Assistant Lecturer. Fouad K.

Mahdi Corrosion Engineering/ Third Stage

M.Sc. in Chemical Engineering Chemical Depart. College of Eng.

2.1 Classification of corrosion:-

Corrosion has been classified in many different ways. One method divides
corrosion into low- temperature and high – temperature corrosion. Another separates
corrosion into direct combination ( or oxidation ) and electrochemical corrosion. The
preferred classification here is (1) Wet corrosion and (2) Dry Corrosion

2.1.1Wet corrosion:-
The metal is exposed to humid mediums or placed in basic, acidic, or salt solutions
Occurs when a liquid is present. This usually involves aqueous solutions or
electrolytes and accounts for the greatest amount of corrosion by far. A common
example is corrosion of steel by water. where different electrophoresis interactions
occur and thus cause corrosion.
2.1.2Dry corrosion:-
It is the rapid oxidation by normal or high temperatures and in an atmosphere free
from moisture, which resulted from the formation of a layer of metal oxide that forms
the layer of the outer surface, which is a corrosive layer. Or dry corrosion occurs in
the absence of a liquid phase or above the dew point of the environment. Vapors and
gases are usually the corrodes. Dry corrosion is most often associated with high
temperatures. An example is a attack on steel by furnace gases.

The presence of even small amounts of moisture could change the corrosion picture
completely. For example, dry chlorine is practically non corrosive to ordinary steel,
but moist chlorine, or chlorine dissolved in water, is extremely corrosive and attacks
of the common metals and alloys.
2.2 Forms of corrosion:-
It is convenient to classify corrosion according to the manner in which it is
manifest. the basis for classification being the appearance of corroded metal. Each
form can be identified by mere visual observation .Examination before cleaning is
particularly desirable

Metallic corrosion is sometimes classified into eight forms: uniform, galvanic,

crevice, intergranular, Filiform ,Selective Leaching ,erosion–corrosion, and
stress corrosion

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Assistant Lecturer. Fouad K. Mahdi Corrosion Engineering/ Third Stage
M.Sc. in Chemical Engineering Chemical Depart. College of Eng.

2.2.1Uniform or (General Corrosion):

It is the uniform thinning of a metal without any localized attack. Corrosion
dose not penetrate very deep inside. The most familiar example is the rusting of
steel in air. This type is the most common to occur on all surfaces of metal equally
.The metal corrode on a regular basis, so it is easy to study this type of corrosion
because the thickness of the metal decreases throughout its surface, and it is possible
to expect the failure of the metal after a known period after calculating the rate of
regular corrosion. It is the corrosion of all parts of the metal surface at approximately
the same rate.
It is one of the common and non-dangerous types because of the possibility of
anticipating its occurrence and feeling it when starting its formation and calculating
its rate and the depth of the wear layer and thus calculating the approximate life of
the metal. An applied example is the corrosion of iron windows, doors and car bodies
due to moisture and oxygen, and the products of corrosion are spongy compounds
that adhere to the surface. In natural environment, oxygen is the primary cause of
uniform corrosion of steels and other metals and alloys.

2 3 1
The photo (2) shows a steel coupon corroded (rusted) uniformly over its entire
surface after immersion in oxygen aerated water while the same batch of coupons
exposed to de aerated water (3) retained their metallic appearance with no visible
corrosion (rust). As for the picture(1), it shows a group of gears and the mechanical
parts attached to them, and all their parts have been regularly corroded.

*Mechanisms of Uniform Corrosion:-

It is probably best demonstrated by putting a small drop of seawater on a piece of
steel .On a metal surface exposed to atmosphere, only a limited quantity of water and
dissolved ions are present, whereas the access to oxygen present in the air is unlimited.
Corrosion products are formed close to the metal surface, unlike the case in aqueous
corrosion, and they may prevent further corrosion.
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Assistant Lecturer. Fouad K. Mahdi Corrosion Engineering/ Third Stage
M.Sc. in Chemical Engineering Chemical Depart. College of Eng.

The following is a simplified mechanism of aqueous corrosion of iron, At anodic

areas, anodic reaction takes place
Fe →Fe+++2e-
At cathodic areas reduction of Oxygen takes place:
O2+2H2O+4e-→ 4OH-
The OH ions react with iron ions , produced at the anode
Fe+++ 2OH-→Fe(OH)2
With more access to Oxygen in the air , Fe(OH)2 oxidizes to Fe(OH)3
4Fe(OH)2+ 2O2+2H2O→ 4Fe(OH)3
Ferrous hydroxide is converted to hydrated ferric oxide or rust by oxygen
4Fe(OH)3+2O2→ 2Fe2.O3.3H2O+ 2H2O
Rust (Fe2.O3.3H2O) is formed halfway between the drop center and the periphery .the
electrons flow from the anode (drop center) to cathode (periphery) in the metallic
circuit. The current flow is shown in above figure. The ferrous ions on the surface of
iron are soluble whereas those in solution are oxidized by oxygen to insoluble
hydrated oxides of ferric called rust. The rust is formed away from the corroding site.
The corrosion rate is very high if the ferrous ion is oxidized to ferric oxide rapidly.
Fe(OH)3 is insoluble and if it forms away from a metal surface, the corrosion reaction
speeds up as equilibrium is to be maintained by supplying more ferrous ions (Fe +2)
from the surface. If, however, Fe(OH)3 is formed on the surface of a metal very
rapidly, the corrosion is prevented (a passive film).

formation of rust in seawater

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Assistant Lecturer. Fouad K. Mahdi Corrosion Engineering/ Third Stage
M.Sc. in Chemical Engineering Chemical Depart. College of Eng.

*Example of uniform corrosion

(1) Tarnishing of silver ware.
(2) Tarnishing of electrical contacts.
(3) Rusting of steels in open air.
(4) Corrosion of offshore drilling platforms.
(5) Corrosion of galvanized steel stairways.
(6) Failure of distillation columns.
(7) Corrosion of electronic components.
(8) Corrosion of underground pipes (composite asphalt coated).
(9) Corrosion of automobile bodies.
(10) Corrosion of heat exchanger tubes.
(11)Corrosion of structural steels
*Prevention of Uniform Corrosion:-
Uniform corrosion or general corrosion can be prevented through a number of
methods:
-Use thicker materials for corrosion allowance
-Use paints or metallic coatings the steel surface with epoxy-phenolic coating.
-Use Corrosion inhibitors or modifying the environment
-Cathodic protection (Sacrificial Anode or Impressed Current -ICCP) .

2.2.2 Galvanic(Bimetallic or Dissimilar Metal) corrosion.

Is defined as the accelerated corrosion of a metal because of an electrical
contact (including physical contact) with a more noble metal or nonmetallic
conductor (the cathode) in a corrosive electrolyte. Galvanic Corrosion occurs when
two metals with different electrochemical potentials or with different tendencies to
corrode are in metal-to-metal contact in a corrosive electrolyte, i.e. when two
dissimilar alloys are coupled in the presence of a corrosive electrolyte one of them is
preferentially corroded while the other is protected from corrosion.

*Mechanisms of Galvanic Corrosion:-

Different metals and alloys have different electrochemical potentials (or

corrosion potentials) in the same electrolyte. When the corrosion potentials of
various metals and alloys are measured in a common electrolyte (e.g. natural
seawater) ,when two metals with different potentials are joined ,such as

4
Assistant Lecturer. Fouad K. Mahdi Corrosion Engineering/ Third Stage
M.Sc. in Chemical Engineering Chemical Depart. College of Eng.

copper(+0.334 v) and iron (-0.44 v) , a galvanic cell is formed. a cell in which the
chemical change is the source of energy is called a "galvanic cell". The corrosion
which is caused due to the formation of the galvanic cell, therefore, called "galvanic
corrosion" .The driving force for corrosion is a potential different between different
materials. Between two different materials connected through the electrolyte, the
less noble will became the anode and tend to corrode. For example a galvanic
corrosion between welded steel and stainless steel. The carbon steel pipe flange is
active to the stainless steel pipe, and is corroded preferentially near the weld.
Preferential corrosion near the junction between dissimilar alloys is characteristic of
galvanic corrosion, which decreases at points farther from the junction due to
higher resistance through a longer electrolyte path.

Photograph showing galvanic corrosion around

the inlet of a single-cycle bilge pump that is found

on fishing vessels. Corrosion occurred between

magnesium shell that was cast around a steel core.

*Factors affecting galvanic corrosion:-

A- Position of metals in the galvanic series

as mentioned earlier, the further apart the metals are in the galvanic series, the
greater is the chance for galvanic corrosion magnitude of galvanic corrosion
primarily depends on how much potential difference exists between two metals. For a
particular environment, the metals selected should be close to each other in the
galvanic series to minimize galvanic corrosion. Active metals should not be joined
with passive metals.

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Assistant Lecturer. Fouad K. Mahdi Corrosion Engineering/ Third Stage
M.Sc. in Chemical Engineering Chemical Depart. College of Eng.

B- The nature of environment

For instance, water containing copper iron, like seawater, is likely to form galvanic

cells on a steel surface of the tank. If the water in contact with steel is either acidic or
contains salt, the galvanic reaction is accelerated because of the increased ionization
of the electrolyte.

C- Area, Distance and Geometric effects.

The anode to cathode area ratio is extremely important as the magnitude of

galvanic corrosion is seriously affected by it. For a given amount of current, the metal
with smallest area has the largest current density, and hence is more damage if
corrosion occurs at it. The rate of corrosion increase with the ratio of cathode to
anode area.
*Prevention of Galvanic Corrosion
Galvanic corrosion can be prevented through a number of methods:
-Select metals/alloys as close together as possible in the galvanic series.
-Avoid unfavorable area effect of a small anode and large cathode.
-Insulate dissimilar metals wherever practical
-Apply coatings with caution. Paint the cathode (or both) and keep the coatings in
good repair on the anode.
-Avoid threaded joints for materials far apart in the galvanic series
Table :- Series of standard electrode potentials (electromotive forces) Electrode
reaction Standard potential at 25 °C (77 °F), SHE(Standard half electrode )
[Reduction Standard potential]=E°
Half-Cell Reactions Eo
F2(g) + 2e-1 ---------> 2F-1(aq) +2.87
O3(g) + 2H+1(aq) + 2e-1 ---------> O2(g) + H2O(l) +2.08
S2O82-(aq) + 2e-1 ---------> 2 SO42-(aq) +2.05
Co3+(aq) + e-1 ---------> Co2+(aq) +1.82
H2O2(aq) + 2 H+1(aq) + 2e-1 ---------> 2 H2O(l) +1.77
MnO4-1(aq) + 4 H+1(aq) + 3e-1 ---------> MnO2(s) + 2 H2O(l) +1.69
+1.63
2 HOCl(aq) + 2 H+1(aq) + 2e-1 ---------> Cl2(g) + 2 H2O(l)

Mn3+(aq) + e-1 ---------> Mn2+(aq) +1.51

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Assistant Lecturer. Fouad K. Mahdi Corrosion Engineering/ Third Stage
M.Sc. in Chemical Engineering Chemical Depart. College of Eng.

MnO4-1(aq) + 8 H+1(aq) + 5e-1 ---------> Mn2+(aq) + 4 H2O(l) +1.49

PbO2(s) + 4 H+1(aq) + 2e-1 ---------> Pb2+(aq) + 2 H2O(l) +1.46
BrO3-1(aq) + 6 H+1(aq) + 6e-1 ---------> Br-1(aq) + 3 H2O(l) +1.44
Au3+(aq) + 3e-1 ---------> Au(s) +1.42
Cl2(g) + 2e-1 ---------> 2 Cl-1(aq) +1.36
Cr2O72-(aq) + 14 H+1(aq) + 6e-1 ---------> 2 Cr3+(aq) + 7 H2O(l) +1.33
O3(g) + H2O(l) + 2e-1 ---------> O2(g) + 2 OH-1(aq) +1.24
MnO2(s) + 4 H+1(aq) + 2e-1 ---------> Mn2+(aq) + 2 H2O(l) +1.23
O2(g) + 4 H+1(aq) + 4e-1 ---------> 2 H2O(l) +1.23
Pt2+(aq) + 2e-1 ---------> Pt(s) +1.20
Br2(aq) + 2e-1 ---------> 2 Br-1(aq) +1.07
NO3-1(aq) + 4 H+1(aq) + 3e-1 ---------> NO(g) + 2 H2O(l) +0.96
NO3-1(aq) + 3 H+1(aq) + 2e-1 ---------> HNO2(g) + H2O(l) +0.94
2 Hg2+(aq) + 2e-1 ---------> Hg22+(aq) +0.91
HO2-1(aq) + H2O(l) + 2e-1 ---------> 3 OH-1(aq) +0.87
2 NO3-1(aq) + 4 H+1(aq) + 2e-1 ---------> 2 NO2(g) + 2H2O(l) +0.80
Ag+1(aq) + e-1 ---------> Ag(s) +0.80
Fe3+(aq) + e-1 ---------> Fe2+ (aq) +0.77
O2(g) + 2H+1(aq) + 2e-1 ---------> H2O2(aq) +0.69
I2(s) + 2e-1 ---------> 2 I-1(aq) +0.54
NiO2(s) + 2 H2O(l) + 2e-1 ---------> Ni(OH)2 + 2 OH-1(aq) +0.49
SO2(aq) + 4 H+1(aq) + 4e-1 ---------> S(s) + 2 H2O(l) +0.45
O2(g) + 2 H2O(l) + 4e-1 ---------> 4 OH-1(aq) +0.401
Cu2+(aq) + 2e-1 ---------> Cu(s) +0.34
Hg2Cl2(s) + 2e-1 ---------> 2 Hg(l) + 2 Cl-1(aq) +0.27
PbO2(s) + H2O(l) + 2e-1 ---------> PbO(s) + 2 OH-1(aq) +0.25

AgCl(s) + e-1 ---------> Ag(s) + Cl-1(aq) +0.2223

SO42-(aq) + 4H+1(aq) + 2e-1 ---------> H2SO3(aq) + H2O(l) +0.172
S4O62-(aq) + 2e-1 ---------> 2 S2O32-(aq)
+0.169
2+ -1 +1
Cu (aq) + e ---------> Cu (aq) +0.16
Sn4+(aq) + 2e-1 ---------> Sn2+(aq) +0.15
S(s) + 2H+1(aq) + 2e-1 ---------> H2S(g) +0.14
AgBr(s) + e-1 ---------> Ag(s) + Br-1(aq) +0.07
2 H+1(aq) + 2e-1 ---------> H2(g) 0.00
Pb2+(aq) + 2e-1 ---------> Pb(s) -0.13
Sn2+(aq) + 2e-1 ---------> Sn(s) -0.14
AgI(s) + e-1 ---------> Ag(s) + I-1(aq) -0.15

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Assistant Lecturer. Fouad K. Mahdi Corrosion Engineering/ Third Stage
M.Sc. in Chemical Engineering Chemical Depart. College of Eng.

Ni2+(aq) + 2e-1 ---------> Ni(s) -0.25

Co2+(aq) +2e-1 ---------> Co(s) -0.28
In3+(aq) + 3e-1 ---------> In(s) -0.34
Tl+1(aq) + e-1 ---------> Tl(s) -0.34
PbSO4(s) + 2e-1 ---------> Pb(s) + SO42-(aq) -0.36

Cd2+(aq) + 2e-1 ---------> Cd(s) -0.40

Fe2+(aq) + 2e-1 ---------> Fe(s) -0.44
Ga3+(aq) + 3e-1 ---------> Ga(s) -0.56
PbO(s) + H2O(l) + 2e-1 ---------> Pb(s) + 2 OH-1(aq) -0.58
Cr3-(aq) + 3e-1 ---------> Cr(s) -0.74
Zn2+(aq) + 2e-1 ---------> Zn(s) -0.76
Cd(OH)2(s) + 2e-1 ---------> Cd(s) + 2 OH-1(aq) -0.81
2 H2O(l) + 2e-1 ---------> H2(g) + 2 OH-1(aq) -0.83
Fe(OH)2(s) + 2e-1 ---------> Fe(s) + 2 OH-1(aq) -0.88
Cr2+(aq) + 2e-1 ---------> Cr(s) -0.91
N2(g) + 4 H2O(l) + 4e-1 ---------> N2O4(aq) +4 OH-1(aq) -1.16
V2+(aq) + 2e-1 ---------> V(s) -1.18
ZnO2-1(aq) + 2 H2O(l) + 2e-1 ---------> Zn(s) + 4OH-1(aq) -1.216
Ti2+(aq) + 2e-1 ---------> Ti(s) -1.63
Al3+(aq) + 3e-1 ---------> Al(s) -1.66
U3+(aq) + 3e-1 ---------> U(s) -1.79
Sc3+(aq) + 3e-1 ---------> Sc(s) -2.02
La3+(aq) + 3e-1 ---------> La(s) -2.36
Y3+(aq) + 3e-1 ---------> Y(s) -2.37

Mg2+(aq) + 2e-1 ---------> Mg(s) -2.37

Na+1(aq) + e-1 ---------> Na(s) -2.71

Ca2+(aq) + 2e-1 ---------> Ca(s)
-2.76
2+ -1
Sr (aq) + 2e ---------> Sr(s) -2.89
Ba2+(aq) + 2e-1 ---------> Ba(s) -2.90
Cs+1(aq) +e-1 ---------> Cs(s) -2.92
K+1(aq) + e-1 ---------> K(s) -2.92
Rb+1(aq) + e-1 ---------> Rb(s) -2.93
Li+1(aq) + e-1 ---------> Li(s) -3.05

8
Assistant Lecturer. Fouad K. Mahdi Corrosion Engineering/ Third Stage
M.Sc. in Chemical Engineering Chemical Depart. College of Eng.

2.2.3 Crevice Corrosion:-

Crevice Corrosion refers to the localized attack on a metal surface at, or
immediately adjacent to, the gap or crevice between two joining surfaces. The gap or
crevice can be formed between two metals or a metal and non-metallic material.
Outside the gap or without the gap, both metals are resistant to corrosion. Crevices
are formed at welds, in condensers, and between metal surfaces and valves. This type
of corrosion is initiated by small volumes of solution captured in crevices under bolt
gasket rivets or surface deposits. It destroys mechanical joint integrity in structures
constructed from stainless steel, aluminum, titanium, and copper. For corrosion to
occur, the aggressive solution must permeate the crevice and be sufficiently narrow
to keep corrosion products inside the crevice. In the case of corrosion by dissolved
oxygen, active passive short circuits are formed between the aggressive solution in
the crevice, which becomes oxygen depleted (anode), and the external metal surface
(cathode). The initiation of crevice corrosion is based on pH decrease in the
bottom ofthe crevice.
The damage caused by crevice corrosion is normally confined to one metal at
localized area within or close to the joining surfaces.

Crevice corrosion under bolt which is Crevice corrosion inside stainless steel piping
system
holding structural beam in place, which
initiated in a crevice created by lack of a full
penetration in an orbital weld.

Crevice corrosion occurs at locations where oxygen cannot freely circulate such as
tight joints, under fastener heads and in other circumstances where the pieces of
metal are in close contact. Chloride salts, pollutants and moisture from the

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Assistant Lecturer. Fouad K. Mahdi Corrosion Engineering/ Third Stage
M.Sc. in Chemical Engineering Chemical Depart. College of Eng.

environment accumulate in the crevice. The environment inside the crevice becomes
depleted of oxygen, enriched in chlorides, and acidified which promotes the
breakdown of the passive film and anodic dissolution. The basic mechanism
underlying crevice corrosion in passive table alloys exposed to aerated chloride-rich
media is gradual acidification of the solution inside the crevice, leading to the
appearance of highly aggressive local conditions that destroy the passivity.

*Several steps can be taken to prevent and/or control crevice corrosion:-

1-Proper design, avoiding crevices, will control crevice corrosion. If lap joints are
used, the crevices caused by such joints should be closed by either welding or
caulking. Welded butt joints are preferable to bolted or riveted joints.

2.Porous gaskets should be avoided. Use an impervious gasket material. During

long shutdown periods, wet packing materials should be removed.

3.The use of alloys resistant to crevice corrosion should be considered. The

resistance of stainless steels to crevice corrosion can be improved by increasing the
chromium nickel, molybdenum,

4.Reduction of crevice corrosion can be accomplished, when possible, by reducing

the temperature, decreasing the chloride content, or decreasing the acidity.

5. Regular inspections and removal of deposits should be scheduled.

*Pitting corrosion:-
Pitting corrosion is usually found on passive metals and alloys such aluminum
alloys, stainless steels and stainless alloys when the ultra-thin passive film (oxide
film) is chemically or mechanically damaged and does not immediately re-passivate.
The resulting pits can become wide and shallow or narrow and deep which can
rapidly perforate the wall thickness of a metal. It is one of the most destructive,
localized forms of corrosion. The pits are small cavities or holes with a depth greater
than or equal to the surface diameter. They penetrate metal, causing equipment
failure due to preformation with minimal weight loss.

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Assistant Lecturer. Fouad K. Mahdi Corrosion Engineering/ Third Stage
M.Sc. in Chemical Engineering Chemical Depart. College of Eng.

The pitting of a 304L stainless steel plate by an acid–chloride solution

*Mechanisms of Pitting Corrosion:-
For a defect-free "perfect" material, pitting corrosion is caused by the
environment (chemistry) that may contain aggressive chemical species such as
chloride. Chloride is particularly damaging to the passive film (oxide) so pitting can
initiate at oxide breaks.
The environment may also set up a differential aeration cell (a water droplet on the
surface of a steel, for example) and pitting can initiate at the anodic site (centre of
the water droplet). Depth of pitting is sometimes expressed by the pitting factor , the
ratio of deepest metal penetration to average metal penetration as determined by the
weight loss of the specimen. A pitting factor of unity represents uniform attack.

A material's resistance to pitting corrosion is usually evaluated and ranked

using the critical pitting temperature (CPT) in accordance with the ASTM
Standard G48-03: Standard Test Methods for Pitting and Crevice Corrosion of
Stainless Steels and Alloys by Use of FeCl3. The critical pitting temperature is the
minimum temperature (°C) to produce pitting corrosion and CPT is usually higher
than the critical crevice temperature(CCT).

11
Assistant Lecturer. Fouad K. Mahdi Corrosion Engineering/ Third Stage
M.Sc. in Chemical Engineering Chemical Depart. College of Eng.

*Prevent Pitting Corrosion:-

Pitting corrosion can be prevented through:
1-Proper selection of materials with known resistance to the service environment.

2-Control on pH, chloride concentration and temperature.

3-Cathodic protection.

4-Use higher alloys for increased resistance to pitting corrosion.

2.2.4Intergranular Corrosion:-
Intergranular corrosion is a localized form of corrosion. also called "inter
crystalline corrosion" or "interdendritic corrosion". In the presence of tensile stress,
cracking may occur along grain boundaries and this type of corrosion is frequently
called "intergranular stress corrosion cracking (IGSCC)". Little or no attack is
observed on the main body of the grain. This results in the loss of strength and
ductility. The attack is often rapid, penetrating deeply into the metal and causing
failure.

The photos above show the microstructure of a type 304 stainless steel. The figure on
the left is the normalized microstructure and the one on the right is the "sensitized"
structure and is susceptible to intergranular corrosion or intergranular stress corrosion
cracking
* Mechanisms of Intergranular Corrosion:-
Intergranular corrosion is caused by Microsegregation of impurities and alloying
elements on the grains boundaries. The driving force of intergranular corrosion is the
difference between the Electrode potentials of the grain boundary and the grain itself,
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Assistant Lecturer. Fouad K. Mahdi Corrosion Engineering/ Third Stage
M.Sc. in Chemical Engineering Chemical Depart. College of Eng.

which form a galvanic cell in presence of an electrolyte.

If the phases segregated at the grain boundaries have lower value of electrode
potainal (higher position in the table of Electrochemical series) they
will oxidize (anodic reaction) and the grain metal having higher value of electrode
potential will provide cathodic reaction (reduction). Dissolution of anodic grain
boundaries starts from the surface and advances along the grains interfaces. The
process results in deterioration of the bonding between the grains and drop of
mechanical properties. If the precipitates at the grain boundaries have higher electrode
potential the grains will dissolve (anodic reaction).
In this case the grain boundaries will not be attacked.
*Prevention of Intergranular Corrosion:-
-Use low carbon (e.g. 304L, 316L) grade of stainless steels
-Use stabilized grades alloyed with titanium (for example type 321) or niobium (for
example type 347). Titanium and niobium are strong carbide- formers. They react
with the carbon to form the corresponding carbides thereby preventing chromium
depletion.
-Use post-weld heat treatment.
- Impact reducing segregation of specific elements or compounds at the grain
boundary, as in aluminum or nickel–chromium alloys.
- Percentage increase of enrichment of one of the alloying elements at the grain
boundary, as in brass Depletion of the corrosion-resisting constituent at the grain
boundary, as in stainless steel. All of these factors contributing to reducing
intergranular corrosion originate in the thermal processing of materials, such as
welding, stress relief, and the heat treatments.

2.2.6 Selective Leaching(Dealloying & Graphitic) Corrosion:-

The removal of one of the components of an alloy by corrosion is termed “selective
leaching.” Dezincification is the term used to describe the leaching of zinc from brass,
which is the most common example of selective leaching. The less noble component of
an alloy is usually the element that is removed, such as zinc in brass. “Graphite
corrosion” is the term used to describe the selective leaching of iron from gray cast iron.
Graphitic corrosion is the deterioration of gray cast iron in which the metallic
constituents are selectively leached or converted to corrosion products leaving the
graphite intact.
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Assistant Lecturer. Fouad K. Mahdi Corrosion Engineering/ Third Stage
M.Sc. in Chemical Engineering Chemical Depart. College of Eng.

Combinations of Alloys and Environments for Selective Leaching

Alloy Environment ElementRemoved
Aluminum Hydrofluoric acid, acid chloride solutions Aluminum
Bronzes, brass Many waters Zinc
Cupronickels High heat flux and low water velocity Nickel
(in refinery condenser tubes)
Gray iron Soils, many waters Iron
Gold alloys Nitric, chromic, and sulfuric acids, Copper or
silver
High-nickel alloys Molten salts Chromium, iron
Molybdenum, tungsten
Iron-chromium alloys High-temperature oxidizing atmospheres Chromium
Medium- and Oxidizing atmospheres, hydrogen Carbon
high-carbon steels at high temperatures

Monel Hydrogen and other acids Copper &nickel in some

acids
Nickel-molybdenum alloys Oxygen at high temperatures Molybdenum
Silicon bronzes High-temperature steam, acidic solution silicon
Tin bronzes Hot brine, steam Tin

*Mechanisms of Selective Leaching:-

Different metals and alloys have different electrochemical potentials (or
corrosion potentials) in the same electrolyte. Modern alloys contain a number of
different alloying elements that exhibit different corrosion potentials. The potential
difference between the alloying elements is the driving force for the preferential
attack on the more "active" element in the alloy. In the case of dezincification of
brass, zinc is preferentially leached out of the copper-zinc alloy, leaving behind a
copper-rich surface layer that is porous and brittle.

*Prevention of Selective Leaching:-

Preventive measures that may be taken include:
1. Use a more resistant alloy. This is the more practical approach. Red brass with less
than 15% zinc is almost immune. Cupro nickels provide a better substitute in
severely corrosive conditions.
2. Periodically remove scales and deposits from the inside surfaces of pipelines.
3. Remove the stagnation of corrosives, particularly acidic ones.
4. Use cathodic protection.

14
Assistant Lecturer. Fouad K. Mahdi Corrosion Engineering/ Third Stage
M.Sc. in Chemical Engineering Chemical Depart. College of Eng.

2.2.7 Erosion–corrosion:-
Refers to the combined action involving erosion and corrosion in the
presence of a moving corrosive fluid or a metal component moving through the fluid,
leading to accelerated loss of metal. Applies to deterioration due to mechanical
force, when the factors contributing to erosion accelerate the rate of corrosion of a
metal, the attack is called “erosion corrosion.
*Mechanisms of Erosion Corrosion:-
Erosion corrosion is usually caused by an aqueous or gaseous corrodent flowing over
the metal surface or impinging on it. The mechanical deterioration may be aggravated
by the presence of a corrodent, as in the case of fretting or corrosive wear. The
acceleration of attack is due to the distribution or removal of the protective surface
film by mechanical forces exposing fresh metal surfaces that are anodic to the un eroded
neighboring film. The initial stage involves the mechanical removal of a metal's
protective film and then corrosion of bare metal by a flowing corrosive occurs. The
process is cyclic until perforation of the component occurs.

Erosion-corrosion is usually found at high flow rates around tube blockages, tube inlet
ends, or in pump impellers. The photo shows erosion corrosion of a cast aluminum
pump casing due to excessively high flow rate of the coolant.

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Assistant Lecturer. Fouad K. Mahdi Corrosion Engineering/ Third Stage
M.Sc. in Chemical Engineering Chemical Depart. College of Eng.

*Prevention of Erosion Corrosion:-

-Changing the design can minimize or completely eliminate erosion corrosion.
-Streamline the piping to reduce turbulence

-Control fluid velocity

-Using more resistant materials

-Using corrosion inhibitors or cathodic protection to minimize erosion corrosion.

-Selecting a harder material of construction is another alternative. Impingement attack

can be avoided by increasing pipe diameters, and installing baffles will restrict the
impact of the fluid.

-The softer coating reflects the shock waves and reduces the damage on metallic parts.
2.2.8 Stress Corrosion Cracking (SCC):-
Stress corrosion cracking (SCC) is defined as crack growth due to
simultaneous tensile stress and corrosive environments on active metals or alloys. In
order for SCC to occur, the metal should be susceptible to SCC and be in a corrosive
environment such as chloride ions, water, oxygen, pH, and so on. SCC leads to
catastrophic failure in aircraft structures, nuclear facilities, boilers, and liquid or gas
transmission pipes. Stress is induced by heat treatment, welding, machining, grinding,
and cold work. The required tensile stresses may occur in the form of residual stress,
applied load (directly applied stress), monotonic straining, or low amplitude cycling

Stress corrosion cracking of austenitic stainless steel

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Assistant Lecturer. Fouad K. Mahdi Corrosion Engineering/ Third Stage
M.Sc. in Chemical Engineering Chemical Depart. College of Eng.

*Mechanisms of Stress Corrosion Cracking:-

Stress-corrosion cracking is a delayed failure process. That is, cracks initiate and
propagate at a slow rate until the stresses in the remaining ligament of metal exceed
the fracture strength. The sequence of events involved in the SCC process is usually
divided into three stages:
*Crack initiation and stage 1 propagation
*Stage 2 or steady-state crack propagation
*Stage 3 crack propagation or final failure.
Many different mechanisms have been proposed to explain the synergistic stress-
corrosion interactions that occur at the crack tip, and there may be more than one
process that causes SCC. The proposed mechanisms can be classed into two basic
categories: anodic mechanisms and cathodic mechanisms. That is, during corrosion,
both anodic and cathodic reactions must occur, and the phenomena that result in
crack propagation may be associated with either type. The most obvious anodic
mechanism is that of simple active dissolution and removal of material from the
crack tip. The most obvious cathodic mechanism is hydrogen evolution, absorption,
diffusion, and embrittlement. However, a specific mechanism must be able to explain
the actual crack-propagation rates, the fractographic evidence, and the mechanism of
formation or nucleation of cracks.

Stress-corrosion crack initiating from a corrosion pit in a quenched-aim-tempered high-

strength turbine disk steel (3.39Ni-1.56Cr-0.63Mo-0.HV) test coupon exposed to
oxygenated, demineralized water for 800 h under a bending stress of 90% of the yield
stress.

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Assistant Lecturer. Fouad K. Mahdi Corrosion Engineering/ Third Stage
M.Sc. in Chemical Engineering Chemical Depart. College of Eng.

*Prevention of Stress Corrosion Cracking:-

To prevent the application of tensile stresses through:-
1- By proper design and installation techniques
2- Removal compressive stress can be accomplished by annealing or by shot peening
must be applied uniformly, it will not be effective if pitting occurs on the
compressive layer.
3-The use of inhibitors may reduce or even eliminate SCC by moving the corrosion
potential outside the range of cracking.
4- when practical and economically feasible, is to select a different material of
construction one that is not susceptible to SCC in the particular environment.
5-Control of hardness and stress level (residual or load),as well as control operating
temperature and the electrochemical potential of the alloy.

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