EP 321

CORROSION

UNIFORM, GALVANIC,
CONCENTRATION CELL
& PITTING CORROSION
Topics
1- UNIFORM Attack

2- GALVANIC Corrosion
Galvanic Series
Contributing Factors
Prevention

3- CONCENTRATION Cell Corrosion

Mechanism
Prevention

4- PITTING Corrosion
Pit Shape and Growth
Pitting Mechanism
Metallurgical Variables
Evaluation of Pitting Damage
Prevention
1- Uniform Attack

Most common form of corrosion.

Accounts for greatest weight loss of metal by
corrosion processes.
Characterized by chemical or electrochemical
reaction.
Proceeds uniformly over exposed area.
Results in general loss of material (thinning),
roughening of the surface and eventually
failure.
 Examples:

Steel immersed in dilute acid. Ferritic stainless steel exposed to

sulphur-containing atmosphere.
Predicting Uniform Attack

Most predictable form of corrosion.

Expected life of equipment can be accurately
estimated by immersing specimen in fluid of
interest.
Corrosion rate of short period can be
determined by Faradays law and extrapolated
to longer times.
Controlling Uniform Attack

Material selection:
- Substitute with more corrosion-resistant material (or
lower uniform corrosion rate).

Protective coatings:
- Use metallic, organic and inorganic coatings to
isolate the susceptible metal from the corrosion
environment.
 Change the environment:
- Inhibitors can be added to the environment to
reduce corrosivity or corrosive species can be
removed.

Change the potential:

- Cathodic protection methods, shifting
electrochemical potential to passive region.

Design:
- Build in a corrosion allowance into the structure.
2- Galvanic Corrosion

Occurs between two dissimilar metals in

contact in a common electrolyte.
Driving force for corrosion is the potential
developed between the dissimilar metals.
In galvanic corrosion, less resistant metal
becomes anodic, more resistant metal
becomes cathodic.
Galvanic Series

A measure of corrosion potential of various

materials in the electrolyte of interest against
a reference electrode half-cell, such as
saturated calomel.
Does not give information on rate of
corrosion.
Active-passive metals may display two widely
differing potentials.
Zinc-coated steel versus tin-plated steel.
 Examples:
Prevention

1. Select combinations of metals as close

together as possible in the galvanic series.
2. Avoid undesirable area effect of small anode
and large cathode.
3. Insulate dissimilar metals where practicable.
If complete insulation is not possible, paint or
use plastic coating at joints.
4. Apply coatings and keep them in good repair.
5. Add chemical inhibitors to decrease
aggressiveness of environment.
6. Avoid joining material far apart in the series.
Use welded joints of same alloy or brazed
joints with brazing alloy more noble than at
least one of the metals to be joined.
7. Design for readily replaceable parts.
8. Use cathodic protection (sacrificial anodes).
Applications
Batteries
- Dry cell batteries operate on the basis of galvanic corrosion of
an electrode.
Cathodic protection by sacrificial anode
- Magnesium is connected to underground steel pipes as
magnesium preferentially corrodes.
Cleaning silver
- Place silver in aluminium pan containing water and baking
soda. Silver sulfide is reduced back to silver.
3- Concentration-Cell Corrosion

Occurs when two or more areas of a metal

surface are in contact with different
concentrations of the same solution.
There are 3 general types of concentration-cell
corrosion:
(a) metal-ion concentration cells
(b) oxygen concentration cells
(c) active-passive cells
 Metal Ion Concentration Cells
-When objects are fastened together, the area
of the metal in contact with low concentration
of metal ions will be cathodic and will be
protected, and the area of metal in contact
with the high metal ion concentration will be
anodic and corroded.
-This condition can be eliminated by sealing
the faying surfaces in a manner to exclude
moisture.
 Oxygen Concentration Cells
An oxygen cell can develop at any point where
the oxygen in the air is not allowed to diffuse
uniformly into the solution, thereby creating a
difference in oxygen concentration between
two points (e.g. under either metallic or
nonmetallic deposits (dirt) on metal surface,
riveted lap joints, under gaskets, etc.).
Corrosion will occur at the area of low-oxygen
concentration (anode).
 Active-Passive Cells
Occurs on metals that depend on a tightly
adhering passive film (usually an oxide) for
corrosion protection; e.g. austenitic corrosion-
resistant steel. If the passive film is broken,
the active metal beneath the film will be
exposed to corrosive attack. An electrical
potential will develop between the large area
of the cathode (passive film) and the small
area of the anode (active metal). Rapid pitting
of the active metal will result.
Example

Crevice corrosion (beneath a seal) on a stainless

steel flange exposed to a chloride-rich medium.
Mechanism

Consider a riveted plate section of metal M

immersed in aerated seawater.
Anodic reaction (oxidation):
M M+ + e-
Cathodic reaction (reduction):
O2 + 2H2O + 4e- 4OH-
 Over time, oxygen
concentration within crevice
decreases and cannot be
replenished by flow or
diffusion from bulk
electrolyte due to
constricted geometry.
 After oxygen is depleted, no further oxygen
reduction takes place.
But metal dissolution continues.
Excess of positive charge is produced in
solution which is balanced by migration of
chloride ions into the crevice.
Hydrolysis occurs:
M+Cl- + H2O MOH + H+Cl-
Solution within crevice becomes more acidic.
Process is autocatalytic.
 As corrosion within crevice increases, rate of
oxygen reduction on adjacent surfaces also
increases.
External surfaces are cathodically protected.
Prevention
1. Use welded butt joints instead of riveted or bolted
joints.
2. Close crevices in existing lap joints by welding,
caulking or soldering.
3. Design vessels for complete drainage, avoid sharp
corners and stagnant areas.
4. Inspect equipment and remove deposits frequently.
5. Provide uniform environments in backfilling of
pipeline trenches.
6. Use solid, non-absorbent gaskets, i.e. Teflon.
4- Pitting

A form of localised attack.

Results in holes or pits
(cavities) in the metal.
Surface areas adjacent to
highly attacked region
show little or no signs of
corrosion.
 Difficult to detect as
they are often covered
with corrosion
products.
Difficult to predict due
to varying depths and
number of pits.
Most destructive form
of corrosion as it
results in unexpected
failure.
Pit Shape and Growth
Pitting Mechanism
Passive metals (e.g. stainless steels) are
susceptible to pitting attack.
Pits tend to initiate at areas with:
- Microstructural features
- Discontinuity in metal surface ,e.g. scratch
- Variation in local chemistry, e.g. deposit
where local increases in corrosion rates occur.
Pitting usually requires an extended initiation
period before visible pits appear.
 Begins with dissolution of metal in the pit.
Anodic reaction:
M Mn+ + ne-
Cathodic reaction takes place at metal surface
surrounding the pit.
O2 + 2H2O + 4e- 4OH-
Chloride ions migrate to pit to maintain charge
neutrality.
M+ + Cl- MCl
 Metal chloride reacts with water.
Produces high concentration of MCl and high
concentration of hydrogen ions.
M+Cl- + H2O MOH + H+Cl-
High acid concentration builds up at the
bottom of the pit.
Both hydrogen and chloride ions stimulate the
dissolution of metal.
Process is repeated and corrosion is
accelerated with time (autocatalytic process).
 Usually occurs in environment containing
chloride ions.
Associated with stagnant (static) conditions
where liquid is trapped.
Increasing velocity often decreases pitting
attack.
Metallurgical Variables

Stainless steel alloy are more susceptible to

pitting than other groups.
Severe cold-working increases pitting attack of
stainless steel in ferric chloride.
Polished surface finish reduces the tendency
to pitting compared to ground or etched
surfaces.
Corrosion pits are harmful and act as stress
raisers, initiating fatigue and SCC.
Evaluation of Pitting Damage

Metal loss is small and does not indicate

depth of penetration.
Usually expressed as measurement of
maximum pit depth but pit depth is a function
of sample size.
Prevention

Material selection.
- Use materials that are more resistant to pitting.
SS304 < SS316 < Hastealloy F < Hastealloy C < Titanium
Use inhibitors.
Avoid stagnant zones.
Reduce aggressiveness of environment.
Example: Pitting of launch pad tubing from
The Kennedy Space Centre

http://corrosion.ksc.nasa.gov/pittcor.htm
Example: Pitting corrosion on an uncoated piece of cast
iron, as a result of Hurricane Ivan in Grand Cayman,
September 2004. The effect of wind carried saltwater
residue that covered over the surfaces of equipments,
leading to pitting corrosion.
Example: Pitting corrosion in sweet and sour environments.

In sweet (CO2) systems, pits are generally small with sharp edges and smooth
rounded bottoms. Pits may become connected as the corrosion damage increases.
Corrosion products are dark brown to grayish black and loosely adhering.

In sour (H2S) systems, the pits are usually shallow round depressions with etched
bottoms and sloping sides. Generally, the pits are not connected, and corrosion
products are black and tightly adhering to the metal surface.

Pitting in CO2 system Pitting in H2S system

- THE END -