrap iron, high silica iron and
platinum
• The anode is buried in back fill such as gypsum to increase the electrical contact between itself and the
surrounding soil

Applications: It is well-suited for large structures and long-term applications

This protection technique is employed in the case of buried structures such as pipe lines, tanks, transmission line
towers and laid-up ships.

6. PREVENTION OF CORROSION BY METAL SELECTION AND DESIGN

Design is the initial stage for protection against corrosion. Before a suitable design is made, careful consideration of
constructional material, atmospheric and environmental conditions, and accessibility for maintenance and repair is
required.

Design and Material Selection Principles

(a) Avoid I, T and U-shaped profiles in constructions as far as possible. This is because, the greater the number of
angles, corners, edges and internal surfaces in any design, it becomes more difficult for efficient surface treatment.

(b) Avoid galvanic corrosion by following methods:

• Never join different metals and alloys especially if they are far apart in galvanic series. If at all they have to
be used together, insulate them with efficient moisture-resistant electrical insulator.

• Never use a design in which relative sizes of the cathode and anode are widely different.

• Screws, bolts, nuts and welds must be made from a more noble material than the joined materials

• Continuous welds should be preferred. The intermittent welds are unsuitable both from the mechanical and
corrosion points of view. The smaller side of weld should be turned toward the corrosive medium.

(c) Avoid improper insulation otherwise leakage of current takes place. Such stray currents cause anodic corrosion,
especially in areas where electric traction is used,

(d) Avoid the contact of metallic object with moisture.

 • The design of a structure should be such that retention of moisture should be as low as possible.

• Design the storage containers in such a manner that they can be completely drained and cleaned.

• Arrange profiles in such a manner that water is completely drained and as far as possible, avoid crevice
corrosion. For example, design electrical boxes (exposed to atmosphere) in such a manner that water does
not collect at the top or in the crevices.

Control of corrosion by design and material selection: (a) Elimination of sharp corners (b) Use of insulating washers,
(c) Making provision for proper air circulation, drainage and washing. (d) Making a design, in which retention of
moisture is minimum.