Pitting corrosion

• Pitting occurs due to localized

breakdown of a passive film,
usually by chloride ions

• seawater, brackish waters, de-icing

salts, and airborne salt

• strong Lewis base (electron

donor), interact with Lewis acids
(electron acceptors), such as metal
cations. chloride ion relatively
small anion and has a high
diffusivity
Pitting caused by presence of an “aggressive” anion in the electrolyte, usually Cl−
ions, but pitting of various metals or alloys has also occurred in the presence of other
anions, including Br-, I-, sulphates, nitrates

Cross-sectional view of a corrosion pit on Al 6061 formed by

anodic polarization in 0.1 M NaCl
amarineblog.com
Critical Pitting Potential

Schematic anodic polarization curve showing the critical pitting potential (for a passive metal)
Presence of chloride - pitting

Experimental anodic polarization curves for type 304 stainless

steel in 0.1 M NaCl or in 1 M Na2SO4

• below Epit, pitting does not occur
• corrosion pits initiate and propagate above Epit
critical pitting potential not a standalone resistance to pitting
parameter
density of pits (number per unit area) and their propagation
rate, which will determine the depths of pits and, determine the
lifetime of the structure !
 Practical support for existence of critical
pitting potential

electrode potential of each alloy was monitored over

a 1-year immersion period, after which the alloys
were removed from seawater, the corrosion products
removed, and the depth of attack measured

pitting potential of Al alloys in sea water

 Experimental Determination of Pitting Potentials
steady-state anodic polarization curves

potentiostatic technique in which a constant

potential is applied, and the current is recorded as a
function of time

below the pitting potential, the current decays to a

constant value

at the pitting potential and above, the current

increases with time as corrosion pits initiate and
grow

Schematic illustration of experimental current–time curves obtained by the potential step method in the measurement of the critical
pitting potential. Below the pitting potential, the current decays with time in response to a potential step. But at and above the
pitting potential, when pits initiate and grow, the current increases with time
Effect of Chloride Ions on the Pitting Potential

Chloride ions cause pitting to occur

critical pitting potential decreases (is less positive) as the

chloride concentration increase

for a dilute chloride solution, it is necessary to drive the

electrode potential farther in the positive direction to cause
pitting to occur

Effect of chloride concentration (activity) on the pitting

potential of aluminum and type 304 stainless steel
Effect of Inhibitors on the Pitting Potential

addition of a corrosion inhibitor to a solution increases the

pitting potential

Effect of sulfate additions on the pitting potential of type 304 stainless steel in 0.1 M NaCl solutions
Mechanism of Pit Initiation

initiation stage to include both the breakdown of the

passive film and the onset of an anodic current at the metal
surface

aggressive anions are transported through the oxide film to

the underlying metal surface where they participate in
localized dissolution at the metal/oxide interface

Cl− migration through oxygen vacancies is a possible

mechanism of chloride entry into the passive film

The penetration mechanism of pitting showing the competing

processes of film rupture and film formation
 Point defect model

cation vacancies migrate from the oxide/electrolyte

interface inward, equivalent to the migration of cations
outward from the metal to the solution.

cation vacancies accumulate at the metal/oxide interface,

the resulting voids which form due to vacancy
condensation lead to stresses within the passive film and
to pit initiation.

Cl− ions are carried inward by migration through oxygen

vacancies so as to assist in localized dissolution at the
metal substrate

One mechanism leading to the breakdown of passive films. Cation vacancies are transported inward and chloride ions adsorb by
occupying anion (oxygen ion) vacancies. VFeʹʹ represents a cation vacancy of effective charge –2, Fe(oxide) represents a metal cation
in a cation site
 Film thinning mechanism

aggressive ions (chloride or others) first adsorb on

the oxide surface (perhaps in clusters) and then
form surface complexes with the oxide film which
lead to local dissolution and thinning of the
passive film

The film thinning mechanism of pitting in which chloride adsorption (a) initiates the process of film thinning (b) leading to pitting
(c)
 Film rupture mechanism

chloride ions penetrate the oxide through

cracks or flaws in the film.

In addition to pre-existing defects in the oxide

film, flaws may further develop by
hydration/dehydration events in the oxide film
and by the intrusion of Cl− ions into the film

presence of a high electric field in the oxide

can lead to an electromechanical breakdown of
the passive film

The film rupture mechanism of pitting

Mechanism of Pit Propagation
during pit initiation, local current density is very high
because the current is confined to a small active
geometrical area

oxide film adjacent to the pit remains passive and

unattacked

As the pit grows, its volume increases, but dissolved

metal cations are confined within the pit,

cations do not diffuse out into the bulk electrolyte

due to the confinement of a restricted geometry or a
cap of porous corrosion products

accumulated metal cations undergo hydrolysis, local

acidity develops within the pit

accumulation of H+ ions and cations within an active

pit, Cl− ions migrate from the bulk electrolyte to the
crevice electrolyte in order to maintain charge
neutrality within the pit solution
Schematic representation of the propagation stage of pitting
 scanned across a corrosion pit on iron using small diameter (5–
25 μm) antimony/antimony oxide pH electrodes

interior of a corrosion pit is acidified and that the pH adjacent to

the pit becomes alkaline because the cathodic reaction
(reduction of O2 to OH−) occurs on the passive surface outside
the pit

measured electrode potentials across the same pit using a

Ag/AgCl micro-electrode

electrode potential above the pit is more active (more negative)

than above the areas adjacent to the pit

Variations in pH (top) and electrode potential (bottom) across a

growing pit on iron in a dilute chloride solution
Protection Potential

cyclic anodic polarization curves in which the scan direction

was changed at anodic potentials beyond the pitting potential

current density decreases with decreasing electrode potential

until the reverse curve crosses the forward curve in the region
of passivity.

electrode potential at this intersection is called the protection

potential, Eprot.

at this potential, the growth of active pits is diminished or

possibly stopped (because the passive current density has been
regained)

Schematic illustration of the pitting potential Epit and the protection potential Eprot. The arrows show the
direction of polarization
 Can protection potential be useful as an indicator of corrosion ?

amount of hysteresis for the open samples, as measured by the

difference (Epit – Eprot), correlates with the amount of crevice
corrosion

less the hysteresis in the cyclic polarization curve, the less the
amount of crevice corrosion observed in the actual seawater
immersion test

The crevice weight loss of several stainless steels versus the difference between the pitting potential Epit and the protection potential
Eprot for open samples. The pitting potential was determined in aerated 3.5% NaCl at 25◦C at a potential sweep rate of 10 mV/min,
and the protection potential determined after reversing the sweep at a current density of 200 μA/cm2. The sample area was 1220
cm2 and the crevice area approximately 20 cm2. Alloy types 4xx and USS 100 are Fe−Cr alloys, alloy types 3xx are Fe−Cr−Ni
alloys, and Hastelloy C (alloy C-276) is primarily a Ni−Cr−Mo alloy
 Does Eprot depend on the amount of propagation
which has taken place within the pit ?

corrosion pits initiate and then propagate with

concomitant acid hydrolysis, buildup of corrosion
products, and increase in chloride ion concentration
within the pit.

When the sweep is reversed, the propagation processes

which are potential dependent decrease until the rate of
propagation becomes zero at the passive current density

Is Eprot a material property ?

Effect of extent of propagation on the value of the protection potential

Experimental Pourbaix Diagrams for Pitting
perfect passivity exists in the
passive range below the
protection potential where
pits do not nucleate or grow

imperfect passivity lies

between the protection
potential and the pitting
potential and is a region
where previously formed pits
can grow before they are
repassivated at potentials at
or below Eprot.

pitting exists above the

pitting potential.

Experimental Pourbaix diagram for iron in 0.01 M Cl− (right) determined from experimental anodic polarization curves, as on the
left. The arrows show the effect of a reverse potential sweep. The polarization curve furthest to the left shows general corrosion
only; the polarization curve in the middle displays a pitting potential and a protection potential; the polarization curve on the right
shows general corrosion or passivity, but not pitting
Effect of Molybdenum on the Pitting of Stainless Steels

addition of molybdenum to Fe-Cr alloys increases the pitting

potential

Active sites are covered with molybdenum oxyhydroxide or

molybdate salts, thereby inhibiting localized attack

Dissolution of Mo in the alloy produce molybdate ions which

act as corrosion inhibitor near the metal surface

Mo6+ species in the passive film interact with cation vacancies

of the opposite sign and reduce the flux of cation vacancies to
the metal substrate

Molybdate ions act as a cation-selective outer layer in the

passive film, and thus hinder the transport of Cl− ions through
the passive film.

Mo interferes with the kinetics of active dissolution at the base

of the developing pit

Effect of molybdenum on pitting potentials of 13% Cr and 18%

Cr stainless steels in 1 M NaCl at 25◦C
Effect of Sulfide Inclusions on the Pitting of Stainless Steels

passive film affected by - compositional heterogeneities at

grain boundaries and disruption of the passive film by
impurity atoms or inclusions

manganese sulfide (MnS), are known to be pit initiation

sites on stainless steels

Sulfur is present in stainless steels as an impurity (0.03%

maximum) or as an intentional additive (approximately
0.3%) to aid in the machining of the metal

anodic dissolution of sulfide inclusions leads to an

aggressive electrolyte composition near the inclusion, so as
to disrupt the passive film

(a) A top view scanning electron micrograph of a sulfide inclusion in anodic zones to be due to an area around the MnS particle
type 304 stainless steel. (b) EDAX (energy dispersive analysis by X- which is depleted in chromium, and thus susceptible to
rays) showed that the sulfide inclusion contained Mn, Fe, Cr, and S. (c) localized attack
Cross-sectional illustration of a MnS particle as a pit initiation site
 Effect of Temperature

pitting potential of the Mo-containing 316 stainless steels is

higher than that of type 304 stainless steel.

pitting potential of each alloy decreases with increasing

temperature. Why ?

With increased temperature the rate increases for all individual steps
which lead to pitting. This includes the rate of Cl− transfer within the
oxide film, the rate of oxide thinning, and the rate of electrochemical
reactions at the metal/oxide interface. Thus, the metal can be driven
to a lower electrode potential to cause pitting to occur

The effect of temperature on the pitting potential of type 304

and type 316 stainless steels in a dilute chloride solution
Differences Between Pitting and Crevice Corrosion

the electrode potential for crevice corrosion is more negative

than the pitting potential

electrode potentials are measured within the crevice but outside

the pit

pitting potential is a mixed potential between events occurring

on the passive surface and within the developing corrosion pit.

current density within a corrosion pit is much higher than that

within a crevice

highest current densities for the iron crevice are about 0.06
Comparison of the pitting potential of open iron with the mA/cm2. By contrast, current densities within corrosion pits can
internal potential of iron within active crevices for various be of the order of A/cm2
chloride concentrations in 0.003 M/L chromate
Protection Against Pitting
1. Maintain the electrode potential below the critical pitting potential
2. Add inhibitors to raise the critical pitting potential
3. Materials selection: metals and alloys which are resistant to crevice
corrosion are also usually resistant to pitting. The resistance to pitting
corrosion increases in the order: Fe-12% Cr < 304 stainless steel < 316
stainless steel < alloy C-276 < titanium

Effect of alloy selection on the pitting potential in solutions of

fixed chloride concentration
Occluded Corrosion Cells

corrosion pits are “microcrevices” or crevices are “macropits”

develop local internal acidities even when the

bulk electrolyte is neutral or alkaline

restrictive geometry “seals off” an active local

corrosion cell by limiting the exchange of
local and bulk electrolytes

Schematic illustration showing geometric similarities between

pitting, crevice corrosion, and stress- corrosion cracking
Detection of Corrosion Pits

From the potential field around a corrosion pit, able to

determine the current distribution, because the current density, i,
is proportional to the normal gradient of the potential E:

σ is the conductivity of the solution and z denotes the direction

normal to the electrode surface

scanning vibrating electrode (SVE) which produces potential

scans and also current scans by sampling the potential gradient
normal to the surface

The distribution of current density over an iron surface showing

the location and progressive growth of a pit in a solution of 1
mM NaCl plus 1 mM Na2SO4, as determined using a vibrating
probe electrode
Example problem
Experimental Determination of Pitting Potentials

Can potentiodynamic measurements be used to find pitting potential ?

Measured value depends on sweep rate - not allowing sufficient time at each electrode potential for pit initiation events to
happen

Rough surfaces vs smooth surfaces - more initiation sites, lower pitting potential values

Pitting potential not seem to depend on oxide film thickness

Shown below are experimentally determined anodic polarization curves in 1 M H2SO4 and 1 M HCl for three alloys [93]
(reproduced by permission of NACE International). These alloys are the conventional 304 stainless steel and two possible
replacements, alloy A and alloy B:

304: Alloy A: Alloy B:

18% Cr, 8% Ni, balance Fe
12% Cr, balance Fe
12% Cr, 10% Ni, 1.5 % Si, 2% Mo, balance Fe

Based on these polarization curves alone, which alloy or alloys can be used instead of 304 stainless steel? Why?