This is localized corrosion concentrated in crevices in which the gap is sufficiently wide for liquid to penetrate into

the crevice and sufficiently narrow for the liquid in the crevice to be stagnant.

Crevice corrosion (CC) occurs beneath flange gaskets, nail and screw heads and paint coating edges, in overlap
joints, between tubes and tube plates in heat exchangers, Small volume of stagnant solutions by holes, gaskets
surfaces, lap joints,crevices under bolt and rivet heads. The same form of corrosion develops beneath deposits of,
e.g. dirt, sand, leaves and marine organisms, permeable corrosion products hence it is called deposit corrosion in
such cases.
Figure shows two stages in the development of crevice corrosion. A flange joint of a metal M is exposed to neutral water
containing oxygen and NaCl. For simplicity, we assume firstly that M is a univalent metal. The development can be
divided into the following four stages:
1. In the beginning the metal corrodes at the same rate inside and outside the crevice (Figure a). The anodic reaction = M+
+ e and the cathodic reaction O2 + 2H2O + 4e– = 4OH– occur on area elements distributed between each other all over the
surface. If the metal is passive beforehand, the corrosion rate is low (corresponding to the passive current density) and the
consumption of oxygen is correspondingly low. In principle, the situation can be illustrated with the potential–log current
diagram. The oxygen is gradually being consumed within the crevice. This is also the case when the metal surfaces are
passive, provided that the crevice is so narrow and deep that oxygen is more slowly transported into the crevice than it is
consumed inside it.
2. When the oxygen has been completely consumed inside the crevice, OH– can no longer be produced there.
Conversely, the dissolution of metal inside the crevice continues, supported by the oxygen reduction outside the
crevice. The concentration of metal ions within the crevice increases, and with missing OH– production in the
crevice, the charge equilibrium (electrical neutrality) is maintained by migration of Cl– into the crevice* (Figure b). In
this way an increasing amount of dissociated metal chloride (M+Cl–) is produced in the crevice. The metal chloride
reacts with water (hydrolyzes):
M+Cl– + H2O = MOH + H+Cl–. (7.3)
Metal hydroxide is deposited and hydrochloric acid is formed in the crevice, which causes a gradual reduction of
the pH. This process leads to a critical corrosion state.
3. When the environment has become sufficiently aggressive, the surface oxideWhen the environment has become
sufficiently aggressive, the surface oxide film is attacked. The crevice surfaces are transferred to an active state and the
corrosion rate increases. film is attacked. The crevice surfaces are transferred to an active state and the corrosion rate
increases.
4. The growth (or propagation) phase. Because of increased corrosion rate, the migration of Cl– increases also, which
contributes to a further acceleration of the corrosion process. The process promotes itself, i.e. it is “auto–catalytic”. Since the
pH has been strongly reduced, the hydrogen reaction 2H++2e– 􀄺 H2 can also possibly contribute as a second cathodic
reaction. pH inside the crevice can reach values of 0–4 depending on the actual material–environment combination. At the
same time, pH may increase to 9–10 on the metal surface outside the crevice, where the oxygen reduction takes place. The
conditions at this stage can in principle be described with the overvoltage curves in Figure 7.16b. The corrosion current Icorr =
Io + IH, where Io is the oxygen reduction current outside the crevice and IH represents the hydrogen reaction 2H+ + 2e– = H2
inside. There is a potential drop 􀄺E = Eo – Ei in the electrolyte from the free surface outside to the inside of the crevice. The
area of the crevice surface is often small compared with that of the outer surface. This means that a large corrosion current is
concentrated on a small area, so that the corrosion current density is very high in unfavourable cases. The anodic polarization
curve for a specimen with an active crevice will be in principle as shown in Figure below
. In this case a very small free external surface is assumed, and any internal hydrogen reduction is disregarded. Eou is the
potential as measured with the reference electrode positioned outside the crevice. As explained above, the real potential in
the crevice, Ein, is more negative. The lower limit for corrosion in an active crevice is the protection (or repassivation) potential
Epr. However, the critical potential that must be exceeded for initiation of the crevice corrosion process, the crevice corrosion
initiation potential, is higher than the protection potential.
Crevice corrosion is affected by several factors, of a metallurgical, environmental, electrochemical, surface
physical, and last but not least, a geometrical nature. One of the most important factors is the crevice gap. This
is indicated in Figure above. We can see that the critical gap size, below which crevice corrosion is possible
under the actual conditions, is smaller the more resistant the material is.
 Prevention of Crevice Corrosion
Crevice corrosion can be prevented or reduced by appropriate:

1. Selection of material. As dealt with in previous sections, conventional stainless steels, with martensitic, ferritic, austenitic or
ferritic–austenitic (duplex) structure, are sensitive to crevice corrosion (Table 7.4). Newer high-alloy steels with high Mo
content show by far better crevice corrosion properties in seawater and other Cl–-containing environments
2. Design and production.
Avoid as far as possible crevices and deposition.
a) Use butt welds instead of overlap joints. Alternatively, overlap joints can be sealed by continuous welds. Be careful
about the use of backing gas in welding processes, and check that the penetration is complete. After welding of
stainless steels, carry out pickling, brushing, blasting or grinding for removal of less protective and less resistant
surface layers.

b) Design in a way that promotes complete drainage and prevents accumulation of deposits. Make it easy to inspect and
clean.

3. Cathodic protection.

The potential must be kept below the protection potential.

An efficient method for internal protection of pipe joints is the “resistance controlled cathodic protection” (RCP)

4. Measures for preventing deposition.

a) Inspection and cleaning during and between service periods.

b) Separation of solid material from flowing media in process plants.
c) Gravel filling around buried piping and structures.
Filliform Corrosion
Although not immediately apparent, filiform corrosion (filamentary cor- rosion occuring on metal surfaces) is a special type
of crevice corrosion. In most instances it occurs under protective films, and for this reason it is often referred to as under
film corrosion. This type of corrosion is quite common; the most frequent example is the attack of enameled or lacquered
surfaces of food and beverage cans that have been exposed to the atmosphere. The red-brown corrosion filaments are
readily visible.
Under transparent surface films, the attack appears as a network of corrosion product trails. The filaments consist of an
active head and a red. brown corrosion product tail as illustrated in Fig. 3-11. The filaments are -to in. or less wide, and
corrosion occurs only in the filament head. The blue-green color of the active head is the characteristic color of ferrous
ions, and the red-brown coloration of the inactive tail is due to the presence of ferric oxide or hydrated ferric oxide.

Filiform corrosion is an unusual type of attack, since it does not weaken or destroy metallic components but only affects
surface appearance. Appearance is very important in food packaging, and this peculiar form of corrosion is a major
problem in the canning industry. Although fiiiform attack on the exterior of a food can does not affect its contents, it
does affect the sale of such cans.

Filiform corrosion has been observed on steel, magnesium, and aluminum surfaces covered by tin, silver, gold,
phosphate, enamel, and lacquer coatings. It has also been observed on paper-backed aluminum foil, corrosion
occuring at the paper-aluminum interface.
Interaction between corrosion filaments is most interesting.
Corrosion filaments are initiated at edges and tend to move in
straight lines. Filaments do not cross inactive tails of other filaments.
As is illustrated in (a), a corrosion filament upon striking the inactive
tail of another filament is reflected. The angle of incidence is usually
equal to the angle of reflection. If an actively growing filament
strikes the inactive taii of another filament at a 90° angle, it may
become inactive or, more frequently, it splits into two new
filamt:nts, each being reflected at an angle of approximately 45
degrees as shown in (b). The active heads of two filaments may join,
forming a single new filament if they approach each other obliquely
(c). Perhaps the most interesting interaction is the "death trap"
illustrated in (d). Since growing
filaments cannot cross inactive tails, they frequently become
trapped and "die" as available space is decreased. Examples of
"death traps" are easily found on the surface of discarded can lids,
which have been exposed to moist atmospheres.
Mechanism. The mechanism of filiform corrosion is not completely
understood. The basic mechanism appears to be a special case of crevice
corrosion as is illustrated in Fig. During growth, the head of the filament is
supplied with water from the surrounding atmosphere by osmotic action
due to the high concentration of dissolved ferrous ions. Osmosis tends to
remove water from the inactive tail, because of the low concentration of
soluble salts (iron has precipitated as ferric hydroxide). Thus, as shown in
Fig. atmospheric water continuously diffuses into the active head and out
of the inactive tail. Although oxygen diffuses through the film at all points,
the concentration of oxygen at the interface between the tail and the head
is high because of lateral diffusion. Corrosion is restricted to the head,
where hydrolysis of the corrosion products produces an acidic
environment. Thus, filiform corrosion can be viewed as a self-propagating
crevice. Although Fig. adequately explains the basic corrosion mechanism,
the unusual growth characteristics (i.e., lack of spreading) and interactions
between filaments are not understood.
 Prevention

There is no completely satisfactory way to prevent filiform corrosion. An obvious method is to store coated metal surfaces in
low-humidity environments. Although this technique can be used in some instances, it is not always practical for long-time
storage. Another preventive measure that has been employed consists of coating with brittle films. If a corrosion
filament begins growing under a brittle coating, the film cracks at the growing head. Oxygen is then admitted to the head, and
the differential oxygen concentration originally present is removed and corrosion ceases. However, as noted above, corrosion
filaments usually start at edges. Hence, a new corrosion filament begins at the point of rupture. Although brittle films sup-
press the growth rate of corrosion filaments, they do not offer much advantage since articles coated with such film must be
handled very carefully to prevent damage. Recent developments with films of very low water permeability hold some promise
in preventing filiform corrosion.
Pitting Corrosion
Pitting corrosion, or pitting, is a form of extremely localized corrosion that leads to the creation of small holes in the metal. The
driving power for pitting corrosion is the depassivation of a small area, which becomes anodic while an unknown but
potentially vast area becomes cathodic, leading to very localized galvanic corrosion. The corrosion penetrates the mass of the
metal, with a limited diffusion of ions. The mechanism of pitting corrosion is probably the same as crevice corrosion.

Pitting is a form of extremely localized attack that results in holes in the metal. These holes may be small or large in diameter,
but in most cases they are relatively small. Pits are sometimes isolated or so close together that they look like a rough surface.
Generally a pit may be described as a cavity or hole with the surface diameter about the same as or less than the depth.

Pitting is one of the most destructive and insidious forms of corrosion. It causes equipment to fail because of perforation with
only a small percent weight loss of the entire structure. It is often difficult to detect pits because of their small size and
because the pits are often covered with corrosion products. In addition, it is difficult to measure quantitatively and compare
the extent of pitting because of the varying depths and numbers of pits that may occur under identical conditions. Pitting is
also difficult to predict by laboratory tests. Sometimes the pits require a long time- several months or a
year- to show up in actual service. Pitting is particularly vicious because it is a localized and intense form of corrosion, and
failures often occur with extreme suddenness.
 Mechanism
We distinguish roughly between the mechanism of pitting initiation and that of pit growth. For more
detailed discussions, however, the pitting process is oftenconsidered to consist of the following stages:
1) Local breakdown of passivity (pit nucleation),
2) 2) early pit growth,
3) 3) late (stable) pit growth,
4) (possibly) 4) repassivation (Strehblow ).
The initial stage is not fully understood, but various theories exist.

On materials that often operate in a less pronounced passive state, such as copper, zinc and tin, pitting corrosion may
start in pores in surface layers of corrosion products. For materials that are typically passive initially, e.g. aluminium and
stainless steels, it is assumed that pitting is initiated by adsorption of halide ions that penetrate the passive film at certain
positions. This happens at weak points of the oxide film, e.g. at irregularities in the oxide structure due to grain
boundaries or inclusions in the metal. Absorption of halide ions causes strong increase of the ion conductivity in the oxide
film so that metal ions can migrate through the film. In this way localized dissolution occurs, and intrusions are
subsequently formed in the metal surface (Kaesche ). Another theory is that the initial adsorption of aggressive
anions at the oxide surface enhances catalytically the transfer of metal cations from the oxide to the electrolyte and thus
causes successive local thinning of the oxide film. A third possibility is that the attacks start at fissures in the passive layer
Which of the mechanisms is the most effective depends on both material and environment.
After pit nucleation there is a transition (i.e. successive stages of early pit growth) to stable pit growth. The transition,
implying development of pits from a few nanometres to the micrometre range, has been studied with scanning tunnelling
microscopes (STM) and further with scanning electron microscopes (SEM).

The next stage, i.e. the stable growth of the pit, proceeds essentially by the same mechanism as that of crevice corrosion .
Generally, the anodic dissolution occurs inside the pit, often mainly at the bottom, while the cathodic reaction is localized
outside the pit, on inclusions or other parts of the surface which are sufficiently efficient cathodes. Hydrolysis in the pit
leads to an acidic, aggressive pit solution, which also may allow an additional cathodic reaction here, namely reduction of
hydrogen ions. Metal cations from the dissolution reaction migrate and diffuse towards the mouth of the pit where they
react with OH– ions from the cathodic reaction, forming metal hydroxide deposits that may cover the pit more or
less.
Factors of general significance for pitting are:

a) pH and chloride concentration. The pitting potential and pitting resistance normally increase with increasing pH and
decreasing chloride concentration.

b) Flow velocity. When pitting is initiated, an aggressive environment is established within the pit, and this is combined with
an increased pH at the adjacent free surface. The increased pH gives an increased resistance to initiation of new pits around
the first one formed (this is the case, e.g. for unalloyed steel, but it is more uncertain with respect to aluminium). If there is
no movement of the liquid, these conditions will be conserved, and the result is large and few pits. Liquid flow gives a higher
probability for washing away the aggressive environment in the pit, and at the same time it increases the transport of oxygen
to the active area, so that the pit may be passivated before it gets the chance to grow to a considerable size. The alkaline layer
around an active pit is also washed away to a higher extent, and pit initiation in the neighbourhood of an active pit occurs
more easily. This means that increased flow velocity results in smaller but more numerous pits, which makes pitting corrosion
less serious.

c) The gravity force. Horizontal top surfaces are often heavily pitted, while underside surfaces are hardly, or not at all,
attacked. Vertical surfaces are intermediate as to the extent of pitting. The reason is that the aggressive environment in the
pits has a higher density than pure water.

d) Cu2+ and Fe3+ ions favour pit initiation and accelerate pit growth because they lead to increased potential (they are
oxidizers, compare Section 6.1). The Cu ions have a double effect because Cu is precipitated on the material surface and
forms efficient cathodes.
e) Metallurgical properties. Impurities and inclusions are important, e.g. AlFe secondary phase, which contributes to the
localization of pits on aluminium because
1) the oxide film on top of and around the inclusion is weak, thin and stressed,
2) such inclusions are efficient cathodes. Pitting of this type will usually last only until the pits are so large that the inclusions
are falling out.

f) The insulating ability of the oxide. If the oxide insulates efficiently, the surface is inactive as a cathode. This is to a certain
extent the case for aluminium in seawater; which is the direct reason for the relative slow growth of pits in this case.

g) Surface roughness. The main trend is that smooth surfaces get few, large pits while rough surfaces get numerous smaller
pits.

h) Temperature. Increasing temperature gives usually decreasing pitting potential and increasing liability to pitting corrosion.

i) Galvanic contact with a more noble material increases the tendency to and the rate of pitting corrosion (the corrosion
potential is lifted).
Metallurgical Variables
As a class, the stainless steel alloys are more susceptible to damage by pitting corrosion than are any other group of metals or alloys. As a
result, numerous alloy studies have been devoted to improving the pitting resistance of stainless
steels. The results are summarized in Table

Holding types 304 and 316 stainless steel in the sensitizing temperature range (950 to l450°F) decreases their pitting resistance.
Austenitic stainless steels exhibit the greatest pitting resistance when solution-quenched above
1800 0 F.
Severe cold-working increases the pitting attack of 18-8 stainless steels in ferric chloride. Preferential edge pitting is usually observed on most
wrought stainless products.

Surface finish often has a marked effect on pitting resistance. Pitting and localized corrosion are less likely to occur on polished than on
etched or ground surfaces. Generally, the pits that form on a polished surface are larger and penetrate more rapidly than those on rough
surfaces.

Ordinary steel is more resistant to pitting than stainless steel alloys. For example, the pitting of stainless steel condenser tubing exposed to
brackish water or seawater often can be alleviated by the substitution of steel tubes.
The best way to prevent pitting is appropriate materials selection. Among aluminium alloys, those alloyed with
magnesium and/or manganese and the commercially pure grades are the best ones. These perform quite well in
seawater.
Aluminium with magnesium (e.g. AlMg 4.5 Mn) is used in hulls of high-speed vessels and small boats, in deck
structures on ships and boats and in helicopter decks on oil and gas platforms. AlMgSi alloys will normally acquire
somewhat larger pits but they are used in profiles, e.g. in marine atmospheres.

Aluminium alloys with Cu and Zn are generally less corrosion resistant.

In stainless steels, increased content of Cr as well as N and Mo gives higher resistance against pitting, while Si, S and C
have the opposite effect. Modern highalloy steels with higher content of Mo (6–7%) have very good pitting resistance.
Some Ni alloys and particularly titanium are even better.
If general corrosion can be accepted, pitting corrosion can be avoided by selecting materials that are sufficiently
active in the environment in question.
Cathodic protection can also be applied to prevent pitting. Regarding aluminium, strong cathodic polarization should
be avoided because this can lead to a large increase of pH close to the metal surface, which can cause so-called
alkaline corrosion . Use of sacrificial anodes of Zn or Al alloys is therefore safer than impressed current.

Pitting can also be counteracted by change of environment. For instance, pitting of copper and copper alloys in hot
water can be prevented by water treatment, implying pH > 8.0 and [HCO3 –]/[SO4 2–] > 1