CORROSION

OXIDATION
CORROSION
PREVENTION AGAINST CORROSION

Principles and Prevention of Corrosion

D.A. Jones
Prentice-Hall, Englewood-Cliffs (1996)

Attack of Environment on Materials

Metals get oxidized
Polymers react with oxygen and degrade
Ceramic refractories may dissolved in contact with molten materials
Materials may undergo irradiation damage

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

Free energy of formation for some metal oxides at 25oC (KJ/mole)

Al2O3

Cr2O3

Ti2O

Fe2O3

MgO

NiO

Cu2O

Ag2O

Au2O3

1576

1045

853

740

568

217

145

13

+163

 For good oxidation resistance the oxide should be adherent to the

surface
Adherence of the oxide
= f(the volume of the oxide formed :
the volume of metal consumed in the oxidation)
= f(Pilling-Bedworth ratio)
PB < 1 tensile stresses in oxide film brittle oxide cracks
PB > 1 compressive stresses in oxide film uniformly cover metal
surface and is protective
PB >> 1 too much compressive stresses in oxide film oxide cracks
Pilling-Bedworth ratio for some oxides
K2O

Na2O

MgO

Al2O3

NiO

Cu2O

Cr2O3

Fe2O3

0.41

0.58

0.79

1.38

1.60

1.71

2.03

2.16

 If the metal is subjected to alternate heating and cooling cycles

the relative thermal expansion of the oxide vs metal determines the
stability of the oxide layer
Oxides are prone to thermal spalling and can crack on rapid heating or
cooling
If the oxide layer is volatile (e.g. Mo and W at high temperatures)
no protection

Progress of oxidation after forming the oxide layer: diffusion controlled

activation energy for oxidation is activation energy for diffusion through
the oxide layer

Oxygen anions

Oxidation occurs
at metal-oxide
interface

Oxide

Metal Cations

Oxidation occurs
at air-oxide
interface

Metal

Diffusivity = f(nature of the oxide layer, defect structure of the oxide)

If PB >> 1 and reaction occurs at the M-O interface expansion cannot
be accommodated

Oxidation resistant materials

As oxidation of most metals cannot be avoided the key is to form a
protective oxide layer on the surface
The oxide layer should offer a high resistance to the diffusion of the species
controlling the oxidation
The electrical conductivity of the oxide is a measure of the diffusivity of the
ions (a stoichiometric oxide will have a low diffusivity)
Alloying the base metal can improve the oxidation resistance
E.g. the oxidation resistance of Fe can be improved by alloying with
Cr, Al, Ni
Al, Ti have a protective oxide film and usually do not need any alloying

Diffusion in Ionic crystals

Schottky and Frenkel defects (defects in thermal equilibrium) assist the
diffusion process
If Frenkel defects dominate the cation interstitial of the Frenkel defect
carries the diffusion flux
If Schottky defects dominate the cation vacancy carries the diffusion
flux
Other defects in ionic crystals impurities and off-stoichiometry
Cd2+ in NaCl crystal generates a cation vacancy s diffusivity
Non-stoichiometric ZnO Excess Zn2+ diffusivity of Zn2+
Non-stoichiometric FeO cation vacancies diffusivity of Fe2+
Electrical conductivity Diffusivity
Frenkel defect
Cation (being smaller get
displaced to interstitial voids
E.g. AgI, CaF2

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

Standard electrode potential of metals

System

Potential in V

Noble end

Au / Au3+

+1.5

Increasing propensity to dissolve

Standard potential at 25oC

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

Corrosion rate of mild steel (mm / year)

Dry

0.001

Marine

0.02

Humid with other agents

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

Zn will corrode at the expense of Cu

or
2H+ + 2e H2
or
O2 + 2H2O + 4e 4OH

Anodic/cathodic electrodes
Anodic/cathodic phases at the
microstructural level

How can galvanic cells form?

Differences in the concentration of the

Metal ion
Differences in the concentration of
oxygen
Difference in the residual stress levels

 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

IR drop through the electrolyte

Vcathode

Steady state current

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