CORRC

for the
metal
combined
f o r mwhich

8 ANO anouno
oher
wOras,
t f
en
c

CONTROL
re

ITS zment.
r t
s
a

h e

ofthe Metallic
Ore
to
metal
(

dency metal
incomk
us and what lies before us
"What lies behind are f o Stable
r Sts
compared to what lies
within us.
small
Ralph Waldo Emcrmasont en
t cONSEQUENCES

numberof
81 Corrosion

8.2 Why metals corrode 8.1/CORROSION hasa n

o fn
Corrosion Waste
8.3 Consequences of Corrosion can be defined as degradation or EnormouSunpredicta
84 Thcories of Corrosion
by chemical or electrochemical reaction deterioration
with its oia mea leadsto
" Chemical or Dry
Corrosion and
" E!ectrochemical or Wet
(gaseous or liquid medium).
Degradation or deterioration means reduction in envtihroen e r o life.
lass f
decrease ir
to expens
t leads
Corrosion properties of the material which include: si an
shichis leakage
8.5 Types of Corrosion Weakening of the material due to loss of cause toxic
8.6 Passivity
8.7 Galvanic Series
LoSs of properties such as malleability, crossectiona;
ductility
I may
leakage
ltcauses
and
of
contamina
Decaying of surfaces of metals.
S.8 Factors Influencing estimatec
Corrosion Cracking of a polymer due to sunlight. has been
b)t
Nature of the metal The materials affected by corrosion are metals, polyner above
discussie
" Environmental factors (plastics or rubbers etc.), ceramics (concrete) etc. But metals i Fun the
engineers and
8.9 Protection Against Corrosion most useful class of materials corrode most frequently and henxe hohthe
thisdiscussion mainly devoted to corrosion in metals.
is merative.
Some of the common examples of corrosion in metals are:
Rusting of Iron: When exposed to the atmospheric condi THEORIES OF CO
tions, a layer of reddish scale and powder of Fe,0, is formed an znber of
the surface. different viev
Formation of green film on the surface of copper: A Ooosion is Oxidation.
layer of basic carbonate consisting of geMers have opinion t
CuCO, +Cu(OH),IS
on the surface of copper when
exposed to moist air 1OOSIONs are discusse
Tarnishing of silver: When silver is exposed to the am
phere, a black coating is formed.
Fa or dry
CHEMICAL OR L
WHY METALS CORRODE
All metals except gold, platinum and palladium corrode spontane. he atmospheric ga corrositypow
atack. This
ously when exposed to 21%of MOS 0norgarnic liquic
atmosphere,
Oxygen) Metals, with the exception of gold,which contains
platinum: andpalladim
are fouhd in nature in combined forms as their oxides. carbonates Sble corrOsion pr
metal afrom
met l, wh
and fresh met
 Corroslon and its Control 427

sulphides, chlorides or silicates.(The metals in the combined form are

combined form of the metal i.e., mineral is more stable known as minerals. The natural
than the metal.) During the extraction of the
metalfron the mineral, a considerable amount of energy is
extraction process, it implies that
metal has a higher energy state
reuired. As energy is consumed in the
metal. Thus, the metal which is than the mineral or
tends to revert backcompound
the in higher energy state of
natural combined form which is of low (unstable)
energy, when it comes in contact with the to its stable
environment. In other words, corrosion elements thein
oteris the amount of energy process is the return of the refined material to its
required to separate the metal from its mineral or ore, natural state.
thetendency ofthe metal to revert back to its natural
state resulting in degradation of thegreater will be
Metallic Ore (Mineral or metal.
Extration of Metal Pure Metal
metal in combined form)
[or Stable State] Corrosion (Reaction
with atmosphere) [Unstable State]
8.3 cONSEQUENCES OF CORROSION
orosion has a number of economic and social
consequences which include:
) Enormous waste of
machineries and different types of metallic materials.
() It leads to unpredictable
Joss of life.
machinery failure which may lead into dangerous situations such as
(GiD) It leads to decrease in efficiency of
which is an expensive proposition. machine and frequent replacement of corroded equipment,
(iv) lt may cause leakage of inflammable gas from the
and leakage of toxic product. corroded pipe line resulting into fire hazards
(v) It causes contamination of potable water.
(vi) It has been estimated that 25% of
annual world production of iron is wasted due to corrosion.
From the above discussion it becomes clear that
study of corrosion and its prevention is essential
to boththe engineers and metallurgists. For this, an understanding of the mechanism of corrosion
is imperative.
8.4 THEORIES OF CORROSION
Anumber of different views have been put
forward to explain as to
Say, corrosion is oxidation or electrochemical phenomena while how corrosion takes place. Some
Still others have opinion that it is electrical phenomena. Each is others say, it is a chemical attack.
Of corrosions are discussed below. partially true. The different theories
B4.1 CHEMICAL OR DRY CORROSION
Chemical or dry corrosion is the simplest case of corrosion, where
Chemical attack. This type of corrosion occurs mainly when corrosion takes place by direct
metal surface come in direct contact
Mth the atmospheric gases such as oxygen, halogens,
hydrogen sulphide, nitrogen etc. or with
dinydrous inorganic liquid.)The corrosion product formed can be insoluble, soluble or liquid product.
Insoluble corrosion product implies that a solid film of the corrosion
Surface of the metal, which goes on thickening as corrosion proceeds. product is formed on the
protects the metal from further corrosion because rate of penetration of theAftercorroding
sometime this layer
environment
decreases and fresh metal is not exposed to it.
 o w il
taeV e
428 Engineering Chemistry

the surface
When the corrosion product is soluble or liquid, it is removed from corrosion. as So0n as
excessive
formed, exposing fresh metal to environment. This leads to itis S a b lt
e

Dry or chemical corrosion is generally of three main types: surtace.

Chemical Corrosion the

und

and pre

Oxidation Corrosion Corrosion by other gases Liquid Metal Corrosion stable

an
otherr e
8.4.1a. Oxidation Corrosion Unstab
fOxidative corrosion takes place by direct action of oxygen on metals, at low or high andoxy
Yorming oxides of the metal.) It generally takes place in absence of moisture. The reaction of a
with air or pure oxygen to form the corresponding oxide can take place spontaneously in caa
temperature,
alkali and alkaline earth metals even at ordinary temperatures. However, most of the metals react w Hencei
Oxygenonly at high temperatures. Almost all the metals except Ag, Au, and Pt, get oxidized at hiot Auand
temperatures.
Volatile
Mechanisms of Dry Corrosion theunde
The growth of the oxide film on metal takes place at the surface as: corrosio
" The oxygen is adsorbed at the surface of the metal by physical adsorption. undergo
" When the temperature rises the physical adsorption turns into yPorous =
gets oxidized to metal ions (M ’ M* + ne) chemisorption, wherein metal
" The electrons are taken up by oxygen which gets of oxyge
The Mt o combine to form metal oxide reduced to oxide ion (n0, + 2ne -’ 2n0 oxides
The reactions can be written as (M,O,) ne
|Pling-Bedw
2 M
2M* + 2 ne (Oxidation of metal) he oxide laye
nO, + 2ne 2n 0, oude to the Ve
(Reduction of OXygen)
2M tO, 2Mt + n02
Metal Oxygen Metal Oxide
ion ion
According t
Metal
" The metal oxide scale so Oxide (M,O) " If th
the metal and the oxygenformed forms a barrier between
and restricts further.
whic
or corrosion of the
metal. For oxidation to oxidation 0,+ 2e of in na
either metal must diffuse continue in na
to the surface. outwards through the scale meta
or oxygen must diffuse through the scale to
underlying metal.
"As the metal cation is much
the Oxide
film
M*
Con?
" If th
smaller in size, the outward
diffusion of metal ion is much it is
diffusion of oxide ion.]Hence more rapid than inward Metal M
M*+2e
Such
rapid diffusion of highly corrosion continues by
mobile cations. (Fig. film
8.1) Fig.8.1 Mechanism of Growth of For
Oxide film
volur
 Corrosion and its Control 429
2ne

Lzureoftheoxide film tormed plays an important part in corrosion process(If the thickness of
Mdelayeris less than 300 ¢ then such layer is called afilm and if the thickness of the film
Athan it is known as scale 'The nature of the film decides the continuation of corrosion
discussed below:
Nable Glm: The stable oxide film is fine
grained in structure and adheres tightly to the metal
surface. This can be
the underlying metal.impervious
in
In otherwords,nature,
such athereby preventing
film forms the penetration
a protective oxygenmetalto
of the
coating over
preventsfurther
and oxidation or corrosion. The oxide films on Al, Cr, Cu, Pb, Sn etc. are
stableand adhere to the surface.
other reactive metal to
Therefore these metals are employed for alloy formation with
Cnstable film: The oxide
protect them from corrosion.
) film formed on the surface of metal back into metal
and oxygen and hence the film is called unstable film. decomposes
Metal Oxide Metal + Oxygen
Hence in such cases corrosion is not
Auand Pt and hence these do
possible. Unstable film is formed by the oxides of
not Ag,
) Volatile film: The metal-oxide film undergo corrosion.
the underlying metal is exposed to thevolatizes from the surface as soon as it is formed. Hence
corrosion. For example, molybdenumfurther attack by oxygen leading to rapid and
oxide (Mo0,) is volatile and hence continuous
undergoes excessive corrosion. molybdenum
ivPorous film: Sometimes the oxide film so formed is
of oxygen takes place through porousor have cracks. Hence the diffusion
these
Oxides of metals like alkali and pores leading to further oxidation or corrosion. The metal
alkaline earth metals fall under this
Piling-Bedworth Rule category.
ie oxide layer can be protective or
nNide to the volume of the metal non-protective depending upon the ratio of volume of the
consumed. This is known as metal
Pilling-Bedworth ratio.
Pilling -Bedworth ratio = Volume of themetal oxide formed
Volume of the metal consumed
According to Pilling-Bedworth s rule,
" If the volume of the
oxide film
which it is formed., the ratio isformed
less
is less than the volume of the
than unity then the oxide film will respective metal from
in nature. In such cases the
oxide film formed over the surfaces of be non-protectiye
in nature and oxygen can the metals is norous
diffuse through these
metal. For example, in case of alkali and alkaline pores to bring about further attack on the
Al) oxide film produced has earth metals such as Na, Ca, Mg
smaller volume than that of the metal (except
Consequently, the oxide film develops cracks and pores in its from which it is formed
formed is equal or greater than the structure.
" If the metal oxide film
it is formed(the ratio is more than unity, the
metal oxide filmrespective metal from which
Such cases the oxide film formed i_ is
protective in
film prevents the diffusion of oxygen andcontinuous, adhering and non-porous. Thisnature) In
type of
For example. in cases of Al, CI, and Whene the rate of corrosion by oxidation decreases
20

etc.,
volume of the respective metal and hence isthevolume of oxide layer is greater than the
protective in nature.
430 Engineering Chemistry

Corrosion by other gase8 SO,, Cl,, H,S, F, etc. also have corrosive
8.4.1b
number of other gases such as CO,,
the chemical affinity between the metal and
to oxygen, aextent of corrosion depends mnay be protective or non-protective
on in
In addition metals./The formed corrosion
nature.
effect on also the film so attack or
In this case protective in nature, the extent of non-porous protective film wh
decreases. For
involved.
the gas formed is
" Ifthe film attacks silver metal surace to form
example. chlorine gas
prevents further corrosion. it destroys the whole metal eventually.
non-protective in nature then
which is volatile and hence lea
formed is film
" Ifthe film chlorine attacks Sn to form SnCl, further attack.
For example, for
exposing the fresh metal porous in nature.
the metal surface
steel forming FeS layer which is
H,S attacks temperatures n
8.4.1c " Liquid-metal corrosion flowing liquid metal at high
of to
corrosion also results due to the actiontransfer media in nuclear reactor. It is shown
(Sometimes the
Liquid sodium is used as heat either dissolution of a solid metal bv o
solid metals or alloys) tubes. The corrosion reaction involves causing corrosion in solid metal
corrosion in carrier the solid metal
cause
by penetration of the liquid metal into
liquid metal or
CORROSION OR WET CORROSIONA nature. This tvpe
ELECTROCHEMICAL electrochèical in
8.4.2.
aqueous medium seems to be the place when:
The corrosion of metals in as immersed corrosion and generally takes
known
of corrosion is also the moist air or any liquid medjum
or
a metal is in contact with solstion.
metals or an alloy is in contact with a We all
i) when two differènt
electrochemical corrosion is the formation of rust on iron. metal
The most familiar example of wet soil or moist atmosphere. In this type of corrosion the
know that iron pipes corrode in
or ionic state.
is oxidized to a soluble form following conditions must be satisfied for the
formation
process takes place, the
Before the corrosive
of electrochemicaB cell:
and an anode.
(i) There must be a cathode
must be an electrical potential between the anode and cathode.
(ii) There
connecting the anode and cathode.
(ii) There must be a metallic path electrically in an electrically conductive medium.
(iv) The anode and cathode must be
immersed
cell" is formed. The corrosion takes place as
Once these conditions are satisfied a corrosion
discussed below:
where metal atoms tose their
(a) Anodic reactions: Atanodic area, oxidation reaction takes place
electrons to the environment and pass into the solution.
M Mnt + ne
(Metal)' (Metal ion)

Thus metal is destroyed by dissolving or changing into metallic ions. Hence, corrosion takes
place at anodic areas or metal, which forms the anode, is corroded.
(b) Cathodic reactions: The electrons released in the anodic reactions are consumed
of the
n e
corrosive
reactions at the cathode or cathodic reactions. Depending upon the nature
envíronment, cathodic reactions may result in:
 Corroslon and Its Control 431

Evolution of hydrogen: In absence of oxygen and in acidic environment evolution of

hydrogen takes plac. The H ions of acidic solution take up electrons released at anode
and are eliminated as hydrogen gas
2H + 2e ’ H, ‘ (in acidic medium)
In alkaline or neutral solution in absence of oxygen, the reaction will be:
2H,0 +2e’H, + 20H (in neutral or alkaline medium)
nle: Rusting of iron in acidic medium in absence of oxygen takes place as follows,
Fe ’ Fe+ 2e (Anode reaction)

E Diffusion of Acidic solution

Eferrous ions (Electrolyte) Cathodic reaction
formed into
electrolyte
-.2H* +2e’ H,():
Fe’ Fe* +2e
Fe ’ Fe*42e

Anodic area Anodic area

(Large) (large)
Anodic area
(Large)
Iron

Fig. 8.2 Mechanism of wet Corrosion by Hydrogen Evolution

The electrons that are released, flow through the metal surface (electronic conductor) from anode
acathode. The Ht ions of acidic solution take up these electrons and are eliminated as hydrogen gas.
2H + 2e ’ H, (Cathodic reaction)
The overall reaction is: Fe + 2H" ’ Fe²t + H
Hence, in this type of corrosion hydrogen ions are displacçdtrom the acidic solution by metal ions.
i Absorption of oxygen: This type of corrosion reaction takes place in the presence of
atmospheric oxygen. In neutral aqueous solution or weakly alkaline solution, containing
Oxygen the reaction, 2H + 2e ’ H,, does not take place and oxygen gets reduced
as, 2H,0+ O, + 4e ’ 40H
rample: Rusting of iron in neutral aqueous solution in presence of oxygen can be explained, with
te following reactions.
Fe ’ Fe* + 2e (Anode reaction )
Ihe electrons travel to cathode through the metal surface and react with oxygen,
1
0,
2
+ H,0+ 2e ’20H (Cathodic reaction)
 432 Engineering Chemistry

the cathodicregion through the moisture

anodetravel to
pduced at
The Fe cathode as follows: ’ Fe(OH),
producedat Fe + 2OH
IOns
is oxidizcd as,
FeOH), produced 4Fe(OH), or 2Pe,0,
The
FeOH), + 0, + 2H,0
which is hydrated iron (I|) oxidecolour
of variable (Rust)
(Fe((Ol), coresponds
nHol The degree
(Fe,0,)
of
to rust,
hydration
toyellow
ofthe iron(l) oxide
brown
or reddishoccurs
from black notedthat although corrosion
affects
(Fe,O,
the
H,0).
at amode, the rust
rapidly
is
of the
rust
formed
towards the near the
Compostion,
is
ma be
hecanse smaller
larger OH ions
towards
anode diffuse
Fe* ions produced at the anode.J cathode
as calhode
the difhusion of region on the surface of the metal can be
anodic and cathodic
The formation of
to the following factors:
rough surface of metal.
explaneS,
() Non-uniform or the bulk of metal
in
(ii) Presence of impurities
Oxygen concentration along the metal surface.
(i) Difference in
Aqueous neutral
solution of electrolyte

Rust Rust
120,+ 2e + H,0’20H
1/20, +2e +H,0-’20H

Cathode Flow of Cathode

Flow of
(Large) electron electron (Large)
Smallanode area (caused
by cracks in the oxide film
Iron where corrosion occurs
Fe ’ Fe+ 2e

Fig. 8.3 Mechanism of wet corrosion by absorption of oxygen

DIFFERENCE BETWEENCHEMICAL CORROSION AND ELECTRO

CHEMICAL CORROSION
CHEMICAL CORROSION ELECTROCHEMICAL CORROSION
SUCh

1. It takes place in dry conditions It takes place in presence of wet conditions

2. It takes place by direct chemical attack
of environment on the metal
3. It can takes place on homogeneous and
heterogeneous surface
4. Corrosion product accumulates at the
same spot where corrosion has occured
5. Uniform corrosion takes place
electrolytes.
presence of aqueous solution or ofa series
It takes place through the formation
Imetalsurfaceso
galvanic cells.
It takes place on heterogeneous cathode wher
Corrosion product accumulates at the
Corrosion occurs at the anode.
Non uniform corrosion takes place.
 Corrosion and its Control 433
TYPES OF CORROSION
number of methods classifying corrosion but no
of
clnssified into folowinguniversally
broad sense, cOrrosion can be
In accepted terminology is
Galvanic Corrosion typcs:
ahaniceorrosionis caused when two dissimilar meals arc

AAre e
to an electrically connected with each other
electrolyte. The two metallic parts constitute
lower "a
galvanic cell" in which the
clectrochemical potential) (i.c., the more active metal)
copper are in contact wifh
example,ifzinc and cach other in presence of anwill get corroded. Por
higherin electrochemical series,
(with lower electrolyte then zinc,
whichis (corroded), electrochemical potential)
dissolved while copper which is lower in forms the anode and
cathode and is protected,- electrochemical series (with higher
S
olectrochemical potential acts as
The use of copper
pipes in conjunction with iron
galvanic corrosion. The iron which acts aspipes in water distribution systems has been the
CANUSeof protected, anode corrodes, whereas the more
ts as cathode and is noble Cu
potential difference between the two metals, greater will be the
Jargerthe
Gal anic corrosion is also known as differential metal corrosion (Fig. 8.4). galvanic corrosion.
Zn ’ Zn-*+2e
Electronic current
Electrolyte

(Less noble
anode is
(More noble)
cathode is
attacked Positive ions protected
Current

Fig. 8.4 Galvanic cell corrosion

V.5.2. Concentration Cell Corrosion

|Concentration cell corrosion takes place Well aerated part
Zn Metal
Wnen tw0 or more areas of a metal surtace (Cathode)
e in contact with different concentration
ULne Same electrolyte or are exposed to an
such as lectrolyte of varying aeration.)
Differential Oxygen Concentration Less aerated part
eries of Cell (Anode)
es only. This is the common type of concentration Electrolytic solution
l corrosion where corrosion takes place (NaCl)
whereas
elo "differential aeration." Differential
eration Occurs when a metallic surface is differential Aeration.
Fig. 8.5 Corrosion by
Partial y immersed in an electrolyte andthe
 434 Engineering Chemistry rerl
s o n
a g

exposed to a
to the air ie., the one part of metal is different
air
concentration than the other. The electrode potential ofa metal will be different at these tWo locations,
of the metal is exposed
other part
This is a direct consequence of Nernst law. In such circumstances, those areas which are exposed
are little exposedsed
s e r a l e

while the areas which

oxygen become cathodic corrosion.)
togreater amount of air or anodic. Theanodic part sufferss the
exposed to air or Oxygen become in a dilute solution of
NaCl and the
For example, if zinc metal is partially immersed
waterline are well aerated and act as solution
Sis
closely adjacent to the
not stirred, the parts above and solution are anodic, since the concentration of oxygen is s e
(Fig. 8.5). Areas deep inside the causes a flow of current between two
areas of the sanme
Thus apotential is developed which
Zn dissolve at the anodic area,
Zn Zn + 2e (At Anode) AMeta

hydroxyl ions:
At the cathodic area oxygen takes up electrons to form
0, + H,0+ 2e- OH (At Cathode) gio
2 sS
the

Other examples of corrosion by differential aeration are: ts

ype
) Drop corrosion: It takes place when a drop of on electrolyte solution is in contact with the
metal surface) For example, if a drop of electrolyte is placed on an iron surface, rusting occurs
in the centrál region beneath the drop. This is because at the periphery of the drop, the
concentration of oxygen/air is higher as compared to the center of the drop. Thus the peripheral SA Pit
region becomes cathodic. The central region beneath the drop has lower
oxygen and hence becomes anodic. At this region, Fe is Oxidized to Fe i.e.,concentration
gets corroded
of
g corro
Fe Fe + 2e (At anode) tion of
At cathode O, is reduced to OH ions. ing
al.An anc
+ H,0+2e-. ’ OH (At cathode) zubroker
iz fomatic
Air
S in se
Rust ring Drop of salt
(iron hydroxide) solution
Rust ring
(iron hydroxide)
120, +2e + H,0 - 20H
Good access of oxygen 1/2 O, +2e + H,O’20H
Fe ’ Fet +2e
Good access of oxygen
Cathode area
(Protected)
Anode Cathode area
Iron (Poor access of oxygen) (Protected)
attacked

Fig, 8.6
Mechanism of
drop differential aeration
of salt caused by the presence Or
solution on the iron
surface.
 Corrosion and its Control 435
Fe+jons move towards the cathode
and
[hein between and form Fe(OH)}) which OH ions move towards the anode. These
The

AWaterline corrosion: You might have subsequently

observed rusting
is oxidized to rust. two
ons, alonga line just beneath the level of the water Cathode
irontank. This is called waterline stored in
ditlerential aeration. The area corrosion and is due Rust
o above the waterline is well (Anode)
aerated and acts as cathode whereas the
as anode (less OXYgenated/aerated) surface below it
and hence gets
de coroded. The reactions at the cathode and
a8 discussed in drop corrosion.
anode are same
Fig. 8.7 Waterline corrosion.
63Crevice Corrosion
contact corrosion
is the corrosion
produced at the
r
nON-metals. For example, it occurs at the crevice between region of contact of metals with
different metallic objects such as metals
washers, nuts etc. When these crevices bolts,
come in contact with the liquids, these
Lotic region because Oxygen supply to these
areas is restricted compared to exposed area become the
eComes the cathode. The corrosion occurs at
the which
This tvpe of corrosion is accelerated by the crevices.
SuDply of oxygen underneath the covereddeposition
of dirt, debris etc. These materials
portion which become anodic and hence suffers restrict
TASion. Crevice corrosion can also be attributed to
concentration cell effect.
54. Pitting Corrosion
Piting corrosion is a localized corrosion resulting in the Cathode (wellaerated)
ormation of pits or holes. Pitting usually takes place due Anode (less aerated)
scracking of the protective film on the surface of the
netal. An anode is formed where the film has broken, while
the unbroken film (or protective layer) acts as a Rust
cathode.
The formation of small anodic and large cathodic areas Fig. 8.8 Crevice Corosion
reSults in severe corrosion of the anode, region. Because of corrosion of
holes or pits are formed on the surface of the metal. smaller anodic region, small
Cathode Fe(OH), Corrosion
(More oxygenated) product
Rusthi

50,+ 2H,0+2e - 2ÕH Anode (less oxygenated)

Fe ’ Fe+ 2e
Iron bar

Fig. 8.9 Pitting Corrosion.

As shown in Fig. 8.9, at the surface of the iron bar, the more
3$ Oxygenated part is anode. The corrosion takes place at anode oxygenated portion iscathode whereas
and rust is accumulated. The rust
her screens the bottom of the pit from oxygen, thus
increasing the rate of corrosion.
.5. Intergranular Corrosion
Na molten metal is solidified, the solidificátion starts at number of randomly distributed nuclei
within the
molten mass. Each of them grow in a regular pattern or atomic array to form grains. Because
 436 Engineering Chemistry

of random distributions of the nuclei, the planes of atom in adjacehnt grains do not match
mismatched area between adjacent grains are known as grain boundaries. and these
Grain boundaries are generally more prone to corrosive attack. This may be due is the
of certain compounds at grain boundaries. The precipitated compound as well as grain centpreerscipitation
as cathode, whereas grain boundaries behave as anode. This is because, the precipitation of behave
compounds at the grain boundaries leaves the solid metal solution adjacent to them depleted in
one
certain
constituent. Thus, a potential difference is created leading to the corrosion at anodic grain
boundaries.
Alloys are generally more susceptible to intergranular corrosion. For example, stainless steel is
alloy of iron, carbon and chromium. During its welding the chromium carbide gets
the grain boundaries. Thus the chromium composition is less in the region adjacent to the gro precipitated
at
boundaries as compared to the grain center and the precipitate. The chromium depleted region become
more anodic and suffers corrosion. The corrosion proceeds along the grain boundary and contin je:
until the affected grain is completely dislodged. Thus type of corrosion cause sudden failure of the
material due to loss of cohesion between the grains. Aluminium copper alloys are also attacked bu
this type of corrosion.
Grain Boundaries
Grain Boundary
(Anode)

Grains
Precipitated
Compound
(Cathode)

Grain Centre
(anode)

Fig. 8.10 Intergranular Corrosion

8.5.6. Stress Corrosion (Stress Cracking)

The term stress corrosion takes place due to the combined effect of mechanical stresses and the
corrosive environment on a material. This type of corrosion is common in fabricated articles of some
alloys such as zinc brasses or nickel brasses. During their fabrication, these materials are subjected to
different types of uneven stresses such as rolling, drawing or insufficient annealing, In such cases, ihe
metal under stress become more anodic as compared to other areas which act as cathodes. In presence
of corrosive environment the anode areas suffer corrosion. These areas become very reacuye
chemically and may be attacked even by traces of corrosive environment, resulting in the formation
cracks.
Stress cofrosion (cracking) is usually unpredictable in nature. Even after a few years of troube
free service, a metal can suddenly crack without any warning or previous deformation.
It may be noted that stress corrosion is due to the combined effect of static tensile stresses e
sheuld be
the corrosive environment. But every type of stress cannot cause corrosion. The stress
of sufficient magnitude to produce cracking. Moreover, stress cracking takes place ordy in n
selective environment i.e., diferent environments are required for different alloys for stress orcros
amines.
traces of ammonia
For example, corrosion cracking of brass takes place only in presence of
 Corrosion and its Control 437

Cathode
Grain B Anodes (Strained part) where
corrosion takes place
oc parl-grain
ndary(aode) Aqueous solution
ertcotroSIon
Bkes
place

Grain A
Cathode
Cathode

Fig, 8.11 Stress Corrosion

o examples
of stress corrosion are:
oAsOCracking: Season cracking dueto stress corrosion is commonly observed in
rass (copper alloy)articles. Pure copper is
immune to stress cold-drawn
ents such as Zn, corrosion presence of alloying
Al, P, Sb etc., make it prone to stress
but
Atmosphere containing traces of ammonia or amines, brass show corrosion. In the presence of
oDper and zinc present in brass can form stable complex ions, intergranular cracking. Both
[Cu(NH)J* and
nammonia solution and this causes
dissolution of brass leading to formation(Zn(NH)*
of fissures.
FiSsures propagates and cause cracking in the presence of high
Caustic embrittlenent of nild steel: When mild steel is exposed to tensile stress.
alkaline solutions at high
emperatures and stresses, it causes failure of the material due to caustic
type of corrosion mainly occurs in boilers or heat transfer embrittlement. This
NaCO, (added for softening purposes) which undergoes equipment. Boiler water contains
decomposition under high pressures
Na,cO, + H,0 ’ 2NaOH + CO,
Ihealkaline water fluws into the hair cracks present at the inner surface of the
Eventually the concentration of NaOH in the cracks/crevices increases.boiler due to capillary
The boiler material
under the two different concentration of the electrolyte, higher inside the crack
and dilute
a
concentration cell sets in.
Cathode Anode
Fe Conc. NaOH || Dil. NaOH | Fe
Ton of
e ices the main body containing dil. NaOH behaves as cathode whereas the iron of the cracks
OH surrounded by conc. NaOH behaves as anode. The anodic iron is corroded by the action
forming
sodium ferroate. The sodium ferroate so formed decomposes as,
2Na,FeO, + 4H,0 6NaOH + Fe-O, t H,
IS
precipitated and NaOH is regenerated causing further corrosion.
Microbiological Corrosion
olbactogicealria, corrosion is the deterioration of materials caused directly or indirectly by mi
algae, moulds or fungi, singly or in combination. These micro-organisms can becrobes
Gr
anaerobic depending upon whether they thrive in presence or absence of oxygen.
438 Engineering Chemistry

(i) AerobicAerobic bacteria(oxygen consuming)such as sulphur bacteria, decrease the concentration

Conditions
of oxygen in the medium in contact with a metal structure. Now if the metal strucite
environment, then corrosion will
partially exposed
isAerobic bacteria canto this oxygen depleted take place
due also produce corrosion by producing a corrosive metabolite usualy
to differential aeration.
genus
an acid, either mineral
or organic. The group
their
of bacteria of the
cell to yield
thiobacil us
suiphuric acid, which ca.
can
oxidize sulphur, thiosulphate present in
ferrooxidants
corrosion.
aerobic bacteria such as ferrobacillus may directy
Some other type of
hydroxides and cause the
formation of precipitates of ferig larp
oxidize iron into iron oxide or
aents
hydroxides. Dezin
(ii) Anaerobic conditions (desulfovibrio desulfuricans) cause Kte.
A

sulphate reducing bacteria

Anaerobic bacteria such as reducing bacteria will not grow even in traceee r is
iron and steel. The sulphate no uniform
corrosion of action but
Various theories have been put forward to explain their and ferous
ncede
of oxygen. sulphide
seems to apply. The main products of the corrosion are iron is recogniz
hanic
theory to sulphate reducing bacteria)
hydroxide. Anaerobicbacterial corrosion (due corrosion product with the strong Simila
surface by a black
able on afreshly exposed metal sulphide. On cast iron, due to corrosion by anerobic bacteria kcast
rotten-egg smellof hydrogen i.e the surface layer takes the appearance of Ins zching
graphitization occurs forming iron sulphide bec
a knife.
graphite and can be easily cut with corrosion that
nfree
that cause corrosion. The
reducible chemicals
The anaerobic bacteria provide the occurred due to anerobic bacteria. 15.11.
Titanic
was found on the hull of the
8.5.8. Ero_ion Corrosion titroge
relative movement between a corrosive fluid and metal surface.l Tesence
Erosion corrosiOF 0s the result of motion of the fluid, the mechanical rubbing
of th¹ la)
turbulent
Generally due to the high velocity of the protective coating at the point of impingement. This resuis
solid metal takes place thereby removing the
differential cells at these points leading to corrosion. Metals that are soft and b)
in the development of of corrosion.
damaged due to mechanical abrasion are quite susceptible to this type corrosion. These
are readily with high velocities can cause eroSion
Many types of corrosive medium moving
and
gases may oxidize a metal
For example, hot
can be gases, aqueous solutions, liquid metals etc. around the metal. Examples S
then at high velocity blow off an protective scale
erosion corrosion.
All types of equipment exposed to moving fluids are subjected to
propellers, hydraulic turbines, pumnp impellers and diesel engine cylinder.
inçjlude, ship
f5.9. Soil Corrosion
The two factors which promote corrosion viz: moisture and dissolved electrolytes are presentinsoil,
\12.
corrosion
to
further leads structures
making it corrosive. Moreover, presence of micro-organisms in the soil
of the underground structures and pipelines for oil gas and water.
embedded in soil is due to the combined effect of the presence of
Thus soil corrosion of
the
eRaUse
(1) Acidity in the soil
(ii) Moisture and electrolytes
 Corrosion and its Control 439

D Micro-organis1ms
Diflerential.acration.
Accordingtothe types of soil the corrosion may be galvanic or micro-biological.
Bunicdpipelines passing from one type of soil to another, (say from highly porous soil to less porous
get
corroded due to differential aeration.
Merabvologicalcoorrosion of the buried structures may take place in
sol)
soils which give
ironment in which bacteria can grow. water-logged
8510 Selective LeachinglCorrosion
leachingis the removal of one element from a solid alloy by corrosion process.
ie,removal of zinc from zinc copper alloy (brass) is a common example of this type Dezincification
of corrosion.
Similar processes occur in other alloy systems in which aluminium, iron, cobalt, chromium and other
elements are removed from their alloys.
Demncification is prevalent in condenser tubes made of brass, where sea water is used as condenser
A
lthough both zinc and copper go into the solution but only zinc ions remain in solution and
aDper is redposited as aspongy layer. This is because zinc is quite reactive whereas copper is nobler.
ane dezincification proceeds continuously. The dezincification results into a porous metal with poor
mechanical properties.
Similarly, gray cast iron and also shows the effects of selective leaching in mild environments.
The castiron appears to become graphitized. Actually,graphite is present in the gray iron. After selective
eaching of the iron, graphite network is left behind. Graphitization does not occur in malleable cast
ions because graphite network is not present to hold together the residue. Similarly white iron has
no free carbon and is not subjected to graphitization.
85.11. Hydrogen Damage
Hydrogen damage is a general termwhich refers to mechanical damage of a metal caused bythe
presence of or interaction with hydrogen. Hydrogen damage can be classified into the following types:
(a) Hydrogen blistering: It is caused by penetration of hydrogen into metal. Surface bulges appear
on the surface of the metal due to hydrogen blistering.
(b) Hydrogen embrittlement: Hydrogen embrittlement is also caused by penetration of hydrogen
into a metal leading to loss of ductility and tensile strength.
(C) Decarburization: Moist hydrogen at high temperatures may cause removal of carbon from
Steel. This is called decarburization. It lowers the tensile strength of steel.
(0) Hydrogen attack: It refers to the interaction between hydrogen and a
component of an alloy
at high temperature. For example the oxygen-containing copper gets disintegrated in
of hydrogen. presence
B.5.12. Stray Current
onducting structures. TheCorrosion:
tbecause Electric current from electric system can leak into adjacent
metal structure such as water pipes, gas pipes etc. thus get corroded
these become anodic due to leakage from the clectric circuits.
B8 PASSIVITY,
In an
Teducionelectrochemical
electrode poteseries,
ntials. Ametal high in the series is more anodic and undergoes corrosion faster
metals are arranged from top to bottom in increasing order of their
 440 Engineering Chemistry
than Fe whiek
example, Zn
laster
corrodes placed higl) above followed inturn corTOdes
metal belowiDFor
clcctrochemicalseries, Zn is by w Fe,
the because
thanHowever,there are
innumber of excepions.For example, Tiis placed above Ag in electtodhe
Sn. Thisis
followed by Sn. isiust the reverse i.e., Ti
Ag. But it
is
corrodefaster than passivity of the metals(A
by
series,andis
eypected
passein a certain
than
to
envionmCntiH
Ag. Thiscan
explained ix
exhibits much lowe corrosion rate than what Is expecled
only be metal sad
lesscr extent
clecmchemicalseries. metal can be rendered
Xston in the cnvironmental a passive active.
s
However, on
changing the
the formation of a highly protective,
film so
but very thin
metalis dueto conditions. The formed- at the
Passivity ofthe particular environmentl
under
ofthe metalalloy, act like a noble metal/ titaniumandla wide
surface makey
nickel, variety of le,
metal or the chromium, aluminium, resistance
in stainles T
For
alloys
example. metals like exhibit outstanding corrosion
and alloyschromium,
metalscontaining

other metals such as

oxidizingénvironmnts.
form insoluble oxide films on their surface in presence of 0xygen and hener'
zinc, cadmium, tin, uranium and thorium
rendered passive. (Some passivity effects under limited conditions.) have :
beenOnobserved exhibit
changingtothe environment i.e., in reducing envionment, all these metals beçome chemica.
active and undergo rapid corrosion. Fig. 8.12 illustrates the effect of passivity on corrosion of amoz
noe.
shows the behaviour of the normal metal i.e. metal which do not show
Fig. 8.12(a)
an air-free acid solution.
For example, metal immersed in
solution
solution
(Electrode
Potential) (Electrode
Potential) Transpassive
of
of
power
power
Passive

Oxidiring Oxidizing --

Active

Corrosion rate Corrosion rate

(a) Corrosion rate of the normal
metal (b) Corrosion rate of an active-passive
Fig. 8.12
Fig. 8.12 (b) illustrates the typical Initiall,t:
metals shows corrosion rate similar to behaviour
normal ofmetal.
a metal
But which
once the passive
protective effect.
oxide filmisfom:
exhibits paswi:
it is rendered passive the
and corrosion rate shows a of
region. Further increase in sudden decrease. This is the beginning rale of
t

material. However, at very oxidizing power produce little, if any. change in corrosion rtl
incres
again
This region is termed as high concentrations of the oxidizers, the corrosion rate
transpassive region. passiviy Fh

an
Significance: Usually 10 to 10 times reduction in on
conn

engineering standpoint, the metals most corrosion rate isof observed the
ofilesemet
engineering and structural materials, including susceptible
iron,
to this kind behaviour are
chromium and alloys
nickel, silicon,
 been
has
resistance.
used successfully
Passive to
oxide filmsdevelareop new
Corrosion and its Control 44A1
or alkaline
medi
a um in
methods of
artificofialstrong
y producedpreonventcertingaincorrosion and to
thin presence
on,
HNO, ALproduce
: to corroSION can
also prbeotemade
resist corrosion. For
ctive OXide film, thoxierebydizing agents. Formetals and alloyspredibyct
such as Cr, Ni andexample, ironpassi ve by alloying maki ng it example, the
is with passi ve. Met als action
attacked by dilute
behavesas a noble metal.
Mo.
HNO, but in conc. rendered one or more
passiv when alloyed withmetals which which
HNO,, it any of the
GALVANIC SERIES forms avery thin
dscussedinthe previous
protective passive
section that
ANTOSionoffthe metals. The electrochemical
faster than the metal metal lying at the top of series can provide the
below it in the series is more basis for
atveoxide film at the
surface some metals
of electrochemicalseries. However, dueanodic and predicting
predictedIby the
electrochemical series. Hence(passia vity), these metals to the undergoesof
VOUIin different
environments is the more reliable behave formatopposi
exactly ion te
the corrosion behaviour of metals andGalvanic Series'. This seriesseries for predicting
Mter is given in table: alloys in different gives the reliable corrosion
environments. The galvanicinformat ion
series for
Table 8.1 Galvanic
Series in Sa
Water
ANODICMOST ACTIVE
Magnesium
Zinc
Aluminium
Cadmium
Duralumin
Steel
Lead Tin Solder
Lead
Tin
Copper and copper alloys
Cupro-nickel
Bronze
Nickel (passive)
Passive stainless steel
Silver
Titanium
Graphite
Gold
CATHODE OR NOBLE METALS Platinum

FACTORS INFLUENCING CORROSION,

On depenÒS
pon number of facters which inctude nture of the metal and (ii) environmental
442 Engineering Chemistry

of the Metal corrosionrate.

Nature metal affect depends upon the
in elcctrical contact in presenceposition
8.8.1 of corrosion
propcrtics
galvanic series. Whentwo netals areof
Extent of an electkpe
numberof Series:
A Galvanic anodic and suffers corrosion.
Positionin becomes faster
Tw
metal higher up in
galvanicseries electrochemical
ditlerenceintheir
positionsinthe
series, is the

increases with the extent of

Morexve,
corrOsiono
the
accelerate
metal.

(b) Purity
the
ofthe
corrosion
metal:
due to
The rate of
corrosion
the

them. The
formation
anodic
impurit es. Amp
of minute/tiny electrochemical cells tesas
part gets
corroded
corrode in very pure
'heterogeneity' caused by
For example, verypure
containing
andsmooth
impurities of Pb
zinc will not
or Fe corrodes rapidly. The
aluminumby
hydrochloric acid
figures hydrocbelhloorwic st it
zinc metal
impurities on corrosion of
effectof 99.998 99.97 99.2
% Aluminium
1
1000 30,000
Relative Corrosion rate

usually weak. Therefore, pure metals 8.8

and they are es
are expensive cost are main
However pure metals
engineering applications
where strength and considerations
be usedin The physical state of the metal such as orientation
of ge
of the metal: highly influence the rate of
T) Physical state loOcalized stresses, scratches etc.,
the when
coosion
structures, rapidly than grain faces exposed
grain
grain boundaries are attacked more alloy, greater will be its sol
example grain-size of the metal or
corosive. Similarly, smaller the and hence, greater will be its
corrosion
macroscopic crystal
as compared to the case of pure metals tend
to be anodic and imie
even in
Further the areas under stress,
corrosion.
in aerated atmosphere, almost l
It was discussed earlier that
d) Nature of the oxide film: film.
oxide
metals get covered with an
metal oxide film formed is lesser than the volume of the zi
" If the specific volume of the todifise
porosity will easily allow oxygen
atom, then the film will be porous. This alkaline earth metals sudch as Be,
the metal and cause further corrosion. For example metals from which
the
smaller volumes than the
Ca etc., form oxides which have
formed and hence are easily corroded even at low temperatures. is
thar
less
film formed
" On the other hand if the specific volume of the metal Oxide todiffuseinto
of the metal from which it is formed, it will not allow the oxygen Corrosion.Fore
this type of oxide film protect the metal from further oxidation or thanthemeta
more
Al and heavy metals form the films whose specific volume is aluge
and hence this film protects the metal from further corrosion. Specitic

The ratio of the volume of the metal oxide to the metal is known as
If, cornSiOn
Specific volume ratio > 1, the metal will be protected from
vSpecific volume ratio < 1, the metal will corrode further.
 Area Effect: Another important factor in corrosion is the area effect i.e., relative areas of
(d)anode and cathode. If the area of cathode is large as compared to anode then the corrosion
ofthe anodeisrapid and severe. This is because, when the cathodic arca is large, it will demand
Imoreelectrons, which can only be met by brisk and rapid corrosion of anodic area, may be
100or1000 times greater than if the anodic and cathodic areas were equal in size. For example,
in copper plates (cathode) with steel (anode) rivets, the steel rivets are compietely corroded
because the smaller steel rivets are coupled to large copper cathodic area.
(e) Solubility of the products of corrosion: If the corrosion product is soluble in the corroding
medium then corrosion proceeds at a faster rate. Whereas insoluble corrosion product
suppressesthe corrosion as it functions as physical barrier. Further, if the product formed
interacts with the medium to form insoluble product then also corrosion is suppressed. For
Cxample the corrosion of Pb in H,SO, proceeds at power much lower rate because of the
fornation of insoluble PbSO,.
(0 yolatility of corrosion product: The volatility of the corTOsion product has a marked
Significance on corrosion rate. It the corrosion product is volatile, it leaves the surface of the
metal as soon as it is forned. Hence it leaves the underlying fresh metal surface exposed to
further attack. This results into excessive corrosion. One of the volatile corrosion product MoO,
is formed by the oxidation corrosion of molybdenum.
RR2, Environmental Factors
e andaggressiveness of the environment determine to a
ent the degree of corrosion. Some of the common
neht variables are: Corrosion
rate

(_Temperature: Temperature increases the rate of almost all

chemical reactions. Therefore rate of corrosion also in
reases with increase in temperature.
t higher temperatures even the passive metal can become
ctive and get corroded. In high pressure boilers intergranular
corrÓsion takes place only at high temperatures.
(b fumidity: One of the important environment variable in
corrosion is relative humidity. Corrosion increases with the Temperature
increase in humidity of the atmosphere. The efects of Fig. 8.13 Effect of
temperature on corosion.
humidity on corrosion of enameled steel is apparent in the
following table.
Relative Humidity 0- 65 65 -80 80 - 90 100

Corrosion No corrosion Thin corrosion Wide corrosion Blisters due to

(Appearance) filaments filaments corrosion

Though presence of moisture increases the corrosion rate, but it should be emphasized that
metal does not rust if covered with ice. This is due to the fact that electrochemical attack
(corrosion) requires water in the form of liquid.
The relative humidity above which the atmospheric corosion rate of metal increases sharply
is known as critical humidity. The increase in corrosion rate due to increase in relative humidity
is due to the following reasons:
 (e)
Engineering
Chemistry
44
(g) (dy
oxidizers the andEfectstructuresfastercompared
() corrosion.Nature reducedat in pH
(cPresence
corrosion
corrosion.
Conductance of alkalinities. However, Effect " by
" corrosion. " pH weakly less smoke "
heading
oxidizers the Chloride increaseliquid The corrosion
process.
the the surface
corrosionof Iron Many such h
corrosion of by 11. than Lower
pH: of Some NaCl Solids in
enhanceFurther, Moisture
an Oxygen corroding rate setting
buried toDry undergoes metals anoSas theincreasing Onamphoteric metals
For
like acidic
7 adjacent
presence
theto and
dust impurities or of
passivity'. have
orrOS0On like
(NH, gases cossosion.partially,
clay ofcracking silicon ions increasing are in of the the
compared under sandy Suen ions example, solutions corrosion
more particles NaCl upacts
or the
been and mineralized medium and
gel as
present
present: of
)SO,
lik e corrosion. met al the as
corroding rapid th e the is H,S, leading
etc
Fig, mineralized soils
rate.Oxidizers:
discussed
alloys
of which Sllicates the zinc
corrosive
H,S, in dissolve electrochemical OXIde solvent
a
to have plays corrosion steel in pH, such rate.
greaterpH, is metal containing if
8.14 dry can the alkalinity
The suffers
but
H,SO4 present atmosphere:SO,, Moreover,
to film
soils. inhibits as for
llustrates inThesandy medium:
or lower an freguently
is
undergo in medium
nature only carbonic AIPb
, than surface
sodium
enhanced in
some clayHenceimportant in th e
further,corrosion alkaline
HCI charcoalabsorb moisture
whicpossesses
h
water rain oXYgen
effectsoils.conductance the the
medium up etc.,go the and near corrosion
details
the soils Conductance
the presence corrosion
corrosion
destroys
the
of to acid.
corrosion. hence the moisture
Atmospheric and corrosion. and water the CO,
of reported a or are
effect oxygen undergo metallic role certain
goes in neutral
into ot h er increase cell
under lead 1ons acidic increaseindustrial capable propertymay etc.,
the
of as in of in th e chlorides
topassive ofinto and
Fig. NH; inthe the value.solution media.This its also present
cyanide th e the medium ofactas
strong of
8.14
Corrosion rate presenceformation implies its areas
adsorbing conductivity absorbing wash
salts. electrolytes in
film solution It Zincconductivity. increases in
n
fect suffers and as
increase away th e
containing and isthat
marine
of complex atrmosphere
Oxiofdiadded
zer cyanide ofexpose minimum
corrosion
as easily
acidic SO,
electrolytes. and oxide
zers insolukle greatly
complex the atmosphere. if
This and air hence
soltions. ions corroded meia acidity
ions. the rate results So is ad
or met a l afect corosion
io ns. at having enhang polue ncI
0)5 nrol higher he
Stres intg of
to h
VariousIMethods
2.methods ne damage. be beThe 89
Corrosiondrastically ik) pEli) ect
ctionby/fmethods
These
Cathodic 1.
Use
6 3, selection.
Modifying
Use
Material
4. 3.
Protection
1. considerably process
CORROSlON
PROTECTION
AGAINST Oxygen
" " "already Formation
aerat ion corrosi
agentvpreos.duct. nitricby of
dirt
characteristicis 3due
environment Howevervela,p oliHicicgahttyions.traighItncreaseto
The metals
the graph
f Modification creviceburied metal
For engineering
of of for changed of
Velocityof when
Velocity:
g
protective
inhibitors. Controlling reduced.
corrosion
pipe-lines
corrosion
washers
cannot been by
of Increasing
velocity acidaofwhich in
chromium
they can formation
protection or the by the
autocatalytically,
reducing thus
For But velocity
,
Oxygen formation because be
discussed. would may if
are of proper whichby mainly if diffuse formation metalstheof exidivided
st into
environment.
the where can th e of
igning
Proper discussedcoatings. The there is velocity cause alsostainless
generally
slow passing
and
readily decrease steam oxide in
properties designing. Corrosion deals main were Concentration
The reduce active
waterline 0Xygenconcentration of corrosion.
corrosion. film :
Electrochemical corrosioncanbe but
sweeps
velocity steel of
below responsibilityin nothe from corrosionisdue the result the such state. three
sections.
applyingcorrosion. surface which
metthaelof
. losses predominant
cannot
one corrosion environment
valves
is
in corrosion.
type Cell:
away Increasing velocitymay increased,increased in as When is
detail. diffuse example, protection protective
copper
scientific incurred the and oxidizer
protection. controlled
preventedand But
(CORROSION
ofCONTROL) ofdifferential
aeration to cells. The the attack
a
while soil in: plugs plays in Section
rate nitrous corrosion
of corrosion
principles are to The under thereby
in corrosion acid in is
he the
enormous. of some give an nature,added, 1
another corrosion corrosion acidstagnant of important solution is
nt corrosion
engineer nitrous acid cases increases
increasing excellent represented
attack.
the
Corroslon
to and also some
behavior
prevent In by
increases by which
conditions,
thus preventing sweep leadingservice For role metals
lays is
is fact differentialor
the and
are: inevitable, at removes as in doexhibited
by
a or to our the awaycorrosion. example, to erosion section
ant corrosion.
controleconomy
control due reaction cathode steel 'w ire in not achieve
2. Its
surfaces to the the Control
aeration most passivate.
its differential one is drawing." hardened
deposition corrosion. passivity by
corrosion cost corrosive
attacked Section normal
role. would where of steam 446
can has the
Some
 Engineering
Chemistry
446
(iv) (üi)
(i) ()
eaned.and
Storage water
retention As words completely.
sarme The rivets keepon if thnobler
be e thancorrosion.
is small
Example throughshouldlargeand As Thein as causilnogcal are The
corrosion.
r rate Example insulator far
moisture usedpresence steel
cathodic fainsulatórs
ntainers is
drained of
welding metal,
instead furnishingrivets :Copper areastherefore as contact
Design
Poor them. apart
two ifof Plastic should in
:
moisture Fig.
is DesignPoor should of reaction is (cathodes), possible,
cathode corrosion
the 8.15 is of
crevices
are steel Thus and betwthe een
should completely. better
riveted used be be
rivets madeshould prevent
place
takes
water main
Collectionof should Different
Rivet
Bolt or
be electrons and the washers galused.vanic
joiningavoided. for hence are a
also different
beFig. factor limitedand Screws If
or
between limited fromdissimilar
be
depends thseries.
is
igned 8.16 be
For techniques bolted joining
to used corrosion. are
as acts avoided.
nuts a
Water governing
that, low technique The the to
as cathodic
more preferred notismetals
jointsadjacent large copper
in anodic
cathode.
fasten and metalsupon followedWhere and
stagnation
such
sharp as of welded noble(refer
possible. joining otherwise cathodicsheet,the bolts the over it
corrosion, than steelreaction are alloys
a corners Welding parts reaction material relative to cannot
way Design
Good the mechanical
butt Due
sheets will section metal then
Properties joints of e contact, the should
be
that to1 occurs act
metals/alloys Design
Good crevice
structure,
copper small materials than
the sizes washers
should the
th
of and e avoided
hey drained
Water is
as 8.9) more
automatically of steelsmall not cathodes the of not
design corrosion the
fastners. sheetareas leading Screws, active
can should
be combination thebecause delete be
same even proceeds area vice
be avoided. thereby of anode made,
should versa metal
be the of and
to bolts, an
tely so
designed be
may
metal/alloy
result. corroding
the
in
slowly.
rivet
thedecreased
because
rate fjoine,
becausethe which
of are
nuts of
cahodetheand
plastic efficient
especialy
will
heif

casete
of copper small getCoTrodet
WasierS
such .In anode and
draine thu th° olha shouk
Wherea
ste wi iER
coppa
welanode
d
electh

2.
Selection
Material (ix) L.2
Selection (vi) (v)
nowever
eterogeneity,
(a) may Sing current site
Insulation Thegiving
velocity)
The
uld Pure
eY
be
Pure the
of Desing
Poor
corrosion.)
from
equipment
rise
reasing
Alowing anodic e Sharp
ac umulatcorners
usually are improved
metals it which ofPipelines
to pipe
not is right the fluids parts Design
Sharp
Bends Poor leading
not Metal:
which corrosion
uild are should
materials
the diameters and
type
should and should
circulationNo
always by to
xpensive leakage recesses
weaka increasing lead As of
airof Accumulated
dust the
ge beensuring
by
is
tomaterial should behelps be
and fruitful
corrosion.
supported
takes differential iree readily corTOSion
of discussed should
ure notdo
8.17
Fig.
toits is
8.Fig.18
place
be laminar from
trom
purity.
use proper on replaceable bybe
one mechanical
on.posses Thus, in obstruction
aeration.
a becomes stands differential
avoided
metal section the of
Desing
Better
otherwise flow
the
equiredthe to (refer or
corrosion
of
8.8,
main anodic allow standpoint, or should Smooth Design
Better
Bends because
aeration.
high insulation
Plastic
leakage crevices, to
factors
circulation
and section be Corosion
purity impurities
because: circulation
Stand Freeair
dust
trength.For resistance of made
for leads
current in by
which 8.9 thicker
decreasing or
corrosion to of and
in for solid
of corrosiontakes air.
water the ts
xampl, a a for particies
givenmetal Control
control. place. velocity
effects longer
may
metalcause (stray
one The stay life. may 447
of of
448 Englineering Chemlstry Corroslon and te Control 449
Thuscorrosioncan be controlled by
(ii) Using metal alloys: Corrosion resistance of most commercial metals can be slowing down the diffusion of H
suitable aloying elements. (Alloys are
Misiono fH"ionsis
Ronsiderably reduced
substituted ureas and
by organic
inhibitors such as ions to the cathode. The
by alloyingthem with
metals or elements.) There
are two kinds of
alloys: mixtures of two Ata
soaps,
surtacesand thus restrict the
thioureas. These substances are capableamines,
diffusion of H mercaptans, heavy
of being
formation of ions, Antimony or arsenic oxidesadsorbed
of at the
are solid solutions in
which the petal inhibitors because the
(a) Homogeneous alloys e.g., stainless steel. components are athdic

neutral solutions,the cathodic reaction is adherent film on the surface of are

the metal.
used as
soluble in one another
(b) Hetcrogenous alloys
are the mixtures of two
or
more separate
soluble and compe n

H,0 + 2 2+ 2e
sepaprhaatsees. phaTes
are not completely
components of such alloys exist as 20H
The choice between the two types depends on tne neoiaa properties desired corrosion
can be
environiment, the
alloys are more corrosion resistant than
more
alloys with two or phases
because no galva O shisinedium
or by not conducting the controlled by either
removing the oxygen from the
can take place in former case.
developed depending upon the
vanic couçl t oroding
removal
electrons.
of oxygen is achieved by adding reducing
agents such as sodium sulphite or by
Several corrosion-resistant alloys have been
desired
a) Chromium is used as alloying metal for iron and steel as TT produces an exceptionat
the steel from further attack. properOer.80,
The

tie, and MgSO, can added which react with OH ions

eration.
also be
de-
oxide film which protects
Fe) is highly resistant to the pecjpitated
on the cathode surface. The important cathodic inhibitor isand the respective hydroxides
(b) Silicon iron alloy called (15% Si and 85% Ca(HC0,), which is found
the formation of silicon oxide film on its
surface. acids because f water.

(c) Cupro-nickel alloys (70% Cu +30% Ni) containing 0.2% Fe are used for HCOj +OH. ’ H,0+coB
and for bubble trays used in fractionating columns. condenset tuts Comparedto anodic inhibitors cathodic inhibitors are quite
concentrations less
safe. This is because, even if they are
than required for complete protection, the
3. Use of Inhibitors ISedin partially covered cathodic sites
Corrosion inhibitors are the substances which when added in small decrease the surface of
the cathode whereas anodic area remains practically the same. Thus corrosion
monte decre2se the corrosion rate. Inh1bitors are quantities
to the
orgame as wel as inorganic corToSiebreases due to area effect.

that dissolve in the corroding medium.
Inhibitors are generally classified on the basis of electrode at which their action is Dredeni
Thus we have two types of inhibitors, Cathodic inhibitors and Anodic inhibitors
(i) Anodic Inhibitors: The anodic reaction takes place when the ions from the anodic mebl
pass into the solution. (For example, Fe ’ Fe + 2e ). The anodic inhibitors are te
compounds which react with these metal ions to produce insoluble compounds. Th
insoluble compound gets adsorbed on the metal surface forming a film or a protecie
barrier thereby reducing the corrosion rate.
The examples of anodic inhibitors include molybdates, phosphates and chromatesof alkali
and transition elements. Substances like Na,CrO,, NaNO, act as anodic inhibitors eite
by forming less soluble compounds with the anodic metal ions (as discussed above) r
they may also retard the corrosion by oxidative repair of the oxide film.
The organic compounds can also acts as anodic inhibitors and example include soou
benzoate.
Limilations of anodic inhibitors: Anodic inbibitors are not considered satisfactory
to the following
reasons:
(a) The inhibitors can prevent corrosion only above acertain critical concentrationa
solution.
(b) If insufficient concentration is used then the film so formed may not coveralltie
anodic area and corrosion of small areas left corrosions
suffer intense
exposed
cause severe pitting, (due to small anodic area and large cathodic area)
(i) Cathodic
Inhibitors: The catholic reaction in acidic medium is
2H* + 2e
representeu
’ H,
substancsDo0g Inhibitors: These are the inhibitors which readily vapourize and forma
protective
laver of inhibitor on the metal surface. Vapour phase inhibitors (VPI) are used to prevent
corTosion in enclosed spaces and also during storage, packing, shipping etc. Small metals are
Drotected from corrosion by keeping them inthe envelopes made from paper impregnated with
asuitable vapour phase inhibitor.
Dicyclohexylammonium nitrile and cyclohexyl amine carbonate are amongst the most widely
used VPls.
4 Çáthodic Protection or Electrochemical Protection
For the structures immersed in soils or electrically-conducting liquids, the cathodic protection
1s the best way to control corrosion. Cathodic protection is to force the metal to be protected
to behave like a cathode as a result of which it is not corroded.
Cathodic protection can be achieved in two ways:
) Ey using galvanic or sacrificial anode (Galvanic Protection).
(W) By using impressed current.
Gavanic Protection: In galvanic protection or sacrificial anodic protection, the metal
anodic
sudeture to be protected is made the cathode by connecting it by a wire to a more
the metal structure
aterial. As a result. the corrosion takes place at anodic material and
The more active metal used for the purpose is known as
saved from corrosion.
a fresh one when it gets corroded
rycial anode. The sacrificial anode is replaced bymetals used for sacrificial anodic
Consumed from time to time. Most commonly
protection are Mg, Zn, Al and their alloys.
 Engineering
Chemistry
460
Protectlon
Anodlc 5. This ME2eMgls)
reactson)
(Anode
(b) (a) The
ted.films.
10
beAnodic kind (ü)
WatBuried
erimpressed as is to
of anode teminal
(insoluble
In technique pipes, obtained a be scrap hodic (c) (b) (3) The
catImpressed (Anode)
Mg
protection
anodic result
pipelines, protected is iron MagnesiProtection um Protectionapplication
current it buriedanode) protection,
ofDC
otection,
This
is iswater act over or Current Fig,
applicable Fig particularly transmission (Fig, source.
platinum.
in
Soil
is tanks, cathodic asthe in rods ofcatof
of 8.19
done cathodeentire the the the neburied hodic Galvanic Connccting
TheCathodic amari
8.20 8.20) soil
a re
otective
by toImpressed marine opposite The obje ct
useful
+
protection and metalThese or positive inserted
ical the line objective to structures, pipelines,
protectionProtection
for piers is the
in Protection: be
oxidemetals towers.protected. surface. aredirection terminal
Current large
has conducting
protected into
filmwhich
etc. placed is domestic underground
ship include: using
Cathodic structures been The to to is This
means iscan The in thatconnected
apply is hulls Buried
grown electrons such mademethod, water Sacrificial
i.e., beProtection appliedanode medium o the etc.
passivated piIronpe which a the cathode boilers
cables. iron
on to tanks or pipe
bythe tohas Tlmanner
ow corrosioncurrent from known
ying require adjacent insoluble aja Anode (Cathode)
surface protect. to to byas (Cathodic
rescikm)
by bethe that
long to connectingi
ofthe replaced metal acurrent. electrolytic
Current deposthe ition term the
uniform externYal anode
an prevent
r°ditg to

inametal metal The ike

applicaties periodistructure
cl potertia t
gai,
drect stuctue oftoxik so

(0)
Spraying:(4)
Tpping: S e are Metal Metallic
Coatings
) a
of metaie
coait
n sg
o slat
PoeLCoa
ectivtiengs mathatkes
psected. Mietal
Ovenient
cdl Sandwitched
NICKelaction
, bonded
coatMetapplainl igscied with l
metal CoataMere tianl igsc . coatings
Anod
rememberedbe
i
rcas ivated whe n the
nd with and
the It of
Cladding: migrate or
the containing them
Flectroplating: capabl
Zn
or
and e
|
usedstructure protection mettheal
s A method. copper,
the heatfirmly coating
This rollers. between silver Als) from prevents
Cr. insulatethe
stream thickness tectniquescan be forming of aref:or to has
tc. type
alloy to platingIn theto the corrosion. controlling be
lead, and metal that been
ofCoatofing of or
The the two metal corrosion. The protectei
ate
pressure. base cathode ions ABiaqyte This applied
potertal
'atomized'
coating met a l metal silver to their from
of
the
met al cladding ofa Electropiating
layers be of8.Fi2g1.
Ag
The is
metals
zicoat
nc ing to toetc.) The and the
spoondeposited. the by respective
For corosion the can in
can be be bytheofthe metal metal most using used surroundingcAed be has
on Al loys get example, c
droplbeets coat e d
is used cladding pressing deposited to - Non-meallic fo
Ceting(i)r to
iron sted
applied isadjuby protecting alloy When be
to
widelyfollowing
be coatíngs
oxide te
steel,
of
ishas can deposited. plated to mezlk
wih aouZey
the to
bltoown this passed by low mat alsoeria!
wholemetal. be current in used prevent films
are
oroAve tanless
the
squeezi
the process
on nthgrough melting be protected, form The Agae+ ABs
is
mademethod the whúch h
finished theto used usednationThese
combi anode Ni, erismet
martzined
Seel
isout poiant asare
passcd,
of the of rusting
athere Sa, 00-ek
th in zluninsun
ng on layers(knOWn layer. theeitheris
structuressurfacecalled the bath ofclthaenddicorrosi
cathodecoating
of to Ci
znd so
iron
galvanithezofng,excess dithepping through of as coating Fig an metals
in t
tansurfxe Cr
he The
cings
ta
such noloften materiresials stantprotecting
rollers
base inert plating
a becasz vios cicjs
1 ad
metal the is
8.16 metal o be
as
coatincoat
g ing a meta material protect cozed of typesThese
tanks, to very (such under Des! shows ions bath ttese
the
be is
2 Engineering Chemistry

coatings may be inorganic or organiccoatines

The non-metallic
(i)Non-Metallic C'oatings:
following categories. cor:
provide corrosion
which provide
fall under the organic barriers
Coatings: Organic coatings are inert coated. The organic coatings
(a) Organic
decorative the structure which is
value to
resistance as well as
enamels, and lacquers.
include: paints, varnishes, inorganic surface-barriers produced by cheminl
Coatings: These are
(b) ChemicalConversionreactions at the surface of the metal. These coatings provide the
or clectrochemical corrosion and also provide a surface ideal for paintine
protection to the base metal from of chemical coatings include, phosphate coating
measures. Examples
or other decorative
phosphate coating is produced by the chemical reaction of base
chromate coating etc. The and zinc or manganese phosphate. Such
aqueous solution of phosphoric acid
metal with
applied to iron, steel and zinc. The chemical reaction between the phosphating 48Ditte
coatingsare a surface film consistng of crystalline
solution and the base metal results in the formation of
zinc-iron or manganese-iron phosphates.

ASHOKAPILLAR
280 B.C, and is known by his name
This pillar was built by samrat Ashoka who ruled around the testimony of the
A6,8.
Ashoka Pillar. It is situated near Qutab Minar in Delhi. This pillar is
advanced metallurgical technology ancíent India possesed.
The pillar ís solid shaft of iron, sixteen inches in diameter and 23 feet high. What is most astounding
about it is that it has never rusted even though it has been exposed to wind and electrolysis! The onn
technique used to cast such a gigantic, solid pillar is also a mystery, as it would be difficult to
construct another of this size even today. With today's advances only four foundries in the worid 8
could make this piece and none were able to keep it rust free.
The pillar stands as mute testimony to the highly advanced scientific knowledge that was known
in ancient India. The pillar is said to be 1600 years old.
Aprotective layer of misawite'a compound made upof iron, oxygen and hydrogen on the steel the
pillar, which is said to contain phosphorus- is claimed as the reason for the non-corrosive existence.

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