UNIT NO.

6: CORROSION SCIENCE

• CORROSION
• The loss of materials(metal and alloys) or its useful properties, by chemical or electrochemical interaction with its
environment is called corrosion.

• Example:
1. Rusting of iron
2. formation of green layer on copper surface.

CAUSE OF CORROSION

Metal Metal salt

(higher energy state) (lower energy state)

Types of corrosion

Dry corrosion wet corrosion

Mechanism of corrosion:
1. Dry corrosion:
It is occurs due to direct attack of atmospheric gases like oxygen, CO 2, SO2, H2S,NH3, NO2,moisture and by hot flowing
liquids.
Mechanism of dry corrosion:
The corrosion of metals or alloy by oxygen takes place in following steps:
1.Adsorption of O2 molecules on metal surface.
2.Dissociation of O2 molecules into atoms
3.Loss of electrons by metal atom to oxygen atom, resulting in the formation of metal ion and oxide ion.
4.Formation of metal oxide by union of ions, and leading to form thin layer of metal oxide on the surface of metal.

i) Reaction
2M 2Mn+ + 2ne- (oxidation)
n/2O2 + 2ne- nO2- (reduction)
2M + n/2O2 2Mn+ + nO2-
metal oxide
• Nature of Oxide Film :
• The nature of oxide film plays an important part in the further corrosion to continue or not. Oxide films occur in
following forms :
• (i) Porous film :
• If the oxide film is porous, then through the pores, oxygen gas molecules penetrate and continue the corrosion
of the underlying metal until whole metal gets destructed. e.g. oxide films of iron (steel), magnesium, sodium,
potassium, calcium metals are porous.
• 4Na + O2 2Na2O
• 2Fe + O2 2FeO
• 2Mg + O2 2MgO
• (ii) Non porous film :
• If the oxide film is stable, nonporous, strong, well adhered to the metal surface and self - healing, then further
corrosion stops, as the oxide film formed after some initial corrosion of surface, acts as a barrier and detaches
the underlying metal from the corroding oxygen or other gases. Various metals can safeguard themselves by
such impervious metal oxide films eg. chromium, tin, zinc, lead, aluminium, nickel, copper, stainless steels,
monel metal, bronze, aluminium alloys, etc.
• 2Al + 3/2 O2 Al2O3 2Cu + O 2 2CuO
• 2 Zn + O2 4Cr + 3O  2ZnO 2 2Cr2O3
• (iii) Unstable oxide film :
• When the oxide film formed is unstable and it decomposes back into the metal and oxygen, then there is no
corrosion taking place. e.g. metals like gold, platinum and silver.
• 4Ag + O2 ⇌ 2Ag2O
• (iv) Volatile oxide film :
• If the metal oxide film is volatile, then its evaporation takes place simultaneously. The underlying fresh metal is
exposed for the further attack by oxygen. e.g. molybdenum oxide (Mo 2O3) film is volatile.
• 4Mo + 3O2 2Mo2O3 ↑ (evaporation slowly)
 Pilling-Bedworth Rule:

• The rule states that, if the volume of oxide is smaller than the volume of metal consumed in the metal oxide
formation, then the film is porous. On the other hand, the film is non-porous if metal oxide formed has greater
volume than the metal consumed during corrosion.
• Pilling-Bedworth ratio (PBR) =
• Volume of metal oxide
• Volume of metal surface consumed
•
• If the PBR is greater than one but smaller than 1.45 then the metal oxide film is non-porous and protective from
further corrosion by any gases or aqueous media.
• CuO : Cu = 1.68 Ag2O:Ag=1.59
• Al2O3:Al= 1.28 2Mo2O3:Mo=3.4
• Na2O:Na=0.57
mechanism of wet corrosion:
Reaction at anode (Oxidation):
• Metal atoms on the surface of anode, pass into conducting medium by forming metal-ions, leaving behind
electrons.
• M M+n + ne-
• Eg , Fe Fe +2 + 2e-
• Reaction at cathode (Reduction):
• The electrons left on anodic part, flow to cathodic part instantly and depending upon the nature of the conducting
medium, they bring about one of the following reaction,
• 2.Reaction on Cathode (Reduction) :
• The electrons left on anodic part, flow to cathodic part instantly and depending upon the nature of the
conducting medium, they bring about one of the following electron capture or reduction reactions :

• (i)H2 liberation / evolution :

• If the corroding medium is acidic, then H+ from the medium capture electrons (reduction) from cathode
and there is liberation of H2 gas.
• Cathode : 2H  + + 2 e- 2H H2 ↑ ...(b)
• The overall reaction will be addition of (a) and (b)
• Fe + 2H+ Fe++ + H2 ↑
• The product of corrosion is, H2 gas liberation at cathode and the corroding aqueous medium contains the dissolved
compound of the anodic metal.

• (ii)O2 absorption :
• If the corroding medium is neutral or slightly alkaline containing some oxygen gas dissolved, the reaction of oxygen
absorption takes place on cathode.
Hydrogen evolution Oxygen absorption
• Cathode : O 2 + 2H2O + 4 e- 4 OH - (reduction) ...(6.5.3)
• Overall reaction will be (addition of (6.5.1) and (6.5.3))
• 2Fe + 2H  2O + O2 2Fe(OH)2 ↓
• If enough oxygen is present in medium, then the ferrous hydroxide gets oxidized further to rust.
• Thus the O2 gas from the aqueous medium is utilized for reaction and there is formation of metal hydroxide as the corrosion
product . The metal hydroxide if soluble in the aqueous medium, it remains dissolved and if not soluble then it deposits on
cathode area near the anode.
 Factors affecting Rate of corrosion

• 1.Nature of metal:
• (i)Position of metal in galvanic series :
• (a)When two metals or alloys are in electrical contact in a conducting medium, then the
higher placed metal / alloy in galvanic series (more active) acts as anode and get corroded.
• (b)The rate and severity of corrosion further depends upon their difference in positions. More
the metals are apart in galvanic series faster is the corrosion of anodic metal and more is the
current generated during corrosion. Dry corrosion is also faster in more active metals.
• (ii)Relative areas of anode and cathode :
• (a)If the ratio of cathodic area to anodic area is greater, then the rate of wet corrosion is
faster, severe and localised on anodic area.
• (b)Relatively larger cathode area has high demand for electrons and it can be met by smaller
anode only by undergoing rapid corrosion.
• (c)Hence a better design by use of two metals is the one in which anodic area is much larger
than cathodic area i.e. the metal lower placed in galvanic series is used on smaller proportion
than the metal placed higher in galvanic series.
• (iii)Purity of metal :
• (a)Impurities in metal form large number of minute or tiny galvanic cells when there is
conducting medium around the impure metal.
• (b)If the impurity is passive (lower position in galvanic series) then the metal undergoes
corrosion but if impurity is more active, then faster corrosion of impurity takes place with
small pits formation on surface, due to local action.
• (iv)Physical state of metal :
• (a)Smaller the grain size of the metal or alloy, greater is found the rate of corrosion (wet or
dry) e.g. steels get corroded more easily than cast irons because grains in steels are of
smaller size.
• (b)Further, areas under stress in the same metal, tend to be anodic.
• (v)Nature of Oxide Film :
• (a)If the oxide film formed on metal surface is protective, nonporous, strongly adhered,
then neither dry corrosion nor electrochemical corrosion will take place.
• (b)But if the film is porous, loosely adhered (steels) then the corrosion of the metal takes
place until complete destruction, by dry or wet mechanism.
• (vi)Over voltage :
• (a)In the case of metals having higher position in EMF series than hydrogen, the corrosion
of the metal in acidic medium liberates hydrogen gas.
• (b)The tiny bubbles of the hydrogen gas adhere to the metal surface and the acidic solution
is not in well contact of the metal. This fact leads to decreasing the rate of corrosion of
metal after initial corrosion reaction beginned.
• (c)In other words, such metal develops corrosion resistance to some extent or the metal
behaves as if it is placed lower than its actual position in EMF series.
• (d)To restore the position of metal, some extra voltage is necessary. This extra voltage is
known as ‘overvoltage’.
• (e)However all metals do not have hydrogen adsorption and their corrosion takes place in
usual way. The metals having the ‘overvoltage’ nature are, zinc, lead, chromium, nickel, etc.
Nature of environment:
• i)Temperature :
• (a)The rate of atmospheric or dry corrosion is faster at higher temperature because the attacking gas as well
as metal get activated at the higher temperature.
• (b)In the case of electrochemical corrosion, the corrosion of anode depends upon the temperature. As per
Nernst's equation for electrode potential, the potential of a metal is higher at higher temperature. Hence rate
of electrochemical corrosion increases with increase of temperature.

• ii)Moisture :
• (a)Moisture is deciding factor in dry corrosion and wet corrosion.
• (b)Critical humidity is the relative humidity above which atmospheric (dry) corrosion increases sharply.
Oxygen and other reactive gases in atmosphere do not have much corrosive action in the absence of moisture
but the corrosion of metals takes place at much higher rate above the critical humidity.
• (c)High relative humidity, fog, mist in air provides the aqueous conducting medium and causes galvanic or
differential aeration cells formation. The rate of corrosion (anodic part) by cells formation is fast. Moisture in
soil, water, aqueous solutions also cause such cells formation and corrosion of metals.

• (iii)pH :
• (a)Generally acidic media have more corrosive effect on metals. Amphoteric metals are more attacked by
alkaline media Al, Zn, Pb, etc. in general. Corrosion of iron or steel is minimum at pH 5.0 in the oxygen free
water and at lower pH its corrosion rate increases.
• (b)Zn gets minimum corroded at pH 11, tin gets minimum corroded at pH 8.5, Al gets corroded minimum at
5.5 pH. Thus every metal gets corroded minimum at certain pH medium and at the pH of medium higher or
lower than that, the corrosion of the metal is faster.
• (c)Roubaix diagram gives clear idea about the optimum pH for minimum corrosion rate of a metal.
 • (iv)Conductivity of corroding medium :
• Higher the electrical conductivity of the soil, water or any aqueous corroding medium, higher is the
rate of the electrochemical corrosion.

• (v)Nature of ions in medium :

• (i)The Cl-NO3- like ions have ability to break the non porous oxide films on metals surface and cause
enhanced wet corrosion.
• (ii)On the contrary the presence of oxalate ions, phosphate ions, silicate ions etc. have ability to
slow down the rate of wet corrosion.

CORROSION PROTECTION METHODS:

1CATHODIC PROTECTION
2.ANODIC PROTECTION
3.METALLIC COATING
4.SURFACE CONVERSION COATING
5.ELECTROLESS PLATING
6.CORROSION INHIBITORS
7.POWDER COATING
• cathodic protection :

• Principle of cathodic protection :

• Principle of this method is, the metal to be protected is forced to behave as cathode.

• There are two ways of doing so :

• i)Using sacrificial anode
• ii)Using impressed current

• i)Using Sacrificial Anode :

• (i)Method :
• The metallic structure to be protected from corrosion, is connected to anodic metal (active) by an insulated
wire. The more active metal like Zn, Al, Mg, etc. acts as anode and gets corroded, protecting the main metal,
hence it is called as sacrificial anode. For the purpose of increasing electrical contact, the active metal is placed
in back fill (coal and NaCl). When the sacrificial metal is consumed completely, it is replaced by fresh piece.
• (ii)Applications :
• Application of the method are :
• (i)buried steel pipelines,
• (ii)ship hull
• (iii)hot water tanks
• (iv)buried cables, etc.
• Magnesium or zinc rods are bolted along the sides of ship. Zinc rods are inserted into boiler or hot water tanks
to prevent corrosion. The protection of underground pipelines is shown in Fig. 6.11.
cathodic protection :
• ii)Using Impressed Current :
• (i)Method :
• In this method, an impressed current is applied in opposite direction to nullify the corrosion current and
convert the corroding metal from anode to cathode. The impressed current is derived from a D.C. Source
and given to insoluble anode like graphite, stainless steel or scrap iron, buried in soil. The negative terminal
of D.C. is connected to pipeline to be protected. The anode is kept in back - fill (composed of gypsum or
coke breeze), to increase electrical contact with the surrounding soil.
• Fig. 6.12 : Cathodic protection by impressed current
• (ii)Applications :
• This type of cathodic protection is applicable to :
• (i)open water box coolers
• (ii)water tanks
• (iii)buried water or gas pipeline,
• (iv)condensers
• (v)transmission line towers
• (vi)laid - up ships.
• (vii)marine piers, etc.
• Anodic Protectic Method
• Principle:
• A metal or alloy having wider range of passivity voltage, is made anodic and the voltage in the
passivity range, is applied over it to control its corrosion even by strongly corroding media.
• Construction and Working :
• (i)The metallic installation (reactor, water tank, industrial water coolers, industrial condensers,
etc.) is made anodic by use of reference electrode and auxiliary electrode, as shown in Fig.
6.14.
• (ii)There is a potentiostat for applying the desired voltage and an ammeter to watch the
corrosion current. The minimum or negligible current indicates that anodic protection is
taking place successfully.
• Fig. 6.14 : Anodic protection
• (iii)If system goes out of the corrosion control any time, the corrosion current will be high and
the electrical connections are removed immediately.
• The cathodic metal taken for protection of steel is generally a high corrosion resistant metal
or platinum and the auxiliary electrode as graphite.
• Applications :
• (i)Chemical reactors.
• (ii)Complex metallic installations on ground or under sea water.
• (iii)Industrial water coolers.
• (iv)Industrial metal condensers.
• (v)Pipe lines for carrying corrosive liquids or solutions. etc.
Anodic protection
• Metallic coating
• Metallic coatings are of two types :
• (i)Anodic coatings :
• •If the coating metal is higher placed in galvanic series than the base metal, then
the coating is called as anodic coating. e.g. Zn, Al, Cr coated on steel.
• •If any pores, breaks, or discontinuities occur in such anodic coating and there is a
conducting medium around it, then a galvanic cell sets up. In the galvanic cell,
coating metal being anode, starts getting attacked and as long as the coating
metal is on surface, the base metal remains protected. As, even after the coating
ruptured, the base metal does not get corroded, therefore, the anodic coating are
preferred.
• (ii)Cathodic coatings :
• •If the coating metal is lower placed in galvanic series than the base metal, then
the coating is called as cathodic coating. e.g. coating of tin on steel, silver or gold
on brass, etc.
• •As long as coating is uniformly present on base metal surface, the base metal is
protected from corrosion. But if the cathodic coating is ruptured the base metal
acts as anode and gets corroded, in the galvanic cell set up. It causes the intense
local attack on exposed part resulting in pitting / cracking.
• Methods of metallic coating
• (A)Hot dipping :
• Hot dipping is used for producing a coating of low melting metals such as Zinc (419°C) or tin
(232°C), lead, etc. on metal like steels, copper, brass, etc. The process consists of immersing the
base metal in a bath of molten coating metal, covered by a molten flux layer (usually ZnCl 2). The
flux prevents oxidation of molten coating metal. For a good adhesion, base metal should be
clean and well prepared.

• (a)Galvanising :
• (i)Method :
• Coating of zinc on iron or steel, is called galvanising. The steel article is cleaned well with dil.
H2SO4, washed well with water and dried. Then it is dipped in bath of molten zinc maintained at
425-450 °C. Surface of bath is covered with
• flux like NH4Cl. After taking it out, the article (sheet, pipe, wire) is rolled to make coating of
uniform thickness and to remove any excess of zinc. Then it is cooled slowly.
•
• (ii)Applications of galvanising :
• It is used widely for protection of iron. Various galvanised iron (G.I.) articles are in use. e.g. G.I.
Sheets (plane or corrugated), wires, pipes, buckets, tubes, screws, nails, etc. G.I. vessels cannot
be used for storing foods as there is formation of poisonous products by action of foods on
zinc. Zinc is anodic coating.
 Galvanising

(b)Tinning :
(i)Method :
Coating of tin on steels, is known as tinning. The cleaned steel article (sheet) passes through molten
tin bath (as in Fig. 6.9.6) maintained at about 240 °C and then through palm oil. Palm oil protects the
hot tin - coated surface against corrosion. The rollers finally remove excess of tin and makes uniform
coating. Tin is cathodic coating. ii)Applications of tinning :
Tin has greater corrosion resistance and better glaze.
(i)Tinned containers can be used for storing foods, ghee, oils, pickles, medicines because it has high corrosion
resistance and does not form poisonous products after action by foods.
(ii)Copper wires before insulation by rubber, are tinned to avoid attack of sulphur of rubber.
(iii)Tinned copper or brass vessels or sheets are used for cooking utensils and refrigeration equipments.
Applications:
1.Chemical reactor ,Complex metallic installations on ground or
under sea water.
2.Industrial water cooler , Industrial metal condensers, Pipelines
for carrying corrosive liquids
Tinning
Distinguish between anodic coating and cathodic
coating.
• Anodic coating
• If the coating metal is higher placed in
galvanic series than the base metal,
then the coating is called as anodic
coating.
• If the anodic coating is ruptured due
to any pores, breaks, then the coating
metal acts as anode, starts getting
attacked as long as the coating metal
is on the surface and the base metal
remains protected in the galvanic cell
set up.
• Anodic coating is mostly preferred.
• Coating of Zn, Al, Cr on steel
• It is carried out by galvanizing process
• Cathodic coating
• If the coating metal is lower
placed in galvanic series than the
base metal, it is known as cathodic
coating.
• If the cathodic coating is ruptured
the base metal acts as anode and
gets corroded, in the galvanic cell
set up.
• Cathodic coating is less preferred.
• Coating of tin on steel, Ag or Au
on brass
• It is carried out by tinning process.
2.Metal Cladding

• It is the process of sandwitching the base metal between two

thin layers of coating metal by hot-rolling the composite to
produce a firm bonding.
• The coat metals are usually metals of least reactivity (Cu, Ni, Ag,
Pt, Ti)
• The cladding layer should be very thin and its thickness is only
5% of the total composite metal.
• Duraluminium sandwiched between Al sheets and hot rolled to
produce Alkad composite which is free from stress corrosion

24
• b) Electroplating:
• (i)Definition :
• Electroplating is the method in which coating metal is coated on a base metal on the basis of electrolysis principles.
• (ii)Method :
• The article to be electroplated is cleaned well. There is a nonconducting (plastic or concrete) tank containing solution of a salt of
the coating metal. The article is connected to negative terminal of a D.C. supply to make it cathode. Anode is the coating metal
rod/strip. After adjusting the suitable pH and current density on article surface, the electroplating begins.
• At Cathode (article) :
• Cr+3 + 3e- Cr (if chromium plating)
• Ag + e- Ag (if silver plating)
• Ni+2 + 2e- Ni (if nickel plating)
• The metal ions in solution migrate towards article and capture electrons on reaching there to get discharged as metal atoms.
• Fig. 6.17 : Electroplating
• At anode :
• Cr Cr+3 + 3e- (if chromium anode)
• Ag Ag + + e- (if silver anode)
• Ni+2 + 2e- Ni (if nickel anode)
• The coating metal (anode) passes in solution as its ions. The quantity of metal ions discharged on article in certain time, is equal
to the quantity anode metal atoms passed in solution. There is no change in concentration of salt solution in the pot. The
decrease in weight of anode is equal to increase in weight of article due to plating (coating) formed.
• (iii)Advantages :
• Electroplating can be done on articles of any shape; the coating is strongly adhered, it can be applied on surfaces of plastic,
glass, wood also (e.g. PCB), gives brighter look.
• (iv)Applications of electroplating :
• (i)corrosion protection.
• (ii)decoration or better appearance.
• (iii)to have surface of plastic, glass, wood conducting.
• (iv)for electroforming of many parts of machines by electrodeposition of thick layer.
 Electroplating

C) Cementation.
In the cementation technique, there is formation of strong layer of alloy of coating metal and base metal, on the
surface of base metal.
•Well cleaned base metal articles are packed in powder of coating metal and heated to a temp. below the M.P. of
lower melting component of them.
•Due to diffusion of coating metal into base metal, alloy formed.
•Composition of alloy is different in metal. i.e C.M. is higher at surface layer than inner layers and B.M. is richer
in inner layers than surface layer.
•It is Sherardising if coating metal is Zn.
•It is Colouring if coating metal is Al.
It is Chromining if coating metal is Cr
 Cementation

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.

d)Metal Cladding
It is the process of sandwitching the base metal between two thin layers of coating metal by hot-rolling the
composite to produce a firm bonding.
The coat metals are usually metals of least reactivity (Cu, Ni, Ag, Pt, Ti)
The cladding layer should be very thin and its thickness is only 5% of the total composite metal.
Duraluminium sandwiched between Al sheets and hot rolled to produce Alkad composite which is free from stress
corrosion
• 4)Corrosion inhibitors.
• Def: Corrosion inhibitors are a substance which when added in a small quantity to the aqueous
corrosive environment effectively decreases the corrosion of metal.
• Anodic inhibitors:
• Anodic inhibitors are those which prohibit the reaction at anode by forming a sparingly soluble
compound. This compound formed gets adsorbed on anode to form a thin film.
• Exam. Chromates, phosphates, tungustates etc.
• Cathodic inhibitors:
• In the acidic medium, H2 liberated at cathodic part of corroding metal. Hence corrosion can be
reduced by slowing down the diffusion of H+ to cathode. It can be done by organic inhibitors like
amines, mercaptans, or by salts of heavy metals soaps, oxides of antimony, sodium meta-arsenite.
These inhibitors adsorb on the cathode to form a film and slow down the H 2 liberation at cathode
finally to reduce the rate of overall corrosion due to cell formation on metal.
• 2H+ + 2e- H2
• In the alkaline or neutral medium, absorption of O2 on cathode takes place. It can be slow down by
removing O2 from the medium or by retarding diffusion of O2 towards cathode. O2 removed by
addition of reducing agents Na2SO3 or de-aeration. Diffusion of O2 reduced by addition of Mg, Zn, Ni
salts as Cathodic inhibitors. These metal ions react with HO - to form insoluble hydroxide which
deposit on cathode to retard the Cathodic reaction.
• H2O + 2e- + ½ O2 2HO -
• 2HO - + Mg Mg(OH)2
•
7)Powder coating:

• Definition: Powder coating is the technique of forming a thin coat of a

thermoplastic material along with some additives, on the surface on a
metal.
• There are two methods of powder coating.
• A)Electrostatic spraying
• B)Plasma spraying

• Electrostatic spraying
• The dry constituents of powder coating i.e thermo softening plastic, colour
pigments, filler, and other additives are crushed and milled to particle size 40-90
µm then the mixture is sieved to separate higher sized particles.
• These coating particles are dispersed in air stream and passed through a high
voltage gun where the coating particles pick up negative electrostatic charge.
• The electrostatic powder particles deposit on the base metal, due to force of
attraction between electropositive metal and negatively charged powder particles.
• Then the base metal having the electrostatic powder deposited is baked where the
powder particles melt to form uniform, strong coating.
• 2.Plasma Spraying
• (i)Method :
• Plasma arc spraying produces denser coatings. The coatings are less porous, strongly adhered.
• Fig. 6.19 : Plasma spraying
• The mixture of the fine powder of coating constituents is converted to plasma by the arc produced,
having temperature 1500°C. The plasma is directed on the surface of work piece, to produce a thin
coating of 250-450 mμ i.e. thicker than electrostatic spray method.

• 3.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.
•
•