Crevice Corrosion and Pitting

Corrosion Engineering
ChE 291

We will discuss the following topics

Why study corrosion? An introduction

Basic concepts of corrosion science and engineering
Charged interfaces
Review of thermodynamic principles for corrosion
Electrochemical cells and Galvanic corrosion
Poubaix Diagrams
Kinetics of Corrosion
Concentration Polarization and Diffusion
Passivity
- Introduction; Electrochemical Basis
- Theories of Passivity; Surface Analysis Techniques for the Examination of Passive Films
- Properties of Passive Oxide Films; Passivity in Binary Alloys; Passivity in Stainless Steels; Anodic Protection

Crevice Corrosion and Pitting

- Crevice Corrosion Initiation and propagation; Testing; Area Effects; Protection
- Pitting Critical pitting potential; Effect of chloride ions, inhibitors, Mechanism of pit initiation and propagation;
protection potential; metastable pits and repassivation; Effect of molybdenum and sulfide inclusions;
temperature
- Occluded corrosion cells (OCC) on iron, aluminum, and copper; differences between pitting and crevice
corrosion
- Detection of corrosion pits

What is crevice corrosion?

Localized corrosion that occurs within narrow clearances or under shielded metal
surfaces; can occur in geometrical clearances (e.g. under gaskets or seals; between
overlapping metal sheets; etc

Can also occur under deposits (corrosion products; dust particles; barnacles in
seawater)

Alloy 625 after crevice corrosion testing at 65C in natural seawater

(a) +200 mV vs. Ag/AgCl for 24 h
(b) +400 mV vs. Ag/AgCl for 24 h
The crevice was provided with a compressed gasket

How does crevice corrosion initiate?

Crevice corrosion initiates due to the operation of a differential oxygen cell

Oxygen reduction occurs both on the metal surface which is exposed to the bulk
electrolyte and also on the portion of the metal surface which is contained within the
crevice

How does crevice corrosion initiate?

Metal exposed to the bulk electrolyte is in contact with an open supply of oxygen from the
atmosphere, so as O2 is consumed near the external metal surface

When O2 molecules are consumed within the narrow clearance of the crevice, they are
not easily replaced due to the long narrow diffusion path formed by the crevice

How does crevice corrosion initiate?

Variation of the oxygen concentration within crevices on a Cr-containing stainless steel

Oxygen becomes depleted within the crevice

Oxygen concentration cell is formed between the metal surface outside the
crevice and the metal surface within the crevice

How does crevice corrosion initiate?

Metal exposed to the lower concentration of oxygen has a more negative potential for
oxygen reduction than does the metal exposed to a higher concentration of oxygen

Limiting current density iL for O2 reduction within the crevice is decreased relative to that
for the bulk solution; limiting current density is proportional to concentration

How does crevice corrosion initiate?

Electrode potential for metal within the crevice becomes more negative with time
before leveling off

How does crevice corrosion initiate?

Establishment of steady-state potentials for open iron and iron within crevices in 0.6 M NaCl

Electrode potential for metal within the crevice becomes more negative with time
before leveling off

How does crevice corrosion initiate?

Limiting cathodic density is less for
the creviced iron than for open iron

Limiting cathodic rate is
suppressed to a constant value for
crevice heights between 0.13 and
0.50 mm

Crevice height of 0.50 mm ~
thickness of oxygen diffusion layer
near the metal surface

Cathodic polarization curves for open iron and

iron in crevices in 0.06 M NaCl

When crevice height ~ thickness of

oxygen diffusion layer, diffusion of
oxygen into crevice is impeded; rate of
oxygen reduction is decreased

How does crevice corrosion initiate?

Evans diagrams for the crevice corrosion of iron

If iron within the crevice were not coupled to external open iron (an isolated crevice)
then the corrosion rate would be given by icorr,1

When the crevice iron is coupled to external iron, the initial corrosion rate is given by the
larger value icorr,2

How does crevice corrosion propagate?

Propagates by changes in the electrolyte composition within the crevice

Crevice electrolyte will become acidic in nature and will also contain concentrated
amounts of cations discharged from the metal or alloy

Expressions for the pH of various crevice hydrolysis reactions

A local internal pocket of acidity develops within the active crevice even though the
external electrolyte has a neutral pH of 7

Example 1
Chromium contained within a crevice of 0.5
cm2 area and 0.2 mm in height corrodes at the
rate of 1 A/cm2. What is the pH within the
crevice after 10 days if Cr corrodes as Cr3+, and
Cr3+ ions hydrolyze to form Cr(OH)3? Assume
that all Cr3+ ions produced by crevice
corrosion remain within the crevice.

Example 1 Solution
Amount of Cr3+ ions produced

Volume of the crevice

Concentration of Cr3+ within the crevice

How does crevice corrosion propagate?

With the accumulation of H+ ions and metallic cations within an active crevice, Cl ions then
migrate from the bulk electrolyte to the crevice electrolyte in order to maintain charge neutrality

Propagation stage of crevice corrosion involves formation of a highly corrosive internal electrolyte
which is acidic and also concentrated in chloride ions and dissolved cations of the metal or alloy

Initiation stage of crevice corrosion can be quite prolonged (months to years), but propagation
may proceed rapidly due to the highly corrosive crevice environment which is formed

How to test for crevice corrosion?

A crevice corrosion
electrochemical cell
(remote crevice assembly)

A split electrode is used in which the metal in the crevice is physically separated (but
electrically connected) to the open metal outside the crevice; studies mechanism of crevice
corrosion

Crevice corrosion current can be measured as a function of time for various parameters,
such as crevice dimensions, alloy composition, and electrolyte concentration

How to test for crevice corrosion?

For a fixed chloride concentration in the
electrolyte, increasing concentrations of
chromate decrease the crevice corrosion rate

Crevice corrosion can be inhibited by using
an appropriate minimum amount of CrO42
inhibitor

Effect of chromate concentration on the crevice

corrosion of iron in 0.6 M NaCl; Crevice height =
0.25 mm, area of crevice iron = 7.9 cm2, area of
outer iron electrode = 50 cm2

How to test for crevice corrosion?

Composition of CrNiMo alloys and of crevice electrolytes formed in natural seawater
after immersion for 160170 days; pH measured in separate experiments using synthetic
crevice electrolytes

As a result of crevice corrosion, the crevice electrolyte contained dissolved cations of
each of the major alloying elements for each of the alloys

What are area effects in crevice

corrosion?

Rate of crevice corrosion increases with an increase in the area of open metal
outside the crevice

Effect of the area outside the crevice on the weight loss of an Fe-17% Cr
steel inside a crevice in natural seawater.

What are area effects in crevice

corrosion?

Polarization curve for the limiting cathodic current density for oxygen reduction intersects the
anodic polarization curve of the creviced metal (in the propagating electrolyte) at increasingly
higher values of current

How to protect metals from crevice

corrosion?
Use of corrosion inhibitors, such as chromates, dichromates,
nitrites, or phosphates
Cathodic protection (using anodes located outside the
crevice)
Design considerations to minimize the existence of crevices
Materials selection: titanium and its alloys and Mo-containing
alloys such as alloy 625 or alloy C-276 are more resistant to
crevice corrosion (at ambient temperatures) than
conventional stainless steels; Presence of nitrogen is also
beneficial to crevice corrosion resistance in alloys which
contain molybdenum

How to protect metals from crevice

corrosion?

Cathodic protection (using anodes located outside the crevice)

Cathodic polarization of type 304 stainless steel

in 0.05 mm crevices in 0.6 M; Numbers indicate
the distance (in cm) from the crevice opening

How to protect metals from crevice

corrosion?

Design considerations to minimize the existence of crevices

Continuous welds in (b) are preferable to

intermittent welds in (a) because intermittent
welds introduce additional crevices

How to protect metals from crevice

corrosion?

Design considerations to minimize the existence of crevices

Discharge valves can be re-designed as in (b) to

prevent crevice corrosion under deposits

What is Pitting?

Form of localized corrosion in which the attack is confined to a small fixed area of
the metal surface

Due to localized breakdown of a passive film, usually by chloride ions

Pits can serve as sites to initiate stress-corrosion cracking

Pits can be covered by corrosion products

Cross-sectional view of a corrosion pit on Al 6061

formed by anodic polarization in 0.1 M NaCl

What is the critical pitting potential?

In the absence of chloride ions, the metal retains its passivity up to the
electrode potential of oxygen evolution

In the presence of chloride ions, the passive film suffers localized attack, and
pitting initiates at the critical pitting potential

Schematic anodic polarization curve showing the critical pitting potential (for a passive metal)

What is the critical pitting potential?

SS remains passive up to E = +1.2 V (potential for oxygen evolution)

In 0.1 M NaCl, SS pitting occurs at E = +0.35 V

Experimental anodic polarization curves for type 304 stainless steel

in 0.1 M NaCl or in 1 M Na2SO4

What is the critical pitting potential?

Critical pitting potentials, Epit, in 0.1 M NaCl for various metals and alloys

Epit is a characteristic property of a given metal; value depends on [Cl-]

More positive the value of Epit, the more resistant the metal to pit initiation

E < Epit (pitting does not occur); E > Epit (pitting initiates and propagates)

How do we determine experimentally

the pitting potential?

Usually determined from steady-state anodic polarization curves

Potentiostatic technique; a constant potential is applied and the current is
recorded as a function of time

When E < Epit, current decays to a constant value

When E > Epit, current increases with time

Schematic illustration of experimental currenttime curves obtained by the potential step

method in the measurement of the critical pitting potential

What is the effect of chloride ions

on the pitting potential?

Critical pitting potential decreases (is less positive) as the chloride
concentration increases; Epit is a linear function of log [Cl-]

Effect of chloride concentration (activity) on the pitting potential of aluminum

and type 304 stainless steel

What is the 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

What is the penetration

mechanism of pit initiation?

Aggressive anions are transported through the oxide film to the underlying metal
surface where they participate in localized dissolution at the metal/oxide interface

Recent evidence from X-ray photoelectron spectroscopy and X-ray absorption
spectroscopy that Cl ions penetrate passive films on both stainless steel and
aluminum

Cl migration through oxygen vacancies (Cl ion only slightly larger than oxide
ion

The penetration mechanism of pitting showing the

competing processes of film rupture and film formation

What is the film thinning

mechanism of pit initiation?

Aggressive ions (Cl-, Br-, or I-) 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

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

What is the film rupture

mechanism of pit initiation?

Chloride ions penetrate the oxide through cracks or flaws in the film

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

The three mechanisms are not mutually exclusive

The film rupture mechanism of pitting

What is the mechanism of pit propagation?

Similar to propagation of crevice corrosion

When corrosion pit has been initiated, local current density is very high because
the current is confined to a small active geometrical area

Volume increases during pit growth; dissolved metal cations are confined within
the pit and 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

Cl ions migrate from bulk electrolyte to the
crevice electrolyte in order to maintain charge
neutrality within the pit solution

Schematic representation of
the propagation stage of
pitting

What is the mechanism of pit propagation?

Interior of a corrosion pit is acidified; pH adjacent to the pit becomes alkaline
because the cathodic reaction (reduction of O2 to OH) occurs on the passive
surface outside the pit

Electrode potential above the pit is more active (more negative) than above the
areas adjacent to the pit

When the corrosive pit electrolyte has been formed, pitting is autocatalytic

Variations in pH and electrode potential across a growing pit on iron in

a dilute chloride solution.

What is protection potential?

Concept arose from cyclic anodic polarization curves in which the scan direction
was changed at anodic potentials beyond the pitting potential

At Epit, 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

What is protection potential?

Alloys immersed under crevices in natural seawater for 4.25 years

Cyclic anodic polarization curvess determined in 3.5% NaCl solutions for open
samples cut from the same specimens previously immersed

Amount of hysteresis for the open

samples (Epit Eprot) correlates with
amount of crevice corrosion (first cousin
to pitting corrosion)

Less hysteresis in cyclic polarization

curve, less amount of crevice corrosion

Protection potential is useful as an
indicator of corrosion behavior
Crevice wt loss versus difference bet. Epit and
Eprot for open samples

What is protection potential?

Measured protection potential depends on the experimental conditions used in
its determination

Depends on the amount of propagation which has taken place within the pit

Should not be regarded as a material property but can be used to rank alloys
accdg to their pitting behavior

Effect of extent of propagation on the value of

the protection potential

What are metastable pits and

repassivation?

At electrode potentials below the pitting potential, the currenttime curves often
contain transient excursions

Metastable pits - pits that grow for a limited time but are repassivated and stop
growing; have a limited lifetime because the concentrated acidic chloride solution
which promotes pit propagation has not yet developed within the metastable pit

Idealized curves

Metastable pitting current transients

observed for type 302 stainless steel in
0.1 M NaCl at +0.420 V vs. SCE.

What are metastable pits and

repassivation?

Corrosion rate of pure (open) iron in concentrated acidic chloride solutions
depends on both the chloride ion and hydrogen ion concentrations

Open-circuit corrosion rate increased as the chloride concentration increased

Synergistic effect of H+ and Cl ions in promoting corrosion

Effect of the concentration of H+ and Cl on the

corrosion of open iron in concentrated solutions

How to establish experimental

Pourbaix diagrams for pitting?

Regions of immunity, general corrosion, perfect passivity, imperfect passivity,
and pitting; perfect passivity = pits do not nucleate or grow

Imperfect passivity = previously formed pits can grow before they are
repassivated at potentials at or below Eprot
a pitting potential
and a protection
potential

general corrosion or
passivity but not pitting

general
corrosion only

Experimental Pourbaix diagram for iron in 0.01 M Cl (right) determined from experimental
anodic polarization curves, as on the left

What is the effect of molybdenum

on the pitting of stainless steels?

Addition of molybdenum to Fe-Cr alloys increases the pitting potential

Reasons: 1) Active sites are covered with molybdenum oxyhydroxide or molybdate salts;
2) Dissolution of Mo in the alloy produces molybdate ions (corrosion inhibitor);
3) Mo interferes with the kinetics of active dissolution at the base of the developing pit; etc

Effect of molybdenum on pitting potentials of 13% Cr

and 18% Cr stainless steels in 1 M NaCl at 25C

What is the effect of sulfide inclusions

on the pitting of stainless steels?

Sulfide inclusions, especially manganese sulfide (MnS), are known to be pit
initiation sites on stainless steels

Top view scanning electron micrograph of a

sulfide inclusion in type 304 stainless steel

EDAX (energy dispersive analysis by Xrays) showed that the sulfide inclusion
contained Mn, Fe, Cr, and S

What is the effect of sulfide inclusions

on the pitting of stainless steels?

Pits initiate at the edge of the sulfide inclusion and that anodic zones exist
around the inclusion

Anodic zones to be due to an area around the MnS particle which is depleted
in chromium, and thus susceptible to localized attack

Pitting resistance of type 304 stainless steel can be improved by laser
surface melting

Cross-sectional illustration of a MnS

particle as a pit initiation site

What is the effect of temperature

on pitting potential?

At all temperatures, the 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

The effect of temperature on the pitting potential of type 304 and

type 316 stainless steels in a dilute chloride solution

What is the effect of temperature

on pitting potential?

First signs of pitting occurred at the critical pitting temperature

The higher the critical pitting temperature, the more resistant the alloy to pitting

Pitting resistance increases with the Mo content

Critical crevice temperature is lower than the critical pitting temperature
Critical pitting temperature and critical crevice
temperature as a function of molybdenum
content for several different stainless steels
having the nominal composition Fe-18 Cr-20
Ni-x Mo in 10% FeCl3

Critical crevice temperature is

lower than the critical pitting temperature.

Severe conditions already exist within
the occluded crevice in the FeCl3 solution,
but must develop within a corrosion pit on
an open surface

What are some methods of

protection against pitting?
1) Maintain the electrode potential below (more negative, i.e., less positive than) the critical
pitting potential.
2) Add inhibitors to raise the critical pitting potential.
3) Metals and alloys which are resistant to crevice corrosion are also usually
resistant to pitting.

Effect of alloy selection on the

pitting potential in solutions of
fixed chloride concentration

What are occluded corrosion cells?

Active crevices, corrosion pits, and stress-corrosion cracks each develop local
internal acidities even when the bulk electrolyte is neutral or alkaline

A special restrictive geometry seals off an active local corrosion cell by limiting
the exchange of local and bulk electrolytes

All three forms of localized corrosion are different geometric manifestations of
the same general phenomenon of OCC

Schematic illustration showing geometric

similarities between pitting, crevice corrosion, and
stress corrosion cracking

What is occluded corrosion cell

(OCC) on iron?

M. Pourbaix suggested that when pitting, crevice corrosion, or stress-corrosion
cracking occurs on iron in chloride solutions, the solution within the active cavities
becomes saturated with respect to ferrous chloride (FeCl2) and also contains
magnetite (Fe3O4)

Three solid phases = FeCl24H2O, Fe3O4, and Fe in aq. solution

Pourbaixs sketch of a corrosion pit or stresscorrosion crack on iron

What is occluded corrosion cell

(OCC) on iron?

Equilibrium E and pH within the OCC are given at the triple point

E=0.368 V vs. SHE (0.590 V vs. Ag/AgCl) and pH 4.8

These results have been verified in various experimental studies

The Pourbaix diagram for iron in a localized

corrosion cell in a chloride solution

What are occluded corrosion cells

on copper and aluminum?

Pit contains a layer of green malachite, CuCO3 Cu(OH)2, white crystals of
cuprous chloride (CuCl), and a loose deposit of red cuprous oxide, Cu2O

Solution at the bottom of the pit is in contact with Cu, Cu2O, and CuCl

E = +0.326 V vs. SHE and pH 2.45 in Pourbaix diagram

Sketch of a copper pit in cold tap water

What are occluded corrosion cells

on copper and aluminum?

Hydrogen evolution is thermodynamically possible in each form of
localized corrosion in aluminum

Hydrogen bubbles have been observed for aluminum in active crevices

Electrode potential and pH within occluded cells on aluminum superimposed on a

partial Pourbaix diagram for aluminum. CC refers to crevice corrosion and SCC to
stress-corrosion cracking

What are differences between

pitting and crevice corrosion?

Electrode potential for crevice corrosion is more negative than the pitting
potential

Current density within a corrosion pit is much higher than that within a crevice

Comparison of the pitting potential of open iron with the internal potential of iron within
active crevices for various chloride concentrations in 0.003 M/L chromate

How do we detect corrosion pits?

We can detect propagating pits on a metal surface by pH and electrode
potential scanning over metal surfaces

Detect the physical location of corrosion pits on a metal surface

Variations in pH and electrode potential across a growing pit on iron in

a dilute chloride solution.

How do we detect corrosion pits?

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

Distribution of current density

from sampling of potential
gradients normal to the surface

is the conductivity of the solution