CORROSION - Basics and Types

S.K.SESHADRI
IIT MADRAS
 SELECTION of MATERIALS

À COST
À DURABILITY
À FABRICATION
À AVAILABILITY
À PROPERTIES
– Physical
– Electrical
– Mechanical
– Environmental
 FAILURES

À Deficiencies in Design
À Deficiencies in Choice of Material
À Imperfections in the material
À Deficiencies in Processing
À Errors in Assembly / Poor Workmanship
À Improper Service Conditions
 What is Corrosion?

ÀDestruction or deterioration of a
material because of reaction with its
environment.
 Corrosion
Inadverten
d t Deliberate
lib
Desirable Desirable
Undesirable Undesirable
 Some common examples
of corrosion

À Steel → Rust Fe2O3.H2O → Inadvertent & undesirable

À Copper → Bronchantite CuSO4.3Cu(OH)2 → Inadvertent

& desirable

À Anodising & Chemical Milling → Deliberate & Desirable

 ELECTROCHEMICAL
ASPECTS OF CORROSION
AQUEOUS CORROSION

Characteristics of aqueous
electrochemical corrosion
M t l
Metal
Oxidation À Electrified interface between
metal/solution
À Transfer of p
positive charge
g
e-
from metal to solution
À Transfer of positive charge
from solution to metal
Reduction À Transfer of charge through
solution
À Transfer of charge
g through
g
metal
+
 ELECTROCHEMICAL
ASPECTS OF CORROSION
Common anodic and cathodic reactions

Anodic reaction : M Æ Mz+ + ze-

Cathodic reactions
a) H2 evolution : 2H+ + 2e- Æ H2
b) O2 reduction : O2 + 4H+ + 4e- Æ 2H2O (acidic)
c)) O2 reduction
d ti 4 - Æ 4OH- (neutral
: O2 + 2H2O + 4e ( t l / basic)
b i )
d) Metal ion redn. : Mz+ + e- Æ M(z-1)+
e) Metal deposition : Mz+ + ze- Æ M
 ELECTROCHEMICAL
ASPECTS OF CORROSION

Rusting of iron

Iron in water, pH=7

À Fe Æ Fe
F F 2+ + 2e
2 -
À O2 + 2H2O + 4e- Æ 4OH-
À 2Fe + 2H2O + O2 Æ Fe2+ + 4OH- Æ 2Fe(OH)2
À 2Fe(OH)2 + H2O + ½ O2 Æ 2Fe(OH)3
Polarization
 Polarisation

Polarisation is the phenomenon , while

Overpotential is the extent of deviation of the
polarised potential from the
reversible potential.

Reversible potential can be calculated using

NERNST Equation and requires the standard
potential.
 Polarisation
À Activation Overpotential
To help overcome activation energy barrier

À Concentration overpotential
because of difficulty in transport

À Resistance Polarisation
Electrode Kinetics
Passivation
Pourbiax Diagram

Simplified (domain) diagram of iron

TYPES OF CORROSION
 TYPES OF CORROSION
ATMOSPHERIC CORROSION

Atmospheric
p corrosion depends
p on
¾ Moisture present / relative humidity
¾ Dust
D st
¾ Other pollutants / gaseous impurities
 TYPES OF CORROSION
ATMOSPHERIC CORROSION

Factors Affecting Atmospheric Corrosion

À Time of Wetness
À Rain
À Dew
À Fog
À Dust
À T
Temperature
À Initial Exposure Conditions
À Shelteringg
À Wind Velocity
 TYPES OF CORROSION
ATMOSPHERIC CORROSION
Air (H20 + O2 + SO2 + SO3)

SO3 + H20 Fe2O3.H2O 2Fe2O3 + SO2 Æ FeSO4 +Fe3O4

Fe2O3.H2O (Red Rust)

H2SO4
Fe3O4 (Magnetite – Black) Fe(OH)2 + O2

2Fe(OH)2 FeSO4 + Fe2O3 + H2O Æ H2SO4 + Fe3O4

Fe(OH)2 (Green) + FeSO4
4OH- +2Fe2+

H+
Aqueous solution
Fe2+ + SO44-

Fe2+
2H2O + O2
Sulphate Nests
FeO Low pH

4e- Acid Pits

Fe

2e-
STEEL STEEL
 TYPES OF CORROSION
GALVANIC CORROSION
À Galvanic corrosion effects, result from
electrical connection of two corroding metals.
À Usually both steel and zinc corrode by
themselves; but when they are coupled zinc
corrodes and steel is protected.

À Environment: atmospheric moisture

À Distance : localized, close to junction

À Area : unfavourable area ratio consists of a

large cathode coupled to small anode

À Prevention:
– Metals
M t l close
l t th in
together i galvanic
l i series
i
– Avoiding unfavourable area contact
– Insulating dissimilar metals
– Coating – applying with caution
– U off inhibitors
Use i hibit
– Avoiding threaded joints
– Using readily replaceable anodic parts
– Installing a third metal – anodic to both
 TYPES OF CORROSION
PITTING & CREVICE CORROSION
 TYPES OF CORROSION
INTERGRANULAR CORROSION
À Localized attack at or adjacent to grain
boundaries,
b d i with
ith relatively
l ti l little
littl corrosion
i off
the grains
À IGC due to
– enrichment or depletion of one alloying
element
l t
– impurities at grain boundary
À Examples:
– small amounts of iron in aluminum
– austenitic stainless steel; AISI 304 type

À Sensitization : 500 – 800 °C( 940 - 1450 °F )

À Theory:

– Chromium depletion
– Formation
F i off Cr
C 23C6
– C content > 0.02% and Cr drops to <<
10%
À precipitates
 TYPES OF CORROSION
INTERGRANULAR CORROSION

À WELD DECAY
– Prevention:
• Solution quenching from
1100°C
• Stabilising with Ti or Cb
• Extra low carbon below
0.02%
À KNIFE LINE ATTACK
• 1300°C ---- Cb-C dissolves
& Cr-C dissolves
• 850°C ---- Cb-C precipitates
& Cr-C dissolves
• 500°C ---- Cr-C precipitates
 TYPES OF CORROSION
SELECTIVE LEACHING
À Most common example : dezincification of brass
À Alloy assumes red copper colour in place of original yellow
À Two
T o ttypes:
pes:
1. Uniform / layer type:
• Higher zinc content
• Acidic environment
2. Plug type:
• Lower zinc
i content
• Neutral environment
À Detrimental: Temperature and Stagnant conditions
À Mechanism:
– Zinc dissolves leaving vacant sites in brass lattice
– Brass dissolves; Zn stays in solution ; Cu plated back on
À Analysis of dezincified areas show 90 – 95% with some of it as oxide
À Prevention:
– Reducingg aggressiveness
gg of environment like removal of oxygen
yg
– Usage of a low susceptible alloy
– Cathodic protection
– 1% Sn with As, Sb to 70 – 30 brass

GRAPHITIC CORROSION
ƒ Grey cast iron
Dezincification
corrosion of an
Admiralty brass
exchanger
h ttube
b iin
cooling water service.
 TYPES OF CORROSION
EROSION CORROSION
a

À Metall
M
À Film
À Environment
À Relative Motion

À Erosion corrosion in pipe Source: Web

(http://www.bmsgroup.ca/qs/page/2830/0/)
 TYPES OF CORROSION
CAVITATION DAMAGE
À Formation and collapse of vapor bubbles. The collapse
can cause much damage due to change in pressure or
stress
À E.g. in impellers in turbine blades: collapse of vapor on
surface leads to breaking of oxide layer and formation
of cavity
À Common in systems where there is circulation of fluid
À The implosion or collapse of bubble causes huge
pressure changes (10,000 – 20,000psi)
À Prevention:
– There must not be anyy inhomogeneity
g y in ppressure ((which
causes vapor bubble formation)
– The surface must be very smooth, no cracks or scratches
on surface, which prevents nucleation of fresh bubbles
– Polymeric coatings which can absorb the impact of
explosion. Sometimes metallic coatings will peel off due
to impact of implosion, if adhesion is very low.
 TYPES OF CORROSION
FRETTING

À Removal of material from contact point of two surfaces, under load, due to small
oscillations occurring in them
– Occurs in body implants, railway tracks (at contact between rail and sleepers), in cars
wheels when they are transported in trucks.
À Mechanism of wear:
– Wear-oxidation
• 2 metallic surfaces in contact
• Cold welding occurs at high loads
• When sheared, high temperature present and wear debris are formed due to surface getting
sheared
• The wear debris, which are at high temperature, undergo oxidation
• Wear occurs first, then oxidation
– Oxidation-wear
• Two passivated materials are brought in contact
• On shearing, the oxide layers break and fall down
• The material may spontaneously repassivate
 TYPES OF CORROSION
ENVIRONMENT ASSISTED CRACKING

Stress Corrosion Cracking

Features common to SCC

1. Existence of a tensile stress either applied or present as a

residual stress.
stress
2. SCC for a given alloy usually occurs in a limited number
of specific environments.
3. The appearance of SCC is that of a brittle fracture in
spite
i off the
h fact
f that
h the h metall itself
i lf may still
ill be
b quite
i
ductile. Cracks frequently exhibit multiple branching.
Cracks may be intergranular, transgranular or a
mixture of both.
4. Pure metals exhibit greater resistance to SCC.
5. In order for SCC to occur a threshold stress must be
exceeded.
6
6. The onset of SCC is delayed and the rate of propagation
is retarded or stopped by the application of cathodic
protection.
À Chloride stress corrosion cracking
of a stainless steel buried pipeline

À Temperature operating from 60 to

100 deg C

À Service
S i timeti off 7 years

À Thermal and residual stresses

present in this component exposed
to seawater conditions induced
SCC
 TYPES OF CORROSION
HYDROGEN EMBRITTLEMENT
– Is an Environment Assisted Crackingg ((EAC)) and is similar to SCC
in the fact that both fail by brittle fashion and due to stress
– Normal amount of hydrogen = 10 ppm and embrittlement occurs
even att these
th low
l levels.
l l
– HE can be avoided because nascent hydrogen can diffuse out,
uunless
ess itt co
combines
b es to form
o molecular
o ecu a hydrogen
yd oge
• Baking: Heat treatment process which leads to difusing out of nascent
hydrogen
– Cathodic protection:
• Prevents SCC (since it is anodic dissolution)
• Aggravates HE (HER occurs)
• This is used to differentiate if the mechanism is HE or SCC
 TYPES OF CORROSION
HYDROGEN DAMAGE

À Hydrogen blistering Source: Web

((http://webwormcpt.blogspot.in/2007/09/high-temperature-hydrogen-
p p gp g p y g
attack-in.html)
À Hydrogen embrittlement Source: Web
(http://peswiki.com/energy/PowerPedia:Hydrogen_Embrittlement)
 TYPES OF CORROSION
CORROSION FATIGUE
• In a corrosive environment the stress level at which
it could be assumed a material has infinite life is
lowered or removed completely. Contrary to a pure
mechanical fatigue, there is no fatigue limit load in
corrosion-assisted fatigue.

• Corrosion fatigue belongs to this class. Much lower

failure stresses and much shorter failure times can
occur in a corrosive environment compared to the
situation where the alternating
g stress is in a non-
corrosive environment.

• The fatigue fracture is brittle and the cracks are most

often transgranular, as in SCC, but not branched.

• The picture shown here reveals a primary corrosion-

fatigue crack that in part has been widened by a
secondary corrosion reaction.

• The corrosive environment can cause a faster crack

growth and/or crack growth at a lower tension level
than in dry air.
 CORROSION PROTECTION

À 1) Selection of p
proper
p metal or alloy
y
À 2) Design
À 3) Alteration of environment
– Lowering temperature
temperature,
– Decreasing velocity
– Removing oxidizer
– Changing concentration
– Use of inhibitors
• i) adsorption type
• ii) hydrogen evolution poison
• iii) scavengers
• iv) oxidizers
• v) vapour – phase inhibitor
 CORROSION PROTECTION

À 4) Coatings
Metallic and inorganic coatings
• Hot dipping
• Electro and electroless deposition
• Metal spraying/Thermal spraying
™ Molten metal
™ Metal powder
™ Metal wire
™ Detonation
• Diffusion coatings
™ solid state diffusion
™ liquid (molten metal)
™ Gas phase
• Chemical conversion coating
• Claddingg
• Vapour deposition

Organic and paint coatings

À 5)Anodic & Cathodic Protection