Corrosion Basics: Dr. Deepashri D. Nage

CORROSION
BASICS
Dr. Deepashri D. Nage
 2010, Larsen & Toubro Limited FEB. 13, 2010

Visual testing , LEVEL II 1
Contents
 What is corrosion?
 Why does it occur?
 Various types
 Forms of corrosion
 2010, Larsen & Toubro Limited Visual Testing, LEVEL II FEB. 13, 2010 2
Illustrations
Corrosion
 Definition
 Significance
 Cost of corrosion
 Types
 Thermodynamics
 Kinetics
 Electrochemistry
 Electrochemical cell- Area effects, concentration,
galvanic, thermogalvanic, active passive.
Definition
 Corrosion is deterioration or degradation of the
material properties because of its reaction with
the environment.
 Interaction can be
 Electrochemical (aqueous)
 At high temperature (gaseous)
 Automobiles, boiler tubes, water pipes, erosion corrosion of
impellers, cavitation of condensate pipe, dezincification of brasses,
graphitization of cast iron exhaust etc.
Significance
 Economic
 Social
 Direct losses due to corrosion are more
than $400 billion in U.S. that include
domestic, industry and public
infrastructure.(3% of Gross national
production) reducing this cost increases
effective productivity.
 Over $375 billion/annum in U.S.A.
 ( $1,000 per U.S. Citizen)
Over Rs. 20,000/- crores p.a in India
Cost of corrosion
 Excessive maintenance/repair/replacement
 Lost production/downtime($500000 per shut
down for fossil fuel)
 Product contamination
 Loss of product
 Loss of efficiency - over sizing, excess energy
cost
 Accidents Insurance-social implication
 Environmental clean up fines
Eiffel Tower (Paris)
1989 refurbishment costs of 200 million FF.
About 50-60 tons of paint is applied every 7 years
by some 25 painters, as corrosion protection for
the > 7 thousand ton steel structure
Statue of Liberty (USA))

> $200 million restoration project necessitated
largely due to significant internal
galvanic corrosion damage.
 2010, Larsen & Toubro Limited Visual Testing, LEVEL II FEB. 13, 2010
Indirect consequences
 Safety
 Structural collapse
 Leaks
 Product contamination (food water
pharmaceuticals)
 Customer confidence (automobile)
 Appearance
 Increased regulations.
Why does corrosion occur
 Every system tend to reduce energy and
get back to its low energy state.
 E=E0-RT/nF ln(reaction product/reactants)
 Potential –pH diagrams-stability of
corrosion products, possibility of corrosion
and its prevention.
 Kinetics-potential vs. current. (dynamics,
rates)
 Heat
 Electrical flow
Natural Cycle
ORE
REFINING
FINISHED
PRODUCT
FABRICATION PROCESSING
Causes of Corrosion
Contamination Instrumentation Design

Human Error 8% 2%
20%
10%
Mal-operation
12%
Wrong
Unforeseen Condition Selection
Material Faults 19%
18%
11%
13  2010, Larsen & Toubro Limited Visual Testing, LEVEL II FEB. 13, 2010
Types of corrosion
 AQUEOUS / WET and DRY
 Liquid
 pH, temperature, pressure, flow etc.
 Atmospheric
 Marine
 Industrial
 Rural
 Tropical
 indoor
 Underground
 High temperature
Mechanism-Electrochemical process
 Exchange of electrons at separate sites
Components of corrosion cell:
 Electrolyte
 Electron flow through the metal path
 Oxidation occurs on anode
 Reduction on cathode
Schematic of aqueous corrosion
Cathodic reactions (reduction)

O2 + 2H2O + 4e- 4OH- - Oxygen reduction
2H2O + 2e- H2 + 2OH- - Hydrogen reduction
Electrochemical process
Evans diagram and typical plot
exhibiting passivity
Measures to control corrosion
 Design
 Material selection
 Environment modification
 Cathodic protection/anodic protection
 Protective coatings/ Surface treatment
Forms of corrosion
 General/uniform  Environmental induced
corrosion cracking
 Localized  Stress corrosion cracking
 Pitting  Hydrogen induced cracking
 Crevice  Liquid metal embrittlement
 Filliform  Corrosion fatigue
 Galvanic  Flow assisted corrosion
 Intergranular cracking  Cavitation
 Dealloying  Impingement
 Erosion
 Fretting
 High temperature
corrosion
Schematic of common forms of corrosion
General or uniform corrosion
 Uniform thinning of the material when
exposed to environment by
electrochemical action (local anodes and
cathodes-composition, orientation diff.)
 Occur due to misapplying materials in
corrosive environment.
General Corrosion
 Manifestation:
 Thinning
 Roughening of surface
 Corrosion product may or may not be present.
(depending on the flow)
Predictability/Measurement
 It is predictable and is measured in terms of
penetration rates (mm/yr or mils/yr)
 Weight loss measurements
 In field by thickness measurements
 Proper design, inhibition protective coating and

Cathodic protection can be a measure for
mitigation.
Atmospheric corrosion
Corrosion Map of India
Localized corrosion
 Occurs at discrete concentrated sites
leaving surrounding unattacked.
 3 types of localized corrosion

 Pitting
 Crevice
 Filliform
Pitting corrosion
 A deep narrow corrosive attack which
often causes rapid penetration of the
substrate thickness.
 Characterized by local pit with unattacked
surrounding.
 It can initiate in statistical manner on open
surface or at random imperfection where
protective surface ruptures.
Mechanism
 Local cell is set up between pit inside and
external surface (cathode).
 Interior has hydrolyzed salts and acid

formed. Autocatalytic in nature.
Autocatalytic process of pitting
•Initiation
(incubation)
•Propagation
•Termination
•Reinitiation.
Pit morphology
Videoscopic image
Photographs of pitting corrosion
Predictability/Measurement of pits
 Depth of pit is measured by calibrated
microscopy (statistically distributed)
 Dial gauge with needle probe
 Metallographic sectioning
 Rooting
 Criteria
 Deepest pit
 Avg. pit (10 pits)
 Number of pits per unit area.
Occurrence in various alloys.
 In Al occurs due to presence of Cl, Cu, Pb
or Hg ions eg. Cooling water, manometers
break.
 S.S. in chlorides
 Ni rarely occur
 Cu in hot oxygenated water CO2, CO,
Ammonia, Fe and sulphides contaminants.
 Pb used as external shield in underground
cables pit by stray currents.
Pitting Resistance Equivalent
Number
 Depending in alloying elements the number
or an index can be given to various alloys.
 Higher the number better is the localized
corrosion resistance.
 PREN = %Cr + 3.3% Mo + 16% N.
Effect of chloride and pH
PREN
 74.5
 45.7
 27.3
 27.3
 18
Crevice corrosion
 It is a form of corrosion in
which site of attack is
area where free access to
surrounding is restricted
(shielded area).
 A concentration cell
 Occur at metal to metal or
non-metal, under deposit
or corrosion product.
 Caused due to
 differential aeration
(Oxygen concentration)
 Concentration of metal ion
Occurrence
 Threaded fasteners
 Coupling/joints
 Under gasket
(poultice attack)
 Al in marine, S.S. , Ni
Ti in brine, Zr due to
Fe+3 and Cu++ ions.
Crevice corrosion of bolt
Crevice corrosion susceptibility for
different crevice gap and chloride
content.
Critical Pitting Temperature and Critical
Crevice Temperature for Stainless Steels
Alloy PREN Critical Pitting Critical Crevice

Temperature, Deg. Temperature, Deg. C
C
904L SS 35 30 18
2205 Duplex SS 35 30 18
2507 Duplex SS 41 80 ( welds = 50 ) 50
SMO 254 60 80 ( welds = 50 ) 50
Filliform Corrosion
 Special form of oxygen
cell corrosion occurring
beneath organic or
metallic coatings on the
material surface.
 Network of threads.
 At humidities >60%
 Potential difference bt’
advancing head and
trailing end.
Proper cleaning surface preparation and decrease in
humidity.
Galvanic corrosion
 Bimetallic or Two metal
corrosion due to difference in
their potential.
 Direct electrical contact
(physical or external) in
presence of corrosive media.
 More reactive metal becomes
anode and corrodes faster.
 More noble metal becomes
cathode and its corrosion
slows down or even stops.
MAGNESIUM
ZINC Anodic or reactive
ALUMINUM (PURE)
CADMIUM
Galvanic Series is a list of metals
ALUMINUM ALLOYS
MILD STEEL AND IRON and alloys ranked in order of their
UN-PASSIVATED STAINLESS tendency to corrode in that specific
STEELS environment. Predicts galvanic
LEAD-TIN SOLDERS corrosion
LEAD
TIN
UN-PASSIVATED NICKEL ALLOYS
BRASS
COPPER
GALVANIC
BRONZE
SILVER SOLDER
PASSIVATED NICKEL ALLOYS
SERIES IN SEA
PASSIVATED STAINLESS STEELS
SILVER
TITANIUM
WATER
GRAPHITE
GOLD
PLATINUM
Cathodic or noble
Major factors governing severity of
galvanic corrosion
 Potential difference
 Spatial effects of area, geometry, sharp edges
 Nature of environment (resistivity) concentration
and composition
 Shift in potential of coupled materials.
 Temperature
 Agitation
 Metallurgical conditions
 Surface conditions
C.S. nipple in Stainless steel
Measurements
 Model the couple
 Measure the current flow
With zero effective resistance
Ammeter
 Corrosion rates in
Uncoupled materials.
Control:
Material selection close in galvanic series, avoid
unfavourable area ratio, isolate, inhibition, Barrier
coating, replaceable anodes, 3rd metal anodic to both,
nobel metal for fasteners.
Advantages of galvanic couples
 Cathodic protection.
 Batteries
 Cleaning of silver articles in Al vessel with
baking soda.
Intergranular corrosion (IGC)
 Preferential attack at or adjacent to the grain boundaries
leaving the surrounding unattacked or relatively little
corrosion.
 This is localized attack with loss of grain boundary
material.
 G.B. (high strain energy misalignment of atoms) is
anodic w.r.t. surrounding.
- impurities or precipitation at grain boundaries,
- enrichment or depletion of one of the alloying
elements at grain boundary areas.
Ni-Cu alloys in HF & chromic acids
Ni-Mo and Ni-Cr alloys suffer IGA.
Schematic of IGA
The areas adjacent to precipitates are depleted of chromium

and is attacked in certain corrosive environments.
Precipitation reaction
SOLUTIONIZING Titanium and Chromium in solution
1150’C
STABILIZATION Titanium carbide precipitation
870’C
760’C
SENSITIZATION Chromium carbide precipitation
425’C
No reaction
Manifestation
 Sensitization, Weld decay and knife line
attack.
Oxalic acid test results
DUAL STRUCTURE
STEP STRUCTURE DITCH STRUCTURE
Control or prevent IGA
 Avoid heating in sensitization range

 Low Carbon S.S.
 Use of stabilized grades of stainless steels
and Stabilization treatment.
Exfoliation in Al alloys
 IGA in Al alloys is called exfoliation.
 Parallel to rolling direction.
Addtion of Mg and Cu retards exfoliation.

Solution heat treatment at ~4900C and
water quench.
Dealloying
 Selective removal of one constituent of an
alloy leaving altered residual sponge like
(plug) structure. Also referred as
‘pseudomorph’
Dezincification of
admiralty brass.
Dealloying
 1st reported in 1866 as dezincification of
brasses.
 Graphitic corrosion in C.I. (can be
scrapped by knife)
Dezincification
(brasses)
Destanification(phosph
or bronze)
Denickelification
Dealuminification (Al
bronze)
Characteristics and identification
 Change in color (yellow to red), (silvery grey to grey in
C.I.)
 Change in Mechanical strength.
 Automated inspection
 Metallography
 X-ray
 SEM
 1st reported in 1866 as dezincification of brasses.
 Graphitic corrosion in C.I. (can be scrapped by knife)
Prevention of Dealloying
 Inhibited brasses (Sn/As/P)
 Ni-resist over Grey C.I.
 Nodular or malleable C.I.
over Grey C.I.
 Coating –barrier
 Cathodic Protection
 Design: reduce hot
wall effect.
Environmental induced cracking
 Occurs rapidly catastrophically a brittle
failure of an otherwise ductile material
resulting from combined action of
corrosion and tensile stress.
 Recognization
 Tight cracks at right angle to maximum
direction of tensile stress
 Single or multiple cracks.
 Usually clean surface
 Intergranular or transgranular.
Types of environmental induced
cracking
 Stress Corrosion cracking
 Hydrogen induced cracking
 Liquid metal embrittlement
 Corrosion fatigue
 Factors contributing to EAC: Alloy composition,

structure, tensile stress, Environment,
Temperature, corrosion potential
Stress Corrosion Cracking
 Synergistic effect of tensile stress, susceptible
microstructure and specific corrosive
environment.
 Specific metal/environment combination
 SS/Cl
 Brass/Ammonia
 Steel/ Caustic.
 Ferritic in caustic and oxidizing,
 Ni in HF and hydroclurosilicic acid,
 Ti in chloride at 2750C, 10% HCl, NO3, Methanol,
 Steam silicon bronze
Requisites for SCC
IGA
Susceptible Aggressive
environment Susceptible Aggressive
structure environment
structure
Stress Mechanical Stress

SCC
Commonly recognized SCC
 Season cracking of cartridge due to
ammonical environment.
 Caustic embrittlement of steels-boilers.
 Temperature
 Composition
 Stress
 Structure
Illustrations
Intergranular SCC of SCC in 316 SS

inconel H.E. tube
Process
 Incubation
 Origination at microscopic level
 Self arresting crack to large extent
 Typical multibranched SCC.
Relative SCC behavior of major
A.S.S. in boiling MgCl solution
Influence of chloride and oxygen concentration
on SCC behaviour of SS304 in 3000C water
SCC resistance of various stainless steels
Mitigation of SCC
 Lowering the stress

 Eliminate Critical species
 Material-environment selection
 Cathodic protection
 Inhibitors (phosphates)
 Coating
 Shot-peening
Hydrogen induced cracking and
SSC
Combined action of tensile strength and
hydrogen in metal.
 Atomic hydrogen absorbed by metal
(corrosion reaction) producing
embrittlement.
 Hydrogen poisons: cyanides, Arsenic,
Antimony, phosphide, sulphides.
 Presence of sulphides suppresses
Hydrogen evolution- SSC.
 CP aggravates the process.
 eg. Scrubbers, waste water treatment.
a. Blistering
b. Stepwise cracking
c. SSC
d. In high strength steels
Mechanism
Factors affecting HIC and control
measures  Baking of pickled
 Hydrogen components.
concentration  Baking of the welding
 Strength levels electrodes.
 Cold work  Susceptible alloys:
 Temperature  Ferritic, martensitic,
Mn bronze in ship
propellers, Ti, Zr etc.
Liquid metal embrittlement
 Decrease in ductility of metal or alloy as a
results of contact with liquid metal.
 Not time dependent, cracks immediately upon
application of stress when wetted by liquids.
 Gallium, Hg, In, Sn embrittles Al alloys

 Zn –C. Steel
 Zn, Al, Cd for S.S.
 Hg, Bi, Li for Cu alloys
 Hg for Ti
 Sulphides in Ni
 Na, Zn for Mg alloys.
Cu embrittlement of carbon steel at 11000C
Corrosion fatigue
 Combined action of the cyclic stress and a
corrosive environment leading to
premature failure at low cycles.
 Petroleum industry encounters major trouble
with corrosion fatigue-drill pies, sucker rods to
bore crude.
 Cu alloys with Be and P Al bronze, Ti in aircraft,

Cu-Ni in springs switches, diaphragms, bellows
automobiles, aircraft gasoline lines, tubes of
condensers, heat exchangers
Effect of notch on the corrosion
fatigue behaviour of 13 Cr steel
50Hz, 230C
Measures to mitigate Corrosion
fatigue
 Material selection (Cr,
Mo increases fatigue
limit)
 Coatings
 Inhibition
 Reduction in stress
Flow assisted corrosion
 Attack due to flow of substance.
 Affected surface may be stationary or moving
e.g. valve seat and impeller, propeller.
 Turbulance in flow due to aberrations.
 Ripples, directional features, craters due to
plastic flow.
 Types
 Erosion corrosion
 Impingement
 Cavitation
Erosion corrosion
Erosion corrosion Pump rotor

inside a pipe destroyed by
erosion corrosion
Impingement corrosion
 Mechanical wear of the surface
film produce grooving.
 Entrained bubbles accelerate
action of suspended solids
 Observed in pumps, Valves
elbows, tees of heat exchanger
tubes, jets steam turbines, rotor
blades, separators, cyclones
etc
 Remedy :CP at inlet, Ni resist
alloy, increase in line size.
Cavitation
 Mechanical damage caused by collapsing
bubbles (high forces of 700,000KPa
(100,000psi) in flowing liquids.
 Characterized by deep aligned pits.
 Bubbles form in low pressure and move to high

pressure collapsing forming high pressure
waves in liquid, rupturing protective film and
process repeats.
 Control: Inhibition, CP and coating can control
cavitation.
Schematic of Cavitation corrosion
Cavitation of the valve in desulphurization plant
Solution/Remedy to combat FAC
 Reduce the velocity
 Design
 Limiting velocity:
 Al– 0.75m/s
 C.S. – 1m/s
 S.S. & Ni alloys stagnancy is undesirable.
 Cu – 2-4m/s.
Fretting/ Friction wear oxidation
 Deterioration of metal caused by repetitive slip at
interface due to relative motion of two surfaces
in contact.
 Burnished appearance.
 Galling, seizing then fatigue then cracking.
 Effects: loosening of rivets bolts, destruction of

bearing surface.
 Control: Use of different materials at interface,

lubrication, decrease the load at bearing surface
and increase in relative motion.
Fretting corrosion at heavily loaded surfaces
Corrosion fatigue/Fretting
High temperature corrosion
 Direct chemical reaction with specific
environment at certain temperature that
deteriorate material properties.
 Oxygen, H2O, S, Hydrogen.
 Temperature ~ 30-40% M.P.
 Mg &Al alloys 2040C

 Fe and Steel 4260C
 S.S. 425-8700C
 Ti 3150C.
Various forms of high temperature corrosion
 Oxidation (Si, Cu, Cr reduces internal oxidation)

 Sulfidation
 Carburization (Alternate oxidizing and reducing
atmosphere exposure). Also called Metal dusting.
 Decarburization (Hydrogen effect)
 Halide effect Volatile oxides when reach vapor pressure
Cl attacks)
 Molten phase formation (Gasoline, sea salt in turbines,
welding slag, V2O5).
 Effects: internal swelling, spalling.
Mod. Mc Conomy curves showing effect of temperature on steels.
Metal dusting of 304H Stainless
steel pipe.
High temperature Hydrogen
attack
 Decarburization as methane is
formed locally at the impurity
or void in material.
 Steam or methane pressure
increases locally resulting in
blisters which rupture.
 It is irreversible reaction.
 Cr, Mo addition, clean steels

shall be selected.
API 941-operating limits for steel in hydrogen service
Microbial Induced Corrosion
 Biological activity in a
relatively low velocity
fluids form tubercules
on the surface.
 Underneath the
corrosion product
balloon shaped pits
are formed.
Sea water corrosion
 MARINE ATMOSPHERIC CORROSION
 Corrosion of steel on a sea coast is 400 to 500
times greater than it is in a desert.
 Steel specimens 80 feet from a coast corroded
12 times faster than those 800 feet away.
 Salt is the chief contaminant.
Sheltered corrosion as it occurs in an area

where moisture condenses or accumulates and
does not dry out for long periods of time.
Corrosion of steel in sea water.
Summary
 Corrosion is an unavoidable natural mechanism.
 It is significant economic and social point of view.
 Awareness of the corrosion losses.
 Every corrosion is unique of its own
 Recognize the manifestation of corrosion forms.
 Measures to control corrosion followed based on type of
corrosion.
 It can be controlled by proper material selection, design,
control environmental parameters, provide barriers,
inhibition.
Thank you

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CORROSION

Dr. Deepashri D. Nage

 2010, Larsen & Toubro Limited FEB. 13, 2010

Statue of Liberty (USA))

Contamination Instrumentation Design

Cathodic reactions (reduction)

 Proper design, inhibition protective coating and

Corrosion Map of India

 3 types of localized corrosion

 Interior has hydrolyzed salts and acid

 Number of pits per unit area.

 PREN = %Cr + 3.3% Mo + 16% N.

Alloy PREN Critical Pitting Critical Crevice

The areas adjacent to precipitates are depleted of chromium

SOLUTIONIZING Titanium and Chromium in solution

STEP STRUCTURE DITCH STRUCTURE

 Avoid heating in sensitization range

Addtion of Mg and Cu retards exfoliation.

 Factors contributing to EAC: Alloy composition,

Stress Mechanical Stress

Intergranular SCC of SCC in 316 SS

 Lowering the stress

 eg. Scrubbers, waste water treatment.

 Gallium, Hg, In, Sn embrittles Al alloys

 Cu alloys with Be and P Al bronze, Ti in aircraft,

Erosion corrosion Pump rotor

 Bubbles form in low pressure and move to high

 Effects: loosening of rivets bolts, destruction of

 Control: Use of different materials at interface,

 Mg &Al alloys 2040C

 Oxidation (Si, Cu, Cr reduces internal oxidation)

 Effects: internal swelling, spalling.

 Cr, Mo addition, clean steels

Sheltered corrosion as it occurs in an area

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