Eight forms of Corrosion: Wk2b

Eight forms of corrosion:

1. Uniform or general corrosion
2. Galvanic corrosion
Identifiable by
visual inspection 3. Pitting corrosion
4. Crevice corrosion
5. Intergranular corrosion
6. Selective leaching
Identifiable with special
inspection tools
7. Erosion corrosion
8. Stress corrosion
 3. Pitting Corrosion
Localized form of corrosion
Creates cavities or holes
More dangerous than uniform corrosion damage
because it is more difficult to detect, predict and design
against

Local failures
in passive film

Pits/holes ordinarily penetrate from the top of a horizontal

surface downward in a nearly vertical direction.
 3. Pitting Corrosion

Pitting corrosion occurs at the locations of

dissimilarity in the metal rather than inside a crevice.

Once a pit is formed from localized corrosion, the pit

continues to act as the anode (losing electrons and
mass) while the cathodic reaction remains O2 + 2H2O +
4e- 4OH-.

Corrosion products (scale) often form chimneys that

cover the pits and lead to an increased rate of corrosion
as the corrosive products become trapped within the pit.
 Pitting corrosion is initiated by chemical and mechanical
damage to the protective film, local damage to coatings
and the presence of non-metallic inclusion.

The major species responsible for pitting is chloride ion.

In general all halogen ions, sulfate, and heavy metal
ions present in sea water may induce pitting.

Pitting occurs only in the presence of oxygen. In

petroleum industry, pitting failures are caused by CO2
and H2S.
 Mechanism of Pitting:

At the anodic sites (within the pit) oxidation occurs as

M Mz+ + ze.
The anode forms the site of the pit.

At the cathodic sites, reduction of oxygen takes place as

O2 + 2H2O + 4e- 4OH-. Increase acidic of
surface

Due to continued oxidation at the anode, positive ions (Mz+)

are accumulated and excess positive charge is established in
the pitted area.
 These positively charged ions attract the negative Cl- ions
present in the electrolyte in which the metal is exposed.
M+ + Cl- MCl

The metal chloride reacts with the electrolyte (water) to

produce metal hydroxide and hydrochloric acid as
MCl + H2O MOH + HCl

The acid produced dissolves the metal.

The pitting process is auto catalytic i.e. once it starts, it

continues to accelerate with time and it only ends when the
metal is perforated.
Example: Carbon steel in sulphide inclusion
Mechanism of Pitting: (Carbon steel in sulphide inclusion)
 Pitting corrosion in stainless steel
The pitting corrosion in stainless steel makes small hole on
metal caused by the small damage of passive film on its surface
The pit is mainly caused by CI ion but exact mechanism is not
established.

When the corrosion is widely generated by pitting, it is hardly

seen with eyes because of its small-sized hole
The following is a situation where pitting corrosion would most likely occur:

i. Reusing a bent rod that has been re-straightened.

ii. When a bent rod is straightened, the rod-straightening machine will

put spiral grooves around the rod, which will then lead to corrosion
adjacent to grooves. The grooves will then become continuously
deeper as pitting corrosion proceeds.
 3. Pitting Corrosion
Major characteristics of pitting corrosion:

The area which is in lack of oxygen becomes anodic while

the area with excess of oxygen becomes cathodic.
Severe problems happen in stagnant solutions.
Gravity causes pit to grow downward corrosion rate can
increase with time.

Very destructive since highly localized may go

undetected until failure occurs.

This can be seen where local failures in the film on

stainless steel may be anodic to the remainder of the
surface.
This is more commonly seen on aluminum, and most
commonly on steel in heterogeneous soil.
 3. Pitting Corrosion

Pitting is initiated by:

i. Localized chemical or mechanical damage to the
protective oxide film;
ii. water chemistry can cause breakdown of a passive film
iii. low dissolved oxygen concentrations (which tend to
render a protective oxide film less stable) and high
concentrations of chloride (as in seawater).
iv. The presence of non-uniformities in the metal structure
of the component, e.g. nonmetallic inclusions.
 3. Pitting Corrosion

Types of Pitting corrosion:

 3. Pitting Corrosion

Pitting corrosion on outside

surface of cast iron bathtub

SEM Analysis
 3. Pitting Corrosion
Pitting Corrosion Prevention
Material selection
Use higher alloys to increase resistance to pitting corrosion

Stainless steels are somewhat susceptible to this form of

corrosion; however, alloying with about 2% molybdenum
enhances their resistance significantly.

Proper selection of materials with known resistance to the

service environment

Avoid stagnant flow

Control pH, chloride concentration and temperature
Cathodic protection and/or Anodic Protection
 3. Pitting Corrosion
Test and Design Considerations (Pitting)

Design Considerations
Crack initiator
Can cause perforation
Can lead to wear problems

Measurement
Depth/Diameter
Density of pits
Shape

Misapplication of Data
There is no way to isolate pitting from other forms of corrosion
May be difficult to distinguish from uniform corrosion
Difficult to predict penetration rate Challenging area to find
penetrate rate
 4. Crevice Corrosion
Crevice Corrosion is the attack on the surface of a metal partly
shielded from contact with the corroding fluid.

Typically, this is a concentration cell effect, the shielded area

being anodic.
Crevice corrosion initiates due to changes in local chemistry.

Changes in local chemistry within the crevice could be:

a. Depletion of inhibitor in the crevice
b. Depletion of oxygen in the crevice
c. Increase of hydrogen concentration or chlorine ions
d. A shift to acid conditions in the crevice
e. Build-up of aggressive ion species (e.g. chloride) in the
crevice
 4. Crevice Corrosion
This is also an electrochemical oxidation-reduction (redox)
process.

It normally occurs within localized volumes of stagnant

solution trapped in pockets, corners or beneath a
shield (seal, deposit of sand, gasket, fastener, etc.).

It could be under
Gaskets
Washers
insulation material
fastener heads
surface deposits
disbonded coatings
threads,
lap joints and clamps.
 4. Crevice Corrosion

Crevice corrosion mechanism (Steel in chloride solution):

First, metal ions are formed by

realising electrons in a crevice
zone.

The positively charged metal ions in

electrolyte then attracts negative
ions of chlorine Cl- in the crevice

This increases acidity of the

electrolyte by the following reaction
and thereby keep continue in
changing electrolyte chemistry.

FeCl2 + 2H2O = Fe(OH)2 + 2HCl

 4. Crevice Corrosion

The mechanism for crevice corrosion for an iron joint in a brine

solution where oxygen present:

Stage 1: Corrosion occurs both inside and outside the crevice.

Anodic reaction: Fe Fe2+ + 2e- E(V) = 0.45

Cathodic reaction: O2 + 2H2O + 4e- 4OH- E(V) = 0.40

Note: The positively charged iron ions inside the crevice are
electrostatically balanced by the OH-.
 4. Crevice Corrosion

Stage 2: In this stage, the cathodic reaction inside the crevice

consumes most of the oxygen available.

Stage 3: Cl- and OH- diffuse into the crevice to maintain a minimum
potential energy. Iron chloride is formed and the hydrolysis of the
iron chloride lowers the pH.

FeCl2 + 2H2O Fe(OH)2 + 2HCl

Note: HCl is strong acid and hence dissociates into H+and Cl- ions. As the
H+ ions cause an increase in acidity most of the protective iron(II) oxide
corrosion deposit dissolves.

Stage 4: More Fe2+ ions attack and more Cl- leads to lower the pH
inside the crevice, metal dissolution accelerates and more Fe2+
ions will be produced.
 4. Crevice Corrosion

Major characteristics of crevice corrosion:

i. Highly accelerated if chloride, sulphate or bromide ions are

present in the electrolyte solution.

ii. This is much more dangerous than uniform corrosion since its
rate is 10-100 times higher.

iii. Stainless steels, Aluminum alloys and other metals forming a

passive oxide layers on their surfaces are sensitive to crevice
corrosion.

iv. Mechanism of crevice corrosion is similar to that of Pitting

corrosion: dissolution of the passivating film and gradual
acidification of the electrolyte caused by its insufficient aeration
(Oxygen penetration).
 4. Crevice Corrosion

Depending on the environment developed in the crevice

and the nature of the metal, the crevice corrosion can
take a form of:

Pitting (i.e., formation of pits),

Filiform corrosion (this type of crevice corrosion that
may occur on an aluminium surface underneath an
organic coating),
Intergrannular attack, or
Stress corrosion cracking.
 4. Crevice Corrosion

KEY In crevice there are high

concentrations of H+ and Cl- ions which are
especially corrosive!
 4. Crevice Corrosion

Crevice corrosion between pipe

and I-beam: Rubber pads just accelerated the
attack why???
 4. Crevice Corrosion
Crevice Corrosion

Crevice corrosion beneath a seal on a stainless

steel flange

Figure 6. Crevice corrosion

 4. Crevice Corrosion
Crevice Corrosion

Schematic illustration of the mechanism of crevice

corrosion between two riveted sheets.
Crevice corrosion on screws.
 4. Crevice Corrosion

Crevice Corrosion

Crevice corrosion. Crevice corrosion of through hull bolts.

 4. Crevice Corrosion

Crevice Corrosion Protection

i. Use Welded joint instead of riveted or bolted joints
ii. Use non-absorbing gaskets, such as Teflon
iii. Remove accumulated deposits frequently

iv. Designing containment vessels to avoid stagnant areas

and ensure complete drainage.

v. Use higher alloys for increased resistance to crevice

corrosion
 4. Crevice Corrosion
Test and Design Considerations (Crevice corrosion)

Design Considerations
Crack initiator
Can cause perforation
Can lead to wear problems

Measurement
Depth/Diameter
Density of pits
Shape

Misapplication of Data
No way of isolating pitting from other forms of corrosion
May be difficult to distinguish from uniform corrosion
Difficult to predict penetration rate
Identifiable by visual inspection

Uniform Corrosion Pitting Corrosion

Crevice Corrosion Galvanic Corrosion