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OXIDATION
CORROSION
PREVENTION AGAINST CORROSION
Oxidation
Oxide is the more stable than the metal (for most metals)
Oxidation rate becomes significant usually only at high temperatures
The nature of the oxide determines the rate of oxidation
Cr2O3
Ti2O
Fe2O3
MgO
NiO
Cu2O
Ag2O
Au2O3
1576
1045
853
740
568
217
145
13
+163
Na2O
MgO
Al2O3
NiO
Cu2O
Cr2O3
Fe2O3
0.41
0.58
0.79
1.38
1.60
1.71
2.03
2.16
Oxygen anions
Oxidation occurs
at metal-oxide
interface
Oxide
Metal Cations
Oxidation occurs
at air-oxide
interface
Metal
Schottky defect
Pair of anion and cation vacancies
E.g. Alkali halides
Alloying of Fe with Cr
A protective Cr2O3 layer forms on the surface of Fe
(Cr2O3) = 0.001 (Fe2O3)
Upto 10 % Cr alloyed steel is used in oil refinery components
Cr > 12% stainless steels oxidation resistance upto 1000oC
turbine blades, furnace parts, valves for IC engines
Cr > 17% oxidation resistance above 1000oC
18-8 stainless steel (18%Cr, 8%Ni) excellent corrosion resistance
Kanthal (24% Cr, 5.5%Al, 2%Co) furnace windings (1300oC)
Other oxidation resistant alloys
Nichrome (80%Ni, 20%Cr) excellent oxidation resistance
Inconel (76%Ni, 16%Cr, 7%Fe)
Corrosion
THE ELECTRODE POTENTIAL
When an electrode (e.g. Fe) is immersed in a solvent (e.g. H 2O) some metal ions
leave the electrode and ve charge builds up in the electrode
The solvent becomes +ve and the opposing electrical layers lead to a dynamic
equilibrium wherein there is no further (net) dissolution of the electrode
The potential developed by the electrode in equilibrium is a property of the
metal of electrode the electrode potential
The electrode potential is measured with the electrode in contact with a solution
containing an unit concentration of the ions of the same metal with the standard
hydrogen electrode as the counter electrode (whose potential is taken to be zero)
Metal
-ve ions
+ve
System
Potential in V
Noble end
Au / Au3+
+1.5
Ag / Ag+
+0.80
Cu / Cu2+
+0.34
H2 / H +
0.0
Pb / Pb2+
0.13
Ni / Ni2+
0.25
Fe / Fe2+
0.44
Cr / Cr3+
0.74
Zn / Zn2+
0.76
Al / Al3+
1.66
Li / Li+
3.05
Active end
Alloys used in service are complex and so are the electrolytes (difficult to
define in terms of M+) (the environment provides the electrolyte
Environment
Dry
0.001
Marine
0.02
0.2
Metals and alloys are arranged in a qualitative scale which gives a measure
of the tendency to corrode The Galvanic Series
Galvanic series
Galvanic series in marine water
Noble end
18-8 SS
Passive
Active end
More reactive
Ni
Cu
Sn
Brass
18-8
SS
Active
MS
Al
Zn
Mg
Galvanic Cell
e flow
Anode
Zn
(0.76)
Zn Zn2+ + 2e
oxidation
Cathode
Cu
(+0.34)
Cu2+ + 2e Cu
Reduction
or
2H+ + 2e H2
or
O2 + 2H2O + 4e 4OH
Anodic/cathodic electrodes
Anodic/cathodic phases at the
microstructural level
Different phases (even of the same metal) can form a galvanic couple at the
microstructural level (In steel Cementite is noble as compared to Ferrite)
Galvanic cell may be set up due to concentration differences of the metal ion in the
electrolyte A concentration cell
Metal ion deficient anodic
Metal ion excess cathodic
A concentration cell can form due to differences in oxygen concentration
Oxygen deficient region anodic
O2 + 2H2O + 4e 4OH
Oxygen rich region
cathodic
A galvanic cell can form due to different residual stresses in the same metal
Stressed region more active anodic
Stress free region
cathodic
Polarization
Anodic and Cathodic reactions lead to concentration differences near the
electrodes
This leads to variation in cathode and anode potentials (towards each other)
Polarization
Potential (V)
Vcathode
Vcathode
Current (I)
Passivation
Iron dissolves in dilute nitric acid, but not in concentrated nitric acid
The concentrated acid oxidizes the surface of iron and produces a thin protective
oxide layer (dilute acid is not able to do so)
potential of a metal electrode in current density (I/A)
On current density reaching a critical value fall in current density
(then remains constant) Passivation
Prevention of Corrosion
Basic goal protect the metal avoid localized corrosion
When possible chose a nobler metal
Avoid electrical / physical contact between metals with very different electrode
potentials (avoid formation of a galvanic couple)
If dissimilar metals are in contact make sure that the anodic metal has a larger
surface area / volume
In case of microstructural level galvanic couple, try to use a course
microstructure (where possible) to reduce number of galvanic cells formed
Modify the base metal by alloying
Protect the surface by various means
Modify the fluid in contact with the metal
Remove a cathodic reactant (e.g. water)
Add inhibitors which from a protective layer
Cathodic protection
Use a sacrificial anode (as a coating or in electrical contact)
Use an external DC source in connection with a inert/expendable electrode