Department of

Materials I Energy

Lecturer: Van Tang NGUYEN

Email: nguyen-van.tang@usth.edu.vn
 Chapter IV
Corrosion Process
 Corrosion Process

Corrosion is defined as the destructive and unintentional attack of a

metal

It is electrochemical and ordinarily begins at the surface

For metallic materials, the corrosion process is normally electrochemical,

that is, a chemical reaction in which there is transfer of electrons

from one chemical species to another
 ELECTROCHEMICAL CONSIDERATIONS

Metal atoms characteristically lose or give up electrons in what is called an

oxidation reaction

𝑀 → 𝑀𝑛+ + 𝑛𝑒 − (Oxidation reaction)

Fe→ 𝐹𝑒 2+ + 2𝑒 −

AL→ 𝐴𝑙 3+ + 3𝑒 −

The site at which oxidation takes place is called the anode; oxidation is
sometimes called an anodic reaction.
 ELECTROCHEMICAL CONSIDERATIONS

The electrons generated from each metal atom that is oxidized must be
transferred to and become a part of another chemical species in what is
termed a reduction reaction

For some metals undergo corrosion in acid solutions, which have a high
concentration of hydrogen (H+ ) ions

2𝐻 + + 2𝑒 − → 𝐻2

2𝐻 + are reduced and H2 gas is evolved

 ELECTROCHEMICAL CONSIDERATIONS

For an acid solution having dissolved oxygen, reduction according to

𝑂2 + 4𝐻 + + 4𝑒 − → 𝐻2 𝑂

for a neutral or basic aqueous solution in which oxygen is also dissolved,

𝑂2 + 2𝐻2 𝑂 + 4𝑒 − → 4(𝑂𝐻)−

Any metal ions present in the solution may also be reduced; for ions that can
exist in more than one valence state (multivalent ions), reduction may occur by

𝑀𝑛+ + 𝑒 − → 𝑀(𝑛−1)

Or a metal may be totally reduced from an ionic to a neutral metallic state

𝑀𝑛+ + 𝑛𝑒 − → 𝑀

The location at which reduction occurs is called the cathode

 ELECTROCHEMICAL CONSIDERATIONS

An overall electrochemical reaction must consist of at least one oxidation and

one reduction reaction, and will be the sum of them,

the individual oxidation and reduction reactions are termed half-reactions

There can be no net electrical charge accumulation from the electrons and
ions; that is, the total rate of oxidation must equal the total rate of
reduction, or all electrons generated through oxidation must be consumed
by reduction

Zn → 𝑍𝑛2+ + 2𝑒 − Oxidation process

2𝐻 + + 2𝑒 − → 𝐻2 Oxidation process
 ELECTROCHEMICAL CONSIDERATIONS

the total electrochemical reaction is just the sum of reactions

Zn → 𝑍𝑛2+ + 2𝑒 −

2𝐻 + + 2𝑒 − → 𝐻2

𝑍𝑛 + 2𝐻+ → 𝑍𝑛2+ + 𝐻2
 Electrode Potentials

If the iron and copper electrodes are connected

electrically, reduction will occur for copper at the
expense of the oxidation of iron, as follows

𝐶𝑢2+ + 𝐹𝑒 → 𝐶𝑢 + 𝐹𝑒 2+

the two half-cell reactions are represented

by the relations

Fe → 𝐹𝑒 2+ + 2𝑒 −

𝐶𝑢2+ + 2𝑒 − → 𝐶𝑢

When a current passes through the external circuit, electrons generated from the
oxidation of iron flow to the copper cell in order that Cu2+ be reduced
 Electrode Potentials

two metals electrically connected in a liquid

electrolyte wherein one metal becomes an
anode and corrodes, while the other acts as a
cathode

called “galvanic couple”

An electric potential or voltage will exist

between the two cell halves, and its
magnitude can be determined if a voltmeter is
connected in the external circuit
 Electrode Potentials

Considering another galvanic couple

In this case the zinc is the anode and corrodes,

whereas the Fe now becomes the cathode

𝐹𝑒 2+ + 𝑍𝑛 → 𝐹𝑒 + 𝑍𝑛2+
 The Standard emf Series

These measured cell voltages represent only differences in electrical potential

it is convenient to establish a reference cell

This reference cell, arbitrarily chosen, is the standard hydrogen electrode

It consists of an inert platinum electrode in a

1M solution of H+ ions, saturated with
hydrogen gas that is bubbled through the
solution at a pressure of 1 atm and a
temperature of 25oC

The platinum itself does not take part in the

electrochemical reaction, it acts only as a surface
on which hydrogen atoms may be oxidized or
hydrogen ions may be reduced
 The Standard emf Series

The electromotive force (emf) series is generated by coupling to the standard hydrogen
electrode standard half-cells for various metals and ranking them according to measured
voltage

Table 1. The Standard emf Series

those at the top (i.e.,
gold and platinum) are
noble, or chemically
inert

Those at the bottom

are more susceptible to
oxidation

The voltages are for the

half-reactions as
reduction reactions
 The Standard emf Series

Consider the generalized reactions involving the oxidation of metal M 1 and the
reduction of metal M 2 as

𝑀1 → 𝑀1 𝑛+ + 𝑛𝑒 − (−𝑉1 0 )

𝑀2 𝑛+ + 𝑛𝑒 − → 𝑀2 (+𝑉2 0 )

(𝑉 0 ) are the standard potentials as taken from the standard emf series

Since metal M1 is oxidized, the sign of 𝑉1 0 is opposite to that as it appears in Table 1

 The Standard emf Series

Combination of the two oxidization and reduction processes:

𝑀1 + 𝑀2 𝑛+ → 𝑀1 𝑛+ + 𝑀2 (*)

And the overall cell potential ∆𝑉 0 = 𝑉2 0 − 𝑉1 0

For reaction (*) to occur spontaneously ∆𝑉 0 must be positive;

If ∆𝑉 0 is negative (*) will reverse

 Influence of Concentration and Temperature on Cell
Potential

Altering temperature or solution concentration or using alloy electrodes instead

of pure metals will change the cell potential

The cell potential depends on the absolute temperature T and the molar
ion concentrations [𝑀2 𝑛+ ] and [𝑀1 𝑛+ ] according to the Nernst equation:

𝑅𝑇 *𝑀1 𝑛+ +
∆𝑉 = 𝑉2 0 − 𝑉1 0 − 𝑙𝑛
𝑛𝐹 *𝑀2 𝑛+ +

R is the gas constant

n is the number of electrons participating in either of the half-cell reactions

F: is the Faraday constant, 96,500 C/mol

 Influence of Concentration and Temperature on Cell
Potential

At 25oC

0 0 0.0592 *𝑀1 𝑛+ +
∆𝑉 = 𝑉2 − 𝑉1 − 𝑙𝑛
𝑛𝐹 *𝑀2 𝑛+ +
 Applications

Determination of Electrochemical Cell Characteristics

One-half of an electrochemical cell consists of a pure nickel electrode in a solution

of Ni2+ions; the other half is a cadmium electrode immersed in a Cd2+ solution.

(a) If the cell is a standard one, write the spontaneous overall reaction and
calculate the voltage that is generated.

b) Compute the cell potential at 25oC if the Cd2+ and Ni2+ concentrations are
0.5 and 10-3 M, respectively. Is the spontaneous reaction direction still the
same as for the standard cell?
 The Galvanic Series

The galvanic series is more realistic and practical than the the Standard emf Series

This represents the relative

reactivities of a number of
metals and commercial alloys in
seawater

The alloys near the top are

cathodic and unreactive

Those at the bottom are most

anodic
 CORROSION RATES

The corrosion rate, or the rate of material removal as a consequence of

the chemical action, is an important corrosion parameter

This may be expressed as the corrosion penetration rate (CPR), or the

thickness loss of material per unit of time

𝐾𝑊
Corrosion penetration rate (CPR) =
𝜌𝐴𝑡

W is the weight loss after exposure time t

𝜌 and A represent the density and exposed specimen area, respectively

𝜌 and A represent the density and exposed specimen area, respectively

K is a constant
 CORROSION RATES
 The CPR is conveniently expressed in terms of either mils per year (mpy) or
millimeters per year (mm/yr)

For mpy unit K = 534

For mm/y unit K = 87.6

• For most applications a corrosion penetration rate less than about 20 mpy
(0.50 mm/yr) is acceptable.

• Inasmuch as there is an electric current associated with electrochemical

corrosion reactions, we can also express corrosion rate in terms of this current

𝑖
𝑟=
𝑛𝐹
𝑛 is the number of electrons associated with the ionization of each atom.
F: Faraday constant: 96,500 C/mol
 PASSIVITY

Some normally active metals and alloys, under particular environmental

conditions, lose their chemical reactivity and become extremely inert
termed passivity

displayed by chromium, iron, nickel, titanium, and many of their alloys

Stainless steels are highly resistant to corrosion in a rather wide variety of

atmospheres as a result of passivation

contain at least 11% chromium that, as a solid-solution alloying element in iron,

minimizes the formation of rust; instead, a protective surface film forms in
oxidizing atmospheres

Aluminum is highly corrosion resistant in many environments because it also

passivates. If damaged, the protective film normally reforms very rapidly
 ENVIRONMENTAL EFFECTS

The variables in the corrosion environment:

fluid velocity

temperature ~ corrosion rate

composition

can have a decided influence on the corrosion properties of the materials

 FORMS OF CORROSION

Metallic corrosion is sometimes classified into eight forms:

uniform intergranular

galvanic selective leaching

crevice erosion–corrosion

pitting stress corrosion

 FORMS OF CORROSION

Uniform Attack

Uniform corrosion is characterized by corrosive attack roceeding evenly over the

entire surface area, or a large fraction of the total area.

General thinning takes place until failure

 FORMS OF CORROSION

Galvanic Corrosion

Galvanic corrosion occurs when two metals or alloys having different compositions
are electrically coupled while exposed to an electrolyte

steel screws corrode when in contact with brass in a marine environment

copper and steel tubing are joined in a domestic water heater, the steel will
corrode in the vicinity of the junction
 FORMS OF CORROSION

Galvanic Corrosion

The rate of galvanic attack depends on the relative anode-to-cathode surface

areas that are exposed to the electrolyte, and the rate is related directly to the
cathode–anode area ratio

for a given cathode area, a smaller anode will corrode more

rapidly than a larger one

The reason for this is that corrosion rate depends on current

density
 FORMS OF CORROSION

Galvanic Corrosion

A number of measures may be taken to significantly reduce the effects

of galvanic corrosion

If coupling of dissimilar metals is necessary, choose two that are close

together in the galvanic series.

Avoid an unfavorable anode-to-cathode surface area ratio; use an anode

area as large as possible.

Electrically insulate dissimilar metals from each other.

Electrically connect a third, anodic metal to the other two; this is a form of
cathodic protection
 FORMS OF CORROSION
Crevice Corrosion

Electrochemical corrosion may also occur as a consequence of concentration

differences of ions or dissolved gases in the electrolyte solution, and between two
regions of the same metal piece

For such a concentration cell, corrosion occurs in the locale that has the lower
concentration

A good example of this type of corrosion occurs in crevices and recesses or under
deposits of dirt or corrosion products where the solution becomes stagnant and
there is localized depletion of dissolved oxygen
 FORMS OF CORROSION
Crevice Corrosion

After oxygen has been depleted within the crevice, oxidation of the metal occurs

𝑀 → 𝑀𝑛+ + 𝑛𝑒 −

(Oxidation reaction)

Electrons from this electrochemical reaction

are conducted through the metal to
adjacent external regions, where they are
consumed by reduction

𝑂2 + 2𝐻2 𝑂 + 4𝑒 − → 4(𝑂𝐻)−
 FORMS OF CORROSION

Crevice Corrosion

Crevice corrosion may be prevented by:

using welded instead of riveted or bolted joints

using nonabsorbing gaskets when possible,

removing accumulated deposits frequently

and designing containment vessels to avoid stagnant areas and ensure

complete drainage.
 FORMS OF CORROSION

Pitting

Pitting is another form of very localized corrosion attack in which small pits or holes
form

They ordinarily penetrate from the top of a horizontal surface downward in a nearly
vertical direction

The mechanism for pitting is probably the

same as for crevice corrosion in that oxidation
occurs within the pit itself, with
complementary reduction at the surface
 FORMS OF CORROSION

Pitting

A pit may be initiated by a localized surface defect such as a scratch or a slight

variation in composition

it has been observed that specimens having polished surfaces display a

greater resistance to pitting corrosion
 FORMS OF CORROSION

Intergranular Corrosion

Intergranular corrosion occurs preferentially along grain boundaries for some

alloys and in specific environments

 a macroscopic specimen disintegrates along its grain boundaries

This type of corrosion is especially prevalent in some stainless steels

When heated to temperatures between 500

and 800 oC for sufficiently long time periods,
these alloys become sensitized to
intergranular attack
 FORMS OF CORROSION

Intergranular Corrosion

Intergranular corrosion is an especially severe problem in the welding of stainless

steels, when it is often termed weld decay
 FORMS OF CORROSION

Intergranular Corrosion

Stainless steels may be protected from intergranular corrosion by the following

measures:

(1) subjecting the sensitized material to a high-temperature heat treatment in

which all the chromium carbide particles are redissolved,

(2) lowering the carbon content below 0.03 wt% C so that carbide formation
is minimal,

(3) Alloying the stainless steel with another metal such as niobium or
titanium, which has a greater tendency to form carbides than does
chromium so that the Cr remains in solid solution.
 FORMS OF CORROSION

Selective Leaching

Selective leaching is found in solid solution alloys and occurs when one element
or constituent is preferentially removed as a consequence of corrosion processes

The most common example is the dezincification of brass, in which zinc is

selectively leached from a copper–zinc brass alloy

The mechanical properties of the alloy are significantly impaired, since only a
porous mass of copper remains in the region that has been dezincified
 FORMS OF CORROSION

Erosion–Corrosion

Erosion–corrosion arises from the combined action of chemical attack and

mechanical abrasion or wear as a consequence of fluid motion

Virtually all metal alloys, to one degree or another, are susceptible to erosion–
corrosion

It is especially harmful to alloys that passivate by forming a protective surface

film; the abrasive action may erode away the film, leaving exposed a bare
metal surface
 FORMS OF CORROSION

Erosion–Corrosion

The nature of the fluid can have a dramatic influence on the corrosion behavior

Increasing fluid velocity normally enhances the rate of corrosion

Erosion–corrosion is commonly found in piping, especially at bends, elbows,

and abrupt changes in pipe diameter—positions where the fluid changes
direction or flow suddenly becomes turbulent
 FORMS OF CORROSION

Stress Corrosion

Stress corrosion, sometimes termed stress corrosion cracking, results from the
combined action of an applied tensile stress and a corrosive environment; both
influences are necessary

Small cracks form and then propagate in a

direction perpendicular to the stress, with
the result that failure may eventually
occur

stress corrosion cracks formed along the bend at

those regions where the tensile stresses are the
greatest.
 FORMS OF CORROSION

Stress Corrosion

Most alloys are susceptible to stress corrosion in specific environments, especially at

moderate stress levels

Most stainless steels stress corrode in solutions containing chloride ions, whereas
brasses are especially vulnerable when exposed to ammonia

The stress that produces stress corrosion cracking need not be externally applied;
it may be a residual one that results from rapid temperature changes and uneven
contraction, or for two-phase alloys in which each phase has a different coefficient
of expansion
 FORMS OF CORROSION

Stress Corrosion

 best measure to take in reducing or totally eliminating stress corrosion is to

lower the magnitude of the stress

This may be accomplished by reducing the external load or increasing the

cross-sectional area perpendicular to the applied stress

Furthermore, an appropriate heat treatment may be used to anneal out any

residual thermal stresses
 FORMS OF CORROSION

Hydrogen Embrittlement