Defence University

College of Engineering
Department of Chemical Engineering
Specialization: Electrochemical Engineering

Advances in Corrosion Engineering(CE-7341)

Chapter 5: Forms of Corrosion

Instructor: Wondalem Misganaw(PhD., M.Tech, B.Tech)

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 Introduction
 It is convenient to classify corrosion by the forms in which
it manifests itself , the basis for this classification being the
appearance of the corroded metal.
 In most cases the naked eye is sufficient , but sometimes
magnification is helpful or required .
 Valuable information for the solution of a corrosion
problem can often be obtained through careful
observation of the corroded test specimens or failed
equipment .
 There are eight forms of corrosion.

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 1. Uniform or General Corrosion
 It is uniform thinning of a metal without any localized attack.

 This kind of corrosion happen mostly in one phase materials and is

unformed throughout the surface.

 Corrosion dose not penetrate very deep inside.

 This kind of corrosion can be happened in most environments , such

as dry and wet atmospheres , acids , brines … etc .

 Uniform Attack is a form of electrochemical corrosion that occurs

with equivalent intensity over the entire exposed surface and often

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leaves behind a scale or deposit.
 Mechanism of uniform Corrosion
 Corrosion mechanism in aqueous solution has been amply demonstrated.
 In atmospheric corrosion which also exemplifies uniform corrosion, a very
thin layer of electrolyte is present.
 It is probably best demonstrated by putting a small drop of seawater on a
piece of steel.
 On comparing the atmospheric corrosion with aqueous corrosion , the
following differences are observed:
 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 limited.
 Corrosion products are formed close to the metal surface , unlike the case in
aqueous corrosion , and they may prevent further corrosion by acting as a
physical barrier between the metal surface and environment, particularly if
they are insoluble as in the case of copper or lead .
 The following is a simplified mechanism of aqueous corrosion of iron . At the
anodic areas , anodic reaction takes place

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 Mechanism of uniform Corrosion

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 Mechanism of uniform Corrosion

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 Mechanism of uniform Corrosion 7

Examples include general rusting of steel and iron and the

tarnishing of silverware. The life of equipment can be accurately
estimated .
Uniform corrosion can be prevented or reduced by :-
1)proper materials , including coatings .
2)inhibitors .
3)Cathodic protection .
 2) Galvanic or Two-Metal corrosion

 Galvanic corrosion occurs when two

metals or alloys are electrically
coupled while exposed to an
electrolyte.
 The more reactive metal in the
particular environment will
experience corrosion, the more inert
metal, will be protected from
corrosion.
 For example, steel screws corrode
when in contact with brass in a marine
environment; or if copper and steel
tubing are joined in a domestic water
heater, the steel will corrode in the
vicinity of the junction.

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 Mechanism of Galvanic corrosion
 For the formation of a galvanic cell, the following components are
required :
1. A cathode.
2. An anode.
3. An electrolyte.
4. A metallic path for the electron current .
 In case of copper and steel pipe joint , Iron is more negative potential
in the emf series ( -0.440 V ).It is the anode ,moisture acts an
electrolyte and metal surface provides a metallic path for electron
current to travel. A piece of copper is the cathode .Galvanic cell will
formed and galvanic corrosion proceeds .

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 Factors affecting galvanic corrosion

 The following factors significantly affect the magnitude of

galvanic corrosion:-
1. Position of metals in the Galvanic series
2. The Nature of Environment
3. Area , Distance and Geometric Effects

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A. Position of metals in the Galvanic series
 The 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 galvanic series to minimize galvanic corrosion . ( Al

should not be joined to Fe ).

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 The Galvanic Series

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 B. The Nature of Environment
 The environment that surrounds the metal must be consider . Water
containing copper ions like seawater is likely to form galvanic cell on
a steel surface of the tank.
 The marine environments , galvanic corrosion may be accelerated
due to increased conductivity of the electrolyte.
 Galvanic corrosion of buried material is reduced because of the
increased resistivity of soil.
 Tantalum is very corrosion resistant metal. It is anodic to platinum
and carbon , but the cell is active only at high temperatures. Zn is
anode with respect to iron at room temp. with presence of water ,
but if the water temperature became higher ( 60 -75 Co ). The
polarity will reverse and iron will be anode ( corroded ).

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C. Area , Distance and Geometric Effects :
a. Effect of Area: The anodic to Cathodic area is extremely important as
the magnitude of galvanic corrosion is seriously affected by it. An
unfavorable area ratio consists of a large cathode and a small anode.
b. Effect of Distance: It is a known principle that the solution
conductivity varies inversely with the length of the conduction path. The
greatest galvanic damage is likely to encountered near the junction of two
metals and severity would be decreased with increased length.
c. Effect of Geometry : Geometry of components and their design also
influence galvanic corrosion. As current does not flow around the
corners , the geometry of the circuit affects the degree of galvanic
corrosion .Any obstacle to polarization would accelerate galvanic
corrosion .
 The rate of galvanic attack depends on the relative anode-to-cathode
surface areas that are exposed to the electrolyte. For a given cathode area, a
smaller anode will corrode more rapidly than a larger one.

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 Measures taken to reduce galvanic corrosion are:
1. If coupling of dissimilar metals is necessary, choose two that are
close together in the galvanic series.
2. Avoid an unfavorable anode-to-cathode surface area ratio; use an
anode area as large as possible.
3. Electrically insulate dissimilar metals from each other.
4. Electrically connect a third, anodic metal to the other two; this
is a form of Cathodic protection.

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 3 ) Crevice Corrosion
 This is a localized form of corrosion, caused by the deposition of

dirt, dust, mud and deposits on a metallic surface or by the

existence of voids , gaps and cavities between adjoining surfaces.

 An important condition is the formation of a differential aeration

cell for crevice corrosion to occur .This type of attack is usually

associated with small volumes of stagnant solution .

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 Causes for Crevice Corrosion
a. Presence of narrow spaces between metal-to-metal or non-
metal to metal components.

b. Presence of cracks , cavities and other defects on metals.

c. Deposition of barnacles, befouling organisms and similar

deposits.

d. Deposition of dirt, mud or other deposits on a metal surface

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 Factors affecting crevice corrosion
A. Crevice Type
 Crevice type means whether the crevice is between metal- to-

metal, metal to non-metal or a marine growth, like barnacles or

other marine befouling organisms, on the metal surface.

 It is important to know whether factors affecting crevice are

man-made or natural in order to select appropriate methods for

prevention.

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B. Alloy Composition. It is important to know whether or not
the alloy is resistant to crevice corrosion . Example Hastelloy
and Inconel were highly resistant to crevice corrosion in
ambient and elevated temperature seawater. The alloying
elements in various grade of steel affect both the
electrochemical and chemical processes, such as hydrolysis,
passive film formation , passive current density and metal
dissolution .
C. Passive Film characteristics. The type of passive film
formed is important, as the breakdown of a passive film results
in the onset of crevice corrosion.

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D. Geometry of Crevice : The magnitude of crevice corrosion
also depends on the depth of the crevice, width of the gap,
number of crevices and ratio of exterior to interior crevice.
E. Effect of Temperature

F. Bulk Solution Composition

G. Mass Transfer in and out of Crevice , and

H Oxygen .

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 Combating Crevice Corrosion
 Methods and procedures for combating or minimizing crevice corrosion are
as follows :
1. Use welded butt joints instead of riveted or bolted joints in new
equipments.
2. Close crevices in existing lap joints by continuous welding, caulking, or
soldering.
3. Design vessels for complete drainage; avoid sharp corners and stagnant
areas.
4. Inspect equipment and remove deposits frequently.
5. Remove solids in suspension early in the process or plant flow sheet, if
possible.
6. Remove wet packing materials during long shutdowns.
7. Provide uniform environment, if possible as in the case of backfilling a
pipeline trench.
8. Weld instead of rolling in tubes sheets.

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 4 ) Pitting Corrosion
 It is a form of localized corrosion of a metal surface where small

areas corrode preferentially leading to formation of cavities or

pits, and bulk of the surface remains un -attacked.

 Metals which form passive films , such as aluminum and steel are

more susceptible to this form of corrosion. It causes failure by

penetration with only a small percent weight-loss of the entire
structure.

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 Environment :
 Generally the most conductive environment for pitting is the marine
environment.
 Ions such as Cl- , Br- and I- in appreciable concentrations tend to
cause pitting of steel .
 Thiosulfate ions also induce pitting of steels. Aluminum also pits in a
same environments of steel .
 Present of dust or dirt particles in water may lead to pitting
corrosion in copper pipes transporting seawater.
 With soft water pitting in copper occurs in the hottest part of
system , whereas with hard waters pitting occurs in the coldest part
of the system.

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 Conditions :
 The most important condition is that the metal must be in passive
state for pitting to occur.
 Metals which become passive by film formation have a high
resistance to uniform corrosion.
 The process of pitting destroys this protective film at certain sits
resulting in the loss of passivity and initiation of pits on metal
surface .
 The following are the conditions for pitting to occur:-
1. Breaks in the films or other defects .( lack of film homogeneity)
2. The presence of halogen ions ,such as Cl-, Br-,and I- and even
S2O3-.
3. Stagnant conditions in service. (pumps serve in seawater with
longer life than kept out of service ).

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 Mechanism
 In order for pitting to take place, the formation of anode is a prerequisite.
With the formation of an anode, a local corrosion cell is developed. The
anode may be formed as a result of :-
1. Lack of homogeneity at the metal corrosive interface , which caused by
presence of impurities, grain boundaries, niches, rough surface ,…etc.
The difference in the environments can cause formation of
concentration cells on the metal surface.
2. Destruction of a passive film. Resulting to formation a small anode,
results in several anode sits and the surrounding surface acts as cathode.
Thus, an unfavorable area ratio results.
3. Deposit of debris or solids on the metal surface. This generally leads to
the formation of anodic and Cathodic sites.
4. Formation of an active – passive cell with a large potential difference.
5. The formation of small anode on the passive steel surface, leads to the
25 formation of the above cell.
 Pitting Processes
1. The formation of anodic sits by disruption of the protective passive film on the metal
surface.

This is balanced by the Cathodic reaction of oxygen on the adjacent surface

2. Due to the continuing metal dissolution , an excess of positive ions ( M+ ) is

accumulated in the anodic area. The process is self-stimulating and self-
propagating. To maintain charge neutrality negative ions (anions), like chloride,
migrate from electrolyte ( for example seawater or a 5% NaCl solution ).

( OH- ) ions also migrate to neutralize the positive charges. This process is called
hydrolysis.
3. The presence of ( H+ ) ions and chloride content , prevents repassivation. The above
process generates free acid and the pH value at the bottom of pit is substantially
lowered.

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4. The increase in the rate of dissolution at the anode increases the
rate of migration of the chloride ions and the reaction becomes
time dependent and continues, resulting in the formation of
more and more M+Cl- , generation of more and more H+Cl- by
hydrolysis.
5. The process continues until the metal is perforated. The process
is autocatalytic and it increases with time resulting in more and
more dissolution.
6. Finally, the metal is perforated and the reaction is terminated.
 As shown above ,basically three processes are involved :
1. Pitting Initiation .
2. Pitting Propagation .
3. Pitting Termination.

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 Pitting is an insidious and destructive form of corrosion:
 difficult to detect (pits may be small on surface, but extensive below
surface from undercutting; may be covered with deposit).
 can cause equipment to fail (by perforation) with very little weight
loss.
 difficult to measure as pit depth and distribution vary widely under
(nominally) identical conditions.
 “incubation” period may be months or years.

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 Prevention :
 The methods suggested for combating crevice corrosion generally
apply also for pitting. Or using inhibiters e.g Chromates( CrO4 )-2,
Phosphates( PO4 )-3, Silicates( SiO4 )-4 .
Some alloys developed especially to resist pitting

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 5 ) Selective Leaching (Dealloying, Parting)
 Corrosion in which one constituent of an alloy is preferentially
removed, leaving behind an altered (weakened) residual
structure, can occur in several systems.

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 Dezincification :
 It is a form of corrosion in which zinc is selectively attacked in zinc-
containing alloys, like brasses. De-alloying and selective leaching are
broader terms which refer to the corrosion of one or more constituent of a
solid solution alloy.
 Dezincification is a form of de-alloying. As the phenomenon was first
observed in brass in which zinc separated by dissolution from copper. All
Cu-Zn alloys (Brasses) containing > 15% Zn are susceptible e.g. common
yellow brass . . . 30 Zn 70 Cu, dezincifies to red copper-rich structure

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 Dezincification can be in two types ,
1. Uniform type ,like the potable water inside. In the uniform the
active area is leached out over a broad area of the surface and it is
not localized to certain point of the surface. Uniform
dezincification...usually found in high brasses (high[Zn]), acid
environments;
2. Plug type, like (boiler water inside, combustion gases outside.
the plug type of attack is localized, at a certain point on the
surface and surrounding area remains unaffected. Plug-type
dezincification usually found in low brasses, alkaline, neutral or
slightly acid environments.
 Overall dimensions of original material tend to be retained . . .
residual is spongy and porous . . . often brittle.
 Can go unnoticed, especially if covered with dirt/deposit, etc.

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 Mechanism:-
 The basis of dissolution and re-deposition mechanism.

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 (2) Generally accepted . . .
 brass dissolves;
 Zn stays in solution;
 Cu re-deposits.
 Possibility for local anode-cathode couples ..
 Cu deposits accelerate attack.
 Dezincified areas generally 90-95% Cu;
 Some Cu2O/CuO present if O2 in the environment.

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 Prevention:-
 Make environment less aggressive (e.g., reduce O2 content);
 Cathodically protect;
 Use a better alloy (common cure - above not usually feasible)...
 “red” brass (<15% Zn) almost immune
 Admiralty Brass. . ( 70 Cu, 29 Zn, 1 Sn ).
 arsenical Admiralty. . ( 70 Cu, 29 Zn, 1 Sn, 0.04 As ).
 (Sn and Sn-As in deposited films hinder redeposition of Cu).
 For very corrosive environments likely to provoke dezincification,
or for critical components, use cupronickels ( 70-90 Cu , 30-10
Ni ).

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 Graphitization
 Graphitization :- (misnomer . . . graphitization is the breakdown of
Pearlite to ferrite + C at high temperature).
 Grey cast iron is the cheapest engineering metal 2-4% C, 1-3% Si.
Hard, brittle, easily cast; carbon present as microscopic flakes of
matrix graphite within microstructure.
 In some environments (notably mild, aqueous soils affecting buried
pipe) the Fe leaches out slowly and leaves graphite matrix behind . .
appears graphitic . . .soft . . . can be cut with a knife.
 Pores usually filled with rust. Original dimensions are retained.

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 6) Intergranular Corrosion Or Sensitization
 Intergranular corrosion , can be caused by impurities at the grain
boundaries, enrichment of one of alloying elements, or depletion of one of
these elements in grain boundary areas.
 Small amounts of iron in aluminum ,wherein the solubility of iron is low ,
have been shown to segregate in grain boundaries and cause Intergranular
corrosion.
 Depletion of chromium in grain boundary regions results in Intergranular
corrosion of stainless steels. Cr is added to steels to make them “stainless”.
The elements in grain boundary Cr-rich oxide film (based on Cr2O3) is
thin, adherent and very protective. But if heated into range 510-790°C, the
steels “sensitize” and become prone to Intergranular corrosion .
 Sensitization involves the precipitation of Cr carbide (Cr23C6) at the grain
boundaries; at the high temperature its solubility is virtually zero. The C
diffuses readily, and the disorder in the boundaries provides nucleation
sites. This depletes the boundaries of Cr.

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Sensitization by welding, or “Weld Decay”
 During welding, the weld “bead” and the metal on either side pass
through the temperature range for sensitization.
 Temperature and time are crucial for carbide precipitation: sensitized
areas are on either side of the bead.
 Sensitized SS can be used in many environments which are not too
aggressive or where selective corrosion not a problem (domestic,
architecture)

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 7 ) Erosion Corrosion

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 8. Stress corrosion Cracking(SCC)

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 9) Filiform corrosion 58

 Filiform corrosion is a type of localized corrosion that is often associated with

aluminum and magnesium alloys that have an organic coating.
 This type of corrosion has occurred on other coated metals such as zinc, iron
and steel.
 Filiform corrosion tends to occur at high humidity, e.g. greater than about
75% and temperatures at or slightly above room temperature.
 The corrosion appears as thread-like filaments under the coating.
 The corrosion products cause the coating to bulge giving the surface the
appearance akin to that of a lawn riddled with mole tunnels.
 The filaments proceed from points where the coating is no longer
continuous.
 Numerous coating systems are susceptible. Condensates containing halides,
sulfates, carbonates, or nitrates have been associated with filiform corrosion.
 Damage to the metal tends to be limited but the effect on appearance tends
to be detrimental.
 Filiform corrosion occurs under surface layers such as paint. It
depends on the relative moisture of the air and the quality of the
surface treatment preparation prior to coating.
 Filiform corrosion has the appearance of thin threadlike attacks
progressing along the surface beneath a surface layer. The mode of
attack is similar to pitting corrosion in that the front of the attack is
supported by moisture which penetrates the surface layer and
becomes depleted of oxygen making the area anodic.
 Filiform corrosion mainly has an aesthetic effect, but the corrosion
products formed may cause deformation in narrow crevices or
delimitation of surface treatment.

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The mechanism of filiform corrosion is shown in the figure below:-

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 The mechanism has a number of characteristics that are similar to
Crevice corrosion, e.g. differential aeration and hydrolysis of metal
ions resulting in increasing acidity in the region of dissolution. This
type of corrosion has the following characteristics.
1. The coating allows oxygen and water to migrate through it.
2. The concentration of dissolved oxygen becomes highest at the back
of the head near the region of the tail. This region becomes the
cathode.
3. Oxygen becomes depleted at the head. This region becomes the
anode.
4. Corrosion is driven by the potential difference between these
regions, a potential difference which can rise to several tenths of a
volt.
5. Metal ion formation and dissolution proceeds at the head while
61 oxygen is reduced closer to the tail.
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 10) Corrosion Fatigue

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 11) Hydrogen Damage

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End of Chapter 5

Thank You