Crevice Corrosion

Forms of corrosion

™ General corrosion (uniform corrosion over the whole anode)

™ Localized Corrosion (corrosion at isolated areas in the anode)
 Galvanic corrosion
 pitting corrosion
 Crevice corrosion
™ Metallurgically Influenced Corrosion (corrosion is related to microstructure)
 intergranular corrosion of stainless steel
™ Mechanically Assisted Corrosion (corrosion is accelerated due to mechanical
factors)
 Erosion corrosion
 Corrosion Fatigue
™ Environmentally Assisted Cracking (corrosion results in cracking)
 Stress corrosion cracking
 Hydrogen damage

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 Forms of Corrosion

Factors affecting forms of corrosion :

Microstructure ↔ Environment ↔ Stress ↔ Geometry ↔ Time

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CREVICE CORROSION
Narrow openings, gaps, spaces, pores etc. between metal‐metal components or metal‐
non‐metal components may provoke intense localized corrosion.

NOTE: unintentional crevices (seams, cracks etc.) can also act in the same way

Passive alloys (especially stainless steels) are more vulnerable than more active alloys.

Crevice corrosion at a metal‐to‐metal

crevice site formed between components
of type 304 stainless steel fastener in
seawater

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Â Crevice corrosion is caused by the existence of small volumes of stagnant
(corrosive) solution. Small holes, gasket surfaces, lap joints, bolt or rivet heads,
nuts, washers, surface deposits all can cause C.C. (Crevice Corrosion).

 Type 304 SS sheet can be cut by stretching a rubber band around it, immersing it
in seawater. The crevice between the rubber and the metal acts as the cutting
zone.

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Mechanism of Crevice Corrosion
Consider a riveted plated section of metal M immersed in aerated sea water.

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Mechanism

1. Initially, the following anodic and cathodic reactions occurs uniformly on the
entire metal surface, inside and outside the crevice ;
 Anodic reaction : M → Mz+ + ze‐
 Cathodic reaction : O2 + 2H2O + 4e‐ → 4OH‐
2. After induction period, O2 in crevice is used up due to restricted convection ;
 Crevice → low O2 region → low Ea → small anode.
 External surface → high O2 region → high Ec → large cathode

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Mechanism

3. Electromigration of Cl‐ due to ∆E = Ea – Ec

Anodic reaction in crevice : M → Mz+ + e‐
 Excess positive charge (Mz+) is building up, which is balanced by the
electromigration of Cl‐ and other anions from outside.
 Anion migration : Anions such as Cl‐, OH‐, CO32‐, and SO42‐ diffuse into the
crevice with a velocity depending on its diffusion rate. Among the anions, Cl‐
ion is the most fast.
 Cation migration : the metal ions accumulated in the crevice are transported
slow out of the crevice by diffusion and electromigration.

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Mechanism

4. Acidification by hydrolysis reaction of metal ion ;

 The abundance of metal ions inside the crevice gives rise to their
hydrolysis with water molecules;
 Mz+ + H2O →M(OH)z↓ + z H+......... This reduces pH in the crevice. The
low pH or acidity prevents passivation and facilitates anodic
dissolution.

Hydrolysis reactions and

equilibrium pHs for metal ions in
an occluded cell in stainless
steels.
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Mechanism
 In the case of pure metals, the pH values were found to be lower than those
calculated from the metal ion conc., and the experimentally determined pHs were
as follows ;
Fe :4.71, Cr :0.09, Ni :2.93, Mo :0.02, which indicates that Cr and Mo in an alloy
would have the greatest effect in lowering the pH within the crevice or pit.

5. Depassivation
 Passivation does not occur in the crevice when the critical pH and [Cl‐] in
electrolyte of crevice have been achieved.

6. Cathodic protection of external surface

 Cathodic reaction at external surface : O2+ 4H2O +4e‐→4OH‐..........High pH
facilitates passivation of external surface and the external surface is
cathodically protected by the electrons liberated by the anodic reaction.

Low pH, high [Cl-], depassivation lead to an

accelerating or autocatalytic corrosion in the crevice.

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Prevention of crevice corrosion

1. Use welded butt joints instead of riveted or bolted joints in new equipment.
Sound welds and complete penetration are necessary to avoid porosity and
crevices on the inside (if welded only from one side).
2. Close crevices in existing lap joints by continuous welding, caulking, or soldering.
3. Design vessels for complete drainage; avoid sharp corners and stagnant areas.
Complete draining facilitates washing and cleaning and tends to prevent solids
from settling on the bottom of the vessel.
4. Inspect equipment and remove deposits frequently.
5. Remove solids in suspension early in the process, if possible.
6. Remove wet packing materials during long shutdowns.
7. Provide uniform environments, if possible, as in the case of backfilling a pipeline
trench.
8. Use "solid," nonabsorbent gaskets, such as Teflon, wherever possible.
9. Weld instead of rolling in tubes in tube sheets.

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FlLIFORM CORROSION
~ Although not immediately apparent, filiform corrosion (filamentary corrosion
occurring 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 underfilm 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.
~ Filiform corrosion usually on metals covered with thin organic film (∼0.1 mm)
BUT also reported for:
 steel; magnesium; aluminum; tin; silver; gold; phosphate; enamel
 as well as with organics (lacquer, paper; seen on paper‐backed Al foil,
between metal and paper).
~ Attack usually occurs when relative humidity between 65 and 90%; has been
seen at lower R.H. (Relative Humidity).
~ Average filament width ∼ 0.05 ‐ 3 mm .. depending on coating (thickness,
porosity, etc.), R.H., and corrosiveness of environment (presence of SO2, H2S,
etc.).
~ Filament height ∼ 20 µm. Growth rates observed between 0.01 mm/d and 0.85
mm/d.
~ Filaments are like minute tunnels, full of corrosion products.
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A lacquered steel can lid exhibiting filiform corrosion showing both large and small
filaments partially oriented in the rolling direction of the steel sheet. Without this 10 x
magnification by a light microscope, the filiforms look like fine striations or minute
tentacles; (often mistaken for biologically – induced corrosion).
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Mechanism

Head supplied with H2O by osmosis (high concentration of Fe2+ inside) through
coating and from precipitated hydroxide/oxide. Oxygen reduction creates
hydroxide; precipitation creates corrosion product tail. . . . further oxidation to
Fe3+ oxide etc. Hydrolysis of salts in head creates acidic conditions.

Details of mechanism
not understood………….
e.g., why do filaments
“reflect” off other filaments? etc.

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† Liquid in “head” is typically acidic. . . . pH 1‐ 4.

† IN ALL CASES.... O2 (or air) and water are needed to sustain filiform
corrosion … indicates a form of a DIFFERENTIAL AERATION CELL.

Discuss:

differential aeration cell

concentration cell.

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An aside on differential aeration . . (differential) concentration cell
remember example: remember Cu ‐ alloy crevice:

(potential ∝ log [Cu+])

Attack usually begins at imperfections in coating e.g., cuts, knicks, pores, etc.
CO2 can stimulate process by dissolving in water → carbonic acid.
Chlorides, SO42-, S2- which can dissolve in condensing atmospheric moisture also increase
attack.
Optimum temperature for filiform attack between 20 & 35°C.

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Effect of humidity on filiform corrosion of enameled steel
Relative humidity, % Appearance
0-65 No corrosion
65-80 Very thin filaments
80-90 Wide corrosion filaments
93 Very wide filaments
95 Mostly blisters, scattered filiform
100 Blisters
Source: M. Van Loo, D. D. Laiderman, and R. R. Bruhn, Corrosion, 9:2 (1953).

Appearance:
Schematic diagram of a corrosion
filament growing on an
iron surface (magnified).

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Schematic diagrams illustrating the
interaction between corrosion filaments:

(a) Reflection of a corrosion filament;

(b) splitting of a corrosion filament;
(c) joining of corrosion filaments;
(d) “death trap”.

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Filiform Corrosion on PVC‐Coated Al Foil

Advancing head and cracked tail of a Gelatinous corrosion products oozing out
filiform cell. of porous tail section.
Scale: 0.125 mm Scale: 1.25 µm

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Close‐up of the advancing head shown in adjacent
figure. Minute cracks can be seen at the head/tail
interface of a filiform corrosion cell. These cracks
are entry points for water and air to provide a
source of hydroxyl ions and an electrolyte.
Intermediate corrosion products are just
beginning to form in the head, and they undergo
further reaction to form an expanded tail. The tail
region is a progressive reaction zone that
ultimately forms spent corrosion products.
Between the head and porous end, ions gradually
react with water and oxygen and are slowly
transported in the direction of the tail to form
final corrosion products.

Scale: 15 µm

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