U.

Kamachi Mudali
Associate Director, Corrosion Science and Technology Group
Indira Gandhi Centre for Atomic Research,
Kalpakkam, India
Email: kamachi@igcar.gov.in

CPC 2014, 12th September 2014, IIT Madras

 Wh iis ….
What

Corrosion?
What is Corrosion?
™ The
Th word d corrode
d isi derived
d i d
from the Latin word
‘corrodere’, which means “to
gnaw to pieces.
pieces ”

™ Corrosion can be defined as a

chemical or electrochemical
reaction between a material,
usually a metal, and its
environment that p produces a
deterioration of the material
and its properties.

™ Corrosion rate is measured in

mils/year (mpy) as wall
thickness or in
milligrams/sq dm/da (mdd) as
milligrams/sq.dm/day
weight loss.
Rusting car

Corrosion

Leaks in a water jug

Corrosion on the nose of the
Statue of Liberty

International 
problem

Discoloration of the marble due

to sulfur compounds in air
Electronic components

Copper pipes

Brass plate

Iron tray

Affects the 
Affects the
individual 
too
Electric Power Industry Transmission pipelines Highway Bridges

Pulp & Paper Petrochemical Industry

Defense

No industry 
is exempted
Nuclear Power Industry
Why corrosion is important?

‰ Aesthetics

‰ Economy…………
……Money matters

¾Cost of corrosion in India alone is estimated to touch Rs 3.7 lakh crores

¾Cost of corrosion in US is over $360 billion

Thorough understanding of corrosion is necessary

Why Metals and Alloys Corrode ?
 Corrosion can be Fast or Slow
By the nature of the material or environment,
environment corrosion can be
fast or slow.

Ship wreck exposed to

Delhi iron pillar- Exposed to atm. conditions
Marine conditions -
No corrosion for the ppast 1600 y
years !!
Hi h corrosion
High i !!
Where it happens ?

On road On rail

Anywhere &
everywhere

In water In air
Forms of corrosion
Uniform
Stress 
corrosion  Pitting
cracking

Fretting Crevice

Corro
sion

Inter 
Erosion
granular

Microbio
‐logically 
Galvanic
induced 
Hydrogen 
Hydrogen corrosion
embrittle
ment
Localised Corrosion in Engineering Components

General/Uniform Corrosion Corrosion Fatigue

Pitting Corrosion Filiform Corrosion
Crevice Corrosion Erosion Corrosion
Intergranular Corrosion Fretting Corrosion
Stress Corrosion Cracking Galvanic Corrosion
Hydrogen Embrittlement High Temperature Corrosion
Cavitation Corrosion Microbially Influenced Corrosion
Pitting corrosion
It is
i a highly
hi hl llocalized
li d corrosion
i occurring
i on a metal t l surface.
f
Pitting is commonly observed on surfaces with little or no
general corrosion.
corrosion
Pitting typically occurs as a process of local anodic dissolution
where metal loss is exacerbated by the presence of a small
anode and a large cathode.
Pre ention or Control
Prevention

Reduce aggressive ions causing pit initiation and growth

Increase velocity of media and/or remove deposits of solids
from exposed metal surface.
Selection of alloy with higher alloy content (e.g. in stainless
alloys-higher Cr, Mo and N) and modify the microstructure.
 S h
Schematics
ti off processes occurring
i att an actively
ti l growing
i pit
it iin iiron.

Jones, D.A., Principles and Prevention of Corrosion, Macmillan Publishing Company, NY (1992).
Schematics of autocatalytic pitting process occurring
at an actively growing pit in stainless steel.
PITTING CORROSION
 Factors Influencing Pitting Corrosion
Environment ((electrolyte
y Compositions)
p )
⇒ Cathodic reactants – (O2, H+, M+n, Cl-), sulfur compounds (SO42-, S2O32-, HsS), biocides
(ozone and chlorine), dissolved gases etc.
⇒ cupric, ferric and mercuric ions - accelerate pitting.
Inhibitor Ions
Sulfates, hydroxides, chlorates, perchlorates, nitrates, chromates, molybdates, phosphates,
carbonates, acetates etc.
Metallurgical
g Variables
Thermal aging, welding, grain size, cold work, composition, defects etc.

Standard Test Methods for Pitting Corrosion

™ ASTM G-5 - Standard Reference Test Method for Making Potentiostatic and
Potentiodynamic Anodic Polarization Measurements.
™ ASTM G-46 - Practice for Examination and Evaluation of Pitting Corrosion.
™ ASTM G-48G 48 A&C-
A&C Test
T t Methods
M th d forf Pitting
Pitti and
d Crevice
C i corrosion i R it
Resistance off
Stainless Steels and Related Alloys by the use of Ferric Chloride Solution.
™ ASTM G-61 - Test Method for Conducting Cyclic Potentiodynamic Polarization
Measurements for Localized Corrosion Susceptibility
p y of Iron, Nickel or Cobalt Based
Alloys.
™ ASTM G-150-99 - Standard Test Method for Electrochemical Critical Pitting
Temperature Testing of Stainless Steels.
 Pitting Corrosion from Inside ─► Out
Main factor: Corrosion due to small volumes of stagnant water
with salt trapped in holes

C door after
Car f 10 years off service

Blistering Total damage

Pitting Attack in Type 304 SS Heat Exchanger
Failure occurred within six months of service as compared to the
guaranteed life of 5 to 10 years.
Coil is filled with 70% methanol brine with 30% water, and the
outside of the coil was exposed to acetone vapour containing
nitrogen.

Reasons for failure

Use of Carbon Steel in Stainless Steel Unit
Ingress of ordinary water Into DM water system
Crevice corrosion
Crevice corrosion is localized corrosion which might
occur in smaller areas of stagnant solution in crevices,
joints and under corrosion deposits .
(a)

(b)

(a) Crevice corrosion of type 316 stainless steel in acid condensate

under
nder a PTFE spacer;
spacer (b) typical
t pical schematic morphology
morpholog with ith attack
greatest at the mouth of the crevice.
Relative Resistance to Crevice Attack
in Natural Waters

Limiting Chloride
Alloy level, ppm

400 series attack occurs in

fresh waters

304 SS 100 - 200

316 SS 1000
 Crevice corrosion - prevention or remedial action

- Redesign of equipment to eliminate crevices.

- Close crevices with non-absorbent materials or
incorporate a barrier to prevent moisture penetration into
crevice.
i
- Prevent or remove builds-up of scale or other solids on
surface of material
material.
- Use of one-piece or welded construction versus bolting or
riveting.
riveting
- Select more corrosion-resistant or inert alloy (note: see
pitting corrosion for more information).
 Standard Test Methods for Crevice Corrosion

™ ASTM G-48 B & D - Test Methods for Pitting and Crevice Corrosion Resistance of
Stainless Steels and Related Alloys by the use of Ferric Chloride Solution.
™ ASTM G-78 - Guide for Crevice Corrosion Testing of Iron-base and Nickel-base
Stainless Alloys in Sea Water and other Chloride-Containing Aqueous Media.
™ ASTM 78-01 - Standard Guide for Crevice Corrosion Testing of Iron-base and Nickel
base stainless alloys in seawater and other chloride containing Aqueous environments.
environments
™ ASTM F-746-87(1999) - Standard Test Method for Pitting or Crevice Corrosion of
Metallic Surgical Implant Material.
 Heat Exchanger Failure
in Fertiliser Industry

Corrosion failure of a carbomate heat exchanger was due to design failure in providing
excessive gap between the tubes and tube sheet leading to crevice corrosion attack

Failed
F il d
location
Microbiological corrosion
Microbiological corrosion (MIC) refers to corrosion
and ensuing loss of metal caused by biological
organisms.

MIC can occur iin any aqueous environments,

i t andd
because of the omni present nature of microbes in
fluid systems
systems, MIC is a commonly occurring
phenomenon.

MIC is a common problem in industrial processes due

to the presence of microbes, adequate nutrients and
corrosive byproducts.
Most MIC, however, manifests as localized corrosion because
most organisms do not form in a continuous film on the metal
surface.
Microscopic organisms also tend to settle on metal
surfaces in the form of discrete colonies or at least spotty,
rather than continuous bio films.
Biological organisms fall under two groups based on the type of
corrosion they engender:
(a) Anaerobic corrosion; (b) Aerobic corrosion.
Sulfate reducingg bacteria ((SRB)) from the g
genera desulfovibrio
are a typical example of anaerobic MIC.
Aerobic sulfur oxidizing bacteria of the type thiobacillus can
create an environment of up to 10% sulfuric acid, thereby
encouraging rapid corrosion.
Microbiologically Influenced Corrosion

CONDITIONS
surfaces in contact with water, RH > 90%
temperature = 4 to 80 °C C
availability of nutrients
exposure to sunlight

WHERE
Metals, Concrete, Plastic, Wood

RECOGNITION
p
presence of biofilm
distinguishable odour
Discolouring
soft corrosion products
high water contents
presence of crevice
 Influence of biofilms on localized corrosion of stainless steel

CREVICE CORROSION
Biofilm on 304SS Crevice on 304 SS below biofilm CHIEF CULPRITS
(MOB)

SRB attack on 304 SS Gallionella mounds

Gallionella (IOB) condenser on SS weld
Manifestation of Localised Corrosion

Pitting Corrosion Crevice Corrosion

Intergranular Corrosion Stress Corrosion Cracking

 Stress corrosion cracking
Stress corrosion cracking (SCC) is caused by the
simultaneous
i lt effects
ff t off tensile
t il stress
t and
d a specific
ifi
corrosive environment. Stresses may be due to
applied loads, residual stresses from the
manufacturing process,
process or a combination of both.
both
Chloride induced cracking of stainless steels, caustic
cracking of plain carbon steels and ammonia damage
t copper alloys
to ll are typical
t i l examples
l off SCC.
SCC

http://corrosion.ksc.nasa.gov/html/stresscor.htm

Cross sections of SCC frequently show branched

cracks This river branching pattern is unique to
cracks.
SCC and is used in failure analysis to identify when
this form of corrosion has occurred.
 STRESS CORROSION CRACKING
Unfortunate Facts of SCC
Material Environments
Cracking takes place in Al alloys Chlorides, moist air
otherwise best alloys Mg alloys Chloride-chromate mixtures,
moist air
Passive alloys resistant
to general corrosion Nitric acid, fluorides.

High strength steels Sodium hydroxide

prone to cracking
Ammonia, moist air, moist sulfur
Cu alloys
Cracking at RT dioxide
in pure water C steels Nitrates, hydroxides, carbonates

Anhydrous ammonia

Austenitic steels Chlorides sulfur acid

Chlorides,

High strength Moist air, water, chlorides,

steels sulfates, sulfides
Ni alloys
ll H d id
Hydroxides
Ti alloys Halides, methanol
Intergranular Stress Corrosion Cracking

HAZ
SENSITISATION
 Schematic anodic polarization curve showing zones of
susceptibility to stress corrosion cracking.
Jones, D.A., Principles and Prevention of Corrosion, Macmillan Publishing Company, NY (1992).
SCC in Helium Storage 304 SS Tank
Presence of water
with chloride content
after hydro testing,
and residual
stresses after
weldingg lead to
intergranular SCC of
304 SS
Corrosion Fatigue
Corrosion-fatigue differs from SCC by the fact that the applied
stresses are no longer static, but cyclic (periodically fluctuating
or alternating loads)
loads).
Occurs in metals as a result of the combined action of a cyclic
stress and a corrosive environment.
Corrosion fatigue is dependent on the interactions among
g, environmental,, and metallurgical
loading, g factors.
For a given material, the fatigue strength generally decreases in
the presence of an aggressive environment. The effect varies
widely, depending primarily on the particular metal-environment
combination. The environment may affect the probability of
f ti
fatigue crackk initiation,
i iti ti th
the ffatigue
ti crackk growth
th rate,
t or both.
b th
 Fatigue life data, S-N curves, for a high-strength steel under different
environmental conditions
The cracks are generally transgranular in nature,
with little tendency for branching. However, a few
ssmall
a seco
secondary
da y c
cracks
ac s may
ay appea
appear in the
e vicinity
c y
of the main crack.
Although there is no direct relationship between
the sensitivity to corrosion-fatigue
corrosion fatigue and the
mechanical properties of the material, high
strength alloys tend to be most highly prone.
 Corrosion Fatigue of A Pump Shaft

PREVENTION

Ø Using high tensile strength alloys improves fatigue resistance but detrimental
to CF resistance Æ use high ductility material
Ø Reduce stress on the component Æ altering design, stress-relieving heat
treatments, shot-peening
p g to introduce compressive
p stresses
Ø Use electrodeposited coatings that do not produce tensile stresses in the
coating or charge hydrogen into the metal
HYDROGEN EFFECTS ON MATERIALS
Hydrogen can degrade materials by: Cross section of a carbon steel plate
removed from a p petroleum p
process stream
• hydrogen blistering; showing a large hydrogen blister. Exposure
time: 2 years.
• hydrogen embrittlement;
• decarburization;
• hydrogen attack
attack.

Blistering
Hydrogen enters the lattice of a metal,
metal diffuses to
voids, creates high internal stresses → blisters are
created Prevention of Blistering
Blistering may occur during exposure to: – use steels with few or no voids;
• hydrocarbons; use coatings; use inhibitors;
• electroplating of metals; remove impurities that can
• chemical
h i l process streams;
t promote hydrogen evolution . . .
• pickling treatments; S2- (particularly bad), As, CN-,
• H-containing contaminants during welding; etc.; use different materials (Ni-
• generall corrosive
i environments.
i t
base alloys have low diffusion
rates for hydrogen).
 Fish-mouth opening in Feed Super Cracking of adjacent hydrogen fissures
heater Tube in Hydrogen Unit
HB a problem – vapour recovery section of catalytic cracking unit, overhead
system of sour water stripper tower, amine regenerator towers, bottom
portion of the amine absorber tower.
tower
Corrosion Control by : Decrease the concentration of cyanides and
bisulfides, dilution by water washing, Inhibitor injection, Use of clean steels
Hydrogen Embrittlement
¾ A process resulting
lti i a decrease
in d off the
th toughness
t h or ductility
d tilit off a metal
t l
due to the presence of atomic hydrogen.
¾ The exact mechanism of embrittlement depends on the rate of hydrogen
t
transport
t and
d the
th amountt and
d location
l ti off available
il bl hydrogen.
h d
¾ Similar to blistering . . . hydrogen enters metal lattice . . .BUT . .
interaction with metal lattice different. High-strength (and more brittle)
steels are susceptible.
susceptible
¾ H-embrittlement different from SCC in nature of cracks . . . Stress
corrosion cracks usually propagate anodically;
Hydride Embrittlement
• Hydride-forming metals are susceptible to H- embrittlement . . .e.g., Zr-alloy
pressure tubes (in CANDUs) and fuel sheathing (in all water- cooled reactors)
pick up hydrogen (or deuterium in heavy water) by general corrosion.
• The hydrogen (or D) migrates through the metal lattice to cool regions and to
regions of high tensile stress - can precipitate as zirconium hydride.
hydride
• These hydrides are brittle, and the crack can propagate through the material, with
more hydride progressively precipitating at the crack tip.

Prevention of Embrittlement
– reduce corrosion rate (inhibitors, coatings, etc.); change electroplating process to
minimize H effects
ff (voltage,
( current density, bath composition, etc.);
)
– bake material to remove H; minimize residual stresses; use less susceptible
material; maintain clean conditions during welding.
Decarburization and Hydrogen
Attack
High temperature process - C or carbide in
steels can react with gaseous hydrogen to form
Methane
C + 2H2 → CH4
Note that the reaction can occur even with
atomic H in the metal lattice . . .
C + 4H → CH4
This may crack the steel by high internal
pressure and also cause loss of strength,
pressure, strength as
carbon disappears.

The mechanism of hydrogen uptake by

materials must involve ATOMIC HYDROGEN
as molecular hydrogen cannot diffuse through
metal lattices.
BUT . . . remember that molecular hydrogen
may absorb and dissociate on metal surfaces.
Intergranular Corrosion of Austenitic Stainless Steels

9% Cr

sensitized

65% Cr HAZ
annealed HAZ
Sensitisation
S iti ti is
i
influenced by cold
18% Cr work, grain size,
composition Weld Decay

Formation of chromium-rich M23C6 carbides (~ 65% Cr) at grain boundaries during slow
heating/cooling of austenitic stainless steels (18% Cr) between 400-750°C leads to
development of chromium-depleted zones (< 9% Cr) along the grain boundaries. This is
known as Sensitisation.
Any sensitised microstructure will undergo selective localised corrosion along grain
boundaries leading to Intergranular Corrosion.
 Factors Affecting IGC

900˚C
0.06% C

800˚C

700˚C
700 C Increasing
g carbon

600˚C
0.019% C
500˚C

400˚C
10 sec 1 min 10 min 1h 10 h 100 h 1,000 h 10,000 h

time

Kinetics of sensitisation influenced by cold work, grain size, composition

 Weld Metal

Base Metal Sensitised HAZ

1 2 3 4
Temperature, °C

B C
850 HAZ

A D
550 E G H F

1
2
3
4

Time, s

¾Sensitisation of HAZ Æ 723-1123 K and thermal cycling

¾Increase in heat input Æmore time in sensitisation temperature range
¾Higher interpass temperature Æ more time in sensitisation temp. range
Weld decay

• Heating between 450 and 800˚C causes

Cr-rich carbide precipitation (Cr23C6) at
grain boundaries which lowers Cr level
in adjacent matrix (<9%)

• Corrosion occurs at the denuded areas

of sensitised steels if they are in
aggressive chemical environments
 Practical situations leading to sensitization

• Welding (IGC in heat affected zone of weldment - weld decay)

• High temperature service
• Heat treatment - Stress relieving, solution annealing
• Hot forming
g operations
p

How to Avoid Sensitisation ?

• Use low carbon content SS (max. 0.03%)
–‘L’ grade stainless steel, 304LSS
• Stabilise carbon with Ti or Nb ((Cb)) which form carbides that are stable at high
g
temperatures
–Grades 347 or 321 SS are stabilised versions of 304 SS
• Solution treat after welding g
–Heat to 1100˚C and water quench through sensitisation range
• Add nitrogen to delay carbides
- 304LN SS
 ASTM Tests for Sensitisation & Intergranular Corrosion
ASTM Test Potential Phases Evaluation
Practice Environment Range Attacked Criterion
A Electrolytic +1.76 V (SCE) Carbides Step, Dual,
Oxalic Acid Ditch
Etching Microstructure
B Fe2(SO4) – 50% +0.6 V (SCE) σ in 321 & 347 Weight loss
H2SO4
C HNO3 +0.96 V (SCE) Cr-depleted Weight loss
regions,
carbides &
Mo-bearing σ
D HNO3 – HF +0.3 to -0.1 Cr-depleted Weight loss
V (SCE) region
E Cu–CuSO4/16% Cr-depleted U-bend test;
H2SO4 +0.34 V (SCE) region Tensile
properties

F Cu–CuSO4/50% -- Cr-depleted U-bend test;

H2SO4 regions weight loss
 Erosion Corrosion "Horseshoe" type erosion-corrosion
damage in a copper pipeline
¾ Erosion-corrosion is caused by the relative
movementt between
b t a corrosive
i fluid
fl id andd a
metal surface.
¾ The mechanical aspect involving friction
and wear leads to formation of grooves,
valleys, wavy surfaces, holes, etc., with a
characteristic directional appearance (comet
t il horseshoe
tails, h h marks, k etc).
t )
¾ Most metals and alloys, particularly soft

ge in
materials (e.g. copper, lead, etc.) or those

on-corrosiion damag
whose corrosion resistance depends on the
existence of a surface film (aluminium,

pipeliines
stainless steels).
Means of limiting erosion-corrosion :
• Choose a more resistant material
• Improve the plant design
• Adjust
Adj t the
th medium
di (control
( t l oxygen
Erosio

content, lower the temperature, use

inhibitors, filter out solid particles)
Cavitation Corrosion
Cavitation-corrosion is particular form of erosion
caused by the "implosion" of gas bubbles on a
metal surface. It is often associated with sudden
variations in pressure related to the hydrodynamic
parameters of the fluid (e.g. hydraulic turbine
blades, propellors, stirrer blades, etc.).
Cavitation
C it ti off a nickel
i k l alloy
ll pump impeller
i ll blade
bl d
exposed to a hydrochloric acid medium.

9A ggood surface condition decreases the number

of potential sites for the formation of vapour
bubbles.
9 An increase in fluid pressure is often sufficient
to maintain a single phase fluid, thus avoiding
the formation of vapour bubbles.
9 Plastic or rubber coatings have often proved to
be effective,
effecti e although
altho gh the problems of
adherence between the coating and the metal
are frequently an obstacle.
Fretting Corrosion
• Fretting-corrosion is a combined damage mechanism
involving corrosion at points where two moving metal
surfaces make rubbing contact.
• It occurs essentially when the interface is subjected to
vibrations ((repeated relative movement of the two
contacting surfaces) and to compressive loads.
• The amplitude of the relative movement is very small,
typically of the order of a few microns.
• When the frictional movement in a corrosive medium
is continuous, the resulting process is termed
tribocorrosion.
Means of preventing fretting corrosion :
• Lubrication with oils or greases, to reduce friction and exclude oxygen from the
interface.
• Increase in the hardness of one or both materials in contact. Certain material
combinations
bi ti show
h b tt
better f i ti
friction b h i
behaviour th
than others.
th S f
Surface h d i
hardening
treatments can be beneficial.
• Use of seals to absorb vibrations and exclude oxygen and/or moisture.
• Reduction of the friction loads in certain cases,, or on the contrary,
y, increase of the
friction loads to attenuate vibrations.
• Modification of the amplitude of the relative movement between the two contacting
surfaces.
Filiform Corrosion
Filiform corrosion is a thread-like form of corrosion that occurs under paints / organic
coatings The source of initiation is usually a defect or mechanical scratch in the
coatings.
coating.
¾ Filiform corrosion occurs under surface layers such as paint.
¾ It depends on the relative moisture of the air and the quality of the surface
treatment preparation prior to coating.
¾ Filiform corrosion has the appearance of thin threadlike attacks progressing
along the surface beneath a surface layer.
¾ The mode of attack is similar to pitting corrosion in that the front of the attack is
supported by moisture which penetrates the surface layer and becomes depleted
of oxygen making the area anodic.
¾ Filiform
Filif corrosion
i mainly
i l has
h an aesthetic
th ti effect,
ff t butb t the
th corrosion
i products
d t
formed may cause deformation in narrow crevices or delamination of surface
treatment.
¾ Mainly noticed in laminated/coated Al alloys and Steels.
Steels
¾ To avoid: Improved alloy, Inhibiting primer, Anodisation

Typical characteristics for filiform corrosion:

¾ Occurs
O att a relative
l ti humidity
h idit b between
t 40 and
d 90 %
%;
¾ Filaments follow pre-existing directionality;
¾ Filaments never cross each other
 Filiform Corrosion on Aluminium Wheel Hub

• Addition of Cu to increase formability may lead to higher susceptibility to

corrosion
• Lab studies on AA6016 (<0.01% Cu, 0,07% Cu) & AA6111 (0.7% Cu)
have shown that Cu has an influence on filiform corrosion
 Sulphur Halogen

Ash/Salt
D
Deposits
it Carbon
Flue Ash/Hot
Corrosion O2, H2, H2O
CO, CO2,
H2S, SO2
NH3, N2, NO2
Cl Nitridation
Eutectics Nitrogen
g

Molten Metal Molten Salts

Applications above 650˚C

- More than one mechanism acts to degrade the material
Principal modes of high temperature corrosion in industrial environments, as well
as the interaction between oxygen activity and principal corrodent activity
High Temperature Corrosion / Oxidation
¾ High
g temperature corrosion "dryy corrosion" or "scaling“
g is a form of corrosion that
happens at temperatures well above room temperature and does not require the
presence of a liquid electrolyte.
¾ The most important high temperature corrosion is “Oxidation” which is refer to the
formation of oxides due to high temperature corrosion reaction.
¾ High temperature corrosion is a widespread problem in various industries such as:
power generation (nuclear and fossil fuel), aerospace and gas turbine, heat treating
mineral and metallurgical processing, chemical processing, refining and
petrochemical, automotive, pulp and paper, waste incineration

g – Bedworth Ratio : Oxidation resistance is

Nature of oxidation is related to Pilling
related to volume ratio of oxide and metal per gram atom of the metal.

¾If the volume ratio is less than 1, insufficient oxidation occurs leaving metal surface
unprotective – Li,
Li K,
K etc.
etc
¾If the volume ratio is much greater than 1, large volume of oxide with compressive
oxides are formed leading to spalling and cracking – Si, Mo, V, W, Nb, Ta etc.
¾Under ideal conditions the ratio is 1, with a protective scale on the surface
This is only empirical criterion, and to be protective an oxide scale must possess good
adherence, high melting point, low vapour pressure, and high temperature ductility
Theory of Oxidation
Highg temperature
p oxidation byy g
gaseous oxygen
yg is an electrochemical p
process.
It is not the simple chemical combination of metal oxygen on a molecular scale,
Like M + ½ O2 ---Æ MO, but consists of two partial processes,

M -----Æ
Æ M 2+ + 2e- (metal oxidation at metal-scale
metal scale interface)
½ O2 + 2e- ----Æ O2 (oxidant reduction at scale-gas interface)

M + ½ O2 ------Æ MO (overall reaction)

New MO lattice is produced either at the metal-scale interface or at the scale-gas

interface.
The rate of oxidation is measured and expressed
Linear
as weight gain per unit area.
Parabolic
W = k Lt
W = kpt + C Cubic

∆w
Logarithmic
W = ke log (Ct + A)
W3 = k ct + C
•Sodium and Potassium oxidise linearly and have
oxide
id to
t metal
t l volume
l ratio
ti less
l th 1.
than 1
•Tantalum and Niobium oxidise linearly and have
Time
Oxide to metal volume ratio of 2.5
 High Temperature Refinery Corrosion
9Serious problem – Temperature and
pressure, Hydrocarbon – danger of fire –
if rupture occurs.
9“Oxidation” “Sulphidation” “Carburisation”
“Metal Dusting” “Chloridation” “Hot
Corrosion"
9Sulfide corrosion, >2600C – 5400C - no
liquid water - common problem in
refineries
9Sulphur compounds from crude oil,
polysulfide, H2S, mercaptans, aliphatic
s lfides disulfides
sulfides, dis lfides
9Sulfur compounds react with metal
surface and form sulphide products
 Refinery Corrosion Problems
Corrosion - integral and unavoidable part of petroleum refining operation.
operation
Refinery operations involve inflammable hydrocarbons, highly toxic or
explosive gases, strong acids, caustic operating at high temperatures.

Low temperature refinery corrosion : < 260ºC, water

High
g temperature
p refinery
y corrosion : > 260ºC,, No water

Corrosive Agents in Refineries

Inorganic compounds – salts – MgCl2, CaCl2, Hydrogen sulphide, HCl,
H2SO4, NaOH, crude oil contaminants, process chemicals

Corrosion failure of boiler tube

Corrosion of Economizer Coil in

Catalytic Reforming Unit
 Protection Measures Against Corrosion
Good Engineering
g ee g Practice
act ce

Select material/environmental combination based on literature & experience

Reduce service and residual Stress
F ll
Follow procedure/code/practice
d / d / ti ini Design/Fabrication/Operation
D i /F b i ti /O ti

Improve Environment

™ Control of Impurities
™ Inhibitor/biocide addition

Improve
p o e Material
ate a

Adopt Protective Measures

9 Painting
9 Coating
9 Anodic protection
9 Plating
9 Cathodic protection
 Electrochemical Protection Systems
Cathodic Protection

Cathodic protection is the most widely applied

electrochemical
l t h i l corrosion
i control
t l technique.
t h i

This is accomplished by applying a direct current to the

structure which causes the potential to change from
the corrosion potential (Ecorr) to a protective potential in
the immunity region.
region

The required cathodic protection current is supplied by

sacrificial anode materials or by an impressed current
system. Most metals in contact with an aqueous
environment having a near neutral pH can be
cathodically protected.
Cathodic Protection
Advantages
- can be used for all metals
- installation cost is low
- corrosion rate can be reduced to zero
Limitations
- can only be used in weak to
moderate environments
- operating conditions must be
determined by empirical testing. Impressed Current

Sacrificial Anode
 Anodic Protection
For metals exposed to strongly alkaline or acid environments,
where the metal exhibits active-passive behaviour, anodic
protection can be applied to control corrosion.

Here the metal potential is shifted to the passive zone from

the active region by the application of a direct current.

Potential
P t ti l Adjustment
Adj t t Protection
P t ti
Normally, passive metals, when exposed to oxidizing halide
environments might suffer from pitting and crevice corrosion
environments, corrosion.
By the application of a direct current, the structure potential
can be shifted back to the ppassive region
g from the
transpassive region.
Anodic Protection
Advantages
- can be used in extremely aggressive environment
- operating conditions can be easily controlled
- operation cost low

Limitations
- only applicable to active-passive metals
- installation cost is high
 Corrosion Inhibitors
¾ A corrosion
i i hibit is
inhibitor i a chemical
h i l compound
d that,
th t when
h added
dd d in
i smallll
concentration, stops or slows down corrosion of metals and alloys.
9 Inhibitors slow corrosion processes by either:
► Increasing the anodic or cathodic polarization behavior (Tafel slopes)
► Reducing the movement or diffusion of ions to the metallic surface
► Increasing the electrical resistance of the metallic surface.
Classification of inhibitors
- passivating inhibitors
- cathodic inhibitors
- organic inhibitors
- precipitation inhibitors
- volatile corrosion Inhibitors

Examples of Corrosion inhibitors

Hexamine, phenylenediamine,
Hexamine phenylenediamine dimethylethanolamine,
dimethylethanolamine sodium nitrite,nitrite
cinnamaldehyde, condensation products of aldehydes and amines (imines),
chromates, nitrites, phosphates, hydrazine, ascorbic acid, and others.
 I have
h made
d the
h
Everyday I am sick of
best design, and
this leaking…….
chosen the best material…..
I do not know why they
Everything is prefect !
designed like this ??!!

Designer
and
Operator
 Design and Corrosion

Corrosion and its control is an important, but often neglected,

element in the practice of engineering

For controlling corrosion, the process should start at design stage

itself. Corrosion control at the design stage does not just happen by
itself it should be planned.
itself, planned

Engineers should consider the extent to which corrosion protection

is to be built in and the extent to which corrosion prevention during
maintenance can be depended upon by conditioning the
environments or by temporary protection.

Adhering to the guidelines at various stages is the only possible way

to minimize losses due to corrosion
 SELECTION OF MATERIALS

For the
F th best
b t equipment
i t or structural
t t l design,
d i th materials
the t i l off
construction must be carefully selected from a corrosion resistance
standpoint.
Concise and clearly written specifications should be provided to the
supplier to ensure that the material needed is accurately ordered.

To avoid bimetallic corrosion the following guidelines can be followed:

a) Metals which are well separated in galvanic series should not be
connected.
connected
b) Dissimilar metals should be insulated / separated from each other
c) Separation materials should not be porous

d) When insulation is not feasible, eg. high temperature or aggressive

solutions, where insulation will deteriorate, the more noble metal
should be used for joining or fastening the less resistant metals
(a) For dissimilar metals, the two materials should be insulated,
(b) For dissimilar metals that cannot be insulated, the nobler of
the two should be made of smaller area (cathode )
In su la tio n
In su la tio n

In s u la tio n

In su la tio n

W e ld m e n t B o lts & n u ts

R iv e ts
B ra c k e t
Crevice corrosion & proper drainage are the most
important factors in design

P o t e n t ia l
c o r r o s io n s it e T ube sheet

Tube

Contd.
RECOMMENDED NOT RECOMMENDED

Contd.
 RECOMMENDED NOT RECOMMENDED

I-BEAM CONCRETE
FOUNDATION

RECOM M ENDED N OT RECO M M ENDED

H ot Fluid
H ot Fluid Steel Steel
Condensation and corrosion
tank tank

Steel Heat
Insulation prevents Steel support
Insulation
tem peratute drop at shell radiates heat

Contd.
 L iq u id c a n n o t d r a in
F o r e ig n m a t t e r c a n
c o lle c t in c o r n e r s

B e c a u s e t a n k c o n n o t d r a in p r o p e r ly
w it h r ip p le s o n t h e b o t t o l, liq u id in
t h e r ip p le s c a n c a u s e c o r r o s io n

D r a in n o z z le
Contd.
Designer
g should know that how the component
p will be
made.

The residual
Th id l stress
t shall
h ll be
b keptk t tot a minimum
i i b
by
employing manufacturing processes that leave minimum
residual stress.
stress Tight-fits,
Tight-fits ill-fitting or over-tightened bolt
assembly designs, which cause high stresses are to be
avoided.

In a severely corrosive environment, austenitic stainless

steels
t l are susceptibletibl to
t a form
f off selective
l ti corrosion
i
termed the end grain attack. Where there are holes in
process equipment exposed to aggressive solutions,
solutions the
interior of the holes should be coated with weld material.
Contd.
E n d g r a in
 Weld Defects and Corrosion

Welding
W ldi always
l introduces
i d
heterogeneous structure
similar to casting which
easilyy make weld to undergo
g
corrosion prior to base metal

Weld Defects
Stress risers
Inclusions
Incomplete welding
Improper filler metal / flux used
Coatings and Surface Modification

Corrosion Protection through

Noble action
sacrificial action
barrier action

Surface Modification provides

Energy Conservation
Material Preservation
Cost effectiveness
Cost-effectiveness
Defect Elimination
Corrosion Protection
Surface Treatment / Modification / Coatings

MECHANICAL
C C
Shot Peening
Laser Peening
Roll bonding
PHYSICAL THERMAL
Sputtering Flame Hardening
Laser Treatment Laser Treatment
Physical vapor deposition Induction Hardening
(PVD) Electron Beam Heating
Evaporation Diffusion (Hot Dip)
Surface Cladding
Ion implantation
Spraying (cold)
Modification / Spraying (hot)
Coatings

CHEMICAL
THERMOCHEMICAL
Electroplating
Boriding
Anodising
Nitriding
Electroless plating
Carburizing
Self Assembly
Metallizing
Electrophoritic deposition
Plasma, Ion Treatment
Chemical vapor deposition
Laser Alloying
(CVD)
Coatings Development and Application
Process
P s

Thickness
Coatings For High Temperature Corrosion
• Resistance to oxidation
oxidation, hot corrosion
• Combination of strength and ductility
• Good thermal / structural stability
• Should not degrade base components

Selection Criteria
• High melting point: less diffusion of ions
• No phase changes
• Low thermal conductivity
• Thermal expansion match with component
• Good adherence
• Low sintering rate
Thermal Barrier Coatings
TBC consists of an insulating ceramic outer layer and metallic inner layer (bond coat)
between ceramic and the substrate
Top coat (300-400 μm): Ceramic material like stabilized Zirconia, Mullite, etc;
generally stabilized Zirconia (6-8%yttria)
Bond coat ((50-100 μμm):) MCrAlY type
yp metallic coatings
g
Stabilized Zirconia Coatings
ceramic outer layer
9 Thermal strain tolerant
9 Resistance to Na2SO4 and V2O5 bond coat
9 Low thermal conductivity
9 Ideal thermal expansion match component
9 High thermal stability

What is thermal spraying ? A process by which a material is heated rapidly in a

hot gaseous medium & simultaneously projected at high velocity on to a prepared
substrate surface where it builds up the desired coating
“ Rust Never Rests ”