Module 8, Objective 2

(part 1/3)
Types of Corrosion, pg. 8-16
Objectives
• Identify the corrosion mechanisms for various given conditions.

1) General or Uniform
2) Galvanic
1) Uniform
3) Crevice and Pitting 2) Galvanic
3) Crevice and Pitting
4) Temperature gradient
5) Velocity gradient

4) Temperature gradient
6) Cavitation
7) Fretting
8) Atmospheric (dry, damp, wet)
9) Stray current 5) Velocity gradient
10) Biological
11) Intergranular (IGC), Exfoliation
12) Stress corrosion cracking (SCC)
13) Hydrogen induced (HIC/SSC), Hydrogen blistering
14) Corrosion fatigue cracking
15) Graphitization
16) Selective leaching
1) Uniform Corrosion (AKA “general corrosion”)
• Uniform corrosion occurs when the material is all the same.
• Ex: a steel pipe can corrode with only water and oxygen present (no other metal).
• Certain regions are naturally more reactive than other areas
• Difference in reactivity/potential = an anode and a cathode!
• Water acts the electrolyte
• Electrical contact is through the metal itself

 All four conditions for corrosion can exist in

one piece of steel surrounded by water!
1) Uniform Corrosion
What can create the difference in reactivity?
• Rough surfaces or microscopic imperfections
• Different orientation of grains at the surface
• Iron carbide is more noble/less reactive than iron alone (ferrite)
• Fe3C becomes the cathode, while the iron crystal is less noble and becomes the anode.
• More Fe3C (pearlite) = more cathodes = smaller anode to cathode ratio = more corrosion!
The higher the carbon content, the faster the corrosion

• The reactive regions (ex: grains of ferrite) are spread throughout the material.
• The noble regions (ex: grains of Fe3C) will eventually fall out as the corrosion
spreads beneath them.
 Relatively uniform corrosion occurs because the grains are extremely small and
the anode location continually changes as corrosion proceeds.
1) Uniform Corrosion
 The anode moves around, corroding the surface evenly.

• Uniform corrosion is the most desirable form of corrosion.

• No localized anode and cathode
• Relatively slow (small potential differences)
• Relatively predictable (constant rate of corrosion over time)
• Uniform loss in thickness (no unexpected failure due to cracking/pitting)

• If I must have corrosion, I’d prefer it to be uniform!

• Spreading out the corrosion due to the moving anode ✓
 2) Galvanic Corrosion*
• Galvanic corrosion occurs when two
different metals are electrically connected
and in the same electrolyte.
• Corrosion of the less corrosion resistant (less
noble) material increases and its surface
becomes an anode.
• Corrosion of the more corrosion resistant (more
noble) material decreases and it becomes the
cathode.
• The driving force is the potential (voltage)
difference between the different metals.
 Can you determine which is the anode and
cathode in these two images?
*Corrosion types with stars next to them are most important (and will be on the exam!)
2) Galvanic Corrosion
The rate of galvanic corrosion depends upon:
• The nature of their environment.
• Higher concentration of dissolved solids (ex: salts) → more conductive electrolyte
• Lower pH → more acidic environment
• Increasing the distance between the dissimilar materials
• More distance = increased electrical resistance.
• Corrosion is always greatest near the junction and decreases the farther the metal is
from the joint. This occurs because the electrons will always take the shortest path.
• The potential difference between the materials
• If the difference is less than 0.3V, then the galvanic corrosion is minimal.
 Standard Reduction
Reduction Half-Cell Reaction
Potential E0 (volts)
Mg+2 + 2 e- → Mg(s) -2.37 V
Al+3 + 3 e- → Al(s) -1.66 V
Mn+2 + 2 e- → Mn(s) -1.18 V
2 H2O + 2 e- → H2(g) + 2 OH- -0.83 V
Zn+2 + 2 e- → Zn(s) -0.76 V

Cr+3 + 3 e- → Cr(s) -0.74 V

S(s) + 2 e- → S-2 -0.48 V
Fe+2 + 2 e- → Fe(s) -0.44 V
Cd+2 + 2 e- → Cd(s) -0.40 V
Co+2 + 2 e- → Co(s) -0.28 V

Ni+2 + 2 e- → Ni(s) -0.25 V

Sn+2 + 2 e- → Sn(s) -0.14 V
2 H+ + 2 e- → H2(g) 0.00 V
S(s) + 2 H+ + 2 e- → H2S(g) 0.14 V
Cu+2 + 2 e- → Cu(s) 0.34 V

O2(g) + 2 H2O + 4 e- → 4 OH- 0.40 V

Cu+1 + 1e → Cu(s) 0.52 V
Ag+1 + 1e → Ag(s) 0.80 V
O2(g) + 4 H+ + 4 e- → 2 H2 O 1.23 V
Cl2(g) + 2e → 2 Cl- 1.36 V

Au+3 + 3e → Au(s) 1.50 V

2) Galvanic Corrosion Prevention
Galvanic corrosion can be controlled by:
• Selecting metal combinations as close as possible to each other in the
galvanic series (i.e., keep voltage < 0.3V).
• Electrically isolating dissimilar metals
• Breaks the electrical connection; without current flow there is no corrosion
• Often done with a gasket, with washers and sleeves preventing contact
3) Crevice and Pitting Corrosion*
• Crevice and pitting corrosion will occur in shielded areas
• Surface deposits, severe gouges, large inclusions/defects, crevices, etc.
• Anywhere that lacks easy access to the electrolyte
• As corrosion takes place, certain ions will be consumed.
• Most often oxygen, consumed by the cathode reaction (O2 + 2H20 + 4e- → 4OH-)
• The consumed ions/oxygen cannot be replaced in the shielded areas
because the electrolyte cannot get easy access to replenish the lost ions.
• This creates a concentration cell
• Concentration cell: a difference in electrolyte concentration in different areas
• That concentration difference leads to a difference in reactivity → corrosion
• Most common is the oxygen concentration cell
• The oxygen concentration cell is what causes both crevice and pitting corrosion
3a) Pitting Corrosion
• Any kind of surface deposits will prevent the electrolyte from replenishing
oxygen
• Creates a low oxygen region, which will initiate a pit (under deposit corrosion)
• Examples include:
• sediments settling in pipelines
• road mud in the wheel arch of a car
• barnacles on a ships' hull
• hard water deposits in cooling tubes
• bacterial colonies
• local breaks in the oxide layer (e.g., Cl on stainless steel)

• Regular cleaning can be a very effective method of preventing pitting!

3a) Pitting Corrosion
• Small area under deposit (anode), large area around deposit (cathode)
• Fast corrosion rate!

• Once the pit forms, it will continue to grow straight into the material, 90° to
the surface
• The anode is at the bottom of the pit where the oxygen content is lowest
• May continue to grow even if the surface has been cleaned!
• If the pits are not too deep, remove by grinding, or the area can be cleaned and coated

• Pits can be as small as a pinhead!

• Very difficult to detect until they have travelled through the full thickness
• In a pressure vessel (pipeline, boiler, etc.), this can result to an explosion
 Figure: a riveted metal joint that is immersed in aerated
3b) Crevice Corrosion seawater (oxygen is present)

Crevice corrosion proceeds by the following steps:

1. Uniform corrosion both in and outside the crevice.
• The anodes and cathodes are very small and very close
together.
Oxidation: M → M+ + e-
Reduction: O2 + 2H2O + 4e- → 4(OH)-
2. After some time, the crevice becomes depleted of
oxygen because fluid cannot easily flow into the
crevice.
• Reduction of oxygen stops in this area, but metal oxidation
continues.
• Low oxygen crevice becomes the anode, outside area
becomes the cathode where there is high oxygen content
(high O2 = easy reduction reaction).
3. Corrosion is accelerated because of the small
anode to cathode ratio.
3b) Crevice Corrosion
• Coatings (ex: paint) are especially prone to crevice corrosion if they are
damaged (scratched).
• Corrosion will follow just under the surface of the paint, causing the paint to lift.
• Water will be retained in the porous corrosion product under the paint, which will
cause corrosion to continue even when the rest of the structure is dry.
• Any damage to coatings must be repaired immediately!

• Will stainless steel prevent crevice corrosion?

• No! The passive oxide layer of stainless steel (or aluminum), cannot form at the low
oxygen anode.
• Lack of passive layer causes the metal to become even more active in the crevice,
which increases the corrosion rate even further.
3) Crevice and Pitting Corrosion Prevention
• Remove crevices (welds are better than rivets or bolts).
• Use nonabsorbent solid gaskets.
• Avoid sharp corners and stagnant fluid areas (causing settling of particles)
• Design pressure vessels and tanks to ensure complete drainage.
• Keep packing materials dry (porous materials such as rags should never be in
contact with metal).
• Frequent inspections to remove deposits (cleaning).
• Use metals designed for pitting resistance.
• Ex: PREN (Pitting Resistance Equivalent with Nitrogen) can be calculated for stainless steels.
• PREN = (%Cr) + (3.3 x %Mo) + (30 x %N)
• Molybdenum oxides are more adherent then chromium oxides so improves pitting resistance.
• Nitrogen reacts with chromium to form chromium nitride → 30 times more effective than Cr-oxide!
4) Temperature Gradient
A temperature gradient (temperature cell) occurs when there’s a difference
in temperature over a short distance.
• A hotspot will have higher activity (anode) and will corrode more compared
to nearby cooler regions (cathode).
• Ex: compressor on a gas pipeline, heat exchanger systems
5) Velocity Gradient
A velocity gradient (velocity cell) may be created in two ways:
1. High velocity fluid (usually liquid but may be gas)
• Erodes the passive oxide layer
• Exposed metal is the anode (more active)
• Surrounding pipe is the cathode
• Sometimes called “erosion corrosion”

2. Low velocity fluid (carrying suspended particles)

• Particles settle to the bottom of the pipe
• Creates an oxygen concentration cell → pitting
5) Velocity Gradient Prevention

Can be controlled by:

• Selecting the proper material (high hardness? pitting resistant?)
• Redesigning components (use smooth bends, no sharp corners)
• Reducing the flow velocity and turbulence
• Removing particles from the fluid
 Exercise 2 (pg. 28,29)
1. To produce galvanic corrosion, there must be ____________ metals, immersed
in ______________ and connected by a ___________ path.
11. A steel pipe that has copper fittings is buried in damp soil. Identify the type of corrosion and the four
elements of the electrochemical corrosion cell. Describe one element in detail.

16. When zinc and copper are electrically connected and immersed in HCl, zinc goes into solution at the
___________ and hydrogen is generated on the copper _______________.
20. Temperature variations within a metal will cause the warmer parts to become ______________.
22. Small deep anodic sites causing concentrated destruction of the metal is called _____________.

• Identify the likely cause of failure for the following:

26. An aircraft handler had difficulty operating a magnesium alloy fuel pipe coupling. She found that lubricating
the coupling with a graphite grease solve the problem. The next time it rained, the coupling seized.
28. A series of stainless steel heat exchangers, cooled with treated water, performed for 10 years without
problems. During an emergency, untreated chlorinated city water was used instead for 36 hours. Some
weeks later, five units failed. 19
 Bonus Questions
Why is uniform corrosion the most desirable form of corrosion?

True or False: Stainless steel is immune to crevice corrosion.

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 Bonus Questions
Why is uniform corrosion the most desirable form of corrosion?
• No localized anode and cathode
• Relatively slow (small potential differences)
• Relatively predictable (constant rate of corrosion over time)
• Uniform loss in wall thickness (no surprise failure due to
cracking)

True or False: Stainless steel is immune to crevice corrosion.

• False. Crevice corrosion occurs because of a low oxygen
concentration in the crevice. Low oxygen means the stainless
steel’s passive chromium oxide layer cannot form.
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