Pitting and Crevice Corrosion

Sotya Astutiningsih
From ASM Metals handbook vol. 11
• Pitting and crevice corrosion are forms of
localized corrosion that are significant causes
of failure in metal parts. Both forms attack
passivated or otherwise protected materials.
 pitting
• Pitting, characterized by sharply defined holes,
is one of the most insidious forms of
corrosion. It can cause failure by perforation
while producing only a small weight loss on
the metal. This perforation can be difficult to
detect and its growth rapid, leading to
unexpected loss of function of the
component.
 Crevice corrosion
• Crevice corrosion is pitting that occurs in slots
and in gaps at metal-to-metal and metal-to-
nonmetal interfaces. It is a significant
contributor to component failure because
such gaps often occur at critical joining
surfaces.
 pitting
• Causes of pitting corrosion include:
– · Local inhomogeneity on the metal surface
– · Local loss of passivity
– · Mechanical or chemical rupture of a protective oxide
coating
– · Discontinuity of organic coating (holidays)
– · Galvanic corrosion from a relatively distant cathode
– · Formation of a metal ion or oxygen concentration
cell under a solid deposit (crevice corrosion)
Every engineering metal or alloy is susceptible to pitting.
Pitting occurs when one area of a metal surface becomes
anodic with respect to the rest of the surface or when highly
localized changes in the corrodent in contact with the metal,
as in crevices, cause accelerated localized attack.

Pitting on clean surfaces ordinarily represents the start of

breakdown of passivity or local breakdown of inhibitor-produced
protection. When pits are few and widely separated and the
metal surface has undergone little or no general corrosion, there
is a high ratio of cathode-to-anode area. Penetration progresses
more rapidly than when pits are numerous and close together.
 common causes of pitting in steels
• The most common causes of pitting in steels are surface deposits that set
up local concentration cells and dissolved halides that produce local
anodes by rupture of the protective oxide film.
• Anodic corrosion inhibitors, such as chromates, can cause rapid pitting if
present in concentrations below a minimum value that depends on the
metal-environment combination, temperature, and other factors.
• Pitting also occurs at mechanical ruptures in protective organic coatings if
the external environment is aggressive or if a galvanic cell is active. Buried
pipelines that fail because of corrosion originating on the outside surface
usually fail by pitting corrosion.
• Another form of corrosion affecting pipelines involves a combination of
pitting and erosion (erosioncorrosion). This form of corrosive attack is
discussed in the section “Velocity-Affected Corrosion”
Pitting normally occurs in a stagnant environment. With
corrosion-resistant alloys, such as stainless steels, the most
common cause of pitting corrosion is highly localized
destruction of passivity by contact with moisture that contains
halide ions, particularly chlorides. Chloride-induced pitting of
stainless steels usually results in undercutting, producing
enlarged subsurface cavities or caverns.
 Rate of pitting
• The rate of pitting is related to the aggressiveness of
the corrodent at the site of pitting and the electrical
conductivity of the solution containing the corrodent.
• For a given metal, certain specific ions increase the
probability of attack from pitting and accelerate that
attack once initiated.
• Pitting is usually associated with metal-environment
combinations in which the general corrosion rate is
relatively low; for a given combination,the rate of
penetration into the metal by pitting can be 10 to 100
times that by general corrosion.
 Depth of Penetration
• The depth of pitting can be expressed by the pitting
factor (Fig. 17) (Ref 21). A value of 1 would represent
uniform corrosion.
• The maximum depth of penetration (p) can be
measured by several methods, including
metallographic examination, machining, use of
micrometer, or microscope.
• The average penetration depth (d) is calculated from
the weight lost by the sample. The maximum
penetration depth is extremely significant if the metal
is part of a barrier or tank, or is part of a pressurized
system.
.
The micrograph
(Fig. 18) shows the profile of pits that have degraded an
austenitic stainless steel thin-walled bellows.

Fig. 17 Measurements used to determine the pitting

factor, p/d, where p is maximum penetration and d is
the average penetration depth.
Fig. 18 Light micrograph showing the general microstructure and
cross section of corrosion pits in an austenitic stainless steel thin-
walled bellows. Total thickness of sheet approximately 0.5 mm (0.02
in.). 10% oxalic acid etch. 100×. Courtesy of M.D. Chaudhari,
Columbus Metallurgical Service
 Density and Size of Pitting.
• For a mechanical component, the density of pits (number per
unit surface area) and size may be a more critical
characteristic than maximum depth. The loss of effective cross
section can decrease the strength of the component and pits
can become sites of stress concentrations.
 Crevice Corrosion
• A crevice at a joint between two metallic
surfaces, between a metallic and a nonmetallic
surface, or beneath a particle of solid matter on a
metallic surface provides conditions that are
conducive to the development of the type of
concentration-cell corrosion called crevice
corrosion.
• Crevice corrosion can progress very rapidly (tens
to hundreds of times faster than the normal rate
of general corrosion in the same given solution).
 example
• The classic example of this is a demonstration
that a sheet of stainless steel can be cut
(corroded) into two pieces simply by wrapping a
rubber band around it, then immersing the sheet
in seawater or dilute ferric chloride solution.
• The open surfaces will pit slowly, but the metal
under the rubber band will be attacked rapidly for
as long as the crevice between the rubber band
and the steel surface exists.
In a metal-ion concentration cell, the accelerated corrosion
occurs at the edge of or slightly outside of a crevice.
In an oxygen-concentration cell, the accelerated corrosion
usually occurs within the crevice between the mating
surfaces. Riveted and bolted joints must be considered
prime sites for crevice corrosion; therefore,
they require careful attention in design and
assembly to minimize crevices, as well as
provisions to ensure uniform aeration and

moderate but not excessive flow rates at the

joints. Not only does the geometry of the joint
itself promote crevice corrosion, but corners
and cracks can collect debris, which
exacerbates the potential for corrosion.
Replacement with welded joints can eliminate
crevice corrosion, provided special care is
taken in welding
Fig. 24 Crevice corrosion pitting that has taken place where type 316
bubble caps contact a type 316 stainless steel tray deck. The oxygen-
concentration cell corrosion occurred in concentrated acetic acid with
minimal oxidizing capacity. 1/8 actual size
Differential aeration beneath solid deposits or at cracks in
mill scale is a frequent cause of crevice corrosion in boilers
and heat exchangers. Suitable water treatment to provide
thin protective films, together with special
attention to cleaning, rinsing, and drying when boilers are
shut down, minimizes the occurrence of crevice corrosion
in such equipment. Breaks (holidays) in protective organic
coatings or linings on vessels containing
corrosive chemicals are also likely sites for the
development of crevice corrosion.
Example 9: Crevice Corrosion on Stainless Steel Tube. A steel tube meeting
type 304 specification (0.008 max C,18.00 to 20.00 Cr,2.00 max Mn, 8.00 to
10.50 Ni) was found to be corroded as shown in Fig. 25. The tube was part of
a piping system, not yet placed in service, that was exposed to an outdoor
marine environment containing chlorides. As part of the assembly, a fabric
bag containing palladium oxide (PdO2) was taped to the tube.
The palladium served as a “getter.” The corrosion in this area was discovered
during routine inspection. A close-up (Fig. 26) of the tube shows the corrosion
products. Pits are the darkest areas. Slightly lighter areas
include remnants of the fabric bag.
Fig. 25 Austenitic stainless steel tube that was
corroded where a fabric bag was taped to
it. Courtesy of M.D. Chaudhari, Columbus
Metallurgical Service
Fig. 26 Micrograph of an area about 10 mm (
3/8in.) wide from the tube shown in Fig. 25.
Pits are the dark areas in the center. Lighter
areas include fragments of the bag among
the corrosion products. Courtesy of M.D.
Chaudhari, Columbus Metallurgical Service
Analysis. Corrosion debris was analyzed using an electron-dispersive
spectrometer (EDS). The profiles confirmed the presence of chlorides and
palladium. Both contributed to corrosion in the crevice created by the tape
on the tube, which was periodically exposed to water.
Corrective Measures. Steps were taken to prevent water from entering and
being trapped in this area of the assembly
 Reducing Failures Due to Pitting and
Crevice Corrosion
• · Reducing the harshness of the environment
• · Selecting appropriate materials
• · Avoiding galvanic couples
• · Avoiding rupture of any natural or applied protective
coatings
• · Avoiding contact with stagnant solutions or providing
circulation of otherwise stagnant solutions
• · Modifying component design to eliminate crevices and
ensure proper drainage
• · Inspecting and maintaining critical components so that
pitting and crevice corrosion do not develop into
• more catastrophic failures