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 1576 Cr2O3 1045 Ti2O 853 Fe2O3 740 MgO 568 NiO 217 Cu2O 145 Ag2O 13 Au2O3 +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 0.41 Na2O 0.58 MgO 0.79 Al2O3 1.38 NiO 1.60 Cu2O 1.71 Cr2O3 Fe2O3 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

Oxide

Metal Cations

Oxidation occurs at air-oxide interface

Oxidation occurs at metal-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. H2O) 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

Standard potential at 25oC

System Noble end

Increasing propensity to dissolve

Potential in V +1.5 +0.80 +0.34 0.0 0.13 0.25 0.44

Au / Au3+ Ag / Ag+ Cu / Cu2+ H2 / H + Pb / Pb2+ Ni / Ni2+ Fe / Fe2+

Cr / Cr3+
Zn / Zn2+ Al / Al3+ Li / Li+

0.74
0.76 1.66 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 Marine Humid with other agents Corrosion rate of mild steel (mm / year) 0.001 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 Ni Cu Sn

More reactive
Brass 18-8 SS Active MS Al Zn

Active end Mg

Galvanic Cell

e flow

Anode Zn (0.76)

Cathode Cu (+0.34)

Zn Zn2+ + 2e oxidation

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

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

How can galvanic cells form?

 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

Vcathode

Potential (V)

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