Mechanical & Aerospace

Engineering Department
Materials Engineering
MECH 390
Spring 2023

Dr. Ibrahim Shaban

Lecture 9 – Corrosion

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Class Objectives
Upon completing studying the material of this part of the chapter,
students should be able to:
• Understand the electrochemical mechanism of corrosion in metals, involving anodic
reaction and different possible cathodic reactions.
• Understand the concept of electrode potential.
• Define what is meant by a standard half cell.
• Use the standard EMF series in calculating standard overall cell potential.
• Use Nernst equation to calculate cell potential under non-idealized cell conditions.
• Understand the use of the galvanic series in ranking the reactivity of metals in
seawater.
• Use the corrosion penetration rate, as a corrosion parameter, in the design against
uniform corrosion.
• Understand the concept of passivity in metals. 3
 Introduction
• Deteriorative mechanisms are different for the three material types.

• In metals, there is actual material loss either by corrosion or by the formation

of nonmetallic scale or film (oxidation).

• Ceramic materials are relatively resistant to deterioration, which usually

occurs at elevated temperatures or in rather extreme environments; the
process is frequently also called corrosion.

• For polymers, mechanisms differ from those for metals and ceramics, and the
term degradation is most frequently used.
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 Corrosion
• Corrosion: is defined as gradual destruction of materials (usually a metal) by
chemical and/or electrochemical reaction with their environment. It ordinarily begins at
the surface.
Capone's ship, Sapona, off the coast of Bimini.

Photos courtesy L.M. Maestas, Sandia National

Labs. Used with permission.

• Cost:
- 4 to 5% of the Gross National Product (GNP) 5

- this amounts to just over $400 billion/yr

Corrosion

Figun_18_p638b
 Electrochemical mechanism of corrosion
in metals
• For metallic materials, the corrosion process is electrochemical, that is the corrosion is a chemical
reaction in which there is a transfer of electron from one chemical species to another.
• Two reactions are involved in the corrosion process; the oxidation or anodic reaction and reduction
or cathodic reaction. The site at which oxidation takes place is called anode. The site at which
reduction takes place is called cathode.
• In the oxidation reaction, metal atoms lose or give up electrons as follows:

• The released electrons from the anodic reaction must be collected by a cathodic reaction.

• https://www.youtube.com/watch?v=hfmD1RyUWgY
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 Possible cathodic reactions
• Individual oxidation or reduction reactions are called half cell reactions.
• Five cathodic reactions are possible depending on the surrounding solution
(environment):

 In an acidic solution, which have a high concentration of hydrogen (H+) ions, the
following cathodic reaction will take place:

 In an acidic solution having dissolved oxygen, the following reduction will take place:

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 Possible cathodic reactions

• In a neutral or basic solution, in which oxygen is also dissolved:

• In solution containing metal ions, they may be partially reduced:

• In solution containing metal ions, they may be totally reduced to metal

atoms:

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 Corrosion of Zinc in Acid
• Consider zinc metal immersed in an acid solution containing H+ ions, zinc will be
oxidized (oxidation reaction) as follows :
Zn  Zn 2  2e 
• Generated electrons will reduce H+ ions (reduction reaction) as follows:
  H+
2H  2e  H 2 (gas) Oxidation reaction
Zn Zn 2+ H+

Zinc flow of e- H+
Acid
2e - H+ solution
in the metal H+
H+
H 2 (gas)
H+
reduction reaction

• The total electrochemical reaction is the summation of the above two reactions

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 Standard electrode potentials
 The ease with which an electrode material can corrode or
in other words its corrosion tendency is called the
electrode potential.
 Different metals immersed in conductive solutions
develop potential difference when coupled through a
voltmeter.

 In the figure, Fe is the anode and Cu is the cathode.

 A pure metal electrode immersed in a 1 M solution of its
ions and at 25 oC is termed a standard half-cell
 molarity, M, is the number of moles of solute per million
cubic millimeters (106 mm3, or 1000 cm3) of solution. 11
 Standard electrode potentials
 The figure shows the standard
hydrogen electrode (SHE).

 The potential developed when

coupling SHE to a platinum electrode
immersed in a solution containing a 1
M solution of H+ ions, and at a
temperature of 25oC is called the
standard electrode potential of that
metal.
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 The standard electromotive force (EMF) series

 The standard EMF series is

generated by coupling to the
standard hydrogen electrode,
standard half-cells for different
metals and ranking them
according to the measured
voltage. See table 18.1 in your
text book.

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 The standard electromotive force (EMF) series
 The emf series represents the corrosion tendencies for different metals. Those at the top (gold and
platinum) are noble or chemically inert. Moving down the series, the metals become increasingly more
active. Sodium and potassium have the highest reactivates.
 The voltages in the EMF series are for the half reactions as reduction reactions. For oxidation, the sign of
the voltage must be changed. Consider metal M1 is connected to metal M2 and metal M1 is assumed to be
the anode, and metal M2 is assumed to be the cathode,

 Where 𝑉10 s are the standard potentials as taken from the EMF series. Since metal M1 is oxidized, the sign
of 𝑉10 is opposite to that as it appears in the EMF series.
 Adding the above two reactions, yields the following spontaneous reaction:
and the overall cell potential is
If ΔVo is negative, assumed anodic and cathodic reactions should be reversed.

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 STANDARD EMF SERIES
• EMF series o • Metal with smaller
metal Vmetal o
V metal corrodes.
Au +1.420 V
• Ex: Cd-Ni cell
more cathodic
Cu +0.340 o o
Pb - 0.126 VCd < VNi  Cd corrodes
Sn - 0.136 - +
Ni - 0.250
Co - 0.277 DV o =
Cd - 0.403 0.153V
Fe - 0.440
more anodic

Cr - 0.744 Cd 25°C Ni
Zn - 0.763
Al - 1.662
1.0 M 1.0 M
Mg - 2.363
Cd 2 + solution Ni 2+ solution
Na - 2.714
Data based on Table 18.1, Adapted from Fig. 18.2,
K - 2.924 Callister 9e. Callister & Rethwisch 9e. 15
Question (AL):
Briefly explain the difference between oxidation and reduction
electrochemical reactions. Indicate which reaction occurs at the
anode and which at the cathode.

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 The Galvanic Series
 Galvanic series represents the relative reactivates of a number of metals and
commercial alloys in seawater. It provides more realistic and practical ranking for
metals than the standard emf series. The alloys near the top are cathodic and
unreactive, whereas, those at the bottom are most anodic, no voltage is provided.

• Ranks the reactivity of metals/alloys in seawater

Based on Table 18.2, Callister 9e.

(Source of Table 17.2 is M.G.
Fontana, Corrosion Engineering, 3rd
ed., McGraw-Hill Book Company,
1986.)

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 Corrosion Rates
Corrosion penetration rate
 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. The formula for this calculation is

Where W is the weight loss after exposure time t. ρ and A represent the density and exposed area
respectively, and K is a constant dependent on units.
 The CPR is conveniently expressed in terms of either mils per year (mpy) or millimeters per year
(mm/yr). In the first case, to give
 CPR in mpy (where 1 mil = 0.001 in.), k = 534 and W, ρ, A, and t are specified in units of milligrams,
grams per cubic centimeter, square inches, and hours, respectively.
 CPR in mm/yr, k = 87.6 a units for the other parameters are the same as for mils per year, except that A is
given in square centimeters.
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Corrosion penetration rate

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 Corrosion rate
• Since there is an electric current associated with electrochemical corrosion
reactions, we can also express corrosion rate in terms of current density

• Current density: the current per unit surface area of material corroding,
designated as i.

• The rate corrosion r, in units of mol/m2.s is determined using the expression:

i
r
nF
Where,
i : Average corrosion current density in (A/m2).
n : Number of electrons in the half reaction.
F : Faraday’s constant = 96500 (C). 20
 Passivity of metals
 Passivity of metals is the process through which normally active metals
and alloys, under particular environmental conditions, lose their reactivity
and become extremely inert.

 This passive behavior results from the formation of a highly adherent and
very thin oxide film on the metal surface, which serves as a protective
barrier to further corrosion.

 Typical metals that show passivity under certain environmental conditions

are chromium, nickel, aluminum and stainless steels.
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 FORMS OF CORROSION
• Stress corrosion
Corrosion at crack tips when
• Uniform Attack a tensile stress is present. • Erosion-corrosion
Oxidation & reduction Combined chemical attack and
reactions occur uniformly mechanical wear (e.g., pipe
over surfaces. elbows).
• Selective Leaching Forms • Pitting
Preferred corrosion of Downward propagation
of
one element/constituent of small pits and holes.
[e.g., Zn from brass (Cu-Zn)]. corrosion Fig. 18.17, Callister & Rethwisch 9e.
(From M.G. Fontana, Corrosion
• Intergranular Engineering, 3rd ed., McGraw-Hill
Book
Corrosion along Company, 1986.)

grain boundaries,
often where precip. • Galvanic • Crevice Narrow and
particles form. Dissimilar metals are confined spaces.
g.b. physically joined in the Rivet holes
prec. presence of an electrolyte.
The
attacked Fig. 18.15, Callister & Rethwisch 9e.
zones
more anodic metal (Courtesy LaQue Center for Corrosion 22
Technology, Inc.)
Fig. 18.18, Callister & Rethwisch 9e.
corrodes.
CORROSION PREVENTION (i)

• Materials Selection
-- Use metals that are relatively unreactive in the
corrosion environment -- e.g., Ni in basic solutions

-- Use metals that passivate

- These metals form a thin, Metal oxide
Metal (e.g., Al,
adhering oxide layer that stainless steel)
slows corrosion.

• Lower the temperature (reduces rates of oxidation and

reduction)

• Apply physical barriers -- e.g., films and coatings 23

 CORROSION PREVENTION (ii)
• Add inhibitors (substances added to solution that decrease
its reactivity)
-- Slow oxidation/reduction reactions by removing reactants
(e.g., remove O2 gas by reacting it w/an inhibitor).
-- Slow oxidation reaction by attaching species to
the surface.

• Cathodic (or sacrificial) protection

-- Attach a more anodic material to the one to be protected.
Galvanized Steel Using a sacrificial anode
Adapted Zn 2+ Cu wire Adapted
from Fig. e- from Fig.
18.24, zinc zinc steel Mg Mg 2+ 18.23(a),
Callister &
Rethwisch 2e - 2e - pipe anode Callister &
Rethwisch
9e. steel Earth 9e.
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e.g., zinc-coated nail e.g., Mg Anode
 SUMMARY
• Corrosion occurs due to:
-- the natural tendency of metals to give up electrons.
-- electrons are given up by an oxidation reaction.
-- these electrons then used in a reduction reaction.
• Metals with a more negative Standard Electrode
Potential are more likely to corrode relative to
other metals.
• The Galvanic Series ranks the reactivity of metals in
seawater.
• Increasing T speeds up oxidation/reduction reactions.
• Corrosion may be controlled by:
- using metals which form
- adding inhibitors
a protective oxide layer
- painting 25
- reducing T - using cathodic protection.
Corrosion of ceramic materials

 Ceramic materials can be considered as already corroded materials as they

consist of combinations of metallic and non-metallic elements. Therefore
ceramics are resistant to corrosion in almost all environments.
 Corrosion of ceramics involves simple chemical dissolution in contrast to the
electrochemical mechanism found in metals.

Degradation of polymers
 Polymer degradation is a physiochemical process as it involves physical as
well as chemical changes.
 Upon exposure to liquids, polymer may deteriorate by swelling or dissolution.
Covalent bond of polymeric molecules may rupture as a result of weathering,
radiation, most commonly ultraviolet, chemical reactions and heat energy.

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