Corrosion and Its Control NF

Corrosion and
its control
Prof. Dr. F. Nawaz Khan, VIT

UNIVERSITY 1
Module-4 Types and mechanism – dry and wet corrosion; Forms of corrosion
[Differential aeration, pitting, Galvanic and stress corrosion
cracking];
Module-5 Corrosion control methods: Inhibitors – anodic and cathodic and
their action; Cathodic protection – sacrificial anodic and impressed
current protection methods; galvanizing and tinning; electroplating-
process and typical applications, metal cladding; Coating processes
– PVD and CVD and applications.
Module-6 Basic concepts of cells and batteries-nominal voltage, operating
voltage, capacity, self discharge, depth of discharge, energy density,
service life, shelf life. Electrochemistry of Primary cells –
Comparative features and applications of Lechlanche, alkaline and
Li-primary cells.
Module-7 Secondary cells - Lead – acid, Ni-Cd, Ni-MH cells; Rechargeable
lithium cells – chemistry and applications.
Fuel cells – Electrochemistry of a H2–O2 fuel cell, Basics of solid
oxide fuel cells-applications
UNIVERSITY 2
Significance of Corrosion on Infrastructure

UNIVERSITY 3
UNIVERSITY 4
UNIVERSITY 5
Corrosion
“Gradual eating away (or) disintegration (or) deterioration of a
metal by chemical or electrochemical reaction with the
environment”
 Reasons for corrosion:
o metals compounds are more stable thermodynamically.
o Metal will always have a strong tendency to convert itself

into more stable compound state.
o Hence, metals will try to go to lower energy states through
formation of compounds and thus attain stability.

UNIVERSITY 7
UNIVERSITY 8
Types of corrosion
a) Chemical corrosion (dry corrosion)
b) Electrochemical corrosion (wet corrosion)
a) Dry corrosion (chemical):
o Classified depending on the corroding agent

i) oxidation corrosion
o Oxygen present in the atmosphere attacks the metal forming
oxide layer on the surface of the metal.
M M2+ + 2 e-
½ O2 + 2e- O2-
M + ½ O2 M2+ + O2- metal + O2
o Oxidation corrosion will lead to an oxide film which may be porous

or non-porous.
o Depends on chemical affinity, temperature, corrosion products
UNIVERSITY 9
Types of corrosion
Pilling-Bedworth Rule:
o “If the volume of metal oxide is equal to or greater than the volume
of the metal getting corroded, then the oxide film is non-porous and
protects the metal from further corrosion;
o If the volume of the metal oxide is less than the volume of the metal
getting corroded, it will promote further corrosion of the metal”.
o Cu, Al, Ni, Cr form non-porous oxide layers while Li, Na, K, Mg form
porous oxide layers.
o Types of oxide layers:
i) Stable oxide layer:

o It is a fine grain of oxide layer which is non-porous and adheres strongly to the
metal.
o Oxides of Al, Sn, Cu forms such impervious layers which prevents oxygen
from diffusing through the metal and hence further attack is stopped.
UNIVERSITY 10
Types of corrosion
ii) Unstable oxide layer:
o These are produced on noble metal surfaces and these oxide
layers decompose back to the metal.
Metallic oxide Metal + Oxygen

o Pt, Ag etc. form such oxide films.
Unstable
Exposed surface metal oxide
+ O2 Metal oxide
metal Of air metal metal + O2
decomposes
Unstable oxide layer

UNIVERSITY 11
Types of corrosion
iii) Porous oxide layer:
o These oxide layers have minute pores and are not impervious
layers.
o Oxygen will diffuse through the pores and promote further
corrosion.
o Fe is a good example of this type of corrosion.
Exposed Porous
surface metal oxide
Further Attack
metal + O2 through pores &
Of air metal
cracks continues
Porous oxide layer

UNIVERSITY 12
Types of corrosion
iv) Volatile oxide layer:
o These are oxide layers which evaporate as soon as they are

formed and hence further corrosion is facilitated.
o After some time the metal itself will disappear.
o Molybdenum is an example of volatile oxide layer corrosion.
Exposed
Volatile Fresh surface
surface
metal oxide Exposed for
Further attack
+ O2 Metal
metal oxide
Of air metal volatalizes metal
Volatile metal oxide

UNIVERSITY 13
Types of corrosion
ii) corrosion by other gases:
o CO2, Cl2, SO2, F2 etc. are gases which can attack the metal and corrode
o Extent of corrosion depends on the affinity of the metal to the gas.
o These gases chemically react with the metal forming either porous or non-
porous layers of films.
o Hydrogen corrosion: Hydrogen gas attacks the metal to make them brittle
(Hydrogen embrittlement)
Fe + H2S FeS + 2H (atomic hydrogen)
iii) liquid metal corrosion:
o Flowing liquid metal (Hg) can penetrate through another metal to corrode.
o Gold (Au) can be corroded by mercury (Hg).
o Such corrosion is found in nuclear devices

UNIVERSITY 14
Types of corrosion
b) Wet or Electrochemical Corrosion:
o In this type of corrosion, a conducting liquid is in contact with a
metal or two dissimilar metals or alloys
o One part becomes anode and the other part cathode.
o At the anodic part corrosion (oxidation) occurs while reduction
takes place at the cathode.
At the anode: M Mn+ + ne-

o Mn+ either dissolved in solution or forms compounds such as
oxides.
The rate of the electrochemial corrosion will depend on:
a) If the corrosion product is soluble in the medium, rate of

corrosion will be high.
b) If the corrosion product is insoluble in the medium, rate of
corrosion will be very low.
UNIVERSITY 15
Types of corrosion
Electrochemical corrosion is present in the following types:
1. Hydrogen evolution type corrosion
2. Oxygen consumption type corrosion
3. Galvanic corrosion
4. Concentration cell corrosion
5. Pitting corrosion
6. Stress corrosion
1. Hydrogen evolution type corrosion

occurs when base metals are in contact with an acidic solution.
Eg. Anode : Fe Fe2+ + 2e- (oxidation)
Cathode : 2H+ + 2e- H2

The overall reaction is:
Fe + 2H+ Fe2+ + H2
o Simultaneously, metal ion will be produced at the anode while hydrogen will
evolve at the cathode
o Displacement of H+ ions All metals above H in the EC series Large anodic
areas
UNIVERSITY 16
Types of corrosion
2.Oxygen absorption type corrosion:
Occurs when base metals are in contact with neutral solutions like water with
Dissolved oxygen (DO).
Rusting of iron is an example of this.
Anode : Fe Fe2+ + 2e- (oxidation)

These electrons move from anode to cathode and react with the electrolyte
and oxygen giving:
Cathode : ½ O2 + H2O + 2e- 2 OH- (Reduction)
The Fe2+ at the anode and OH- at the cathode diffuse and react to produce
Fe(OH)2: Fe + 2 OH- Fe(OH)2
If sufficient oxygen is present, Fe(OH)2 gets oxidised to ferric hydroxide (rust)
4 Fe(OH)2 + O2 +2H2O 4 Fe(OH)3 or 2(Fe2O3.3 H2O)

UNIVERSITY 17
Types of corrosion

UNIVERSITY 18
Types of corrosion
3. Galvanic corrosion:
o Occurs when two dissimilar metals in the electrochemical series

are in contact with each other (Joined by rivetting or welding) and
exposed to corroding environment.
o The metal with more negative potential (higher in EC series ) will

become anode and corrodes.
o Nature of corrosive environment decides cathodic reaction
o This can be avoided or minimized by:
a) coupling metals which are close in the electrochemical series.
b) Making the cathode metal smaller in area than the anodic metal.

UNIVERSITY 19
Table of Electrode Potentials
Metal Electrode Potential (V)

Magnesium -2.40 (Anodic – more basic)
Aluminium -1.76 CORRODED END
Zinc -0.76
Chromium -0.65
Iron -0.44
Nickel -0.23
Tin -0.14
Lead -0.12
Hydrogen (REF) 0.00
Copper +0.34
Silver +0.80 PROTECTED END
Gold +1.40 (Cathodic – more noble)
UNIVERSITY 20
UNIVERSITY 21
Galvanic
 Dissimilar metals are physically
joined in the presence of an
electrolyte.
 The more anodic metal corrodes.
Bilge pump -
Magnesium shell cast
UNIVERSITY around a steel core. 22
Common Corrosion Problems
Metals in contact Corrosion Rectify
Galvanised tank Zinc corrodes Sacrificial anode

& copper pipes or plastic tank
Copper ball-cock Solder corrodes Plastic ball

Soldered to brass in damp atmospheres
Copper flashing Steel corrodes Copper nails

secured by steel nails
Steel radiators with Steel corrodes Corrosion

inhibitors
copper pipes

UNIVERSITY 23
4. Concentration cell corrosion: (Differential aeration corrosion)
o When a metal is exposed to different concentration of oxygen or any

other electrolyte, a concentration cell is formed.
o The part of the metal exposed to lower concentration of oxygen (or)
electrolyte becomes anode and the one exposed to higher
concentration becomes cathode.
o Corrosion starts at the anode (dissolves).
o This type of corrosion occurs when metals are partly dipped in
solutions, partly covered with dust, oil marks, sand etc.
o Eg. Zinc rod dipped in brackish water solution, water line corrosion.
Anode: Zn Zn2+ + 2e-

½ O2 +H2O + 2 e- 2 OH- Zinc rod
More oxygenated part Cathode:½O2+ H2O+2e- 2 OH-
(Cathode)
Water-line
e- Flow of electrons
Zn2+ NaCl solution
Corroding anode
Zn2+
Zn2+ Zn Zn2+ + 2 e- (less oxygenated part)
24
(Anode)
Cathode
(Protected part)
Anode Cathode Sand
Anode
Metal Metal (Less
Oxygenated
part)
Scale
(a) (b)
Metals partly covered with dirt, dust, sand, scale, oil marks become
oxygen deficient areas – Anodes
M Mn+ + 2e-
The other area which is more exposed to oxygen becomes oxygen

rich and acts as cathode

UNIVERSITY 25
5. Pitting corrosion:
o Due to rapid penetration of oxygen through some cracks in the

oxide film or pin holes on metallic surfaces, pitting takes place
leading to corrosion.
pitting start at the oxygen poor region at the bottom of the pit is
anodic – pit tends to deepen leading to premature failure due to
fatigue or brittle fracture
o Eg. Al, Ti and stainless steel undergo pitting corrosion in acidic

environment.
METAL Cathodic
Oxygen poor at
base of crack
Anodic
UNIVERSITY 26
UNIVERSITY 27
Pitting
Pitting is a localized form of corrosive attack. Pitting
corrosion is typified by the formation of holes or pits
on the metal surface. Pitting can cause failure, yet
the total corrosion, as measured by weight loss, may
be minimal.
5th Century sword

UNIVERSITY Boiler tube
28
6. Stress Corrosion Cracking, SCC
 Static tensile stress and specific environments
produce cracking
i.e A structure that has SCC sensitivity, if subjected to
stresses and then exposed to a corrosive
environment, may initiate cracks and crack grow
well below the yield strength of the metal.
 Consequently, no corrosion products are visible,
making it difficult to detect or prevent; fine cracks
can penetrate deeply into the part.
 Eg.
 Brass in the presence of ammonia ,
 Stainless steel in the presence of
NaOH or chloride solution at high
temperature
 Ti alloys in nitrogen tetroxide
UNIVERSITY 29
UNIVERSITY 30
Cause Anode Examples Rectify
Grain structure Grain boundary Steel/damp Isolate steel
Concentration Low Soil types Protective coatings

variations in concentration
electrolyte areas
Differential Oxygen remote Underground Protective coatings

aeration areas steel pipes
Stressed areas Most heavily Steel rivets Protect from

stressed area or nails dampness

UNIVERSITY 31
UNIVERSITY 32
Factors influencing corrosion
Factors influencing corrosion depend on:
a) Nature of the metal
b) Nature of the corroding environment
 Nature of the metal:
i) Position in the galvanic series:
o When two dissimilar metals are in contact, the more anodic metal
(Higher up in the series) will corrode.
o The extent of corrosion depends on how far apart are the two metals in
the galvanic series.
ii) Over voltage:
o When a metal (eg. Zn) is dipped in 1 N sulphuric acid, the initial rate of
corrosion is quite slow since hydrogen evolution takes place on Zn at
0.7V.
o If a few drops of CuSO4 are added, the hydrogen over voltage comes
down to 0.33V and corrosion rate increases.
o Reduction in hydrogen over voltage increases the rate of corrosion.
UNIVERSITY 33
iii) Relative areas of cathode and anode:
o When two dissimilar metals are in contact, the rate of corrosion is directly
proportional to the ratio of cathodic part to anodic part.
o If anodic area is small, the corrosion is rapid.
iv) Purity of the metal:

o Purer the metal, lesser is the rate of corrosion.
o Due to impurities, local galvanic cells are formed and anode gets corroded.
v) Physical state of the metal:

o The rate of corrosion will depend on the physical state of the metal such
as grain size, orientation of crystals, stress etc.
vi) Nature of surface film: (Pilling-Bedworth rule):
o Corrosion depends on the nature of surface film i.e. the oxide film is stable
or unstable or volatile or porous or non-porous will decide the rate of
corrosion of the metal.

UNIVERSITY 34
vii) Passive character of the metal:
o Some metals eg. Tl, Al, Cr, Mg, Ni and Co are passive and show resistance
to corrosion.
o They form highly protective oxide layers on their surfaces which gives the
metal passive character and protects it from further corrosion.
viii) Solubility of corrosion product:

o If the corrosion product is soluble in the environment in which the metal is
working, then the corrosion will proceed faster.
o If the product is insoluble in the environment, then the corrosion is very

slow since the corrosion product becomes a protective layer on the
metallic surface. Eg.PbSO4.
viii) Volatility of the corrosion product:

o If the corrosion product is volatile, it evaporates as soon as it is formed
exposing fresh metal for corrosion and hence the corrosion becomes very
rapid and the metal will disappear over a period of time.
UNIVERSITY 35
b) Nature of the corroding environment:
i) Temperature:
o As temp. increases, the rate of corrosion also increases.
ii) Humidity in environment:

o “Critical humidity” is the humidity above which the metallic corrosion rate
increases sharply.
o Critical humidity depends on the nature of the metal as well as the
corrosion product.
o When the humidity is higher, the gases eg. CO2, O2 dissolved in the
moisture and provide the conducting medium for electrochemical couple to
get formed and anode corrodes.
iii) Presence of impurities in the atmosphere:

o Gases like CO2, SO2, H2S and fumes of HCl, H2SO4 which are present in
the industrial areas provide conductive environment for enhancing the
electrochemical corrosion.
o In marine environment, the Cl- is responsible for enhanced rate of
corrosion.
UNIVERSITY 36
iv) Presence of suspended solids in the environment:
o Particles like NaCl, (NH)4SO4 together with moisture act as conductive
electrolyte and enhance the rate of electrochemical corrosion.
v) Effect of pH: (Pourboux-Evans diagram may be explained)
Acid medium facilitates corrosion than neutral and basic media as a
general rule.
o The corrosion rate of Fe in oxygen free water is very slow up to pH 5.0 but
in the presence of oxygen, the corrosion at pH 5.0 enhances greatly.
o At pH 4.0, the corrosion rate of Fe is very high since Fe2+ gets oxidised to
Fe3+.
o Zinc corrodes rapidly in acidic solutions but the rate of corrosion is low in
alkaline medium (pH 11.0).
o Aluminium corrodes less at pH 5.5 but the rate of corrosion is very high in
pH 8.5.
vi) Nature of ions present:
o Anions like silicates form insoluble salts in the medium and inhibit further
corrosion.
o But, Cl- present in the atmosphere destroy the protective oxide film and
enhance rate of corrosion.
UNIVERSITY 37
vii) Conductance of the corroding environment:
o In corrosion of underground and submerged structures, the
conductance of the medium plays a critical role in corrosion.
o Conductance due to stray currents through the soil will promote the
corrosion.
viii) Formation of oxygen concentration cell:
o If one part of the metal is exposed to higher levels of oxygen, it
becomes cathode and the other part which is exposed to lesser
levels of oxygen will become anode.
o This is called oxygen concentration cell which promotes corrosion
by anodic oxidation/dissolution.
2 H2O + O2 + 4e- 4 OH- (Cathodic reaction-higher O2)
o This OH- will move to the cathode where Fe2+ reacts to form
Fe(OH)2 which later converts into rust (Fe2O3.3H2O).
o Buried pipelines, cables etc., experience this kind of
electrochemical corrosion.
UNIVERSITY 38
Control of Corrosion
Corrosion can be controlled by:
a) Proper designing
b) Use of pure metals, alloys
c) Cathodic protection
d) Changing the environment
e) Use of inhibitors
f) Application of protective coatings

UNIVERSITY 39
Corrosion control
a. Proper designing:
o Proper selection of metal or alloy or design will play an important
part in corrosion control.
o To the extent possible, contact of dissimilar metals far apart from

each other in the electrochemical series should be avoided.
o Metals which are close in potentials in the electrochemical series are

preferable.
o While working with dissimilar metals, larger anodic area and lesser
cathodic area are necessary to minimize corrosion.
o Insulating materials (washers, spacers) can be used when two

dissimilar metals have to be put together in a fabrication.
o When two dissimilar metals are together, painting or electroplating

the anodic metal will help in reducing corrosion.
o Sharp corners and edges should be avoided in a fabrication since

these act as anodes getProf.
more easily corroded.
Dr. F. Nawaz Khan, VIT
UNIVERSITY 40
Corrosion control
Weld Sharp corner Smooth bend

Poor designs - more corrosion Best design-least corrosion
Bolt joint crevices

Weld joints
Poor design – more corrosion Better design – lesscorrosion
Weld joint
Best designs
Prof. Dr. F.–Nawaz
leastKhan,
corrosion
VIT
UNIVERSITY 41
Corrosion control
b. Use of pure metal:
o Impurity in the metal can create anodic and cathodic parts and
hence leads to electrochemical corrosion.
o Metals like Mg, Al when used in the purest form become corrosion
resistant by impervious oxide film formation.
o But production of pure metals is a very expensive process and
metal will lose some of its mechanical properties during
purification.
c. Use of metal alloys:

o Alloying is a very good method for corrosion protection.
o Alloying metals like Fe, Cu etc. with noble metals makes the metal
passive and reduces corrosion.
o Eg. Addition of Cr, Ni etc. to iron as alloying metals will give
corrosion resistance. (stainless steel)
UNIVERSITY 42
Corrosion control
d. Cathodic protection:
o Principle is to make the base metal to be protected as
cathode by connecting to a highly anodic metallic plate.
o Two methods of cathodic protection are known:
i) Sacrificial anodic protection
ii) Impressed current cathodic protection
i) Sacrificial anodic protection:

o The metallic structure to be protected is connected through a
metal wire to a more anodic metal.
o This will induce corrosion at the anodic metal.
o Thus the more anodic metal sacrifices itself and gets corroded
protecting the metallic structure.
o Sacrificial anodes known are Zn, Mg, Al and their alloys.
o Applications are: protection of underground pipelines, ship hulls
and other marine devices, water tanks.
UNIVERSITY 43
Sacrificial anodic protection
Sacrificial anodic protection - concept
e-
Mg
Mg2+

UNIVERSITY 44
Cathodic Protection - Preventing Corrosion
To protect underground
pipelines, a sacrificial
anode is added.
The water pipe is turned

into the cathode and an
active metal is used as the
sacrificial anode.
Magnesium is used as the

sacrificial anode, since it is
more easily
oxidized than the
iron water pipe.

UNIVERSITY 45
Corrosion control
Insulated
Insulated copper
copper wire
wire
Sacrificial zinc
Soil
Sacrificial
anode
Mg
Underground Sacrificial Zn or Mg
Pipeline (Cathode) Ship hull rod
Sacrificial
Prof. Dr. F.anodic protection
Nawaz Khan, VIT
Hot water tank
UNIVERSITY 46
 Use of sacrificial anodes – Zinc, lead, etc.
 Used on small structures
 Anodes welded or bolted to fixtures
 Need regular checks for wastage
 Recently aluminium oxides have become more popular due to
better performance to weightUNIVERSITY 47
Sacrificial Anodes
This field is located in Viosca Knoll, block 786, southeast of New Orleans. It lies in
water depths of approximately 1754 feet (535 meters). Petronius is the largest free-
standing structure in the world. Texaco's choice was Galvotec-CW-III Aluminum
Sacrificial Anodes for their Petronius cathodic protection
system. http://www.galvotec.com/img/texaco.jpg
UNIVERSITY 48 48
Corrosion control
ii) Impressed current cathodic protection:
o Impressed direct current is applied in the opposite direction to the

corrosion current to nullify it.
o Usually, one terminal of a battery is connected with an insoluble

anode e.g. graphite electrode is immersed in black fill containing
coke, gypsum, bentonite and sodium sulphate for good electrical
conductivity.
o The other terminal is connected to the metallic structure to be

protected.
o Since the current is impressed on the metallic structure, it acts as

cathode and thus gets protected.
o This method is usually used to protect underground water pipe

lines, oil pipe lines, transmission lines, ships etc.
UNIVERSITY 49
Impressed current cathodic protection
Impressed current cathodic protection - concept
e-

UNIVERSITY 50
Corrosion control
Graphite anode + Source for
_
impressed DC
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
Soil
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
_
::::::::::: Insulated
:::::
::::::::::: copper wire
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
:::::
:::::::::::
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
:::::::::::
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
+
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
Buried
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
Pipe
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
Made
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
Cathodic
(protected)
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
ImpressedProf.
current cathodic protection
Dr. F. Nawaz Khan, VIT
UNIVERSITY 51
Mg
Magnesium Anode
Impressed current
Early anodes made from scrap steel but most modern ICCP
systems use lead silver alloy, titanium or niobium

UNIVERSITY 52
f. Corrosion inhibitors
o Corrosion can be reduced by using corrosion inhibitor, which is a
substance when added in small quantities to the aqueous
corrosive environment, effectively decreases the corrosion of a
metal.
o Inhibitors are divided as anodic inhibitors and cathodic inhibitors.
o Anodic inhibitors are the substances which reduce the corrosion

occurring at anode by forming sparingly soluble salts with the
metal ions produced. Eg. tungstates, chromates, phosphates etc.
o Metal surface adsorbs metal ions to form a protective layer to

reduce the corrosion rate. Even though the corrosion control is
highly effective, local corrosion may occur in case of exposure of
even small area.

UNIVERSITY 53
o Cathodic inhibitors are mainly added to reduce the diffusion of

hydrated H+ ions to the cathode. The H+ ions formed are
combining to form hydrogen gas, which is evolved
2H+(aq) + 2e- → H2(g)
o The formation of H2 gas can be controlled by increasing the

overvoltage of hydrogen evolution.
o Organic inhibitors like amines, mercaptans, heterocyclic nitrogen

compounds, substituted urea, thioureas, heavy metal soaps
reduce the diffusion of H+ ion considerably.
o These inhibitors get adsorbed on the metal surfaces and form an

adherent film of metals at the cathodic area thereby increase the
hydrogen overvoltage considerably.

UNIVERSITY 54
o However, in neutral solution, the cathodic reaction is
H2O + ½ O2 + 2e- → 2OH-
o Hence, the corrosion can be controlled either by removing

oxygen from the corroding environment or by reducing its
diffusion to the cathodic areas.
o The oxygen can be eliminated by adding reducing agents

like Na2SO3 or by deaeration. The diffusion of oxide ion is
reduced by using inhibitors like Mg, Zn or Ni salts.
o These react with hydroxyl ions forming corresponding

insoluble hydroxides, which are deposited on the cathode
forming impermeable self barrier.

UNIVERSITY 55
Passivity
o Any metal exhibiting lower rate of corrosion than normal in a
certain environment is said to be passive.
o Fe, Cr, Ni, Ti and their alloys exhibit passive character.
o Eg. i) Iron dipped in conc. HNO3 becomes passive.

ii) Stainless steel immersed in conc. HNO3 (for one hour)
becomes passive.
o This passivity is attained because of the formation of a passive film

on the surface of the metal in the environment.
o Passivity is not a permanent property and depends on the

environmental conditions.

UNIVERSITY 56
Protective coatings
o Protective coating provide a physical barrier between the
metal and the environment .
o They not only give corrosion protection but also add to
the decorative value of the article.
o Coatings are broadly divided as:
a) Inorganic coatings : metallic and chemical conversion
coatings
b) Organic coatings : paints, varnishes, enamels, lacquers
o Protective coatings are classified as:

i) metallic coatings
ii) chemical conversion coatings
iii) organic coatings and linings
iv) ceramic protective coatings
UNIVERSITY 57
Protective coatings
o The most important step before protective coatings are applied to
metals is surface preparation.
o Surface preparation is a process to remove rust, oxide scales, oil,

grease, dust etc.
o If these materials are not removed, the protective coating will not
be smooth, uniform, cohesive and will not adhere to the metallic
surface.
o Hence, mechanical and electrical methods are used to prepare the

surface of the metallic article to be coated clean and free of these
impurities.
o Mechanical cleaning, sandblasting, solvent cleaning, alkali cleaning,

acid pickling and etching are normal processes followed for surface
preparation of the article to be coated.
UNIVERSITY 58
Protective coatings
a) Mechanical cleaning:
o Useful for removing loose scales and rust.
o Hammering, wire brushing, grinding, blasting, polishing are the
methods commonly used.
b) Sandblasting:
o Fine sand or abrasive material along with air stream at a pressure
of 25-100 atm. is impinged on the metal surface.
o This will produce enough roughness for good adherence of the
protective coating.
o Though the method is expensive, it is quite fast and useful.
c) Solvent cleaning:
o Solvent cleaning is mainly used to remove oil, grease and rust from
the base metal.
o Alcohols, xylene, toluene, chlorinated hydrocarbons are used.
o Hot water cleaning is followed after solvent cleaning is done.
UNIVERSITY 59
Protective coatings
d) Alkali cleaning:
o Cleaning of the base metal with sodium hydroxide, trisodium
phosphate, sodium silicate, soda ash etc., is carried out to remove
old paint coatings soluble in alkaline medium.
o After alkali cleaning, washing is done with 1% chromic acid
solution.
e) Acid pickling and etching:

o Base metal is dipped inside the acid solution at higher
temperature for long periods of time.
o This treatment ensures cleaning of the base metal surface free
from all kinds of impurities including oils, greases, rust etc.,
o H2SO4, HCl, HF, H3PO4, HNO3 are the acids commonly used for
pickling and etching.

UNIVERSITY 60
Protective coatings
Metallic coatings:
a) Anodic coatings
b) Cathodic coatings
a) Anodic coatings:
o Anodic coatings are given on cathodic metals using metals which
are more anodic.
o Zinc, aluminium, cadmium coatings on iron are anodic coatings.
o If the coating breaks, then a galvanic couple is set up and
corrosion rate gets enhanced.
o During this process, the anodic coating gets disintegrated but it
protects the cathodic base metal.
o Hence, the anodic metal sacrifices itself to protect the base
metal.
o This type of coating is known as galvanisation.

UNIVERSITY 61
Anodic coating
Corroding environment  Iron can be protected
from corrosion by
Exposed part (cathode)
Zinc
coating it with zinc metal
Zinc coating
coating
flow of electrons
- a metal that will oxidize
Unexposed area first, instead of the iron
Steel
 Note that E°oxidation

of zinc is greater
than that of iron. Prof. Dr. F. Nawaz Khan, VIT
UNIVERSITY 62
Protective coatings
Cathodic coatings:
o Cathodic coatings are given on anodic metals using metals which
are more cathodic.
o Coating of tin, chromium, nickel on iron surface are cathodic

coatings.
o If there is a discontinuity in the coating, then galvanic couple will

form with base metal as anode and the coated metal as cathode.
o Then the process of corrosion will start by the base metal ions
going into solution and the metal deteriorating.
o To avoid this, the article is checked and re-plated periodically so

that there is no discontinuity in the coating.

UNIVERSITY 63
Cathodic coating
Corroding environment
Exposed part (anode)
Tin Tin
coating coating
flow of electrons
Unexposed area
Steel

UNIVERSITY 64
Protective coatings
Methods of metallic coatings:
a) Hot dipping
b) Metal cladding
c) Electroplating
d) cementation
e) Vacuum metalizing
f) Metal spraying
a) Hot dipping:
Two types of hot dipping techniques are known.
i) Galvanizing: Dipping the base metal iron in molten zinc metal

solution.
i) Tinning : Dipping the base metal iron in molten tin metal
solution.
UNIVERSITY 65
Protective coatings
a) Hot dipping:
i) Hot dipping:
o Iron or steel part is dipped in molten zinc bath to get a thin coat of zinc.
o Before hot dipping, the steel or iron part is cleaned by acid pickling in dilute
H2SO4 at 60-90oC for 15-20 minutes.
o The base metal is then dipped in molten zinc bath maintained at 415-430oC
(M.P. of Zn is 419oC).
o The surface of zinc bath is covered with NH4Cl flux to prevent oxide formation.
o The coated part is then passed through a set of rollers to get the correct
thickness of coating and then annealed at 225oC and cooled slowly.
o Galvanizing is used for protecting iron in the form of sheets, wires, nails, bolts
and screws.
o Galvanised iron articles are not suitable for storing food items since some of
the zinc compounds are poisonous.
UNIVERSITY 66
Schematic diagram of hot dipping
Drying Ammonium Pairs of Galvanized

Iron chamber chloride flux hot rollers sheet
sheet
Hot air
Annealing
water chamber
Dil. H2SO4 Molten zinc Excess zinc

Washing removed
at 60-90oC at 425-430oC
bath
Galvanizing a sheet of iron

UNIVERSITY 67
Protective coatings
ii) Tinning:
o Tinning is s a process of coating tin over steel sheets, iron sheets
by dipping the sheets in molten tin bath.
o Before tinning, the sheets are pickled in dilute H2SO4 to remove
surface impurities.
o Tin bath is covered with a flux of ZnCl2 to prevent oxidation.
o After tinning, the sheet is passed through palm oil to protect the
tin coating from immediate oxidation.
o The sheets are passed through a set of rollers to achieve required
thickness of tinning.
o (Set up is similar to hot dipping.)

UNIVERSITY 68
Protective coatings
Rollers
Tin
plated
sheet
Acid pickling bath

Molten tin
Fig.: Tinning of sheet
Tank
69
corrosion.

UNIVERSITY
Electroplating
o It is a process by which a coating metal is deposited on the base
metal by passing direct current through an electrolytic solution,
containing the soluble salt of the coating metal.
o Electroplating is done for improving
a) corrosion resistance
b) wear resistance
c) chemical resistance
d) surface hardness
e) appearance
o Both ferrous and non-ferrous metals are plated with Ni, Cr, Cu, Zn,
Pb, Al, Ag, Au, Sn etc.
o Electroplating is mainly used in automobile, aircraft, refrigerator,
chemical and electrical appliances etc.
On non metals to increase the strength (wood, plastics, glass etc), for
decorative purposes, for surface conductivity
Electroplating

UNIVERSITY 71
Important Factors of electroplating
o Cleaning of the article is essential for strong adherence of

the electroplating:
- Scraping, grinding, sand blasting, wire brushing, solvent cleaning
and acid pickling are used for surface cleaning.
- A well cleaned and properly pre treated surface of any material to

be electroplated is necessary for obtaining the coating of long life.
o Concentration of the electrolyte is another important factor:
-Low concentration of metal ions will give uniform coherent

deposition.
-To maintain low conc. of metal ions, complexing agents are added
to the electrolyte. CN-, sulphamate, hydroxide
In plating Cu on Fe, CN- is added so that Cu2+ is complexed with CN-
to avoid Fe + Cu2+ giving Fe2+ and Cu
This also produces smooth and UNIVERSITY
adherent deposit 72
Important Factors of electroplating
o Thickness of the deposition should be optimised to get a
strong and adherent deposition:
- For corrosion protection multiple coatings are given to get

impervious coating without any discontinuity.
- For decorative purpose, thin coating is given.
 Current density
 - Current density is the current per unit area of the article being
plated (amps cm-2).
 - The C.D should be maintained at optimal level (low) to get
uniform and adherent deposition
At low current density diffusion is faster than the electron transfer so
smooth and uniform deposit
 Additives to electrolytic bath (Adherence)

- Additives to electrolyte are added in small quantities to get
strong adherent deposition.
- Commonly used additives Prof.are
Dr. F. gelatin,
Nawaz Khan,glue,
VIT glycine, boric acid
etc. and brighteners for bright plating.
UNIVERSITY 73
Choice of the electrolyte:
Good conductor, highly soluble, do not undergo hydrolysis,
oxidation, reduction, sufficient throwing power
Sometimes single, sometimes mixture of electrolytes
In copper plating, CuSO4 and H2SO4 is used
Brighteners Aromatic sulphonates or sulphones, and compounds

like thiourea, coumarin used to produce microscopic fine deposits
which reflect the light
Throwing power
Ability of the electrolytic cell to give a deposit of uniform thickness
over the entire cathode area, max throwing power attained when
cathode is regular shape, if irregular then agitating the solution to
minimize local electrolytic resistance
Electroplating
o pH of the bath:
- For a good electrodeposit, the pH of the bath must be properly
maintained (using buffers). For most plating baths, pH ranges
from 4 to 8.
pH lower than the optimum value means stronger hydrogen
evolutions, resulting in burnt deposit, at higher pH hydroxides
deposits
o Method of Electroplating:
- Method depends upon the type of metal to be electroplated, the

size and type of article to be electroplated.
- its main objectives and economics are also considered.

UNIVERSITY 75
Plating bath solution
o It is a highly conducting salt solution of the metal which is to be
plated.
o However, non-participating electrolytes are added to the bath

solution to increase the conductivity and the throwing power.
o The level of the plating bath should cover completely the cathode
and sufficient area of anode.
o Heating if required is provided by heating coils or hot gases.
o Air sparger or nitrogen sparger is employed to introduce convection

current in the plating bath solution.
o It should possess sufficient throwing power. Hence mixture of two

or more electrolytes is used for preparing electrolytic bath.
o It should be good conductor and highly soluble.
o It should not undergo hydrolysis, oxidation, reduction and other

chemical changes. Prof. Dr. F. Nawaz Khan, VIT
UNIVERSITY 76
Physical vapor deposition (PVD)
 The physical vapor deposition technique is based on the
formation of vapor of the material to be deposited as a thin
film.
 The material in solid form is either heated until
evaporation (thermal evaporation) or sputtered by ions
(sputtering).
 In the last case, ions are generated by a plasma discharge
usually within an inert gas (argon).
 It is also possible to bombard the sample with an ion beam
from an external ion source.
 This allows to vary the energy and intensity of ions
reaching the target surface.
Physical Vapour Deposition
o This is a process of depositing some material by atom by atom or
molecule by molecule or ion by ion.
Applications:
1. This process is widely used to produce decorative coatings on plastic
parts those are resembling shiny metal.
2. Many automobile parts are plastic with a PVD coating of aluminium.
3. A lacquer coating is applied over the decorative coating to provide

corrosion protection.
4. This process is also used to apply relatively thick (1mm) coatings of

heat resistant materials on jet engine parts, A special alloy of
chromium, aluminium and yttrium is used for this type of coating.
UNIVERSITY 78
PVD – Thermal Evaporation

UNIVERSITY 79
PVD - Sputtering
1. High technology coatings such as ceramics, metal alloys and organic and
inorganic compounds are applied by sputtering.
2. The substance to be coated is connected to a high voltage dc power supply.
3. When the vacuum chamber has been pumped down, a controlled amount of
argon or another gas is introduced to establish a pressure of about 10-2 to 10-3
torr.
4. On energizing current supply, plasma is established between the work and the
material to be coated.
5. The gas atoms are ionized, and they bombard the material to be coated.
6. The energy of impinging ions cause atoms of the target material to be

sputtered off, and they are transported through the plasma to form a coating.
7. Direct current sputtering is used when the target is electrically conductive.
8. Radio-frequency sputtering, which uses a RF power supply is used when the

target is a non conductor such as polymer.
UNIVERSITY 80
Sputtering
The substrate is placed in a vacuum chamber with the source material,

named a target, and an inert gas (such as argon) is introduced at low
pressure. A gas plasma is struck using an RF power source, causing the
gas to become ionized. The ions are accelerated towards the surface of
the target, causing atoms of the source material to break off from the
target in vapor form and condense on all surfaces including the substrate.
81
PVD – Ion plantation
1. A third variation of the PVD process is ion plating, which involves
the evaporation.
2. They physically implant into the substrate to produce an extremely

strong coating bond.
3. Sputter and ion plated coatings are used in design for very thin
films for electrical, optical and wear-resistant applications.
4. The wear properties of tools are widely enhanced by hard thin film
coatings.
5. Sputtered coating processes produce microscopic modules of

diameter of several micrometers and they are called macros.
6. These macros are undesirable for metal to metal sliding systems.
7. On the other hand they are usually beneficial to cutting tools.

UNIVERSITY 82
Applications of PVD

UNIVERSITY 83
Evaporation and sputtering: comparison
Evaporation Sputtering
Rate Thousand atomic layers per second One atomic layer per second
(e.g. 0.5 µm/min for Al)
Choice of materials Limited Almost unlimited
Purity Better (no gas inclusions, very high Possibility of incorporating
vacuum) impurities (low-medium vacuum
range)
Substrate heating Very low Unless magnetron is used
substrate heating can be
substantial
Surface damage Very low, with e-beam x-ray Ionic bombardment damage
damage is possible
In-situ cleaning Not an option Easily done with a sputter etch
Alloy compositions, Little or no control Alloy composition can be tightly
stochiometry controlled
X-ray damage Only with e-beam evaporation Radiation and particle damage is
possible
Changes in source Easy Expensive
material
Decomposition of High Low
material
Scaling-up Difficult Good
Uniformity Difficult Easy over large areas
Capital Equipment Low cost More expensive
Number of depositions Only one deposition per charge Many depositions can be carried
out per target
Thickness control Not easy to control Several controls possible
Adhesion Often poor Excellent
Shadowing effect Large Small
Film properties (e.g. Difficult to control Control by bias, pressure,
grain size and step substrate heat
coverage) Prof. Dr. F. Nawaz Khan, VIT
UNIVERSITY 84
What is CVD Process?
 Chemical Vapor Deposition is the formation of a non-volatile solid
film on a substrate by the reaction of vapor phase chemicals
(reactants) that contain the required constituents.
 The reactant gases are introduced into a reaction chamber and are
decomposed and reacted at a heated surface to form the thin film.

UNIVERSITY 85
CVD vs. PVD
 Chemical Vapor Deposition (CVD) relies
on chemical reactions between reactants
in the gas phase and/or on the substrate
surface.
 Physical Vapor Deposition (PVD) is a
thermal evaporation driven or energy
driven process.

UNIVERSITY 86
Applications of CVD

UNIVERSITY 87
Chemical vapour deposition

UNIVERSITY 88
Chemical vapour deposition
Advantages and Disadvantages:
• This coating finds application on glass containers to make
explosion or shatter resistant glasses.
• The main advantage of CVD process over PVD is that it is

not line of sight.
• All surfaces in the reaction chamber get coated.
• Separate process and reaction must be developed for each

coating. Some of the gases are toxic and dangerous.
• But greatest disadvantage is temperature should be very

high at 700°C. At this temperature, many metals soften.
UNIVERSITY 89
Plasma Enhanced (PE)CVD
As the thermal budget gets more constrained while more layers are
added for multi-layer metallization, we want to come down with the
temperature for the oxide ( or other) CVD processes. One way for doing
this is to supply the necessary energy for the chemical reaction by
ionizing the gas, thus forming a plasma. UNIVERSITY
90
Applications of CVD
1. A newer process known as plasma assisted chemical vapour
deposition. This process is used to apply diamond and diamond
like carbon coatings.
2. Silicon carbide barrier coatings are applied on plastic films and

semiconductors.
3. Chemical Vapour Deposition is used to produce bulk shapes of
high purity silicon carbide. Reactants are deposited on a
chamber wall to a thickness in terms of millimeters.
4. Thin-film coatings are key to the manufacture of many electronic

devices. They involve the application of dopant, sealant and
other microelectronic paste.
5. Thermal evaporation is a low cost process, but all these

processes are normally batch processes because of vacuum
chamber requirements.
UNIVERSITY 91
CVD Used in Semiconductors
Temperature
Layer Reaction equations (ºC)
SiO2 LTO SiH4 + O2 -> SiO2 + 2H2 400-450

TEOS Si(OC2H5)4 -> SiO2 + gas.RP 650-700
HTO SiCl2H2 + N2O -> SiO2 + 2N2 + 2HCl 850-900
SiH4 + CO2 H2 -> SiO2 + gas.RP 850-950
Si3N4 3SiH2Cl2 + 4NH3 -> Si3N4 + 6HCl + 6H2 700-900
Polysilicon SiH4 -> Si + 2H2 600-650
selective 2WF6 + 3Si -> 2W + 3SiF4 300

Tungsten
blanket WF6 + SiH4 -> W + SiF4 + 2HF + H2 400-450
UNIVERSITY 92
Metal cladding:
Metal cladding is sandwiching the base metal

between two thin layers of coating metal by hot
rolling process to give strong bonding between the
two.
More cathodic metals are used to clad base metal;

Eg. Cu, Ni, Ag, Pt, Ti.
Duraluminium sandwiched between aluminium

sheets and hot rolled gives “Alkad” which is free
from stress

UNIVERSITY 93

Corrosion and Its Control NF

Încărcat de

Informații document

Titlu original

Drepturi de autor

Formate disponibile

Partajați acest document

Partajați sau inserați document

Opțiuni de partajare

Vi se pare util acest document?

Este necorespunzător acest conținut?

Drepturi de autor:

Formate disponibile

Corrosion and Its Control NF

Încărcat de

Drepturi de autor:

Formate disponibile

Corrosion and

Prof. Dr. F. Nawaz Khan, VIT

Prof. Dr. F. Nawaz Khan, VIT

o Metal will always have a strong tendency to convert itself

Prof. Dr. F. Nawaz Khan, VIT

o Classified depending on the corroding agent

M + ½ O2 M2+ + O2- metal + O2

o Oxidation corrosion will lead to an oxide film which may be porous

o Types of oxide layers:

i) Stable oxide layer:

Metallic oxide Metal + Oxygen

Unstable oxide layer

Porous oxide layer

o These are oxide layers which evaporate as soon as they are

o After some time the metal itself will disappear.

o Molybdenum is an example of volatile oxide layer corrosion.

Volatile metal oxide

Fe + H2S FeS + 2H (atomic hydrogen)

iii) liquid metal corrosion:

Prof. Dr. F. Nawaz Khan, VIT

At the anode: M Mn+ + ne-

The rate of the electrochemial corrosion will depend on:

a) If the corrosion product is soluble in the medium, rate of

1. Hydrogen evolution type corrosion

Cathode : 2H+ + 2e- H2

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

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

If sufficient oxygen is present, Fe(OH)2 gets oxidised to ferric hydroxide (rust)

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

Prof. Dr. F. Nawaz Khan, VIT

Prof. Dr. F. Nawaz Khan, VIT

o Occurs when two dissimilar metals in the electrochemical series

o The metal with more negative potential (higher in EC series ) will

a) coupling metals which are close in the electrochemical series.

Prof. Dr. F. Nawaz Khan, VIT

Metal Electrode Potential (V)

Galvanised tank Zinc corrodes Sacrificial anode

Copper ball-cock Solder corrodes Plastic ball

Copper flashing Steel corrodes Copper nails

Steel radiators with Steel corrodes Corrosion

Prof. Dr. F. Nawaz Khan, VIT

o When a metal is exposed to different concentration of oxygen or any

Anode: Zn Zn2+ + 2e-

The other area which is more exposed to oxygen becomes oxygen

Prof. Dr. F. Nawaz Khan, VIT

o Due to rapid penetration of oxygen through some cracks in the

o Eg. Al, Ti and stainless steel undergo pitting corrosion in acidic

5th Century sword

Grain structure Grain boundary Steel/damp Isolate steel

Concentration Low Soil types Protective coatings

Differential Oxygen remote Underground Protective coatings

Stressed areas Most heavily Steel rivets Protect from

Prof. Dr. F. Nawaz Khan, VIT

ii) Over voltage:

o If anodic area is small, the corrosion is rapid.

iv) Purity of the metal:

v) Physical state of the metal:

vi) Nature of surface film: (Pilling-Bedworth rule):

Prof. Dr. F. Nawaz Khan, VIT

viii) Solubility of corrosion product:

o If the product is insoluble in the environment, then the corrosion is very

viii) Volatility of the corrosion product:

ii) Humidity in environment: