FUNDAMENTALS of CORROSION:

When Metal Corrodes??

1. When there is Anode
2. When there is Cathode
3. When there is electron path connecting anode and cathode
4. When there is ionic path/electrolyte.
metal + oxidizing agent→ oxidized metal + reducing agent

For example, the corrosion of iron (Fe) in the presence of

hydrochloric acid, HCL:

Fe + 2 HCl (s) (aq) → FeCl 2(aq) + H2(g)

Anode Reaction
All redox reactions consist of two partial reactions, also sometimes called
halfcell reactions: the partial oxidation reaction, also referred to as the
anodic partial reaction; and the partial reduction reaction or cathodic
partial reaction.

 Oxidation occurs – corrodes

 Produces electron (e-)
 Produces cations ( positive-charged species)
Examples:
Zn Zn 2+ + 2e-
Fe Fe 2+ + 2e-
Cathodic Reaction
 Reduction occurs.
 Consumes electrons
 Produces lower valency species

2H+ + 2e- H2 Hydrogen evolution

O2 + 2H2O + 4e- 4OH- Oxygen reduction, neutral/basic solution
O2 + 4H+ + 4e- 2H2O Acid solutions
Chemical vs Electrochemical Reactions

 Chemical reactions = elements are added or removed

from chemical species. No change in valence
 Electrochemical = chemical reactions + change in
valence

Example:
Precipitation of iron hydroxide (Fe (OH)2) is pure chemical
reaction

Fe 2+ + 2 OH- --- Fe(OH)2

Atmospheric Corrosion: Brown Rust
 Fe2O3·H2O or hydrous ferrous oxide,

 Fe3O4·H2O or hydrated magnetite, also called ferrous

ferrite (Fe2O3·FeO), is most often green but can be deep
blue in the presence of organic complexants.

 Fe3O4 or magnetite is black.

White Rust
Gray / black Film
Corrosion may be CORROSION
classified in different ways

WET DRY
 Wet / Aqueous corrosion & CORROSION CORROSION
Dry Corrosion
CORROSION

 Room Temperature/ High

Temperature Corrosion ROOM HIGH
TEMPERATURE TEMPERATURE
CORROSION CORROSION
 Wet / aqueous corrosion is the major form of
corrosion which occurs at or near room
temperature and in the presence of water

 Dry / gaseous corrosion is significant mainly at high

temperatures
 Based on the appearance of the corroded metal,
wet corrosion may be classified as:
 Uniform or General
 Galvanic or Two-metal
 Pitting
 Environment-assisted cracking
 Intergranular
 Crevice
 Velocity-assisted
 Dealloying
 Fretting
 This one is common in steel that is unprotected by
any surface coating. Most noticeable. Surface effect,
leaving rust on the surface.
 The good thing about this, if there is one, is that the
corrosion is widely spread around.
 Corrosion over the entire
exposed surface at a uniform
rate. e.g.: Atmospheric
corrosion.
 Maximum metal loss by this
form.
 Not dangerous, rate can be
measured in the laboratory.
EXAMPLES:
1. rusting of iron
2. tarnishing of silver
3. Fogging of nickel
4. high - temperature
oxidation of metals
 mm/y – millimeters penetration per year
 gmd – grams per square meter per day
 ipy – inches penetration per year
 mpy – mils penetration per year (1000 mil = 1 inch)
 mdd – milligrams per square decimeter per day
A. <0.005 ipy (<0.15 mm/y) : Metals in this
category have good corrosion resistance and
can be used for critical parts
B. 0.005 to 0.05 ipy (0.15 mm/y to 1.5 mm/y) :
Metals in this group are satisfactory if a
higher rate of corrosion can be tolerated
C. >0.05 ipy (>1.5 mm/y) : Usually not
satisfactory
 Possibility when two dissimilar metals are electrically
connected in an electrolyte*
 Results from a difference in oxidation potentials of metallic
ions between two or more metals. The greater the
difference in oxidation potential, the greater the galvanic
corrosion.
 Refer to Galvanic Series
 The less noble metal will corrode (i.e. will act as the anode)
and the more noble metal will not corrode (acts as
cathode).
 Perhaps the best known of all corrosion types is galvanic
corrosion, which occurs at the contact point of two metals
or alloys with different electrode potentials.
 When two dissimilar metals
are joined together and
exposed, the more active of
the two metals corrode
faster and the nobler metal
is protected. This excess
corrosion is due to the
galvanic current generated
at the junction

 Fig. Al sheets covering

underground Cu cables
Galvanic Series:

Questions:
1. Worst combination?
2. Aluminum and steel?
3. Titanium and Zinc?
4. Stainless Steel and
Copper?
GALVANIC SERIES

Mercury
Platinum
Gold
Zirconium Graphite
Titanium
Hastelloy C Monel
Stainless Steel (316-passive)
Stainless Steel (304-passive)
Stainless Steel (400-passive)
Nickel (passive oxide)
Silver
Hastelloy 62Ni, 17Cr
Note, positions of
Silver solder
Inconel 61Ni, 17Cr
SS and Al
Aluminum (passive AI203)
70/30 copper-nickel
90/10 copper-nickel
Bronze (copper/tin)
Copper
Brass (copper/zinc)
Alum Bronze Admiralty Brass
Nickel
Naval Brass Tin
Lead-tin
Lead
Hastelloy A
Stainless Steel (active)
316 404 430 410
Lead Tin Solder
Cast iron
Low-carbon steel (mild steel)
Manganese Uranium
Aluminum Alloys
Cadmium
Aluminum Zinc
Beryllium
Magnesium
Big Cathode, Small Anode = Big Trouble
Note that the area ratio of the
anode: cathode is an important
variable affecting the dissolution
current density (and hence
corrosion rate) pertaining to the
anode. The area ratio is also
important when considering the
relative amount of current
"available" from the cathodic
reaction.
 Liquid Cell Battery:

dry cell is a galvanic electrochemical cell with a pasty low-moisture

electrolyte. A wet cell, on the other hand, is a cell with a liquid electrolyte,
such as the lead-acid batteries in most cars.
 Dry Cell - Zinc-carbon battery

- oxidation reaction that happens at zinc = anode :

Zn(s) → Zn2+(aq) + 2 e-

- reduction reaction at carbon rod = cathode

 Galvanic Corrosion

 Dissimilar metals are physically

joined in the presence of an
electrolyte.

 The more anodic metal corrodes.

Bilge pump - Magnesium shell

cast around a steel core.
Steel screws and brass Steel screw in Mg
Dissimilar metals, the damage occurs
at the anode.
 Material Selection: Do not connect dissimilar
metals! Or if you can’t avoid it:
◦ Try to electrically isolate one from the other (rubber
gasket).
◦ Make the anode large and the cathode small
 Bad situation: Steel siding with aluminum fasteners
 Better: Aluminum siding with steel fasteners

 Eliminate electrolyte

 Galvanic of anodic protection

 Galvanic severity depends on:
◦ NOT
 Not amount of contact
 Not volume
 Not mass

◦ Amount of separation in the galvanic series

◦ Relative surface areas of the two. Severe corrosion if anode

area (area eaten away) is smaller than the cathode area.
Example: dry cell battery
Steel bolt (less noble) is
isolated from copper plates.
 Intensive localized
corrosion within
crevices & shielded
areas on metal
surfaces
 Small volumes of
stagnant corrosive
caused by holes,
gaskets, surface
deposits, lap joints
Crevice Corrosion

Narrow and confined spaces.

This is a concentration cell in action. Notice how the damage
occurs in out of sight places.
 It is based on low oxygen concentration at the
bottom of the pit.
 This is very common in materials that protect
themselves with a passive layer, i.e. stainless
steel and aluminum.
Highly localized. Goes
deep into the metal.
 A form of extremely
localized attack causing
holes in the metal

 Most destructive form

 Autocatalytic nature

 Difficult to detect and

measure

 Mechanism
 Pitting
Pitting is a localized form of corrosive
attack. Pitting corrosion is typified by the
formation of holes or pits on the metal
surface. Pitting can cause failure, yet the
total corrosion, as measured by weight loss,
may be minimal.
304 stainless steel /
acid chloride solution

5th Century sword

Boiler tube
 When one element in an alloy is anodic to the
other element.
 Example: Removal of zinc from brass (called
dezincification) leaves spongy, weak brass.
 Brass alloy of zinc and copper, and zinc is anodic
to copper (see galvanic series).
 Two common types:
◦ Dezincification: preferential removal of zinc in brass
 Try to limit Zinc to 15% or less and add 1% tin.
 Cathodic protection

◦ Graphitization : preferential removal of Fe in Cast Iron

leaving graphite (C).
Dealloying

Preferred corrosion of
one element/constituent
[e.g., Zn from brass (Cu-Zn)].
Dezincification.
 Alloys exposed to
corrosives experience
selective leaching out
of the more active
constituent. e.g.
Dezincification of
brass.
 Loss of structural
stability and
mechanical strength
 Danger!
◦ The alloy may not appear damaged
◦ May be no dimensional variations
◦ Material generally becomes weak – hidden to inspection!
 Again, stainless steel is the ideal victim here. The
problem is triggered by improper heating, and often
this comes with welding. Carbides of chromium form
in the grain boundary regions.
 The chromium is tied up in the carbides. It can’t
protect by forming the passive layer.
 PLUS, there is a dissimilarity in metals producing a
small but definite galvanic corrosion.
 Corrosion which occurs preferentially at grain
boundaries.
 Why at grain boundaries?
◦ Higher energy areas which may be more anodic
than the grains.
 The grain boundaries in
metals are more active
than the grains because of
segregation of impurities
and depletion of protective
elements. So preferential
attack along grain
boundaries occurs. e.g.
weld decay in stainless
steels
 How to recognize it?
◦ Near surface
◦ Corrosion only at grain boundaries
◦ Corrosion normally at uniform depth for all grains.
 Sensitization of stainless steels:

◦ Heating up of austenitic stainless steel causes chromium

carbide to form in the grains. Chromium is therefore
depleted near the grain boundaries causing the
material in this area to essentially act like a low-alloy
steel which is anodic to the chromium rich grains.
◦ Preferential Intergranular Corrosion will occur parallel
to the grain boundary – eventually grain boundary will
simply fall out!!
 Intergranular corrosion
Corrosion along
grain boundaries,
often where precipitate
particles form.
Intergranular Corrosion
 Exfoliation corrosion in Aluminum that has been
heavily worked, such as in extrusion.
 Corrosion products start to build up in between the
long elongated grains, separating them and lead in to
increased corrosion propagation through the metal.
 Watch welding of stainless steels (causes
sensitization). Always needs proper annealling
after welding to redistribute Cr.
 Use low carbon grade stainless to eliminate
sensitization (304L or 316L).
 Add alloy stabilizers like titanium which ties up the
carbon atoms and prevents chromium depletion.
 Fast moving corrosives cause:

 a) Erosion-Corrosion
 b) Cavitation damage
 c) Impingement attack
 This is caused by the impingement of a high
velocity turbulent flow on a surface.
 The flow is often multi-phase. This means there
can be entrained solid particles, or even gas
bubbles, as in cavitation of a propeller.
 The flow will carry away any protective layer
that was intended to protect the material, and
even abrade the flow surface.
 Erosion-corrosion
Combined chemical attack and
mechanical wear
(e.g., pipe elbows)

Brass water pump

 Cavitation is a special case of
Erosion-corrosion.

 In high velocity systems,

local pressure reductions
create water vapour bubbles
which get attached to the
metal surface and burst at
increased pressure, causing
metal damage.
Type of corrosion directed at
locations where applied or
residual stresses are imparted to
the metal:

a) STRESS CORROSION
CRACKING
b) FATIGUE CORROSION
c) Hydrogen Embrittlement
 CORROSION FATIGUE
 Fatigue cracking is mechanical degradation
(brittle failure) when exposed to corrosion and
cycling loading.
 Corrosion fatigue cracking (CFC) should not be
confused with SCC, because the only
requirement for CFC is exposure under tensile
stress.
CORROSION FATIGUE
 CORROSION FATIGUE
 Fatigue cracks propagate after a certain
number of cycles and below yield stress and
stops propagating until the material separates
by overload fracture.
 At this point, the load applied to the material
exceeds the ultimate tensile stress.
 The corrosive environment effect on fatigue is
evaluated by variation of fatigue fractures
stress as a function of number of cycles
applied in the corrosive environment and in air
(S-N curves).
Forms of Corrosion

A B C

D E
 Forms of Corrosion

Environmentally Induced General Corrosion Localised Corrosion

Corrosion

 Stress Corrosion Cracking  Atmospheric corrosion

 Pitting

Mechanically Assisted Metallurgical Influenced

Corrosion Corrosion
General Bibliography
1. M. Fontana, Corrosion Engineering, 3rd edition, McGraw
Hill International Edition,New York, 1987, 556 pp.

2. H. H. Uhlig, R. W. Revie, Corrosion and Corrosion Control,

3rd edition, JohnWiley, New York, 1985, 441 pp.

3. G. Wranglen, An Introduction to Corrosion and Protection,

Chapman and Hall,London, 1985, 288 pp.

4. Jones, Principles and Prevention of Corrosion, Prentice

Hall