CORROSION AND ITS CONTROL
Module 4 /Dr R Jeyalakshmi
CORROSION
CLASSIFICATION OF CORROSION
THEORIES OF CORROSION
CAUSES OF CORROSION
TYPES OF CORROSION
FACTORS INFLUENCING CORROSION
CORROSION AND ITS CONTROL
ELECTRODE POTENTIAL
• A metal (M) consists of metal ions (Mn+) with
the valence electrons that binds them
together.
• If a metal is in contact with a solution of its
own salt, the positive ions in the metal comes
into equilibrium with those in the solution,
leaving behind equivalent number of
electrons on the metal.
• Thus the metal acquires a negative charge,
since it is now left with excess of electrons
and lesser number of metallic positive ions .
• When the metal is placed in the solution of its salt, the
chemical reaction takes place.
Positive metallic ions passing into solution
M → Mn + + ne −
Positive ions depositing on the metal electrode
Mn + + ne − → M
• dynamic equilibrium is established between the positive
(negative) charge of the metal with negative (positive)
charges in the solution. This is known as Helmholtz
electrical double layer.
Electrodes
Single electrode potential of Zn and Cu
The potential difference for an electrode and solution
of unit activity is known as standard electrode
potential.
NERNST EQUATION
The expression for electrode potential considering
general redox reaction
M n+ + n − M
G 0 = − nFE
G 0 = − nFE 0
RT A product
E=E + 0
in
nF A reac tan t
2+ −
Zn = Zn + 2e
RT ( M n+ )
E=E − 0
in M
nF
EM = E M 0
E = Electrode potential
E 0 = S tan dard electrode potential
Corrosion thermodynamics
Electrochemical series
•The elements are arranged according to
their standard electrode potential – series is
called electrochemical series .
Provides information regarding chemical
reactivity of metals
Galvanic Series
Information about corrosion behaviour in a
particular set of environmental conditions.
STANDARD OXIDATION REDUCTION EDOX)POTENTIALS AT 25 0C
K K+ + e - 2.92 Active
Na Na+ + e - 2.71
Mg Mg2 = 2 e - 2.38
Al Al3++ 3 e -1.66
Zn Zn2+ + 2 e -0.763
Cr Cr 3+ + 3 e -0.71
Fe Fe2+ + 2 e -0.44
Cd Cd2 + 2e -0.402
Co Co2 + 2e -0.27
Ni Ni2 + 2e -0.23
Sn Sn2+ + 2e -0.14
Pb Pb2+ + 2e -0.126
2H+ + 2e H2 0.000 – Ref.
Sn4+ + 2 e Sn2+ 0.154
Cu Cu2+ + 2e 0.34
O2 + 2H2O + 4 e 4 OH- 0.401
Fe3++e Fe2+ 0.771
2Hg Hg2+ + 2e 0.798
Ag Ag+ + e 0.799
Pd Pd2+ + 2 e 0.83
O2 + 4H++ e 2H2O 1.23
Pt Pt2+ + 2e 1.20
Au Au3+ + 3e 1.42 Noble
GALVANIC POTENTIAL SERIES FOR METALS IN SEAWATER vs. SCE
Magnesium -1.48 V
Zinc - 1.03 V
Aluminium - 0.79 V
More Active
Wrought iron and carbon steel -0.61 V
Cast Iron -0.61 V
Stainless Steel Type 400 AISI (17% Cr) -0.57 V
Stainless Steel type 304 AISI (18% Gr, 18% Ni) -0.53 V
Rolled brass -0.40 V
Copper -0.36 V
Aluminium brass -0.32 V
Less Active
Nickel -0.20 V
Titanium -0.15 V
Silver -0.13 V
Graphite 0.25 V
Platinum 0.26 V
CORROSION
DEFINITION
Deterioration or transformation of substances
by chemical or electrochemical reaction with
their environments.
– STEEL EXPOSED AIR + MOISTURE
– COPPER EXPOSED TO ATMOSPHERE
IMPORTANCE OF CORROSION
ECONOMIC AND SOCIAL LOSSES
DIRECT:
- REPLACEMENT OF CORRODED EQUIPMENT
- LABOUR CHARGES,
- MATERIAL CHARGES
- PREVENTIVE MAINTENANCE
INDIRECT
• SHUT DOWN
• PRODUCT CONTAMINATION
• LOSS OF EFFICIENCY
• OVER DESIGN
HUMAN SAFETY
CONSERVATION OF RESOURCES
DIMENSIONS OF CORROSION
PROBLEMS
Corrosion is an
important factor in
– chemical plant
– Storage tank
– Pipelines carrying
oil, gas, water, etc.,
•
• Civil Engineers find
that a number of
bridges and buildings
begin to crack due to
corrosion of steel
used.
• Mechanical Engineers
find that steam, fuels
etc.,escape through
the corroded pipes,
reducing efficiency.
CLASSIFICATION OF CORROSION
• DRY CORROSION
Interaction of metal with dry gases at higher temperature.
• WET CORROSION
Interaction with aqueous media or electrolytes.
It involves flow of electrons between anodic and cathodic
areas.
– ANODE
– CATHODE
– ELECTROLYTIC CONDUTANCE
– ELECTRONIC CONDUCTANCE
Theories of Corrosion
• Oxidation corrosion
• Corrosion by other gases
• Electrochemical attack in the
presence of
• Acids – evolution of hydrogen
• Neutral – absorption of oxygen
• Concentration cell formation -
differential aeration condition.
CORROSION REACTIONS
ANODE:
Fe Fe 2+ + 2 e-
Zn Zn 2+ + 2 e-
Al Al 3+ + 3 e-
CATHODE:
2H+ + 2 e- H2
O2 + 4H + 4e- 2H2O
O2 + 2H2O + 4e- 4OH-
MORE THAN ONE ANODIC REACTION IS POSSIBLE
MORE THAN ONE CATHODIC REACTION IS POSSIBLE
Wet corrosion
Dry corrosion
CAUSES OF CORROSION
• SURFACE HETEROGENITY
• IMPURITIES, GRAINS AND GRAIN BOUNDARIES, CUT
EDGES
• ENVIRONMENTAL VARIATIONS
• INDUSTRIAL: H2S, NH3, SO2
• MARINE: SALT
• URBAN
• RURAL
Dissimilar soil corrosion cell
Low resistivity (anodic area) – Higher resistivity
Wet soil (anodic) – Drier soil
Clay – Silt
Dense soil – Loose soil
Alkaline soil – Neutral or acid soil
Pitting Corrosion
Paint / Coating flaws
Mill scale disruption
Points of impact or abrasion
Exposing bright metal
Differential aeration corrosion cell
Clay vs. silt or sand
Buried under ground vs. exposed above ground
Small anode / large cathode - corrosion
Rivets used to fasten structural members or plates
Bolts and nuts in pipe joints, valves, sleeves and other water works equipments
Crevice Corrosion
Crevices under bolt and rivet heads
Bolt holes
Under surface deposits
Corrosion cell by differential pH
Concrete vs. soil
Old pipe – new pipe corrosion cell
Corrosion
influences
Erosion Corrosion
FORMS OF CORROSION
UNIFORM CORROSION
UNIFORM CORROSION
PITTING CORROSION
UNIFORM CORROSION
STRESS CORROSION CRACKING
UNIFORM CORROSION
GALVANIC CORROSION
UNIFORM CORROSION
INTERGRANULAR CORROSION
UNIFORM CORROSION
CAVITATION CORROSION
UNIFORM CORROSION
DEZINCIFICATION
UNIFORM CORROSION
EROSION CORROSION
UNIFORM CORROSION
FRETTING CORROSION
CORROSION CONTROL
METHODS
CORROSION CONTROL MEASURES
• CORROSION – METAL SOLUTION
INTERFACE
• MODIFICATION OF THE METAL
• MODIFICATION OF THE ENVIRONMENT
• ELECTROCHEMICAL METHODS
• NON METALLIC MATERIALS FOR
CONSTRUCTIONS
INHIBITORS
• ACID INHIBITORS
• NEUTRAL
• ALKALINE
• VAPOUR PHASE
ACID INHIBITORS
• ACID PICKLING
• EFFECTIVE PREVENTION OF METAL DISSOLUTION
• NO OVER PICKLING
• NO DELAY IN PICKLYING
• EFFECTIVE AT LOW CONCENTRATION
• EFFECTIVE AT HIGH TEMPERATURE
• EFFECTIVE PREVENTION H2 UPTAKE
HCl
AMINES, ALDEHYDES,THIOUREA MERCAPTONS
ACID INHIBITORS
SCALE REMOVAL:
HCL 5-15% at 1800C
14%HCL 33-37% g/l
Hexamethylene tetramine
Oil and Gas well acidising:
propargyl alcohol
Cu2 I2
SULPHURIC ACID PICKLING BATH
OIL WELL ACIDIZATION
NEUTRAL INHIBITORS
Potable water
Industrial cooling water system
Automobile radiators
Refrigeration brines
Alkaline inhibitors
Vapour phase inhibitors
COOLING TOWER
PAINTS AND COATINGS
• MIXTURES OF PIGEMENTS WITH SYNTHETIC
RESINS PLUS SOLVENTS, PLASTICIZERS
• NATURALLY OCCURING ASPHALTIC
BITUMINOUS
• ALKYDS
• ACRYLICS – HOUSE. AUTOMOBILES
• BITUMINOUS – UNDERGROUND SERVICES
• CHLORINATED RUBBER- SPLASH ZONE
IMMERSION
• EPOXIES- RESISTANT TO ACID ALKALIES
• EPOXY ESTERS- RESISTANT TO MOISTURE
PAINTS AND COATINGS
• PHENOXIES
• POLYESTERS-HIGH BUILD BARRIERS
• URETHANE- ABRASION RESISTANCE,
GLOSS
• VINLYS- INDUSTRIES & MARINE
ENVIRONMENTS
• ZINC SILICATE- C.P TO SYSTEM
• NICKEL ELECTROPLATING/ ELECTROLESS
• CHROMIUM PLATING MOLTEN SALT
• METALLIZING- ZINC ALUMINIUM
• SPRAYING MOLTEN METAL
Phosphate Conversion Coating
Acrylic Coating
Chlorinated Rubber
Coating
Epoxy Coating
COATINGS FOR PIPELINES
• COAL TAR ENAMEL
• POLYETHYLENE TAPE COATINGS
• FUSION BONDED EPOXY
COATINGS
• THREE LAYER POLYOLEFIN
COATINGS
• CONCRETE WEIGHT COATINGS
PIPELINE COATINGS
METALLIC COATINGS
MODIFICATION OF THE METALS
CARBON STEEL
HIGH STRENGTH & LOW ALLOY STEELS:- C-0.19%, Mn
0.2- 0.5, P 0.07-0.16,Si- 0.75%, Cu 0.30- 0.50, Cr 0.50-
1.25, Ni 0.55%
STAINLESS STEEL 18.8 austenitic 304 (Nitric acid), 316
chloride
NICKEL ALLOYS - handling Dil. HCL,H2SO4,H3PO4
Nickel Copper alloys:-
Monel – H2SO4, H3PO4
Ni-Cr Iron alloys:-
Inconel Ni 16% Cr; 7% Fe – handling dry halogens
Incoloy 800 :-
20% Cr, 32% Ni, 46% Fe petroleum industries
Nickel chromium – Molybdenum iron copper alloys:-
Hastelloy G
Ni- 22%Cr,19%Fe,6.5% Mo and 2%Cu
Combination of sulphuric acids of halides SO2 scrubbing
systems
STAINLESS STEEL BALCONY
CUPRO-NICKEL
ALLOYS
ELECTROCHEMICAL
METHODS OF PROTECTION
• CATHODIC PROTECTION
• ANODIC PROTECTION
CATHODIC PROTECTION
SACRIFICIAL ANODE SYSTEM
• ZINC ALLOY ANODES
• MAGNESIUM ALLOY ANODES
• ALUMINIUM ALLOY ANODES
CATHODIC
PROTECTION
CATHODIC PROTECTION
IMPRESSED CURRENT SYSTEM
• DC SOURCE
• CABLES
• ANODES
– STEEL
– ALUMINIUM
– GRAPHITE
– MAGNETITE
– HIGH SILICON IRON
– LEAD
– PLATINISED TITANIUM
– PLATINISED NIOBIUM
– PLATINISED TANTALUM
- TITANIUM ANODES
ANODIC PROTECTION
• PASSIVATION
• EQUIPMENTS
– POTENTIOSTAT
– CATHODES
– REFERENCE ELECTRODES
ANODIC PROTECTION
NON-METALLIC MATERIALS
PVC, POLYTHENE
CORROSION PREVENTION
Source of corrosion Methods of detection Remedy
EXTERNAL CORROSION
Surface preparation Visual instrument Repair, recoat
Coating defects during Coating evaluation surveys Excavation repair cathodic
construction stone damage soil close interval potential protection
stress age determination surveys
disbonding
Contact with metal surface Close interval potential Increase current output
surveys install additional cathodic
protections
Third party damage Coating evaluation surveys,
close interval potential
surveys
Metal loss Intelligent pigging Repair
INTERNAL CORROSION
Corrosion product Corrosion coupons probes Inhibitors, internal lining
Ingress of oxygen Oxygen monitoring Oxygen scavengers
Microbiologically induced corrosion Analyze, culture growth Biocide
Metal loss Intelligent pigging caliper Repair or replace
pigging
Pourbaix diagram of
iron water solution
How to draw?
What is its importance?
Pourbaix diagram, contd.
The lines of the diagrams dividing different
zones of the equilibrium states are calculated
by the Nernst equation
0
E = E - (0.059/n)*lnCion
Where:
0
E - Standard electrode potential, V;
n - number of electrons transferred;
Cion - molar activity (concentration) of ions.
Pourbaix diagram
Pourbaix diagram
Pourbaix diagram reactions
Four types of reactions:
Independent of H+ ions (pH) and E (electrons):
Fe2+ + 2OH- ----------------------------------- Fe(OH)2
pH dependent and E independent:
Fe2+ + 2H2O------------------ Fe(OH)2 + 2H+
E dependent and pH independent:
Fe2+ Fe3+ + e-
E and pH dependent
2Fe2+ + 3H2O Fe2O3 + 6H+ + 2e-
18CYB101J-Chemistry 36
How to draw the diagram
See the you tube link
https://www.youtube.com/watch
?v=Twlj4Zun44k
Summary
What is corrosion?
What are the types of corrosion?
Corrosion potential/electrode
potential.
What are the different forms of
corrosion?
Electrode potential/thermodynamics
Pourbaix diagram of iron water
solution
