Preamble

Metals

made by smelting (reduction of ore or

mineral).
Mineral is more stable than metal.
Metals in air want to return to their oxidized state.
Corrosion is a natural process!!

Corrosion cycle of steel

Definition
Corrosion

is defined as
degradation or destruction of
metal or an alloy because of
chemical or electrochemical
reaction with the surrounding
environment or medium.
Rusting is the corrosion related
to iron and iron-based alloys.
Non-ferrous metals corrode but
do not rust.

Four requirements of
corrosion
Anode

Cathode
Current

flow
Electronic path

Cell

Reasons for corrosion

studies
Economic

(due to material

losses).
Safety (to prevent catastrophic
consequences resulting from
operation failure of equipment).
Conservation (to conserve
metal resources, which are
limited).

Responsibility for corrosion

failure

Bhopal disaster (1984)

4,000 dead
500,000 affected

(Methyle iso cyanate)

Accident description
As part of routine procedures, the pipes leading from the MIC
distillation column to the storage tanks were regularly flushed with
pressurized water. MIC and any associated products can be quite
corrosive and could form corrosion deposits in the pipe. These
deposits would contaminate the MIC in the tanks and could
initiate unwanted reactions. During cleaning, valves in the product
lines were to be closed and a blank or slipblind placed in the
product line leading to the storage tank to prevent contamination.
However the valves, although closed, were not sealing properly
because of corrosion and the maintenance crew forgot about the
blank. It appears that about 1000 kg of water plus metal debris
entered into the tank and initiated an exothermic reaction.

Safety features of MIC

tank
Operative:
Usual practice: Tank should be filled upto 50%.
Prime protection: External jacketed cooling
system (0C).
Safety valve.
Located under ground.

Inoperative:
Refrigeration system was turned off 6 months
ago due to economic crisis of the company.
Valves were defective due to lack of
maintenance.
Tank filled with more than 50%.

MIC tank

Economic factors
Direct

loss

Replacing

corroded
structure and
equipment
Adding corrosion
inhibitors
Cost for
corrosionresistant metals

Indirect

loss

Shutdown
Loss

of product
Contamination of
product
Loss of efficiency
Overdesign

Some examples
rusted

chilled water
piping penetration at
deck, due to water
wicking under
insulation that is flush
to deck

rusted

steam piping
under insulation at
a fuel oil heater

Some examples (contd)

steel

deck support
brackets for topside
vertical ladder
(Naval ship)

topside

rusted steel
electrical conduit clamps

Some examples (contd)

pipe

hanger (Naval

ship)

floodlight

positioning bracket
(Naval ship)

Examples (contd)

14

Examples (contd)
Bicycle

Al - 1.66 volt
Cr - 0.74 volt

rim

Aluminum rim
Chromium plated brass
spoke
15

Some examples (contd)

Railing of a bridge (Karatsu, Saga, Japan 6 May 2014)

Some examples (contd)

Cast

iron pump
impeller

Household examples (conted)

Mail

box corrosion

Plumbing

fixtures
corrosion

Pemex Refinery explosion

Mexico (19 Sept 2012)
State-owned

petroleum company
Process crude oil to produce petrol,
diesel, kerosene etc.
Explosion occurred
26 died, 40+ injured
Financial loss: $300 million $1000
million
19

Guadalajara Sewer Explosion

Mexico (1992)
Gasoline

pipeline (Steel) was

underneath the water pipeline (Zn
coated iron)
Corrosion occurred in both
pipelines
Gasoline came out and entered in
a nearby sewer line
252 died; 500 injured; 15000
homeless
20

Consequences of corrosion
Waste

of metals

25% of annual world production of iron is

wasted due to corrosion
Decrease
Failure

in efficiency of machineries

of machineries

Leakage

in the process

Health & fire hazard

Causes

contamination
21

Who will study corrosion???

Distribution of disciplines
Chemical
Engineering
Civil engineering
None
Business

Chemistry
Electrical
engineering
Materials
engineering
Physics

Expectation from you

Ensuring

maximum life of new

equipment through corrosion
protection.

Preservation

of existing

equipment.
Improving
Prevention
Reducing

the quality of product.

of spillage or leakage.

hazards to life and

Theories of corrosion
Chemical

or Dry corrosion

Electrochemical

corrosion

corrosion or Wet

Chemical or Dry corrosion

Simplest

case of corrosion.

Corrosion

takes place due to direct

chemical attack.

Oxygen,

halogens, hydrogen
sulphide, nitrogen etc.

Corrosion

product may be
insoluble, soluble or liquid product.

Classification
Oxidatio Takes place by
n
direct action of O2
corrosio
Absence of moisture
n

Chemical or
Dry corrosion

Corrosio
n by
other
gases

Liquid
metal
corrosio
n

CO2, SO2, Cl2,

H2S, F2
Extent of
corrosion varies

Flowing liq at
high temp.

Electrochemical or Wet corrosion

There

must be an anode & a

cathode.

There

must be an electrical potential

difference between the electrode.

There

must be a metallic path

electrically connected with both
electrodes.

There

must be an electrically
conductive medium.

Difference
Chemical corrosion
Electrochemical corr.
1. Takes place in dry condition. 1. Takes place in presence on
2. Takes place by direct
wet condition.
chemical attack.
2. Takes place through the
3. Can take place on
formation of cell.
heterogeneous or
3. Can take place only on
homogeneous metal surface.
heterogeneous metal
surface.
4. Uniform corrosion.
4. Non-uniform corrosion.
5. Corrosion product
accumulates at the spot.
5. Corrosion product
accumulates at the
cathode.

Mechanism (general)
Carbon

electrode &
zinc cup
Reduction occurs
at carbon electrode
while oxidation
occurs at zinc cup
Zn0Zn2+ + 2eAmnt. of Zn corrosion
W = kIt
Corrosion occurs at
zinc cup

Mechanism of corrosion
(iron)

2(Fe Fe2+ + 2e-)

O2 + 2H2O + 4e- 4OH -

2Fe + O2 + 2H2O 2Fe(OH)2

2Fe(OH)2 + O2 + 2H2O 2Fe(OH)3
Redish-brown
30

Local-action current & localaction cell

Observed

at metal surface while

exposed in solution (water, salt
solution, acids, or alkalies).
Accompanied by chemical
conversion of the metal to
corrosion products.
This happens due to impurities of
a metal constitute the electrodes.

Types of cells
Dissimilar

electrode cells (e.g.

dry cell)
Salt concentration cells
Differential aeration cells
Differential temperature cells

While connected, Cu dissolves at the anode and deposited

at the cathode.
Tending the CuSO4 solution to reach the same concentration.

Types of cells

Same electrode material

Same electrolyte

Only difference is O2 concentration (causes potential difference)

Example: crevice corrosion at the lamp post.

Differential temperature
cell
Same

electrode material.
Same electrolyte.
Temperature difference in electrodes.
Example: corrosion inside heat exchangers,
boilers.

Forms of Corrosion
General
Identified by uniform formation of corrosion
product

Localized
Caused by different chemical or physical
conditions

Bacterial
Caused by formation of bacteria that has
affinity to metal

Galvanic

/ Dissimilar metal

Caused when dissimilar metals come to

35

Corrosion damages
Based on the appearance of corrosion damage:
Uniform
Pitting

corrosion

corrosion

Crevice

corrosion

Galvanic

corrosion

Intergranular
Stress

corrosion

corrosion cracking (SCC)

36

Corrosion damages
Uniform

attack

Pitting

Impingement attack
Fretting corrosion
Cavitation-erosion
Dezincification

and parting
Intergranular corrosion
cracking

Corrosion rate expression

mm/y-

millimeter penetration per year

gmd- grams per square meter per day
ipy- inches-penetration per year
mpy- mils-penetration per year (1 mil = 0.001 in)
Corrosion rate < 0.005 ipy (good corrosion resistance).
0.005 < Corrosion rate < 0.05 ipy (satisfactory).
Corrosion rate > 0.05 ipy (unsatisfactory).

Free energy change (G)

Chemical

reaction mechanism

More (-)ve G, greater tendency of reaction to

occur.
1
Mg H 2O O2 Mg (OH ) 2
2
1
Cu H 2O O2 Cu (OH ) 2
2
Au

3
3
H 2O O2 Au (OH ) 2
2
4

Electrochemical

G 0 142.6 kCal
G 0 28.6 kCal
G 0 15.7 kCal

reaction mechanism

G = - EnF
Higher the value of E, greater tendency of reaction to
occur.

Nernst equation
General

reaction for Galvanic cell:

lL mM ....... qQ rR .......
q
r
a

a
RT
Q
R
0
EE
ln l m
nF aL aM

Nernst

equation provides an exact emf of a cell

in terms of activities of products and reactants.

Homework: Derive this equation.

EMF series
Metals

arranged according to standard potential

values.
More positive noble metals
More negative active metals
Only useful to predict which metal is anodic to
other.
Valid when activity of metal ions in
equilibrium are unity i.e. 1.
Alloys are not included (Only pure metals are
considered).

Electromotive force series

Noble metals

Active metals

Galvanic series
Arrangements

of both metals and alloys.

Well representative of particular
environment.
More appropriate for practical situation.

Pourbaix diagram
Represents

thermodynamic state
(thermodynamic data: Potential vs pH)
Represents chemical & electrochemical
equilibria between metal and aqueous
solution and relates corrosion.
Does not give any data on rate of
reaction.

Pourbaix diagram for iron

Sloping lines involve H+ or OH- and electron.
Fe2O3 + 6H+ + 2e- 2Fe2+ + 3H2O

Horizontal lines represent reaction, which does not involve H + or OH-.

Vertical lines involve H+ or OH- but no electrons.Fe Fe2+ + 2e- ; activity 10-6

POLARIZATION
What

is polarization?
Linkage between polarization and
corrosion.
Types of polarization.
Corrosion control through
polarization.

What is polarization?
Electrodes

are no longer in
equilibrium when a net current flows.
In a Galvanic cell:
Anode potential moves towards cathode.
Cathode potential moves towards anode.
Thus the difference in potential becomes
smaller.

So

the extent of potential change

caused by net current flow to or from
an electrode is called polarization.

Cu

A
V

Potential

corr

I(Re+ Rm)
ImaxRe

Cu
CuSO4

Zn
ZnSO4

Zn

Imax
log current
Polarization curves can never intersect.

Types of polarization
Concentration

polarization
Activation polarization
Polarization due to IR drop

Concentration polarization
Cu = 0.342 volt
1 = Potential of Cu electrode before current passing
1 0.342

0.0592
log Cu 2 1
2

When current flows, Cu2+ + 2e- Cu0

0.0592
2 0.342
log Cu 2
2

Cu 1
0.0592
2 1
log
2
Cu 2 2
2

Significance of Concentration
polarization

Cu 2 1
0.0592
2 1
log
2
Cu 2 2
Larger current flow causes smaller Cu ion
concentration (Cu2+)2, which results larger polarization
When (Cu2+)2, 0 then (2 1)
The current density at this situation is called limiting current
density.

Activation polarization
Causes

by slow electrode
reaction
Requires activation energy
Example: reduction of hydrogen
ion
2H+ + e- H2

Influence of polarization
Anodically

controlled polarization
Cathodically controlled
polarization
Resistance control

Anodically controlled
Polarization
C

occurs mostly at

anode.

Potential

corr
Example: Impure lead
surface immersed in
sulfuric acid.
Lead sulfate film will
be formed and Cu
(the impurity) will
be exposed for
corrosion.

corr

Icorr
log current

Imax

Cathodically controlled
Polarization

Potential

occurs mostly at

cathode.
Examples: Zn
corrodes in sulfuric
acid.
Iron corrodes in
water.

corr

corr
A

Icorr
log current

Imax

Resistance control
Electrolyte

resistance is very high.

Resultant current is not sufficient to polarize either anode or
cathode.

RIcorr

Potential

A
log current

Icorr

Examples: Porous
coating covering a
metal surface.

Principle of cathodic protection

Polarization

of cathode is done by
supplying external current
Electrochemical potential of cathode
moves in negative direction (towards
anode)
Auxiliary anode is used to spread current
The material is protected when it
reaches protection potential

57

Types of cathodic protection

CP

with sacrificial anode

CP with impressed current

Fe - 0.44 v (noble)
Mg - 2.37 v (active)

58

Cathodic protection

Sacrificial anode

line
e
p
i
P

Anode

Passivity
Fe

in concentrated
HNO3 No reaction
(Passive state)
Fe in dil. HNO3
Rapid corrosion
reaction (Active state)
Passivity is the
phenomenon that
demonstrate how the
corrosion is inhibited in
any given environment.

Dilute
Fe
70% concentrated
HNO3

Characteristics of Active-Passive
metal
The

same metal can act as active

as well as passive depending on
the situation.
Passivity occurs because a film is
produced on the metal surface.
Thickness of film 30. (1 = 110-7
mm)

Potentiostatic polarization curve

of active-passive metal (Fe)
Active

passive

siv
s
a
p
s
tran

active

log i

icritical

ipassive

Potential ()

state: metal
corrodes (Fe0 Fe2+ + 2e-)
Passive state: insulative
film is formed & no
corrosion occurs
Transpassive zone:
Formation of Fe3+ as
well as O2 evolution

Flade potential of Fe
applied potential is
withdrawn, passivity
decays
Passivity decays in a very
short time
At Flade potential, active
state of the metal is reestablished.

Potential ()

When

Time (sec)

Important
P and are roughly equal (but not same). WHY?
change in pH
IR drop due to insulating film

Passivators of iron
Passivators

are inorganic
oxidizing agents, which reacts
slowly when in direct contact with
iron.
They are adsorbed on the metal
surface.
Higher the concentration of
passivator, more readily it
adsorbs
CrO42-, NO2-, MoO42-, WO42-, FeO42-

Theory of passivity
Oxide

film theory

Metal oxide or other compound is

formed
This oxide separates metal from the
environment
Eventually slows down the rate of
reaction
Effectiveness of corrosion reduction
depends on the nature & properties
of thin protective film.

Theory of passivity
Adsorption

theory

Passivity is achieved due to

chemisorbed film of O2 or other
passivating agents
This film separates metal from water
or other corroding environment
Film may be of monolayer or
H
H Thick layer
multilayer
monolayer
(multilayer)
Oxygen
Metal
H Hydrogen

Corrosion Rate

Passivity in iron alloys

Fe

10

12

14

Chromium (wt%)

16

18

20

alone is not naturally passive (i.e. corrodes in short time)

Cr is a naturally passive metal (i.e. remains bright & tarnish-free)
Fe-alloy have passive property when at least 12% Cr is there

Factors affecting corrosion

n
of
iro

Ra
te

io
at
iv

co
n

c.

Critical concentration

ss
Pa
n

Corrosion rate (gmd)

Effect of oxygen on MS corrosion

Concentration of dissolved O2 (ml/L)

Critical

concentration may change:

Increases with increasing T

Decreases with increase in velocity

Corrosion rate (ipy)

Effect of temperature

Corrosion

rate increases with increase in T

In open system:

ed
s
o
Cl

em
t
s
sy

Open system
100C

Temperature (C)

Rate

increases first
Then falls down at 100C
In

closed system:

O2

can not escape

Rate increases with T, until all O 2 is consumed

Such falling off is related to

decrease of O2 solubility in
water as T is raised.

Corrosion Rate (ipy)

Effect of pH on iron
corrosion

14

12

10

pH

pH >10
Higher surface pH
Because of alkali & dissolved O2 iron gets
passivated

Corrosion Rate (ipy)

Effect of pH

14

12

10

pH

pH 4 ~10
Corrosion rate is independent of pH
Rate depends on O2 diffusion to the iron surface
Diffusion barrier (FeO) is regenerated
Surface pH always remains at 9.5 throughout this range (Why??)

Corrosion Rate (ipy)

Effect of pH

14

12

10

pH

pH < 4
FeO film dissolved
Surface pH decreases
Corrosion increases (because of H 2 evolution & O2 development)

Corrosion Rate (ipy)

Effect of velocity
(Freshwater)

Corrosion

Rough steel

Polished steel

V (ft/s)

increases with velocity because O2 contact with

the surface
At sufficient high velocity, enough O2 reach at the surface,
which causes partial passivation
At further increase in velocity, corrosion-product film is
eroded

Corrosion Rate

Effect of velocity
(seawater)
High concentration of Cl-

Corrosion

V (ft/s)

increases with velocity

Passivity is never achieved

Corrosion damages
Based on the appearance of corrosion damage:
Uniform

corrosion
Pitting corrosion
Impingement attack
Fretting corrosion
Cavitation-erosion
Crevice

corrosion
Galvanic corrosion
Intergranular corrosion
Stress corrosion cracking (SCC)

Uniform corrosion
Results

from uniform penetration over the

surface
Also results from multiple local-action cell
Location of anodic & cathodic areas move on
the surface
Examples: atmospheric exposure of metal
(rusting of steel, green patina formation of copper),
exposure in salt water or soil or chemicals

Rusting of steel
highway
bridge

Prevention of uniform corrosion

Proper

material selection
Use of coating or inhibitor
Cathodic or anodic protection
Individual or combination of all the above

Pitting corrosion
Highly

localized form of corrosion

Causes from local inhomogeneneity on metal
surface, local loss of passivity, rupture of
protective oxide coating.
Produce sharp holes (small or large in
diameter)
Examples: iron buried in soil (shallow pits),
carbon steel in contact with HCl (deep pits),
SS immersed in seawater.

Pitting factor
p
d

Deepest metal penetration

p
Pitting factor =
=
Average metal penetration
d

Pitting factor = 1 (uniform attack)

Mechanism of Pitting
Example: Metal in NaCl solution

Mechanism of Pitting
Example: Metal in NaCl solution
M+ is pitted by aerated NaCl solution
Once a pit is created, local environment &
surface film become unstable
Rapid dissolution occurs within the pit while O 2
reduction takes place on the adjacent surface
(self propagating process)
Rapid dissolution of M+ causes excess +(ve)
charge in the pit, which causes migration of Clin the pit.
High concentration of metal chlorides (M +Cl-) &
hydrogen ion in the pit.
H+ and Cl- stimulate dissolution of metals and
alloys.

Impingement attack
Moving

liquid particles cause the damage.

Metals subject to high-velocity liquid.
Corrosion-erosion is another name.
Example: Copper and brass condenser
tubes.

Fretting corrosion

Combination of corrosion and wear

Oxidation is the most common element
Relative movement between two surfaces
Metal oxides become trapped between two surfaces and
causes wear
Examples: rolling contact bearing

Prevention:
Lubrication
Restricting the degree of
movement

Cavitation-erosion
Cavitation

Repetitive low & high pressure areas

developed
Consequently bubbles form & collapse
at metal-liquid surface
Damage

caused by cavitation is
called cavitation damage
Metal surface becomes pitted
Examples: blade/rotor of pumps,
water turbine blades

Prevention of Pitting
Lessen

the aggressiveness of the

environment (e.g. Cl- concentration,
temperature, acidity etc.)
Upgrade materials of construction (e.g. Cr
(12%) containing SS, Mo (4-6%) containing SS etc.)
Modify the design of system (e.g. ensure
proper drainage, avoid crevices etc.)

Galvanic corrosion
Metal

or alloy electrically coupled with another

metal or conducting nonmetal
The system should have common electrolyte
Materials possessing different surface
potential
Driving force ->>>> potential difference
between two dissimilar metal

Aluminium rim and chromium plated brass spoke.

Mud on the rim acts as electrolyte.

Galvanic and electrolytic

cell
In

Galvanic cell
reactions occur
spontaneously when
connected by
electrolyte.
Chemical energy is
converted to
electrical energy.
Examples: AA
batteries, car
battery (when it is
being discharged).

In

electrolytic cell
reactions do not occur
without applying an
external potential.
Electrical energy is
used to cause the
desired chemical
reaction.
Examples:
electroplating of Cu,
Au, Ag etc., Car
battery (when it is
being charged).

Area concept of corrosion

Corrosion

of the anode may be 100 ~ 1,000 times

greater than if the two areas were the same.
What to do!!!!!!!
Fe => = - 0.403 volt
Cu => = + 0.521 volt

(i)

Rivet = Fe
Plate = Cu

(ii) Rivet = Cu
Plate = Fe

Corrosion of (i) >> corrosion of (ii)

Aloha aircraft incident

Why this occurred??
Corrosion occurred in lap joint.
Corrosion product was Al(OH)3.
Al(OH)3 expanded inside the lap joint and lead to
pillowing.
This created undesired increased level of stress.
This stress produced cracking.
1 fatality and 7 injured.

Prevention of Galvanic
corrosion
Avoid

combinations in which the area of the

less noble material is relatively small.
Insulate dissimilar metals if possible.
Apply coating e.g. teflon coating.
Use chemical inhibitors, which reduces
corrosiveness of the environment.

Inter-granular corrosion

Localized

type of attack at the grain boundary

of metal.
Grain boundary (small in area) acts as anode.
Rest of the grain (larger area) acts as cathode.
Attack penetrates deeply into the metal.
Causing catastrophic failure.

Stress corrosion cracking (SCC)

Metal

subjectEnviron
to constant tensile stress
mental
& exposed simultaneously
to a
conditio
corrosive environment.
ns
Thus metal suffers cracking called
Material SCC
Stress
SCC.
s
Compressive stress is not damaging.
Example: Riveted steam boiler.

High strength alumina alloy

Riveted steam boiler

Boiler

water generally treated with alkali.

Crevice between rivets & boiler plate allow alkali to
concentrate.
Concentration of alkali in crevices induce corrosion.
Such type of corrosion is often called caustic
embrittlement.

Remedy from SCC

cold working.
Heat treatment (quenching or slow cooling).
Cathodic protection.
Use of special alloy (addition of Al, Ti etc.).
Use of inhibitors (NaNO3 in boiler water, crude
quebracho extract).
Corrosion Rate

Severe

Carbon steel (0.076% C)

Zone refined steel (pure steel)

0

200

400

600

Temp (C)

800

1000

Atmospheric corrosion
Atmosphere:

79% N2, 21% O2 (CO, CO2, NH3,

H2S, SO2, NOx, suspended particles)
Based on the pollutants:

Rural atmosphere (little or no contaminants)

Marine atmos. (high moisture & Cl-)
Urban atmos. (NOx, CO, CO2)
Industrial atmos. (CO, CO2, SO2)

One

metal is resistive to a particular

atmosphere but not effective in the other.
Example: (i) Galvanized steel (C.I. sheet) in
rural atmos. but less resistive in industrial
atmos. (ii) Lead performs better in industrial
atmos. Because PbSO4 film is developed.

Corrosion film-product
Metal

surfaces retaining moisture

corrode rapidly compared to
those exposed fully.
Why???? Because H2SO4
1
1
3

Fe absorbed
FeSO by

Fe
SO

Fe
O

H SO
rust
accelerates
2
2
2
corrosion.
1
H 2 SO4 O2
2

Painting

1
O2 H 2 SO4
4

4 3

1
H 2O
2

just after rainy season is

very efficient than painting in
winter.

Atmospheric corrosion of
steel
Loss of weight (kg/m2)

Pure iron => powdery loose product (i.e. unstable film)

Cu bearing low-alloy steel => compact rust film (i.e. stable

Time (years)

10

Factor affecting atm.

corrosion
Dust content, gases in the atmos.,
moisture etc.
Dust content:
Suspended particle matters (SPM) e.g.
carbon and carbon compound, metal oxides, NOx
etc.

SPM combines with moisture and produces

Galvanic or differential aeration cell.
Dust free air is less responsible for
corrosion.
In Dhaka: 3000 g/m3
(allowed 400 g/m3)

Factor affecting atm.

corrosion
Gases in atmosphere:

H2S causes tarnishing of Ag, Cu, Ni.

SO2 is most harmful
S + O2 SO2
2SO2 + O2 + 2H2O H2SO4

Patina: Cu exposed to industrial atmosphere

forms a greenish protective layer
(CuSO43Cu(OH)2).
Fogging: Ni exposed to industrial atmosphere
forms a tarnish of nickel sulfate. (But Ni is
resistant to marine atmosphere).

Remedial measures of atmos.

cor.
Use

of organic, inorganic or
metallic coating.
Reduction of relative humidity.
Use of alloy.
Slushing compounds (greases, oil,
wax, organic additives etc.).

Underground corrosion
Important

because protection needed for

thousands of kilometers of underground
cross-country pipeline.
NG, crude oil, water.
Soil corrosion resembles atmospheric
corrosion.
Performance of any particular metal varies
from one place to another over the country.
Differences in pH
Differences in soil composition
Differences in moisture content

Factors affecting underground

corr.
Aeration

of soil (depends on porosity).

Electrical conductivity or
resistivity.
Dissolved salts (Na2SO4, NaCl are
harmful).
Moisture or water content (in
desert, corrosion of buried metal is almost
zero).

pH (acidity or alkalinity).

Pitting characteristics of buried

metal
p

= ktn (p: depth of the deepest pit, t: time, k & n:

constant).
n 0.1 for steel in well-aerated soil
n 0.9 for steel in poorly-aerated soil

Pits

tend to occur more on the

bottom side of the pipeline.
Pipe settles down & air space produced on the top

Remedial measures of soil

cor.
Use

of organic or inorganic
coating (coal tar, pigments, portlant cement,
vitreous enamel etc.).
Metallic coating (Zn coating).
Alteration of soil (layer of limestone chip
surrounded the buried pipe).
Cathodic protection (CP).

Corrosion prevention
How to do this????
Change the metallic material.
Altering the corrosive
environment (pH, acidity, temp.).
Separating the metal from
environment (insulation).
Providing appropriate design.

Other aspects of corrosion

prevention
Welding

is preferable from riveting

(crevice corrosion).
Easy drainage and cleaning ( design
aspect).
Avoid sharp bends (erosion-corrosion).
Hot spots should be avoided ( corrosion
due to temperature gradient).
Avoid electric contact (galvanic corrosion).

Factors influence the

service life

Corrosion control by proper

design
(a)

(b)

Prevention of excessive turbulence

Design for drainage (a) poor, (b) better

Avoid condensation droplets

Fluid trap between two metal joints

Corrosion control by proper

design

Mixing vessel (a) poor, (b) better

Prevention of localized cooling
(a) poor, (b) better

Cathodic protection (CP)

Basics of CP:
External electric current is applied
Cathodic potential is lowered to anodic direction
Surface becomes equipotential
Corrosion current no longer flows
CP can not be used- Where???
In nonconducting liquids (oil)
In extremely corrosive environment
(theoretically possible but incurs huge cost )
In electrically screened areas
In vapor

CP with sacrificial
anode
Directly

connect with a more active

metal.
Anode of this system is called
sacrificial anode.

Application of CP
Underground

tanks
Condenser water boxes
Structures e.g. bridges
Evaporators
Valves, piping and other metal
surfaces submerged in a liquids
or constructed underground

11

CP with sacrificial anode

Sacrificial

anode is useful when

electric power is not readily
available.
Low cost installation.
Low maintenance cost.
Combination with coating is better.
8 km coated pipe
Mg anode
30 m bare pipe only

Overprotection
Moderate

overprotection is not

harmful.
Waste of electric current.
Increased consumption of
auxiliary anode.
So much H2 may be produced,
this may create H2 overvoltage
(H2 embrittlement).

Alteration of environment
Corrosion

can be reduced by

(i) changing the corrosive environment

(ii) using inhibitors and passivators
Moisture

can be removed by
dehumidification
Dissolved O2 (by deaeration, saturation with
N2, using O2 excavengers e.g. Na2SO3, N2H4).
Cl- ions can be removed.
Particulate solids can be removed.

Use of inhibitors
Very

specific to particular
environment.
Developed by empirical
experiments.
Sometimes proprietory in nature
& composition is not disclosed.
Usually used in closed or recirculating system.
Not used in once-through system.

Classification of inhibirots
Passivators (inorganic oxidizing

substances e.g. Na2CrO4, NaNO2,

MoO42-).
Organic

inhibitors (Slushing
compounds: wax, greases, oil).
Vapor phase inhibitors
(dicyclohexyl ammonium nitrite:
nontoxic
odorless
3
1 g of DAN&
saturates
550 m).
(20,000 ft3) of air.

Corrosion control through

coatings
Metallic

coatings
Inorganic coatings
Organic coatings

Metallic coating
How to do???
Hot dipping (specimen immersed in molten Zn or
Steel bath).
Electroplating (Nickel on brass).
Metal spraying.
Cementation (specimen put into metal powder at
3
3
high temperature).
CrCl 2 Fe FeCl3 Cr
2
2
Coating by gas phase reaction
Coating by chemical reduction (electroless plating
of Ni: Nickel phosphorus or Nickel-boron alloy coating ).
Ion implantation

Classification of metal
coatings
Noble

coating (with Ni, Ag, Cu, Pb,

Cr on steel).
Sacrificial coating (Zn, Cd on steel).

Noble coating

Metal cladding
Cladding

is a physical process in which a thin

layer of one metal is brought in contact with a
heavy layer of a base metal and binding by a
combination of heat and pressure.
Metal-to-metal laminar composite.
Techniques: hot-roll bonding, cold-roll bonding,
explosive bonding, weld cladding etc.
Most engineering metals & alloys can be clad.
Applied in pressure vessels, reactors, heat
exchangers, storage tanks.

Inorganic coating
Vitreous enamel coating
Powdered

glass applied on metal surface and heated in

furnace.
Hard glassy external layer.
Susceptible to mechanical damage or cracking by thermal
shock.

Portland cement coating

Used

to protect cast iron or steel on water or soil or both.

Thickness is 5 to 25 mm.
Low cost coating.
Susceptible to mechanical damage and thermal shock.

Chemical conversion coating

Formed

in situ by chemical reaction with metal surface.

Anodic oxidation (anodizing) of metal ( e.g. Al2O3).
Phosphate coating on steel (Parkerizing /Bonderizing); (e.g.
ZnH2PO4 plus H3PO4)

Organic coating
Includes paints, varnishes and lacquers.
Paint: mixture of insoluble pigments ( metal
oxides; e.g. TiO2, Pb3O4, Fe2O3, ZnCrO4, PbCO3,
BaSO4, clay etc.) in organic vehicle (natural oil).
Paint is not useful to protect buried structures.
Natural oil based paints not recommended for metal
structures totally immersed in water.

Varnishes:

mixture of drying oil, dissolve

resin and volatile thinner.
Lacquers: resin dissolved in volatile thinner.

Filiform corrosion
Self

propagating crevice corrosion.

Localized form of corrosion that occur under
the coating or paint.
Steel, aluminum and other alloys are affected.
Particular concern in food packaging industry.
Wormlike visual appearance.
Occurred due to microenvironment effect.

Basics of a boiler
operation

Steam

boiler consists
of lowprotective
carbon steel.
Magnetite:
Water inside the tube;film
hot(@570C)
gases around
the tube.
Generated steam passes through higher
alloy steel.
Dissolved O2 is removed (deaeration).
3Fe+4H2OFe3O4+4H2 (Inside the tube)
At T>570C: FeO formation.
Four-pass fire-tube boiler
Cooling of steam: 4FeOFe3O4+Fe

Corrosion in boiler
Protective

magnetite layer may be

damaged either chemically or
mechanically.
Pitting may occur in localized
region.
Excess OH- concentration (chemical
damage).
Differential concentration of oxide &
metal (mechanical damage).

Boiler water treatment

Why needed???
To control corrosion.
To prevent scaling of boiler tubes
(lowers heat transfer rate).
To reduce SiO2 (damages turbine blades).
Steps???
Removal of dissolved gases (O2, CO2).
Addition of alkali.
Use of inhibitors.

Removal of dissolved
gases
Dissolved

gases causes pitting

corrosion in tubes.
Deaerated by steam
Deaerated by O2 scavengers (Na2SO3,
N2H4).
Dissoved

CO2 should be removed

(carbonic acid is corrosive to steel).
CO2 accumulation is avoided by CO2
release during boiler blowdown.

Alkali addition
1

4 7 13

(NaOH) addition is usual

practice.
Caustic embrittlement may
occur.
NH3 is sometimes added instead
of NaOH.
Relative attack

Alkali

pH

NH3 is volatile.
Does not accumulate in crevices.
HCl (ppm)
NaOHor
(ppm)
Crevice
corrosion
SCC do not
occur.

Corrosion testing
What is it??
Is a powerful tool to control corrosion (flight).
Is needed in design stage and in
operational phase.
Provides data useful for selection of
materials: existing or alternative or new.
Classification???
Laboratory testing
Pilot-plant testing
Field testing

Purpose of corrosion
testing
To

evaluate and select materials.

To obtain reference or database
information.
To determine quality-control and
material acceptance requirement.
To monitor corrosion-control programs.
To identify research parameters and
corrosion mechanisms.
<Lack of service history, lack of time and budget.>

Testing, inspection, monitoring

Data Management
Analyses
Forecasting

Operational data
(On-line and off-line)
Testing
Inspection
Monitoring

Decision making
Engg. Review
Assessment
Maintenance