The Corrosion Current and Polarization

 To protect metals from corrosion we wish to make current

as small as possible
 A change in the potential of an anode or cathode which in
turn affects the current in the cell is called polarization
 Three Types of Polarization:
 Activation Polarization
 It is related to the energy required to cause the anode or
cathode reactions to occur
 If we can increase the degree of polarization, these reactions
occur with great difficulty and the rate of corrosion is
reduced.
 Small differences in composition and structure in the anode
and cathode materials dramatically change the activation
polarization.
 Segregation effects in the electrodes cause the activation
polarization to vary from one location to another
 Concentration Polarization
 After corrosion begins, the concentration of ions at the
anode or cathode surface may change.
 A higher concentration of metal ions may be produced at the
anode if the ions are unable to diffuse rapidly into the
electrolyte.
 Hydrogen ions may be depleted at the cathode in a hydrogen
electrode or a high OH- concentration may develop at the
cathode in an oxygen electrode.
 When above situations occur, either the anode or cathode
reaction is stiffed, because fewer electrons are released at the
anode or accepted at the cathode
 In any of above examples, the current density and thus the
rate of corrosion decreases because of concentration
polarization
Activation Polarization Curve of a hydrogen electrode
Electrode Kinetic behaviour of pure Zn in acid solution
Effects of polarization at electrodes
Aeration depolarizes hydrogen at cathode

Concentration polarization-
Hydrogen ions diffuse to cathode
slower than reduction reaction
Passivity Alters Anodic Polarization

The tendency for passivation is a

property of the anode, and so it shows up
in the anodic polarization curve.
Whether passivity is achieved is also very
much dependent upon the cathode
reaction

Anodic Polarization influences the ability

to achieve passivity in different media
 Types of Corrosion
Corrosion

uniform localized

Macroscopic
Galvanic Microscopic
Crevice Intergranular
Pitting Stress Corrosion Cracking
Selective leaching
Erosion
 Galvanic or Bimetallic Corrosion
Common in orthopaedics implants
Titanium femoral stems coupled with CoCr heads

A large cathode area , small A large anode area , small

anode area showing relatively cathode area showing
pronounced attack of the rivet relatively insignificant attack
head over a wide area of sheet
 Galvanic corrosion does not occur when the metals
are completely dry since there is no electrolyte to carry
the current between the two electrode areas
Galvanic corrosion is greater near the seashore than in a dry
rural atmosphere
Condensate near a seashore contains contains salt and therefore
is more conductive then condensate in an inland location even
under equal humidity and temperature conditions.
Accelerated corrosion due to galvanic effect is usually more
near the junction with attack decreasing with increasing
distance from the point
Beneficial Applications:
Dry cells and other primary batteries derive their electric power by
Galvanic corrsion of an electrode
Cathodic protection
Cleaning siver
• Beneficial Applications:
• Dry cells and other primary batteries derive their
electric power by Galvanic corrsion of an electrode
• Cathodic protection
• Cleaning siver
 The basic requirements necessary to
cause bimetallic corrosion are:
 An electrolyte bridging the two metals – It may be
in the form of a bulk volume of solution, a
condensed film, or a damp solid such as soil, salt
deposits, or corrosion products.
 Electrical connection between the metals. This
usually involves direct physical contact but it can
also arise where electrical continuity is established
between two metals. It is not necessary for the metal
junction to be immersed in the electrolyte.
 A sufficient difference in potential between the two
metals to provide a significant galvanic current.
 A sustained cathodic reaction on the more noble of
the two metals
 Intergranular Corrosion
 SELECTIVE ATTACK
 Any corrosion which occurs at preferred site on a metal
surface, for whatever reason, can be described as
SELECTIVE ATTACK.
 DEFECTS in metal crystal structures have
electrochemical characteristics different from the rest.
 Most engineering metals contain VOLUME
DEFEATS:
» Voids
» Cracks
» Inclusions
 To reveal the grain structure of a metal/alloy, polishing
and etching of its sample are necessary.
 The etching process is an example of grain boundary
corrosion.
• INTERGRANULAR CORROSION
 Impurities at the grain boundaries
 Enrichment of one of the alloying elements
 Depletion of one these elements in the grain boundary areas

 Occurs when a grain boundary area is preferentially attacked

because of the presence of precipitates in these regions.
 Any metal in which intermetallics or compounds are present at
grain boundaries will be susceptible to intergranular corrosion
cracking.
 Methods of prevention

 Lower the C content to below 0.03%, so that

the carbides are not stable.
 Add alloying elements that are strong carbide
formers (e.g. Ti and Nb are preferentially
combined with C, no Cr is consumed). %Ti/Nb
= 5/10 x %C : stabilized steel
 Use high temperature solution heat treatment
to dissolve the precipitates. (post weld heat
treatment of sensitized steel).
 Crevice Corrosion and Pitting
The Nature of Metal/Environment
 uniform composition of alloy + uniform composition of
environment => uniform corrosion
 non-uniform composition of alloy + uniform composition
of environment => Galvanic corrosion/Intergranular
corrosion
 non-uniform composition of alloy + non-uniform
composition of environment=> localised corrosion:
crevice/pitting
 Most of practical situations are non-uniform.
 Crevice Corrosion
 Localised corrosion resulting from the formation of a concentration cell
in a crevice formed between a metal and nonmetal, or between two
metal surfaces.
 Two prerequisites:

Crevice Corrosion- Initial Stage

one of the most serious problems in the US nuclear industry
was "denting" (localised attack) of Inconel 600 tubing
because of the corrosion in crevices between the tubes and
carbon steel support plates.
With about 60 steam generators affected, the COST of
rectifying the known problems was estimated to be US$6000
million..

Crevice Corrosion- later Stage

 Stage 1
• M=>Mn+ + ne
• cathodic reaction: O2+2H2O +4e=4OH-
 Stage 2
• Inside the Crevice Outside the Crevice
• O2 depleted O2 readily available
• Anodic reaction cathodic reaction
 Stage 3
• Inside the Crevice Outside the Crevice
• O2 depleted O2 readily available
• Anodic reaction cathodic reaction
• High [Mn+]concentration High [OH-] concentration
• High [Cl-] concentration Normal [Cl-] concentration
• Cl- and OH- diffuse into the crevice to maintain a minimum potential energy.
=>Metal chloride is formed. Hydrolysis of metal chloride lowers pH=>
• MCln + nH2O = M(OH)n + nHCl
 Stage 4
• Inside the Crevice Outside the Crevice
• Low pH Normal pH
• High [Cl-] concentration Normal [Cl-] concentration
• High [Mn+] concentration Low [Mn+] concentration
• More Mn+ ions attrack more Cl- leads to lower pH inside crevice
=> accelerate metal dissolution=>More Mn+ ions produced =>attrack more Cl-
 Combating Crevice Corrosion
 Design vessels for complete drainage where
stagnant solution may accumulate
 Inspect equipment and remove deposits
frequently
 Use soundly welded butt joints instead of
riveted or bolted ones in engineering
structures
 Use non absorbent gaskets such as Teflon if
possible
• Pitting Corrosion
 Pitting corrosion is the result of the local destruction of the passive film and
subsequent corrosion of the steel below.
 It generally occurs in chloride, halide or bromide solutions.
 Mechanism same as that of crevice corrosion and pH is dropped locally to 2 or
3, and can prevent regeneration of the passive layer.

 In the passive condition, the current density is in the scale of nanoamperes/cm2;

in the pit, however, it may be above 1A/cm2. Similarly, the concentration in
chloride ions can be thousands of times greater than that in the solution.
 The initiation of pitting is also associated with the presence of MnS inclusions
which are difficult to avoid in the steel making process.
 inclusions are surrounded by a Cr depleted region which is believed to cause
the initiation
 The pitting resistance of a stainless steel is affected by its composition.
 Increasing the Cr content, or adding Mo or N both enhance the pitting
resistance.
 PITTING CORROSION
Extremely localised attack that results in holes in metals.
• Characteristics of pitting:
• (1) difficult to detect
– small in size, covered by corr products
– undercut surfaces, damage to sub-surfaces are severe.
– initiation/incubation period uncertain
• (2) difficult to measure/compare
– depth of penetration varies, number of pits varies
• (3) difficult to predict
– requires long time to initiate
• (4) vicious
– highly localised, intense attack
– equipment fails with extreme suddenness
• (5) shape of pits
– sharply defined holes, no attack on most metal surface.
– rough surface, pits close together
– line in direction of gravity
• (6) growth of pits
– requires 0.5-1 year to initiate
– once started penetrate metal fast
 Corrosion of Metallic Implants
• The first requirement for any material to be placed
in the body is that it should be biocompatible and
not cause any adverse reaction in the body.
• The material must withstand the body environment
and not degrade to the point that it cannot function
in the body as intended.
• Metals and alloys used as implants undergo an
active-passive transition; therefore corrosion
resistance results from the growth of a protective
surface film. These metals are in the passive state
with a protective surface oxide film when used as
implants and are highly corrosion resistant in saline
environment.
• Micromotion between components results in fretting
corrosion that can lead to initiation of crevice corrosion.
• Metallic implants rely on passive oxide film for protection
from corrosion.
• Repetitive motion leads to continuous breakdown and
repassivation.
• Repeated breakdown consumes oxygen in crevice and results
in drop in pH--crevice corrosion.
• At onset of loading, interfacial shear stresses are sufficient
to fracture oxide film
• Unpassivated metal is exposed to initially oxygen rich fluid.
Oxidation occurs--depleting oxygen in crevice fluid--
increases free metal ions--which attract Cl ions-->metal
chlorides
• Metal chlorides react with water to form metal hydroxide
and HCl--lowers pH
• Cr2O3 is unstable below pH of 3-- results in active attack of
CoCr alloy
• Stress corrosion cracking is an important phenomenon often
related to pitting corrosion.
• Cracking caused by the simultaneous presence of a tensile
stress and a specific corrossive medium
• The metal or alloy is virtually unattacked over most of its
surface while fine cracks progress through it.
• The cracking phenomenon has serious consequences since it
can occur at stress within the range of typical design stress.
• Stress corrosion cracking is particularly dangerous because it
may take thousands of hours for a crack to nucleate, but
considerably less for it to propagate.
• It has been suggested that 6%Mo austenitic stainless steels
should be used in these environments.
• Season Cracking of Brass
• Caustic embrittlement of steel
Intergranular Stress corrosion Stress corrosion cracking of the head
cracking of Brass of a 6Al-4V-Ti alloy tank exposed to
Anhydrous N2O4

Cross section of Stress corrosion Stress Corrosion Cracking of Stainless Steel

cracking in stainless steel
Prevention of SCC

Select a material not known to crack in the

specific environment involved; ensure that
the microstructure is not susceptible to
intergranular corrosion cracking.
Lower internal stresses on the metal and use
stress relief anneal
 Design to minimize tensile stresses and
stress raisers.Eliminate the specific species
(Cl-, NH3, etc) from the environment.